WO2008023748A1 - Procédé pour formation d'un film d'oxyde et appareil pour le procédé - Google Patents
Procédé pour formation d'un film d'oxyde et appareil pour le procédé Download PDFInfo
- Publication number
- WO2008023748A1 WO2008023748A1 PCT/JP2007/066312 JP2007066312W WO2008023748A1 WO 2008023748 A1 WO2008023748 A1 WO 2008023748A1 JP 2007066312 W JP2007066312 W JP 2007066312W WO 2008023748 A1 WO2008023748 A1 WO 2008023748A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- oxide film
- gas
- light
- substrate
- ozone
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 109
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 31
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 105
- 239000000758 substrate Substances 0.000 claims abstract description 88
- 230000008569 process Effects 0.000 claims abstract description 74
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims description 207
- 238000012545 processing Methods 0.000 claims description 47
- 239000002994 raw material Substances 0.000 claims description 42
- 229910052710 silicon Inorganic materials 0.000 claims description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000010703 silicon Substances 0.000 claims description 26
- 230000002829 reductive effect Effects 0.000 claims description 11
- 239000011261 inert gas Substances 0.000 claims description 7
- 230000001678 irradiating effect Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 230000003111 delayed effect Effects 0.000 claims description 5
- 239000000203 mixture Substances 0.000 abstract description 5
- 239000010408 film Substances 0.000 description 168
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 44
- 238000010586 diagram Methods 0.000 description 21
- 238000007254 oxidation reaction Methods 0.000 description 21
- 230000003647 oxidation Effects 0.000 description 20
- 125000004430 oxygen atom Chemical group O* 0.000 description 19
- 239000013067 intermediate product Substances 0.000 description 15
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000005281 excited state Effects 0.000 description 11
- 230000007423 decrease Effects 0.000 description 10
- 238000000151 deposition Methods 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- 239000010409 thin film Substances 0.000 description 10
- 230000008021 deposition Effects 0.000 description 9
- 238000009826 distribution Methods 0.000 description 9
- 230000006378 damage Effects 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000006557 surface reaction Methods 0.000 description 4
- 238000011144 upstream manufacturing Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 230000005283 ground state Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000008832 photodamage Effects 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- 238000004050 hot filament vapor deposition Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 235000011470 Adenanthera pavonina Nutrition 0.000 description 1
- 240000001606 Adenanthera pavonina Species 0.000 description 1
- 101100061513 Arabidopsis thaliana CSI3 gene Proteins 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- DSPMXOXIEZFNIQ-UHFFFAOYSA-N O[SiH2]N[SiH3] Chemical compound O[SiH2]N[SiH3] DSPMXOXIEZFNIQ-UHFFFAOYSA-N 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/314—Inorganic layers
- H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
- H01L21/31604—Deposition from a gas or vapour
- H01L21/31608—Deposition of SiO2
- H01L21/31612—Deposition of SiO2 on a silicon body
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- H01—ELECTRIC ELEMENTS
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- 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
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/02227—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process
- H01L21/0223—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate
- H01L21/02233—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate of the semiconductor substrate or a semiconductor layer
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/401—Oxides containing silicon
- C23C16/402—Silicon dioxide
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/48—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating by irradiation, e.g. photolysis, radiolysis, particle radiation
- C23C16/482—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating by irradiation, e.g. photolysis, radiolysis, particle radiation using incoherent light, UV to IR, e.g. lamps
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- 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
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
- H01L21/02164—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon oxide, e.g. SiO2
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- 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
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
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- H—ELECTRICITY
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- 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
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
- H01L21/02277—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition the reactions being activated by other means than plasma or thermal, e.g. photo-CVD
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- 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
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
- H01L21/02299—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment
- H01L21/02304—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment formation of intermediate layers, e.g. buffer layers, layers to improve adhesion, lattice match or diffusion barriers
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- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/26—Bombardment with radiation
- H01L21/263—Bombardment with radiation with high-energy radiation
- H01L21/268—Bombardment with radiation with high-energy radiation using electromagnetic radiation, e.g. laser radiation
- H01L21/2686—Bombardment with radiation with high-energy radiation using electromagnetic radiation, e.g. laser radiation using incoherent radiation
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- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/312—Organic layers, e.g. photoresist
- H01L21/3121—Layers comprising organo-silicon compounds
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- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/314—Inorganic layers
- H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
- H01L21/31604—Deposition from a gas or vapour
- H01L21/31633—Deposition of carbon doped silicon oxide, e.g. SiOC
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
- H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/49—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET
- H01L29/4908—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET for thin film semiconductor, e.g. gate of TFT
Definitions
- the present invention relates to a method for manufacturing a thin film transistor used for an organic EL, a flexible display, and the like and an apparatus therefor.
