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WO1997008362A1 - Procede et dispositif d'attaque amelioree de substrats par des electrons a faible energie - Google Patents

Procede et dispositif d'attaque amelioree de substrats par des electrons a faible energie Download PDF

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Publication number
WO1997008362A1
WO1997008362A1 PCT/US1996/013915 US9613915W WO9708362A1 WO 1997008362 A1 WO1997008362 A1 WO 1997008362A1 US 9613915 W US9613915 W US 9613915W WO 9708362 A1 WO9708362 A1 WO 9708362A1
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WIPO (PCT)
Prior art keywords
substrate
cathode
semiconductor
plasma
etching
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1996/013915
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English (en)
Inventor
Kevin P. Martin
Harry P. Gillis
Dmitri A. Choutov
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Georgia Tech Research Institute
Georgia Tech Research Corp
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Georgia Tech Research Institute
Georgia Tech Research Corp
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Priority to AU68636/96A priority Critical patent/AU6863696A/en
Publication of WO1997008362A1 publication Critical patent/WO1997008362A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • H10P90/126—
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
    • H01J37/32018—Glow discharge
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
    • H01J37/32018—Glow discharge
    • H01J37/32027—DC powered
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
    • H01J37/32321—Discharge generated by other radiation
    • H01J37/3233—Discharge generated by other radiation using charged particles
    • H10P50/242—
    • H10P50/246—
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2237/00—Discharge tubes exposing object to beam, e.g. for analysis treatment, etching, imaging
    • H01J2237/32—Processing objects by plasma generation
    • H01J2237/33—Processing objects by plasma generation characterised by the type of processing
    • H01J2237/334—Etching

