TWI382104B - 於ａｌｄ／ｃｖｄ製程中作為ｇｓｔ膜的銻前驅物 - Google Patents
於ａｌｄ／ｃｖｄ製程中作為ｇｓｔ膜的銻前驅物 Download PDFInfo
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- TWI382104B TWI382104B TW098103029A TW98103029A TWI382104B TW I382104 B TWI382104 B TW I382104B TW 098103029 A TW098103029 A TW 098103029A TW 98103029 A TW98103029 A TW 98103029A TW I382104 B TWI382104 B TW I382104B
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- ruthenium
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- 239000002243 precursor Substances 0.000 title claims description 29
- 238000000034 method Methods 0.000 title claims description 25
- 229910052787 antimony Inorganic materials 0.000 title 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 title 1
- 229910052707 ruthenium Inorganic materials 0.000 claims description 37
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 34
- 125000003118 aryl group Chemical group 0.000 claims description 31
- 125000004432 carbon atom Chemical group C* 0.000 claims description 31
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 29
- 125000003342 alkenyl group Chemical group 0.000 claims description 21
- 238000000231 atomic layer deposition Methods 0.000 claims description 19
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 18
- -1 decylene ruthenium Chemical compound 0.000 claims description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- 239000007983 Tris buffer Substances 0.000 claims description 9
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 229910000929 Ru alloy Inorganic materials 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- 238000000277 atomic layer chemical vapour deposition Methods 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- WMOJAWPGEQWAMM-UHFFFAOYSA-N [Ir].[Ru].[Ru] Chemical compound [Ir].[Ru].[Ru] WMOJAWPGEQWAMM-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- 150000001924 cycloalkanes Chemical class 0.000 claims description 3
- FFGPTBGBLSHEPO-UHFFFAOYSA-N carbamazepine Chemical group C1=CC2=CC=CC=C2N(C(=O)N)C2=CC=CC=C21 FFGPTBGBLSHEPO-UHFFFAOYSA-N 0.000 claims description 2
- 229960000623 carbamazepine Drugs 0.000 claims description 2
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 claims 2
- 229960003105 metformin Drugs 0.000 claims 2
- SFFUHUGVJGVRCJ-UHFFFAOYSA-N CCCCCCCCCC.[Ru] Chemical compound CCCCCCCCCC.[Ru] SFFUHUGVJGVRCJ-UHFFFAOYSA-N 0.000 claims 1
- MDMXQSXFPASRFQ-UHFFFAOYSA-N [Ru].[Ru].[Re] Chemical compound [Ru].[Ru].[Re] MDMXQSXFPASRFQ-UHFFFAOYSA-N 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 7
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 7
