WO1996015550A1 - Silicon-germanium-carbon compositions and processes thereof - Google Patents
Silicon-germanium-carbon compositions and processes thereof Download PDFInfo
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- WO1996015550A1 WO1996015550A1 PCT/US1995/013883 US9513883W WO9615550A1 WO 1996015550 A1 WO1996015550 A1 WO 1996015550A1 US 9513883 W US9513883 W US 9513883W WO 9615550 A1 WO9615550 A1 WO 9615550A1
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- 238000000034 method Methods 0.000 title claims abstract description 75
- 230000008569 process Effects 0.000 title claims abstract description 52
- 239000000203 mixture Substances 0.000 title abstract description 25
- AXQKVSDUCKWEKE-UHFFFAOYSA-N [C].[Ge].[Si] Chemical compound [C].[Ge].[Si] AXQKVSDUCKWEKE-UHFFFAOYSA-N 0.000 title description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 110
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 109
- 239000010703 silicon Substances 0.000 claims abstract description 107
- 239000000758 substrate Substances 0.000 claims abstract description 86
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 57
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 29
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 29
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000577 Silicon-germanium Inorganic materials 0.000 claims abstract description 4
- 229910005742 Ge—C Inorganic materials 0.000 claims abstract 34
- 239000002019 doping agent Substances 0.000 claims description 18
- LUMVCLJFHCTMCV-UHFFFAOYSA-M potassium;hydroxide;hydrate Chemical compound O.[OH-].[K+] LUMVCLJFHCTMCV-UHFFFAOYSA-M 0.000 claims description 18
- 238000005530 etching Methods 0.000 claims description 17
- 229910052796 boron Inorganic materials 0.000 claims description 16
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- 239000000126 substance Substances 0.000 claims description 14
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- 229910017604 nitric acid Inorganic materials 0.000 claims description 13
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- 239000004065 semiconductor Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 6
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- 239000013078 crystal Substances 0.000 claims description 5
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- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 239000012212 insulator Substances 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 229910001339 C alloy Inorganic materials 0.000 claims description 2
- 229910021483 silicon-carbon alloy Inorganic materials 0.000 claims 5
- 229910052785 arsenic Inorganic materials 0.000 claims 1
- 238000004140 cleaning Methods 0.000 claims 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims 1
- 239000011261 inert gas Substances 0.000 claims 1
- 238000010926 purge Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 238000004377 microelectronic Methods 0.000 abstract description 3
- -1 Si-Ge-C) Chemical compound 0.000 abstract 1
- 238000005229 chemical vapour deposition Methods 0.000 description 19
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 18
- 235000012431 wafers Nutrition 0.000 description 18
- 229910005705 Ge—B Inorganic materials 0.000 description 15
- 125000004429 atom Chemical group 0.000 description 10
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- 229910008310 Si—Ge Inorganic materials 0.000 description 7
- 230000007547 defect Effects 0.000 description 7
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 6
- QUZPNFFHZPRKJD-UHFFFAOYSA-N germane Chemical compound [GeH4] QUZPNFFHZPRKJD-UHFFFAOYSA-N 0.000 description 6
- 229910052986 germanium hydride Inorganic materials 0.000 description 6
- 230000003746 surface roughness Effects 0.000 description 6
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- 238000012545 processing Methods 0.000 description 5
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910010271 silicon carbide Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 229910018540 Si C Inorganic materials 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 229910000078 germane Inorganic materials 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 2
- 241000233805 Phoenix Species 0.000 description 2
- 229910003811 SiGeC Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000001451 molecular beam epitaxy Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
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- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
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- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910003818 SiH2Cl2 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910008423 Si—B Inorganic materials 0.000 description 1
- 229910006367 Si—P Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000001015 X-ray lithography Methods 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000001505 atmospheric-pressure chemical vapour deposition Methods 0.000 description 1
- ONRPGGOGHKMHDT-UHFFFAOYSA-N benzene-1,2-diol;ethane-1,2-diamine Chemical compound NCCN.OC1=CC=CC=C1O ONRPGGOGHKMHDT-UHFFFAOYSA-N 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
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- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- MEUKEBNAABNAEX-UHFFFAOYSA-N hydroperoxymethane Chemical compound COO MEUKEBNAABNAEX-UHFFFAOYSA-N 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
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- 230000000873 masking effect Effects 0.000 description 1