Definitions

  • the present invention relates generally to the preparation of etched substrates.
  • the present invention relates to an improved process for low-damage, anisotropic etching of substrates such as semiconductors, and improved anisotropically etched substrates.
  • Dry etching is an absolutely critical process in the fabrication of all micrometer and nanometer scale features on high speed electronic and opto-electronic devices.
  • the fabrication of such chips and devices involves the following process.
  • a substrate of some semiconductor or metal is selected and a pattern is laid down over it, the pattern having open areas in it.
  • the overlying structure containing the pattern is sometimes called a mask.
  • Etching chemistry is then performed through the open areas, which means that in effect some of the underlying material exposed through the open areas is dissolved away so that the pattern is transferred into the underlying layer(s).
  • the mask is stripped away and what is left behind is the original substrate, but now the pattern has been transferred into it.
  • the process is similar to silk screening or stamping a pattern into material.
  • the resulting pattern has a three dimensional structure.
  • most etching was done using a wet chemical process that is quite similar to conventional photography.
  • the water is first placed in a high temperature, oxidizing environment and a layer of silicon dioxide is grown on the top surface of the wafer.
  • the oxidized wafer is covered with a thin photosensitive layer of gelatinous organic material called a "photoresist”.
  • a piece of material analogous to a photographic negative, called a "photomask” is placed over the photoresist. Ultraviolet light is shined through openings in this photomask.
  • the ultraviolet light changes the solubility of the photoresist.
  • areas of photoresist that have been illuminated with the ultraviolet light display a different solubility than areas which have not been exposed to the light.
  • a solvent is used which dissolves away only the areas of the photoresist which have had their solubility increased by the ultraviolet light.
  • the original pattern on the photomask has been transferred to the photoresist layer.
  • a wet chemical, hydrofluoric acid (HF) dip is used to dissolve away the silicon dioxide which has been exposed through each of the openings in the overlaying photoresist. Then, the photoresist is stripped off. At this point, it is apparent that the pattern originally appearing on the photomask has been transferred to the silicon dioxide layer overlying the silicon wafer. This patterned layer of silicon dioxide is sometimes referred to as a "hard mask”.
  • the wafer is dipped into a caustic etch, such as potassium hydroxide (KOH) which etches away the silicon exposed under the openings in the hard mask.
  • KOH potassium hydroxide
  • ion implantation or high temperature diffusion could optionally be used to place dopant atoms through the openings in the hard mask.
  • Isotropic etching is adequate for making a line that is 20 microns wide through a film that is 1 micron deep.
  • the resulting inaccuracy in the edges of such a feature is a small percentage of the overall device structure; and therefore, it does not compromise performance.
  • isotropic etching is inadequate.
  • the industry is moving toward fabrication of structures with so called sub-micron features, which are essential for high speed computer chips, optical structures, and electronic and optoelectronic devices. In other words, the accurate transfer of a pattern which is half a micron wide into a material which is half a micron thick requires absolutely straight vertical side walls, or anisotropic etching. Isotropic etching is inadequate because the associated rounded undercut would be a very high percentage of the active device material and would destroy its performance.
  • Reactive-ion etching provides anisotropic etching.
  • the ions are heavy ions like argon or CF 3 + and are traveling at a few hundred electron volts of kinetic energy. Thus, they carry enough momentum to displace lattice atoms from their normal position. This damages the surfaces and often, the optical and electrical properties of the substrate have been detrimentally changed.
  • ion enhanced plasma etching processes e.g. reactive ion etching (RIE) and electron cyclotron enhanced RIE (ECR)
  • RIE reactive ion etching
  • ECR electron cyclotron enhanced RIE
  • reactive species generated in the plasma should have energies larger than the activation energy of the etch reaction (a fraction of an eV), but less than the energy required for atomic displacement (3 to 10 eV for -U-V semiconductors).
  • the ion energies available in reactive-ion (about 300 eV) and electron cyclotron resonance plasma etching (about 50 eV) are not ideally suited for fabricating nanometer scale devices.