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229910052762 osmium Inorganic materials 0.000 description 4
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 229910052715 tantalum Inorganic materials 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 3
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CJEAKKMNOSJYMY-UHFFFAOYSA-N 2-chloro-2-methylundecane Chemical compound CCCCCCCCCC(C)(C)Cl CJEAKKMNOSJYMY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PNKUSGQVOMIXLU-UHFFFAOYSA-N Formamidine Chemical group NC=N PNKUSGQVOMIXLU-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 description 2
- 229910000103 lithium hydride Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229960000485 methotrexate Drugs 0.000 description 2
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 150000002923 oximes Chemical class 0.000 description 2
- 239000012782 phase change material Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 150000003303 ruthenium Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- LBAANPWUYHUCJL-UHFFFAOYSA-N 1,2-dimethylhydrazine hydrazine Chemical compound CNNC.NN LBAANPWUYHUCJL-UHFFFAOYSA-N 0.000 description 1
- ZQBSPSZMRYBLLZ-UHFFFAOYSA-N CC(CCCCCCCCCCl)(C)C Chemical compound CC(CCCCCCCCCCl)(C)C ZQBSPSZMRYBLLZ-UHFFFAOYSA-N 0.000 description 1
- KSSJBGNOJJETTC-UHFFFAOYSA-N COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC Chemical compound COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC KSSJBGNOJJETTC-UHFFFAOYSA-N 0.000 description 1
- FBOZXECLQNJBKD-ZDUSSCGKSA-N L-methotrexate Chemical compound C=1N=C2N=C(N)N=C(N)C2=NC=1CN(C)C1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 FBOZXECLQNJBKD-ZDUSSCGKSA-N 0.000 description 1
- KFMLSKLCIQLEQK-UHFFFAOYSA-N [SiH3].[Sb] Chemical compound [SiH3].[Sb] KFMLSKLCIQLEQK-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- CVXBEEMKQHEXEN-UHFFFAOYSA-N carbaryl Chemical compound C1=CC=C2C(OC(=O)NC)=CC=CC2=C1 CVXBEEMKQHEXEN-UHFFFAOYSA-N 0.000 description 1
- 229960005286 carbaryl Drugs 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000003800 germyl group Chemical group [H][Ge]([H])([H])[*] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- JKUUTODNPMRHHZ-UHFFFAOYSA-N n-methyl-n-[tris(dimethylamino)germyl]methanamine Chemical compound CN(C)[Ge](N(C)C)(N(C)C)N(C)C JKUUTODNPMRHHZ-UHFFFAOYSA-N 0.000 description 1
- KAHVZNKZQFSBFW-UHFFFAOYSA-N n-methyl-n-trimethylsilylmethanamine Chemical compound CN(C)[Si](C)(C)C KAHVZNKZQFSBFW-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- IOJMHYLAOTZEKB-UHFFFAOYSA-N tetrakis(dimethylamino)phosphanium Chemical compound CN(C)[P+](N(C)C)(N(C)C)N(C)C IOJMHYLAOTZEKB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C23C16/06—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 metallic material
