JP2001113381A - Method for machining transparent material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To generally solve various problems in such conventional methods of machining transparent materials as etching, scribing, cutting and joining. SOLUTION: A super exothermic solution 220 is made to flow, while a transparent material 120 such as a glass plate is arranged with the face 122 to be machined down on the surface 221 of the solution; then, the upper side, namely, the face opposite 123 from the face to be machined, is irradiated with an energy beam, for example, a laser beam through a photo mask 230; thus, etching is performed on the transparent material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to processing of transparent materials, in particular, etching, scribing, notching, fusion bonding,
It relates to each processing of cutting or forming a through hole.

[0002]

2. Description of the Related Art <Cutting Technology> Among brittle materials such as glass, semiconductors, and ceramics, quartz glass is mainly used for parts for manufacturing semiconductors, and borosilicate glass is mainly used for substrates for displays. When a brittle material is used as a component material, a scribe line is formed on the surface of the plate-like material to cut it to the required dimensions, and a method of applying an external force to cause breakage, or irradiating a laser beam to cut the material (Toshihiro Okiyama: Laser cutting, Journal of the Japan Society for Precision Engineering, 6
0, 2 (1994) 196). In the laser scribing method, a laser beam is irradiated on a line to be cut, the surface of the material is melted and evaporated to form a concave groove, and the groove is broken by applying an external force. As a problem of the laser scribing itself, there is a problem that the melted and evaporated material adheres to and deposits (recast) on the material surface, thereby contaminating the material. And there are problems such as generation of a large amount of fragments at the time of breaking. IARC (International Agency for Research on Cancer)
Carcinogenicity assessment of dust of silicon dioxide (silica) by 2A (probably carcinogenic) in 1996
Since it has been changed to (carcinogenic), the generation of broken glass material is a serious problem. Laser cutting method is
The irradiation position of the laser beam is moved under conditions where the stress field coefficient due to heat generated when the material surface is irradiated with the laser beam exceeds the fracture toughness of the material, and the cracks in the material are enlarged and cut. Is everything. This method has problems in that it is difficult to control the generation of the first crack, it is difficult to control the direction in which the crack propagates, the expected cutting line deviates from the actual cutting position, and the processing speed is slow. <Side pressure cutting> The side pressure cutting method (Hiroyoshi Tanaka: side pressure cutting technology, Journal of the Japan Society of Precision Engineering, 60, 2 (1994) 192) is a method of cutting a brittle material by hydraulic pressure, in which a liquid pressure is directly applied to the material. In some cases, hydraulic pressure is applied via an elastic member.
It is used for cutting glass rods for optical lenses, ceramics, steel materials and the like. In the lateral pressure cutting method, in order to control the cutting position, a notch (small indentation or cut) is formed by pressing a diamond needle or cutter against the material, that is, notching is performed. In the case of notching, microcracks are formed around the notch at the time of pressure welding (Sakamitsu Saka, Shunsuke Abe:
Observation of a crack and a defect structure around the crack by electron microscopy, Materia, 36, 3 (1997) 201). The direction of crack propagation is not always desired, and the actual cutting position may deviate from the planned cutting line. There is a problem that arises. <Joining technology> In the liquid crystal display device, an active matrix method is currently mainstream, and a TFT is provided for each pixel.
An information signal holding circuit such as (ThinFilm Transistor) is formed by a semiconductor manufacturing technology such as a thin film forming technology, a photolithography technology, and an etching technology. As a method of increasing the screen size of a liquid crystal display element, for example, there is a method of forming a large panel including a connection substrate obtained by melting and connecting TFT substrates and CF (color filter) substrates with laser light. In such a method in which the substrate is irradiated with the laser beam and directly heated and melt-bonded, the bonding end of the TFT substrate and the CF substrate is heated and denatured by the laser beam with a fixed width (about the diameter of the laser spot). Therefore, a pixel or an electrode cannot be formed in this portion, and a region without pixels, that is, a non-display region exists in a lattice shape along each joint end, and the display quality is reduced. This has resulted in lowering. Further, since the end of the substrate is usually sealed with a sealant, the sealant is melted or peeled off due to heating near the joint by direct irradiation of laser, and the sealing property of the liquid crystal layer is impaired. There is also a problem that it is. In addition, for high-precision bonding, it is necessary to smooth the bonding end face, so a polishing step of the substrate end face is required before the bonding step, which complicates the process, generates dust during polishing, and reduces noise. There are problems such as occurrence. Furthermore, when the entire liquid crystal element has a slight warp or when a substrate made of a relatively flexible material is used, the substrate is sandwiched between the two substrates in order to make the surface heights of the two substrates uniform during bonding. Or it is desirable to fix with a pressing jig or the like, but such a jig can not be used in the conventional joining method by laser irradiation, or the laser beam irradiation side of the jig,
There is a problem that it is necessary to provide a window for transmitting laser light. <Etching> In a semiconductor element manufacturing process, various semiconductor manufacturing technologies such as photolithography technology, etching technology, and film forming technology are used. However, when a concave portion needs to be formed on the surface of a glass substrate, it is usually used. A step of forming a patterned resist layer on a glass substrate, etching the surface with an etchant such as hydrofluoric acid, and then removing the resist layer is used. In such a method, since a resist film is formed directly on a glass substrate, it is necessary to remove the resist film before the next step, and since it depends on a chemical reaction in a liquid phase,
Although the etching rate is sensitive to changes in the concentration or temperature of the etchant, strict control of these conditions is difficult, and it is necessary to use means such as forming an etch stop layer in advance. The problem of difficulty in controlling the etching conditions is the same in dry etching performed using SF ₆ or the like. When a DNA chip such as a polynucleotide probe chip is formed, a plurality of square holes are arranged in a matrix on one surface of a transparent substrate. In some cases, etching using oxygen plasma is used to provide the uneven shape, but strict control of the environmental temperature is required, and high temperatures may damage parts that do not require etching. However, there is a problem that a by-product such as an oxide film is formed.
<Laser Ablation> On the other hand, in recent years, an etching technique using laser beam irradiation has been used. In this method, a substrate or a thin film material formed on a substrate surface is directly heated by irradiating a laser beam, and is melted and removed by ablation. However, similar to the laser scribing technique described above, a molten material generated in an ablation process is used. Adheres and accumulates on the substrate and contaminates the surface of the substrate, causing a problem of causing a defect of the device. <Report of super heat generation mechanism> Compared with the conventional processing technology as described above,
Processing using a super heating mechanism has been proposed (Akira Yabe, Hiroyuki Shinno, Shun Wang: Fine processing of quartz glass using laser-excited organic molecules, Materials Research Institute, NEWS, No. 39 (199)
9)) When a laser beam of an excimer laser is irradiated to an acetone solution of pyrene, pyrene molecules as a solute become super heaters to induce ablation of acetone as a solvent, thereby etching quartz glass in contact with the acetone solution. Is reported to be possible.

[0003]

SUMMARY OF THE INVENTION The present invention provides a conventional etching technique, scribing technique, notching technique for transparent materials or brittle materials as described above.
It is intended to propose a method of processing a transparent material that comprehensively solves the problems of cutting technology or fusion bonding technology, and in particular, proposes various processing methods of a transparent material using the above-described super-heating mechanism. is there.

[0004]

Means for Solving the Problems In order to solve the above-mentioned problems, the present invention provides a liquid phase material containing a dye forming a dimer or a dark complex while flowing the liquid phase material. A method of processing a transparent material that irradiates an energy beam and processes a transparent material that is in contact with the liquid phase substance. After notching the material, a lateral pressure cutting is performed by pressurizing the liquid phase material. A processing method for a transparent material. In this case, a method of processing a transparent material in which a laser beam is introduced into the bonding portion and fusion bonding is performed is adopted.

[0005]

