JP2011062666A - Film formation apparatus, vibrator using film formation apparatus, and film formation method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To heighten the accuracy of a coating region in object treatment regain of object to be coated with a coating liquid. <P>SOLUTION: A sensitive film solution L is suctioned by and kept in a micro-capillary 20 and the sensitive film solution L is applied to a vibrator 100 to form a sensitive film 150 while the pressure to be applied to the micro-capillary 20 being adjusted correspondingly to the size of a region of the vibrator 100 on which the sensitive film 150 is to be formed. At that time, it is preferable that the region of the vibrator 100 on which the sensitive film 150 is to be formed is defined by a film, a line, or a groove of a material with high compatibility with the sensitive film solution L. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a film forming apparatus, a vibrator formed using the same, and a film forming method.

Conventionally, there have been sensors for detecting the presence of explosive hazards and harmful gases, or their quantitative concentrations. This sensor adsorbs a specific type of molecule contained in a gas and detects the presence or concentration of the gas or the like by detecting the presence or absence or the amount of adsorption. Such a sensor is installed in a facility, equipment, device or the like that handles gas or the like, and is used to control gas leakage or gas amount.
In recent years, fuel cells have been actively developed. Since the fuel cell uses hydrogen, it is preferable to monitor the hydrogen station and vehicles, devices, equipment, etc. that use the fuel cell for hydrogen leakage. The sensor can be applied to such applications.
In addition to the above applications, sensors that detect the presence or amount of adsorption by adsorbing specific types of molecules can detect organic molecules and odor molecules floating in the air. It can be used for analysis, environmental control for providing / maintaining a comfortable space, and detection of the state of a living body such as a human body.

  A sensor element that detects organic molecules and odor molecules floating in the air with its minute molecular mass causes the vibrator to vibrate in a gas containing these molecules, and when the molecules are attached or adsorbed to the vibrator surface. Is detected as a change in the resonance frequency of the vibrator.

A QCM (Quartz Crystal Microbalance) method is given as the most basic method for obtaining the adhesion mass from the change in the resonance frequency of the vibrator. In QCM, a crystal single crystal having piezoelectricity is cut into a plate shape to form a vibrator, and by applying a voltage to the vibrator, shear vibration called “thickness shear vibration” is caused. The resonance frequency f decreases by Δf from the original resonance frequency f ₀ when an object of mass Δm adheres to the surface, and the amount is Δf / f ₀ = −Δm / (m ₀ ) (1)
It is known that m ₀ is the mass of the vibrator.

  On the other hand, a technology called MEMS (Micro Electrical Mechanical Systems) that precisely processes silicon thin films and the like by photographic technology (photolithography) has been developed, and it is the same as the QCM that has been manufactured in the mm (millimeter) unit area until now. It has become possible to manufacture a simple vibrator in an area of μm (micrometer) unit. By reducing the size of the vibrator, the mass of the vibrator in the formula (1) is greatly reduced, and the detection sensitivity for the attached mass is increased.

Other vibrators that perform mass detection are mainly cantilever type that uses lateral vibration of a cantilever beam, and disk type vibrator that uses in-plane vibration of a plate-like vibrator (for example, Patent Document 1).
In either case, the resonance frequency change is Δf / f ₀ = −Δm / (2m ₀ ) (2)
Thus, although the coefficient is different from that of the equation (1), the dependence on the oscillator mass is not changed.

  In such a vibrator, in order to detect molecules and gases, a sensitive film (film) such as an organic film that adsorbs or adheres a specific molecule is formed on the vibrator. The sensitive film is applied by being diluted with a solvent, or formed on the vibrator by a spray coating method, a sputtering method, or the like (for example, see Non-Patent Documents 1 and 2 and Patent Document 2).

  In order to form a film, a method (for example, refer to Patent Document 3) in which the internal pressure of an ejection head that ejects a liquid material is controlled by a pressure control device has been proposed.

JP 2007-240252 A Japanese Patent No. 4136811 JP 2007-229676 A

F.M Battiston et al "A chemical sensor based on a microfabricated cantilever array with simultaneous resonave-frequency and bending readout" 2001 Sensors and Actuators B 77 P.122-P.131 Dirk lange et al "Complementary Metal Oxide Semiconductor Cantilever Arrays on a Single Chip: Mass-Sensitive Detection of Volatile Organic Compounds" 2002 Anal. Chern. 74, P.3084-P.3095

  However, although the spray coating method and the sputtering method are suitable for applications in which a large amount of sensors are deposited, these methods of sprinkling a large amount of sensitive film material on the deposition region can reduce the deviation of the coating region. There was a problem that the film could not be formed accurately.

Patent Document 3 discloses a method of controlling the internal pressure of a discharge head that discharges a liquid material by a pressure control device. This method does not show a method for controlling the pressure so as to form a film on the coating region with high accuracy, and it is very difficult to form a film on the surface to be coated of the coating object with high accuracy.
The present invention has been made in view of the above circumstances, and an object of the present invention is to form a film forming apparatus, a vibrator, and a film forming method with improved accuracy of a liquid application region to be applied to a processing target surface of a coating object. Is to provide.