  • Vepfek "Reactivity of Solid Silicon With Hydrogen Under Conditions of a Low Pressure Plasma", Chemical Physics Letters, Vol. 62, No. 1, p. 173 (1978). That publication describes an apparatus including a DC glow discharge device with the sample immersed in the positive column.
  • the cathode was a standard hot cathode (heated to between 1500-2000 K) having a tungsten filament coated with thorium oxide. While this technique apparently worked for etching Si(lll) with hydrogen, it would not work using other reactive gases such as oxygen, chlorine, and fluorine because the hot filament would be immediately consumed.
  • the apparatus described by Vepfek and Sarott is cumbersome. Other experiments, reported by Gillis et al.
  • the present invention involves low energy electron enhanced etching (LE4), as opposed to reactive ion enhanced etching.
  • LE4 low energy electron enhanced etching
  • the process gives straight side walls, and it does not damage the substrate.
  • the low energy electrons that are used in the present invention travel at less than about 100 electron volts (eV) kinetic energy (KE), preferably at less than about 20 eV.
  • eV electron volts
  • KE kinetic energy
  • the mass of electrons is many orders of magnitude smaller than the mass of ions and the electrons carry essentially no momentum to the surface. Therefore, they do not damage the surface.
  • the present invention provides a low damage alternative to ion enhanced processes, using low energy electron enhanced etching (LE4), in which the substrate sits on the anode of a DC glow discharge.
  • LE4 low energy electron enhanced etching
  • the energy of electrons and negative ions arriving at the substrate on the anode of a DC discharge is limited to a value not greater than the ionization potential of the reaction gas; energies above this limit are effectively dissipated by inelastic collisions in the gas phase. No such fundamental limit is imposed on the positive ions produced in RF and microwave plasmas.
  • the invention involves a process for low-damage, anisotropic etching of a substrate that includes the steps of placing the substrate on the anode of a direct-current plasma reactor and subjecting the substrate to a plasma including low energy electrons and a gaseous species that is reactive with the substrate.
  • the substrate can be a Group IV semiconductor, a Group -U-V semiconductor, a Group II-VI semiconductor, an oxide, a nitride, a metal, or an alloy or mixture ofthe foregoing.
  • the reactive species can be any that reacts with the substrate and that volatilizes within the temperature and flow of the device. Typical reactive species to be used are hydrogen, halogens, interhalogen compounds, hydrogen halides, and volatile organic compounds.
  • the low energy electrons are generated using a cold cathode. A voltage of about
  • 0.5-2 kV is applied between the cathode and the anode, generating a glow discharge in which electrons having a kinetic energy of less than about 100 eV, or, preferably less than about 20 eV arrive at the anode.
  • the invention is an apparatus for conducting low-energy anisotropic etching of a substrate.
  • the apparatus includes a chamber formed by a pair of connected tubes, at an angle from one another.
  • the chamber is, of course, able to be placed under a vacuum.
  • a cathode is in one tube and an anode is in the other, so that the anode is located at an angle of about 30° to 120° or, preferably, about 90° from the cathode.
  • the cathode is a cold cathode, capable of generating a DC glow discharge in which low energy electrons having a kinetic energy of less than 100 eV, or preferably less than about 20 eV arrive at the anode.
  • the cathode has one end that can be connected to a power supply that is preferably located outside the tube.
  • the anode has means for mounting the substrate thereupon.
  • the anode and the substrate are surrounded by dielectric shielding to prevent plasma from "jumping" to alternative electrodes.
  • the shield includes an aperture, the size and shape of which determine the area of the sample exposed to plasma.
  • the apparatus further includes means for introducing the reactive gas into the sealed chamber.
  • the cold cathode is a hollow cathode formed with permeable, meshed, or perforated, generally referred to as permeable, walls rather than the typical solid walls.
  • the cathode in a preferred embodiment, may be cylindrically shaped with a side wall of a permeable conductive material, such as stainless steel mesh, and having one end that is open or closed and an open end.
  • the cathode is connected to a cathode mounting post and to the power supply.
  • the cathode may comprise a plurality of nested side walls, each connected to the power supply. The use of this cathode allows the generation of a large flux of low energy electrons at low pressure and temperature.
  • An advantage of the method and apparatus of the present invention is that low damage sub-micron anisotropic etching of a substrate is achieved.
  • Another advantage of the method and apparatus of the present invention is that it is applicable to a variety of substrates using a variety of reactive species.