The dye in the liquid phase material generates heat by the irradiation of the energy beam, and the adjacent transparent material is processed.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a transparent material according to the present invention will be described.
A processing method and a processing apparatus of the material will be described. <Processing> Here, processing refers to etching and scribe-bin
Including notching, notching, fusion bonding, cutting, and through-hole formation
No. Etching is the formation of a concave structure on the surface of a material,
Refers to a process for flattening a convex structure. Out of etching
Cutting by applying bending moment or impact force to the material
When forming a linear groove for
The material is used to cut the material by tensile stress.
The formation of recesses on the surface of the material is called notching.
U. In addition, they are in contact with each other or opposed to each other with a very small space between them.
At least one of the two or more materials
By melting the material, the material that joins the other material
The process is called fusion bonding. For processing, usually perylene
Dissolve liquid dyes such as carbon disulfide
Inject into a reaction tank or the like to make a super-heat-generating liquid phase substance. Super exothermic
The liquid phase material is maintained at the liquid level by appropriate means.
The controlled flow state may be controlled by the energy beam.
May be replaced before and after the irradiation. Transparent material in this liquid
Will be fixed.
At least the part to be processed becomes liquid phase material throughout the processing process
It is desirable to be touched or immersed. Usually processed
If you fix it so that the entire surface is slightly below the liquid level
Is enough. For transparent material fixed as described above,
Is patterned according to the processing shape as needed
Through a photomask and further through an optical system such as a condenser lens
Laser beam irradiating laser beam as incident energy beam
Processing can be performed by irradiating from a step. One pal
The amount of etching per unit depends on the transparent material and irradiation conditions.
However, in the case of a glass material, it is several tens nm. Ma
In addition, the liquid phase material is supplied dropwise from above and
Laser irradiation can also be performed. For example, Polynuk
For making DNA chips such as leotide probe chips
In this case, multiple square holes are masked on one surface of the transparent substrate.
In a configuration in which the openings are arranged in a trix-shape,
To hold the gel holding the peptide probe in the stoma
To provide molecular level irregularities on the inner surface of each small hole
However, in such a case, fluid super heat is generated in the pores.
After dropping the liquid-phase material, the liquid should be placed below or beside the transparent substrate.
Is an optical system corresponding to the desired uneven pattern from diagonally above
Laser beam as an energy beam through the
By this, it is possible to form nano-level uneven shape
You. Is the transparent material itself an optical waveguide, one end of the transparent material?
Light from the other end is emitted from the other end,
Irradiation may be applied to the dye. Therefore, like optical fiber
Work on the cut surface or longitudinal end of long transparent material
be able to. Among transparent materials, super heat-generating liquid phase material
Process only the surface in contact. Of transparent materials,
Laser light is incident from a part that does not require
At least the incident light is emitted
No processing is caused at the part where no processing is performed. Incident light
Make the transparent material incident on the transparent material from unnecessary parts.
Inject from transparent material processing part after transmitting transparent material
The super-heat-generating liquid phase material in contact with the transparent material, or
Super exothermic dye located near the processed part of transparent material
Is irradiated. In the processing of the present invention, the vicinity of the transparent material
Irradiate the energy beam to the dye molecules located next to it.
Thereby, the processing of the transparent material is realized. In other words, the dye
By irradiating the molecule with an energy beam, the pigment
Processing of transparent material close to the child. Photomass
Surface instead of a transparent material, or the opposite side
A photomask layer made of an opaque member is
The pattern may be formed by a thin film forming technique. Was
However, when forming a photomask layer on a transparent material,
Between the etching step and the next step.
In some cases, it is necessary to provide a removing step. Opacity
If a polysilicon layer is patterned as a member,
It can also be a circuit element in the SOG structure. Transparent
Is the transparent member on the part of the surface to be processed of the clear material that does not require processing?
The etching sacrificial layer is formed by a known thin film forming technique.
In other words, turn the surface opposite to the surface to be machined
If processing is unnecessary, that is, the supply side of the liquid phase material
Laser irradiation may be performed from the opposite side. Etching sacrifices
In the part where the layer was formed, etch instead of the transparent material
Etching sacrificial layer is etched to form an etching sacrificial layer
The transparent material will be processed in the portions that have not been processed.
The transparent etching sacrificial layer is formed of an insulating material such as glass or resin or I.
It is necessary to form a pattern with a transparent conductor such as
Etching by laser irradiation as necessary
Circuit, COG structure such as capacitance, resistance, conductive path, etc.
It is also possible to form elements. Etching sacrificial layer
If it becomes unnecessary after the next step,
When the etching is completed,
Etching sacrificial layer to be removed by etching
If the film thickness is set, an etching sacrificial layer removal process is provided.
It is suitable because it is not necessary. Laser beam is emitted
A transparent member or opaque part of the surface
In the part where the layer made of the bright member is formed, the transparent material
No processing will occur. In addition, etching sacrifices
The part of the layer where the laser beam is emitted
Only causes etching of the etching sacrificial layer.
You. If necessary, the above photo mask and etching
The etching depth can be increased by using the sacrificial layer together.
Complex etching patterns with variations
It can be formed. Without going through a photomask
Sweep laser light or use transparent material on XYZ table
To form an etching pattern.
Can also be. The etching method of the present invention can be applied to a semiconductor acceleration
Not only a degree sensor, but also an inkjet nozzle
Etc. can be widely used in the manufacture of semiconductor elements and devices,
In particular, it includes the step of forming a polysilicon layer on a glass substrate.
Semiconductor devices such as polysilicon liquid crystal devices, polysilicon
It can be suitably used for manufacturing a capacitor integrated circuit and the like. This
In the case of, if only the circuit configuration of the element and the manufacturing process of the internal structure
For break splitting when manufacturing multiple devices
Can also be suitably used in the scribe line forming process.
 Scribing, notching
When etching, make the super-heat generating solution flow
Direction and the longitudinal direction of the scribe line etc.
If they are set to be approximately parallel, fine particles formed by etching
Ultra-heat-generating solution is supplied evenly to fine pattern details
This is preferable. In this case, the flow rate of the super-pyrogenic solution is low.
At least a layer near the surface of the transparent material to be processed
It is sufficient to form a flow, but of course it may be turbulent
No. On the other hand, the longitudinal direction of the scribe line
If the flow directions of the liquids are not parallel,
Turbulence near the surface of the bright material
Preferably. Furthermore, if possible,
At the bottom of a transparent material, an ascending flow of super-pyrogenic solution is formed.
It is also suitable to supply them. Thus, etching
Super-uniformity even to the details of the fine pattern formed by
By setting the thermal solution to be supplied,
Since the thermal dye is uniformly supplied to the processing section at a constant concentration,
The etching reaction can proceed stably,
Keep the area around the processing area at a constant temperature and
Removal of formed by-products such as melts from processed parts
And the like. The super-pyrogenic solution is thus fluidized
When irradiating the laser pulse,
Time sufficient to provide the superpyrogenic dye at a constant concentration
It is desirable to set the irradiation cycle with a margin. Ma
Also, if the super-heating solution is not allowed to flow,
Solution concentration fluctuates extremely over the entire etching process.
The irradiation cycle should be set with sufficient time
Is desirable. Conversely, according to the concentration change of the super-pyrogenic solution,
Laser light irradiation intensity, irradiation time, irradiation frequency or irradiation cycle, etc.
Increase or decrease the dye concentration by adjusting the light amount
The light amount may be adjusted according to the following. Etching of the present invention
Other methods include diffraction grating, scale and hologram display
For optical devices such as optical devices, DVDs, near-field optical disks, etc.
It can be applied to the production of media,
Transparency represented by glass, such as decorations and watch protective covers
It is also suitable for forming letters and patterns on bright materials.
You. The recess formed on the surface to be processed of the material is on the opposite surface
Cutting of transparent material is possible by continuing processing until
It is. Also, the direction of incidence of the laser beam on the transparent material is changed.
And the part and direction in which the laser light exits from the transparent material.
Forming a bent through hole by changing it sequentially
It is also possible. In the side pressure cutting of the present invention,
The transparent material as the processing member corresponds to the shape of the transparent material.
On one side of a pair of O-rings
In contact with the laser light introduction liquid on the other side.
It is inserted into the pressure vessel to touch. In this state,
Laser light introduction window and laser light introduction provided in pressure vessel
Laser light is applied from a laser light irradiating means through a liquid to a transparent material.
A point on the planned cutting line or a fixed length along the planned cutting line
Is irradiated. Laser light is transmitted through transparent material and
Reaches thermal liquid phase material, but laser light is emitted from transparent material
At the position where the transparent material is heated
The surface is notched and a notch is formed. Then
Pressure without moving the transparent material from the notching position
A superheated liquid phase material pressurized from the generator
At the same time as the pressurized laser from the pressure generator.
When the laser light introduction liquid is introduced into the pressure inlet, the transparent material
Compressive stress on the surface and tensile stress in the center
You. The generated internal stress increases in proportion to the applied pressure,
It is generated inside the notched
When the tensile stress exceeds the tensile strength of the transparent material,
At that point, the transparent material is broken and cut. And
The next cut can be made by advancing the light material. Book
In the lateral pressure cutting method of the present invention, a cylindrical glass rod is used.
Not only can it be applied to materials of other shapes,
By changing the shape of the
Columnar material, plate-like material, and multiple
It is also possible to apply to a seed semiconductor element substrate and the like. Book
In the fusion joining of the invention, at least one is made of a transparent material.
Abut two materials at the end face connecting them
Contact, or facing each other at a small distance,
It is immersed and fixed in a thermal liquid phase material. At this time, at least
Also, the connections at each end face are immersed in
Is enough. When fixing both materials, the end face to be joined
When aligning the substrates, align the surface heights of both substrates.
For this purpose, secure it with a jig or the like
It is desirable to specify. The shape, mechanism and translucency of this jig
Etc. can be set freely as long as they do not prevent contact or opposition of both end faces.
can do. Also, the joints are the same as for laser beam irradiation.
Time or immediately after irradiation, compressive stress is applied by pressing means as appropriate.
Is desirable. As described above, the connecting end of both materials
After fixing the part, from the end on the side where the transparent material does not connect,
Laser light radiated from the laser irradiator in the transparent material
Is introduced. The laser light introduced into the transparent material
Edge where the transparent material itself is used as a waveguide and joined inside the transparent material
Proceed until it is ejected from the joining end. At this time,
Between the joining edges of both materials, very little
Due to the thin layer, butt each end to be joined
In contact with each other, or on a part facing
The super-pyrogenic liquid phase material generates heat,
Alternatively, at least one of the opposed ends is melted.
Let And by pressing by pressing means or pressing
The two materials are joined without any problems. Melt bonding odor of the present invention
In other words, the transparent material itself, which is the workpiece, is used as an optical waveguide.
Before the light reaches the junction
The laser light should not leak from the transparent material
desirable. Specifically, the refractive index of the transparent material and the super-heating liquid
The relationship between the refractive index of the phase material and the incident angle of the laser beam
When the laser light is not reflected on the end face inside the workpiece other than the joint end face,
It is desirable to set it to shoot. In addition, laser light
Is totally reflected at the end face inside the workpiece other than the joint end face
To be processed by a substance having a lower refractive index than the workpiece.
Coating a workpiece to form a so-called cladding layer
Is also possible. In addition, opaque filler
A transparent etching sacrificial layer.
Also, the melting of the workpiece only at the joint
Melt can be generated, and suitable for fusion bonding
I do. In addition, this fusion bonding method applies only to liquid crystal display elements.
Not only can it be applied to members made of transparent materials,
For connecting transparent substrates for semiconductor devices, for example, glass plates, for lighting
It can also be used to connect optical fibers for communication.
is there. With the processing method of the present invention, the end face of the optical fiber is etched.
When performing the etching, the above transparent member or opaque part
Kazuhiro Hane (Tohoku University)
They propose a method of spraying a photoresist
Using film forming technology to create a film of uniform thickness on the fiber end face
Can be In this case, the optical fiber itself is
Laser light can reach the processing end face as a wave path.
Wear. Etching the optical fiber end face
Enables three-dimensional processing on surfaces, miniaturization of optical connectors,
It is possible to form active parts directly. Optical fiber
Immerse in a super-heat-generating liquid phase material, and from one end into the optical fiber
When introducing laser light, scratches on the surface of the optical fiber
Laser light leaks out of the optical fiber
The heat generated by the super-pyrogenic liquid phase material in
As a method to inspect for defects such as scratches on the fiber surface
It can also be used. <Energy beam> This specification
Energy beam means radio wave, microwave, infrared
Ray, visible light, ultraviolet ray, X-ray, gamma ray, sink
Rotron radiation or flash lamp light or other electromagnetic waves
As well as the flow of charged particles such as electron beams
Excite molecules and / or induce association, dimerization and
Energy required for de-dimerization of the dimerized dye
Means energy transportation means that can supply
Coherent light in the visible or ultraviolet wavelength range, especially
But it refers to laser light. The energy beam of the present invention
It must have a property that is hardly absorbed by
Is desirable. The laser used in the present invention is particularly
Without limitation, absorption of selected liquid phase substances or dye molecules
It is desirable that the wavelength should correspond to the collection region,
KrF, ArF, XeCl, XeF excimer lasers,
Nd-YAG laser, CO₂Laser, CO laser, nitrogen
Laser, solid-state laser, ruby laser, semiconductor laser,
It can be appropriately selected from a tunable diode laser or the like.
 In the processing of the present invention, the laser light source, pulse width,
The energy or frequency is determined by the absorption characteristics of the selected workpiece.
Suitable for heat resistance, processing characteristics and heat generation characteristics of super-heat-generating liquid phase materials.
Laser beam irradiation
Time may be controlled. In the present invention, the laser light
Processing when direct processing by irradiating transparent material with
Laser light with an energy smaller than the light intensity threshold
For example, it is possible to process quartz glass.
In this case, a pulse wave of an excimer laser such as FWHM
= 30-50 ns, energy density 400-1400 mJ
/ Cm²2-10 Hz can be used. pulse
Use of ruby laser that can change width greatly
Is also convenient. <Transparent material> In this specification, transparent means energy
Beam, especially the property of transmitting light, especially laser light
Optical transparency that transmits coherent light represented by
It refers to translucency. Transparent material used in the present invention
Does not need to transmit 100% of the incident light, but was selected
Depending on the transmission of the incident light itself, changes such as destruction, melting, and phase transition may occur.
Before and after transmitting the incident light without quality
It is desirable not to change the property of transmitting light. Follow
The term “transparent material” refers to the property of transmitting an energy beam.
Glass, resin, ceramics, metal, etc.
Point, especially glass or resin that is transparent to light
Point to. Here, what is used as glass
Is silicate glass, borate glass, phosphate glass,
Acid glass, tellurite glass, vanadate glass
, Chalcogenide glass, fluoride glass, oxynitride
It can be appropriately selected from glass and the like and used.
Typically, fused silica glass (quartz glass), 96%
Kagurasu, soda-lime glass, lead alkali silicate glass
, Borosilicate glass, aluminosilicate glass, alumino
Borosilicate glass, aluminosilicate glass, glass
Sceramics, alumina ceramics, pyrex, pie
Roseram, Corning 7740, Corning 0211,
Corning 7059, sapphire, calcium fluoride, etc.
Can be mentioned. In addition, as ceramics,
Including translucent alumina, Y₂O₂, MgO, Zr
O₂, ThO₂, (Pd, La) (Zr, Ti) O
₃(PLZT) or the like can be used. Also, resin
As various transparent polymers, specifically, polymethylmeth
Tacrylate, polycarbonate, diethylene glycol
Rubis allyl carbonate, methyl methacrylate
Tylene copolymer, acrylonitrile / styrene copolymer
Body, poly (4-methylpentene-1), tetrafluoro
Ethylene / hexafluoropropylene copolymer, poly
(-2,2,2-trifluoroisopropyl methacrylate
), Polycyclohexylmethyl methacrylate,
N-butyl methacrylate, polyvinyl naphthalene,
Poly α-naphthyl methacrylate, cellulose acetobu
Tylate, cellulose propionate, polyvinyl chloride
Ride, styrene-acrylonitrile copolymer, police
Tylene, styrene / maleic anhydride copolymer, polyteto
Ramethylene terephthalate, polymethyl isocyanate
Etc. can be used. The processing method of the present invention
Materials that can be processed include plate, wire with arbitrary cross section, and circle
Columnar material of arbitrary cross section including cross section / rectangular cross section, circular / rectangular outer shape
Hollow cylindrical materials, spherical materials, and other
Wood. Here, the field of application of plate materials
As for liquid crystal display devices, plasma display devices and other tables
Indicating element substrate, semiconductor sensor, LSI and other semiconductor elements
Substrate and substrate for semiconductor integrated circuit, diffraction grating, scale
Hologram display element, other optical elements, DVD,
Decorative items such as recording media such as optical discs and photo stands
And a protective cover for a watch. Circular section
The field of application of columnar materials is to manufacture optical lenses
Rod material, and as a linear material, an optical fiber for lighting or communication.
Optical lenses are used as application fields for spherical materials.
Can be <Super heating mechanism> With "super heating mechanism"
Is dissolved in the liquid phase material due to the irradiation of the energy beam.
Dyes that are dissolved, dispersed or mixed can be efficiently used by surrounding substances.
This is a mechanism that gives high energy, especially when the phosphor in the solution
After being excited by a laser pulse, heat
Emits energy and / or emits laser pulses
The energy of the meeting as heat energy due to the accompanying heat generation
Release mechanism. In this specification,
Properties are sometimes referred to as "super-heating". General
Polyatomic molecules, especially organic molecules having a conjugated π-electron system
After being excited (pumped), the dye molecules
The child absorbs the ground state S₀
→ Excited singlet state
state) S₁, But the Frank-Cond
According to the Frank-Condon principle,
In a very short time, S₁To the lowest level of vibration
Non-radiative transition. Lowest excited singlet state dye
The child is partly in the form of fluoresence
Emit photons, and partly due to non-radiative transition due to vibrational relaxation
By the transfer, the ground state S₀To S₀Dye that has transitioned to
The molecule is S in a short time₀Non-radiative transition to the lowest level of
Is generated. In addition, another dye molecule in the lowest excited singlet state
The section is intersystem crossing
ng) to the excited triplet state (excited trit state).
Plet state) T₀Produces a radiative transition at
Some of them are ground state S₀To T₀→ S₀What
Transitions can be phosphorescent or non-radiative.
You. Also, S₁And T₁Dye molecules undergo further photoexcitation
S with higher energy level_nAnd T_nTransition to (n> 1)
And this S_nAnd T_nOf the dye molecule also
Department conversion (internal conversion) or
Is in a low excited state due to non-radiative transition due to vibration relaxation, etc.
May transition. That is, organic molecules are photoexcited
To an excited singlet state in which electrons are excited by
Singlet state molecules absorb more photon energy and
It is known to transition to a highly excited singlet state.
The light absorption corresponding to the transition of is "singlet / singlet absorption".
It is called. In addition, molecules in the excited singlet state are external
Subject to these perturbations, the spin multiplicity varies with time.
Transition to the multiplet state. The excited triplet state molecule is a photon
Absorb energy and transition to higher excited triplet state
However, the corresponding light absorption is called "triplet / triplet absorption".
It is called. In these wavelength regions, molecules in the ground state
It may be in a region that does not absorb. Also, single excitation
A molecule in a singlet state or excited triplet state is, for example, an intramolecular
Radical species are generated by a cleavage reaction or the like. like this
Waves without absorption of ground state molecules even in radical species
It may have strong absorption in the long region. Collectively
Is referred to as intermediate absorption in intermediate molecules.
Rays corresponding to ground state or intermediate absorptions such as
When the light is irradiated on the molecule, the molecule absorbs the photon energy
To become an excited intermediate, and then the intermediate molecule, for example,
Emitting as thermal energy in the form of non-radiative transitions due to partial conversion
You. S_nOr T_nHigh energy levels like
The molecule is S₀Or T₀Up to the nonradiative transition
When excited, almost all absorbed photon energy is
Will be released as heat energy,
Is high in conversion efficiency. Also, the emission spectrum of the dye
The vector shifts to a longer wavelength side with respect to the absorption spectrum.
Talks shift), but emission on the long wavelength side, especially in the infrared region
Light can contribute to heating of the workpiece. <Quenching> By the way, a certain threshold value of the concentration of fluorescent molecules in the solution
When the value exceeds, the fluorescence efficiency is rapidly reduced. This is
Called light. Such fluorescence quenching can be attributed to fluorescence resonance energy.
Giu Transmission (Fluorescence Resonance)
e Energy Transfer: FRET)
Cross relaxation, light guidance
Electron transfer, promoting intersystem crossing, paramagnetic enhancement, Dexter crossing
Exciton coupling such as exchange coupling or dark complex formation
By any of several mechanisms, including
Happen. The transfer of fluorescence energy is
Dependencies (eg, Forste
r, T. (1984) Ann. Physik 2:55
-75; Lakowicz, J .; R. , Princi
ples of Fluorescence Spec
troscopy, New York: Plenum
Press, 1983; Herman, B .; , Reso
nonce energy transfer mic
roscopy: Fluorescence Mic
roscopy of LivingCells in
 Culture, Part B, Methods i
nCell Biology, Vol 30, Editing Ta
ylor, D.E. L. And Wang, Y .; L. , San
Digo: Academic Press, 1989,
pp. 219-243; Turro, N .; J. , Mo
dern Molecular Photochemi
try, Menlo Park: Benjamin
/ Cummings Publishing Co. I
nc. , 1978, p. 296-361). This
In addition, photoinduced electron transfer, facilitating intersystem crossing, paramagnetic enhancement, De
xter exchange coupling is when two molecules collide and
Is effectively generated by approaching a distance of 1 nm or less.
You. <Fluorescence resonance energy transmission> Fluorescence resonance energy transmission
(FRET) is the localization center of the phosphor at high concentration
Between the excitation and the corresponding de-excitation
The simultaneous transfer causes the excitation energy to be localized
The phenomenon of walking between spaces. In this case, some localization center
Near the center with high probability of nonradiative transition
While the Nergies are moving, they come close to them and make a nonradiative transition
Excitation energy is released as heat energy for transfer
It will be. The probability of FRET is that both transitions are electric dipoles
In the case of the transition, the distance between the localization centers is-
If it is proportional to the sixth power and is due to electric quadruple transition, the station
It is shown that the distance between the centers is proportional to the −10th power.
 Unlike FRET, a radiative transition that emits fluorescence
The excitation transition of almost the same energy is
Interaction of simultaneous energy transitions due to interactions between minds
It is called difference mitigation. The probability of cross mitigation is similar to FRET
Given by For radiative transitions, the actual emission of fluorescence
・ Has a localized center that accepts energy through the absorption process
None is the decay time constant of the fluorescence at the localization center that supplies the energy
But does not affect energy in the case of FRET.
Localization donating energy with the concentration of the accepting localization center
Both are distinct because the decay time constant of the central fluorescence is shorter.
Can be distinguished. As described above, FRET and radiation transition
Are competing as a form of energy transfer, so F
For RET to occur more efficiently than fluorescence,
The distance between the localization centers of the donor and recipient of energy is sufficiently small
It is necessary to set it up, specifically, one hundred to several
It is necessary to be less than + Å. Observed on FRET
Of non-radiative Forster-type energy transfer
Is the donor by light of a certain wavelength in the absorption region of the donor.
It is accompanied by the excitation of body molecules. A small amount of excitation energy
Delivered to the surroundings in the form of vibrational energy of the
Transition of the initiated molecule to the lowest vibrational state), the rest
Released primarily by energy transfer to the receptor molecule
You. FRET depends strongly on the distance between centers
In general, this is not so significant when the concentration of fluorescent molecules is high.
You. In addition, fluorescent molecules form aggregates (dimers,
Includes bodies, clusters and aggregates. ) May form
In such cases, the localization
The distance between them may be small, and FRET becomes remarkable.
You. In particular, in the H-association type dimer or laminate, the fluorescence
The distance between localized centers in the molecule is very small
It is considered that the occurrence of FRET becomes remarkable. You
That is, when the fluorescent molecules are dimerized or laminated,
Electrons inside are closed in the space between the fluorescent molecules due to the quantum effect.
The electronic excitation generated in a certain molecule is
Between the dipoles by dipole-dipole or multipole interactions.
Molecular excitons that propagate resonantly to other molecules
And As a result, molecules that are fluorescent in monomers
Even reduce its fluorescence by dimerization or lamination,
Or loss increases the probability of non-radiative transitions and increases
Release the collected energy mainly as heat energy.
And In the present specification, "donor"
Means that energy is absorbed and that energy is
Color that can be transferred to a child or part of a compound
Element, especially phosphor. As a suitable FRET donor
Is a coumarin and related dyes, xanthene dyes, such as
Fluorescein, fluorescein
Senisothiocyanate (fluorescein i
sothiocyanate: FITC), Lodore
(Rhodol) and rhodamine, resorufin,
Anine dye, bimane, acridine, i
Soindole, dansyl dye, aminophthalhydrazi
Such as luminol and isoluminol derivatives,
Minophthalimide, aminonaphthalimide, aminoben
Zofran, aminoquinoline, dicyanohydroquinone and
And terbium complexes and related compounds
But not limited to these. Here, "color
"Element" means a specific frequency, including but not limited to ultraviolet light
Refers to a part of a molecule or compound that absorbs a number of light.
"Fluorescent substance" is a dye that can emit fluorescence.
is there. The term “acceptor” refers to FR
When located at an energy exchange distance with the ET donor,
Molecules capable of receiving energy transfer from a donor or
Refers to a dye as part of a compound. For example, x-low
Damine (x-Rhodamine), Tetramethyl Rho
Damine isothiocyanate (Tetramethylr)
hodamine isothiocyanate)
(TRITC) and CY3 (carbocyanine)
3) can be mentioned. Acceptor FRET
Quencher that operates through
is there. Many FRET receptors transmit energy as fluorescence
Can emit light. Examples are coumarin and
Related fluorophores, xanthenes such as fluorescein, rhodo
And rhodamine, resorufin, cyanine, diph
Ruoloboradiazaindacene and phthalocyanine
Can be mentioned. Other chemical classes of receptors are generally
Does not emit transition energy. For example, Inge
Go, benzoquinone, anthraquinone, azo compounds, nitro
B compound, indoaniline, di- and triphenyl meta
And so on. Donor and acceptor via linker
Even when covalently bonded by
Giant transitions are possible and are called intramolecular energy transfer.
In this case, "donor" and "acceptor"
In each case, energy is applied to other fluorogenic molecules by FRET.
Fluorescent molecules that can be transferred, and FRET
Fluorescent molecules that can accept more energy
Point. In this case, the linker is
Have multiple bonds to allow conjugation of
Don't do it. Use of FRET is a fluorescent probe
Technology, labeling technology, immunoassay or nucleic acid
Analyte detection, protein, poly
Of peptides, nucleotides, nucleic acids and their analogs
By binding, the presence of these substances in biological fluids
Detection or DNA detection (Kronick et a
l. "Clinical Chemistry" vo1
29, 1582-1586 (1983)), saccharides, DN
A fragments, such as hormones, drugs and immunoglobulins
Determination of the concentration of the substance in the subject, reporter gene
Measurement of gene promoter activity in
orman, C.I. M. et al. , Mol. Cell
 Biol. 2: 1044-1051 (1982); A
lam, J.M. and Cook, J.M. L. , Anal.
Biochem. 188: 245-254 (199
0)), relationships within proteins, RNA and peptides
Spectroscopic criterion for knowing
ew of biochemistry (197
8), 47, 819-846), geometric details within the particle
Physical review lett
ers (1988) 61, 641-644), polymerization
Kinetic studies (Paczkowski and Nec)
kers "Following Polymeriza
Tion Kinetics of Multifunc
temporal Acrylates in Real T
im by Fluorescence Probe
 Methodology "Macromolecule
es, 25, 548-553 (1992)), living cells
It has been reported in fields such as measurement of membrane potential. <Den
Efficiency> FRET efficiency is the fluorescence quantum yield of the donor phosphor
(Quantum yield), the excited state of the donor
Lifetime, donor emission spectrum and acceptor absorption spectrum
Overlap integral (overlap integer)
al), depending on orientation and distance between donor and acceptor
I do. This is the formula of FRET forter: ET∝
K²Φ_DJ / R⁶τ_D To follow. Where the expression
ET is the energy transfer coefficient, K²Are donors and
Relative orientation of the transition moment of the puter, Φ_DIs the donor molecule
Quantum yield, R is the center of the donor and acceptor phosphor
Distance, J is the emission spectrum of donor phosphor and acceptor
Overlap with the absorption spectrum of the_DIs a donor
The lifetime of the excited state of the molecule. To the degree of conformity of the above conditions
Depending on the distance approach of the acceptor and the donor, the donor
The fluorescence lifetime of some phosphors, and in some cases
To form a dark complex. Selection of phosphor used for FRET
Indicates energy transfer at the appropriate excitation wavelength of the donor.
Ability (singlet-singlet energy transmission: si
nglet-singleenergency trans
fer). High fluorescence quantum
Donor fluorescence with yield (preferably close to 100%)
Large extinction number at wavelengths matching the emission of the donor to the donor
Energy transfer is most effective when paired with
Good rate. In practice, the energy transfer efficiency is 100%
It is not so close that the donor dye
Fluorescence may be observed. Generally, donor phosphor
And the absorption peak of the receptor are approximately 10 nm
When it is within the range, the transmission efficiency increases. Spectrum
Tables of overlap integrals are readily available to those skilled in the art.
(See, for example, Bellman, IB, Energy
transfer parameters of ar
omatic compounds, Academic
 Press, New York and London
n, 1973). Colors that indicate overlapping excitation and emission wavelengths
A specific set of elements (eg, Proceedings of
 national academy ofscien
ce USA 1969, 63, 23-30)
However, they do not show FRET, or have an appropriate value (8
0%).
Not. Two or more dyes provide effective energy transfer
The appropriate spectral overlap criteria.
After it is done, it will be judged by experiment. General
Emission spectra of dimers dimerized in the ground state
Is better for the emission spectrum of the monomer.
Shift to longer wavelength side. For example, introduced into the side chain of a polymer
In the pyrenyl group used, the emission spectrum of the monomer
For the peak of 380 nm, the dimer has a peak of 380 nm.
nm or 345 nm for carbazolyl group (monomer
ー) is known to be 375 nm (dimer).
ing. In some cases phosphors form intermolecular excitons
I do. The intermolecular exciton comprises a molecule in an excited state and a ground
Diffusion with other molecules in state-formed by control
It is an excited dimer. A^*+ A → A + A + hν
 Such an intermolecular exciton has a different emission from the monomer.
It has an optical spectrum. Long wavelength region of dimer emission,
In particular, light emission in the infrared region can contribute to heat generation of the workpiece.
Donor phosphor and acceptor colors where FRET occurs at 50% efficiency
The distance between the element and R₀And the overlap integral of the spectrum
Can be calculated from the value. By measuring distance in proteins
Commonly used fluorescein-tetramethylrhodamine
For this donor-acceptor pair, this distance R₀Is about 50-
70 ° (dos Remedios, C.G.e.
t al. , J. et al. Muscle Research a
nd Cell Mobility, 8: 97-11
7, 1987). The energy transfer of this pair exceeds 90%
Obtained distance is about 45 °. FRET efficiency is high enough
If the donor phosphor is excited,
Nevertheless, FRET from the donor to the acceptor is observed. if
When the receptor is a non-fluorescent dye, the energy is
And the fluorescence of the donor is quenched. The receptor itself is a firefly
If it is a photoreceptor, the fluorescence emission at the emission wavelength of the receptor
May get up. Energy existing at energy exchange distance
At least two fluorescent molecules, each molecule very close to each other
Therefore, fluorescence quenching may occur. Paraphrase
Each fluorescent molecule is held at an energy exchange distance from each other
Singlet-singlet energy transmission possible
Performance and the probability of non-radiative transitions may increase.
You. For organic phosphors, FRET is generally less than 100 °
It is efficient in the region of
Preferably. FRET at a distance of 10-30−
Extremely efficient. However, high transmission efficiency immediately
Note that this does not mean that the heat generation efficiency is high
Should. On the other hand, lanthanoids such as complexes
If a substance containing a rare earth cation such as
If the distance between centers is less than 10 mm, especially less than 7 mm
It is known that the extinction becomes remarkable. Electric dipole
Or in multipole-based interactions,
The direction of the orientation greatly affects the efficiency of transmission. one
Generally, when different types of phosphors are used, the same phosphor is used.
In the direction organized at the same angle as in the case of light bodies
No stacking occurs and the transmission efficiency is reduced. More than
In such a situation, the donor and the acceptor are linked with a linker (l
linker), a covalent bond by
That is, the same applies to the case of intramolecular energy transmission. An example
For example, a plurality of rod-shaped phosphors
If it is. Fluorescein and Rhodamine are Sepha
When attached to the rosporin backbone, donor and acceptor
The body distance is 1 depending on the size of the linker and dye used.
0 ° to 20 °. If the distance is 20 °, the donor
90% transfer its energy to the acceptor and reduce the donor fluorescence
90% is quenched. <Dark complex> Many phosphors are fine
It has aromaticity and has 4n + 2pi electrons. This aromatic
Water-insoluble molecules in aqueous solution or in aqueous solution due to
Promotes the association or stacking of molecules
This promotes fluorescence quenching. Also, such as water
In polar solvents, where fluorescent dyes are present in high concentrations
Joint and rod-shaped hydrophobic donor and acceptor fluorescence
When the bodies are separated by a short flexible linker
Can also be laminated. This association or lamination in the ground state
For the sake of "dark complex"
Is formed (Yaron, A. et al., Ana).
l. Biochem. , 95: 228-235, 197.
9). In this complex, none of the phosphors can emit light,
The fluorescence of both dyes may be quenched (Bojar
ski, C.I. and Sienikki, K .; , Ene
rgy transfer and migration
 in fluorescutions:
 Photochemistry and Photo
Physics, edited by Rabek, J. et al. F. Boca
Raton: CRC Press, Inc. , 199
0, pp. 1-57). As an association to form a dark complex
It is assumed that H-association type dimerization and lamination
Consider formation of other clusters or aggregates, dimerization of J-association type, etc.
available. In addition, a chain molecule, a polymer, etc.
When the fluorophore is introduced and becomes a fluorogenic molecule part
In addition, these fluorogenic molecules are associated or layered
By doing so, a dark complex can be formed. For example,
Fluorescein and B attached to the phalosporin skeleton
In the case of -damine, in phosphate buffer at ph7, full
Both olecein and rhodamine are excited at their respective maximum excitations
Does not show much fluorescence. This is the phosphor overlap
(Dark complex) formation. This is the linker cleavage
Fluorescent properties increase significantly with the collapse of the stacking structure
It can be confirmed from the great things. Fluoresce as phosphor
Cephalosporin with in and rhodamine
The cleavage of the cephalosporin skeleton as a linker
Thus, the fluorescence increases about 70 times. Low fluorescence before increase
Non-fluorescent ground state complex due to overlapping light bodies
It means the formation of coalescence. This fluorescent property
When added to a solution, the FRET increases significantly,
It is thought to be due to elementary dimer formation. In other words,
Addition of methanol causes hydrophobic overlap
This overlap is destroyed and the donor
Fluorescence energy observed in the body or transferred to the receptor
Giants are observed to be emitted as fluorescence
Conceivable. <Dimerization> The dimerization reaction itself
It is also understood as the process of storing light energy. For example, Ann
Toracene forms H-associated dimer in liquid phase material
However, this dimerization reaction absorbs light of 400 nm or less.
The reverse reaction proceeds, for example, by heating.
The energy released by the dedimerization of anthracene is 65 kJ.
/ Mol, the concentration of the dye in a concentrated solution above the threshold
When a monomer is formed, it is necessary to
Heat to the system to trigger de-dimerization.
To give a dimer with dedimerization
Heat promotes the de-dimerization of nearby dimers, and thermal energy
It will be released in a chain. For example, as a dye
When the dye for rhodamine 6G is used, the liquid phase substance is water
And 10^-2 mol / dm³Order, organic solvent
10 in case of^-2mol / dm³At a concentration higher than the order
In some cases, such dimerization occurs and the dye is non-fluorescent.
Sexual transformation occurs. In this case, the absorbed energy is
The probability of release as giant is extremely small, and the heat generation efficiency
Is significantly improved. In this case, of course, the donor-acceptor
Body pairs are identical dye molecules (two rhodamine 6G molecules)
It is a pair consisting of In this case, the dimer form
A + A + hν → (A + A) ... dimer
Body, (A + A) → A + A + Δ
It is. The first equation states that the phosphor absorbs light energy and dimerizes
The second equation is heating the dimer.
Is a de-dimerization reaction that proceeds by
It involves the release of giants. In general, the fluorescence efficiency is
Decreases with increasing ambient temperature, increasing the probability of non-radiative transition
A phenomenon called temperature quenching occurs. This is
FRET energy at the center of the high probability of non-radiative transition
Is likely to increase with increasing environmental temperature
It is considered to be. Therefore, non-radiation
The release of thermal energy from the phosphor, which has been
I cannot deny that it contributes to Ming. "Super heating mechanism"
Is the fluorescence resonance energy transfer of a dye as described above.
(FRET), release of thermal energy by non-radiative transition, and
And / or release of thermal energy by de-dimerization
It is considered reasonable. <Dye> Dye of the present invention
Energy supplied from the energy beam,
Efficiently absorbs the photon energy of the laser pulse into heat
Conversion or efficient heat energy due to laser light irradiation.
Release liquid and heat the liquid phase material, especially the solvent,
A substance that can process nearby materials;
Element is preferably used. Dissolve such super-pyrogenic dyes
Superheated liquid phase material that is dissolved, dispersed or mixed
In particular, a solution containing a super-pyrogenic dye as a solute
Sometimes referred to as a thermal solution. Industrially, now practical
Wavelength range of laser light source, especially visible light or purple
Absorption due to the above-mentioned dimerization reaction, ground state absorption
Substances having a wavelength region corresponding to the absorption or absorption of intermediates are preferred.
It is suitable and has an absorption peak near the wavelength of the laser beam used.
Is more preferred. However, if necessary
Change the wavelength of laser light by up-conversion etc.
In this way, the wavelength of the laser light is
It may be close to the peak of the spectrum. In addition,
Absorption associated with quantification reaction, ground state absorption or intermediate absorption
If two or three of the absorption regions overlap, the common
Irradiation of laser light of different wavelengths
Energy and the transition energy from the ground state to each excited state.
Supply of energy corresponding to energy or intermediate absorption
It can be provided by two laser irradiation means. Book
Dyes of the invention include dyes that can be dimerized or laminated,
To polycyclic aromatic hydrocarbons, 5-membered or 6-membered heterocyclization
Compounds and compounds having carbonyl groups are optimally used
And use a metal complex having a coordination group of an organic molecule.
Can also be. Among them, fluorescent organic dyes that can be dimerized,
Peri such as pyrene, perylene and coronene
Polycyclic aromatics are optimal. Using two or more types of dyes
Multiple dyes are linked by a linker
Is also good. More specifically, as a peri-fused polycyclic aromatic
Are pyrene, perylene, coronene, biolanthrene,
And soviolantrene. Polycyclic aromatic charcoal
Naphthalene, anthracene, naphthacene
Polyacene and its derivatives, phenanthrene, pen
Polyphene such as tufen and its derivatives, terphenyl,
Direct or multiple phenyl groups such as t-stilbene
And polycyclic aromatics linked via a heavy bond.
You. Examples of 5-membered heterocyclic compounds include pyrrole and oxa.
Sol, thiazole, pyrarizone, oxadiazole,
Fluorescein is a 6-membered heterocyclic compound
Has pyridine, quinoline, pyrazine, quinosazarine, etc.
Compounds can be used. Having a carbonyl group
Coumarins such as 7-hydroxycoumarin
Conductor, 4'-methoxynaphthrylenebenzimidazole
Naphthalimides and naphthalene anhydrides represented by
Naphthalene acid derivative, metal having a coordination group of organic molecule
Complexes include porphyrin metal complexes and quinolinols
Can be mentioned. Also these dyes
Derivatives or other phosphors that emit fluorescence
For example, 1-phenylnaphthalene, 1,3,
6-naphthalenetriol, (5 or 8) -amino-2
-Naphthol, di-1-naphthyl ether, salicylic acid
2-naphthyl, 2-naphthol-6-sulfonic acid, 2-naphthyl