- an oxide film made of SiO 2 having a film thickness of about 50 to 100 nm is mainly used as an insulating film provided on a thin film transistor on a glass or plastic substrate in a liquid crystal display or a flexible display.
- the current manufacturing process is required to be about 300 ° C or less due to the limitation of the heat resistance temperature of inexpensive glass substrates (eg non-alkali glass).
- inexpensive glass substrates eg non-alkali glass.
- Non-Patent Document 1 It is necessary to calcinate in C for about 2 hours, it is difficult to reduce the film thickness for high performance, and the carbon impurity concentration in the film increases by an order of magnitude when the film formation temperature is lowered to 200 ° C in the future.
- Next-generation TFTs need to realize stable transistor characteristics as devices with high electron mobility and low threshold voltage. This is the power of how to improve the quality of the gate insulating film.
- the first insulating film is formed by low-temperature thermal oxidation of silicon. Since the thermal oxidation rate is very low at a low temperature of 300 ° C or less, plasma oxidation or photooxidation using plasma or light is used as an alternative to heat.
- the second insulating layer (upper layer) is formed by a high-density high-frequency plasma CDV D method that secures withstand voltage and achieves low leakage current, and does not damage the oxide film and interface of the first layer.
- the oxide film of the first layer is not used, when a photo-oxide film having a force of 2 nm having an interface state density of 1 ⁇ 10 U [cm 2 / eV] is formed, 4 ⁇ 10 10 [cm 2 / eV ] To decrease.
- a processing time of about 2 minutes is required for plasma oxidation at 300 ° C for 10 minutes to form a 2 nm thermal oxide film. Both processes are expected to require additional processing time at 200 ° C. Therefore, when using a two-layer structure, it is necessary to minimize the reduction in throughput.
- Patent Document 1 a method of depositing a SiO film near room temperature by irradiating an ultraviolet light such as an excimer lamp in an O atmosphere containing a source gas composed of organic silicon is also disclosed (Patent Document 1).
- TEOS tetraethoxysilane
- the irradiation of the ultraviolet light is conducted toward the substrate, vapor phase
- the photons that are not absorbed in the step are irradiated onto the substrate material through the silicon thin film.
- OA-10 manufactured by JEOL Glass
- JEOL Glass which is a typical substrate for low-temperature polysilicon thin film transistors, absorbs light with a wavelength shorter than 250 nm, so that light damage is introduced into the substrate.
- light irradiation may cause problems such as a decrease in adhesion between the substrate and the silicon thin film.
- plastics that absorb more ultraviolet light than glass and exhibit severe photodegradation.
- Non-Patent Document 5 and Non-Patent Document 6 As for the film quality, at 300 ° C or lower, as with the film formed by plasma CVD, hydrogen and carbon remain as impurities in the film, resulting in a porous structure. It has been reported that the film has a large amount of leakage current that is lower than the low value (3.9) and has insulating properties (Non-Patent Document 5 and Non-Patent Document 6).
- Non-Patent Document 1 Yukihiko Nakata et al., Sharp Technical Report, 80, 31 (2001)
- Non-Patent Document 2 Shuji Ohzono et al., “Applied Physics”, Vol. 73, No. 7, pp. 0935—0938 (20 04)
- Non-Patent Document 3 Yukihiko Nakata et al., Journal of the Japan Vacuum Association, “Vacuum”, 47, 5, pp. 357 (2004) Patent Document 1: JP 2001-274155 A
- Non-Patent Document 4 Shareef et al., J. Vac. Sci. Techol. B14, 744 (1996)
- Non-Patent Document 5 A. M. Nguyen, J. Vac. Sci. Technol. B8533 (1999)
- Non-Patent Document 6 HU Kim, and SW Rhee, J. Electrochem. Soc. 147 (2000 Disclosure of the invention
- the present invention has been made in view of the above circumstances, and an object thereof is an oxide film forming method capable of forming an oxide film having a good characteristic as an insulating film uniformly and at high speed on a substrate at 200 ° C. or lower, and its method In providing equipment.
