TW201608052A - 用於多孔低介電常數薄膜密封之紫外線輔助矽烷化 - Google Patents
用於多孔低介電常數薄膜密封之紫外線輔助矽烷化 Download PDFInfo
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- 238000007789 sealing Methods 0.000 title claims abstract description 82
- 238000006884 silylation reaction Methods 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 104
- 238000000151 deposition Methods 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims description 69
- 239000000758 substrate Substances 0.000 claims description 51
- 150000001875 compounds Chemical class 0.000 claims description 32
- 239000002243 precursor Substances 0.000 claims description 31
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 14
- 238000007740 vapor deposition Methods 0.000 claims description 10
- LNEJJQMNHUGXDW-UHFFFAOYSA-N CC(C(OCC)(OCC)C)CCCCCCCC Chemical compound CC(C(OCC)(OCC)C)CCCCCCCC LNEJJQMNHUGXDW-UHFFFAOYSA-N 0.000 claims description 8
- 239000012159 carrier gas Substances 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 6
- QDKSGHXRHXVMPF-UHFFFAOYSA-N 2,2-dimethylundecane Chemical class CCCCCCCCCC(C)(C)C QDKSGHXRHXVMPF-UHFFFAOYSA-N 0.000 claims description 5
- HNQJCSOWZNVWAF-UHFFFAOYSA-N CN(C)C(CCCC(CCCC)(C)C)N(C)C Chemical compound CN(C)C(CCCC(CCCC)(C)C)N(C)C HNQJCSOWZNVWAF-UHFFFAOYSA-N 0.000 claims description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- DRRKAOITJFLWET-UHFFFAOYSA-N CN(C)C(C(C)(C)C)CCCCCCC Chemical compound CN(C)C(C(C)(C)C)CCCCCCC DRRKAOITJFLWET-UHFFFAOYSA-N 0.000 claims description 3
- -1 tetraethylene Dimethyl dioxane Chemical compound 0.000 claims description 3
- WYDCLGLWAMNKTO-UHFFFAOYSA-N 1-N,1-N,1-N',1-N',1-N",1-N"-hexamethyldecane-1,1,1-triamine Chemical compound CN(C)C(CCCCCCCCC)(N(C)C)N(C)C WYDCLGLWAMNKTO-UHFFFAOYSA-N 0.000 claims description 2
- LOLANUHFGPZTLQ-UHFFFAOYSA-N 1-ethoxydecane Chemical compound CCCCCCCCCCOCC LOLANUHFGPZTLQ-UHFFFAOYSA-N 0.000 claims description 2
- JPEWDCTZJFUITH-UHFFFAOYSA-N 1-methoxydecane Chemical compound CCCCCCCCCCOC JPEWDCTZJFUITH-UHFFFAOYSA-N 0.000 claims description 2
- GCGOSWDCNJRBCH-UHFFFAOYSA-N 2,2-diethoxyundecane Chemical compound CCCCCCCCCC(C)(OCC)OCC GCGOSWDCNJRBCH-UHFFFAOYSA-N 0.000 claims description 2
- GCZWJRLXIPVNLU-UHFFFAOYSA-N 2,2-dimethoxy-3-methylundecane Chemical compound CC(C(OC)(OC)C)CCCCCCCC GCZWJRLXIPVNLU-UHFFFAOYSA-N 0.000 claims description 2
- JIUCOPHLJPKIKI-UHFFFAOYSA-N C(=C)C(C(C)(C)C=C)CCCCCCCC Chemical compound C(=C)C(C(C)(C)C=C)CCCCCCCC JIUCOPHLJPKIKI-UHFFFAOYSA-N 0.000 claims description 2
- QTLGGUNVIFNLAL-UHFFFAOYSA-N C(=C)C1(OC(C(OC1)(C=C)C=C)(C=C)C=C)C=C Chemical compound C(=C)C1(OC(C(OC1)(C=C)C=C)(C=C)C=C)C=C QTLGGUNVIFNLAL-UHFFFAOYSA-N 0.000 claims description 2
- BSEDPEFHOWOZRG-UHFFFAOYSA-N CC(=C(C)C)N1N(N1C=C)C=C Chemical compound CC(=C(C)C)N1N(N1C=C)C=C BSEDPEFHOWOZRG-UHFFFAOYSA-N 0.000 claims description 2
- LQSSTOWXSHKHLH-UHFFFAOYSA-N CC(CCCCCCCCC(OCC)(OCC)OCC)OC Chemical compound CC(CCCCCCCCC(OCC)(OCC)OCC)OC LQSSTOWXSHKHLH-UHFFFAOYSA-N 0.000 claims description 2
- JDRRJOCIZJJGDC-UHFFFAOYSA-N CN(C)C(C(C)(C)N(C)C)CCCCCCCC Chemical compound CN(C)C(C(C)(C)N(C)C)CCCCCCCC JDRRJOCIZJJGDC-UHFFFAOYSA-N 0.000 claims description 2
- OBXIZAUFQABQNO-UHFFFAOYSA-N CN(C)C(C(N(C)C)(N(C)C)N(C)C)CCCCCCCC Chemical compound CN(C)C(C(N(C)C)(N(C)C)N(C)C)CCCCCCCC OBXIZAUFQABQNO-UHFFFAOYSA-N 0.000 claims description 2
- QCYDIPJCGFDBKO-UHFFFAOYSA-N CN(C)C(N(C)C)(N(C)C)CCCCCCCCCC Chemical compound CN(C)C(N(C)C)(N(C)C)CCCCCCCCCC QCYDIPJCGFDBKO-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- QNNALNZLUPVUBO-UHFFFAOYSA-N triaziridine Chemical compound N1NN1 QNNALNZLUPVUBO-UHFFFAOYSA-N 0.000 claims description 2