Naphthol-7-sulfonic acid, 2-naphthol-3,6
-Disulfonic acid, 4,5-dihydroxy-2,7-naph
Talendisulfonic acid, naphthonic acid, 1-naphthylami
8-sulfonic acid, 2-naphthylamine- (5 to
8) -sulfonic acid, (7 or 6) -amino-4-hydro
Xy-2-naphthalenesulfonic acid, 4-amino-5-h
Droxy-2,7-naphthalenedisulfonic acid, 1,8-
Naphthosultam, 2-naphthylamine, N-methyl-1
-Naphthylamine, N, N-dimethyl- (1 or 2)-
Naphthylamine, N-phenyl- (1 or 2) -naphthy
Luamine, di-2-naphthylamine, 1-methylantho
Helix, 9-ethylanthracene, 2,6-dimethyla
Anthracene, 9-phenylanthracene, 1-anthro
, (1 or 2) -anthracenecarboxylic acid, (1,
2 or 9) -anthrylamine, fluorene, 9-fe
Nilfluorene, dibenzo [a, j] anthracene,
Nzoanthrene and aceanthrene
You. In addition, use a substance having a fluorescent substituent.
And pyrenyl (pyrenyl) as a fluorescent substituent.
A radical. Same in the following enumeration. ), Pheni
, Triphenylmethyl, biphenyl, terphenyl,
Anthryl, phenanthryl, carbazolyl, nafti
, Pentalenyl, indenyl, azulenyl, heptare
Nil, biphenylyl, as-indacenyl, fukuole
Nil, s-indacenyl, acenaphthylenyl, preia
Denenyl, acenaphthenyl, phenalel, phenantry
, Alkylaminophenyl, diarylaminophenyl
, Alkoxyphenyl, methoxyphenyl, methylphenyl
Phenyl, chlorophenyl, anthryl, fluorantheni
, Triphenylenyl, chrysenyl, pyridyl, free
, Thienyl, tinolinyl, benzpyranyl, acridi
Nil, thiazolyl, benzothiazolyl, ethyl carbazo
Ryl, phenylcarbazolyl, tolylcarbazolyl, etc.
Each organic substituent can be mentioned. These substituents
Is equivalent to the fluorogenic moiety in intramolecular energy transfer
I do. Here, the substance having a pyrenyl group is 1-vinylpi
Len, pyrene butyric acid, pyrene trisulfonic acid ester (eg
For example, besides the product name “Cascade Blue”)
The same applies to other substituents listed, including
You. In addition, the dye of the present invention includes various polymethine-based colors.
Element, xanthene dye, coumarin dye, scintillator
Dyes, oxadiazole derivatives, rhodamine dyes, etc.
Laser dyes, azo dyes, cyanine dyes, benzes
Thiol nickel complex, metal phthalocyanine dye,
Suitable for phthalocyanine dyes and naphthoquinone dyes
And specifically, 2,5-diphenyloxa
Sol (PPO), α-naphthylphenyloxazole
(Α-NPO), POPOP, 4-methylambellife
Ron, 4-methylcoumarin, fluorescein, rhodami
6G, acridine red, rhodamine B, 3,3'-
Dimethyl-2,2'oxatricarbocyanine ioda
Id, 1,1'-diethyl-4,4'-quinotricarbo
Laser dyes such as cyanine iodide and indigo,
Phenol blue and the like can be mentioned. In addition, fireflies
A rare earth complex can also be used as the optical body.
Specific examples of rare earth cations include La²⁺, L
a³⁺ , Ce²⁺, Ce³⁺, Ce⁴⁺, Pr²⁺, P
r³⁺, Pr⁴⁺, Nd²⁺, Nd³⁺, Nd⁴⁺, P
m²⁺, Pm³⁺, Sm²⁺, Sm³⁺, Eu²⁺, E
u³⁺, Gd²⁺, Gd³⁺, Tb²⁺, Tb³⁺, T
b⁴⁺, Dy²⁺, Dy³⁺, Dy⁴⁺, Ho²⁺, H
o³⁺, Er²⁺, Er³⁺, Tm²⁺, Tm^{3 +}, Y
b²⁺, Yb³⁺, Lu²⁺, And Lu³⁺Etc. Lanta
Noid cations, and scandium and yttrium
And other cations of Group 3A elements in the periodic table. So
In addition, a substance having a condensed polycyclic aromatic compound or a hetero ring
Is a substance having a plurality of ring structures.
Equivalent molecules, especially aromatic molecules having multiple aromatic rings
Use of substance molecules having multiple bonds or ring structures in the
, Unsaturated aliphatic carbohydrates, aromatic hydrocarbons, aromatic
Aromatic halogen compounds, aromatic nitro compounds, aromatic nitro
Loxo compound, aromatic amine, aromatic nitrile, phenol
Phenol ether, aromatic carbonyl compound, aromatic
Aromatic carboxylic acids and their derivatives, azo compounds and derivatives
Conductor, sulfonic acid derivative, furan group compound, thiophene
Group compounds, pyrrole compounds, pyran compounds, pyridine groups
Compounds, diazine compounds and other organic compounds
It can be selected as needed. Specifically, Trife
Nil, pentacene, chrysene, fluorene, acenaphte
, Fluoranthene, 3-aminopyrene, 1,2,3
4-tetramethylnaphthalene, 1- (dimethylamino)
-Pyrene, 1-pyrenebutyric acid, butylpyrene, 4-methyl
-2H-1-benzopyren-2-one, benzoquinone,
Naphthoquinone, anthraquinone, pyrrole, 2-phenyi
Lupyrrole, indole, pyridine, fluoropyridi
, 2-ethoxypyridine, aminopyridine, pyrido
Pyridine-N-oxide, 4-nitropyridine-N
-Oxide, 4-aminopyridine-N-oxide, quino
Phosphorus, isoquinoline, carbazole, coumarin, 2,6
-Dimethyl-4-pyrone, proflavine, 1,2-ben
Zoazulene, dimethylbiphenyl, tetramethylbiphe
Nil, hexamethylbiphenyl, (trans or ci
s) stilbene, 5,5'-dimethylbiphenyl, 6,
6'-dinitrobiphenyl, p-nitro- (trans
Or cis) -stilbene, p-methoxy-p-nitro
-Trans-stilbene, phenyl ether, (α,
β) -naphthol, benzophenone, 7- (dimethylamine)
Mino) -4-methylcoumarin, nitrophenylazoben
Zen, trifluoromethylsulfonyl tolan, Azure
, Benzoin, benzotriazole and their derivatives
And the like. In addition, these dye molecules
When a substituent called an auxiliary fluorophore is introduced into
Can increase or decrease the quantum yield,
Thus, the heat generation efficiency can be increased or decreased. Ingredient
Physically, -OH, -CH₃, -NH₂, -N (C
H₃)₂Addition of an electron donating group such as
You. In addition, electron-withdrawing groups such as -COOH and -CN also emit light.
Has the effect of increasing the On the other hand, -NO₂, -NO, etc.
When fluorescence is introduced, the fluorescence disappears and the probability of non-radiative transition
improves. Therefore, these dominant effects
By selectively introducing the substituent of
Efficient processing can be realized. However, for processing
Therefore, the fine concave structure on the surface of the transparent material formed sequentially
It is more efficient to disperse even the part
For this purpose, the volume occupied by the solution is small.
In general, the smaller the molecular weight, the more advantageous. This view
In terms of polyacene, naphthalene and ant
Examples of dyes having a low molecular weight such as a helix are exemplified. On the other hand,
The amount of heat released in dimerization is large if it is of the same family.
Dyes tend to be larger, so the higher the molecular weight
For example, if a substance having a large degree such as a peri-condensed polycyclic aromatic is used,
Dyes having a molecular weight of at least perylene or coronene are preferred.
You. Dissolve or disperse the super-pyrogenic dye in the present invention
When the liquid phase material is used, the dye
Transition between excited states and / or dimerization and de-dimerization
Energy transfer to surrounding substances by repeating
Only the pigment itself is hardly consumed, but near the processed part
Liquid molecules are consumed one after another by vigorous evaporation
As the processing progresses, the concentration of the pigment in the liquid phase material increases.
May be locally high near the surface of the workpiece
is there. This makes it possible to irradiate the same amount of laser beam.
As the processing progresses, etching per irradiation energy
There may be a problem that the amount increases. This is
Etchant concentration in etching in the next liquid phase
Is that, as the process progresses, it gradually decreases
This is a problem inherent in a completely different configuration of the present invention. Reverse
The laser light intermittently for a long time.
In some cases, the pigment may be destroyed or worn. In this case
With the same amount of incident light,
The amount of processing per irradiation energy is reduced
Occurs. For this reason, in order to maintain a constant machining accuracy,
Liquid-phase substance containing a certain concentration of dye by pump or other means
Supply or flow to the workpiece to be processed or laser
Liquid phase material can be exchanged before and after beam irradiation
desirable. When flowing a liquid phase material to form a laminar flow
Means that the liquid phase material is supplied directly to the workpiece surface.
Is more preferable. When turbulent flow is formed,
The boundary between the viscous layer formed next to the turbulent boundary layer is
The liquid phase is disturbed by violent evaporation, etc., causing mass exchange.
An increase in the concentration of a substance can be reduced or prevented. or,
The upward flow of the liquid phase substance is placed below the transparent material to be processed.
It may be formed by an injection means such as a chisel. Further liquid phase material
Can be supplied from above and laser irradiation can be performed from below.
It is possible. The liquid phase material of the present invention is viscous or compressed
Not only fluids with negligible properties but also viscous fluids and compressible fluids
It can also be used, using sol, thixotropic substance
You can also. In this case, the further selected dye is dimeric
It is desirable to be able to cause a chlorination-dedimerization reaction. Sol
When used, adhesive such as silica or alumina in the above solvent
May be added for use. In this case, the work piece
Instead of contacting or dipping the working part with the liquid phase material,
Liquid material is uniformly or patterned on the surface to be processed by cloth means
It can be used after being applied in a shape. In addition,
When a problem occurs such that only part of the material comes into contact with the liquid phase material
There is a “Nu” for the transparent material of the selected fluid.
To reduce the angle of れ
Quality, such as surfactants, can be added to the fluid.
You. However, the presence of surfactant promotes the association of dye molecules.
Care must be taken because it may progress or hinder it.
 <Liquid phase substance> Liquid phase substance in the present invention, especially super heat generation
As a solvent constituting the neutral solution, the selected dye molecule is used.
It can be dissolved and collected in normal industrial manufacturing processes.
Liquid under the applicable pressure and temperature conditions
It absorbs the thermal energy emitted by the dye and becomes hot,
If it is possible to process materials in contact with
Can be in the liquid phase,
A solvent may be constituted. Intense evaporation, etc. with heat generation of dye
If a material that causes
By removing from the processing part by gas pressure, the processing effect
In some cases, the rate may improve. However, touched liquid phase material
Transparent material chemically etched by its liquid phase material
A strong acidic or basic solution,
Substances and solutions with strong oxidation / reduction actions are inappropriate.
You. However, it should be adjusted to an appropriate pH or redox property
Of the transparent material caused by etching, etc.
Dissolves fragments and destructed or worn dye fragments to produce a super-heat-generating liquid phase
It is also possible to keep the quality transparent. Specifically, general purpose
Organic solvents, inorganic solvents and the like, for example, acetone, heptane,
Xan, methyl alcohol, ethyl alcohol, chloro
Form, benzene, cyclohexane, isooctane, i
Sopentane, heptane, ether, water, carbon tetrachloride,
Niline, α-chloronaphthalene, toluene, bromben
Zen, chlorobenzene, nitrobenzene, carbon disulfide,
Ethyl ether, n-hexane and the like are preferably used.
 However, the fine groove structure that is formed sequentially by processing
Efficiently penetrates into details and performs etching efficiently
In order to reduce the volume occupied by one molecule,
The smaller is the more advantageous. Furthermore, such small molecules
If the material is used as a liquid phase material and side pressure cutting is
The required pressure for cutting one material and the same shape is reduced
This has the effect. From these viewpoints, the molecular weight is small.
Solvents such as methyl alcohol, ethyl alcohol,
Examples include water, ether and the like. Strong absorption in the visible light region
Substances that do not have a liquid phase are defined as liquid phase substances or dyes contained in them.
Using a dye that evaporates with the volatile liquid phase material
There is no visual contamination of the transparent material. Of the present invention
In practice, the absorption spectrum of the dye should be
Can vary depending on the quality, especially the type of solvent
It is necessary to keep in mind. This application includes the following inventions.
You. 1 Laminar flow to the super-pyrogenic liquid phase material in contact with the transparent material,
Form a turbulent or updraft flow and pass the liquid through the transparent material.
By injecting laser light into the phase material, the transparent material
Etch on the surface of the surface of the
Processing method of transparent material to be applied. 2 Energy in transparent materials
Before the step of injecting the beam, the following steps a) to e) are performed.
In other words, there is a process for specifying at least one machined part.
Processing method of a transparent material, a) the surface to be processed of the transparent material and
Pattern a layer of opaque material on the opposite side.
B) forming a transparent material on the surface to be processed of the transparent material;
C) forming a pattern of the transparent material.
Process to form a layer of opaque material on the processing surface
D) the part of the transparent material that does not require processing is
Coating with a substance having a smaller refractive index than the material,
e) At the end face of the transparent material other than the work surface, energy
Touch the transparent material so that the lugi beam is totally reflected
The refractive index of the substance and the incident angle of the energy beam.
The process of setting. 3 Energy beam processing of transparent material
Unnecessary parts enter the transparent material and the transparent material
Through the transparent material after processing
Irradiating the exothermic liquid phase substance, dissolving and dissolving the dye;
The liquid phase material being dispersed or mixed is laminar at the same time as the irradiation,
Create turbulence or ascending flow or before the irradiation or
In addition to the steps to be replaced later, the following a) to f)
In other words, there is a process for specifying at least one machined part.
A) a method of processing a transparent material,
A pattern is formed on the surface of the transparent material opposite to the surface to be processed.
B) a layer comprising a transparent member or an opaque member
Forming a pattern on the surface to be processed of the transparent material;
The energy beam is used for processing the transparent material
And d) the energy beam is incident
The surface of the processed part of the transparent material
Part where the layer made of the member or the opaque member is formed
Is not processed by the energy beam irradiation
E) removing the portions of the transparent material that do not require processing
Coating with a substance having a lower refractive index than the bright material
F) on the end surface of the transparent material other than the surface to be processed.
The transparent material is applied so that the energy beam is totally reflected.
Refractive index of the substance in contact with or incident energy beam
The step of setting the angle. 4 In the vicinity of the transparent material
Color that is dissolved, dispersed or mixed in the liquid phase material
A method for processing a transparent material that is irradiated with a laser beam,
The dye is at least one of the following a) to g):
Processing of transparent material with features, a) in ground state
Absorption region, absorption region corresponding to intermediate absorption or dimerization
Of the absorption region accompanying, two or three are overlapping,
b) forming dimers, laminates or aggregates in the liquid phase material
C) to the extent exemplified by naphthalene and anthracene
D) the molecular weight, as exemplified by perylene and coronene
E) Peri-condensed polycyclic aromatic compounds having a molecular weight of at least
F) forms a dark complex, g) between other dyes
Performs energy transmission by FRET. 5 Transparent materials
The process of irradiating the dye near the workpiece with the energy beam
Before or after or simultaneously with the following a) to k)
Of a transparent material having at least one process.
Method a) Dissolve the dye between the edges of the transparent dye material
Forming a layer of dissolved, dispersed or mixed material;
b) in a substance in which the dye is dissolved, dispersed or mixed,
Butt the edges of the transparent material or separate them
C) causing the molten surface of the transparent material to
Pressing the material, d) dissolving, dispersing or mixing the dye.
Move the transparent material in contact with the mating substance
Step, e) a substance dissolving, dispersing, or mixing the dye;
Flow to form laminar, turbulent, or ascending flow
Step f): dissolving, dispersing, or mixing the dye;
Exchanging step, g) keeping the dye constant near the part to be processed
H) dissolving, dispersing or mixing the dye;
Pressing the combined substance, i) dissolving the dye,
Disperse or mix materials with methyl alcohol,
Extent exemplified by alcohol, water or ether
A step consisting of:
Irradiation intensity and irradiation of the energy beam
Changing the irradiation time or the number of irradiations, k) the energy
The step of sweeping the giant beam. 6 Edges of transparent material and other materials
Butts at the ends of the material or facing each other with a small gap
To form a thin layer of super-pyrogenic liquid phase material between the ends,
The transparent material is used as an optical waveguide to guide laser light to the thin layer.
Processing method of transparent material that inserts and joins both materials. 7 Transparent material
After side-cutting the material, melt it with other materials on the cut surface.
A method for processing transparent materials for fusion bonding. 8 The following A) to C)
And the components a) to s)
Processing equipment for transparent material having at least one component
A) a liquid phase substance in which a dye is dissolved, dispersed or mixed,
B) Energy beam irradiation means, C) Density change of the dye
Depending on the irradiation intensity, irradiation time, or
Means for changing the number of irradiations, a) applying pressure to the transparent material
Means for insertion into the container, b) a hand for moving the transparent material
Step, c) on the surface of the transparent material opposite to the surface to be processed,
Means for patterning a layer of opaque material, d)
On the surface to be processed of the transparent material, from a transparent member or an opaque member
Means for patterning a layer comprising: e) in the liquid phase material
Means for abutting the ends of the transparent material, f) the
Form a thin layer in the liquid phase material between the edges of the transparent material
G) laminating or turbulently flowing the liquid phase material
Or means for forming an ascending flow, g) dissolving and dispersing the dye.
Or means for exchanging the liquid phase material being mixed, i) the color
A constant concentration of silicon to the part to be processed of the transparent material.
Step, j) Maintaining a constant temperature around the unprocessed portion of the transparent material
K) adding by-products generated by etching;
Means for removing from the working part, l) pressurizing the liquid phase material
Means, m) a material having a lower refractive index than the transparent material.
To coat portions of the transparent material that do not require processing.
Step, n) At the end face of the transparent material other than the processed part,
Touch the transparent material so that the energy beam is totally reflected.
The refractive index of the liquid phase material or the energy beam
Means for setting the angle of incidence, o) the part to be processed of the transparent material
So that it is in contact with or immersed in the liquid phase material.
Means for fixing the material, p) the molten surface of the transparent material to another
Means for pressing against the material, q) sweeping the energy beam
R) the transparent material is disposed on the side opposite to the processed part.
S) optical system. 9 Dissolve super-pyrogenic dye
The liquid phase material that is
Supplying the super-heat-generating dye at a constant concentration to the processed part of the transparent material
And a constant concentration around the processed part of the transparent material.
Means for processing transparent material having means for maintaining. 10 Transparent material
Material position coincides with notching process and side pressure cutting process
And apply a transparent material that is notched by laser light irradiation.
Engineering equipment. 11 Liquid phase in which dye is melted, dispersed or mixed
Add transparent material that cuts transparent material by pressure
Engineering equipment. 12 At least any of the following a) to c)
Transparent material with features to identify the processed part
A) The sacrificial etching layer made of a transparent member
Is formed on the surface of the material that does not require processing.
B) the clad layer is processed on the surface of the transparent material.
C) formed on an unnecessary part, on the opposite side of the processing surface
The surface is patterned with a layer of opaque material.
D) Pattern formation of a layer made of a transparent member on the surface to be processed
Have been. 13 of recess formed by laser beam irradiation
A transparent material that has broken at a location due to tensile stress.
14 Patterning a thin film on the cross section of one end of optical fiber
Laser light enters the optical fiber from the other end and
End face forming a thin film using the optical fiber as an optical waveguide
And apply etching corresponding to the pattern.
A method for processing an end face of an optical fiber applied to the end face. Fifteen
At least two dyes are linked by a linker and
Light energy is maintained at a certain distance and orientation.
Or, the distance or orientation is changed by the supply of thermal energy.
Releases thermal energy without changing or changing
Heating element. 16 Heating element consisting of a dye pair is one heating element
Heat from other heaters in the vicinity
Liquid phase substance contained at a concentration that emits. Embodiment 1 FIG. 1 shows a known semiconductor device.
I have. This semiconductor element is a semiconductor acceleration sensor 110.
Fixed electrode 130 fixed on glass substrate 120
The movable electrode 140 is provided between the first and second electrodes 131. Fixed electrode 13
0 and 131 and the movable electrode 140 are respectively
It is made of silicon (polycrystalline silicon) and has a movable electrode 140
Fixed electrode 130, movable electrode 140 and fixed electrode 131
The parts facing each other can be understood by referring to the drawings.
It is formed like a comb. The movable electrode 140 is made of glass
It is located above the concave portion 121 formed on the substrate 120,
Both ends are supported by beams 150 and 151,
Floating with respect to the substrate 120. Both beams
The respective base ends 150a and 151a of 150 and 151 are:
It is fixed on the glass substrate 120. Base end 15 of each beam
0a and 151a, and fixed electrodes 130 and 131
Are individually provided with electric wiring (not shown). this
In such a semiconductor inertial sensor 110, the movable electrode 140
On the other hand, a line connecting the base ends 150a and 151a of the beams.
Acceleration that has a component in the horizontal plane
Then, the movable electrode 140 supports the beams 150 and 151.
Vibrates as an axis. As a result, the movable electrode 140 and each fixed
Movable due to the change in the distance from the constant electrode 130 or 131
Electrostatic capacitance between electrode 140 and fixed electrode 130 or 131
The amount changes. By detecting this change in capacitance, the sensor
This is for obtaining the acceleration acting on. Next,
A method for manufacturing a conductor element will be described. FIG. 2 is an illustration of FIG.
Done in the manufacture of the shown semiconductor inertial sensor 110
FIG. 3 illustrates an etching process of a glass substrate. Etch
Of pyrene as a super-exothermic solution
Acetone solution (concentration: 0.6 mol / dm³) Injected
To form a super-pyrogenic liquid phase material 220. Super exothermic
The liquid phase substance 220 is continuously supplied by an appropriate means such as a pump.
It is supplied and in a fluid state, and the inflow and discharge
The liquid level 221 of the super-pyrogenic liquid phase material 220
Is controlled so as to maintain the height. This liquid level 2
A glass substrate 120, which is a workpiece, is fixed at 21 (not shown).
Fixed by means. In this case, the glass substrate 120
At least a portion of the processing surface 122 to be etched
Minute, that is, the concave portion 121 is formed by etching.
Parts touch the hyperpyretic solution over the etching process,
Or it is desirable to be immersed. Usually, the work surface
The whole 122 is located slightly below the liquid level 221.
If it is fixed horizontally,
Liquid phase material enters. Glass substrate in such a state
120, from above, that is, of the glass substrate 120
From the surface 123 side opposite to the processing surface 122, the concave 121
Photomask 23 patterned according to the shape of
0, and further through an optical system 250 such as a condenser lens.
A laser beam irradiating means 24 for applying a laser beam as an energy beam;
Irradiate from 0. The laser light used here is
Pulse wave of Shima laser (KrF, 248 nm), for example,
FWHM = 40 ns, maximum energy density 1400 mJ /
cm²Can be used to control the number of pulse irradiations
Thereby, the concave portion 121 is formed to a desired depth.
FIG. 3 is a view showing a process of manufacturing the semiconductor inertial sensor 110 shown in FIG.
Out of the etching process for the glass substrate 120
The outside process is shown. First, the silicon wafer 310
Film 320 that can be etched without eroding silicon on both sides
To form As the film 320, a chemical vapor deposition method (CV
D method)₂Cl₂And NH₃Formed using gas
Silicon nitride film. Silicon wafer 310
After forming the film 320 on both surfaces of the film 320, the film 320 on one surface is formed.
Is removed by etching with hydrofluoric acid. This silicon wafer 3
Polysilicon of about 5 μm thickness on both sides of CVD by CVD method
The layers 330 and 331 are formed. On the side where the film 320 remains
On the surface of the polysilicon layer 331 by sputtering or the like
After an Al film 340 is formed and patterned, SF₆Moth
Anisotropic dry etching at a low temperature is performed by using This
As a result, the polysilicon is used as the film 320 as an etch stop layer.
The silicon layer 331 is etched, and the polysilicon
A movable electrode 140 made of a capacitor,
A pair of polysilicon, spaced slightly on both sides
The fixed electrodes 130 and 131 are formed. Al film 340
After removal, the movable electrode 140 and the pair of fixed electrodes 130,
The movable electrode 1
40 faces the recess 121 of the glass substrate 120 described above.
Bonding to the glass substrate 120 as described above. Then
Silicon wafer 310 bonded to glass substrate 120 and the residue
The existing polysilicon layer 330 to the film 320
Wet layer with an etchant such as KOH
Remove by ching. Then, such as hydrofluoric acid
The film 320 is removed by an etchant. This allows
The movable electrode 140 is sandwiched between a pair of fixed electrodes 130 and 131.
The semiconductor device formed in a floating state above
A sex sensor 110 is obtained. Etchin of this embodiment example
According to the laser method, a laser beam is
As the heat is emitted, the super-heat-generating dye is uniformly
To ensure that the etching reaction proceeds stably
To prevent unnecessary overheating of the workpiece and
Remove the generated dye molecule fragments or transparent material molecule fragments,
The transparency of the liquid phase material can be maintained. Also, transparent material
Compared to the conventional method of directly processing by laser beam irradiation,
The laser intensity may be several orders of magnitude lower, and
There is no damage to the periphery and patterning at the μm level is possible
Yes, for controlling the etching depth, such as the number of laser pulses
Since it can be controlled at the nanometer level, the amount of etching can be controlled.
Easy, does not require the formation of an etch stop layer, etc.
Etching by simple process with the advantage of
It is. <Embodiment 2> FIG. 4 is a side pressure cutoff according to this embodiment.
A pressure cutoff device having pressure inlets 441 and 451.
The power container 420 and the pressure inlet 441 are filled.
Super heat generating liquid phase material 440 and filled in pressure inlet 451
Laser light introducing liquid 450 having no heat generation
And the laser light introduction liquid 450 is sealed, and the laser light is
A laser light introduction window 460 for introduction into the vessel 420;
Laser light irradiation means 430 and a pressure
And a collar 421 provided on the inner peripheral side of the collar 421.
A pair of O-rings 422 and 423, and a pressure inlet 441.
From the pressure vessel 42 between the pair of O-rings 422 and 423
A pressure generator that supplies a superheated liquid phase material pressurized in 0
442 and a pressure vessel between the pair of O-rings 422 and 423
Pressure generation to supply laser pressurized liquid into 420
452. Hereinafter, this embodiment example
Will be described. Addition made of transparent brittle material
The glass rod 410 as a working member is a pair of O-rings.
On one side between 422 and 423, the super-pyrogenic liquid phase material 4
Introduce laser light on the other side so that it touches 40
Inserted into the pressure vessel so as to come into contact with liquid 450
You. In this state, the laser light provided in the pressure vessel 420
The laser beam is introduced through the introduction window 460 and the laser light introduction liquid 450.
The laser beam is applied from the light irradiating means 430 to the glass rod 410.
A point on the planned cutting line or a fixed length along the planned cutting line
Is irradiated. The laser beam passes through the glass rod 410
To reach the super-pyrogenic liquid phase material 440, but the laser light
At the position ejected from the glass rod 410, the glass rod
The surface of 410 is notched to form notch 411
It is. Next, move the glass rod from the notching position
Without the pressurized super-power from the pressure generator 442
Simultaneously when the thermal liquid phase material is introduced into the pressure inlet 441
, The laser light introducing liquid pressurized from the pressure generator 452
Is introduced into the pressure inlet 451, the glass rod 41
0 surface has a compressive stress, and the center has a glass rod
Tensile stress occurs in the axial direction. The internal stress that occurs is
Tensile stress that increases in proportion to pressure and is generated inside
At the position corresponding to the notch on the glass rod 410
If the tensile strength exceeds the
At this point, the glass rod 410 is broken and cut. Soshi
Then, advance the glass rod 410 in the direction of the arrow to
Cutting can be performed. Super power in this embodiment example
The thermal liquid phase substance may be the same as that of the first embodiment.
However, here, for example, a solution of perylene in carbon disulfide (concentration:
0.8mol / dm³) Can be used. Use
Laser light irradiating means is appropriately selected according to the absorption area
I have. The laser light introduction window 460 is provided with a light transmitting element.
Formed from materials that do not break even under high pressure loads
It is desirable to use tempered glass etc.
Can be. As the laser light introduction liquid 450, selected
Any liquid that does not exhibit super-heat generation by laser light
Such a thing can be used, but the laser light introduction window
Desirably, it does not corrode 460. Follow
For example, the laser introduction window 460 is formed from a glass material.
If it has strong oxidizing / reducing action,
・ Basic solutions are not suitable. In addition, the laser light introduction liquid 4
50 is super heat-generating when pressurized by the pressure generator 452
A structure that can contact and possibly mix with the liquid phase material 440
The glass rod 410 on the laser irradiation side.
In order not to cause any processing, the superheatable liquid phase material 440 contains
Those that do not dissolve the superpyrogenic dye are preferred. However,
At the time of pressurization by the pressure generators 442 and 452, and
When releasing, lower the pressure on the pressure generator 442 side by a small amount.
The super-heat-generating dye is controlled by the laser light
It is possible to prevent entry into the 450 side.
In this case, heat generation in the super-heat-generating liquid phase substance 440, etc.
In order not to adversely affect the action of
It is desirable that the laser light
Alternatively, they may be the same substance. In these configurations
About the configuration described in the other embodiments, etc.
It is a matter of course that variations can be adopted. So
For other configurations, materials, etc., use a known side pressure cutting device.
It is possible to adopt the configuration, material, etc.
It is not limited. In the cutting method of this embodiment example
According to the report, the super-heat-generating liquid phase material is directly used in the side pressure cutting process.
Is used as a medium for applying pressure to the workpiece.
Position in the cutting process and positioning in the cutting process
Position is the same in one device,
The process of moving the workpiece only once,
And cutting position with high accuracy
Can be controlled. Also for low energy lasers
Notching is possible, and the notch depth can be
It can be controlled at the nm level by controlling the number of pulses and the like. Ma
In addition, since there is no damage around the notch, high-precision cutting position
A controllable cutting process can be realized. In addition, break at break
No splinters, no noise, no material cross-section
Extremely smooth fracture surface that can be cut with constant pressure
(For example, in the case of a glass material, the cutting pressure is 80MP.
a, When cutting with an outer diameter of 8 mm and a thickness of 2 mm, the surface roughness is
(About 0.005 μm). <Embodiment 3> FIG. 5 shows a processing method according to this embodiment.
FIGS. 6A and 6B show examples of the liquid crystal display element obtained as described above.
FIG. 7 is a diagram illustrating a manufacturing process of the liquid crystal display device of FIG.
The liquid crystal display element 510 in FIG.
This large panel 511 is made of a transparent material.
The formed TFT substrates 530 and 531 are
The connection substrate 520 connected and the CF substrates 540, 5
41 is connected to a connection substrate 521 having its side surface connected.
TF is provided between these connection substrates 520 and 521.
A liquid crystal layer 550 is provided between the T substrate 530 and the CF substrate 540.
But also between the TFT substrate 531 and the CF substrate 541.
The liquid crystal layers 551 are independently formed. Sand
The liquid crystal display element 510 has two small liquid crystal elements 610,
611 on its side, and the same reinforcing substrate 620
Large panels 51 arranged adjacent to each other on one plane
1 for connecting the small liquid crystal elements 610 and 611.
Are TFT substrates 530 and 531 and CF substrates 540 and 54
Are directly connected to each other.
You. In addition, on both front and back sides of the liquid crystal display element 510,
A pair of polarizing plates 560 and 561 are arranged in a Nicol positional relationship
Have been. The small liquid crystal elements 610 and 611 have the above-described communication.
TFT substrate 530, CF substrate 540, and TFT substrate
The plate 531 and the CF substrate 541 are arranged to face each other,
In the meantime, liquid crystal layers 550 and 551 are respectively sealed.
You. Large panel 511 is reinforced by adhesive layer 590
The TFT substrates 530 and 53 are bonded to the substrate 620.
1, CF substrates 540 and 541, insulating films 570 and 571,
Sealing materials 580, 581 and other components are known in the art.
Normally used in the liquid crystal element of the active matrix drive type
The configuration described can be used. Next, this embodiment
Manufacturing method of liquid crystal display element 510 including various examples of fusion bonding method
Explain the law. First, the small liquid crystal elements 610 and 611 are connected to each other.
Butts or contact at the connecting end faces
Facing each other at a small distance,
Soak and fix. At this time, at least the connection part of each end face
Need only be immersed in the super-pyrogenic liquid phase material. Small liquid
To fix crystal elements 610 and 611
When aligning surfaces, align the surface height of both substrates
For this reason, the jigs that pinch or press
Set. At the same time, the joint is irradiated or irradiated simultaneously with laser beam irradiation.
Immediately after this, a compressive stress is applied by a pressing means (not shown).
As described above, the ends where the small liquid crystal elements 610 and 611 are connected.
Are fixed, one small liquid crystal element 610 is constituted.
Each of the TFT substrate 530 and the CF substrate 540 is connected.
The TFT substrate 530 and the CF substrate 54
The laser light irradiated from the laser irradiation means 630 within 0
Is introduced. In the TFT substrate 530 and the CF substrate 540
The introduced laser light uses these substrates themselves as waveguides.
To the end where the inside of the board is joined.
Be injected. At this time, the contact between the small liquid crystal elements 610 and 611 is made.
Between the edges that follow, a very thin layer of superpyrogenic liquid phase material 640
Butts each end to be joined due to layer formation
The super-heat-generating liquid phase material 640 generates heat in the
Any joined ends will melt. This allows
TFT substrates 530 and 531 and CF substrate 5
40 and 541 are directly joined, respectively. That's all
Large size consisting of small liquid crystal elements 610 and 611 joined together
The panel 511 has a supplementary surface on the side of the CF substrates 540 and 541.
A strong substrate 620 is attached with an adhesive layer 590, and a pair of
By disposing the polarizing plates 560 and 561, a liquid crystal display
The device 510 is manufactured. Super heat generation in this embodiment example
As the liquid phase substance, the same as that of the embodiment 1 may be used.
Here, for example, a solution of coronene in carbon tetrachloride (concentration: 0.1%).
4mol / dm³) Can be used. Sucking to use
Select and use laser light irradiation means appropriately according to the collection area
You. In addition, the burr having the configuration described in the other embodiment example.
Can be appropriately combined, for example,
By continuously supplying and flowing the thermal liquid phase material,
A constant temperature can be maintained around the joint of the workpiece,
Unnecessary alteration or the like due to this can be prevented. This implementation
According to the bonding method of the embodiment, the transparent material, which is the workpiece,
The laser beam to reach the junction using the body as a waveguide
Is the end face of the workpiece from which the laser light is emitted
Localized only in areas that are in direct contact with superheated liquid phase material
And melting of the workpiece occurs,
There is little deterioration around the part,
It is possible to realize a joint that is inconspicuous. Also,
When joining materials cut by the side pressure cutting method
Is not necessarily before joining
It is not necessary to grind,
The joining process that does not generate noise can be achieved.
You. <Embodiment 4> FIG. 8 is a view showing the processing method of the present invention.
Polynucleotide probe chips that can be created
It is a figure showing an example of. FIG. 9 is a partially enlarged sectional view of FIG.
(A) when the small hole has a bottom, (b) penetrates
(C) is penetrated and the side wall surface is tapered
Is shown. Polynucleotide probe chip 8
Ten substrates 811 are made of plastic and have a hydrophobic surface.
With a flat bottom surrounded by hydrophobic parts 820 that have been treated
FIG. 9 (b)
A plurality of small holes 840 opening at the upper and lower ends as in
Are formed in a grid pattern on the bottom surface of the concave portion. Hydrophobic part
The surface is treated with hydrophilic treatment between the bottom of the concave portion and the bottom of the concave portion.
A hydrophilic portion 830 is formed. Top of small hole 840
Opening is 0.5mm x 0.5mm, between upper and lower openings
Is 1 mm. The shape of the opening of the small hole 840 is positive
The shape is not limited to a square, but may be an arbitrary shape such as a rectangle and a circle. small
The holes 840 are in the x and y directions through a 0.5 mm partition wall 830.
To form a 16 × 16 matrix.
That is, the center of each small hole 840 is 2 mm apart from each other by 1 mm.
Are arranged in a dimension. When the small hole 840 is penetrating
In this case, as shown in FIG.
Make the polynucleotide probe smaller than the area of the opening
Acrylamide gel holding
Noh. That is, the small hole 840 is inserted from the upper opening to the lower opening.
Taper toward opening to form acrylamide gel
To facilitate retention of acrylamide gel when formed
Can also. By hydrophobic part 820 and hydrophilic part 830
Easily transfer the sample solution to a small
It can be held in a recess with a hole 840. Side of substrate 811
Has an optically polished detection laser for introducing a detection laser beam
The light introduction part 850 is formed. The laser beam for detection is in each small hole
840 is irradiated on the side wall surface 841. Plastic material
Laser light of 400 nm to 650 nm
Optically transparent polymethyl methacrylate (PMM
A) is used. A laser light source (not shown, for example, 59
4 nm, He-Ne laser) and emitted from a fluorescent label
Samples using a high-sensitivity cooled CCD camera that detects fluorescent light
(Eg, a fluorescence-labeled DNA fragment) is detected. Furthermore,
An electrode for electrophoresis is formed on the substrate 811 and each small hole is formed.
Fluorescence detection photodiode and its output wiring
May be formed. Next, the side wall surface 841 of each small hole 840
In the surface treatment described above, the inner surface of the small hole 840 is
When a lilamide gel is formed,
Etching to ensure retention of the acrylamide gel
As a result, the side wall surface 841 of the small hole 840 has irregularities at the molecular level.
The shape is formed. In the etching of this embodiment
Drops a fluid super-heat-generating liquid phase substance into small holes 840
Or super gel or thixotropic
After applying or sticking the exothermic liquid phase material to the side wall surface of the small hole
From the diagonally lower side or from the side or diagonally above the transparent substrate.
Diffraction grating as an optical system corresponding to the desired uneven pattern
Laser light through the
An uneven shape can be formed. Forms that cause interference fringes
When using a diffraction grating of the type
Interference fringes in the depth direction of small holes 840 to ensure
It is desirable to arrange them side by side. Laser light for detection
Even if a laser beam for processing is introduced from the introduction unit 850
good. After forming irregularities on the side wall 841, straight-chain fat
A reagent in which an acryl group has been introduced into a part of the
840 is applied to the side wall surface 841 of each of the small holes 840.
A state where an active acrylic group is introduced into the surface 841 is obtained. Each small
The acrylamide gel is held in the hole 840. At this time,
An active acrylic group and an acrylic resin are provided on the side wall surface 841 of each small hole 840.
The connection between the gel and the luamide gel is established. Reagents are directly plus
Does not chemically bond to the surface of
Due to the hydrophobic binding of the fat part, the reagent is on the plastic surface
Fixed to Polynucleotide probe tip
Different in holding nucleotide probes
Prepare 256 types of probes. Amino residue at 5 'end
Each polyoligonucleotide probe with a group
It is synthesized and used by the midite method. 10 μM water for each probe
Mix acrolein in solution at 2 mM concentration
You. After reacting at 20 ° C for 30 minutes, Sephadex
Unreacted acrolein is removed by gel filtration according to. This
Of amino acid residue in polynucleotide probe and acro
The aldehyde group of the rhine reacts and the active acrylic
A polynucleotide probe having a
You. After vacuum drying, an acrylic group is introduced at the 5 'end.
Aqueous solution having a concentration of 10 μM
In a helium atmosphere at -20 ° C.
The acrylamide monomer and N, N'-me
Using a 39: 1 mixture of Tylene bisacrylamide
You. 1.5M containing 0.015% ammonium persulfate
2.5 μL of squirrel hydrochloric acid buffer (pH 8.5)
Tolu), Polynucleotide Pro with Acrylic Group
0.5 μL (15 μM), 15% acrylamide
40 nM of N, N, N ', N'-
Add 0.5 μL of tetramethylethylenediamine, and add
Then, the solution is dropped into the small hole 840 of the chip. Heliu polymerization reaction
This is performed under an atmosphere. Radical polymerization reactions involve oxygen or plastic
Polymerization inhibition is caused by the stick surface itself. this
Prevents polymerization inhibition and prevents the generation of bubbles in fine parts
In a helium atmosphere. By helium substitution
Although it is not possible to completely prevent polymerization inhibition,
If the taper is applied, the gel is more reliably
Can hold. Helium replacement reduces the formation of air bubbles in small holes.
This is to prevent it. The reaction solution is a certain amount due to capillary action, small
The holes 840 are filled and gelled. N, N, N ', N'-
Apply a solution other than tetramethylethylenediamine to all
N, N, N ', N'-tetra
Add lamethylethylene diamine and immediately into small hole 840
Efficient polynucleotide probing by dropping
Buchip can be obtained. Or N, N,
Tests other than N ', N'-tetramethylethylenediamine
Drugs, i.e., acrylamide, N, N'-methylenebisurea
Tris buffer containing acrylamide and ammonium persulfate
Impulse solution and polynucleotide probe with acrylic group introduced
And a solution prepared by mixing
Fill the small holes by dripping onto the surface of the probe tip
You. Then, gasified or atomized (misted) N, N,
N ', N'-tetramethylethylenediamine,
Exposure of nucleotide probe tip to initiate polymerization reaction
To easily create a polynucleotide probe tip
it can. By the method described above, the polynucleotide
The lobe is made of polyacrylamide gel chain (gel matrix
Is fixed to a polyacrylamide gel chain (gel
Rix) is fixed to the side wall surface 841 of the small hole 840.
You. DNA chips such as polynucleotide probe chips
In making biochips, small holes 840
Only the fine uneven pattern provided on the side wall surface 841
The formation of the small holes, the formation of the recesses, and other uneven structures
Even when formed on the surface of a transparent material, the etchant of the present invention may be used.
Can be used. In addition, the above-mentioned electrode, photo
A well-known thin film is also used for forming a circuit element such as a diode or a wiring.
By using film forming technology together, the etching of the present invention
Can be used.