  • Another advantage of the method and apparatus of the present invention is that the apparatus is fairly simple to assemble and operate.
  • Another advantage of the method and apparatus of the present invention is that the permeable wall hollow cathode can generate a higher flux of low energy electrons, at a lower pressure.
  • Figure 1 is a top plan view of an apparatus of the present invention.
  • Figure 2 is a perspective view of a permeable wall hollow cathode of the present invention.
  • FIG. 1 A preferred embodiment of an etching apparatus suitable for practicing the present invention, referred to generally as 10, is illustrated in FIG. 1.
  • the apparatus includes a chamber 12 made of one or more adjoined 2" to 4" diameter PYREXTM glass pipes. Alternatively, larger hardware could be used to accommodate work pieces having diameters of 100-150 mm, or more.
  • the device 10 includes three sections: the cathode containing section 14, the anode containing section 16, oriented at 90° from the cathode containing section, and a third section 18, located near the cathode and also at 90° from the cathode containing section.
  • the chamber can be set up having various configurations, an important aspect is that the anode containing section be at an angle, preferably at about 30° to about 120°, most preferably about 90°, from the cathode containing section so that the cathode material is not sputter deposited onto the anode or the substrate.
  • a plurality of clamps 20 are employed to hold sections of the chamber together and for clamping end plates to the chamber.
  • End plate 15 is clamped to one end of cathode containing section 14.
  • End plate 21 is preferably made of glass and serves as a view port to cathode containing section 14.
  • End plate 22 is also preferably made of glass and serves as a view port to the sample, as described below.
  • End plate 17 seals the other end of anode containing section 16.
  • the third section 18 provides access to the chamber for a pair of pump members.
  • a gate valve 24 is connected to a ultra high vacuum (UHV) pumping station (not shown) and a butterfly valve 28 is connected to a rotary vane pump (not shown).
  • a barocell manometer 26 monitors the pressure in the system.
  • the UHV pump should be able to achieve and maintain hold a base vacuum of down to about IO "8 Torr on the chamber.
  • the rotary vane pump should be able to achieve and maintain a vacuum of about 0.025 to 2 Torr during the etching process. Of course, one pump can be used if it is able to achieve and regulate the before-listed vacuums.
  • the cathode 32 is mounted in the cathode containing section 14.
  • the cathode 32 is preferably a cold cathode, sometimes referred to as a field emission cathode, meaning it functions without the application of heat.
  • the cathode is activated using an external power source (not shown) that applies a direct current (DC) voltage between the cathode and the anode.
  • DC direct current
  • the chamber contains a gas (described below), the chamber functions as a DC glow-discharge tube or DC plasma reactor.
  • the cathode may be a standard cold cathode such as are known in the art.
  • the cathode is a permeable wall hollow cathode of the present invention, more clearly illustrated in FIG. 2.
  • Cathode 32 includes a tubular wall 36 made of a permeable, meshed, or perforated conductive material such as stainless steel mesh.
  • the wall can have a variety of shapes, the cathode shown in FIG. 2 is designed to fit in a cylindrical cavity such as cathode containing section 14 of chamber 12 of the apparatus shown in FIG. 1.
  • the cathode has two ends, a first, open, end 38 facing the anode containing section of the chamber, and a second end 40.
  • the second end can be open or closed with an end piece (not shown).
  • the end piece may be a solid piece of material or made of the same meshed material.
  • Other materials such as aluminum may be preferred for the cathode material and the cathode may be coated with gold or other conducting material.
  • a mounting post 42 is attached to the cathode for mounting the cathode within the chamber.
  • the mounting post may be attached to the end piece as described below. However, the mounting post can be attached to the wall 36 or altemative mounting means can be employed.
  • Mounting post 42 is a metal rod having one end attached to the cathode and a second end attached to a coupler 43. Preferably, the second end threads into coupler 43. The coupler connects mounting post 42 to a high voltage feed-through
  • a glass tube 45 encloses mounting post 42 and coupler 43 and shields the metal mounting post from electrons.
  • the length of mounting post 42 is adjustable so that cathode 32 can be moved closer to or further from the anode. This can be done by replacing the post 42 with a post of another length or by using a telescoping-type post.