- the substrate is irradiated with light in an ultraviolet region, and an oxide film is formed on the surface of the substrate by supplying a source gas composed of organic silicon and ozone gas to the substrate.
- a source gas composed of organic silicon and ozone gas to the substrate.
- the oxide film forming method of claim 2 is the method of forming the oxide film of claim 1, wherein the substrate is irradiated with light having a wavelength longer than 210 nm as light in the ultraviolet region.
- the oxide film forming method of claim 3 is the oxide film forming method of claim 1 or 2, wherein the supply of the source gas is delayed from the supply of the ozone gas in the process of starting the formation of the oxide film.
- the oxide film formation method according to claim 4 is the oxide film formation method according to claim 3, wherein the supply of the source gas is stopped before the supply of the ozone gas is stopped in the process of completing the formation of the oxide film. .
- the oxide film forming method according to claim 5 is the same as the oxide film forming method according to claim 3 or 4, and the intensity of light in the ultraviolet region in the course of supplying the organic silicon raw material.
- the oxide film forming method according to claim 6 is the same as the oxide film forming method according to any one of claims 1 to 5, wherein the light in the ultraviolet region passes through a gas layer through which an inert gas flows. Irradiate the substrate
- the oxide film forming apparatus irradiates the substrate with light in an ultraviolet region, and forms an oxide film on the surface of the substrate by supplying a source gas made of organic silicon and ozone gas to the substrate.
- An oxide film forming apparatus in which a processing furnace in which a substrate is stored and light in an ultraviolet region is introduced, and a source gas made of organic silicon and ozone gas are mixed at room temperature. And a pipe provided to the substrate in the processing furnace, and the amount of ozone gas mixed with the raw material gas supplied to the pipe is at least equal to or more than the chemical equivalent necessary for completely oxidizing the raw material gas.
- An oxide film forming apparatus is the oxide film forming apparatus according to the seventh aspect, wherein the substrate is irradiated with light having a wavelength longer than 21 Onm as light in the ultraviolet region.
- the oxide film forming apparatus according to claim 9 is the oxide film forming apparatus according to claim 7 or 8, wherein the supply of the source gas is delayed from the supply of the ozone gas in the process of starting the formation of the oxide film. Make it.
- the oxide film forming apparatus according to claim 10 is the oxide film forming apparatus according to claim 9, wherein the supply of the raw material gas is stopped before the supply of the ozone gas is stopped in the process of ending the formation of the acid film. To stop.
- the oxide film forming apparatus according to claim 11 is the oxide film forming apparatus according to claim 9 or 10, wherein the light in the ultraviolet region has an intensity in the process of supplying the organic silicon raw material. Controlled to reduce.
- the oxide film forming apparatus is the oxide film forming apparatus according to any one of claims 7 to 11, wherein the processing furnace includes a light introducing portion that introduces light in the ultraviolet region.
- a gas layer in which an inert gas flows is interposed between the light entrance and the processing furnace, and light in the ultraviolet region is irradiated onto the substrate through the gas layer.
- the utilization efficiency of the raw material gas is increased and the manufacturing temperature is 200 ° C or lower)!
- An oxide film with excellent electrical characteristics can be formed in a huge process.
- FIG. 1 is a schematic configuration diagram of an oxide film forming apparatus according to a first embodiment.
- FIG. 3 Timing chart according to Embodiment 1 (U: ultraviolet light intensity, G: ozone gas flow rate, G:
- FIG. 4 A characteristic diagram showing the relationship between the illuminance of ultraviolet light and the deposition rate when films are deposited at deposition temperatures of 260 ° C, 200 ° C, and 150 ° C.
- FIG. 5 is a characteristic diagram showing the difference in film forming speed with and without ultraviolet light irradiation.
- FIG. 10 Characteristic diagram showing the insulating properties of oxide films deposited at deposition temperatures of 260 ° C, 200 ° C, and 150 ° C with an illuminance of ultraviolet light of 300mW / cm 2 .
- FIG. 11 Timing chart according to Embodiment 2 (U: ultraviolet light intensity, G: ozone gas flow rate, G
- FIG. 12 is a characteristic diagram showing the oxidation rate of thermal oxidation of a substrate made of hydrogen-terminated Si (100) when no source gas is introduced.
- FIG. 13 Timing chart according to Embodiment 3 (U: ultraviolet light intensity, G: ozone gas flow rate, G
- FIG. 14 Timing chart according to Embodiment 4 (U: ultraviolet light intensity, G: ozone gas flow rate, G
- FIG. 15 is a schematic configuration diagram of an oxide film forming apparatus according to Embodiment 5.