[0007]

According to the processing method of the present invention, compared with the conventional method of directly processing a transparent material by laser beam irradiation,
The laser output may be several orders of magnitude smaller, there is no damage or contamination around the processing area, and the number of laser pulses is controlled by several n.
The processing amount can be controlled at a level of m to several hundred nm.

[Brief description of the drawings]

FIG. 1 is a diagram showing a semiconductor acceleration sensor according to a first embodiment of the present invention.

FIG. 2 is a view showing a glass substrate etching step performed in the manufacture of the semiconductor device of FIG. 1;

FIG. 3 is a view showing a manufacturing process of the semiconductor device of FIG. 1;

FIG. 4 is a diagram showing a cutting method according to a second embodiment of the present invention.

FIG. 5 is a view showing a liquid crystal display device according to a third embodiment of the present invention.

FIG. 6 is a view showing a manufacturing process of the liquid crystal display device of FIG. 5;

FIG. 7 is a view showing a manufacturing process of the liquid crystal display device of FIG. 5;

FIG. 8 is a diagram showing a polynucleotide probe chip according to Embodiment 4 of the present invention.

FIG. 9 is a partially enlarged cross-sectional view of the polynucleotide probe chip of FIG.

[Description of sign]

110: semiconductor acceleration sensor, 120: glass substrate, 1
21: recess, 130, 131: fixed electrode, 140: movable electrode, 220, 440, 640: super-heat-generating liquid phase substance, 2
40, 430, 630: laser beam irradiation means, 420: pressure vessel, 441: pressure inlet, 510: liquid crystal display element,
610, 611: small liquid crystal element, 810: polynucleotide probe chip, 840: small hole

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission Date] October 2, 2000 (2000.10.
2)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Full text

[Correction method] Change

[Correction contents]

[Document Name] Statement

[Title of the Invention] Transparent material processing method

[Claims]

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to processing of a transparent material, and more particularly to processing of etching, scribing, notching, fusion bonding, cutting, or forming a through hole.

[0002]

2. Description of the Related Art <Cutting Technology> Among brittle materials such as glass, semiconductors and ceramics, quartz glass is mainly used for semiconductor manufacturing parts and the like, and borosilicate glass is mainly used for display substrates and the like. When a brittle material is used as a component material, a scribe line is formed on the surface of the plate-shaped material to cut it to the required dimensions, and a method of applying an external force to cause breakage, or irradiating a laser beam to cut the material (Toshihiro Okiyama: Laser Cleaving, Journal of the Japan Society for Precision Engineering, 6
0, 2 (1994) 196).

[0003] In the laser scribing method, a laser beam is applied to a line to be cut, the surface of the material is melted and evaporated to form a concave groove, and further, an external force is applied to break the groove. As a problem of the laser scribing itself, there is a problem that the melted and evaporated material adheres to and deposits (recast) on the material surface, thereby contaminating the material. And there are problems such as generation of a large amount of fragments at the time of breaking. The fact that the IARC (International Agency for Research on Cancer) evaluated the carcinogenicity of silicon dioxide (silica) for dust from 2A (probably carcinogenic) to 1 (carcinogenic) in 1996, indicating that glass material fragments Is a major problem.