  • the cathode used in the present invention can be a single-walled permeable wall hollow cathode or may include a plurality of nested, similarly shaped stmctures, all having permeable walls, as shown in FIG. 2. Plasma current is increased even more with such a design.
  • a cathode according to the present invention can be made as follows. A length of stainless-steel mesh is wrapped around a mandrel having the desired shape (such as cylindrical). The length of mesh is cut to size, so that it has two adjoining edges mnning lengthwise of the mandrel. The two edges are spot welded or otherwise fastened together. One end of the shaped wire mesh tube is shaped into a cone by hand and attached to the first end of the mounting post by welding or crimping. The mandrel is removed.
  • the nested, permeable wall hollow cathode, shown in FIG. 2 can be made by fashioning a set of cylinders of varying diameters.
  • a solid stainless plate is welded to the mounting post. The cylindrical walls are concentrically welded to the other side of the plate, beginning with the smallest diameter cylinder.
  • cathode in accordance with the invention, it should be understood that altemative ways are anticipated.
  • the cathode could have two open ends and the cathode mounting post could be attached along the cathode wall.
  • the presently disclosed cathode allows the operating voltage of the apparatus to be decreased by at least 2-fold because of its greater electron emitting surface area.
  • the permeable walls allow the free flow of plasma and improve operating parameters such as pressure, temperature, and plasma stability.
  • inventive cathode is disclosed specifically for use in the presently discussed etching method and apparatus it should be appreciated that it has utility in other applications in which cold cathodes are used.
  • inventive cathode may prove advantageous for use in gas lasers, and glow discharge lighting such as for advertising, illumination, and decoration.
  • the anode assembly 50 is mounted in the anode containing section of the chamber.
  • the anode assembly includes a solid upper anodic disk 52 connected to a cylindrically shaped hollow support 53.
  • a hollow cylindrically shaped support tube 54 supports the anode and includes an upper portion 55 made of stainless steel which has one end connected to the anodic disk 52 and a second end attached to an intermediate portion 56 which is made of ceramic and functions as a ceramic break.
  • the lower portion 57 is made of stainless steel and has one end attached to the ceramic break 56 and the lower end attached to an end plate 58.
  • a sample heater 59 extends through end plate 58, the support tube 54 and into hollow support 53. In the preferred embodiment, heater 59 is a resistive cartridge heater measuring about 4 " diameter by about V-.” length. By heating the hollow support 53 and the anodic disk 52, the heater also heats the sample.
  • Support tube 54 exits chamber 12 through an aperture in end wall 17. Support tube 54 then passes through a gas manifold 60 that is in commumcation with chamber 12. Since manifold 60 is in communication with chamber 12 it must also be able to hold a base vacuum down to about IO "8 Torr. Thus, all of the manifold ports must be air ⁇ tight. Manifold inlet port 61 connects manifold 60 to chamber 12. Outlet port 62 allows passage of support tube 54 from manifold 60.
  • thermocouple 63 passes through port 64, through manifold 60, into chamber 12 and attaches to anodic disk 52.
  • the thermocouple measures the temperature of the anodic disk.
  • An electrical lead 65 passes through port 64, through manifold 60, into chamber 12 and attaches to anodic disk 52. This lead may be used to maintain the anode at, for example, ground potential.
  • the apparatus as described includes the anodic assembly horizontally placed, the sample must be retained on the anodic disk. Also, it is desirable to cover the anodic disk and a portion of the anodic assembly with a dielectric shield to prevent the discharge current from contacting the metallic anodic disk and support tube. The dielectric shield is also used to retain the sample on the anodic disk.
  • the dielectric shield 70 is made of PYREXTM glass and includes a cylindrical wall 72 enclosing a portion of the anodic assembly and a bottom portion 74 overlying the anodic disk 52 and substrate 68.
  • the bottom portion 74 contains an aperture defining the substrate area exposed to the plasma.
  • the area of the aperture should be selected so that the plasma reactor does not suffer from a loading effect during the etch process.
  • an aperture having an area of approximately 0.2 cm 2 proved to be useful.
  • an aperture is not necessarily required.
  • an aperture can be employed which has the ability to be moved relative to the substrate being etched. This permits different portions of the substrate to be exposed to the plasma at different times.
  • the shield is retained in position by appropriate means.
  • the shield may be fastened with a number of springs to end plate 17.