- C23C16/18—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 metallic material from metallo-organic compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G17/00—Compounds of germanium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G30/00—Compounds of antimony
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/90—Antimony compounds
- C07F9/902—Compounds without antimony-carbon linkages
-
- 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
-
- 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
- C23C16/305—Sulfides, selenides, or tellurides
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Vapour Deposition (AREA)
- Semiconductor Memories (AREA)
Description
本專利申請主張享有2008年1月28日申請的美國臨時專利申請，序號61/023989的利益。
本發明涉及一種製造鍺-銻-碲合金膜的方法，該方法使用選自原子層沉積和化學氣相沉積的製程，其中使用甲矽烷銻前驅物作為合金膜中銻的來源。
作為一種新興技術，相變材料引起越來越多興趣。因為它們可應用於製造新型高度積體的、永久的儲存裝置：相變隨機存取記憶體(PRAM)。相變隨機存取記憶體(PRAM)裝置通過在經歷晶相和非晶相之間可逆相變時具有明顯的不同電阻的材料合成。最通常使用的相變材料是含有14族和15族的硫族化合物組成的三元化合物，如鍺-銻-碲化合物，通常的縮寫為GST。
在設計PRAM單元時的一個技術障礙是克服GST材料在一定溫度下從晶態向非晶態轉變的過程中的散熱問題，這個過程需要應用高水準的重定電流。通過將GST材料限制在接觸插頭，可以減少上述過程對復位電流的需求，從而可以大大減少散熱。為了在基體上構建GST插頭，採用原子層沉積(ALD)製程，製造具有高保形性和化學成分一致性的膜。
相關的現有技術包括：
sang-Wook Kim,S. Sujith,Bun Yeoul Lee,Chem. Commun.,2006,4811-4813頁。
Stephan Schulz,Martin Nieger,J. Organometallic Chem.,570,1998,275-278頁。
Byung Joon Choi，等. Chem Mater. 2007,19,pp 4387-4389;Byung Joon Choi，等. J. Electrochem. Soc.,154,pp H318-H324(2007)。
Ranyoung Kim,Hogi Kim,Soongil Yoon,Applied Phys. Letters,89,pp 102-107(2006)。
Junghyun Lee,Sangjoon Choi,Changsoo Lee,Yoonho Kang,Daeil Kim,Applied Surface Science,253(2007)pp 3969-3976。
G. Becker,H. Freudenblum,O. Mundt,M. reti,M. Sachs,Synthetic Methods of Organometallic and lnorganic Chemistry,vol. 3,H.H. Karsch,New York,1996,p. 193。
Sladek,A.,Schmidbaur,H.,Chem. Ber. 1995,128,pp 565-567。
美國專利申請：
US2006/0049447
A1；
US2006/0039192
A1；
US2006/0072370
A1；和
US2006/0172083
A1。
本發明是一種製造鍺-銻-碲合金膜的方法，該方法利用了原子層沉積和化學氣相沉積中的一種製程，其中使用甲矽烷銻(silylantimony)前驅物作為合金膜中銻的來源。
優選的，本發明是一種製造鍺-銻-碲合金膜的方法，該方法利用了選自原子層沉積和化學氣相沉積中的製程，其中使用甲矽烷銻前驅物作為合金膜中銻的來源。其中甲矽烷銻前驅物選自：
其中R2-10
獨立地為氫原子，具有1到10個碳原子的直鏈、支鏈、或環狀的烷基基團或鏈烯基基團，或者芳香基團；R1
獨立地為氫原子，具有2到10個碳原子的直鏈、支鏈、或環狀的烷基基團或鏈烯基基團，或者芳香基團；R11
和R12
獨立地為具有1到10個碳原子的直鏈、支鏈、或環狀的烷基基團或鏈烯基基團，或者芳香基團；其中所述鍺前驅物是具有以下通式的胺基鍺：
其中R1
和R2
獨立地為具有1到10個碳原子的直鏈、支鏈、或環狀的烷基基團；其中碲前驅物是甲矽烷碲，其選自：
並且R1
、R2
、R3
、R4
、R5
和R6
獨立地為氫原子，具有1到10個碳原子的直鏈、支鏈、或環狀的含有或不含雙鍵的烷基基團，或者芳香基團。
本發明也涉及一種物質組成(化合物)，其選自如下的通式結構：
其中R2-10