- ABVVEAHYODGCLZ-UHFFFAOYSA-N tridecan-1-amine Chemical compound CCCCCCCCCCCCCN ABVVEAHYODGCLZ-UHFFFAOYSA-N 0.000 claims description 2
- CPODUYNDWWHKGW-UHFFFAOYSA-N CCCCCCCC(NC)C(C)(C)C Chemical compound CCCCCCCC(NC)C(C)(C)C CPODUYNDWWHKGW-UHFFFAOYSA-N 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 abstract 2
- 238000009826 distribution Methods 0.000 description 24
- 230000005855 radiation Effects 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 12
- 239000002826 coolant Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 238000010926 purge Methods 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000005137 deposition process Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HPCIXPCAAKYXOL-UHFFFAOYSA-N CN(C)C(C(C)(C)C)CCCCCCCC Chemical compound CN(C)C(C(C)(C)C)CCCCCCCC HPCIXPCAAKYXOL-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 238000003848 UV Light-Curing Methods 0.000 description 2
- 239000002168 alkylating agent Substances 0.000 description 2
- 229940100198 alkylating agent Drugs 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 238000005019 vapor deposition process Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- 229910017109 AlON Inorganic materials 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- 229910007991 Si-N Inorganic materials 0.000 description 1
- 229910006294 Si—N Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- BCZWPKDRLPGFFZ-UHFFFAOYSA-N azanylidynecerium Chemical compound [Ce]#N BCZWPKDRLPGFFZ-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- PUIYMUZLKQOUOZ-UHFFFAOYSA-N isoproturon Chemical compound CC(C)C1=CC=C(NC(=O)N(C)C)C=C1 PUIYMUZLKQOUOZ-UHFFFAOYSA-N 0.000 description 1
- GJJSDZSDOYNJSW-UHFFFAOYSA-N lanthanum(3+);borate Chemical compound [La+3].[O-]B([O-])[O-] GJJSDZSDOYNJSW-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 125000003544 oxime group Chemical group 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- SITVSCPRJNYAGV-UHFFFAOYSA-L tellurite Chemical compound [O-][Te]([O-])=O SITVSCPRJNYAGV-UHFFFAOYSA-L 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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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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- 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
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- 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
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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 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
- H01L21/31—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
- H01L21/3105—After-treatment
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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
- H01L21/70—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
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
- H01L21/76822—Modification of the material of dielectric layers, e.g. grading, after-treatment to improve the stability of the layers, to increase their density etc.
- H01L21/76825—Modification of the material of dielectric layers, e.g. grading, after-treatment to improve the stability of the layers, to increase their density etc. by exposing the layer to particle radiation, e.g. ion implantation, irradiation with UV light or electrons etc.