  • Three protmding ears are formed at equal spacing along the lip of wall 72.
  • Three spatially corresponding fasteners, such as screws, are placed on end plate 17.
  • a spring is then fastened between each ear and its corresponding screw.
  • the reactive species is supplied through gas entry port 66 into manifold 60.
  • Leak valve 67 is used to adjust the flow rate of the gaseous reactive species. From the manifold, the gaseous reactive species is able to enter chamber 12.
  • the gas can be introduced into the chamber by any regulated means.
  • the reactive species may be molecular or atomic.
  • the entire anode assembly 50 can be removed from chamber 12 by removing clamp 20 holding end wall 17 to the anode containing section 16. After the anode assembly is removed, the substrate 68 can be mounted onto the anodic disk 52.
  • the apparatus includes means to view the substrate. These means are preferably a He/Ne laser 80 that passes through glass plate 22 and illuminates the substrate. A beam splitter 82 separates incoming from reflected light and transmits reflected light to the viewer.
  • the substrate is preferably a Group IV semiconductor, a Group BI-V semiconductor, a Group ⁇ -VI semiconductor, a metal, a superconductor, or a polymer. Also, it is anticipated that alloys or mixtures of the foregoing can be used. Also, oxides and nitrides of the foregoing can be used. Examples of substrates are Si, SiC, GaAs, AlGaAs, AIN, gold, chromium, high T e superconductors, aluminum, tungsten, and platinum. In prefe ⁇ ed embodiments, the substrate is Si, GaAs, or GaN.
  • the substrate comprises any workpiece, a portion of the workpiece, or a layer of the workpiece wherein the inventive etching method is being used.
  • the substrate being etched may be an epitaxial layer of single crystal silicon which has been deposited by chemical vapor deposition (CVD) over a raw silicon wafer.
  • the substrate being etched may be a thin film of thermal silicon dioxide which has been grown on the wafer, or a thin film of silicon dioxide deposited on the wafer.
  • the substrate being etched may comprise a region of polycrystalline silicon, or a silicide, or a polycide.
  • the substrate is patterned with a mask of the desired configuration, through methods known in the art.
  • a silicon dioxide (SiOj) or silicon nitride mask may be laid down over the substrate using plasma enhanced chemical vapor deposition followed by photolithographic patterning and wet etching of the mask in a 1:6 buffered oxide etch.
  • Other methods of laying down masks and other mask materials may be used as well.
  • SiO 2 is particularly prefe ⁇ ed because the present method is selective for substrate over SiO 2 at the conditions used.
  • the substrate may be chemically etched before being subjected to the presently disclosed etching process, to remove native surface oxides.
  • This chemical etching can be done by methods known in the art such as dipping the substrate in a 10% HF solution for about 5 seconds.
  • Other chemicals that can be used for etching are HCl and ammonium hydroxide.
  • the substrate preferably masked and pre-etched, is mounted on to the anode.
  • the UHV pumping station is activated to achieve a pressure in the chamber of about IO "8 Ton. This pressure is maintained for about 2 hours at a temperature of about 150°C in order to degas the system and remove all H 2 0.
  • the substrate can be annealed by heating at about 200 °C in pure H 2 plasma for about 10 minutes.
  • the gate valve is closed and the butterfly valve is opened and the leak valve is opened so that a pressure of about 0.025 to 2.0 Ton is maintained in the chamber.
  • the sample temperature is regulated to the desired degree. Voltage within the range of about
  • 0.5 to 2 kV is applied between the cathode and the anode to produce an electron cu ⁇ ent density up to about 0.5 A/cm 2 .
  • reactive gas is fed into the anode containing portion of the device at a flow of about 5-60 seem.
  • etching After etching is complete, power to the cathode is stopped, gas flow is stopped, and the vacuum is removed. The substrate is removed and is then available for evaluation of the etch rate and degree of anisotropy and further processing, if desired.
  • Si(100) samples were chemically etched in 10% HF before loading into the chamber.
  • the etching cycle for each sample comprised these steps: (1) degas for two hours at 150°C in UHV (about 10 "8 Ton); (2) anneal for 10 min. at 200 C C in pure H 2 plasma to remove any residual thin oxide layer; (3) etch for a selected time at selected H 2 /He composition, process pressure, and discharge cunent, maintaining sample temperature at 60 °C which is known to be the temperature for highest reaction rate between Si(100) and H atoms.
  • Heated silicon wafers downstream from the anode enhanced the reaction rate by facilitating removal of the reaction products by thermal decomposition of silane on the wafers.
  • the H 2 /He composition ranged from 100% H 2 to 10% H 2 .