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- 238000000206 photolithography Methods 0.000 description 1
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- 239000002244 precipitate Substances 0.000 description 1
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- 238000005001 rutherford backscattering spectroscopy Methods 0.000 description 1
- 238000001004 secondary ion mass spectrometry Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
- H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/16—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only elements of Group IV of the Periodic Table
- H01L29/161—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only elements of Group IV of the Periodic Table including two or more of the elements provided for in group H01L29/16, e.g. alloys
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02367—Substrates
- H01L21/0237—Materials
- H01L21/02373—Group 14 semiconducting materials
- H01L21/02381—Silicon, silicon germanium, germanium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02436—Intermediate layers between substrates and deposited layers
- H01L21/02439—Materials
- H01L21/02441—Group 14 semiconducting materials
- H01L21/0245—Silicon, silicon germanium, germanium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02524—Group 14 semiconducting materials
- H01L21/02529—Silicon carbide
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02524—Group 14 semiconducting materials
- H01L21/02532—Silicon, silicon germanium, germanium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/76—Making of isolation regions between components
- H01L21/762—Dielectric regions, e.g. EPIC dielectric isolation, LOCOS; Trench refilling techniques, SOI technology, use of channel stoppers
- H01L21/7624—Dielectric regions, e.g. EPIC dielectric isolation, LOCOS; Trench refilling techniques, SOI technology, use of channel stoppers using semiconductor on insulator [SOI] technology
- H01L21/76251—Dielectric regions, e.g. EPIC dielectric isolation, LOCOS; Trench refilling techniques, SOI technology, use of channel stoppers using semiconductor on insulator [SOI] technology using bonding techniques
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S148/00—Metal treatment
- Y10S148/059—Germanium on silicon or Ge-Si on III-V
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S148/00—Metal treatment
- Y10S148/15—Silicon on sapphire SOS
Definitions
- the present invention relates to silicon-germanium-based compositions comprising silicon, germanium, and carbon (Si-Ge-C), methods for growing Si-Ge-C epitaxial layer(s) on a substrate, etchants especially suitable for Si-Ge-C etch-stops, and novel methods of use for Si-Ge-C compositions.
- the present invention relates to Si-Ge-C compositions, especially for use as etch-stops, related processes and etchants useful for microelectronic and nanotechnology fabrication.
- etching we remove a film or layer from a substrate, in some instances defining the layer to be removed by photolithography.
- One way to etch is to immerse the substrate in a bath of some chemical that attacks the fim.
- the chemical should react with and etch the film or layer in a smooth and reproducible manner, producing soluble products that can be carried away from the substrate.
- an ideal etchant will not attack any layer underneath the film being etched, so that the etch process will be self-limiting.
- the etching is often not self-limiting and therefore goes below the desired depth. Etch-stops are designed to address this problem.
- Semiconductors have the interesting property that when they are alloyed with certain elements, the rate of wet chemical etch in the alloy will vary from that of the unalloyed semiconductor. Alloys with different etch rates can be used to cause etching to slow at a pre-defined interface. Typically, a layer with a particular composition etches at a known rate in a etchant. A second adjacent layer may etch at a different rate because it has a different composition. The layer with the lower etch rate is often referred to as the etch-stop layer.
- Etch-stops are used to fabricate devices for a wide variety of applications. Membranes and diaphragms formed via etch-stops are used in sensors such as pressure transducers, as elements in experimental x-ray lithography systems, as windows for high energy radiation, and as low thermal mass supports for microcalorimeter and bolometric radiation detectors. Additional uses for selective etch-stops are in micromachining applications such as accelerometers, gears, micro-beams, miniature fluid lines, pumps and valves, and in flow sensors. Another application with a potentially large commercial market is in fabricating silicon-on-insulator (SOI) substrates by the bond-and-etch-back silicon-on-insulator (BESOI) process.
- SOI silicon-on-insulator
- BESOI bond-and-etch-back silicon-on-insulator
- Silicon-based selective chemical etch-stop layers such as Si-B, Si-Ge, Si-Ge-B, Si-P, and Si-As have major problems and disadvantages which are overcome by the present invention.
- the disadvantages can be illustrated by examining examples pertaining to the commonly used Si-Ge-B etch-stops.
- the specially doped layer e.g. Si-Ge-B
- the lightly doped silicon have limited selectivity. Selectivity is defined as the etch rate of lightly doped silicon divided by the etch rate of the etch-stop layer, or in some cases its reciprocal as discussed below. Limited selectivity increases the manufacturing cost by creating a need for tightly controlled, and sometimes labor-intensive processing to prevent the etch from going beyond the intended depth.