The present invention based on such an object is a film forming apparatus for forming a film by discharging a liquid containing a film material onto a surface to be processed of an object, and an opening formed at the tip of the liquid A liquid holding unit that holds the liquid after suction, a pressure adjustment unit that adjusts the pressure applied to the liquid inside the liquid holding unit, so that the liquid holding unit sucks or discharges the liquid from the opening, and the liquid holds And a moving unit that moves the tip of the liquid holding unit to a processing position that faces the processing surface of the object, and according to the size of the processing surface at the processing position by the pressure adjusting unit. The pressure of the liquid holding part for discharging the liquid to the surface to be processed is adjusted.
Thus, by adjusting the pressure of the liquid holding portion according to the size of the surface to be processed, the amount of liquid ejected on the surface to be processed can be controlled. Thereby, the precision of the application range of the liquid apply | coated to a to-be-processed surface can be improved.

  Here, the film forming apparatus can further include an observation unit capable of observing the liquid discharge range with respect to the surface to be processed. In this case, the liquid discharge range obtained by the observation unit is compared with the size of the surface to be processed, and the pressure of the liquid holding unit in the pressure control unit is adjusted based on the comparison result.

The pressure adjustment in the pressure adjusting unit can be performed manually, but is preferably performed automatically. For this reason, the present invention further includes an automatic control unit connected to the moving unit and the pressure adjusting unit, and the automatic control unit executes a process based on a predetermined computer program so that the liquid in the moving unit is The moving operation of the tip of the holding unit and the adjustment of the pressure of the liquid holding unit in the pressure adjusting unit can be automatically performed.
In addition, when the observation unit is provided, an automatic control unit connected to the moving unit, the pressure adjusting unit, and the observation unit is further provided, and the automatic control unit is based on a predetermined program and information by the observation unit. The moving operation of the tip of the liquid holding unit in the moving unit and the adjustment of the pressure of the liquid holding unit in the pressure adjusting unit are automatically performed.

In order to discharge a minute amount of liquid, the liquid holding unit preferably sucks the liquid by capillary action.
At this time, the liquid holding portion can be formed into a tube shape having a hollow portion for reducing the diameter toward the tip portion and holding the liquid. Such a liquid holding part preferably has a shape formed by pulling a glass tube and having a diameter that decreases toward the tip.
By using, for example, ruby for the liquid holding part, a tip diameter equivalent to that of the liquid holding part made from the glass tube can be realized, but such a liquid holding part is very expensive. When the liquid has hardened in the liquid holding part, the liquid holding part must be replaced. Therefore, when an expensive material such as ruby is used for the liquid holding part, the manufacturing cost of the vibrator becomes very high. End up.
Further, when the liquid holding part is made of metal, it is difficult to reduce the tip diameter due to the limit in machining accuracy, and the machining cost increases as the tip diameter is reduced.
In that respect, the liquid holding part formed by heating and pulling the glass tube can also have a very small tip diameter, so that it is possible to visually position the liquid holding part in a very small region, and such liquid Since the holding part can be manufactured at a low cost in units of several tens of yen, the cost can be reduced.

The surface to be treated of the object can further include a film application range defining material that has an affinity higher than the affinity of the surface of the object for the liquid and defines the film application range. As such a film application range defining material, a thin film made of gold formed corresponding to the range, or a line portion made of gold formed linearly along the outline of the range can be used.
Moreover, a groove | channel or a step part can be formed in the to-be-processed surface of a target object along the outline of a range as a film | membrane application range definition material which prescribes | regulates a film application range.

  As the film material, a polybutadiene, polyisoprene, polystyrene, polyacrylonitrile, polycaprolactan and a copolymer thereof, a medium molecular organic material having a molecular weight of 1000 or more such as a phthalocyanine complex having an oligophenyl group or a tertiary butyl group, or the like is used. be able to. In addition, metal oxide nanoparticles that can be colloidally dispersed in a liquid, such as titanium oxide nanoparticles, are also effective.

  The membrane material is sucked up by the liquid holding portion in a state of being dissolved or dispersed in the solvent. The solvent is a high boiling point solvent capable of dissolving the membrane material by 0.1% to 10% or colloidally, and includes at least one of tetralin, o-dichlorobenzene, mesitylene, xylene, and ethylene glycol. preferable.

  The present invention can also be a vibrator including a vibrator body and a sensitive film formed on the surface of the vibrator body to which a substance having a mass adheres or adsorbs. The film is formed on the vibrator body using the film forming apparatus according to any one of claims 1 to 12.