獨立地為氫原子，具有1到10個碳原子的直鏈、支鏈、或環狀的烷基基團或鏈烯基基團，或者芳香基團；R1
獨立地為氫原子，具有2到10個碳原子的直鏈、支鏈、或環狀的烷基基團或鏈烯基基團，或者芳香基團；R11
和R12
獨立地為具有1到10個碳原子的直鏈、支鏈、或環狀的烷基基團或鏈烯基基團，或者芳香基團；如果結構(A)中，R1-9
中的一個是苯基，那麼在承載苯基的矽原子上的剩餘的R1-9
不能全是甲基；如果結構(A)中R1-9
中的任一個是C1-3
或苯基，那麼不是所有的R1-9
全都相同。
本發明涉及一類銻前驅物，其在ALD製程中產生銻層。該銻層與隨後在ALD循環中沉積的鍺和碲層發生反應，並形成GST三元材料膜，該膜適用於PRAM裝置。
GST材料在PRAM裝置中通常在溫度範圍180-300℃下沉積。已發現，在200℃沉積的膜具有最好的化學和結構特性。ALD製程要求前驅物具有高的化學反應性和反應選擇性。目前存在的前驅物，如二烷基碲(dialkyltellium)、三烷基銻(trialkylantimony)、和烷基鍺(alkylgermanes)，在用於ALD循環中的沉積條件下，不具有要求的反應性。經常的，電漿被用於促進沉積。
本發明提供甲矽烷銻化合物作為ALD前驅物，它與醇類或水反應生成銻層。該銻層與隨後從四胺基鍺(tetraaminogermanium)和有機碲(organotellurium)前驅物沉積的鍺和碲形成沉積在基體上具有高保形性的GST膜。
本發明涉及一類銻前驅物，其在ALD製程中產生銻層。該銻層與隨後在ALD循環中沉積的鍺和碲層發生反應，並形成GST三元材料膜，該膜適於用於PRAM裝置。本發明公開了幾個甲矽烷銻前驅物具有高反應性和熱穩定性，並且該化學作用連同其他化學製品用於ALD製程以沉積GST膜。
本發明提供甲矽烷銻化合物作為ALD前驅物，它與醇類或水反應生成銻層。該銻層與隨後從四胺基鍺和碲前驅物沉積的鍺和碲形成沉積在基體上具有高保形性的GST膜。
銻前驅物可以包含三矽烷銻(trisilylantimony)、二矽烷甲基銻(disilylalkylantimony)、二矽烷銻(disilylantimony)或者二矽烷胺基銻(disilylaminoantimony)，選自：
其中R2-10
獨立地為氫原子，具有1到10個碳原子的直鏈、支鏈、或環狀的烷基基團或鏈烯基基團，或者芳香基團；R1
獨立地為氫原子，具有2到10個碳原子的直鏈、支鏈、或環狀的烷基基團或鏈烯基基團，或者芳香基團；R11
和R12
獨立地為具有1到10個碳原子的直鏈、支鏈、或環狀的烷基基團或鏈烯基基團，或者芳香基團；優選如果結構(A)中，R1-9
中的一個是芳香基，那麼在承載芳香基的矽原子上的剩餘的R1-9
不能全是甲基。
甲矽烷銻化合物與醇類或水具有高反應性。該反應在低溫下產生元素銻：
這些反應可以發生在室溫到300℃的溫度範圍內。
在ALD製程中，銻前驅物、醇類、鍺和碲前驅物，例如(Me2
N)4
Ge和(Me3
Si)2
Te(其中“Me”是甲基)，通過氣體抽吸或直接液體噴射(DLI)以循環方式被引入沉積室。沉積溫度優選在100到400℃之間。
ALD反應可以由以下方案說明：
步驟1. 四(二甲胺基)鍺
[Tetrakis(dimethylamino)germane}被引入，在基體表面上形成胺基鍺的分子層。
步驟2. 六甲基二矽烷碲(Hexamethyldisilyltellurium}與胺基鍺層發生反應，形成Te-Ge鍵，並消除二甲胺基三甲基矽烷(dimethylaminotrimethylsilane)。形成具有甲矽烷基的Te層。
步驟3. 甲醇與剩餘的甲矽烷基團在碲層上發生反應，形成Te-H鍵，以及不穩定副產品甲氧三甲基矽烷(methoxytrimethylsilane)，其被淨化消除。
步驟4. 三(三甲基甲矽烷)銻被引入，並在碲層之上形成銻層。
步驟5. 甲醇與剩餘的甲矽烷基團在銻層上發生反應以形成Sb-H鍵，以及不穩定副產品甲氧三甲基矽烷(methoxytrimethylsilane)，其被淨化消除。
步驟6. 六甲基二矽烷碲(Hexamethyldisilyltellurium)被再次引入，並形成碲層。
步驟7. 甲醇被再次引入以消除碲上的甲矽烷基團。
ALD循環然後完全重複，可能很多次，直到獲得理想的膜厚度。下一個循環從步驟1再次開始，等等。
該製程中的甲矽烷銻化合物選自：
其中R2-10
獨立地為氫原子，具有1到10個碳原子的直鏈、支鏈、或環狀的烷基基團或鏈烯基基團，或者芳香基團；R1
獨立地為氫原子，含有具有2到10個碳原子的直鏈、支鏈、或環狀的烷基或鏈烯基基團，或者芳香基團；R11
和R12
獨立地為具有1到10個碳原子的直鏈、支鏈、或環狀的烷基或鏈烯基基團，或者芳香基團；優選如果結構(A)中，R1-9
中的一個是芳香基，那麼在承載芳香基的矽原子上的剩餘的R1-9
不能全是甲基；更優選，如果結構(A)中R1-9
中的任一個是C1-3
或苯基，那麼不是所有的R1-9
全都相同。
該方法中的胺基鍺具有通式：
其中R1
和R2
獨立地為1到10個碳原子形成的直鏈、支鏈、或環狀的烷基基團。
碲前驅物可以包含二甲矽烷碲、甲矽烷烴基碲或甲矽烷胺基碲，選自：
其中R1
，R2
，R3
，R4
，R5
和R6
獨立地為氫原子，具有1到10個碳原子含有或不含雙鍵的直鏈、支鏈、或環狀的烷基基團，或者芳香基團。
該方法中的醇類具有通式：
ROH
其中R是具有1到10個碳原子的直鏈、支鏈、或環狀的烷基基團。
1.22g(0.01mol)200目的銻粉，0.72g(0.03mol)的氫化鋰，和40ml的四氫呋喃(THF)置於100ml燒瓶。伴隨攪拌，混合物被迴流4小時。所有含銻的黑色粉末消失，土色沉澱物形成。然後，混合物冷卻到-20℃；加入3.3g(0.03mol)三甲基氯矽烷。混合物被加熱至室溫，攪拌4小時後，混合物在惰性氣氛下被過濾。溶劑通過蒸餾除去。三(三甲基甲矽烷)銻通過真空蒸餾純化。