- lightly doped means less than approximately 1E17 dopant atoms per cm 3
- heavily doped means more than approximately IE 19 dopant atoms per cm 3 .
- etch-stop compositions especially those containing a high boron concentration, are they leave an insoluble staining residue on the surface of the substrate. This residue both roughens and contaminates the substrate surface.
- Increasing the KOH concentration of the etch solution for example, from 21 wt% to 40 wt% will eliminate the surface staining, but also substantially decreases the etch selectivity.
- conventional formulations of 1 :3 :8 and 1:3:12 parts by volume of HF-HNO 3 -CH 3 COOH (HNA) etch lightly doped silicon somewhat less rapidly than heavily doped silicon and are therefore used to preferentially remove etch-stop layers.
- selectivity is defined as the etch rate of etch-stop layer divided by the etch rate of the lightly doped silicon.
- Figure 2 A illustrates the boron (21) and germanium (22) concentration profiles in the substrate (23), the etch-stop layer (24), and in the device layer (25) after epitaxial layer growth and before the bonding anneal.
- Figure 2B shows the changed boron (26) and germanium (27) concentration profiles after the bonding anneal. Because boron diffuses through the material faster than germanium during the bonding anneal, its profile is broadened such that significant "diffusion tails" extend from the etch-stop layer into the substrate (23) and the device layer (25). In a BESOI structure the boron diffusion tail causes an unacceptable level of electrically active dopant to exist in the device layer (25).
- a Si-Ge-C alloy film was purportedly formed on the substrate by a thermal CVD method.
- methane at the stated process temperature is far too stable to fiinction as a carbon source for thermal CVD formation of the silicon-germanium-carbon film.
- Furukawa et al. do not recognize or discuss the use of Si-Ge-C as an etch-stop.
- This invention describes a silicon-based etch-stop which is composed of an alloy containing silicon, germanium and carbon (Si-Ge-C).
- this alloy demonstrates etch selectivity of 8000 to 1 compared with lightly doped silicon. High etch selectivity is demonstrated for both the case in which the Si-Ge-C epitaxial layer acts as the etch-stop, and for the opposite case in which the Si-Ge-C layer is preferentially removed.
- This invention further describes a method by which the etch-stop layer is grown epitaxially and with excellent crystal quality by CVD onto a silicon substrate.
- One or more high quality, undoped or deliberately doped epitaxial silicon-based layers can be grown before and/or after the etch-stop layer.
- This invention further describes an innovative range of etch solution compositions which, combined with the unique composition of the etch-stop layer, enhance the selectivity for removal of the etch-stop layer by more than two orders of magnitude over previous processes for etch-stop layer removal, and compared with previous formulations, provide an etch rate which varies far less with time. Further advantages will be apparent from the following description of the preferred embodiments.
- Figures 1A-B are cross-sections illustrating surface roughness of conventional etch-stop layers.
- Figures 2A-B are graphs illustrating the dopant diffusion tail that is common with conventional etch-stop layers.
- Figure 3 is a perspective view illustrating a SOI substrate.
- Figures 4A-F are cross-sections illustrating a BESOI process using an etch-stop layer.
- Figures 5A-B are cross-sections illustrating reduced surface roughness with a Si-Ge-C etch-stop layer.
- Figures 6 A-B are graphs illustrating the absence of an electrically active dopant tail with a Si-Ge-C etch-stop layer.
- Figures 7A-F are ball-and-stick representations of crystal structure illustrating the effect of carbon and germanium atoms on stress in silicon alloys.
- Figure 8 is a graph illustrating the superior etch selectivity of Si-Ge-C in KOH-H 2 O compared with Si-Ge-B.
- Figure 9 is a graph illustrating the superior etch selectivity of Si-Ge-C in HNA compared with Si-Ge-B.
- Figures 10A-C are cross-sections illustrating a process for making a membrane using an etch-stop layer
- Figures 11A-C are cross-sections illustrating a process for making a cantilever beam using an etch-stop layer.
- Figure 11D is a perspective view illustrating the cantilever beam formed using the process of Figures 11A-C.
- BESOI Fabrication One important application of the present invention is in fabricating BESOI substrates.