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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
- H01L21/70—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
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
- H01L21/76829—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing characterised by the formation of thin functional dielectric layers, e.g. dielectric etch-stop, barrier, capping or liner layers
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Abstract
本案所述之實施例提供用於密封多孔低介電常數介電薄膜的方法。該方法包括藉由使用循環製程在多孔低介電常數介電薄膜上形成密封層。循環製程包括重複以下序列:在多孔低介電常數介電薄膜上沉積密封層且處理密封層直至密封層達到預定厚度。每一中間密封層之處理在每一中間密封層表面上產生更多反應性位點,從而改良所產生之密封層的品質。
Description
本案中所述之實施例係關於用於處理低介電常數介電薄膜之製程。更特定言之,本案中所述之實施例係關於用於密封多孔低介電常數介電薄膜之製程。
在半導體製造中,介電薄膜之介電常數(k)隨著裝置尺寸持續縮小而不斷降低。將對低介電常數(低k)薄膜之整合損害降至最低對能夠繼續縮小特徵尺寸而言十分重要。然而,隨著特徵尺寸縮減,介電薄膜之阻抗電容及可靠性的改良變為嚴重挑戰。
包括例如碳摻雜氧化物(carbon doped oxide;CDO)之多孔低介電常數介電薄膜在經歷後端製程(back end of line;BEOL)整合之後由於曝露小孔中之污染而遭受嚴重損害,該污染導致更大的電阻電容(resistive-capacitive;RC)延遲。為維持多孔低介電常數介電薄膜之完整性並最小化多孔低介電常數介電薄膜之介電常數降級,需要用於減輕對多孔低介電常數介電薄膜之損害之方法。
本案所述之實施例提供用於密封多孔低介電常數介電薄膜的方法。該方法包括藉由使用循環製程在多孔低介電常數介電薄膜上形成密封層。循環製程包括重複以下序列:在多孔低介電常數介電薄膜上沉積密封層且處理密封層直至密封層達到預定厚度。每一中間密封層之處理在每一中間密封層表面上產生更多反應性位點,從而改良所產生之密封層的品質。
在一個實施例中,揭示用於在多孔低介電常數介電薄膜上形成密封層之方法。該方法包括藉由使用紫外線輔助紫外線光化學氣相沉積在多孔低介電常數介電薄膜上沉積中間密封層,利用紫外線能或射頻能處理中間密封層,及重複沉積及處理製程直至形成具有預定厚度之密封層。
在另一實施例中,揭示用於在多孔低介電常數介電薄膜上形成密封層之方法。該方法包括開啟一或更多個紫外線燈以向安置在製程腔室中之基板傳送紫外線能,且多孔低介電常數介電薄膜安置在基板上。該方法進一步包括使第一前驅物化合物流入製程腔室中,且第一前驅物化合物包含單官能基。該方法進一步包括使第二前驅物化合物流入製程腔室中,且第二前驅物化合物包含多官能基。
在另一實施例中,揭示用於在多孔低介電常數介電薄膜上形成密封層之方法。該方法包括開啟一或更多個紫外線燈以向安置在製程腔室中之基板傳送紫外線
能,且多孔低介電常數介電薄膜安置在基板上。該方法進一步包括使第一前驅物化合物流入製程腔室,且第一前驅物化合物包括乙醯氧基三甲基矽烷或二甲基胺基三甲基矽烷。該方法進一步包括使第二前驅物化合物流入製程腔室,且第二前驅物化合物包括二甲基二乙醯氧基矽烷或雙(二甲基胺基)二甲基矽烷。
100‧‧‧流程圖
102‧‧‧步驟
104‧‧‧步驟
106‧‧‧步驟