  The present invention relates to a film forming method for forming a film by discharging a liquid containing a film material onto a surface to be processed of an object, and the liquid is held from the opening to the liquid holding part having the opening formed at the tip. A step of moving the tip of the liquid holding unit holding the liquid to a processing position opposite to the processing surface of the object, and a size of the processing surface at the processing position. And a step of discharging the liquid from the opening to the surface to be processed while adjusting the pressure of the liquid holding portion according to the thickness.

  Then, in the step of discharging the liquid onto the surface to be processed, the liquid discharge range with respect to the surface to be processed is observed, the liquid discharge range is compared with the size of the surface to be processed, and the liquid is retained based on the comparison result. The pressure of the part can also be adjusted.

  In the step of discharging the liquid onto the surface to be processed, by increasing the pressure of the liquid holding unit, after the liquid is discharged from the tip of the liquid holding unit to the surface to be processed, the discharged liquid becomes a film to be formed. When the pressure reaches the range, the pressure of the liquid holding unit can be reduced and the tip of the liquid holding unit can be separated from the surface to be processed.

  Further, by increasing the pressure of the liquid holding unit, when the liquid is discharged from the tip of the liquid holding unit onto the surface to be processed, the tip of the liquid holding unit and the surface to be processed are opposed to each other with an interval. It is preferable that the liquid discharged from the tip of the liquid holding unit and adhered to the surface to be processed is bridged between the tip of the liquid holding unit and the surface to be processed.

  According to the present invention, by adjusting the pressure of the liquid holding unit according to the size of the surface to be processed and controlling the amount of liquid discharged to the surface to be processed, the liquid applied to the surface to be processed The accuracy of the application range can be increased.

It is a figure which shows schematic structure of the film-forming apparatus in this Embodiment. It is a figure which shows an example of a cantilever type vibrator. It is a figure which shows an example of a disc-type vibrator. It is the schematic which shows the manufacturing method of a microcapillary. It is a step figure showing a flow when forming a sensitive film. It is a figure which shows the example of application of the film-forming apparatus in this Embodiment. (A) is a diagram showing a gold film formed on a vibrator as a sensitive film application range defining material, (b) is a diagram showing a line part in which gold is formed as a sensitive film application range defining material, c) is a diagram showing grooves formed in a vibrator as a sensitive film application range defining material. (A) is an image showing a sensitive film formed on a cantilever type vibrator, (b) is an image showing a sensitive film formed on a disk type vibrator on which a gold film is formed, (c) is an image showing An image showing a sensitive film formed on a disk-type vibrator in which grooves are formed, and (d) is an image showing a sensitive film formed on a disk-type vibrator in which no film or grooves are formed. It is a figure which shows the film thickness distribution of the sensitive film | membrane which carried out the cross sectional view of the vibrator | oscillator in the dashed-dotted line of FIG.8 (c).

Hereinafter, the present invention will be described in detail based on embodiments shown in the accompanying drawings.
FIG. 1 is a diagram for explaining a configuration of a film forming apparatus 10 according to the present embodiment.
As shown in FIG. 1, a film forming apparatus 10 includes a holder 11 that holds a microcapillary (liquid holding unit) 20, and a Z-axis stage (moving unit) 12 that moves the holder 11 up and down (Z-axis direction). An XY-axis stage (moving part) 13 that moves the Z-axis stage 12 in a horizontal plane (XY-axis direction), a vibrator support stage 14 that supports a vibrator to which a sensitive film is applied, and a sensitive film solution (Film material, liquid) The coating liquid storage part 15 in which L is stored is provided.

  The holder 11 is held on the Z-axis stage 12 via the base plate 16. The base plate 16 includes a camera (observation unit) 17 such as a CCD camera or a CMOS camera for magnifying and observing the vibrator (object) 100 set on the vibrator support stage 14, and a vibrator support stage. An illumination 18 for irradiating light to the vibrator 100 set on 14 is integrally provided. The camera 17 is connected to a monitor 19 that displays video shot by the camera 17.

The operations of the Z-axis stage 12 and the XY-axis stage 13 are controlled by a stage drive unit (not shown). As a result of the operator appropriately inputting the movement amounts in the X, Y, and Z directions to the stage drive unit by the operation means, the Z-axis stage 12 and the XY-axis stage 13 operate.
Here, when the XY axis stage 13 is operated, the Z axis stage 12 is thereby moved in the XY directions. When the Z-axis stage 12 is operated, the base plate 16, the holder 11, the camera 17, and the illumination 18 held on the Z-axis stage 12 are moved together in the Z-axis direction.
In this manner, the holder 11, the camera 17, and the illumination 18 can be moved to arbitrary positions in the X, Y, and Z directions with respect to the vibrator 100 set on the vibrator support stage 14. .

  The vibrator support stage 14 supports the vibrator 100 that is a target for forming the sensitive film (film) 150. The vibrator 100 is supported and fixed by a mechanical chuck, vacuum suction, electrostatic force suction, or the like. To do. Here, the vibrator 100 supported by the vibrator support stage 14 may be of any type such as a cantilever type or a disk type as long as the sensitive film 150 is formed on the surface thereof.