- BESOI is used for advanced integrated circuit applications in which the device semiconductor layer (31) shown in Figure 3 is isolated from the base wafer (32) by an insulating layer (33).
- the following description illustrates advantages of the invention.
- An embodiment of a BESOI process is illustrated in Figures 4A-F.
- BESOI fabrication starts with two substrates, a base wafer (32) of a silicon wafer which can be either a lightly or heavily doped silicon wafer doped with either P-type or N-type dopant, such as boron or phosphorous, and a device wafer (41) of lightly doped silicon wafer of either of the same P-type or N-type dopants, and preferably a P-type dopant, such as boron.
- a Si-Ge-C layer (42) is grown epitaxially onto the device wafer (41), and a device epitaxial silicon layer (31) is grown epitaxially onto the Si-Ge-C layer.
- the Si-Ge-C layer (42) is 50-500 nm thick, is preferably 75-200 nm thick, and is most preferably about 100 nm thick.
- the Si-Ge-C layer (42) includes 2-6 atomic percent carbon, preferably 4-5 atomic percent carbon, and most preferably about 4.5 atomic percent carbon, and includes 18-65 atomic percent germanium, preferably 35-50 atomic percent germanium, and most preferably about 40 atomic percent germanium.
- the device silicon epitaxial layer (31) is 500-2000 nm thick, is preferably 100-150 nm thick, and is most preferably about 120 nm thick, and contains electrically active dopant of the P-type or N-type in the range of 1E13-1E19 atoms per cm 3 , preferably 1E14-1E18 atoms per cm 3 , and most preferably about 1E15 atoms per cm 3 .
- thermal oxide layers (43, 44) shown in Figure 4B are grown by a conventional technique such as exposing the surface of either one or preferably both of the wafers (32, 41) to water vapor at 800-1000°C for about 5-300 minutes.
- W. S. Ruska, Microelectronic Processing (1987) describes such conventional techniques and is hereby incorporated by reference in its entirety.
- the base wafer oxide layer (43) thickness is 50-1000 nm, preferably 100-500 nm, and most preferably about 200-300 nm.
- the device wafer oxide (44) thickness is 20-100 nm, preferably 40-70 run, and most preferably about 50-60 nm.
- the oxide layer thickness is preferably less on the device wafer (41) than on the base wafer (32) so that the thermal oxidation step will not diffuse or precipitate the carbon out of the Si-Ge-C layer.
- the next step is to invert the device wafer (41) and to bond it to the base wafer (32) by contacting the respective oxide surfaces (44, 43) firmly together to form an oxide layer (33) as shown in Figure 4C.
- Figure 4D illustrates that in the next step most of the device wafer (41) is removed by lapping or grinding, and optionally polished by a conventional technique to form a sacrificial silicon layer (43).
- the thinning is preferably stopped when approximately 10 to 50 micrometers of the sacrificial layer (43) remains over the etch-stop layer (42).
- Figure 4E illustrates the structure after the first selective etch step in which the final 10 to 50 micrometers of the sacrificial layer (43) is removed using a chemical solution such as 10 to 45 wt% and preferably 21 wt% KOH-H 2 O, and in a temperature range of from 50 to 100°C, and preferably at about 70°C, which will etch the sacrificial layer (43), but will substantially stop etching when it reaches the etch-stop layer (42).
- a chemical solution such as 10 to 45 wt% and preferably 21 wt% KOH-H 2 O
- Figure 4F illustrates the result of the final etch step in which the etch-stop layer (42) shown in Figure 4E is removed using a chemical solution such as HNA at room temperature which etches the Si-Ge-C layer rapidly, but essentially stops etching when it reaches the lightly doped epitaxial device layer (31).
- the final structure, shown also in Figure 3, is the lightly doped epitaxial device layer (31) separated from the substrate (32) by the insulating oxide (33).
- Figures 5 A-B illustrate how the present invention solves the surface roughness problem involved in BESOI processing by the conventional method shown in Figure 1B.
- Figure 5A again shows a solution of KOH-H 2 O (11) will rapidly etch lightly doped silicon (12). Again if a small particle (13) adheres to the surface of the lightly doped silicon (12), the etch rate is locally retarded under the particle (13), and the slow etching planes (14) on the (111) plane form as the particle (13) is undercut by the etch solution. However, in the present invention, the resulting pyramidal defect will no longer propagate into the etch-stop layer (15) because of the improved selectivity of the etch-stop layer. As shown in Figure 5B, the surface roughness (51) is substantially reduced when the etch front reaches the etch-stop layer (15) due to the pyramidal defects being substantially etched away before the etch front significantly proceeds into the etch-stop layer (15).