200‧‧‧氣相沉積設備
202‧‧‧腔室主體
204‧‧‧腔室蓋
206‧‧‧內部體積
208‧‧‧基板支撐組件
210‧‧‧基板
212‧‧‧中央開口
214‧‧‧紫外線透明視窗
216‧‧‧第一紫外線透明氣體分配噴淋頭
218‧‧‧上部夾持構件
220‧‧‧下部夾持構件
222‧‧‧分配體積
224‧‧‧第二紫外線透明氣體分配噴淋頭
226‧‧‧第一凹槽
228‧‧‧第二凹槽
230‧‧‧氣體體積
232‧‧‧第一流道
234‧‧‧第二流道
236‧‧‧流道
238‧‧‧開口
240‧‧‧通孔
242‧‧‧通孔
250‧‧‧紫外線源
252‧‧‧紫外線燈
254‧‧‧淨化氣體源/載氣源
256‧‧‧導管
258‧‧‧前驅物化合物源/製程氣源
260‧‧‧導管
262‧‧‧冷卻氣室
264‧‧‧冷卻劑導管
266‧‧‧加熱元件
268‧‧‧導管
270‧‧‧冷卻劑源
272‧‧‧加熱源
274‧‧‧清潔氣源
為可詳細理解本揭示案之上述特徵,可藉由參考實施例對上文中簡短概述之揭示內容進行更特定之描述,該等實施例中之一些者在附圖中進行圖示。然而,將注意,附圖僅圖示本揭示案之典型實施例,因此將不被視作限制本揭示案之範疇,因為本揭示案可承認其他同等有效的實施例。
第1圖是製程流程圖,該圖圖示根據本案中描述之一個實施例用於形成密封層之一種方法。
第2圖是根據本案中描述之一個實施例之一設備的示意性剖面視圖。
為便於理解,在可能之情況下已使用相同元件符號以指定圖式中共有之相同元件。設想在一個實施例中揭示之元件可以有利方式利用於其他實施例,無需特定詳述。
本案所述之實施例提供用於密封多孔低介電常數介電薄膜的方法。該方法包括藉由使用循環製程在多
孔低介電常數介電薄膜上形成密封層。循環製程包括重複以下序列:在多孔低介電常數介電薄膜上沉積密封層且處理密封層直至密封層達到預定厚度。每一中間密封層之處理在每一中間密封層表面上產生更多反應性位點,從而改良所產生之密封層的品質。
第1圖是製程流程圖100,該圖圖示根據本案中描述之一個實施例用於形成密封層之一個方法。在步驟102中,將密封層沉積在多孔低介電常數介電薄膜上。多孔低介電常數介電薄膜可為任何習用多孔低介電常數的矽基介電薄膜,該介電薄膜具有低於約3之介電常數值。在一個實施例中,多孔低介電常數介電薄膜是有機矽酸鹽玻璃(OSG,如SiCOH),該玻璃是包含碳及氫原子之氧化矽。多孔低介電常數介電薄膜可具有直徑在約0.5nm至約20nm範圍中之微孔。密封層可藉由使用紫外線(ultraviolet;UV)輔助光化學氣相沉積而沉積在多孔低介電常數介電薄膜上。
可在沉積多孔低介電常數介電薄膜之腔室中,或在不同的腔室中執行紫外線輔助光化學氣相沉積。在一個實施例中,紫外線輔助光化學氣相沉積在紫外線處理腔室中執行。將具有多孔低介電常數介電薄膜之基板置於處理腔室中。紫外線輔助光化學氣相沉積製程包括將前驅物化合物及載氣引入處理腔室中,及藉由開啟一或更多個紫外線燈而將紫外線能傳送至安置在基板上之多孔低介電常數介電薄膜。前驅物化合物可為矽烷化劑,如四乙
烯基矽烷、三乙烯基甲基矽烷、三乙烯基矽烷、二乙烯基二甲基矽烷、六乙烯基二矽氧烷、四乙烯基二甲基二矽氧烷、三乙烯基乙氧基矽烷、三乙烯基甲氧基矽烷、二甲基二乙醯氧基矽烷、三乙醯氧基甲基矽烷、乙醯氧基三甲基矽烷、甲基二乙氧基矽烷、二甲基二乙氧基矽烷、二甲基二甲氧基矽烷、三甲基三乙烯基環三矽氧烷、八甲基環四矽氧烷、三(二甲基胺基)甲基矽烷、四(二甲基胺基)矽烷、三(二甲基胺基)矽烷、雙(二甲基胺基)二甲基矽烷、雙(二甲基胺基)甲基乙烯基矽烷、三矽烷基胺、二甲基胺基三甲基矽烷、環三矽氮烷、三甲基三乙烯基環三矽氮烷、六甲基環三矽氮烷、九甲基環三矽氮烷,或包含Si、H及C的其他化合物。諸如He、Ar、N2,及上述各者之組合的載氣可用以協助使前驅物化合物流入處理腔室中。在一個實施例中,基板是300mm基板,且前驅物化合物之流速範圍可自約100毫克每分鐘(milligrams per minute;mgm)至約2000mgm,及載氣流速範圍可自約500標準立方公分每分鐘(standard cubic centimeters per minute;sccm)至約5000sccm。