- a source gas made of organic silicon (hereinafter referred to as source gas) and Preliminary verification was made whether an oxide film could be formed at 200 ° C in a CVD process using ozone gas.
- the processing furnace used for this verification was an ordinary reduced pressure CVD furnace.
- the ozone gas was supplied and exhausted so that the gas flow direction was parallel to the surface of the Si substrate after the raw material gas was mixed in advance.
- the ozone gas produced by Meiden's ozone generator (MPOG-31002) was used.
- Several organic silicon gases (hexamethyldisilazane, tetraethoxysilane, and tetramethylsilane) were used for comparative experiments.
- the raw material gas is instantaneously intermediated (only weak bonds in the raw material gas) while flowing through the piping at room temperature after mixing with ozone.
- the intermediate product does not further react with the excess ozone gas at room temperature, and is stably supplied in this state. It became clear that this can be done (Nishiguchi et al., Japan Vacuum Association Journal “Vacuum”, 48 (5), 313 (2005)).
- the intermediate product reacts with ozone gas in an environment with a gas temperature of 200 ° C or higher, and SiO is deposited on the substrate.
- ozone in the gas phase is thermally decomposed as it moves downstream. Because of the reaction between ozone and the intermediate product, both gases decrease as they move downstream, and a finite amount of time is required from the production of the intermediate product to deposition.
- the structure of the equipment reservation of gas flow rate, gas temperature (processing temperature), ratio of raw material gas flow rate to ozone gas flow rate, etc.
- the oxide film forming method and apparatus of the present invention improve the film forming speed, improve the film quality of the CVD film including interface cleaning, and perform uniform processing when processing a large substrate. Is achieved at the same time. Specifically, by irradiating the mixed atmosphere of source gas and ozone gas with light in the ultraviolet region, particularly light having an emission line with a wavelength longer than 210 nm that does not induce photodamage damage to the substrate (hereinafter referred to as ultraviolet light), High quality oxide film with high SiO power Form.
- FIG. 1 is a schematic configuration diagram of an oxide film forming apparatus according to the present embodiment.
- the oxide film forming apparatus 1 includes a processing furnace 2, pipes 3, 4, a light source 5, and a light source 6.
- Processing furnace 2 is a horizontal laminar pressure reduction furnace.
- the processing furnace 2 stores a substrate 7 on which an oxide film is formed.
- the pipe 3 is a pipe for supplying a mixed gas composed of a raw material gas composed of organic silicon and ozone gas to the processing furnace 2.
- the raw material gas G1 and ozone gas G2 are mixed at room temperature.
- the mixing amount of ozone gas with respect to the source gas is set so as to be equal to or more than the chemical equivalent required for completely oxidizing the source gas, for example, twice or more.
- the residence time of the mixed gas composed of the raw material gas G1 and the ozone gas G2 introduced into the pipe 3 is set so as to ensure a longer time than the reaction time of both gases Gl and G2.
- the pipe 4 is a pipe for exhausting the gas in the processing furnace 2.
- a suction arch I pump (not shown) for sucking the mixed gas is connected to one end of the pipe 4.
- the light source 5 a light source that emits light in the ultraviolet region having an emission line having a continuous or discrete wavelength longer than the wavelength 21 Onm is employed.
- a UV lamp DEEP-UV lamp, lamp output 2000 W
- the light is directed toward the surface of the substrate 7 perpendicular to the gas flow.
- the illuminance of the light is adjusted in accordance with the required uniformity of the processing surface of the substrate 7 so that the fluctuation of the illuminance on the entire surface of the substrate 7 is reduced.
- the film is formed by the CVD method using ozone gas, the surface of the substrate 7 is modified, and the voltage applied to the light source 5 is controlled depending on the purpose. As a result, the illuminance of the light is adjusted, or the light source 5 is provided with an optical element to adjust the spectrum of the light.
- a light introducing plate 22 for introducing light emitted from the light source 5 is provided in the opening 21 so as to close the opening 21. Further, an optical filter 8 and a biconcave lens 9 are disposed between the light source 5 and the light introducing plate 22.
- an opening for introducing light emitted from the light source 6 into the bottom 23 of the processing furnace 20 24 is formed.
- the opening 24 is provided with a light introduction plate 25 for introducing light emitted from the light source 6 so as to close the opening 24.