- One aspect of the present invention is that we have discovered a method to grow Si-Ge-C layers epitaxially by a commercially viable CVD method onto silicon at temperatures that are low enough to "quench" carbon into the epitaxial layer.
- Low temperature is important because whereas the germanium-silicon system exhibits complete solid solubility, carbon is nearly insoluble in silicon.
- the maximum solubility of carbon in silicon is about 1 part per million at the melting point of silicon.
- the epitaxial layer growth takes place at a low enough temperature so that the carbon atoms are essentially immobile in the silicon lattice.
- the growth temperature is preferably less than about 800°C.
- the following process produces Si-Ge-C epitaxial layers with 42 atomic percent germanium, 5 atomic percent carbon, and a low defect density.
- a lightly doped, P-type (100) 200 mm diameter prime silicon substrate is cleaned and loaded into a CVD reactor using a robotic transfer arm.
- a suitable reactor for this application is an Epsilon One, Model E-2, manufactured by ASM America, Phoenix Arizona. Initially, the reactor temperature is held in the range from 25-900°C, preferably 800-900°C, and most preferably about 850°C.
- Hydrogen gas is introduced into the reactor at preferably atmospheric pressure, or at reduced pressure of, for example, 5-100 torr, at a flow rate of 10-100 standard liters per minute (slm), preferably 15-40 slm, most preferably about 20 slm.
- the substrate is heated to 1000-1200°C, preferably to 1100-1190°C, and most preferably to about 1150°C.
- the reactor is most preferably held at about 1150°C for 30 to 600 seconds, preferably 60 to 300 seconds, and most preferably about 90 seconds to remove the native oxide layer from the substrate.
- the substrate is then cooled to 900oC in the H 2 atmosphere before the deposition of silicon.
- the substrate is cooled still further, and at 550-750°C, preferably 600-700°C, and most preferably about 625°C the low flowrate of GeH 4 is increased over a span of 15 seconds to a final flowrate of from 1.0 to 20.0 seem, preferably 1.4 to 5.0 seem, and most preferably about 1.8 seem.
- C 3 H 6 cyclopropane
- the low flowrate of cyclopropane is increased over a span of 15 seconds to a final flowrate of from 50 to 200 seem, preferably 75 to 150 seem, and most preferably about 100 seem.
- All final gas flowrates are then held constant for 1 to 100 minutes, preferably 5 to 10 minutes, and most preferably about 6.5 minutes while a Si-Ge-C layer of approximately 200 nm thickness is grown.
- the reactor is purged with 20 slm of pure H 2 for about 45 seconds. Afterward the robotic transfer arm removes the substrate from the reactor.
- an alkene such as ethylene can be substituted for cyclopropane in a similar process.
- the reasons for the above process improvements are as follows.
- the surface of silicon forms a tenacious silicon dioxide (SiO 2 ) when exposed to air.
- This oxide is removed from silicon during heating in hydrogen to high temperature such as 1150°C, but the oxide tends to reform when the silicon surface is exposed to trace amounts of oxygen or water vapor at lower temperature.
- the GeH 4 concentration is held low and ramped up quickly to keep the thickness and stress of the layer well below the critical thickness for formation of misfit dislocations.
- the C 3 Hg flowrate is ramped from a low value to the final value for a totally different reason.
- the best crystalline quality is obtained by starting the Si-Ge-C deposition with a low concentration of hydrocarbon and then ramping the flowrate up until the desired carbon concentration is obtained.
- the reason may be related to the low solubility of carbon in silicon.
- Starting the Si-Ge-C deposition with a low surface concentration of carbon may be important in establishing a steady-state growth process in which carbon is incorporated in non-equilibrium concentrations into the silicon-germanium lattice.
- An economical epitaxial layer growth process is important if the epitaxial single Si-Ge-C layers are to be used for commercial applications.
- the process which we discovered can be operated in a commercial CVD epitaxial reactor, at rates sufficiently high that the Si-Ge-C layers can be produced at prices comparable to present epitaxial silicon layers.
- a suitable reactor for this application is again the Epsilon One, Model E-2, manufactured by ASM America, Phoenix Arizona.
