CN101497999A - 在ald/cvd工艺中用于gst膜的锑前驱体 - Google Patents
在ald/cvd工艺中用于gst膜的锑前驱体 Download PDFInfo
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- 229910052787 antimony Inorganic materials 0.000 title claims abstract description 49
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000002243 precursor Substances 0.000 title claims abstract description 18
- 230000008569 process Effects 0.000 title claims abstract description 13
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 12
- 239000000956 alloy Substances 0.000 claims abstract description 12
- 229910000618 GeSbTe Inorganic materials 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 31
- 125000003118 aryl group Chemical group 0.000 claims description 30
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 27
- 229910052714 tellurium Inorganic materials 0.000 claims description 24
- 229910052799 carbon Inorganic materials 0.000 claims description 23
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 22
- 125000003342 alkenyl group Chemical group 0.000 claims description 21
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 18
- 238000005516 engineering process Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- -1 dimethylamino silane antimony Chemical compound 0.000 claims description 11
- 229910052732 germanium Inorganic materials 0.000 claims description 10
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 235000013399 edible fruits Nutrition 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- GMEFXBFKMIZRMO-UHFFFAOYSA-N aminogermanium Chemical compound [Ge]N GMEFXBFKMIZRMO-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000005229 chemical vapour deposition Methods 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 4
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- KFMLSKLCIQLEQK-UHFFFAOYSA-N [SiH3].[Sb] Chemical compound [SiH3].[Sb] KFMLSKLCIQLEQK-UHFFFAOYSA-N 0.000 abstract 2
- 238000000231 atomic layer deposition Methods 0.000 abstract 2
- 238000000277 atomic layer chemical vapour deposition Methods 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 150000001462 antimony Chemical class 0.000 description 4
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 4
- 150000001463 antimony compounds Chemical class 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 4