  For example, as shown in FIG. 2, the cantilever type vibrator 100A is formed on a substrate made of a silicon-based material, more specifically, polysilicon or single crystal silicon, by using a MEMS technique such as a photolithography method. . The vibrator 100A has a rectangular shape in plan view, and is preferably made of a silicon-based material constituting the substrate, particularly preferably single crystal silicon. As an example of the dimensions of the vibrator 100A, it is preferable that the thickness is 2 to 10 μm, the length is 30 to 1000 μm, and the width is 10 to 300 μm. A sensitive film 150A is formed on the surface of the vibrator 100A.

As shown in FIG. 3, the disc-type vibrator 100B is made of the same material as that of the cantilever type and has an outer shape such as a circle or a rectangle. A sensitive film 150B is also formed on the surface of such a disk-type vibrator 100B.
In the following description, except that it is necessary to distinguish between the cantilever type vibrator 100A and the disk type vibrator 100B, these are referred to as the vibrator 100, and the sensitive films 150A and 150B are similarly sensitive. This is referred to as membrane 150.

  The coating liquid storage unit 15 includes a container 15 a that stores a sensitive film solution L that is a material of the sensitive film 150 formed on the surface of the vibrator 100. The container 15a is opened upward, and the tip of the microcapillary 20 is inserted into the coating liquid storage part 15 from the upper opening to suck up the sensitive membrane solution L.

Here, the sensitive film 150 is applied to a predetermined area (surface to be treated) on the vibrator 100 and is formed of a film made of an inorganic or organic sensitive film material (film material). can do.
A typical example of the inorganic sensitive film material constituting the sensitive film 150 is titanium dioxide (TiO ₂ ), and it is preferable to make the titanium dioxide porous to improve the adsorption efficiency. In addition, metal oxide nanoparticles that can be colloidally dispersed in a liquid, such as titanium oxide nanoparticles, are also effective. Examples of the organic sensitive film material constituting the sensitive film 150 include polybutadiene, polyisoprene, polystyrene, polyacrylonitrile, polycaprolactan and a copolymer thereof, and a phthalocyanine complex having an oligophenyl group or a tertiary butyl group. Medium molecular organic materials having a molecular weight of 1000 or more. As the sensitive film material, for example, various materials described in JP 2008-268170 A can be used.
The sensitive membrane 150 may have a selectivity for a molecule that adsorbs only a specific type of molecule or a plurality of types of molecules having a specific property or characteristic. It is considered to be determined by various factors such as the functional group to be formed and the state of crosslinking. The sensitive film 150 is preferably formed so as to cover at least a part of the upper surface of the vibrator 100.

  As the sensitive membrane solution L for forming such a sensitive membrane 150, a solution obtained by dispersing the above-described materials in a solvent is used. The solvent used here is a high boiling point solvent capable of dissolving or colloidally dispersing the organic film material by about 0.1% to 10%, and is at least one of tetralin, o-dichlorobenzene, mesitylene, xylene, and ethylene glycol. It is preferable to contain. When the boiling point is low, the solvent tends to evaporate, and the viscosity of the sensitive film solution L excessively increases or solidifies. These sensitive membrane solutions L need to be selected in consideration of not only the saturated vapor pressure and boiling point but also the dispersibility of the sensitive membrane material.

As shown in FIG. 4, the microcapillary 20 has a hollow tube material having a hollow portion for holding the sensitive membrane solution L therein, for example, a glass tube G, whose outer diameter / inner diameter increases toward the distal end portion 20a. Is formed into a needle shape that gradually decreases. Such a microcapillary 20 can be obtained as follows. That is, as shown in FIG. 4A, the glass tube G was heated as shown in FIG. 4B by pulling both ends with a pulling device called puller while heating the glass tube G. The glass tube G greatly expands at the site, and the tube diameter becomes gradually smaller for both the outer diameter and the inner diameter. Therefore, as shown in FIG. 4C, the glass tube G is thinned, and the microcapillary 20 is obtained by cutting the glass tube G at a portion having a desired outer diameter. Furthermore, by subjecting the cut surface to heat treatment, a smooth tip-shaped microcapillary 20 can be created.
At this time, the outer diameter of the tip of the microcapillary 20 is preferably 10 to 100 μm, and the inner diameter of the conduit is preferably 5 to 90 μm. If the outer diameter of the tip of the microcapillary 20 is too large, the tip of the microcapillary 20 is positioned on the surface of the vibrator 100 while the tip of the microcapillary 20 is visually observed on the monitor 19. It becomes difficult. Further, when the inner diameter of the pipe line of the microcapillary 20 exceeds the above range, it becomes difficult to finely control the discharge amount of the sensitive membrane solution L. Further, if the outer diameter of the tip of the microcapillary 20 and the inner diameter of the pipe line are within the above ranges, there is a problem that the manufacture of the microcapillary 20 itself becomes difficult.