- the reactor can be configured for single wafer, automated processing using vacuum-compatible load lock ports and a nitrogen-purged robotic wafer transfer chamber. The load lock ports and the wafer transfer chamber effectively isolate the process chamber from atmospheric contamination.
- Evacuation of the load lock ports is important to prevent air from entering the process chamber and to remove adsorbed moisture from the surfaces of the substrates before processing.
- High purity materials are important for low temperature, defect-free production of epitaxial Si-Ge-C layers.
- Hydrogen and nitrogen liquid sources having impurity levels less than 10 parts per billion (ppb) can be obtained from Air Products & Chemicals, Inc., in Allentown, PA.
- Dichlorosilane gas of Ultraplus grade can be obtained from Praxair, in Kingman, AZ; and a 1:99 volume ratio and a 10:90 volume ratio of germane:hydrogen of Megabit grade can be obtained from Solkatronic Chemicals, in Fairfield, NJ.
- the 10:90 volume ratio of cyclopropane:helium of semiconductor grade can be obtained from Air Products & Chemicals.
- the hydrogen, nitrogen, germane and cyclopropane gases can be further purified by point-of-use Nanochem purifiers made by Semi-Gas Systems, in Santa Clara, CA.
- Si-Ge-C etch-stop over the most commonly used Si-Ge-B etch-stop is that all three components of the Si-Ge-C alloy are isoelectronic, i.e., none supplies an electrically active dopant. Thus, if there is slight diffusion of one of the elements into the silicon device layer, the electrically active dopant concentration will not be affected. Further, since germanium and carbon affect the band structure and bandgap of silicon, it will be advantageous for some applications to leave the Si-Ge-C etch-stop layer in place to become part of the device structure.
- Figures 6 A-B illustrate the point.
- Figure 6 A illustrates carbon (61) and germanium (62) concentration profiles over a substrate (63), on which an epitaxial Si-Ge-C etch-stop layer (64) and a lightly doped device layer (65) have been epitaxially grown before a bonding anneal.
- This structure represents the starting point for a BESOI process, which can be compared to the Si-Ge-B structure shown in Figures 2 A-B.
- the boron concentration (66) is deliberately low throughout the concentration profile.
- the substrate (63) is shown with a boron concentration of about 1E17 atoms per cm 3
- the epitaxial layers (64, 65) are grown with a boron concentration of about 2E15 atoms per cm 3 .
- Figure 6B shows the concentration profiles after the bonding anneal.
- the carbon (67) and boron (68) profiles broaden during the anneal due to diffusion.
- the carbon (69) in the device layer (65) of Figure 6B does not contribute electrical carriers and the substrate boron diffusion tail (70), residing in the etch-stop layer (64), does not contribute electrical carriers to the device layer (65).
- the present invention also permits strain control in the Si-Ge-C layer.
- Germanium and carbon atoms both differ in size from silicon.
- the fourfold covalent atomic radius of germanium is about 5% larger than silicon, whereas carbon is about 50% smaller.
- the effects of germanium and carbon addition to silicon are shown schematically in Figures 7A-F.
- In undoped silicon there is naturally occurring spacing (71) between the silicon atoms represented as solid dots in Figure 7A.
- the lattice parameter or atomic spacing (72) in the crystalline structure is increased by the larger germanium atoms represented by the large white dots in Figure 7B.
- carbon atoms represented by the small grey dots are added to silicon the atomic spacing (73) is decreased as shown in Figure 7C.
- the epitaxial layer includes Ge and C in a ratio defined by: (atomic radius Si - atomic radius C)/(atomic radius Ge - atomic radius Si), about 9:1 Ge:C, the epitaxial layer will have similar atomic spacing (71) to undoped silicon and be free of stress as shown in Figure 7F. In this case, the epitaxial layer-substrate interface remains free of misfit dislocations.
- Si-Ge-C layers that (1) are strain-free, or (2) have strain that is grown-in to a pre-defined level, or (3) have lattice parameter misfit at so high a level as to cause misfit dislocations to form.
- fabricating of a cantilever beam in an accelerometer application is an example in which the layer should be grown stress free so that the beam will not be bowed.
- a Si-Ge-C layer is to be made into a membrane
- a slightly tensile stress created by increasing the carbon-to-germanium ratio, is desirable so that the membrane will be smooth and "tight".
- both strain and composition are means by which the bandgap and band structure can be varied for particular applications.
- the above-referenced interface misfit stress can be measured in any of several ways.