In the laser cutting method, the irradiation position of the laser beam is moved under the condition that the stress field coefficient due to heat generated when the material surface is irradiated with the laser beam exceeds the fracture toughness of the material. The cracks are enlarged to lead to the fracture. This method has problems in that it is difficult to control the generation of the first crack, it is difficult to control the direction in which the crack propagates, the expected cutting line deviates from the actual cutting position, and the processing speed is slow.

<Side pressure cutting> Side pressure cutting method (Hiroyoshi Tanaka: side pressure cutting technology, Journal of the Japan Society of Precision Engineering, 60, 2 (1994) 192)
Is a method of cutting a brittle material by hydraulic pressure, and there are a case where hydraulic pressure is directly applied to the material and a case where hydraulic pressure is applied through an elastic member. It is used for cutting glass rods for optical lenses, ceramics, steel materials and the like.

[0006] In the side pressure cutting method, a notch (small indentation or cut) is formed by pressing a diamond needle or cutter against a material to control a cutting position.
That is, notching is performed. However, when notching is performed on a brittle material, microcracks are formed around the notch at the time of pressure welding. , Materia, 36,
3 (1997) 201), there is a problem that the propagation direction of the crack is not always desired, and the actual cutting position may be shifted from the planned cutting line.

<Joining technology> In a liquid crystal display device,
At present, the active matrix method is mainly used, and an information signal holding circuit such as a TFT (Thin Film Transistor) is formed for each pixel by a semiconductor manufacturing technique such as a thin film forming technique, a photolithography technique, and an etching technique. As a method for increasing the screen size of a liquid crystal display element, for example, TF
There is a method of forming a large panel including a connection substrate obtained by fusion-connecting T substrates and CF (color filter) substrates by laser light.

In the method of directly heating the substrate by irradiating the substrate with a laser beam and performing the fusion bonding, the laser beam is applied to the bonding end of the TFT substrate and the CF substrate with a constant width (about the diameter of the laser spot). Since a portion to be heated and denatured occurs, a pixel, an electrode, and the like cannot be formed in this portion, and a region without pixels, that is, a non-display region exists in a lattice shape along each joint end portion, This results in lower display quality. Further, since the end of the substrate is usually sealed with a sealant, the sealant is melted or peeled off due to heating near the joint by direct irradiation of laser, and the sealing property of the liquid crystal layer is impaired. There is also a problem that it is. In addition, for high-precision bonding, it is necessary to smooth the bonding end face, so a polishing step of the substrate end face is required before the bonding step, which complicates the process, generates dust during polishing, and reduces noise. There are problems such as occurrence. Furthermore, when the entire liquid crystal element has a slight warp or when a substrate made of a relatively flexible material is used, the substrate is sandwiched between the two substrates in order to make the surface heights of the two substrates uniform during bonding. Or it is desirable to fix with a pressing jig or the like, but it is not possible to use such a jig in the conventional joining method by laser irradiation, or to provide a laser light transmission window on the laser light irradiation side of the jig. There are problems such as the necessity of installation.

<Etching> Various semiconductor manufacturing techniques such as photolithography, etching, and film forming techniques are used in the manufacturing process of a semiconductor element, but it is necessary to form recesses on the surface of a glass substrate. Usually, a step of forming a patterned resist layer on a glass substrate, etching the surface with an etchant such as hydrofluoric acid, and then removing the resist layer is used. In such a method, since a resist film is formed directly on a glass substrate, it is necessary to remove the resist film before the next step. Further, since the method depends on a chemical reaction in a liquid phase, the etching rate is lower than that of an etchant. It reacts sensitively to changes in concentration and temperature, but strict control of these conditions is difficult, and it is necessary to use means such as forming an etch stop layer in advance. Such difficulty problems controlling the etching conditions are the same in the dry etching carried out using SF ₆ or the like.

When a DNA chip such as a polynucleotide probe chip is prepared, a plurality of rectangular small holes are arranged and opened in a matrix on a transparent substrate.
In order to provide irregularities at the molecular level on the inner surface of each pore,
Oxygen plasma etching may be used,
Strict control of the environmental temperature is required. At a high temperature, there is a possibility that a portion that does not need to be etched may be damaged.

<Laser ablation> On the other hand,
In recent years, an etching technique using laser light irradiation has been used. In this method, a substrate or a thin film material formed on a substrate surface is directly heated by irradiating a laser beam, and is melted and removed by ablation. However, similar to the laser scribing technique described above, a molten material generated in an ablation process is used. Adheres and accumulates on the substrate and contaminates the surface of the substrate, causing a problem of causing a defect of the device.

<Report of Super Heating Mechanism> In contrast to the conventional processing techniques described above, processing using a super heating mechanism has been proposed (Akira Yabe, Hiroyuki Shinno, Shun Wang: Laser-excited organic molecules) Processing of Quartz Glass by RIE
EWS, No. 39 (1999)), when an acetone solution of pyrene is irradiated with laser light from an excimer laser, the solute pyrene molecules become superheaters and induce ablation of acetone, a solvent, and come into contact with the acetone solution. It has been reported that the etching of quartz glass is possible.

[0013]

SUMMARY OF THE INVENTION The present invention provides a conventional etching technique, scribing technique, notching technique for transparent materials or brittle materials as described above.
It is intended to propose a method of processing a transparent material that comprehensively solves the problems of cutting technology or fusion bonding technology, and in particular, proposes various processing methods of a transparent material using the above-described super-heating mechanism. is there.

[0014]

Means for Solving the Problems In order to solve the above-mentioned problems, the present invention provides a liquid phase material containing a dye forming a dimer or a dark complex while flowing the liquid phase material. A method of processing a transparent material that irradiates an energy beam and processes a transparent material that is in contact with the liquid phase substance. After notching the material, a lateral pressure cutting is performed by pressurizing the liquid phase material. A processing method for a transparent material. In this case, a method of processing a transparent material in which a laser beam is introduced into the bonding portion and fusion bonding is performed is adopted.

[0015]

The dye in the liquid phase material generates heat by the irradiation of the energy beam, and the adjacent transparent material is processed.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a method and an apparatus for processing a transparent material according to the present invention will be described.

<Processing> Here, processing refers to etching,
Including scribing, notching, fusion bonding, cutting, and forming through holes. Etching refers to a process of forming a concave structure on a surface of a material or flattening a convex structure. In etching, the case where a linear concave groove is formed for cutting by applying a bending moment or an impact force to a material is particularly called scribing, and a concave portion is formed on the material surface to cut the material by tensile stress. Is formed, in particular, is referred to as notching. In addition, a process in which at least one of two or more materials that are in contact with each other or that are opposed to each other with a minute space therebetween are melted to be joined to the other material is referred to as fusion joining.

At the time of processing, a liquid phase substance such as carbon disulfide in which a dye such as perylene is dissolved is usually injected into a reaction tank or the like to obtain a super-heat-generating liquid phase substance. The super-heat-generating liquid phase material may be in a fluidized state controlled so that the liquid level is maintained by appropriate means, or may be replaced before and after the irradiation of the energy beam.

The transparent material is fixed in the liquid, and it is desirable that at least a portion of the surface to be processed of the transparent material to be processed touches or is immersed in the liquid phase material during the processing step. Usually, it suffices to fix the work surface so that it is located slightly below the liquid surface.

The transparent material fixed as described above is applied as an incident energy beam from above through a photomask patterned according to the processing shape as required, and further through an optical system such as a condenser lens. Processing can be performed by irradiating the laser light from the laser light irradiation means. The etching amount per pulse depends on the material of the transparent material and the irradiation conditions, but is several tens nm in the case of a glass material.

It is also possible to supply the liquid phase substance dropwise from above, and to irradiate the laser from below or from the side. For example, when producing a DNA chip such as a polynucleotide probe chip, a gel holding a polynucleotide probe is held in a small hole in a configuration in which a plurality of rectangular small holes are arranged and opened in a matrix on a transparent substrate. In order to achieve this, there may be a case where a concave / convex shape at the molecular level is provided on the inner surface of each small hole. By inputting laser light as an energy beam from the side or obliquely upward through an optical system corresponding to a desired concavo-convex pattern, a nano-level concavo-convex shape can be formed.

Using the transparent material itself as an optical waveguide, light incident from one end of the transparent material may be emitted from the other end to irradiate the super-heat-generating liquid phase substance or dye. Therefore, it is possible to process a cut surface or an end in the longitudinal direction of a long transparent material such as an optical fiber.

Only the surface of the transparent material which is in contact with the super-heat-generating liquid phase material is processed. In the transparent material, laser light enters from a portion that does not require processing and is emitted from a portion that requires processing, so that processing does not occur at least in a portion where the incident light does not exit.

The incident light enters the transparent material from a portion where the processing of the transparent material is unnecessary, and is transmitted through the transparent material. Irradiate a substance or a super-heat-generating dye disposed in the vicinity of a processed portion of a transparent material.

In the processing of the present invention, the processing of the transparent material is realized by irradiating the dye molecules arranged in the vicinity of the transparent material with an energy beam. In other words, by irradiating a dye molecule with an energy beam, a transparent material close to the dye molecule is processed.

Instead of a photomask, a photomask layer made of an opaque member may be patterned on a surface to be processed of a transparent material or on a surface opposite to the surface by a known thin film forming technique. However, when a photomask layer is formed over a transparent material, a step of removing the photomask layer may need to be provided between the etching step and the next step in some cases. If a polysilicon layer is patterned as an opaque member, it can be used as a circuit element in the SOG structure.

An etching sacrificial layer made of a transparent material is formed on a portion of the surface to be processed of the transparent material that does not require processing by a known thin film forming technique, and the surface opposite to the surface to be processed is processed in other words. May be applied from an unnecessary portion, that is, from the side opposite to the supply side of the liquid phase substance.
In the portion where the etching sacrificial layer is formed, the etching sacrificial layer is etched instead of the transparent material, and in the portion where the etching sacrificial layer is not formed, the transparent material is processed. The transparent etching sacrificial layer is patterned with an insulator such as glass or resin or a transparent conductor such as ITO, and is etched by laser irradiation as necessary, so that the capacitance, resistance, conductive paths, etc. It is also possible to form circuit elements.

If the etching sacrificial layer becomes unnecessary in the subsequent steps, the thickness of the etching sacrificing layer is set so that the etching sacrificial layer is completely removed when the etching of the transparent material is completed. This is preferable because there is no need to provide a step of removing the etching sacrificial layer.

The processing of the transparent material is not performed in the portion of the processed portion of the transparent material from which the laser beam is emitted, where the layer made of the transparent member or the opaque member is formed on the surface. Furthermore, the etching of the etching sacrificial layer occurs only in the portion where the laser beam is emitted among the portions where the etching sacrificial layer is provided.

If necessary, a complex etching pattern having a variation in etching depth can be formed by using the above photomask and the formation of the etching sacrificial layer in combination.

An etching pattern can be formed by sweeping a laser beam or moving a transparent material by an XYZ table or the like without using a photomask.

The etching method of the present invention can be applied not only to a semiconductor acceleration sensor but also to an ink jet nozzle or the like.
It can be widely used in the manufacture of semiconductor elements and devices, and can be particularly suitably used in the manufacture of semiconductor elements including a step of forming a polysilicon layer on a glass substrate, for example, a polysilicon liquid crystal element, a polysilicon integrated circuit, and the like. . In this case, not only the manufacturing process of the circuit configuration and internal structure of the element,
In the case of performing multi-cavity manufacturing of an element, it can be suitably adopted also in a process of forming a scribe line for breaking and splitting.

In the case of etching a linear pattern in scribing and notching, if the direction in which the super-heat-generating solution flows and the longitudinal direction of the scribe line or the like are set to be parallel or substantially parallel, the fine pattern formed by etching can be obtained. This is preferable because the super-heat-generating solution is uniformly supplied to the details of the pattern. In this case, the flow rate of the super-heat-generating solution may be such that a laminar flow is formed at least in the vicinity of the surface of the transparent material to be processed, but may be a turbulent flow. On the other hand, when the longitudinal direction of the scribe line or the like and the flow direction of the super-heat-generating solution are not parallel, it is preferable to set so as to form a turbulent flow in the vicinity of the surface of the transparent material to be processed. Furthermore, if possible,
It is also preferable that an ascending flow of the super-heat-generating solution is formed and supplied below the transparent material that is the workpiece. in this way,
By setting the super-heat-generating solution to be supplied uniformly to the details of the fine pattern formed by etching, the super-heat-generating dye is uniformly supplied to the processed part at a constant concentration, so that the etching reaction is stabilized. At the same time, there is an effect that the periphery of the processed portion is maintained at a constant temperature, and by-products such as a melt generated by etching are removed from the processed portion.

When the superheat generation solution is caused to flow and laser pulse irradiation is performed as described above, the irradiation is performed with a sufficient time margin so that the heat generation dye is uniformly supplied to the processing portion at a constant concentration. It is desirable to set the period. When the super-heat-generating solution is not allowed to flow, it is desirable to set the irradiation cycle with a sufficient time so that the solution concentration in the processed portion does not fluctuate extremely over the entire etching process. Conversely, even if the light amount is adjusted in accordance with the increase or decrease in the dye concentration by the light amount adjusting means for changing the laser light irradiation intensity, irradiation time, irradiation frequency or irradiation cycle, etc., according to the change in the concentration of the super-heat-generating solution, good.

The etching method of the present invention can be applied to other optical elements such as diffraction gratings, scales and hologram display elements, DV
D, which can be applied to the production of recording media such as near-field optical discs, and is used for forming characters and patterns on transparent materials such as glass, such as decorative articles such as photo stands, protective covers for watches, etc. It is also preferably used.

The transparent material can be cut by continuing the processing until the concave portion formed on the surface to be processed of the material reaches the opposite surface.

It is also possible to form a bent through hole by changing the direction of incidence of the laser beam on the transparent material and sequentially changing the part and direction of the laser beam emitted from the transparent material.

In the side pressure cutting of the present invention, the transparent material as the workpiece is formed such that one side of the pair of O-rings corresponding to the shape of the transparent material is in contact with the super-heat-generating liquid phase substance, and the other side. Is inserted into the pressure vessel so as to come into contact with the laser light introducing liquid. In this state, the laser beam is irradiated from the laser beam irradiating means through a laser beam introducing window and a laser beam introducing liquid provided in the pressure vessel at a point on the cutting line of the transparent material or at a fixed length along the cutting line. Irradiate the part. The laser beam penetrates the transparent material and reaches the super-heat-generating liquid phase material.At the position where the laser beam is emitted from the transparent material, the surface of the transparent material is notched due to the heating of the super-heat-generating liquid phase material to form a notch. Is done. Then, without moving the transparent material from the notching position, the pressurized super-heat-generating liquid phase substance from the pressure generator is introduced into the pressure inlet, and at the same time, the pressurized laser light from the pressure generator is When the introduction liquid is introduced into the pressure introduction port, a compressive stress is generated on the surface of the transparent material, and a tensile stress is generated at the center. The generated internal stress increases in proportion to the applied pressure, and when the tensile stress generated inside the notched position at the assumed cross section exceeds the tensile strength of the transparent material, the transparent material is broken and cut at that point. You. Then, the next cutting can be performed by advancing the transparent material.

The lateral pressure cutting method of the present invention can be applied not only to a cylindrical glass rod but also to a material having another shape. It is also possible to apply the present invention to a columnar material, a plate-like material having a cross-sectional shape, various semiconductor element substrates that have been multi-faced, and the like.

In the fusion bonding of the present invention, first, two materials, at least one of which is a transparent material, are brought into contact with each other at an end face connecting each other or opposed at a very small distance, so that the super-heat-generating liquid phase material Soak and fix. At this time, it is sufficient that at least the connection portion of each end face is immersed in the super-heat-generating liquid phase substance. In fixing the two materials, it is desirable to fix them with a jig or the like that is sandwiched or pressed over both substrates in order to align the surface heights of the two substrates when aligning the end surfaces to be joined. The shape, mechanism, translucency and the like of this jig can be freely set as long as the contact or opposition of both end surfaces is not hindered. Also, at the joint,
It is desirable to apply a compressive stress by a pressing means as appropriate simultaneously with or immediately after the irradiation with the laser beam. After fixing the connecting end of the two materials as described above, the laser light emitted from the laser irradiation means is introduced into the transparent material from the end on the side where the transparent material is not connected. The laser light introduced into the transparent material travels to the end joining the transparent material using the transparent material itself as a waveguide, and is emitted from the joining end. At this time, since a very thin layer of the super-heat-generating liquid phase material is formed between the joining ends of the two materials, the joining ends are brought into abutting contact with each other, or opposed to each other with a minute interval therebetween. In some parts, the exothermic liquid phase material generates heat,
At least one of the butted or opposed ends is melted. Then, the two materials are joined by or without pressing by the pressing means.

In the fusion bonding according to the present invention, the laser light is introduced to the joint by using the transparent material itself, which is the workpiece, as an optical waveguide, so that the laser light does not leak from the transparent material before reaching the joint. It is desirable to do. Specifically, the relationship between the refractive index of the transparent material and the refractive index of the super-heat-generating liquid phase substance, the incident angle of the laser light, and the like, the laser light is totally reflected at the end face inside the workpiece, other than the joining end face. It is desirable to set as follows. In addition, in order to totally reflect the laser light at the end face inside the work piece other than the joining end face, the work piece may be coated with a material having a lower refractive index than the work piece to form a so-called clad layer. It is possible.
In addition, by forming an opaque photomask in a portion other than the joint end, forming a transparent etching sacrificial layer, and the like, melting of the workpiece can be generated only at the joint, and the melting is preferably performed. The joining process is realized.

This fusion bonding method can be applied not only to a liquid crystal display element but also to a member made of a transparent material, such as connection of a display element, a transparent substrate for a semiconductor element, for example, a glass plate, an optical fiber for illumination or communication. It can also be suitably used for connection and the like.

When the end face of the optical fiber is etched by the processing method of the present invention, a photoresist as proposed by Kazuhiro Hane (Tohoku University) et al. A film forming technique of spraying a material to form a film having a uniform thickness on the end face of the optical fiber can be used. In this case, the laser light can reach the processing end face using the optical fiber itself as an optical waveguide. The etching on the end face of the optical fiber enables three-dimensional processing on the end face of the optical fiber, thereby making it possible to reduce the size of the optical connector and directly form functional components.

When the optical fiber is immersed in the super-heat-generating liquid phase substance and laser light is introduced into the optical fiber from one end, the laser light is transmitted from the optical fiber to the outside at a portion where the surface of the optical fiber has a flaw. Since the superheated liquid phase material generates heat in the leaked portion, it can be used as a method for inspecting the surface of the optical fiber for defects such as scratches.

<Energy Beam> In this specification, an energy beam is a charged particle such as a radio wave, a microwave, an infrared ray, a visible ray, an ultraviolet ray, an X-ray, a gamma ray, a synchrotron radiation, a flash lamp light, other electromagnetic waves, and an electron beam. Energy transport, such as flow, that is absorbed by the dye to excite the molecule and / or induces association and dimerization, and also provides the energy required for the dimerized dye to de-dimerize Means means, especially coherent light in the visible or ultraviolet wavelength range, especially laser light. It is desirable that the energy beam of the present invention has a property that it is hardly absorbed by a transparent material that is a workpiece.

The laser used in the present invention is not particularly limited, but preferably has a wavelength corresponding to the absorption region of the selected liquid phase substance or dye molecule.
F, ArF, XeCl, XeF excimer laser, Nd-YAG laser, C
It can be appropriately selected from an O ₂ laser, a CO laser, a nitrogen laser, a solid-state laser, a ruby laser, a semiconductor laser, a tunable diode laser, and the like.

In the processing of the present invention, the laser light source, the pulse width, the energy density or the frequency are appropriately selected according to the absorption characteristics, processing characteristics and heat generation characteristics of the super-heat-generating liquid phase material. The irradiation time may be controlled by performing continuous irradiation of laser light.

In the present invention, when direct processing is performed by irradiating a transparent material with laser light, processing can be performed using laser light having an energy smaller than a threshold value of the amount of light that can be processed. When processing
Excimer laser pulse waves such as FWHM = 30 to 50 ns, energy density of 400 to 1400 mJ / cm ² , and ² to 10 Hz can be used. It is also convenient to use a ruby laser capable of greatly changing the pulse width.

<Transparent Material> In this specification, the term "transparent" refers to a property of transmitting an energy beam, especially a light beam, and particularly refers to an optical transparency that transmits a coherent light represented by a laser beam, that is, a light transmitting property. . The transparent material used in the present invention does not need to transmit 100% of incident light, but may be broken, melted,
It is desirable that the property of transmitting the incident light is not changed before and after the transmission of the incident light without deteriorating such as phase transition. Therefore, the “transparent material” refers to a material having a property of transmitting an energy beam, such as glass, a resin, a ceramic, and a metal, and particularly refers to a glass or a resin having a light-transmitting property.

The glass used here includes silicate glass, borate glass, phosphate glass, germanate glass, tellurite glass, vanadate glass, chalcogenide glass, fluoride glass, oxynitride It can be appropriately selected from glass and the like, and more specifically, fused silica glass (quartz glass), 96% silica glass, soda-lime glass, lead alkali silicate glass,
Borosilicate glass, aluminosilicate glass, aluminoborosilicate glass, aluminosilicate glass, glass ceramics, alumina ceramics, pyrex, pyroceram, Corning 7740, Corning 0211, Corning 70
59, sapphire, calcium fluoride and the like.

The ceramics include translucent alumina, Y ₂ O ₂ , MgO, ZrO ₂ , ThO ₂ , (Pb, La) (Zr, T
i) O ₃ (PLZT) or the like can be used.

As the resin, various transparent polymers,
Specifically, polymethyl methacrylate, polycarbonate, diethylene glycol bisallyl carbonate, methyl methacrylate / styrene copolymer, acrylonitrile / styrene copolymer, poly (4-methylpentene-
1), tetrafluoroethylene / hexafluoropropylene copolymer, poly (-2,2,2-trifluoroisopropyl methacrylate), polycyclohexylmethyl methacrylate, poly n-butyl methacrylate, polyvinyl naphthalene, poly α-naphthyl methacrylate, cellulose Acetobutyrate, cellulose propionate, polyvinyl chloride, styrene / acrylonitrile copolymer, polystyrene, styrene / maleic anhydride copolymer, polytetramethylene terephthalate, polymethyl isocyanate and the like can be used.

The material shapes that can be processed by the processing method of the present invention include a plate material, a wire material having an arbitrary cross section, a columnar material having an arbitrary cross section including a circular cross section and a rectangular cross section, and a hollow cylinder including a case where the outer shape is a circle or a rectangle. Materials, spherical materials, and other bulk materials.

Here, the field of application of the plate material includes liquid crystal display elements, plasma display elements and other display element substrates, semiconductor sensors, LSI and other semiconductor element substrates and semiconductor integrated circuit substrates, diffraction gratings, scales, hologram displays. And other optical elements, recording media such as DVDs and near-field optical disks, decorative articles such as photo stands, and protective covers for watches.

As a field of application of the columnar material having a circular cross section, a rod material for manufacturing an optical lens, an optical fiber for illumination or communication is used as a linear material, and an optical lens is used as a field of application of a spherical material. be able to.

<Super heat generation mechanism> The "super heat generation mechanism" means that a dye dissolved, dispersed or mixed in a liquid phase substance efficiently gives energy to a peripheral substance due to irradiation with an energy beam. A mechanism that emits thermal energy by non-radiative transition, particularly after a phosphor in a solution is excited by a laser pulse, and / or converts the energy of association into thermal energy due to the heat generated by the irradiation of the laser pulse. Refers to the mechanism of release. In the present specification, such a property is sometimes referred to as “super heat generation”.