  The microcapillary 20 is held by the holder 11 facing downward so that the distal end portion 20a faces the vibrator 100 set on the vibrator support stage. In addition, a pressure adjusting unit 30 including a valve or the like for adjusting the pressure applied to the inside of the microcapillary 20 is connected to the rear end 20 b of the microcapillary 20. A pressure generating source 31 such as a nitrogen cylinder is connected to the pressure adjusting unit 30. Here, it is preferable that the pressure adjusting unit 30 can apply not only positive pressure but also negative pressure to the microcapillary 20.

Next, a method for forming a sensitive film on the vibrator 100 using the film forming apparatus 10 as described above will be described.
First, the microcapillary 20 is prepared. For this purpose, for example, the middle of the glass tube G having an outer diameter of 1 mm, an inner diameter of 0.6 to 0.75 mm, and a length of 90 mm is heated at a high temperature and pulled in the major axis direction, thereby forming a needle with a thin tip. Of course, the size of the glass tube G is only an example, and other sizes can be used as appropriate.
By cutting the needle-like portion at an arbitrary location, the microcapillary 20 having a tip outer diameter of 10 to 100 μm and an inner diameter of 5 to 90 μm is created. Furthermore, by subjecting the cut surface to a heat treatment, a smooth tip-shaped microcapillary 20 can be produced.
The prepared microcapillary 20 is attached to the holder 11.

  In addition, the vibrator 100, which is the target for forming the sensitive film 150, is set on the vibrator support stage 14.

  Next, the sensitive film material L in which the sensitive film material is previously dispersed in the solvent and the concentration is adjusted is accommodated in the coating liquid accommodating unit 15. Here, it is desirable to adjust the concentration of the sensitive film solution L according to the target film thickness, but it is preferable to have a viscosity of about several tens of cp in consideration of controllability of the application region. In addition, a mixed solution of two or more solvents can be used for adjusting the concentration and viscosity.

Next, as shown in FIGS. 5A and 5B, the Z-axis stage 12 and the XY-axis stage 13 are operated, and the tip portion 20 a of the microcapillary 20 held by the holder 11 is moved to the coating liquid storage portion 15. Immerse in the sensitive membrane solution L. Then, the sensitive membrane solution L is sucked up by capillary action, and the sensitive membrane solution L is held in the microcapillary 20.
At this time, depending on the viscosity of the sensitive membrane solution L, the inner diameter of the microcapillary 20, and the like, the pressure can be applied to the microcapillary 20 by operating the pressure adjusting unit 30 so that the sensitive membrane solution L is not sucked up excessively. it can.

Subsequently, as shown in FIG. 5C, the Z-axis stage 12 and the XY-axis stage 13 are operated to move the microcapillary 20 to a position facing the vibrator 100 on the vibrator support stage 14. At this time, the Z-axis stage 12 and the XY-axis stage 13 may be operated while observing the tip position of the microcapillary 20 based on an image captured by the camera 17 and displayed on the monitor 19.
At this time, if the movement of the microcapillary 20 takes time, the concentration of the sensitive membrane solution L increases due to the evaporation of the solvent and the viscosity also increases. Therefore, it is preferable to move the microcapillary 20 quickly. .

  As shown in FIG. 5 (d), the microcapillary 20 is stationary at, for example, a position 1 to 5 μm above the sensitive film forming position in the vibrator 100.

Next, when the operator operates the pressure adjusting unit 30 from the outside, a pressure of about 0.5 to 5 kPa, for example, is applied to the microcapillary 20 for about 10 to 100 msec, for example.
Then, as shown in FIG. 5 (e), the sensitive membrane solution L held in the microcapillary 20 hangs down to be discharged from the tip 20 a of the microcapillary 20 and adheres (contacts) on the vibrator 100. . At this time, if the microcapillary 20 is positioned above the vibrator 100, for example, 1 to 5 μm as described above, the sensitive membrane solution L discharged from the tip 20a of the microcapillary 20 vibrates due to surface tension. A bridge is formed between the surface of the child 100 and the tip 20a of the microcapillary 20.

  As shown in FIG. 5 (f), when the pressure is further applied and the discharged sensitive film solution L spreads to the target region where the sensitive film 150 is to be formed, the pressure adjusting unit 30 is operated. Thus, the pressure applied to the microcapillary 20 is reduced, and the sensitive membrane solution L is sucked. Then, as shown in FIGS. 5F and 5G, the Z-axis stage 12 is operated to pull the microcapillary 20 upward. Then, as shown in FIG. 5 (h), the sensitive film solution L is cut from the tip 20 a of the microcapillary 20, and the sensitive film solution L is spread and applied onto the vibrator 100.

  Thereafter, by allowing a predetermined time to elapse, the solvent of the sensitive film solution L on the vibrator 100 evaporates, whereby a sensitive film 150 made of a sensitive film material is formed on the vibrator 100.