- the light source 6 is a light source for heating the substrate 7, and a halogen lamp is exemplified.
- the light introduction plates 22 and 25 are formed of a material having heat resistance and light transmission exemplified by synthetic quartz.
- the diameters of the openings 21 and 25 are set to be at least larger than the maximum outer diameter of the substrate 7.
- the substrate 7 is held by a susceptor 26 made of a heat-resistant material exemplified by ceramics.
- the susceptor 26 can be moved up and down the processing furnace 2 by a stage 27.
- the stage 27 is formed with an opening 28 for supplying light from the light source 6 introduced from the light introduction plate 25 of the processing furnace 2 to the susceptor 26.
- a thermocouple 10 is connected to the susceptor 26.
- the light source 6 controls the temperature of the susceptor 26 that heats the substrate 7 by adjusting the illuminance based on the heat of the susceptor 26 transmitted to the thermocouple 10.
- the raw material gas and the ozone gas are mixed in the gas phase in the pipe 3 before being introduced into the processing furnace 2.
- the mixed gas of the organic silicon raw material and ozone gas circulates in the pipe 3 maintained at room temperature regardless of the ozone concentration for a certain time (for example, 1 second), it was almost stable as shown in the characteristic diagram of Fig. 2.
- Intermediate states (Si—O and Si with atoms other than oxygen atoms attached) and by-products such as methanol, ethanol, acetoaldehyde, carbon monoxide, carbon dioxide are generated in the gas phase.
- FIG. 6 is a characteristic diagram showing a mass composition of a product. Even if excess ozone is present, further decomposition of the organosilicon gas does not proceed, and excess ozone, intermediate products, and by-products are transported to the furnace (for example, HMDS ( Refer to the stable gas composition spectrum after mixing when using oxamethyldisilazane).
- the flow rate of the ozone gas is required to be higher than the flow rate necessary for completely decomposing the raw material gas with ozone.
- TMS tetramethylsilane
- ozone molecules with a flow rate of 16 times or more of the substrate (TMS) are required, as expected from the chemical reaction equation below.
- ultraviolet light is irradiated toward the substrate 7 through a window (light introduction plate 22) that transmits light.
- ultraviolet light (UV) irradiation is performed simultaneously with the supply of the source gas and the ozone gas at the start of the process, and stops when the supply of the source gas and the ozone gas ends.
- the intensity distribution of the illuminance of ultraviolet light is determined by the allowable fluctuation of the required film thickness of the film, but for example, in order to achieve uniform processing of ⁇ 10%, the intensity in the plane of the substrate It is only necessary that the distribution is within ⁇ 10%.
- the wavelength of light emitted from the light source 5 is a force limited to a wavelength longer than 210 nm in consideration of not inducing photodamage damage to the substrate, and the light illuminance between 210 nm and 300 nm is 50 mW / cm 2 or more.
- the illuminance distribution is not limited.
- the pressure in the processing furnace 2 should be as low as possible in order to maximize the arrival of photons to the substrate, that is, to increase the surface temperature of the silicon thin film and promote the surface reaction associated therewith.
- the pressure in the processing furnace 2 is preferably set to lOPa force, et al., 300 Pa, more specifically in the range of 10 Pa to 200 Pa, which is the process pressure of normal low pressure CVD.
- the ozone gas can be generated by using an industrial ozone generator having a concentration of 10 to 20 vol% as a generation source by discharge or the like.
- oxygen gas coexists in the light irradiation region in the processing furnace 2
- ozone gas having a concentration as high as possible for example, an ozone gas having a concentration of almost 100% introduced in JP-B-5-17164.
- the method of introducing the raw material gas can be used when introducing a low vapor pressure gas by conventional MOCVD or the like. However, for the same reason as described above, when it is introduced together with a dilution gas, it is diluted with an inert gas such as Ar or He which has a slow reaction to deactivate excited oxygen atoms to ground state oxygen atoms. It is good to introduce.
- an inert gas such as Ar or He which has a slow reaction to deactivate excited oxygen atoms to ground state oxygen atoms. It is good to introduce.
- the supply of the raw material gas is stopped only for a certain period of time at the start and end of the process, and only ozone gas is introduced and ultraviolet light irradiation is performed. It is recommended to perform interfacial thermal oxidation and surface modification of the photo-CVD film.