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- 239000006227 byproduct Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- NEXSMEBSBIABKL-UHFFFAOYSA-N hexamethyldisilane Chemical compound C[Si](C)(C)[Si](C)(C)C NEXSMEBSBIABKL-UHFFFAOYSA-N 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
- KAHVZNKZQFSBFW-UHFFFAOYSA-N n-methyl-n-trimethylsilylmethanamine Chemical compound CN(C)[Si](C)(C)C KAHVZNKZQFSBFW-UHFFFAOYSA-N 0.000 description 2
- 239000012782 phase change material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- OIXHIBFNPLDJGB-UHFFFAOYSA-N [Sb].[SiH3][Sb] Chemical compound [Sb].[SiH3][Sb] OIXHIBFNPLDJGB-UHFFFAOYSA-N 0.000 description 1
- YOGDCUXJBTUDNU-UHFFFAOYSA-N [SiH3][Sb].[SiH3][Sb] Chemical compound [SiH3][Sb].[SiH3][Sb] YOGDCUXJBTUDNU-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- YNYBCPCYMAHDCS-UHFFFAOYSA-N dimethylaminogermanium Chemical compound CN(C)[Ge] YNYBCPCYMAHDCS-UHFFFAOYSA-N 0.000 description 1
- AWFPGKLDLMAPMK-UHFFFAOYSA-N dimethylaminosilicon Chemical compound CN(C)[Si] AWFPGKLDLMAPMK-UHFFFAOYSA-N 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QLWFRFCRJULPCK-UHFFFAOYSA-N methylantimony Chemical compound [Sb]C QLWFRFCRJULPCK-UHFFFAOYSA-N 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- GMMAPXRGRVJYJY-UHFFFAOYSA-J tetrasodium 4-acetamido-5-hydroxy-6-[[7-sulfonato-4-[(4-sulfonatophenyl)diazenyl]naphthalen-1-yl]diazenyl]naphthalene-1,7-disulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].OC1=C2C(NC(=O)C)=CC=C(S([O-])(=O)=O)C2=CC(S([O-])(=O)=O)=C1N=NC(C1=CC(=CC=C11)S([O-])(=O)=O)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 GMMAPXRGRVJYJY-UHFFFAOYSA-J 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
Classifications
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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
- C23C16/06—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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G17/00—Compounds of germanium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G30/00—Compounds of antimony
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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
- 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
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- 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
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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
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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