By the way, a series of film forming steps of the sensitive film 150 on the vibrator 100 as described above can be automated by automatically controlling the operations of the stage driving unit and the pressure adjusting unit 30. .
For this purpose, as shown in FIG. 6, the film forming apparatus 10 executes a series of processes based on a computer program set in advance, so that the Z-axis stage 12 and the XY-axis stage 13 in the stage driving unit are operated. An automatic control device (automatic control unit) 40 that automatically controls the operation and the pressure applied to the microcapillary 20 in the pressure adjusting unit 30 is provided.
Thereby, under the control of the automatic control device 40, the sensitive membrane solution L is sucked from the coating liquid storage unit 15, moved to a position facing the vibrator 100 of the microcapillary 20, and sensitive by applying pressure to the microcapillary 20. A series of steps such as ejection of the membrane solution L, depressurization / suction of the pressure applied to the microcapillary 20, and upward pulling of the microcapillary 20 are automatically executed sequentially, and set at a predetermined position on the vibrator support stage 14. The sensitive film 150 can be automatically formed on the vibrator 100 formed.

Further, in the process of automatically performing a series of film formation of the sensitive film 150 on the vibrator 100 as described above, the automatic controller 40 discharges the vibrator 100 on the vibrator 100 based on the image taken by the camera 17. The range of the formed sensitive film solution L and the size of the sensitive film 150 to be formed are compared by image processing, and the pressure applied to the microcapillary 20 in the pressure adjusting unit 30 is controlled based on the comparison result. You can also
That is, in the automatic control device 40, the area of the sensitive film solution L discharged onto the vibrator 100 is calculated every certain minute time, and the difference between the calculated area and the area of the sensitive film 150 to be formed is calculated. However, when it is determined that the pressure is equal to or less than a predetermined size, control to reduce the pressure applied in the pressure adjustment unit 30 can be performed.
In this way, the control of the discharge amount of the sensitive film solution L can be made highly accurate.

  The series of operations described above can be performed in parallel or simultaneously as appropriate. The numerical examples given above are merely examples for facilitating understanding, and the present invention is not limited to the numerical examples.

By the way, when the sensitive film solution L is supplied from the microcapillary 20 onto the vibrator 100 and applied as described above, the sensitive film 150 is formed in a minute region on the vibrator 100 with high accuracy. It is preferable to perform not only the film forming apparatus 10 and the coating method using the film forming apparatus 10 but also the processing and processing for regulating the coating range of the sensitive film 150 with high accuracy on the vibrator 100 side.
For example, as shown in FIG. 7A, in the vibrator 100, a film (sensitive film application range defining material) 200 made of gold (Au) is formed in a range where the sensitive film 150 is formed, for example, by sputtering or vapor deposition. It is preferable to form a film by appropriate means. Compared with the material of the vibrator 100, since gold is significantly superior in affinity with the sensitive membrane solution L as described above, when the sensitive membrane solution L is supplied from the microcapillary 20, the membrane 200 and its surroundings The sensitive film solution L is prevented from spreading to the outer peripheral side of the film 200 due to the difference in affinity between the sensitive film 100 and the vibrator 100, so that the sensitive film 150 is formed in a range where the sensitive film 150 is formed on the film 200. The material is formed with high accuracy.
Of course, as long as the affinity with the sensitive membrane solution L is excellent, the membrane 200 may be similarly formed of a material other than gold. Other materials having excellent affinity with the sensitive film solution L include a silicon oxide film that can be formed by CVD, sputtering, or the like, an alkyl SAM (Self-Assembled Monolayer) film, and the like.

  Further, as shown in FIG. 7B, in the vibrator 100, the affinity for the sensitive film solution L such as gold is significantly greater than that of the material of the vibrator 100 along the outer shape of the range where the sensitive film 150 is formed. The belt-shaped line portion (sensitive film application range defining material) 250 having a certain width may be formed of an excellent material. Even when such a line portion 250 is formed, the sensitive film solution L spreading in the region surrounded by the line portion 250 is caused by the difference in affinity between the line portion 250 and the material forming the vibrator 100. Spreading to the outer peripheral side than the line portion 250 is prevented, and thereby the sensitive film material is accurately formed in the range where the sensitive film 150 is formed.

  Further, as shown in FIG. 7C, in the vibrator 100, a continuous groove (sensitive film application range defining material) 300 (or stepped portion, concave portion) is formed along the outer shape of the range in which the sensitive film 150 is formed. You may do it. By forming the groove 300, the sensitive film solution L spreading in the region surrounded by the groove 300 is prevented from spreading to the outer peripheral side at the corners of the groove 300 due to the surface tension. The sensitive film material is formed with high accuracy in the range where the film 150 is formed. Such a groove 300 is also effective from both the Si sensor chip manufacturing step and the oscillation characteristics of the vibrator 100. Further, if the groove 300 is formed in a circular pattern on the vibrator 100 made of, for example, a Si substrate, a width of 2 μm is sufficiently effective.