- One is to measure the interatomic spacing of a Si-Ge-C layer grown epitaxially onto a silicon substrate, in the direction perpendicular to the substrate surface, by precision X-ray diffraction. As long as the critical stress for formation of misfit dislocations has not been exceeded, the difference in lattice parameter between the epitaxial layer and the substrate is proportional to the stress in the grown layer.
- Another method is to measure the bow of a silicon substrate before and after depositing the epitaxial Si-Ge-C layer. The change in bow is related by a simple formula to the stress in the Si-Ge-C layer (P. Singer, "Film Stress and How to Measure It", Semiconductor International. October 1992, p. 58, which is incorporated by reference in its entirety).
- Si-Ge-C having high etch selectivity As Figures 8 and 9 illustrate the etch selectivity of the Si-Ge-C epitaxial layer is much higher than that of Si-Ge-B in both KOH-H 2 O and HNA etch solutions.
- the etch selectivity of Si-Ge-C in 21 wt% KOH-H 2 O is plotted against carbon content in the epitaxial layer, with the etch selectivity of a Si-Ge-B layer having 1E21 atoms per cm 3 of Ge and 2E20 atoms per cm 3 of B is shown on the left side of Figures 8 and 9 for comparison.
- the germanium content of the carbon-containing etch-stop layers increases approximately in proportion to the carbon content to compensate strain, in atomic percent as follows:
- etch selectivity in KOH-H 2 O is defined as the etch rate of lightly doped silicon divided by the etch rate of the etch-stop layer.
- Figure 8 is a graph of the selectivity of Si-Ge-C and Si-Ge-B etch stops with respect to lightly doped silicon.
- a selectivity of 8000: 1 in 21 wt% KOH-H 2 O at 70°C has been measured by employing black wax to mask the etch-stop layer before exposing to the etchant, measuring the resultant step in the etch-stop layer and comparing that distance against the etch depth in lightly doped silicon under the same etchant.
- the selectivity of the Si-Ge-C etch-stop is apparently higher than that of SiO 2 and is a significant improvement over Si-Ge-B which shows a maximum selectivity of 2000: 1 under the same conditions.
- Figure 9 compares the etch selectivity of Si-Ge-B and Si-Ge-C as a function of carbon concentration in five HNA solutions. For etch-stop removal in HNA, etch selectivity is defined as the etch rate of the etch-stop layer divided by the etch rate of lightly doped silicon. Figure 9 illustrates that in HNA solution, the selectivity of the etch-stop layer is enhanced by two innovations.
- the five HNA solutions are prepared from standard aqueous reagents which are as follows: 49 wt% HF, 70 wt% HNO 3 , and 99 wt% CH 3 OOH.
- selectivity increases with carbon content, reaching a maximum selectivity at about 4 atomic percent carbon.
- selectivity increases as the HNO 3 content of the HNA solution decreases, reaching maximum selectivity of more than 800:1 with the HF:HNO 3 :CH 3 COOH volume ratio of 1:0.3: 12 and 4 atomic percent carbon.
- a further benefit of reducing the HNO 3 concentration in the HNA solution is that the solution is stable against the chemical reduction of HNO 3 to HNO 2 , a problem that plagues users of the conventional 1:3:8 and 1 :3:12 HNA compositions. It is an important advantage that our etch solutions remain colorless and etch selectivity is independent of time for etch times of 30 minutes or more (1 :3:8 and 1 :3: 12 HNA solutions turn yellow and lose selectivity rapidly over the first few minutes of use). We discovered that the novel HNA formulations also will increase the etch selectivity of Si-Ge-B as the HNO 3 concentration of the solution is decreased reaching a maximum of 50.
- the unique properties of the Si-Ge-C etch-stop layers combined with the new HNA etch compositions are suggested by the behavior of the Si-Ge-C surface in the etch solution.
- the etch solution is believed to work by simultaneously oxidizing the surface (performed by the HNO 3 ) and etching the oxide (performed by the HF).
- Si-Ge-C surfaces are hydrophilic when they emerge from the HNA solutions for all etch compositions from 1 :3 : 12 to 1 :0.1 : 12 in contrast to lightly doped Si with hydrophobic surfaces, indicating that the oxide removal performed by HF dominates the etching rate of Si-Ge-C layers.