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- 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
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Abstract
本发明涉及在ALD/CVD工艺中用于GST膜的锑前驱体。本发明是一种制造锗-锑-碲合金膜的方法，该方法利用了选自原子层沉积和化学气相沉积中的一种工艺，其中甲硅烷锑前驱体被用作为合金膜中锑的来源。新的甲硅烷锑化合物也被公开。
Description
交叉引用的相关申请
本专利申请主张享有2008年1月28日申请的美国临时专利申请，序号61/023989的利益。
技术领域
本发明涉及一种制造锗—锑—碲合金膜的方法，该方法使用选自原子层沉积和化学气相沉积的工艺，其中使用甲硅烷锑前驱体作为合金膜中锑的来源。
背景技术
作为一种新兴技术，相变材料引起越来越多兴趣。因为它们可应用于制造新型高度集成的、永久的存储装置：相变随机存取存储器(PRAM)。相变随机存取存储器(PRAM)装置通过在经历晶相和非晶相之间可逆相变时具有明显的不同电阻的材料合成。最通常使用的相变材料是含有14族和15族的硫族化合物组成的三元化合物，如锗—锑—碲化合物，通常的缩写为GST。
在设计PRAM单元时的一个技术障碍是克服GST材料在一定温度下从晶态向非晶态转变的过程中的散热问题，这个过程需要应用高水平的复位电流。通过将GST材料限制在接触插头，可以减少上述过程对复位电流的需求，从而可以大大减少散热。为了在基体上构建GST插头，采用原子层沉积(ALD)工艺，制造具有高保形性和化学成分一致性的膜。
相关的现有技术包括：
sang-WookKim，S.Sujith，BunYeoulLee，Chem.Commun.，2006，4811-4813页。
Stephan Schulz，Martin Nieger，J.Organometallic Chem.，570，1998，275-278页。
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 ofOrganometallic and Inorganic Chemistry，vol.3，H.H.Karsch，New York，1996，p.193。
Sladek，A.，Schmidbaur，H.，Chem.Ber.1995，128，pp 565-567。
美国专利申请：
US 2006/0049447 A1；
US 2006/0039192 A1；
US 2006/0072370 A1；和
US 2006/0172083 A1。
发明内容
本发明是一种制造锗—锑—碲合金膜的方法，该方法利用了原子层沉积和化学气相沉积中的一种工艺，其中使用甲硅烷锑(silylantimony)前驱体作为合金膜中锑的来源。
优选的，本发明是一种制造锗—锑—碲合金膜的方法，该方法利用了选自原子层沉积和化学气相沉积中的工艺，其中使用甲硅烷锑前驱体作为合金膜中锑的来源。其中甲硅烷锑前驱体选自：
其中R2-10独立地为氢原子，具有1到10个碳原子的直链、支链、或环状的烷基基团或链烯基基团，或者芳香基团；R1独立地为氢原子，具有2到10个碳原子的直链、支链、或环状的烷基基团或链烯基基团，或者芳香基团；R11和R12独立地为具有1到10个碳原子的直链、支链、或环状的烷基基团或链烯基基团，或者芳香基团；其中所述锗前驱体是具有以下通式的氨基锗：
其中R1和R2独立地为具有1到10个碳原子的直链、支链、或环状的烷基基团；其中碲前驱体是甲硅烷碲，其选自：
并且R1、R2、R3、R4、R5和R6独立地为氢原子，具有1到10个碳原子的直链、支链、或环状的含有或不含双键的烷基基团，或者芳香基团。
本发明也涉及一种物质组成(化合物)，其选自如下的通式结构：
其中R2-10独立地为氢原子，具有1到10个碳原子的直链、支链、或环状的烷基基团或链烯基基团，或者芳香基团；R1独立地为氢原子，具有2到10个碳原子的直链、支链、或环状的烷基基团或链烯基基团，或者芳香基团；R11和R12独立地为具有1到10个碳原子的直链、支链、或环状的烷基基团或链烯基基团，或者芳香基团；如果结构(A)中，R1-9中的一个是苯基，那么在承载苯基的硅原子上的剩余的R1-9不能全是甲基；如果结构(A)中R1-9中的任一个是C1-3或苯基，那么不是所有的R1-9全都相同。
具体实施方式
本发明涉及一类锑前驱体，其在ALD工艺中产生锑层。该锑层与随后在ALD循环中沉积的锗和碲层发生反应，并形成GST三元材料膜，该膜适用于PRAM装置。
GST材料在PRAM装置中通常在温度范围180-300℃下沉积。已发现，在200℃沉积的膜具有最好的化学和结构特性。ALD工艺要求前驱体具有高的化学反应性和反应选择性。目前存在的前驱体，如二烷基碲(dialkyltellium)、三烷基锑(trialkylantimony)、和烷基锗(alkylgermanes)，在用于ALD循环中的沉积条件下，不具有要求的反应性。经常的，等离子体被用于促进沉积。
本发明提供甲硅烷锑化合物作为ALD前驱体，它与醇类或水反应生成锑层。该锑层与随后从四氨基锗(tetraaminogermanium)和有机碲(organotellurium)前驱体沉积的锗和碲形成沉积在基体上具有高保形性的GST膜。
本发明涉及一类锑前驱体，其在ALD工艺中产生锑层。该锑层与随后在ALD循环中沉积的锗和碲层发生反应，并形成GST三元材料膜，该膜适于用于PRAM装置。本发明公开了几个甲硅烷锑前驱体具有高反应性和热稳定性，并且该化学作用连同其他化学制品用于ALD工艺以沉积GST膜。