In general, polyatomic molecules, especially conjugated π
Dye molecules consisting of organic molecules that emit light
Is absorbed, photons are absorbed and the ground state (ground stat
e) S₀ → excited singlet state S₁of
Makes a transition, but Frank-Condon
The principle of₁At least
A non-radiative transition occurs due to vibration relaxation and so on. Lowest excitation
Singlet dye molecules are partially fluorescent
Emits photons in the form of
Due to radiative transition, ground state S₀To S₀Color that has transitioned to
Elementary molecules are S₀Non-radiative transition to the lowest level of
Is generated. In addition, another dye molecule in the lowest excited singlet state
Part is triple excited by intersystem crossing
Excited triplet state T₀Non-radiative transition
And some of them are ground state S₀Transitions to, but T₀→
S₀The transition to is phosphorescent and non-radiative
There is. Also, S₁And T₁Dye molecules undergo further photoexcitation
S with higher energy level_n And T_n(N> 1)
S_nAnd T_nDye molecules also undergo radiative transition or internal conversion (in
non-radiative transition due to internal conversion) or vibration relaxation
May cause a transition to a low excited state.

That is, it is known that an organic molecule becomes an excited singlet state in which electrons are excited by photoexcitation, and a molecule in the excited singlet state further absorbs photon energy and transits to a higher excited singlet state. The light absorption corresponding to this transition is called “singlet / singlet absorption”. In addition, molecules in the excited singlet state undergo a perturbation from the outside, and transition to a triplet state having a different spin multiplicity with time. Molecules in the excited triplet state absorb photon energy and transition to a higher excited triplet state, and the corresponding light absorption is referred to as "triplet-triplet absorption". These wavelength regions may exist in a region where molecules in the ground state do not absorb. A molecule in an excited singlet state or an excited triplet state generates a radical species by, for example, an intramolecular cleavage reaction. Even such a radical species may have strong absorption in a wavelength region where the ground state molecule does not absorb. These are collectively referred to as intermediate absorption in the intermediate molecule, but when the molecule is irradiated with laser light corresponding to such ground state absorption or intermediate absorption, the molecule absorbs photon energy and the excited intermediate And then the intermediate molecule emits as thermal energy, for example in the form of a non-radiative transition due to internal conversion.

When a molecule having a high energy level such as S _n or T _n is de-excited by non-radiative transition until reaching S ₀ or T ₀ , almost all of the absorbed photon energy becomes thermal energy. As a result, the conversion efficiency into heat energy becomes high.

The emission spectrum of the dye shifts toward the longer wavelength side (Stokes shift) with respect to the absorption spectrum, but emission at the longer wavelength side, particularly in the infrared region, can contribute to heating of the workpiece.

<Quenching> By the way, when the concentration of the fluorescent molecules in the solution exceeds a certain threshold value, the fluorescence efficiency is rapidly reduced.
This is called density quenching. Such fluorescence quenching is caused by fluorescence resonance energy transfer (Fluorescence Resonance Energy Energy).
Transfer (FRET), cross relaxation, photoinduced electron transfer, facilitating intersystem crossing, paramagnetic enhancement, Dexter exchange coupling or exciton coupling such as formation of dark complexes. Cause by either. It has been reported that the transfer of fluorescence energy depends on the above parameters (eg, Forster, T. (1)
984) Ann. Physik 2: 55-75; Lakowicz, JR, Princ
iples of Fluorescence Spectroscopy, New York: Plenu
m Press, 1983; Herman, B., Resonance energy trans
fer microscopy: Fluorescence Microscopy of Living
Cells in Culture, Part B, Methods in Cell Biolog
y, Vol 30, edited by Taylor, DL and Wang, YL, San Dig
o: Academic Press, 1989, pp. 219-243; Turro, N.
J., Modern Molecular Photochemistry, Menlo Park:
Benjamin / Cummings Publishing Co. Inc., 1978, pp.29
6-361). Of these, photoinduced electron transfer, facilitation
Paramagnetic enhancement, Dexter exchange coupling, effectively occurs when two molecules collide or approach a distance of 1 nm or less.

<Fluorescence Resonance Energy Transfer> Fluorescence resonance energy transfer (FRET) is a phenomenon in which, at a high concentration, an excitation and a corresponding de-excitation transition occur simultaneously due to the interaction between the localized centers of the phosphor. , A phenomenon in which excitation energy walks between localized centers. In this case, if there is a center with a high probability of non-radiative transition near any localized center, the excitation energy comes near while the excitation energy is moving, and the excitation energy becomes thermal energy due to the non-radiative transition. Will be released. The probability of FRET is the negative of the distance between localized centers if both transitions are due to electric dipole transitions.
It is shown that it is proportional to the sixth power, and if it is due to electric quadruple transition, it is proportional to the −10 power of the distance between localized centers.

Unlike FRET, a radiative transition that emits fluorescent light and an excited transition having substantially the same energy are energy transitions that occur simultaneously due to the interaction between the localized centers of fluorescent light. This is called cross relaxation. The probability of cross-relaxation is also given in a manner similar to FRET.

In the case of cross relaxation accompanied by radiative transition, the actual emission / absorption process of fluorescence is involved, and the presence or absence of a localized center for receiving energy depends on the decay time constant of fluorescence of the localized center for supplying energy. Although having no effect, in the case of FRET, both can be clearly distinguished because the decay time constant of the fluorescence of the localized center that provides the energy is shortened together with the concentration of the localized center that receives the energy.

As described above, since FRET and cross relaxation involving radiative transition are in a competitive relationship as a form of energy transfer, in order for FRET to occur more efficiently than fluorescence, generally the energy donor and acceptor must be used. It is necessary that the distance between the localization centers is set sufficiently small, specifically, it is required to be one hundred to several tens of squares or less.

A typical example of non-radiative Forster-type energy transfer observed in FRET involves the excitation of the donor molecule by light of a certain wavelength within the absorption region of the donor. A small amount of excitation energy is passed around in the form of the vibrational energy of the molecule (transition of the electronically excited molecule to the lowest vibrational state) and the rest is released mainly by energy transfer to the acceptor molecule.

Since the probability of FRET strongly depends on the distance between the centers, FRET is generally remarkable when the concentration of fluorescent molecules is high. In addition, a fluorescent molecule may form an aggregate (including a dimer, a laminate, a cluster, and an aggregate) in a liquid, and in such a case, the localization center is more than the effect of the concentration. The distance between them may be small, and FRET becomes remarkable.
In particular, in the H-association type dimer or laminate, the distance between the localization centers of the fluorescent molecules is extremely small, so FR
It is considered that the occurrence of ET becomes remarkable. In other words, the fluorescent molecules are dimerized or stacked, and electrons in the molecules are confined in the space between the fluorescent molecules due to the quantum theory effect. Alternatively, molecular excitons that resonately propagate to other molecules due to the multipole interaction are generated. As a result, even if the monomer is a fluorescent molecule, its fluorescence is reduced or lost by dimerization or lamination, thereby increasing the probability of non-radiative transition, and the absorbed energy is mainly used as heat energy. Will be released.

As used herein, “donor”
Refers to a dye, especially a phosphor, that can absorb energy and transfer that energy to a portion of another fluorescent molecule or compound. Suitable FRET donors include coumarin and related dyes, xanthene dyes such as fluorescein, fluorescein isothiocyanate (FITC), rhodol and rhodamine, resorufin, cyanine dye, bimane , Acridine, isoindole, dansyl dyes, aminophthalhydrazides such as luminol and isoluminol derivatives, aminophthalimide, aminonaphthalimide, aminobenzofuran, aminoquinoline, dicyanohydroquinone, and europium and terbium complexes and related compounds. Not exclusively.

Here, the “dye” refers to a part of a molecule or a compound that absorbs light of a specific frequency, including but not limited to ultraviolet rays. "Phosphor" is a dye capable of emitting fluorescence.

Further, “acceptor” is
A dye as part of a molecule or compound capable of receiving energy transfer from an FRET donor when located at an energy exchange distance with the donor. For example, x-Rhodamine, x-Rhodamine, tetramethylrhodamine isothiocyanate
e) (TRITC) and CY3 (carbocyanine 3). The acceptor may be a quencher that operates via FRET. Many FRET receptors can emit transmitted energy as fluorescence. By way of example, mention may be made of coumarin and related phosphors, xanthenes such as fluorescein, lodol and rhodamine, resorufin, cyanine, difluoroboradiazaindacene, and phthalocyanine. Other chemical classes of receptors generally do not emit transfer energy. Examples include indigo, benzoquinone, anthraquinone, azo compounds, nitro compounds, indoanilines, di-
And triphenylmethane.

Even when a donor and an acceptor are covalently bonded via a linker, energy transfer by FRET is possible, which is called intramolecular energy transfer. In this case, "donor" and "acceptor"
It refers to a fluorogenic molecule portion that can transfer energy to another fluorogenic molecule portion by FRET, and a fluorogenic molecule portion that can receive energy by FRET. In this case, the linker must not have multiple bonds that allow for conjugation of the donor and acceptor.

The use of FRET can be used as a fluorescent probe technique, as a labeling technique, in the detection of analytes in immunoassays or nucleic acid assays, in the binding of proteins, polypeptides, nucleotides, nucleic acids and their analogs in biological fluids. Detection of DNA in DNA
Detection (Kronick et al. "Clinical Chemistry" vol2
9, 1582-1586 (1983)), saccharides, DNA fragments, hormones,
Determination of the concentration of drugs and substances such as immunoglobulins in subjects, measurement of the activity of the promoter of the gene in a reporter gene assay (Gorman, CM et al.,
Mol. Cell Biol. 2: 1044-1051 (1982); a
nd Cook, JL, Anal. Biochem. 188: 245-254 (199
0)), an annual review of bioch
emistory (1978), 47, 819-846), Search for geometric details in particles (Physical review letters (1988) 6
1, 641-644), study of polymerization kinetics (Paczkowski and Ne
ckers ”Following Polymerization Kinetics of Mutif
unctional Acryltes in Real Time by FluorescencePro
be Methodology ”Macromolecules, 25, 548-553 (199
2)), it is reported in the field of measurement of biological cell membrane potential.

<Transmission Efficiency> The efficiency of FRET is
Fluorescence yield of the donor, excited state of the donor
Lifetime, donor emission spectrum and acceptor absorption spectrum
Overlap integral between Torr and donor
Depending on the orientation, distance, etc., between the target and the receptor. this is,
Formula for FRET is Forster: ET∝K^TwoΦ_D J / R⁶τ_D  To follow. Where ET is energy transfer
Coefficient, K^Two Is the transition moment of the donor and acceptor
Relative orientation, Φ_DIs the quantum yield of the donor molecule, R is the donor
And center-to-center distance between acceptor phosphor and J is donor fluorescence
Emission Spectrum and Absorption Spectra of Acceptor Dyes
Overlap with τ_DIs the lifetime of the excited state of the donor molecule
is there.

Depending on the suitability of the above conditions, the close proximity of the acceptor and the donor results in a reduction in the fluorescence lifetime of the donor fluorophore and in some cases a dark complex. The choice of the fluorophore used for FRET depends on the ability of the donor to show energy transfer at the appropriate excitation wavelength (singlet-
Singlet energy transfer: singlet-singlet energy t
ransfer).

Energy transfer is most pronounced when a donor phosphor with high fluorescence quantum yield (preferably close to 100%) is paired with an acceptor that has a large extinction coefficient at a wavelength consistent with the emission of the donor. Efficient.

In practice, the energy transfer efficiency is not close to 100%, and fluorescence of the donor dye may be observed even after the energy transfer.

In general, when the emission peak of the donor phosphor and the absorption peak of the acceptor are within the range of about 10 nm,
Transmission efficiency is increased. Tables of spectral overlap integrals are readily available to those of skill in the art (see, eg, Berlman, I. et al.
B., Energy transfer parameters of aromatic compoun
ds, Academic Press, New York and London, 1973).

A specific set of dyes exhibiting overlapping excitation and emission wavelengths (eg, Proceedings of national academy of
science USA 1969, 63, 23-30), they may not show FRET or have an energy transfer efficiency less than the appropriate value (80%). Whether two or more dyes exhibit effective energy transfer will be determined empirically after appropriate spectral overlap criteria have been met.

In general, the emission spectrum of a dimer dimerized in the ground state shifts to a longer wavelength than the emission spectrum of a monomer. For example, for a pyrenyl group introduced into the side chain of a polymer, the emission spectrum peak of the monomer is 380 nm, the dimer is 450 nm, and the carbazolyl group is 345 nm (monomer) and 375 nm (dimer). Body).

In some cases, the phosphor forms intermolecular excitons. The intermolecular exciton is an excited dimer that is likely to be formed by diffusion-control between a molecule in the excited state and another molecule in the ground state. A ^* + A → A + A + hν Such an intermolecular exciton has an emission spectrum different from that of the monomer.

The emission of the dimer in the long wavelength region, particularly in the infrared region, can contribute to the heat generation of the workpiece.

The distance between the donor fluorophore and the acceptor dye at which FRET occurs at 50% efficiency is called R0 and can be calculated from the spectral overlap integral. For a fluorescein-tetramethylrhodamine donor-acceptor pair, which is commonly used to measure distances in proteins, this distance R0 is about 5
0-70 ° (dos Remedios, CG. Et al., J. Muscl
e Research and Cell Motility, 8: 97-117, 1987).
The distance over which the energy transfer of this pair exceeds 90% is about 45 °. If the efficiency of FRET is high enough, excitation of the donor fluorophore will result in the donor's transfer to the acceptor instead of the donor's fluorescence.
FRET is observed. If the acceptor is a non-fluorescent dye, energy is released to the solvent and the donor fluorescence quenches. If the receptor itself is a phosphor, fluorescence emission may occur at the emission wavelength of the receptor.

At least two types of fluorescent molecules present at the energy exchange distance may exhibit fluorescence quenching because each molecule is very close to each other. In other words, when the fluorescent molecules are held at an energy exchange distance from each other, singletlet-singlett energy transfer is possible and the probability of non-radiative transition may increase.

In general, the FRET of an organic phosphor is efficient in a region of 100 ° or less, and preferably, is set to 10-80 °. FRET is extremely efficient over distances of 10-30 °. However, it should be noted that high transmission efficiency does not immediately mean high heat generation efficiency.

On the other hand, when a substance containing a rare earth cation such as a lanthanoid, such as a complex, is selected as the phosphor, it is known that quenching becomes remarkable when the center-to-center distance is 10 ° or less, particularly 7 ° or less. I have.

In the interaction based on electric dipoles or multipoles, the direction of orientation in the stack has a great influence on the efficiency of transmission. Generally, when different types of phosphors are used, they are not stacked in the direction organized at the same angle as in the case of the same phosphor, and the transmission efficiency is reduced.

The above situation is the same when the donor and the acceptor are bound by a covalent bond by a linker, that is, in the case of intramolecular energy transfer. For example, this is the case where a plurality of rod-shaped phosphors are linked by a linker. If fluorescein and rhodamine are attached to the cephalosporin skeleton,
The distance between the donor and the acceptor is between 10 ° and 20 ° depending on the size of the linker and dye used. At a distance of 20 °, 90% of the donor transfers its energy to the acceptor and 90% of the donor fluorescence is quenched.

<Dark Complex> Many phosphors have aromaticity and have 4n + 2pi electrons. Due to this aromaticity, the association or stacking of water-insoluble molecules in the aqueous solution or the molecules in the aqueous solution is promoted, and thereby the fluorescence quenching is promoted. In addition, in a polar solvent such as water, when a fluorescent dye is present at a high concentration or when a rod-shaped hydrophobic donor and an acceptor phosphor are separated by a short flexible linker. Lamination can also occur. Due to this association or lamination in the ground state, a "dark complex" is formed (Yaron, A. et al.,
Anal. Biochem., 95: 228-235, 1979). In this complex, neither phosphor can emit light and the fluorescence of both dyes may be quenched (Bojarski, C. and Sienicki,
K., Energytranfer and migration in fluorescent sol
utions: Photochemistry and Photophysics, Editing Rabe
k, JF. Boca Raton: CRC Press, Inc., 1990, pp.1−
57).

The association for forming the dark complex is assumed to be H-association type dimerization and lamination, but in addition, formation of clusters or aggregates, J-association type dimerization and the like are also conceivable. Also, when a plurality of phosphors are introduced as side chains into a chain molecule, a polymer, or the like to form a fluorescent molecule portion, these fluorescent molecule portions are associated or laminated to darken. A complex may be formed.

For example, in the case of fluorescein and rhodamine bound to the cephalosporin skeleton, both fluorescein and rhodamine do not show much fluorescence in a phosphate buffer at pH 7 when excited by their respective maximum excitations. This indicates the formation of phosphor overlap (dark complex). This can be confirmed from the fact that the fluorescence characteristics are significantly increased with the cleavage of the linker or the collapse of the stacking structure.

In the case of cephalosporin having fluorescein and rhodamine as the fluorescent material, the fluorescence is reduced by the cleavage of the cephalosporin skeleton as the linker.
Increase 70 times. The low fluorescence before the increase is due to phosphor overlap, indicating the formation of a non-fluorescent ground state complex. This fluorescent property is considered to be due to the formation of a dimer of the dye since the addition of methanol to the solution significantly increases the fluorescence properties. In other words, the addition of methanol breaks the hydrophobic interaction that causes the phosphors to overlap, disrupting the overlap and observing the fluorescence of the donor or transferring the fluorescent energy transferred to the acceptor as fluorescence. Is considered to be observed.

<Dimerization> The dimerization reaction itself is understood as a process of accumulating light energy. For example, anthracene forms an H-associated dimer in a liquid phase substance. The dimerization reaction proceeds by absorbing light of 400 nm or less, and the reverse reaction proceeds by, for example, heating. Since the emission energy associated with the dedimerization of anthracene is 65 kJ / mol, if a dimer of the dye is formed in a concentrated solution at or above the threshold, irradiation with laser light or the like will trigger By applying such heat energy to the system, the heat release accompanying the de-dimerization of a certain dimer promotes the de-dimerization of a nearby dimer, and the heat energy is released in a chain. Become.

For example, when rhodamine 6G, which is a laser dye, is used as a dye, when water is used as a liquid phase substance, 10 ^-4 mol / d
dm ³ Order, such dimerization occurs when the concentration of more than 10 ^-2 mol / dm ³ orders in the case of organic solvents, nonfluorescent of dye occurs. In this case, the probability that the absorbed energy is emitted as light energy is extremely small,
Heat generation efficiency is significantly improved. In this case, of course, the donor-acceptor pair is the same type of dye molecule (two rhodamines).
6G molecules). In this case, the formation of a dimer and the generation of heat are as follows: A + A + hv → (A + A)... Dimer, (A + A) → A +
A + Δ is considered. The first equation is a process in which the phosphor absorbs light energy and dimerizes, and the second equation is a de-dimerization reaction that proceeds by heating the dimer and releasing the heat energy. It is accompanied by.

In general, a phenomenon called temperature quenching occurs in which the fluorescence efficiency decreases as the environmental temperature increases, and the probability of non-radiative transition increases. This is considered to be because the probability that the energy due to FRET is transferred to the center where the probability of the non-radiative transition is high increases as the environmental temperature increases.
Therefore, it cannot be denied that the release of heat energy from the phosphor, whose non-radiative transition is promoted by the environmental temperature, contributes to the present invention.

The “super heat generation mechanism” is based on the principle of the emission of thermal energy by fluorescence resonance energy transfer (FRET), non-radiative transition, and / or release of thermal energy by de-dimerization of the dye as described above. It is considered to be.

<Dye> As the dye of the present invention, the energy supplied from the energy beam, in particular, the photon energy of the laser pulse is absorbed and efficiently converted to heat, or the heat is efficiently generated due to the irradiation of the laser beam. Release energy,
A liquid phase substance, in particular, a substance which can heat a solvent to further process a nearby material, that is, a super-pyrogenic dye is suitably used. A liquid phase substance in which such a super-pyrogenic dye is dissolved, dispersed or mixed is called a super-pyrogenic liquid-phase substance, and a solution containing a super-pyrogenic dye as a solute is sometimes referred to as a super-pyrogenic solution. .

Industrially, the wavelength range corresponding to the absorption associated with the above-mentioned dimerization reaction, the absorption in the ground state, or the absorption of the intermediate in the wavelength region of a laser light source currently in practical use, particularly in the visible or ultraviolet region. Are preferable, and those having an absorption peak near the wavelength of the laser beam to be used are more preferable. However, if necessary, the wavelength of the laser light may be changed by up-conversion or the like to make the wavelength of the laser light closer to the peak of the absorption spectrum of the selected dye. Furthermore, if two or three absorption regions of the above-mentioned absorption due to the dimerization reaction, ground state absorption, or intermediate absorption overlap, the laser beam of the common wavelength is irradiated to cause the dimerization reaction. The accompanying absorption energy, transition energy from the ground state to each excited state, or supply of energy corresponding to intermediate absorption can be provided by one laser irradiation means.

As the dye of the present invention, a dye capable of being dimerized or laminated, particularly a polycyclic aromatic hydrocarbon, a 5- or 6-membered heterocyclic compound, or a compound having a carbonyl group can be optimally used. Alternatively, a metal complex having a coordination group of an organic molecule can be used. Among them, fluorescent organic dyes that can be dimerized, particularly peri-condensed polycyclic aromatics such as pyrene, perylene and coronene are most suitable. Two or more types of dyes may be used, and a plurality of dyes may be linked by a linker.

More specifically, the peri-fused polycyclic aromatics include pyrene, perylene, coronene, biolanthrene,
Isobiolanthrene can be mentioned. Polycyclic aromatic hydrocarbons include polyacenes and derivatives thereof such as naphthalene, anthracene, and naphthacene; polyphenes and derivatives thereof such as phenanthrene and pentaphene; and phenyl groups such as terphenyl and t-stilbene, which are directly or through multiple bonds. And linked polycyclic aromatic. As the 5-membered heterocyclic compound, pyrrole, oxazole, thiazole, pyrarizone, oxadiazole, fluorescein and the like can be used, and as the 6-membered heterocyclic compound, a compound having pyridine, quinoline, pyrazine, quinoxalin and the like can be used. . Examples of the compound having a carbonyl group include coumarin derivatives such as 7-hydroxycoumarin, naphthalimides such as naphthalimides and naphthalene anhydride represented by 4′-methoxynaphthylenebenzimidazole, and coordination groups of organic molecules. Examples of the metal complex include a metal complex of porphyrin and a metal complex of quinolinols.

[0100] Derivatives of these dyes having a fluorescent property and other phosphors can also be used. For example, 1-phenylnaphthalene, 1,3,6-naphthalenetriol, (5
Or 8) -amino-2-naphthol, di-1-naphthyl ether, 2-naphthyl salicylate, 2-naphthol-6-sulfonic acid, 2-naphthol-7-sulfonic acid, 2-naphthol-3,6-disulfonic acid , 4,5-dihydroxy-2,7-naphthalenedisulfonic acid, naphthonic acid, 1-naphthylamine-8-sulfonic acid, 2-naphthylamine- (5-8) -sulfonic acid, (7 or 6) -amino-4- Hydroxy-2-naphthalenesulfonic acid, 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid, 1,8-naphthosultam, 2-naphthylamine, N-methyl-1-naphthylamine, N, N-dimethyl- (1 Or 2) -naphthylamine, N-phenyl- (1 or 2) -naphthylamine,
Di-2-naphthylamine, 1-methylanthracene, 9-ethylanthracene, 2,6-dimethylanthracene, 9-phenylanthracene, 1-anthrol, (1 or 2) -anthracenecarboxylic acid, (1,2 or 9) -Anthrylamine,
Fluorene, 9-phenylfluorene, dibenzo [a, j]
Examples include anthracene, benzoanthrene, and aceantrene.