紫外線輔助光化學氣相沉積製程可在約50mTorr與500Torr之間的處理腔室壓力下及在約50℃與約400℃之間的基板溫度下實施。基板與噴淋頭之間的距離範圍為自約400毫米(mm)至約1400mm。處理時間可在約15秒至約900秒之間,且紫外線功率可為約
10%至約100%。密封層可具有範圍自約1埃(Å)至約5Å之厚度。
在步驟104中,將密封層處理成使得在密封層表面上產生更多反應性位點。處理製程可為紫外線輔助處理製程或射頻輔助處理製程。可在沉積密封層之腔室中,或在不同的腔室中執行處理製程。在一個實施例中,在負載鎖定腔室中執行處理製程,該負載鎖定腔室與在其中沉積密封層之處理腔室處於同一主機中。紫外線輔助處理製程可包括使反應性氣體流入腔室,在該腔室中安置有基板,該基板具有多孔低介電常數介電薄膜及在該薄膜上安置有密封層。藉由開啟一或更多個紫外線燈來將紫外線能導引向密封層。腔室壓力範圍可為自約6Torr至約200Torr,且紫外線功率範圍可為自約40%至約100%。反應性氣體可具有範圍自約20sccm至約2000sccm之流速。反應性氣體之實例包括NH3、H2、O2、N2O、CO2,或上述各者之組合。諸如Ar或He之惰性氣體亦可以範圍自約20sccm至約2000sccm之流速被引入腔室中。處理時間範圍可自約10秒至約600秒。
射頻輔助處理製程可包括使反應性氣體流入腔室中,在該腔室中安置有基板,該基板具有多孔低介電常數介電薄膜且在該薄膜上安置有密封層。腔室壓力範圍可為自約2Torr至約20Torr,且射頻功率範圍可為自約20W至約300W。反應性氣體可具有範圍自約20sccm至約2000sccm之流速。反應性氣體之實例包括
NH3、H2、O2、N2O、CO2,或上述各者之組合。諸如Ar或He之惰性氣體亦可以範圍自約20sccm至約2000sccm之流速被引入腔室中。處理時間範圍可自約1秒至約600秒。
負載鎖定腔室中之紫外線輔助處理製程可包括使反應性氣體流入負載鎖定腔室中,在該負載鎖定腔室中安置有基板,該基板具有多孔低介電常數介電薄膜且在該薄膜上安置有密封層。藉由開啟一或更多個紫外線燈來將紫外線能導引向密封層。負載鎖定腔室壓力範圍可為自約0.07Torr至約20Torr,且紫外線功率範圍可為自約40%至約100%。反應性氣體可具有範圍自約20sccm至約2000sccm之流速。反應性氣體之實例包括NH3、H2、O2、N2O、CO2,或上述各者之組合。諸如Ar或He之惰性氣體亦可以範圍自約20sccm至約2000sccm之流速被引入腔室中。處理時間範圍可自約10秒至約600秒。
處理製程可在執行紫外線輔助沉積製程時所在之同一腔室中執行。在一個實施例中,處理腔室能夠執行紫外線輔助沉積製程及射頻輔助處理製程。密封層之處理製程在密封層表面上產生更多反應性位點,從而在隨後之密封層沉積在經處理之密封層時產生改良之薄膜品質。可重複密封層沉積及密封層處理,直至所產生之密封層達到預定厚度。在一個實施例中,預定厚度範圍自約5Å至約200Å。所產生之密封層之厚度可依據應用用途而
定。若一個沉積製程及一個處理製程被視作一循環,則循環數目之範圍自約2至100。
如第1圖中所圖示,在步驟106中,若密封層未達到預定厚度,則重複步驟102及步驟104。每當中間密封層沉積在先前沉積及經處理之密封層上之時,中間密封層之表面經處理以用於在該表面上沉積下一密封層。若所產生之密封層已達到預定厚度,則可不執行隨後之處理製程。循環數目可依據所產生之密封層之預定厚度而定。藉由使用循環製程,密封層共形地沉積在多孔低介電常數介電薄膜上,且可有效地減少多孔低介電常數介電薄膜表面處之多孔低介電常數介電薄膜孔隙率。在一個實施例中,在8個循環之後,表面處之孔隙率從33%降至4%,從而說明所產生之密封層是極為有效之孔密封件。
