JP6941181B2 - シリコン前駆体およびこれを用いたシリコン含有薄膜の製造方法 - Google Patents
シリコン前駆体およびこれを用いたシリコン含有薄膜の製造方法 Download PDFInfo
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- JP6941181B2 JP6941181B2 JP2019554557A JP2019554557A JP6941181B2 JP 6941181 B2 JP6941181 B2 JP 6941181B2 JP 2019554557 A JP2019554557 A JP 2019554557A JP 2019554557 A JP2019554557 A JP 2019554557A JP 6941181 B2 JP6941181 B2 JP 6941181B2
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- 239000010409 thin film Substances 0.000 title claims description 66
- 238000004519 manufacturing process Methods 0.000 title claims description 59
- 239000012686 silicon precursor Substances 0.000 title description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title description 18
- 229910052710 silicon Inorganic materials 0.000 title description 18
- 239000010703 silicon Substances 0.000 title description 18
- 238000000034 method Methods 0.000 claims description 104
- 239000002243 precursor Substances 0.000 claims description 100
- 238000007740 vapor deposition Methods 0.000 claims description 59
- 239000012495 reaction gas Substances 0.000 claims description 49
- 229910052739 hydrogen Inorganic materials 0.000 claims description 42
- 239000001257 hydrogen Substances 0.000 claims description 41
- 239000000203 mixture Substances 0.000 claims description 39
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 34
- 229910052760 oxygen Inorganic materials 0.000 claims description 34
- 239000001301 oxygen Substances 0.000 claims description 34
- 150000001875 compounds Chemical class 0.000 claims description 33
- 238000000231 atomic layer deposition Methods 0.000 claims description 26
- 239000000126 substance Substances 0.000 claims description 22
- 238000005229 chemical vapour deposition Methods 0.000 claims description 21
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000010408 film Substances 0.000 description 69
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 54
- 229910052814 silicon oxide Inorganic materials 0.000 description 53
- 238000000151 deposition Methods 0.000 description 25
- 238000002347 injection Methods 0.000 description 25
- 239000007924 injection Substances 0.000 description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 20
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- 238000006243 chemical reaction Methods 0.000 description 15
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- 125000004432 carbon atom Chemical group C* 0.000 description 7
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- 239000000376 reactant Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
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- 238000004458 analytical method Methods 0.000 description 6
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- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
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- 229920006395 saturated elastomer Polymers 0.000 description 6
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
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- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 5