- Ozone gas is supplied by Meiden's ozone generator (MPOG-31002) and supplied with high purity ozone gas (concentration of 90 vol% or more), and the raw material gas is HMDS (hexamethyldisilazane) gas (no carrier gas) ) 100 sccm and 0.5 sccm, respectively, through the pipe 3 controlled to room temperature, and then mixed uniformly at a position 30 cm before the processing furnace 2. In the processing furnace 2, the gas was supplied from the side so as to be laminar. UV light manufactured by Usio Electric Co., Ltd.
- the gas phase travel distance (distance between the light introduction plate 22 and the substrate 7) is 15 mm over the light introduction plate 22 made of synthetic quartz glass from the top of the processing furnace 2.
- Light from a lamp (DEEP—UV lamp, lamp output 2000 W) was irradiated.
- the light illuminance was set to lOOmW / cm 2 on the upper surface of the quartz glass plate (the light wavelength is 210 nm to 300 nm. The illuminance is defined within this range).
- the pressure in processing furnace 2 was evacuated at a dry point so that the pressure was 130 Pa.
- Substrate 7 has a hydrogen-terminated Si (100) surface used to form an oxide film.
- Fig. 4 is a characteristic diagram showing the relationship between the illuminance of ultraviolet light and the film forming speed when films are formed at film forming temperatures of 260 ° C, 200 ° C, and 150 ° C.
- Fig. 5 is a characteristic diagram showing the difference in the deposition rate with and without ultraviolet light irradiation. According to these characteristic diagrams, the film formation rate of the oxide film on the substrate 7 is that, when light is not irradiated, the film formation hardly proceeds at 200 ° C, and the film formation rate is highly dependent on the processing temperature. Compared with, it is confirmed that it is 7-8nm / min regardless of temperature from 200 ° C to 260 ° C.
- FIG. 6 (a) shows an XPS spectrum showing signals of O (Is), Si (2s), and Si (2p).
- FIG. 6 shows the O gas in the CVD process (temperature condition 200 ° C) using the mixed gas of HMDS and ozone gas and ultraviolet light according to the embodiment of the invention (temperature condition 200 ° C) and the thermal oxidation process (temperature condition 900 ° C) in the comparative example.
- Si Si
- ⁇ 1: 4
- the amount of Si—C bonds and Si—OH bonds in the oxide film is less than lwt%.
- the absorption corresponding to the remaining carbon and hydrogen was not confirmed.
- the peak signal position is the same as the thermal oxide film. It was confirmed that the relative dielectric constant of the oxide film approaches the ideal value of 3.9 when irradiated with light.
- the illuminance was 300 mW / cm 2
- an oxide film with resistance to about 1/4 of that of the thermal oxide film was obtained immediately after deposition.
- the film thickness distribution by making the illuminance distribution on the surface of the substrate 7 uniform within ⁇ 10%, the deposited film thickness distribution was also achieved within ⁇ 10%.
- the oxide film forming process of the present embodiment it can be reduced to 0.5 sccm by using ultraviolet light having an illuminance of lOOmW / cm 2 or more.
- the mass spectrum of (1) shown in Fig. 8 when the HMDS gas flow rate is set to 0.5 sccm under irradiation of ultraviolet light with an illuminance of 300 mW / cm 2
- the mass spectrum of (2) As is clear from the comparison of the HMDS gas flow rate at 2 sccm without irradiation with ultraviolet light, the reaction by-products (for example, HO (mass 18), CO (mass 44), and mass 29 are shown.
- the amount of such alcohols (aldehydes) can be reduced. Therefore, the load on the gas processing system of the film forming process is reduced. This reduces the frequency of cleaning the processing furnace (including the optical window) provided to the gas processing system and the frequency of pump maintenance.
- FIG. 9 is an insulating oxide film formed by film made not mix insulating properties and ultraviolet light of the oxide film obtained by film formation in a combination of ultraviolet light intensity of 100mW / cm 2, 300mW / cm 2
- FIG. 6 is a characteristic diagram showing characteristics.
- Fig. 10 is a characteristic diagram showing the insulating properties of oxide films deposited at deposition temperatures of 260 ° C, 200 ° C, and 150 ° C with an illuminance of ultraviolet light of 300 mW / cm 2 . As is apparent from these characteristic diagrams, it can be confirmed that the combined use of ultraviolet light significantly improves the insulation characteristics, and that the insulation characteristics do not deteriorate significantly even when the temperature is lowered to 150 ° C.