  When forming the line part 250 and the groove 300, the wettability of the sensitive film solution L on the surface of the vibrator 100 is improved by surface-treating the surface of the vibrator 100 by oxygen plasma or UV-ozone treatment. Is preferred.

In this way, by using the microcapillary 20 whose diameter is reduced by pulling the glass tube G, the sensitive membrane solution L is sucked into the microcapillary 20 by capillary action, and the pressure applied to the microcapillary 20 is controlled, The sensitive film 150 can be formed by applying the sensitive film solution L to a minute region on the vibrator 100.
At this time, a region where the sensitive film 150 is to be formed on the vibrator 100 is defined by the film 200 made of a material having a high affinity with the sensitive film solution L, the line portion 250, and the groove 300, whereby the sensitive film 150 is formed. It becomes possible to form a film with high accuracy.
In addition, such a film forming apparatus 10 does not require complicated mechanisms or costly processing. In particular, the microcapillary 20 can be manufactured at a very low cost using a glass tube. This is very suitable for forming the sensitive film 150 on the vibrator 100 in the test research and the trial production stage.

Now, the sensitive film 150 is actually formed on the vibrator 100 using the film forming apparatus 10 as described above, and the result is shown.
Example 1 A film 200 made of gold was deposited on a predetermined region of the surface of the vibrator 100 shown in FIG. 2 (film thickness 100 nm). Here, the size of the film 200 was set to 100 × 500 μm to 100 × 300 μm.

A film in which three types of sensitive film materials of a copolymer (PAB), TiO ₂ , and polybutadiene (PBD) containing acrylonitrile and butadiene as monomer units are dispersed in a solvent on the film 200 is formed as the film. Application was by apparatus 10.
Here, PAB used o-dichlorobenzene as a solvent, and the mixing ratio thereof was 1.5 wt% for PAB and 98.5 wt% for the solvent.
For TiO ₂ , ethylene glycol was used as a solvent, and the mixing ratio was 2.5 wt% for TiO ₂ , 90 wt% for the solvent, and 7.5 wt% for water.
PBD used tetralin as a solvent, and the mixing ratio was 2.5 wt% PBD, and the remainder was tetralin.

In addition, in the disk-type vibrator 100 as shown in FIG. 3, the following three samples were prepared.
Example 2 A film 200 made of gold was deposited on a predetermined region of the surface of the disk-type vibrator 100.
Example 3 A groove 300 having a width of 2 μm and a depth of 500 nm was formed along the outline of a predetermined region on the surface of the disk-type vibrator 100.
(Comparative example): Disc type vibrator 100 in which film 200 and groove 300 are not formed on the surface.
In each of Examples 2 and 3 and Comparative Example, a sensitive film solution L with PBD: 2.5 wt% and solvent: remainder was applied to a predetermined region on the surface of the vibrator 100 by the film forming apparatus 10.

These results are shown in FIGS. 8A, 8B, 8C, and 8D.
In Example 1 (FIG. 8 (a)), Example 2 (FIG. 8 (b)), and Example 3 (FIG. 8 (c)), the film 200, It was confirmed that the sensitive film 150 was formed in a predetermined region defined by the groove 300. On the other hand, as shown in FIG. 8D, it was confirmed that the sensitive film 150 was formed so as to extend beyond a predetermined region in the vibrator 100 in which the film 200 and the groove 300 of the comparative example were not formed.

Further, the thickness distribution of the sensitive film 150 on the vibrator 100 of Example 3 shown in FIG. The result is shown in FIG.
As shown in FIG. 9, it was confirmed that the film thickness of the sensitive film 150 formed in the region defined by the groove 300 on the vibrator 100 was substantially uniform.

  In the above embodiment, the configuration of the film forming apparatus 10 and the film forming method of the sensitive film 150 have been described. However, the configuration described in the above embodiment may be selected without departing from the gist of the present invention. It is possible to appropriately change to other configurations.

  DESCRIPTION OF SYMBOLS 10 ... Film-forming apparatus, 11 ... Holder, 12 ... Z-axis stage (moving part), 13 ... XY-axis stage (moving part), 14 ... Vibrator support stage, 15 ... Coating liquid storage part, 15a ... Container, 17 ... Camera (observation unit), 18 ... illumination, 19 ... monitor, 20 ... microcapillary (liquid holding unit), 20a ... front end, 20b ... rear end, 30 ... pressure adjusting unit, 31 ... pressure generating source, 40 ... automatic Control device (automatic control unit), 100 ... vibrator (object), 150 ... sensitive film (film), 200 ... film (film application range defining material), 250 ... line part (film application range defining material), 300 ... Groove (film coating range defining material), G ... Glass tube, L ... Sensitive membrane solution (membrane material, liquid)

Claims (17)