In addition, a substance having a fluorescent substituent can be used. Examples of the fluorescent substituent include pyrenyl (which means a pyrenyl group; the same applies to the following list), phenyl, triphenylmethyl, and the like. Biphenyl,
Terphenyl, anthryl, phenanthryl, carbazolyl, naphthyl, pentalenyl, indenyl, azulenyl, heptalenyl, biphenylyl, as-indacenyl, fuquenyl, s-indacenyl, acenaphthylenyl, preadenyl, acenaphthenyl, phenalel, phenanthryl, aminophenylphenyl, alkylaminophenyl, alkylaminophenyl Alkoxyphenyl, methoxyphenyl, methylphenyl, chlorophenyl, anthryl, fluoranthenyl, triphenylenyl, chrysenyl, pyridyl, furyl, thienyl, tinolinyl, benzpyranyl, acridinyl, thiazolyl, benzothiazolyl, ethylcarbazolyl, phenylcarbazolyl, tolylcarbazolyl And each organic substituent such as These substituents correspond to the fluorogenic moiety in intramolecular energy transfer. Here, the substance having a pyrenyl group is 1-
The same applies to other substituents listed, including pyrene itself, in addition to vinylpyrene, pyrenebutyric acid, pyrenetrisulfonic acid ester (for example, trade name "Cascade Blue") and the like.

The dyes of the present invention include laser dyes such as various polymethine dyes, xanthene dyes, coumarin dyes, scintillator dyes, oxadiazole derivatives and rhodamine dyes, azo dyes, cyanine dyes, and the like.
Benzenethiol nickel complexes, metal phthalocyanine dyes, naphthalocyanine dyes, and naphthoquinone dyes can be suitably used. Specifically, 2,5-diphenyloxazole (PPO), α-naphthylphenyloxazole (α
-NPO), POPOP, 4-methylumbelliferone, 4-methylcoumarin, fluorescein, rhodamine 6G, acridine red, rhodamine B, 3,3'-dimethyl-2,2'oxatricarbocyanine iodide, 1, Laser dyes such as 1'-diethyl-4,4'-quinotricarbocyanine iodide and indigo, phenol blue and the like can be mentioned.

Further, the use of a rare-earth complex as a fluorescent material is not recommended.
As a specific example of the rare earth cation in this case,
Is La²⁺, La³⁺, Ce²⁺, Ce³⁺, Ce⁴⁺, Pr²⁺, Pr³⁺, P
r⁴⁺, Nd²⁺ , Nd³⁺, Nd⁴⁺, Pm²⁺, Pm³⁺, Sm²⁺, Sm³⁺,EU
²⁺,EU³⁺, Gd²⁺, Gd³⁺, Tb²⁺, Tb³⁺ , Tb⁴⁺, Dy²⁺, D
y³⁺, Dy⁴⁺, Ho²⁺, Ho³⁺, Er²⁺, Er³⁺, Tm²⁺, Tm³⁺, Yb
²⁺, Yb³⁺ , Lu²⁺And Lu³⁺Lanthanoid cations, such as
Group 3A of the periodic table such as scandium and yttrium
Elemental cations.

In addition, a condensed polycyclic aromatic compound or a substance having a hetero ring can be suitably used, and a substance molecule having a plurality of ring structures, in particular, a molecule such as an aromatic substance having a plurality of aromatic rings in a molecule. Substance molecules having a multiple bond or a ring structure can also be used, and unsaturated aliphatic hydrocarbons, aromatic hydrocarbons, aromatic halogen compounds, aromatic nitro compounds, aromatic nitroso compounds, aromatic amines, aromatic nitriles, Phenol, phenol ether, aromatic carbonyl compound, aromatic carboxylic acid and derivatives thereof, azo compound and derivative, sulfonic acid derivative, furan group compound, thiophene group compound, pyrrole compound, pyran compound, pyridine group compound, diazine group compound and others Can be appropriately selected from organic compounds and the like. Specifically, triphenyl, pentacene, chrysene, fluorene, acenaphthene, fluoranthene, 3-aminopyrene,
1,2,3,4-tetramethylnaphthalene, 1- (dimethylamino) -pyrene, 1-pyrenebutyric acid, butylpyrene, 4-methyl-
2H-1-benzopyren-2-one, benzoquinone, naphthoquinone, anthraquinone, pyrrole, 2-phenylpyrrole,
Indole, pyridine, fluoropyridine, 2-ethoxypyridine, aminopyridine, pyridone, pyridine-N-oxide, 4-nitropyridine-N-oxide, 4-aminopyridine-N-oxide, quinoline, isoquinoline, carbazole, coumarin, 2,6-dimethyl-4-pyrone, proflavine, 1,2-benzoazulene, dimethylbiphenyl, tetramethylbiphenyl, hexamethylbiphenyl, (trans
Or cis) stilbene, 5,5'-dimethylbiphenyl, 6,6 '
-Dinitrobiphenyl, p-nitro- (trans or cis) -stilbene, p-methoxy-p-nitro-trans-stilbene, phenyl ether, (α, β) -naphthol, benzophenone, 7- (dimethylamino) -4- Examples include methyl coumarin, nitrophenylazobenzene, trifluoromethylsulfonyl tolan, azulene, benzoin, benzotriazole, and derivatives thereof.

Further, when a substituent called an auxiliary fluorophore is introduced into these dye molecules, the fluorescence quantum yield can be improved or lowered, and the heat generation efficiency can be raised or lowered. it can. Specifically, -OH,-
Addition of electron donating groups such as CH ₃ , —NH ₂ , and —N (CH ₃ ) ₂ increase the emission intensity. In addition, electron withdrawing groups such as -COOH and -CN also have the effect of increasing the emission intensity. On the other hand, when -NO ₂ , -NO, etc. are introduced, the fluorescence disappears and the probability of non-radiative transition is improved. Therefore, by introducing these substituents selectively into the dye by a dominantly contributing action, more efficient processing can be realized.

However, it is more efficient to disperse the details of the fine concave structure on the surface of the transparent material formed sequentially by the processing, so that the etching efficiency is higher. Generally, the smaller the molecular weight, the more advantageous. From this viewpoint, low molecular weight dyes such as naphthalene and anthracene are exemplified by polyacene.

On the other hand, the amount of heat released in the dedimerization tends to be larger for dyes having a higher molecular weight if they are of the same family. Therefore, a substance having a relatively high molecular weight, for example, a perylene-condensed polycyclic aromatic, such as perylene or coronene, is used. Dyes having the above molecular weights are preferred.

In the present invention, when a liquid phase substance in which a super-pyrogenic dye is dissolved or dispersed is used, the dye transitions between a ground state and a plurality of excited states, and / or a dimerization reaction and a de-dimerization. By repeating the reaction and only performing energy transition to the surrounding substances, the dye itself is hardly consumed, whereas the liquid molecules in the vicinity of the processed part may be consumed one after another due to intense evaporation or the like. The concentration of the dye in the liquid phase material may locally increase near the surface of the processed part. This may cause a problem that the amount of etching per irradiation energy increases as the processing progresses even if the same amount of laser beam irradiation is performed. This is a problem inherent in the configuration of the present invention, which is completely different in principle from the fact that the etchant concentration gradually decreases with the progress of processing in the conventional etching in the liquid phase.

Conversely, if the intense laser light is intermittently applied for a long period of time, the dye may be destroyed or worn. In this case, even if the same amount of incident light is irradiated, an effect is produced in that the processing amount per irradiation energy decreases as the processing progresses. For this reason, in order to keep the processing accuracy constant, a dye-containing liquid phase material having a constant concentration is continuously supplied or flown to the portion to be processed by means such as a pump or the liquid phase material before and after laser beam irradiation. It is desirable to replace. When the liquid phase material is caused to flow to form a laminar flow, the liquid phase material is preferably supplied directly to the surface of the workpiece. When a turbulent flow is formed, the interface between the viscous layer formed near the surface of the workpiece and the turbulent boundary layer is disturbed by vigorous evaporation of the fluid and the like, and mass exchange occurs. Can be reduced or prevented. Further, an upward flow of the liquid phase substance may be formed below the transparent material, which is a workpiece, by an injection means such as a nozzle.
Further, it is also possible to supply the liquid phase substance dropwise from above and to perform laser irradiation from below.

As the liquid phase substance of the present invention, not only a fluid whose viscosity or compressibility can be neglected, but also a viscous fluid or a compressible fluid can be used, and a sol or a thixotropic substance can also be used. In this case, it is desirable that the further selected dye can undergo a dimerization-dedimerization reaction. When a sol is used, an adhesive such as silica or alumina may be added to the above solvent. In this case, instead of contacting or dipping the processed portion of the workpiece with the liquid phase substance, the liquid phase substance can be applied to the surface to be processed uniformly or in a pattern by using an application means such as printing.

Further, when the affinity of the selected liquid phase substance, especially the solvent, and the transparent substance to be processed is low, the state of "wetting" is insufficient and only a part of the processed surface comes into contact with the liquid phase substance. In some cases, a material such as a surfactant may be added to the fluid to reduce the angle of `` wetting '' of the selected fluid with respect to the transparent material, preferably to make it sharper, since such a problem may occur. it can. However, care must be taken because the presence of the surfactant may promote or inhibit the association of the dye molecules.

<Liquid phase substance> The liquid phase substance in the present invention,
In particular, as the solvent constituting the super-pyrogenic solution, it is capable of dissolving the selected dye molecules, is liquid at the pressure and temperature conditions that can be employed in ordinary industrial manufacturing processes, and releases the super-pyrogenic dye. As long as it absorbs heat energy and becomes high temperature and can process a material in contact with the material, it can be widely used, and a liquid phase, particularly a solvent, may be constituted by one or a plurality of substances. If the dye generates heat and violent evaporation occurs in some cases, the processing efficiency may be improved by removing the melted / softened transparent material from the processed part by gas pressure.

However, since it is inconvenient if the transparent material touching the liquid phase substance is chemically etched by the liquid phase substance, a strongly acidic or basic solution, a substance having a strong oxidation / reduction action, a solution, etc. Is inappropriate. However, by adjusting the pH to a suitable value from pH to redox, it is possible to dissolve molecular fragments of the transparent material generated by etching or the like and destroyed / damaged dye fragments, thereby maintaining the transparency of the super-heat-generating liquid phase substance. is there.

Specifically, general-purpose organic solvents and inorganic solvents such as acetone, heptane, hexane, methyl alcohol, ethyl alcohol, chloroform, benzene, cyclohexane, isooctane, isopentane, heptane,
Ether, water, carbon tetrachloride, aniline, α-chloronaphthalene, toluene, bronbenzene, chlorobenzene,
Nitrobenzene, carbon disulfide, ethyl ether, n-hexane and the like are preferably used.

However, in order to efficiently penetrate into the details of the fine groove structure formed sequentially by processing and to perform etching efficiently, it is more advantageous that the volume occupied by one molecule is small and that the molecular weight is generally small. . Further, when such a low-molecular substance is used as a liquid phase substance and side pressure cutting is performed, there is an effect that the required pressure for cutting the same material and the same shape is reduced. From these viewpoints, examples of the solvent having a small molecular weight include methyl alcohol, ethyl alcohol, water, and ether.

When a substance having no strong absorption in the visible light region is selected as a liquid phase substance or a dye contained therein, or a dye which evaporates together with a volatile liquid phase substance is used, there is no visual contamination of the transparent material. .

In practicing the present invention, it should be noted that the absorption spectrum of the dye may vary depending on the type of liquid phase substance, particularly the type of solvent.

This application includes the following inventions.

1 A laminar flow, a turbulent flow, or an upward flow is formed in a super-heat-generating liquid phase material in contact with a transparent material, and a laser beam is incident on the liquid phase material via the transparent material to thereby form the transparent material. A method of processing a transparent material in which a portion of the surface of the material that is in contact with the liquid phase substance is etched.

(2) A method of processing a transparent material, which comprises a step of specifying at least one processed portion among the following a) to e) before the step of irradiating the energy beam into the transparent material. A step of patterning a layer made of an opaque member on the surface of the transparent material opposite to the surface to be processed; a step of patterning a layer made of a transparent member on the surface of the transparent material to be processed A step of patterning a layer made of an opaque member on the surface, a step of coating a portion of the transparent material that does not require processing with a substance having a smaller refractive index than the transparent material. Setting the refractive index of a substance in contact with the transparent material and the angle of incidence of the energy beam so that the energy beam is totally reflected

(3) The energy beam enters the transparent material from a portion where the processing of the transparent material is unnecessary, and after passing through the transparent material, is emitted from the processed portion of the transparent material to irradiate the super-heat-generating liquid phase substance. In addition to the step of dissolving, dispersing or mixing the dye, the liquid phase substance forms a laminar flow, a turbulent flow or an upflow simultaneously with the irradiation, or is replaced before or after the irradiation, A) to f), a method for processing a transparent material, the method including a step of specifying at least one processed portion. A step of patterning a layer made of an opaque member on a surface of the transparent material opposite to the surface to be processed a step of patterning a layer made of a transparent member or an opaque member on the surface of the transparent material to be processed Is a step of uniformly entering from a portion where the processing of the transparent material is unnecessary A portion of the processed portion of the transparent material from which the energy beam is emitted, in which a layer made of a transparent member or an opaque member is formed on the surface However, the step of not being processed even by the irradiation of the energy beam is a step of coating the unnecessary portion of the transparent material with a substance having a smaller refractive index than the transparent material. Setting a refractive index of a substance in contact with the transparent material or an incident angle of the energy beam so that the energy beam is totally reflected;

4 A method of processing a transparent material in which laser light is applied to a dye which is in the vicinity of a portion to be processed of a transparent material and which is dissolved, dispersed or mixed in a liquid phase substance, wherein the dye is as follows: A method for processing a transparent material having at least one of a) to g). In the absorption region in the ground state, the absorption region corresponding to the intermediate absorption, or the absorption region accompanying dimerization, two or three overlap.b) Dimer, laminate or coagulation in the liquid phase material A) forming an aggregate c) naphthalene, d) having a molecular weight of the degree exemplified by anthracene d) perylene, having a molecular weight of at least the degree exemplified by coronene e) a peri-condensed polycyclic aromatic compound f) a dark complex Form g) Perform energy transfer by FRET with other dyes

5. Before or after or simultaneously with the step of irradiating the energy beam to the dye near the processed portion of the transparent material, a transparent material having at least one of the following steps a) to k): Processing method. a) forming a layer of a substance that dissolves, disperses, or mixes the dye between the ends of the transparent material; b) ends the transparent material in a substance that dissolves, disperses, or mixes the dye. C) pressing the molten surface of the transparent material against another material d) pressing the molten surface of the transparent material against another material d) touching the transparent material in contact with the substance in which the dye is dissolved, dispersed or mixed Moving the material e) flowing the substance in which the dye is dissolved, dispersed or mixed to form a laminar, turbulent or upflow f) removing the substance in which the dye is dissolved, dispersed or mixed Exchanging step g) supplying the dye at a constant concentration in the vicinity of the processed part h) pressing the substance in which the dye is dissolved, dispersed or mixed i) dissolving, dispersing or mixing the dye Substances, such as methyl alcohol, ethyl alcohol, Or a step consisting of a low molecular weight substance less than or equal to that exemplified by ether j) a step of changing the irradiation intensity, irradiation time or number of irradiations of the energy beam according to a change in the concentration of the dye k) sweeping the energy beam Process

6. The end of the transparent material and the end of the other material are abutted or opposed to each other at a small interval, and a thin layer of the super-heat-generating liquid phase substance is formed between the ends to form the transparent material. A method of processing a transparent material in which laser light is introduced into the thin layer using an optical waveguide as a light guide and the two materials are joined.

7 A method of processing a transparent material that is side-cut with a transparent material and then melt-bonded to another material on the cut surface.

8. An apparatus for processing a transparent material having the following components A) to C) and at least one of the components a) to s). A) Liquid phase substance that dissolves, disperses or mixes the dye B) Energy beam irradiation means C) Means for changing the irradiation intensity, irradiation time or number of irradiation of the energy beam according to the change in the concentration of the dye a) Means for inserting the transparent material into the pressure vessel b) Means for moving the transparent material c) Means for patterning a layer of an opaque member on the surface of the transparent material opposite to the surface to be processed d) Means for patterning a layer made of a transparent or opaque member on the surface of the transparent material to be processed e) means for abutting the edges of the transparent material in the liquid phase material f) between the edges of the transparent material G) means for forming a thin layer of the liquid phase substance, g) means for flowing the liquid phase substance, and forming a laminar, turbulent or upward flow.h) a liquid phase in which the dye is dissolved, dispersed or mixed. Means for exchanging substances i) Apply the dye at a constant concentration. Means for supplying the transparent material to the workpiece; j) means for maintaining a constant temperature around the non-processed part of the transparent material; k) means for removing by-products generated by etching from the processed part; Means for applying pressure m) means for coating a portion of the transparent material that does not require processing with a substance having a lower refractive index than the transparent material n) the energy beam is totally reflected on the end face other than the processed portion of the transparent material Means for setting the refractive index of the liquid phase material in contact with the transparent material or the angle of incidence of the energy beam.o) so that the processed part of the transparent material is in contact with or immersed in the liquid phase material. Means for fixing the transparent material p) means for pressing the molten surface of the transparent material against another material q) means for sweeping the energy beam r) disposed on the side opposite to the processed part of the transparent material Photomask s) Optical system

9. A liquid phase substance in which the super-pyrogenic dye is dissolved, an energy beam irradiating means, a means for supplying the super-pyrogenic dye at a constant concentration to a portion to be processed of the transparent material, A transparent material processing apparatus having means for maintaining a constant temperature around the processing portion.

10. An apparatus for processing a transparent material in which the position of the transparent material is matched in the notching step and the side pressure cutting step, and the notching is performed by laser beam irradiation.

11 A transparent material processing apparatus for laterally cutting a transparent material by pressurizing a liquid phase substance in which a dye is dissolved, dispersed or mixed.

12. A transparent material having features for specifying at least one of the following processed parts a) to c). a) An etching sacrificial layer made of a transparent member is formed on a portion of the surface of the transparent material that does not require processing.b) A clad layer is formed on a portion of the surface of the transparent material that does not require processing. C) A layer made of an opaque member is patterned on the surface opposite to the surface to be processed d) A layer made of a transparent member is patterned on the surface to be processed

13. Transparent material broken by tensile stress at the position of the recess formed by laser light irradiation.

14. A thin film is patterned on one end face of the optical fiber, a laser beam enters the optical fiber from the other end, and is guided to the end face forming the thin film using the optical fiber as an optical waveguide. A method for processing an end face of an optical fiber in which etching corresponding to the pattern is applied to the end face.

15. At least two dyes are linked or unlinked by a linker and held at a certain distance and orientation, and by supplying light energy or heat energy,
A heating element that emits thermal energy without changing or changing the distance or the orientation.

16. A liquid phase substance in which a heating element composed of a dye pair is contained at a concentration such that heat generation from one heating element induces heat generation from another adjacent heating element.

<First Embodiment> FIG. 1 shows a known semiconductor device. This semiconductor element is a semiconductor acceleration sensor
110, a fixed electrode 130 fixed on a glass substrate 120
And a movable electrode 140 between the two. Fixed electrodes 130 and 1
The opposing parts of the movable electrode 140 and the fixed electrode 130, and the movable electrode 140 and the fixed electrode 131, respectively, can be understood by referring to the drawings. It is formed in a comb shape. The movable electrode 140 has a concave portion formed on the glass substrate 120.
It is located above 121, its both ends are supported by beams 150 and 151, and is floating with respect to the glass substrate 120. The base portions 150a and 151a of both beams 150 and 151 are fixed on the glass substrate 120. Each beam base end 150a and 1
Electrical wiring (not shown) is individually applied to the 51a and the fixed electrodes 130 and 131, respectively.

In such a semiconductor inertial sensor 110, when an acceleration that is perpendicular to the line connecting the base ends 150a and 151a of the beams and has a component in the horizontal plane acts on the movable electrode 140, the movable electrode 140 Vibrates with the beams 150 and 151 as pivots. Thereby, the movable electrode 140 and each fixed electrode 1
Since the distance between the movable electrode 140 and the fixed electrode 130 changes, the capacitance between the movable electrode 140 and the fixed electrode 130 or 131 changes. The change in the capacitance is detected, and the acceleration acting on the sensor is obtained.

Next, a method of manufacturing the above semiconductor device will be described.

FIG. 2 shows the semiconductor inertial sensor 11 shown in FIG.
10 illustrates an etching process of a glass substrate performed in the manufacture of No. 0. In the etching reaction vessel 210, an acetone solution of pyrene (concentration: 0.6 mol / d)
m ³ ) has been injected to form the superpyrogenic liquid phase material 220. The super-heat-generating liquid phase material 220 is continuously supplied by a suitable means such as a pump and is in a fluid state, and the inflow amount and the discharge amount are the same, and the liquid surface 221 of the super-heat-generation liquid phase material 220 is Is controlled so as to maintain the height. The glass substrate 120 as a workpiece is fixed to the liquid surface 221 by fixing means (not shown). In this case, at least a portion to be etched of the processed surface 122 of the glass substrate 120, that is, a portion where the concave portion 121 is formed by etching,
It is desirable that the heat generating solution is touched or immersed in the etching process. Normally, if the entire surface to be processed 122 is fixed horizontally so as to be located slightly below the liquid surface 221, the liquid phase substance enters into the sequentially formed concave portions of the processed portion.

With respect to the glass substrate 120 in such a state,
From above, that is, from the surface 123 side opposite to the processing surface 122 of the glass substrate 120, through a photomask 230 patterned corresponding to the shape of the concave portion 121, and further through an optical system 250 such as a condenser lens. Then, laser light as an energy beam is irradiated from the laser light irradiation means 240.

As the laser light used here, a pulse wave of an excimer laser (KrF, 248 nm), for example, FWHM = 40 ns and a maximum energy density of 1400 mJ / cm ² can be used. Recess 12 to depth
Form one.

FIG. 3 shows the semiconductor inertial sensor 11 shown in FIG.
0 shows steps other than the etching step for the glass substrate 120 among the manufacturing steps of FIG. First, silicon wafer 31
Film 320 that can be etched without eroding silicon on both sides of 0
To form As the film 320, a chemical vapor deposition (CVD) method
And a silicon nitride film formed using SiH ₂ Cl ₂ and NH ₃ gas. After the films 320 are formed on both surfaces of the silicon wafer 310, the films 320 on one surface are removed by etching with hydrofluoric acid. Polysilicon layers 330 and 331 having a thickness of about 5 μm are formed on both surfaces of the silicon wafer 310 by a CVD method. Membrane 320
After forming an Al film 340 by sputtering or the like on the surface of the polysilicon layer 331 on the side where
Perform low-temperature anisotropic dry etching with F ₆ gas.