- the oxide film forming process of the present embodiment it is possible to increase the utilization efficiency of the source gas and to form an oxide film having excellent electrical characteristics by a film forming process at 200 ° C. or lower.
- FIG. 11 shows a timing chart according to Embodiment 2 (U: ultraviolet light intensity, G: ozone gas flow rate, G: raw material gas flow rate, S: process start, E: process end).
- Embodiment 1 is a process that aligns the timing of starting and ending the supply of source gas, the supply of ozone gas, and the irradiation of ultraviolet light, whereas in the process of this embodiment, only the timing of introducing the source gas is used. Is delayed. That is, the process of this embodiment is a professional Process PI (ozone light field thermal oxidation process) that only irradiates ultraviolet light and ozone gas at the beginning of the process, and P2 (ozone light CVD process) and power that irradiates ultraviolet light and supplies ozone gas and source gas I ’ll be.
- PI ozone light field thermal oxidation process
- P2 ozone light CVD process
- ozone gas is excited by ultraviolet light. And thermal oxidation occurs by the excited state oxygen atom generated by this.
- This excited-state oxygen atom has higher oxidizing power than the ground-state oxygen atom generated by decomposition from ozone molecules. In particular, it breaks not only unsaturated bonds but also saturated bonds, gasifies as HO and CO, and cleans the surface. It is known to purify (Moon et al, J. Vac. Sci. Technol. A17, 150—154 (1999)).
- FIG. 12 is a characteristic diagram showing the oxidation rate of thermal oxidation of a substrate made of hydrogen-terminated Si (100) when no source gas is introduced.
- the substrate temperature was 200 ° C
- the ozone gas flow rate was 100 sccm
- the processing pressure was 50 Pa
- the light intensity in the range of 210 to 300 nm was 400 mW / cm 2 .
- a 3 nm thermal oxide film can be formed in about 6 minutes.
- This thermal oxide film has excellent interfacial characteristics because it has an As-grown interface state density of 1 X 10 U [ C m- 2 / eV] or less and a fixed charge density of 1 X 10 U [ C m- 2 About 10 [MV / cm], low leakage current density at low electric field, and etching resistance (high density) equivalent to thermal oxide film formed at high temperature. confirmed.
- an SiO 2 / Si interface is created in advance to thereby start the CVD process. It is possible to prevent the deposition from proceeding while the particles remaining in the furnace and impurities due to the source gas remain at the SiO 2 / Si interface at the timing.
- the adhesion with the gate electrode made of MoW or the like formed on this insulating film after the film forming process is improved, the diffusion of metal into the SiO film, and the mixing
- the supply of the source gas is stopped in the final step of the process of Embodiment 1 or 2, and a photo-ozone thermal oxide film having a higher density than the CVD film is generated on the surface of the substrate 7.
- a CVD film having a surface of about 3 nm can be modified with a few minutes of treatment, and the density can be increased particularly.
- the light illuminance or the light spectrum may be changed.
- the light intensity can be controlled by a known optical filter.
- the light spectrum can be controlled by controlling the DC voltage applied to the electrode of the UV lamp. This method is applied in the following cases, for example.
- the absorption cross section is larger than the light absorption of ozone (ozone And intermediate products (produced in the room temperature gas phase of the source gas) may be absorbed.
- the intermediate product is absorbed and consumed on the upstream side of the gas flow, and the concentration of the intermediate product on the downstream side is lowered, so that uniform processing of the film thickness and film quality becomes difficult. Therefore, it is effective to reduce the light illuminance on the short wavelength side in the photo-ozone CVD process as in this embodiment.
- U ultraviolet light intensity
- G ozone gas flow rate
- G raw material gas flow rate
- S process start
- E process end
- process P2 ozone light CVD process
- the film formation speed in process P2 is reduced, improving the film quality, and also during the interface thermal oxidation with the substrate, Alternatively, the throughput for producing the surface protective film is improved.
- FIG. 15 is a schematic configuration diagram of an oxide film forming apparatus according to the fifth embodiment.
- the oxide film forming apparatus 1 of the present embodiment includes a light introduction plate 22 for reaction products in the CVD process.
- an inert gas G3 is circulated between the light introducing plate 22 and the opening 21 of the processing furnace 2 in the acid film forming apparatus of Embodiments 1 to 4.
- a gas layer 11 is formed.
- particles or the like are prevented from adhering to the light introducing plate 22, the effective illuminance decreases with time, the film formation speed decreases due to uneven illuminance, and uneven film formation occurs. Is suppressed.