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 230000006399 behavior Effects 0.000 description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
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- 238000000089 atomic force micrograph Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- AWFPGKLDLMAPMK-UHFFFAOYSA-N dimethylaminosilicon Chemical compound CN(C)[Si] AWFPGKLDLMAPMK-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000000427 thin-film deposition Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- CGRVKSPUKAFTBN-UHFFFAOYSA-N N-silylbutan-1-amine Chemical compound CCCCN[SiH3] CGRVKSPUKAFTBN-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- WZUCGJVWOLJJAN-UHFFFAOYSA-N diethylaminosilicon Chemical compound CCN([Si])CC WZUCGJVWOLJJAN-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- -1 hydrogen hydrogen Chemical class 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- AHKKZIUZTWZKDR-UHFFFAOYSA-N n-[bis(dimethylamino)-methylsilyl]-n-methylmethanamine Chemical compound CN(C)[Si](C)(N(C)C)N(C)C AHKKZIUZTWZKDR-UHFFFAOYSA-N 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 150000003738 xylenes Chemical group 0.000 description 2
- JWZZKOKVBUJMES-UHFFFAOYSA-N (+-)-Isoprenaline Chemical compound CC(C)NCC(O)C1=CC=C(O)C(O)=C1 JWZZKOKVBUJMES-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- BIVNKSDKIFWKFA-UHFFFAOYSA-N N-propan-2-yl-N-silylpropan-2-amine Chemical compound CC(C)N([SiH3])C(C)C BIVNKSDKIFWKFA-UHFFFAOYSA-N 0.000 description 1
- UOERHRIFSQUTET-UHFFFAOYSA-N N-propyl-N-silylpropan-1-amine Chemical compound CCCN([SiH3])CCC UOERHRIFSQUTET-UHFFFAOYSA-N 0.000 description 1
- WKXNTUKZVVFSIN-UHFFFAOYSA-N S(=O)([O-])[O-].[NH4+].S(=O)(O)O.[NH4+].S(=O)(O)O Chemical compound S(=O)([O-])[O-].[NH4+].S(=O)(O)O.[NH4+].S(=O)(O)O WKXNTUKZVVFSIN-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- JQOAQUXIUNVRQW-UHFFFAOYSA-N hexane Chemical compound CCCCCC.CCCCCC JQOAQUXIUNVRQW-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003852 thin film production method Methods 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
-
- 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
-
- 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
- C23C16/455—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 characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
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- H01L21/02211—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 the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound being a silane, e.g. disilane, methylsilane or chlorosilane
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- H01L21/02219—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 the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and nitrogen
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Description
SiR1 a(NR2R3)(4−a)
前記化学式1において、aは、1〜3の整数であり、R1は、置換もしくは非置換の炭素数1〜4の炭化水素、より詳細には、線状もしくは分枝状、飽和もしくは不飽和のアルキル基、またはこれらの異性体であり、R2およびR3は、それぞれ独立に、水素、置換もしくは非置換の炭素数1〜4の炭化水素、より詳細には、線状もしくは分枝状、飽和もしくは不飽和のアルキル基、またはこれらの異性体である。
SiR4 bR5 c(X1)(4−b−c)
前記化学式2において、bおよびcは、それぞれ0〜3の整数であり、bとcとの和は、1〜3の整数であり、X1は、Cl、Br、Iからなる群より選択されるハロゲン基であり、R4およびR5は、それぞれ独立に、置換もしくは非置換の炭素数1〜4の炭化水素、より詳細には、線状もしくは分枝状、飽和もしくは不飽和のアルキル基、または非置換の炭素数6〜12の環状炭化水素、またはこれらの異性体である。