As a result, the polysilicon layer 331 is etched using the film 320 as an etch stop layer. The movable electrode 140 made of polysilicon is formed on the film 320, and the polysilicon is formed on both sides of the movable electrode 140 with a slight space therebetween. Thus, a pair of fixed electrodes 130 and 131 are formed. After removing the Al film 340, the silicon electrode 310 on which the movable electrode 140 and the pair of fixed electrodes 130 and 131 are formed is placed on the glass substrate 120 such that the movable electrode 140 faces the recess 121 of the glass substrate 120 described above. Join. Thereafter, the silicon wafer 310 bonded to the glass substrate 120 and the remaining polysilicon layer 330 are removed by wet etching with an etchant such as KOH using the film 320 as an etch stop layer. Subsequently, the film 320 is removed with an etchant such as hydrofluoric acid. Thereby, the semiconductor inertial sensor 110 in which the movable electrode 140 is sandwiched between the pair of fixed electrodes 130 and 131 and formed in a floating state above the concave portion 121 is obtained.

According to the etching method of this embodiment, laser irradiation is performed while the super-heat-generating solution is flowing, so that the super-heat-generating dye is uniformly supplied to the processing portion at a constant concentration, and the etching reaction is stably performed. It is possible to prevent unnecessary overheating of the processed portion, remove the dye molecule fragments or the transparent material molecule fragments generated around the processed portion, and maintain the transparency of the liquid phase substance. Also, compared to the conventional method of directly processing a transparent material by laser beam irradiation, the laser intensity may be several orders of magnitude lower, there is no damage around the etched area, patterning on the order of μm is possible, and the etching depth is low. Since the amount can be controlled at the nm level by controlling the number of laser pulses, the amount of etching can be easily controlled, and etching can be performed by a simple process having advantages such as not requiring the formation of an etch stop layer.

<Embodiment 2> FIG. 4 shows a lateral pressure cutting device according to this embodiment, which includes a pressure vessel 420 having pressure inlets 441 and 451, and a superheater filled in the pressure inlet 441. The liquid phase material 440, the laser light introducing liquid 450 having no super-heating property filled in the pressure inlet 451, and the laser light introducing liquid 450 are sealed, and the laser light is put into the pressure vessel 420. A laser light introduction window 460 for introduction and a laser light irradiation unit 430
And a collar 421 provided in the pressure vessel 420 and a collar 42
From the pair of O-rings 422 and 423 provided on the inner peripheral side of 1 and the pressure introduction port 441, a super-heated liquid phase material pressurized is supplied into the pressure vessel 420 between the pair of O-rings 422 and 423. The pressure generator 442 includes a pressure generator 442 and a pressure generator 452 that supplies a pressurized laser introducing liquid into the pressure vessel 420 between the pair of O-rings 422 and 423.

The lateral pressure cutting method of this embodiment will be described below. A glass rod 410 as a member to be processed made of a transparent brittle member is in contact with the super-heat-generating liquid phase substance 440 on one side between a pair of O-rings 422 and 423, and on the other side, a laser light introducing liquid 450. Is inserted into the pressure vessel so as to contact the pressure vessel. In this state, the laser beam is emitted from the laser beam irradiation means 430 through a laser beam introduction window 460 and a laser beam introduction liquid 450 provided in the pressure vessel 420 along one point on the cut line of the glass rod 410 or along the cut line. Irradiate the fixed length part. Laser light is glass rod 410
At the position where the laser beam is emitted from the glass rod 410,
The surface of 10 is notched, forming a notch 411.
Then, without moving the glass rod from the notching position, the pressurized super-heat-generating liquid phase material from the pressure generator 442 is introduced into the pressure inlet 441, and at the same time, the pressurized Laser light introduction liquid
, A compressive stress is generated on the surface of the glass rod 410, and a tensile stress is generated at the center in the axial direction of the glass rod. The generated internal stress increases in proportion to the applied pressure, and the tensile stress generated inside the glass rod 410
When the tensile strength is equal to or higher than the tensile strength at the cut plane at the position corresponding to the notch,
Is broken and cut. Then, the next cutting can be performed by advancing the glass rod 410 in the direction of the arrow.

The super-heat-generating liquid phase substance in this embodiment may be the same as that in Embodiment 1, but here a perylene carbon disulfide solution (concentration: 0.8 mol / dm ³ ) can be used. . Laser beam irradiation means is appropriately selected and used according to the absorption region to be used. Laser light introduction window 460
Is preferably made of a material that transmits laser light and does not break even under a high pressure load. For example, tempered glass or the like can be used. Laser light introduction liquid 45
As 0, any liquid can be used as long as it does not exhibit super-heat generation by the selected laser light, but it is preferable that the liquid does not corrode the laser light introduction window 460. Therefore, for example, when the laser introduction window 460 is formed of a glass material, a material having a strong oxidation / reduction action, a strong acid / basic solution, or the like is not suitable.

The laser light introduction liquid 450 is supplied to the pressure generator 4
In pressurization by 52, it comes into contact with the super-pyrogenic liquid phase material 440,
In some cases, it is possible to mix them. Therefore, in order to prevent processing on the laser irradiation side of the glass rod 410, a material that does not dissolve the superpyrogenic dye in the superpyrogenic liquid phase substance 440 is preferable. However, at the time of pressurization by the pressure generators 442 and 452, and at the time of release of the pressurization, by controlling the pressure on the pressure generator 442 side by a very small amount, the super-heat-generating dye is brought to the laser light introduction liquid 450 side. It is possible to prevent intrusion. In this case, it is desirable that the liquid phase material, particularly the solvent, and the laser light introduction liquid have compatibility, so that the action of heat generation or the like in the super-heat-generating liquid phase material 440 is not adversely affected. It may be a substance.

As for these structures, it is a matter of course that the structural variations described in the other embodiments can be adopted.

[0149] Other configurations, materials, and the like can be the same as the configurations, materials, and the like of the known side pressure cutting device, and are not particularly limited.

According to the cutting method of this embodiment, since the super-heat-generating liquid phase material is used as a medium for applying pressure to the workpiece in the side pressure cutting step, the positioning position in the notching step and the positioning position in the cutting step are different. Thus, the configuration is the same in one apparatus, and only one process of moving the workpiece for positioning is required, so that the working time can be reduced and the cutting position can be controlled with high precision.

Further, notching with a low-energy laser is possible, and the depth of the notch can be controlled at the nm level by controlling the number of laser pulses and the like. Further, since there is no damage around the notch, it is possible to realize a cutting step capable of controlling the cutting position with high accuracy.

Further, no broken pieces are generated at the time of breaking, no noise is generated, the cut can be cut at a constant pressure irrespective of the cross-sectional area of the material, an extremely smooth cut surface (for example, in the case of a glass material, the cutting pressure is 80 MPa, In cutting with a diameter of 8 mm and a thickness of 2 mm, a surface roughness of about 0.005 μm can be obtained.

<Embodiment 3> FIG. 5 shows an example of a liquid crystal display device obtained by the processing method of this embodiment, and FIGS. 6 and 7 show the steps of manufacturing the liquid crystal display device of FIG. FIG. The liquid crystal display element 510 in FIG. 5 has one large panel 511, and the large panel 511 includes a connection substrate 520 formed by connecting TFT substrates 530 and 531 formed of a transparent material on their side surfaces. Similarly, a connection substrate 521 having the CF substrates 540 and 541 connected on its side faces is arranged oppositely.A liquid crystal layer 550 is provided between the TFT substrate 530 and the CF substrate 540 between these connection substrates 520 and 521. Further, a liquid crystal layer 551 is independently formed between the TFT substrate 531 and the CF substrate 541. That is, the liquid crystal display element 510 includes a large panel 511 in which two small liquid crystal elements 610 and 611 are connected at their side surfaces and are arranged adjacent to each other on the same plane of one reinforcing substrate 620. The connection between the small liquid crystal elements 610 and 611 is made by connecting the TFT substrates 530 and 53
1. This is achieved by directly connecting the CF substrates 540 and 541, respectively. In addition, a pair of polarizing plates 560, 5
61 are arranged. As described above, the TFT substrates 530 and CF substrate 540, and the TFT substrates 531 and CF substrate 541 are disposed to face the small liquid crystal elements 610 and 611, respectively, and liquid crystal layers 550 and 551 are sealed therebetween. The large panel 511 is bonded to the reinforcing substrate 620 by an adhesive layer 590, and the TFT
As the substrates 530 and 531, the CF substrates 540 and 541, the insulating films 570 and 571, the sealants 580 and 581, and other structures, a structure usually employed in a known active matrix driving type liquid crystal element can be used.

Next, a method of manufacturing the liquid crystal display element 510 including the fusion bonding method of the present embodiment will be described. First, the small liquid crystal element 6
10, 611 are immersed and fixed in the super-pyrogenic liquid phase material 640 by abutting or contacting at end faces connecting each other or facing each other at a small distance. At this time, it is sufficient that at least the connection portion of each end face is immersed in the super-heat-generating liquid phase substance. In fixing the small liquid crystal elements 610 and 611, when aligning the end faces to be joined, in order to make the surface heights of the two substrates uniform, they are fixed by a jig that is sandwiched or pressed across the two substrates. A compressive stress is applied to the joint by pressing means (not shown) at the same time as or immediately after the irradiation with the laser beam.

After fixing the ends to which the small liquid crystal elements 610 and 611 are connected as described above, the TFT substrate 530 and the CF substrate 540 which constitute one of the small liquid crystal elements 610 start from the end on the side to which they are not connected. Then, the laser light irradiated from the laser irradiation means 630 is introduced into the TFT substrate 530 and the CF substrate 540. TFT substrate
The laser light introduced into the 530 and the CF substrate 540 travels to the end where the inside of the substrate is joined using these substrates themselves as a waveguide, and is emitted from the end where the joining is performed. At this time, between the connecting ends of the small liquid crystal elements 610 and 611, the super-heat-generating liquid phase substance 64
Since the very thin layer of 0 is formed, the super-heat-generating liquid phase material 640 generates heat at the portion where the ends to be joined are abutted, and all the abutted ends are melted. As a result, the TFT substrates 530 and 531 to be processed and the CF substrate 540
And 541 are directly joined.

The small liquid crystal elements 610 and 6 joined as described above
By attaching a reinforcing substrate 620 to the CF substrate 540, 541 side of the large panel 511 made of 11 with an adhesive layer 590 and disposing a pair of polarizing plates 560, 561, the liquid crystal display element 51
0 is manufactured.

The super-heat-generating liquid phase substance in this embodiment may be the same as that in Embodiment 1, but here, for example, a coronene in carbon tetrachloride solution (concentration: 0.4 mol / dm ³ ) can be used. . Laser beam irradiation means is appropriately selected and used according to the absorption region to be used. In addition, it is also possible to appropriately combine the variations of the configuration described in the other embodiment examples. For example, by continuously supplying and flowing a super-heat-generating liquid phase substance, the vicinity of the joint of the workpiece is maintained at a constant temperature. It is possible to prevent unnecessary deterioration due to heat and the like.

According to the bonding method of this embodiment, the laser light is allowed to reach the bonding portion by using the transparent material itself, which is the workpiece, as a waveguide, thereby forming the end face of the workpiece from which the laser light is emitted. In addition, the workpiece is locally melted only at the part that is in direct contact with the super-heat-generating liquid phase substance, and the workpiece is melted. It is possible to realize a joint in which joint portions are inconspicuous.

Further, when joining materials cut by the lateral pressure cutting method, a high degree of smoothness is obtained, so that it is not always necessary to grind before joining. It is possible to achieve a bonding step that does not cause any problems.

<Embodiment 4> FIG. 8 is a view showing an example of a polynucleotide probe chip which can be prepared by using the processing method of the present invention. FIG. 9 is a partially enlarged sectional view of FIG. 9 (a), where the small hole has a bottom, (b) penetrates, (c) penetrates, and the side wall surface is tapered. Show the case. The substrate 811 of the polynucleotide probe chip 810 is made of plastic and has a concave portion having a flat bottom surrounded by a hydrophobic portion 820 whose surface has been subjected to the hydrophobic treatment.
A plurality of small holes 840 whose upper and lower ends are opened as shown in FIG. Hydrophobic part
A hydrophilic portion 830 whose surface is subjected to hydrophilic treatment is formed between 820 and the bottom surface of the concave portion. The opening at the top of the small hole 840 is 0.
5 mm x 0.5 mm, the distance between the upper and lower openings is 1 mm.
The shape of the opening of the small hole 840 is not limited to a square, but may be any shape such as a rectangle and a circle. The small holes 840 are arranged in the x and y directions via a 0.5 mm partition 830 to form a 16 × 16 matrix. That is, the centers of the small holes 840 are two-dimensionally arranged at an interval of 1 mm.

When the small hole 840 penetrates,
By setting the area of the lower opening smaller than the area of the upper opening as shown in (c), it is possible to hold the acrylamide gel holding the polynucleotide probe. That is, the small holes 840 can be tapered from the upper opening to the lower opening to facilitate holding the acrylamide gel when the acrylamide gel is formed. The hydrophobic portion 820 and the hydrophilic portion 830 allow the sample solution to be easily held in the concave portion having the small hole 840 in which the acrylamide gel is held.

On the side surface of the substrate 811 is formed a detection laser beam introducing portion 850 which is optically polished for introducing the detection laser beam. The detection laser beam irradiates the side wall surface 841 of each small hole 840. As the material of the plastic, optically transparent polymethyl methacrylate (PMMA) that transmits laser light of 400 nm to 650 nm well is used. The sample (for example, a fluorescence-labeled DNA fragment) is detected using a laser light source (not shown) (for example, 594 nm, He-Ne laser) and a high-sensitivity cooled CCD camera that detects the fluorescence emitted from the fluorescent label. Further, an electrode for electrophoresis may be formed on the substrate 811 and a photodiode for fluorescence detection and an output wiring thereof may be formed for each small hole.

Next, in the surface treatment of the side wall surface 841 of each small hole 840, when the acrylamide gel is formed inside the small hole 840, the small hole 840 is etched by small holes to surely hold the acrylamide gel inside the small hole 840. The 840 has a side wall surface 841 with an irregular shape at the molecular level.

In the etching of this embodiment, the small holes 84
After dripping a fluid super-heat-generating liquid phase substance into 0, or applying or sticking a gel-like or thixotropic super-heat-generating liquid phase substance to the side wall surface of the small hole, obliquely below the transparent substrate to By injecting a laser beam from the side or obliquely upward through a diffraction grating as an optical system corresponding to a desired concavo-convex pattern, a nano-level concavo-convex shape can be formed. When using a diffraction grating that generates interference fringes, it is desirable that the interference fringes be arranged in the depth direction of the small holes 840 so that the acrylamide gel is reliably held.

A laser beam for processing may be introduced from the detection laser beam introducing unit 850. After forming the uneven shape on the side wall 841, a reagent in which an acrylic group is introduced into a part of the linear aliphatic compound is applied to the side wall surface 841 of each small hole 840, and the activated acrylic group is applied to the side wall surface 841 of each small hole 840. Is obtained. The acrylamide gel is held in each of the small holes 840. At this time, the connection between the active acryl group and the acrylamide gel is connected to the side wall surface 841 of each of the small holes 840. Although the reagent does not chemically bond directly to the surface of the plastic, the reagent is immobilized on the surface of the plastic by the hydrophobic bond of the linear fatty moiety in the molecule of the reagent.

In holding a polynucleotide probe on a polynucleotide probe chip, two different
Prepare 56 types of probes. Each polyoligonucleotide probe having an amino residue at the 5 'end is synthesized and used by a phosphoramidite method. Acrolein is mixed with a 10 μM aqueous solution of each probe to a concentration of 2 mM. After reacting at 20 ° C. for 30 minutes, unreacted acrolein is removed by gel filtration using Sephadex. By this operation, the amino residue of the polynucleotide probe reacts with the aldehyde group of acrolein to obtain a polynucleotide probe having an active acryl group introduced at the 5 'end. After vacuum drying, the polynucleotide probe having an acrylic group introduced at the 5 ′ end is stored in a 10 μM aqueous solution at −20 ° C. in a helium atmosphere.

As the gel precursor, a 39: 1 mixture of acrylamide monomer and N, N'-methylenebisacrylamide is used. 2.5 μL of 1.5 M Tris-HCl buffer (pH 8.5) containing 0.015% ammonium persulfate
(Microliter), a mixture of 0.5 μL of an acrylic group-introduced polynucleotide probe (10 μM) and 1.5 μL of 15% acrylamide in a mixture of 40 nM N, N,
N ', N'-tetramethylethylenediamine 0.5 μL
And immediately drop it into the small hole 840 of the chip. The polymerization reaction is performed in a helium atmosphere.

In the radical polymerization reaction, polymerization is inhibited due to oxygen or the plastic surface itself. In order to prevent this polymerization inhibition and to prevent the generation of bubbles in fine parts,
Perform in a helium atmosphere. Although it is impossible to completely prevent polymerization inhibition by helium substitution, the gel can be held more reliably when the small holes 840 are tapered. Helium substitution is for preventing the generation of air bubbles in the small holes.

A certain amount of the reaction solution is filled in the small hole 840 by capillary action and gels. A solution other than N, N, N ', N'-tetramethylethylenediamine was prepared for all the probes, and N, N, N', N'-tetramethylethylenediamine was added and immediately added to the small hole 840. By dropping, a polynucleotide probe chip can be obtained efficiently. Alternatively, a reagent other than N, N, N ′, N′-tetramethylethylenediamine, that is, a tris buffer solution containing acrylamide, N, N′-methylenebisacrylamide, and ammonium persulfate, and a polystyrene into which an acryl group is introduced A solution in which a nucleotide probe and a nucleotide probe are mixed is prepared, and this solution is dropped on the surface of the polynucleotide probe chip and filled into small holes. Next, the polynucleotide probe tip is exposed to gasified or atomized (misted) N, N, N ′, N′-tetramethylethylenediamine to initiate a polymerization reaction, and the polynucleotide probe tip is Easy to create.

According to the method described above, the polynucleotide probe is fixed to the polyacrylamide gel chain (gel matrix), and the polyacrylamide gel chain (gel matrix) is fixed to the side wall surface 841 of the small hole 840.

DNA such as a polynucleotide probe chip
When creating chips and biochips, use small holes 84
Not only the fine uneven pattern provided on the side wall surface 841 of 0,
The etching of the present invention can also be used when forming the small holes, forming the concave portions, and forming other uneven structures on the surface of the transparent material. The etching of the present invention can also be used for the formation of circuit elements such as the above-described electrodes, photodiodes, and wirings by using a known thin film forming technique.

[0172]

According to the processing method of the present invention, the laser output may be several orders of magnitude smaller than the conventional method of directly processing a transparent material by laser beam irradiation, and damage and contamination around the processing area may be prevented. No, several nm or more by controlling the number of laser pulses
The processing amount can be controlled at the level of several hundred nm.

[Brief description of the drawings]

FIG. 1 is a diagram showing a semiconductor acceleration sensor according to a first embodiment of the present invention.

FIG. 2 is a view showing a glass substrate etching step performed in the manufacture of the semiconductor device of FIG. 1;

FIG. 3 is a view showing a manufacturing process of the semiconductor device of FIG. 1;

FIG. 4 is a diagram showing a cutting method according to a second embodiment of the present invention.

FIG. 5 is a view showing a liquid crystal display device according to a third embodiment of the present invention.

FIG. 6 is a view showing a manufacturing process of the liquid crystal display device of FIG. 5;

FIG. 7 is a view showing a manufacturing process of the liquid crystal display device of FIG. 5;

FIG. 8 is a diagram showing a polynucleotide probe chip according to Embodiment 4 of the present invention.

FIG. 9 is a partially enlarged cross-sectional view of the polynucleotide probe chip of FIG.

[Description of Signs] 110: semiconductor acceleration sensor, 120: glass substrate, 121: recess, 130, 131: fixed electrode, 140: movable electrode, 220, 440, 640: super-heat-generating liquid phase substance, 240, 430, 630 : Laser beam irradiation means, 420: pressure vessel, 441: pressure inlet, 510: liquid crystal display element, 610, 611: small liquid crystal element, 810: polynucleotide probe chip, 840: small hole ────────────────────────────────────────────

[Procedure amendment]

[Submission date] January 11, 2001 (2001.1.1)
1)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name]

[Correction method] Change

[Correction contents]

<Embodiment 1> FIG. 1 shows a known semiconductor device (Japanese Patent Application Laid-Open No. 10-163505).
This semiconductor element is a semiconductor acceleration sensor 110, and has a movable electrode 140 between fixed electrodes 130 and 131 fixed on a glass substrate 120. The fixed electrodes 130 and 131 and the movable electrode 140 are each made of polysilicon (polycrystalline silicon), and the movable electrode 140 and the fixed electrode 130 and the movable electrode 140 are formed.
The opposing portions of the fixed electrode 131 and the fixed electrode 131 are formed in a comb shape as can be understood with reference to the drawings. Movable electrode 14
Numeral 0 is located above the concave portion 121 formed on the glass substrate 120, both ends thereof are supported by the beams 150 and 151, and is floating with respect to the glass substrate 120. Both beams 150
And 151 are fixed on glass substrate 120. Electric wires (not shown) are individually applied to the beam base ends 150a and 151a and the fixed electrodes 130 and 131, respectively.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0153

[Correction method] Change

[Correction contents]

<Embodiment 3> FIG. 5 shows an example of a liquid crystal display element obtained by the processing method of this embodiment (Japanese Unexamined Patent Publication No.
FIGS. 6 and 7 are views showing a manufacturing process of the liquid crystal display device of FIG. The liquid crystal display element 510 in FIG. 5 has one large panel 511, and the large panel 511 is a TFT substrate formed of a transparent material.
Connection board 520 connecting 530, 531 on its side, and C
A connection substrate 521 having F substrates 540 and 541 connected on the side thereof is disposed to face each other, and a TFT is provided between these connection substrates 520 and 521.
A liquid crystal layer 550 is formed between the substrate 530 and the CF substrate 540, and a liquid crystal layer 551 is formed independently between the TFT substrate 531 and the CF substrate 541. That is, the liquid crystal display element 510 includes a large panel 511 in which two small liquid crystal elements 610 and 611 are connected at their side surfaces and are arranged adjacent to each other on the same plane of one reinforcing substrate 620. The connection between the small liquid crystal elements 610 and 611 is achieved by directly connecting the TFT substrates 530 and 531 and the CF substrates 540 and 541, respectively. Further, a pair of polarizing plates 560 and 561 are arranged on both front and back surfaces of the liquid crystal display element 510 in a cross Nicol positional relationship. As described above, the small liquid crystal elements 610 and 611 have a TFT substrate 530 and a CF substrate 54.
The TFT substrate 531 and the CF substrate 541 are opposed to each other, and liquid crystal layers 550 and 551 are sealed between them. The large panel 511 is attached to the reinforcing substrate 62 by the adhesive layer 590.
0, TFT substrates 530 and 531 and CF substrates 540 and 54
1. For the insulating films 570 and 571, the sealing materials 580 and 581, and other components, a configuration usually adopted in a known active matrix driving type liquid crystal element can be used.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C03C 15/00 H01L 21/306 D

Claims (3)

[Claims] 1. An energy beam is irradiated to a liquid material containing a dye forming a dimer or a dark complex while flowing the liquid material to process a transparent material in contact with the liquid material. Processing method of transparent material 2. A transparent material in which a transparent material is notched by irradiating a laser in a liquid phase substance in which a super-pyrogenic dye is dissolved, dispersed or mixed, and then the liquid phase substance is pressurized. Processing method 3. A method of processing a transparent material by immersing a joint of a transparent material in a super-heat-generating liquid phase substance, introducing laser light into the joint using the transparent material itself as an optical waveguide, and performing fusion joining.