紫外線能可解離諸如矽烷化劑之前驅物化合物中之大多數Si-C-O鍵或Si-N鍵,以形成碳摻雜氧化矽或氮化矽。依據所使用之矽烷化劑,紫外線輔助矽烷化可由大量碳組成,從而導致相當低之介電常數值。由此,由於矽烷化製程而沉積之薄膜可極為保形及緻密,因為製程大部分在基板表面上由熱驅動。用作前驅物化合物之矽烷化劑可包括單官能基或多官能基。具有單官能基之矽烷化劑僅具有單個附於矽分子之官能基,如乙醯氧基三甲基矽烷或二甲基胺基三甲基矽烷。具有多官能基之矽烷化劑具有附於矽分子之多個官能基,如二甲基二乙醯氧基矽烷或雙(二甲基胺基)二甲基矽烷。在一個實施例中,密封層
可由二步驟製程形成。第一步驟是使包含單官能基之矽烷化劑流入製程腔室中,在該製程腔室中安置有基板,該基板上安置有多孔低介電常數介電薄膜。開啟一或更多個紫外線燈以將紫外線能導引至多孔低介電常數介電薄膜。包含單官能基之矽烷化劑及紫外線能在多孔低介電常數介電薄膜上提供介電常數值回復。在使包含單官能基之矽烷化劑流入製程腔室之前,可藉由使載氣流入製程腔室而使該製程腔室具有預定腔室壓力。
第二步驟是使包含多官能基之矽烷化劑流入製程腔室。一或更多個紫外線燈仍為開啟。包含多官能基之矽烷化劑不僅可與多孔低介電常數介電薄膜反應,亦可與其自身反應以在多孔低介電常數介電薄膜多孔低介電常數介電薄膜上形成網狀薄膜。該網狀薄膜是密封層。密封層可具有自約5Å至約200Å之厚度。可在第一步驟與第二步驟之間執行可選過渡步驟,具體依據薄膜表面性質而定。
或者,作為二步驟製程的替代,可藉由使包含單官能基之矽烷化劑及包含多官能基之矽烷化劑同時流入製程腔室中,同時開啟一或更多個紫外線燈而形成密封層。在另一實施例中,僅使包含多官能基之矽烷化劑流入製程腔室中,同時開啟一或更多個紫外線燈。可在密封層形成於多孔低介電常數介電薄膜上之後執行紫外線固化製程。紫外線固化製程可移除未與包含多官能基之矽烷化
劑反應之羥基,該移除降低介電常數值。此外,紫外線固化製程有助於維持密封層表面疏水性。
本案中所述之方法可藉由使用ONYXTM處理腔室執行,該處理腔室可從美國加利福尼亞州聖克拉拉市的應用材料公司處購得。藉由重複沉積密封層且處理密封層之製程而進行之密封層形成亦可藉由使用諸如第2圖中圖示之設備來執行。第2圖中之設備是氣相沉積設備200,該設備包括紫外線輻射以用於活化前驅物化合物。設備200包括腔室主體202及安置在腔室主體上方之腔室蓋204。腔室主體202及腔室蓋204形成內部體積206。基板支撐組件208安置在內部體積206中。基板支撐組件208在其上接收並支撐基板210以便進行處理。
第一紫外線透明氣體分配噴淋頭216藉由上部夾持構件218及下部夾持構件220而穿過腔室蓋204之中央開口212懸在內部體積206中。紫外線透明氣體分配噴淋頭216定位在面對基板支撐組件208之位置,以在整個分配體積222中分配一或更多種處理氣體,該分配體積222位於第一紫外線透明氣體分配噴淋頭216下方。第二紫外線透明噴淋頭224穿過腔室蓋204之中央開口212懸在內部體積206中於第一紫外線透明氣體分配噴淋頭216下方之位置。每一紫外線透明氣體分配噴淋頭216及224安置在腔室蓋204中形成之凹槽中。第一凹槽226是圍繞腔室蓋204內表面之環形凹槽,且第一紫外線透明氣體分配噴淋頭216裝配至第一凹槽226內。同樣
地,第二凹槽228接收第二紫外線透明氣體分配噴淋頭224。
紫外線透明視窗214安置在第一紫外線透明氣體分配噴淋頭216上方。紫外線透明視窗214定位在第一紫外線透明氣體分配噴淋頭216上方,在紫外線透明視窗214與第一紫外線透明氣體分配噴淋頭216之間形成氣體體積230。紫外線透明視窗214可藉由任何便利手段緊固至腔室蓋204,該手段為諸如夾持器、螺釘或螺栓。
紫外線透明視窗214與第一紫外線透明氣體分配噴淋頭216及第二透明氣體分配噴淋頭224對於紫外線波長內之熱能或輻射能為至少部分透明的。紫外線透明視窗214可為石英或另一紫外線透明矽材料,如藍寶石、CaF2、MgF2、AlON、氧化矽或氮氧化矽材料,或另一透明材料。
紫外線源250安置在紫外線透明視窗214上方。紫外線源250經配置以產生紫外線能,且經由紫外線透明視窗214、第一紫外線透明氣體分配噴淋頭216,及第二紫外線透明氣體分配噴淋頭224向基板支撐組件208發射紫外線能。蓋(未圖示)可安置在紫外線源250上方。在一個實施例中,蓋可經整形以協助從紫外線源250向基板支撐件之紫外線能投射。