  • the pressure ranged from about 0.03 to 2.0 Ton.
  • the discharge current density was about 0.1 to 0.5 A/cm 2 .
  • Gas flow was from about 5 to 50 seem.
  • Voltages within the range 0.5 to 2.0 kV applied between the cathode and the anode produced glow discharge cunent density up to 0.5 A/cm 2
  • the integrated charge passing through the sample was recorded for subsequent calculation of the reaction yield.
  • GaAs(100) substrates were patterned with SiO 2 masks by plasma enhanced chemical vapor deposition of a 3000 A SiO 2 layer followed by photolithographic patterning and wet etching of the SiO 2 in a 1 :6 buffered oxide etch.
  • the substrates were etched at room temperature in 100% Cl 2 , 100% H 2 , and various Cl 2 /H 2 mixtures.
  • the process pressures were 25 to 75 mTon. Gas flows of 10 to 30 seem for chlorine and hydrogen were maintained.
  • the substrates were examined by profilometry to determine the etch rate, scanning electron microscopy (SEM) to determine surface mo ⁇ hology and anisotropy of the etch, and by energy dispersed X-ray spectral analysis to estimate surface composition.
  • SEM scanning electron microscopy
  • the substrates were 1 micrometer thick GaN films grown by metal-organic molecular beam epitaxy (MOMBE) over a 50 nanometer buffer layer of AIN on a Si(100) substrate.
  • MOMBE metal-organic molecular beam epitaxy
  • the substrates were patterned by a deposition of a 0.2 micrometer SiO 2 film by plasma enhanced chemical vapor deposition in which test features of 3 micrometer to 50 micrometer widths were defined by a standard photolithographic technique.
  • the substrates were dipped for five seconds in 10% HF solution and then immediately mounted on the anode of the etching device.
  • the cu ⁇ ent density was kept constant at about 300 mA/cm 2 DC.
  • the sample temperature was in the range 75 °C to 250 °C.
  • Typical process pressure was about 0.20 Ton with a gas flow rate of hydrogen of 60 seem.
  • the reaction efficiency decreases when the energy of incident electrons exceeds 10 eV, where silane disassociation begins (pressure ⁇ 0.6 Ton) and redeposition of etched material takes place.
  • the yield decreases because the electron-stimulated reaction cross section decreases. Dilution of the process gas by helium shifts the equilibrium to higher energies.
  • Silane dissociation at electron energies above 10 eV causes not only a decrease in the reaction yield, but also a change in the quality of the etched surface. All samples etched at lower pressure (high electron energy) show surface roughness of about 300 nm and obvious signs of redeposition. By contrast, at higher pressure/low electron energy, the etched surfaces were mi ⁇ orlike in appearance with a root mean square (RMS) roughness of 2-3 A.
  • RMS root mean square
  • Typical applications in silicon-based technologies include patterning of sub-micron features on integrated circuits and etching of critical elements on silicon sensors and micro-machines.
  • the mo ⁇ hology of the etched surface improves dramatically as the partial pressure of hydrogen increases: from extremely rough surfaces, cracked sidewalls and extensive residues at high Cl 2 to very smooth surfaces and sidewalls at hydrogen concentrations exceeding 75%.
  • the RMS surface roughness for several samples etched at > 75 % H 2 was determined by an atomic force microscope (AFM) in contact mode and found to be 3-5 A (unetched samples had the same roughness).
  • the etch rate dependence on the hydrogen concentration, with total pressure held constant at 50 mTon was measured.
  • the etch rate decreases gradually from 3000 A/min at 100% Cl 2 to 180 A/min at 100% H 2 because of the lower reactivity of hydrogen radicals with GaAs. This allows the practitioner to trade-off between etch rate and surface quality.
  • 75 % H 2 /25 % Cl 2 one can etch GaAs(100) surfaces in LE4 with excellent anisotropy, stoichiometric composition, and RMS surface roughness 3-5 A, at the entirely respectable rate of 250 A/min, all at room temperature.
  • the temperature dependence of the etch rate for different gas compositions at pressure of 50 mTon was measured for: a) 75% H 2 /25% Cl 2 , b) 100% Cl 2 and c) 100% H 2 .
  • chlorine present in any concentration the etch rate increases over 2 orders of magnitude between room temperature and 150°C, reaching spectacular values greater than 4.5 ⁇ m per min.
  • the etch rate does not change significantly over the same temperature range.
  • the etch rate was greatly increased, but at the cost of degrading surface stoichiometry. Nonetheless, according to the measurements it is possible to etch GaN films in hydrogen plasma with a respectable etch rate of 200 A/min, while maintaining surface stoichiometry.
  • the LE4 rate can be significantly improved by adding a small percentage of chlorine to the process gas mixture.
  • the above results with LE4 of GaAs shows that the best combination of stoichiometry and etch rate is achieved for 25 % Cl 2 /75 % H 2 reactive gas composition.