- etch selectivity in HNA when the silicon is in the range of 50 to 90 atomic percent, the germanium is in the range of 9 to 50 atomic percent, and the carbon is in the range of 1 to 10 atomic percent, preferably in the range of 3 to 6 atomic percent. More preferably, the Si-Ge-C is in the range for Si, Ge and C of 50-60 atomic percent, 36-45 atomic percent, and 4-5 atomic percent, respectively.
- Si-Ge-C compositions are: silicon in a range of 0 to 99.9 atomic percent, preferred 45 to 83 atomic percent, further preferred about 55.5 atomic percent, germanium in a range of 1 to 92 atomic percent, preferred 15 to 50 atomic percent, and further preferred about 40 atomic percent, and carbon in the range of 0.1 to 10 atomic percent, preferred 2 to 6 atomic percent, and further preferred about 4.5 atomic percent.
- Si-Ge-C Etch-Stop in Nanotechnology Applications
- FIGS 10A-C One example of silicon membrane fabrication is illustrated in Figures 10A-C.
- Si-Ge-C layer (101) is epitaxially grown onto a lightly doped, conventional polished silicon substrate (102).
- a lightly doped, conventional polished silicon substrate (102) Favorable results can be achieved by using the processes described earlier in the section on epitaxial growth of Si-Ge-C layers by CVD on silicon.
- the silicon substrate (102) and Si-Ge-C layer (101) form a structure which is inverted as shown in Figure 10B and an oxide layer (104) is formed on the back side of the silicon substrate (102).
- a positive photoresist (not shown) is applied to the oxide layer (104), and then exposed through openings in the mask.
- the exposed and developed photoresist is removed and then the underlying exposed oxide layer is removed with a conventional HF solution.
- the exposed portion of the back side of the silicon substrate (102) is etched by a 21 wt% KOH-H 2 O etchant that rapidly removes the lightly doped silicon substrate (102) as indicated by surface ( 103) formed during an intermediate stage of the etch, but then etches at a slower rate when it reaches the Si-Ge-C (101) as shown in Figure 10C.
- the Si-Ge-C layer (101) remains as a membrane supported by a silicon substrate frame (105) defined the remaining portions of the silicon substrate (102).
- the carbon-to-germanium ratio in the etch-stop layer is adjusted so that the Si-Ge-C membrane (101) is preferably in tension. This ensures that the membrane (101) is "tight" and well supported by the frame (105).
- FIG. 11 A Another example of a micromechanical application of a Si-Ge-C epitaxial etch-stop layer is in fabricating a cantilever beam as illustrated in Figures 11 A-C.
- a Si-Ge-C etch-stop layer (111) and a lightly doped silicon layer (112) are grown onto a silicon substrate (113).
- a masking oxide (114) shown in Figure 11B is grown and patterned using a technique like that used in the membrane fabrication, and the exposed portion of the lightly doped silicon (112) is etched by a 21 wt% KOH-H 2 O etchant that rapidly removes the lightly doped silicon but etches very slowly when it reaches the Si-Ge-C layer (111).
- the Si-Ge-C layer (111) is etched by HNA that rapidly removes the exposed Si-Ge-C layer (111) as shown in Figure 11C, but only etches lightly doped silicon very slowly.
- the cantilever beam (115) formed from the lightly doped silicon layer (112) is freed from the surrounding silicon substrate.
- Figure 1 ID is a perspective drawing showing the finished cantilever beam (115) attached to the rest of the lightly doped silicon layer (112) at one end.
- Other precision micro-miniature structures can be fabricated using processes like this.
- Thin heteroepitaxial films of Si 1-x-y Ge x C y have been grown on (100)Si substrates using atmospheric pressure Chemical Vapor Deposition (CVD) at 625°C.
- the crystallinity, composition and microstructure of the SiGeC films were characterized using Rutherford backscattering specuometry, secondary-ion-mass-spectrometry and cross-sectional transmission electron microscopy.
- the crystallinity of the films was very sensitive to the flow rate of C 2 H 2 which served as the C source. Films with up to 2% C were epitaxial with good crystallinity and very few interfacial defects.
- Table I Sample growth conditions in CVD system.
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Also Published As
Publication number | Publication date |
---|---|
US20020081861A1 (en) | 2002-06-27 |
EP0799495A1 (en) | 1997-10-08 |
US5906708A (en) | 1999-05-25 |
EP0799495A4 (en) | 1999-11-03 |
US5961877A (en) | 1999-10-05 |
US6064081A (en) | 2000-05-16 |
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