在一個實施例中,紫外線源250包括一或更多個紫外線燈252以產生紫外線輻射。紫外線燈252可為燈、LED發射器,或其他紫外線發射器。紫外線源可為
放出126nm輻射之氬燈、放出146nm輻射之氪燈、放出172nm輻射之氙燈、放出222nm輻射之氯化氪燈、放出308nm輻射之氯化氙燈、放出254nm或365nm輻射之汞燈、放出214nm輻射之諸如鋅之金屬蒸汽燈、放出368-371nm輻射之諸如銪摻雜硼酸鍶或氟硼酸鹽燈之稀土近紫外線燈,以上僅為少數實例。
設備200包括流道,該等流道經配置以在基板支撐組件208上供應一或更多個處理氣體及前驅物化合物,以處理安置在基板支撐組件208上之基板。第一流道232提供流徑以便使氣體進入氣體體積230並曝露於來自紫外線源250之紫外線輻射。來自氣體體積230之氣體可流經第一紫外線透明氣體分配噴淋頭216以進入分配體積222。第二流道234提供流徑以便前驅物化合物及氣體直接進入分配體積222,無需穿過第一紫外線透明氣體分配噴淋頭216,以在氣體體積230中與先前曝露於紫外線輻射之氣體混合。分配體積222中之混合氣體進一步曝露於穿過第一紫外線透明氣體分配噴淋頭216之紫外線輻射,然後再流經第二紫外線透明氣體分配噴淋頭224以進入鄰近於基板支撐組件208之空間。鄰近於基板支撐組件208之氣體及安置在基板支撐組件208上之基板進一步曝露於穿過第二紫外線透明氣體分配噴淋頭224之紫外線輻射。氣體可穿過開口238而排出。可穿過腔室底部中之開口238提供淨化氣體,以便淨化氣體圍繞基板支撐
組件208流動,從而有效阻止製程氣體侵入基板支撐件下方之空間。
第一紫外線透明氣體分配噴淋頭216包括複數個通孔240,該等通孔允許處理氣體從氣體體積230流至分配體積222。第二紫外線透明氣體分配噴淋頭224亦包括複數個通孔242,該等通孔允許處理氣體從分配體積222流入鄰近於基板支撐組件208之處理空間中。第一及第二氣體紫外線透明氣體分配噴淋頭中之通孔可以相同間隔或不同間隔均勻分佈。
淨化氣體源或載氣源254可經由導管256耦接至第一流道232。在基板處理期間可經由第一流道232提供來自淨化氣體源254之淨化氣體,以阻止製程氣體侵入氣體體積230。清潔氣源274亦可經由導管256耦接至第一流道232,以在不處理基板時提供對導管256、第一流道232、氣體體積230,及腔室202中其餘部分之清潔。
製程氣體或前驅物化合物源258可經由導管260耦接至第二流道234以向腔室主體202提供,如上所述的混合物。製程氣源258亦可耦接至第三流道236。恰當之閥可允許選擇流道234、236中一者或兩者,以便使製程氣體混合物流入腔室主體202。
可藉由在基板支撐組件208中提供加熱及冷卻特徵來控制基板溫度。冷卻劑導管264可耦接至冷卻劑源270以向安置在基板支撐組件208中之冷卻氣室262提供冷卻劑。可使用之冷卻劑之一個實例是按體積計之
50%乙二醇於水中之混合物。冷卻劑流經控制以將基板溫度維持在所需水平或低於所需水平,以促進紫外線活化低聚物或片段在基板上之沉積。亦可在基板支撐組件208中提供加熱元件266。加熱元件266可為電阻加熱器,且可藉由導管268耦接至加熱源272,如電源。在上述硬化製程期間,加熱元件266可用以加熱基板。
儘管前述內容係針對本發明之實施例,但可在不背離本發明之基本範疇之前提下設計本發明之其他及更多實施例,且本發明之範疇由下文之發明申請專利範圍決定。
100‧‧‧流程圖
102‧‧‧步驟
104‧‧‧步驟
106‧‧‧步驟
Claims (20)
- 一種用於在一多孔低介電常數介電薄膜上形成一密封層之方法,該方法包括以下步驟:藉由使用紫外線輔助光化學氣相沉積在該多孔低介電常數介電薄膜上沉積一中間密封層;利用紫外線能或射頻能處理該中間密封層;及重複該沉積及處理製程,直至形成具有一預定厚度之一密封層。
- 如請求項1所述之方法,其中該紫外線輔助光化學氣相沉積包括將一前驅物化合物及一載氣引入該製程腔室中,及將紫外線能傳送至該多孔低介電常數介電薄膜。