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  • Drying Of Semiconductors (AREA)

Abstract

L'invention concerne un procédé d'attaque anisotrope à faible détérioration pour substrats, qui consiste à placer un substrat (68) sur l'anode (52) d'un réacteur au plasma à courant continu (10) et à soumettre ce substrat au plasma d'électrons à faible énergie ainsi qu'à une substance qui réagit avec le substrat (68). On décrit par ailleurs un dispositif (10) qui permet d'utiliser ce procédé d'attaque anisotrope à faible détérioration: il comprend un réacteur au plasma à courant continu (14), une cathode froide creuse à paroi perméable (32), une anode (52), et un système (54) de montage du substrat (68) sur l'anode (52).
PCT/US1996/013915 1995-08-28 1996-08-28 Procede et dispositif d'attaque amelioree de substrats par des electrons a faible energie Ceased WO1997008362A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU68636/96A AU6863696A (en) 1995-08-28 1996-08-28 Method and apparatus for low energy electron enhanced etching of substrates

Applications Claiming Priority (10)

Application Number Priority Date Filing Date Title
US286195P 1995-08-28 1995-08-28
US286295P 1995-08-28 1995-08-28
US283795P 1995-08-28 1995-08-28
US60/002,861 1995-08-28
US60/002,862 1995-08-28
US60/002,837 1995-08-28
US2062996P 1996-06-27 1996-06-27
US2236496P 1996-07-24 1996-07-24
US60/022,364 1996-07-24
US60/020,629 2008-01-11

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WO1997008362A1 true WO1997008362A1 (fr) 1997-03-06

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000032851A1 (fr) 1997-12-03 2000-06-08 Georgia Tech Research Corporation Procede et dispositif servant a ameliorer la gravure aux electrons basse energie et le nettoyage de substrats
JP2003504792A (ja) * 1997-07-23 2003-02-04 ジョージア テック リサーチ コーポレイション ガス放電装置内の動作電圧を減少させる装置及び方法
EP1144735A4 (fr) * 1998-12-03 2007-01-10 Georgia Tech Res Inst Procede et dispositif servant a ameliorer la gravure aux electrons basse energie et le nettoyage de substrats

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4450787A (en) * 1982-06-03 1984-05-29 Rca Corporation Glow discharge plasma deposition of thin films
US4496881A (en) * 1982-09-29 1985-01-29 Tetra Pak Developpement Sa Method of cold cathode replenishment in electron beam apparatus and replenishable cold cathode assembly
US4874459A (en) * 1988-10-17 1989-10-17 The Regents Of The University Of California Low damage-producing, anisotropic, chemically enhanced etching method and apparatus
US5039376A (en) * 1989-09-19 1991-08-13 Stefan Zukotynski Method and apparatus for the plasma etching, substrate cleaning, or deposition of materials by D.C. glow discharge
US5368676A (en) * 1991-04-26 1994-11-29 Tokyo Electron Limited Plasma processing apparatus comprising electron supply chamber and high frequency electric field generation means
US5457298A (en) * 1993-07-27 1995-10-10 Tulip Memory Systems, Inc. Coldwall hollow-cathode plasma device for support of gas discharges

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4450787A (en) * 1982-06-03 1984-05-29 Rca Corporation Glow discharge plasma deposition of thin films
US4496881A (en) * 1982-09-29 1985-01-29 Tetra Pak Developpement Sa Method of cold cathode replenishment in electron beam apparatus and replenishable cold cathode assembly
US4874459A (en) * 1988-10-17 1989-10-17 The Regents Of The University Of California Low damage-producing, anisotropic, chemically enhanced etching method and apparatus
US5039376A (en) * 1989-09-19 1991-08-13 Stefan Zukotynski Method and apparatus for the plasma etching, substrate cleaning, or deposition of materials by D.C. glow discharge
US5368676A (en) * 1991-04-26 1994-11-29 Tokyo Electron Limited Plasma processing apparatus comprising electron supply chamber and high frequency electric field generation means
US5457298A (en) * 1993-07-27 1995-10-10 Tulip Memory Systems, Inc. Coldwall hollow-cathode plasma device for support of gas discharges

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003504792A (ja) * 1997-07-23 2003-02-04 ジョージア テック リサーチ コーポレイション ガス放電装置内の動作電圧を減少させる装置及び方法
EP1151456A4 (fr) * 1997-07-23 2005-10-05 Georgia Tech Res Inst Dispositif et procede servant a diminuer la tension de fonctionnement dans des appareils a decharge gazeuse
WO2000032851A1 (fr) 1997-12-03 2000-06-08 Georgia Tech Research Corporation Procede et dispositif servant a ameliorer la gravure aux electrons basse energie et le nettoyage de substrats
EP1144735A4 (fr) * 1998-12-03 2007-01-10 Georgia Tech Res Inst Procede et dispositif servant a ameliorer la gravure aux electrons basse energie et le nettoyage de substrats

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