- the oxide film forming apparatus 1 includes the light introducing plate 22 so as to be separated in parallel with the upper surface of the ceiling portion 20 of the processing furnace 2.
- the gas layer 11 is formed by connecting a guide plate 12 to an upstream end and a downstream end of the light introducing plate 22.
- the guide plate 12 is arranged so as to be parallel to the upper surface of the ceiling 20 of the processing furnace 2.
- the inert gas G3 a gas having a smaller reaction rate constant with the excited state oxygen atom than the reaction rate constant between oxygen and the excited state oxygen atom, that is, the reaction with the excited state oxygen atom occurs, and the oxygen atom in the ground state
- Examples include Ar gas and He gas.
- the utilization efficiency of the raw material gas is increased, and an oxide film having excellent electrical characteristics is formed by a film forming process at 200 ° C. or lower. become able to.
- the wavelength of ultraviolet light to a wavelength longer than 2 lOnm which does not induce optical damage to the substrate, optical damage to the underlying substrate such as glass can be greatly reduced.
- the raw material gas is used, the absorption to ultraviolet light is small, and only the excited state oxygen atoms generated by the interaction between ozone and light selectively react with the raw material gas, and the gas phase reaction and surface reaction proceed. Therefore, the film thickness distribution is determined only by light irradiation. Therefore, it is possible to simplify mechanisms such as gas introduction, flow studies, substrate studies, and substrate rotations that were required in the past.
- the processing furnace 2 is a cold duel type furnace, and the temperature of the substrate 7 stored in the furnace is as low as 200 ° C. Excited oxygen atoms are generated by light absorption of ozone. Further, the surface of the substrate 7 is irradiated with light. As a result, the surface of the substrate 7 and the gas temperature rise locally, and the frequency of gas phase reactions during the process becomes extremely small compared to the frequency of surface reactions of the substrate 7, so that the production at a place other than the surface of the substrate 7 is performed. The membrane is reduced. As a result, high-speed film formation is realized with a small raw material gas flow rate. That is, the gas utilization efficiency is increased. That is, the utilization rate of the raw material gas is increased, and the load on the exhaust pump is reduced.
- the ozone gas flow rate is sufficient compared to the source gas flow rate (for example, the ozone molecules necessary for stoichiometrically oxidizing the source gas). (2 times the number) to supply surplus ozone gas and intermediate products (Si—O, CO, HO), but since there is no absorption of ultraviolet light except for surplus ozone gas, the intermediate is further converted into an atomic state (for example, These impurities that do not decompose to oxygen atoms or hydrogen atoms) are taken into the film and are exhausted in the form of gas.
- the excited state oxygen atom concentration generated as a result of the light absorption reaction of surplus ozone is sufficiently lower than the ozone concentration and the intermediate product concentration.
- An intermediate product concentration and an excited state oxygen concentration that are almost equal to the upstream flow are realized, and a uniform film forming speed is realized even on the downstream side as compared with the upstream side.
- interface oxidation interface cleaning
- surface oxidation surface modification
- the throughput is increased and the film quality is optimized in accordance with the ozone photo interface thermal oxidation process, the ozone photo CVD process, and the ozone surface thermal oxidation process.
- the optimum light illuminance and light spectrum realized by the above are realized by a single light source.
- the oxide film forming apparatus of Embodiment 5 adhesion of particles or the like to the ultraviolet light transmission window is prevented, and the effective illuminance with time decreases, the film forming speed decreases due to uneven illuminance, and film formation The occurrence of unevenness is suppressed.
Description
Claims
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US9431237B2 (en) * | 2009-04-20 | 2016-08-30 | Applied Materials, Inc. | Post treatment methods for oxide layers on semiconductor devices |
JP2011054894A (ja) * | 2009-09-04 | 2011-03-17 | Meidensha Corp | 酸化膜形成方法 |
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US20100255684A1 (en) | 2010-10-07 |
TWI361464B (en) | 2012-04-01 |
CN101506952B (zh) | 2011-02-16 |
CN101506952A (zh) | 2009-08-12 |
KR101060112B1 (ko) | 2011-08-29 |
KR20090042286A (ko) | 2009-04-29 |
TW200824004A (en) | 2008-06-01 |
JP5052071B2 (ja) | 2012-10-17 |
US8163659B2 (en) | 2012-04-24 |
JP2008053561A (ja) | 2008-03-06 |
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