SiR1 a(NR2R3)(4−a)
前記化学式1において、
aは、1〜3の整数であり、
R1は、置換もしくは非置換の炭素数1〜4の炭化水素、より詳細には、線状もしくは分枝状、飽和もしくは不飽和のアルキル基、またはこれらの異性体であり、
R2およびR3は、それぞれ独立に、水素、置換もしくは非置換の炭素数1〜4の炭化水素、より詳細には、線状もしくは分枝状、飽和もしくは不飽和のアルキル基、またはこれらの異性体である。
SiR4 bR5 c(X1)(4−b−c)
前記化学式2において、
bおよびcは、それぞれ0〜3の整数であり、
bとcとの和は、1〜3の整数であり、
X1は、Cl、Br、Iからなる群より選択されるハロゲン基であり、
R4およびR5は、それぞれ独立に、置換もしくは非置換の炭素数1〜4の炭化水素、より詳細には、線状もしくは分枝状、飽和もしくは不飽和のアルキル基、または非置換の炭素数6〜12の環状炭化水素、またはこれらの異性体である。
フラスコにMeSiCl3 150gを入れて、ヘキサン(hexane)7Lを入れて溶解させ、アセトン(acetone)とドライアイス(dry ice)を用いて温度を下げた。低い温度を維持し、前記溶液にジメチルアミンガス(dimethylamine gas)360gを添加した。添加完了後に混合物を常温で20時間撹拌した。反応終了後、フィルタで濾過して得られた溶液を常圧で沸かして溶媒を除去して、無色の透明な液体を得た。前記得られた液体を減圧精製して、無色の透明な液体123g(収率70%)を得た。
1H−NMR(C6D6):
δ2.46((CH3)Si(N(CH 3)2)3,s,18H);
δ0.13((CH 3)Si(N(CH3)2)3,s,3H)
原子層蒸着(ALD)装備を用いて、前記実施例1により製造された化合物を蒸着してシリコン酸化膜を製造した。本実験に用いられた基板はbare Siウエハであり、蒸着に先立って、アセトン−エタノール−脱イオン水(DI water)にそれぞれ10分ずつ超音波処理(ultrasonic)後、前記bare Siウエハ上の自然酸化膜はHF10%(HF:H2O=1:9)の溶液に10秒間浸して除去した。
製造例1と前駆体(ソースガス)、前駆体注入時間、前駆体パージ時間、反応ガス注入時間、反応ガスパージ時間、サイクル条件などは同一に維持し、反応ガスを水素(H2)と酸素(O2)との混合物(H2+O2)とし、工程温度を600℃(製造例2−1〜2−5)および650℃(製造例3−1〜3−5)として、シリコン酸化物薄膜を製造した。
原子層蒸着(ALD)装備を用い、CH3SiCl3を前駆体として用いて、シリコン酸化膜を製造した。本実験に用いられた基板はbare Siウエハであり、蒸着に先立って、アセトン−エタノール−脱イオン水(DI water)にそれぞれ10分ずつ超音波処理(ultrasonic)後、bare Siウエハ上の自然酸化膜はHF10%(HF:H2O=1:9)の溶液に10秒間浸して除去した。
製造例4において、工程温度を700℃に変更したことを除けば、同一の工程条件で蒸着した。
製造例4において、工程温度を750℃に変更したことを除けば、同一の工程条件で蒸着した。
製造例4において、工程温度を800℃に変更したことを除けば、同一の工程条件で蒸着した。
実施例1のシリコン前駆体化合物の分解特性および前駆体化合物と製造された酸化膜の熱的安定性を分析するために、bare Siウエハに、製造例1と同一の反応条件(前駆体および反応物の組成、前駆体注入時間、前駆体パージ時間、反応物注入時間、反応物パージ時間、サイクルなど)および工程温度を650℃、700℃、800℃に調節してシリコン酸化膜を蒸着した後、蒸着された状態を確認して、図5に示した。
CH3SiCl3シリコン前駆体化合物の分解特性および前駆体化合物と製造された酸化膜の熱的安定性を分析するために、bare Siウエハに、製造例4と同一の反応条件(前駆体および反応物の組成、前駆体注入時間、前駆体パージ時間、反応物注入時間、反応物パージ時間、サイクルなど)および工程温度を850℃、900℃に調節してシリコン酸化膜を蒸着した後、蒸着された状態を確認して、図6に示した。
XPSとFT−IR分析で実施例1の前駆体とそれぞれの反応ガス(オゾン(O3)および酸素と水素との混合物(H2+O2))とを、600℃および650℃の工程温度でそれぞれ蒸着して製造した4種のシリコン酸化膜(製造例1〜3)の組成を分析して、それぞれ図7および図9に示した。
XPSとFT−IR分析法を活用して、CH3SiCl3前駆体と反応ガス(酸素と水素との混合物(H2+O2))とを、600℃、750℃および800℃の工程温度でそれぞれ蒸着して製造した3種のシリコン酸化膜(製造例4、6および7)の組成を分析して、それぞれ図8および図10に示した。
実施例1の前駆体とそれぞれの反応ガス(オゾン(O3)および酸素と水素との混合物(H2+O2))とを、600℃および650℃の工程温度でそれぞれ蒸着して製造した4種のシリコン酸化膜(製造例1〜3)をAFMで観察し、これを通してシリコン酸化膜の表面粗度(roughness、Ra)を測定して、図11に示した。
図12は、CH3SiCl3前駆体と反応ガス(酸素と水素との混合物(H2+O2))とを、600℃、750℃および800℃の工程温度でそれぞれ蒸着して製造した3種のシリコン酸化膜(製造例4、6および7)のAFMイメージと、これを通して表面粗度(Ra)を分析した結果である。図12(a)は600℃の工程温度で蒸着、図12(b)は750℃の工程温度で蒸着、図12(c)は800℃の工程温度で蒸着されたシリコン酸化膜のAFMイメージである。
実施例1の前駆体とそれぞれの反応ガス(オゾン(O3)および酸素(O2)と水素(H2)との混合物(H2+O2))とを、600℃および650℃の工程温度でそれぞれ蒸着して製造した4種のシリコン酸化膜(製造例1〜3)のXRR分析結果を通してシリコン酸化膜の密度を分析して、図13に示した。
CH3SiCl3前駆体と反応ガス(酸素と水素との混合物(H2+O2))とを、600℃、750℃および800℃の工程温度でそれぞれ蒸着して製造した3種のシリコン酸化膜(製造例4、6および7)のXRR分析結果を通してシリコン酸化膜の密度を分析して、図14に示した。図14(a)は600℃の工程温度で蒸着、図14(b)は750℃の工程温度で蒸着、図14(c)は800℃の工程温度で蒸着されたシリコン酸化膜のXRR結果である。
実施例1の前駆体とそれぞれの反応ガス(オゾン(O3)および酸素(O2)と水素(H2)との混合物(H2+O2))とを、600℃および650℃の工程温度でそれぞれ蒸着して製造した4種のシリコン酸化膜(製造例1〜3)の段差被覆特性を透過電子顕微鏡(Transmission Electron Microscope、TEM)で分析して、図15に示した(図15(a)(反応ガス:オゾン(O3)、工程温度:600℃)、図15(b)(反応ガス:オゾン(O3)、工程温度:650℃)、図15(c)(反応ガス:酸素と水素との混合物(H2+O2)、工程温度:600℃)、図15(d)(反応ガス:酸素と水素との混合物(H2+O2)、工程温度:650℃)。
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