1.22g(0.01mol)200目的銻粉，0.72g(0.03mol)的氫化鋰，和40ml的四氫呋喃(THF)置於100ml燒瓶。伴隨攪拌，混合物被迴流4小時。所有含銻的黑色粉末消失，土色沉澱物形成。然後，混合物冷卻到-20℃；加入2.83g(0.03mol)二甲基氯矽烷。混合物被加熱至室溫，攪拌4小時後，混合物在惰性氣氛下被過濾。溶劑通過蒸餾除去。三(二甲基甲矽烷)銻通過真空蒸餾純化。
3.65g(0.03mol)200目的銻粉，2.07g(0.09mol)的鈉，1.15g(0.009mol)的萘和50ml的(THF)置於10ml燒瓶。混合物在室溫下攪拌24小時。所有含銻和鈉的黑色粉末消失，土色沉澱物形成。然後，混合物冷卻到-20℃；加入8.51g(0.09mol)二甲基氯矽烷。混合物被加熱至室溫，攪拌4小時後，混合物在惰性氣氛下被過濾。溶劑通過蒸餾除去。三(二甲基甲矽烷)銻通過真空蒸餾純化。
0.05g的三(二甲基甲矽烷)銻置於100ml耐火玻璃燒瓶底部，裝滿氮氣和橡膠隔片。用注射器緩慢添加0.1g的甲醇。亮黑的膜開始沉積在燒瓶的玻璃內壁。幾分鐘之後，全部的燒瓶內壁包上暗灰色/黑色的銻膜。
Claims (8)
- 一種製造鍺-銻-碲合金膜的方法，該方法使用選自原子層沉積和化學氣相沉積的製程，其中使用甲矽烷銻前驅物作為合金膜中銻的來源，其中所述甲矽烷銻前驅物的沉積後接著進行與具有通式ROH的醇的接觸，其中R是具有1到10個碳原子的直鏈、支鏈、或環狀的的烷基基團，或者芳香基團。
- 如申請專利範圍第1項的方法，其中甲矽烷銻前驅物選自三甲矽烷銻、二甲矽烷銻、烷基二甲矽烷銻、胺基二甲矽烷銻和它們的混合物。
- 如申請專利範圍第1項的方法，其中甲矽烷銻前驅物選自：
- 如申請專利範圍第1項的方法，其中所述甲矽烷銻前驅物是三(三甲基甲矽烷)銻。
- 如申請專利範圍第1項的方法，其中使用具有如下通式的胺基鍺作為鍺的來源：
- 如申請專利範圍第1項的方法，其中使用具有如下通式的甲矽烷碲作為碲的來源：
- 一種製造鍺-銻-碲合金膜的方法，其使用選自原子層沉積和化學氣相沉積的製程，其中甲矽烷銻前驅物被用作所述合金膜的銻的來源，其中所述甲矽烷銻前驅物的沉積後接著進行與具有通式ROH的醇的接觸，其中R是具有1到10個碳原子的直鏈、支鏈、或環狀的的烷基基團，或者芳香基團，其中所述甲矽烷銻選自：
- 一種具有選自下述通式結構的物質組成，
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| JP5718808B2 (ja) * | 2008-04-25 | 2015-05-13 | エーエスエム インターナショナル エヌ．ヴェー．Ａｓｍ Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｎ．Ｖ． | テルルおよびセレン薄膜のａｌｄのための前駆体の合成および使用 |
-
2009
- 2009-01-16 US US12/355,325 patent/US8318252B2/en active Active
- 2009-01-23 TW TW098103029A patent/TWI382104B/zh not_active IP Right Cessation
- 2009-01-27 EP EP09151404A patent/EP2083096B1/en not_active Not-in-force
- 2009-01-28 JP JP2009016913A patent/JP5350819B2/ja not_active Expired - Fee Related
- 2009-01-28 KR KR1020090006706A patent/KR101068013B1/ko active IP Right Grant
- 2009-02-01 CN CN2009101267678A patent/CN101497999B/zh not_active Expired - Fee Related
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2012
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006182781A (ja) * | 2004-12-27 | 2006-07-13 | Samsung Electronics Co Ltd | ゲルマニウム前駆体、これを利用して形成されたｇｓｔ薄膜、前記薄膜の製造方法及び相変化メモリ素子 |
| WO2007133837A2 (en) * | 2006-05-12 | 2007-11-22 | Advanced Technology Materials, Inc. | Low temperature deposition of phase change memory materials |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5778648B2 (ja) | 2015-09-16 |
| CN101497999B (zh) | 2012-08-08 |
| CN101497999A (zh) | 2009-08-05 |
| KR101068013B1 (ko) | 2011-09-26 |
| EP2083096B1 (en) | 2013-01-02 |
| KR20090082873A (ko) | 2009-07-31 |
| EP2083096A1 (en) | 2009-07-29 |
| JP5350819B2 (ja) | 2013-11-27 |
| US8318252B2 (en) | 2012-11-27 |
| TW200934885A (en) | 2009-08-16 |
| JP2013060663A (ja) | 2013-04-04 |
| JP2009215645A (ja) | 2009-09-24 |
| US20090191330A1 (en) | 2009-07-30 |
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