- 如請求項2所述之方法,其中該前驅物化合物包括四乙烯基矽烷、三乙烯基甲基矽烷、三乙烯基矽烷、二乙烯基二甲基矽烷、六乙烯基二矽氧烷、四乙烯基二甲基二矽氧烷、三乙烯基乙氧基矽烷、三乙烯基甲氧基矽烷、二甲基二乙醯氧基矽烷、三乙醯氧基甲基矽烷、乙醯氧基三甲基矽烷、甲基二乙氧基矽烷、二甲基二乙氧基矽烷、二甲基二甲氧基矽烷、三甲基三乙烯基環三矽氧烷、八甲基環四矽氧烷、三(二甲基胺基)甲基矽烷、四(二甲基胺基)矽烷、三(二甲基胺基)矽烷、雙(二甲基胺基)二甲基矽烷、雙(二甲 基胺基)甲基乙烯基矽烷、三矽烷基胺、二甲基胺基三甲基矽烷、環三矽氮烷、三甲基三乙烯基環三矽氮烷、六甲基環三矽氮烷,或九甲基環三矽氮烷。
- 如請求項2所述之方法,其中該載氣包括He、Ar、N2或上述各者之組合。
- 如請求項1所述之方法,其中該紫外線輔助光化學氣相沉積在一腔室壓力下實施,該腔室壓力在約50mTorr與500Torr之間。
- 如請求項1所述之方法,其中該紫外線輔助光化學氣相沉積在一基板溫度下實施,該基板溫度在約50℃與約400℃之間。
- 如請求項1所述之方法,其中該中間密封層具有一厚度,該厚度範圍自約1Å至約5Å。
- 如請求項1所述之方法,其中該利用紫外線能處理該中間密封層之步驟包括以下步驟:使一反應性氣體流入一腔室中,該腔室中安置有一基板,該基板具有該多孔低介電常數介電薄膜及安置在該多孔低介電常數介電薄膜上之該中間密封層。
- 如請求項8所述之方法,其中該反應性氣體包括NH3、H2、O2、N2O、CO2或上述各者之組合。
- 如請求項8所述之方法,其中該利用紫外線能處理該中間密封層之步驟是在一腔室壓力下實施 的,該腔室壓力在約6Torr與200Torr之間。
- 如請求項1所述之方法,其中該預定厚度範圍自約5Å至約200Å。
- 如請求項1所述之方法,其中該沉積及處理製程重複2至100次。
- 一種用於在一多孔低介電常數介電薄膜上形成一密封層之方法,該方法包括以下步驟:開啟一或更多個紫外線燈以向安置在一製程腔室中之一基板傳送紫外線能,其中該多孔低介電常數介電薄膜安置在該基板上;使一第一前驅物化合物流入該製程腔室中,其中該第一前驅物化合物包含一單官能基;及使一第二前驅物化合物流入該製程腔室中,其中該第二前驅物化合物包含多官能基。
- 如請求項13所述之方法,其中該第一前驅物化合物包括乙醯氧基三甲基矽烷或二甲基胺基三甲基矽烷。
- 如請求項13所述之方法,其中該第二前驅物化合物包括二甲基二乙醯氧基矽烷或雙(二甲基胺基)二甲基矽烷。
- 如請求項13所述之方法,進一步包括以下步驟:在該多孔低介電常數介電薄膜上形成該密封層。
- 如請求項16所述之方法,其中該密封層具有一厚度,該厚度自約5Å至約200Å。
- 如請求項16所述之方法,進一步包括以下步驟:利用紫外線能固化該密封層。
- 一種用於在一多孔低介電常數介電薄膜上形成一密封層之方法,該方法包括以下步驟:開啟一或更多個紫外線燈以向安置在一製程腔室中之一基板傳送紫外線能,其中該多孔低介電常數介電薄膜安置在該基板上;使一第一前驅物化合物流入該製程腔室中,其中該第一前驅物化合物包括乙醯氧基三甲基矽烷或二甲基胺基三甲基矽烷;及使一第二前驅物化合物流入該製程腔室中,其中該第二前驅物化合物包括二甲基二乙醯氧基矽烷或雙(二甲基胺基)二甲基矽烷。
- 如請求項19所述之方法,其中該密封層具有一厚度,該厚度自約5Å至約200Å。
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US11017998B2 (en) | 2016-08-30 | 2021-05-25 | Versum Materials Us, Llc | Precursors and flowable CVD methods for making low-K films to fill surface features |
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