A film forming apparatus for forming a film by discharging a liquid containing a film material onto a surface to be processed of an object,
A liquid holding unit for sucking and holding the liquid from the opening formed at the tip, and
A pressure adjusting unit that adjusts a pressure applied to the liquid inside the liquid holding unit so that the liquid holding unit sucks or discharges the liquid from the opening;
A moving unit that moves the tip of the liquid holding unit that holds the liquid to a processing position that faces the processing surface of the object;
The pressure adjusting unit adjusts the pressure of the liquid holding unit for causing the liquid to be discharged onto the surface to be processed in the processing position according to the size of the surface to be processed. Deposition device. The film forming apparatus further includes an observation unit capable of observing a discharge range of the liquid with respect to the surface to be processed.
The liquid discharge range obtained by the observation unit is compared with the size of the surface to be processed, and the pressure of the liquid holding unit in the pressure control unit is adjusted based on the comparison result. The film forming apparatus according to claim 1. An automatic control unit connected to the moving unit and the pressure adjusting unit;
The automatic control unit executes processing based on a predetermined program, thereby moving the tip of the liquid holding unit in the moving unit and the pressure of the liquid holding unit in the pressure adjusting unit. The film forming apparatus according to claim 1, wherein the adjustment is automatically performed. An automatic control unit connected to the moving unit, the pressure adjusting unit, and the observing unit;
The automatic control unit moves the tip of the liquid holding unit in the moving unit based on a predetermined program and information from the observation unit, and the pressure of the liquid holding unit in the pressure adjusting unit. The film forming apparatus according to claim 2, wherein the adjustment is automatically performed.   5. The film forming apparatus according to claim 1, wherein the liquid holding unit sucks the liquid by a capillary phenomenon.   6. The film forming apparatus according to claim 1, wherein the liquid holding portion has a tubular shape having a hollow portion that is reduced in diameter toward the distal end portion and holds the liquid. .   The film forming apparatus according to claim 6, wherein the liquid holding unit has a shape formed by pulling a glass tube and having a diameter that decreases toward a tip.   The treatment target surface of the object is further provided with a film application range defining material that has an affinity higher than the affinity of the surface of the object for the liquid and defines a film application range. The film forming apparatus according to any one of claims 1 to 7.   The film application range defining material is a thin film made of gold formed corresponding to the range, or a line portion made of gold formed linearly along the outline of the range. Item 9. The film forming apparatus according to Item 8.   The groove or step is formed in the said to-be-processed surface of the said target object as the said film application range definition material which prescribes | regulates a film application range along the outline of the said range. The film forming apparatus according to claim 9.   The film material is a medium molecular organic material having a molecular weight of 1000 or more, such as polybutadiene, polyisoprene, polystyrene, polyacrylonitrile, polycaprolactan and a copolymer thereof, and a phthalocyanine complex having an oligophenyl group or a tertiary butyl group. The film forming apparatus according to claim 1, wherein the film forming apparatus is a film forming apparatus. The film material is sucked into the liquid holding portion in a state dispersed in a solvent,
The film forming apparatus according to claim 11, wherein the solvent includes at least one of tetralin, ethylene glycol, o-dichlorobenzene, mesitylene, and xylene. A vibrator body;
A sensitive film formed on the surface of the vibrator main body, to which a substance having a mass is attached or adsorbed,
13. A vibrator, wherein the sensitive film is formed on the vibrator main body using the film forming apparatus according to claim 1. A film forming method for forming a film by discharging a liquid containing a film material onto a surface to be processed of an object,
Holding the liquid after sucking the liquid from the opening in a liquid holding part having an opening formed at the tip; and
Moving the tip portion of the liquid holding portion in which the liquid is held to a processing position facing the processing surface of the object;
Discharging the liquid from the opening to the processing surface while adjusting the pressure of the liquid holding unit according to the size of the processing surface at the processing position;
A film forming method comprising:   In the step of discharging the liquid onto the surface to be processed, the liquid discharge range with respect to the surface to be processed is observed, and the observed liquid discharge range is compared with the size of the surface to be processed. The film forming method according to claim 14, wherein the pressure of the liquid holding unit is adjusted based on a result.   In the step of discharging the liquid onto the surface to be processed, the liquid was discharged after being discharged from the tip portion of the liquid holding portion onto the surface to be processed by increasing the pressure of the liquid holding portion. The pressure of the liquid holding part is decreased when the liquid spreads over the range of the film to be formed, and the tip part of the liquid holding part is separated from the surface to be processed. Item 16. The film forming method according to Item 14 or 15.   By increasing the pressure of the liquid holding portion, when the liquid is discharged from the tip portion of the liquid holding portion to the surface to be processed, the tip portion of the liquid holding portion and the surface to be processed are The liquid that has been ejected from the tip of the liquid holding unit and adhered to the surface to be processed is allowed to flow between the tip of the liquid holding unit and the surface to be processed. The film forming method according to claim 16, wherein the film is bridged.