本发明提供甲硅烷锑化合物作为ALD前驱体，它与醇类或水反应生成锑层。该锑层与随后从四氨基锗和碲前驱体沉积的锗和碲形成沉积在基体上具有高保形性的GST膜。
锑前驱体可以包含三硅烷锑(trisilylantimony)、二硅烷甲基锑(disilylalkylantimony)、二硅烷锑(disilylantimony)或者二硅烷氨基锑(disilylaminoantimony)，选自：
其中R2-10独立地为氢原子，具有1到10个碳原子的直链、支链、或环状的烷基基团或链烯基基团，或者芳香基团；R1独立地为氢原子，具有2到10个碳原子的直链、支链、或环状的烷基基团或链烯基基团，或者芳香基团；R11和R12独立地为具有1到10个碳原子的直链、支链、或环状的烷基基团或链烯基基团，或者芳香基团；优选如果结构(A)中，R1-9中的一个是芳香基，那么在承载芳香基的硅原子上的剩余的R1-9不能全是甲基。
甲硅烷锑化合物与醇类或水具有高反应性。该反应在低温下产生元素锑：
这些反应可以发生在室温到300℃的温度范围内。
在ALD工艺中，锑前驱体、醇类、锗和碲前驱体，例如(Me2N)4Ge和(Me3Si)2Te(其中“Me”是甲基)，通过气体抽吸或直接液体喷射(DLI)以循环方式被引入沉积室。沉积温度优选在100到400℃之间。
ALD反应可以由以下方案说明：
步骤1.四(二甲氨基)锗[Tetrakis(dimethylamino)germane}被引入，在基体表面上形成氨基锗的分子层。
步骤2.六甲基二硅烷碲(Hexamethyldisilyltellurium}与氨基锗层发生反应，形成Te-Ge键，并消除二甲氨基三甲基硅烷(dimethylaminotrimethylsilane)。形成具有甲硅烷基的Te层。
步骤3.甲醇与剩余的甲硅烷基团在碲层上发生反应，形成Te-H键，以及不稳定副产品甲氧三甲基硅烷(methoxytrimethylsilane)，其被净化消除。
步骤4.三(三甲基甲硅烷)锑被引入，并在碲层之上形成锑层。
步骤5.甲醇与剩余的甲硅烷基团在锑层上发生反应以形成Sb-H键，以及不稳定副产品甲氧三甲基硅烷(methoxytrimethylsilane)，其被净化消除。
步骤6.六甲基二硅烷碲(Hexamethyldisilyltellurium)被再次引入，并形成碲层。
步骤7.甲醇被再次引入以消除碲上的甲硅烷基团。
ALD循环然后完全重复，可能很多次，直到获得理想的膜厚度。下一个循环从步骤1再次开始，等等。
该工艺中的甲硅烷锑化合物选自：
其中R2-10独立地为氢原子，具有1到10个碳原子的直链、支链、或环状的烷基基团或链烯基基团，或者芳香基团；R1独立地为氢原子，含有具有2到10个碳原子的直链、支链、或环状的烷基或链烯基基团，或者芳香基团；R11和R12独立地为具有1到10个碳原子的直链、支链、或环状的烷基或链烯基基团，或者芳香基团；优选如果结构(A)中，R1-9中的一个是芳香基，那么在承载芳香基的硅原子上的剩余的R1-9不能全是甲基；更优选，如果结构(A)中R1-9中的任一个是C1-3或苯基，那么不是所有的R1-9全都相同。
该方法中的氨基锗具有通式：
其中R1和R2独立地为1到10个碳原子形成的直链、支链、或环状的烷基基团。
碲前驱体可以包含二甲硅烷碲、甲硅烷烃基碲或甲硅烷氨基碲，选自：
其中R1，R2，R3，R4，R5和R6独立地为氢原子，具有1到10个碳原子含有或不含双键的直链、支链、或环状的烷基基团，或者芳香基团。
该方法中的醇类具有通式：
ROH
其中R是具有1到10个碳原子的直链、支链、或环状的烷基基团。
实施例1 三(三甲基甲硅烷)锑的合成
1.22g(0.01mol)200目的锑粉，0.72g(o.03mol)的氢化锂，和40ml的四氢呋喃(THF)置于100ml烧瓶。伴随搅拌，混合物被回流4小时。所有含锑的黑色粉末消失，土色沉淀物形成。然后，混合物冷却到—20℃；加入3.3g(0.03mol)三甲基氯硅烷。混合物被加热至室温，搅拌4小时后，混合物在惰性气氛下被过滤。溶剂通过蒸馏除去。三(三甲基甲硅烷)锑通过真空蒸馏纯化。
实施例2 三(二甲基甲硅烷)锑的合成
1.22g(0.01mol)200目的锑粉，0.72g(0.03mol)的氢化锂，和40ml的四氢呋喃(THF)置于100ml烧瓶。伴随搅拌，混合物被回流4小时。所有含锑的黑色粉末消失，土色沉淀物形成。然后，混合物冷却到—20℃；加入2.83g(0.03mol)二甲基氯硅烷。混合物被加热至室温，搅拌4小时后，混合物在惰性气氛下被过滤。溶剂通过蒸馏除去。三(二甲基甲硅烷)锑通过真空蒸馏纯化。
实施例3 三(二甲基甲硅烷)锑的合成
3.65g(0.03mol)200目的锑粉，2.07g(0.09mol)的钠，1.15g(0.009mol)的萘和50ml的(THF)置于100ml烧瓶。混合物在室温下搅拌24小时。所有含锑和钠的黑色粉末消失，土色沉淀物形成。然后，混合物冷却到—20℃；加入8.51g(0.09mol)二甲基氯硅烷。混合物被加热至室温，搅拌4小时后，混合物在惰性气氛下被过滤。溶剂通过蒸馏除去。三(二甲基甲硅烷)锑通过真空蒸馏纯化。
实施例4 锑膜的生成
0.05g的三(二甲基甲硅烷)锑置于100ml耐火玻璃烧瓶底部，装满氮气和橡胶隔片。用注射器缓慢添加0.1g的甲醇。亮黑的膜开始沉积在烧瓶的玻璃内壁。几分钟之后，全部的烧瓶内壁包上暗灰色/黑色的锑膜。
Claims (9)
1、一种制造锗—锑—碲合金膜的方法，该方法使用选自原子层沉积和化学气相沉积的工艺，其中使用甲硅烷锑前驱体作为合金膜中锑的来源。
2、权利要求1的方法，其中甲硅烷锑前驱体选自三甲硅烷锑、二甲硅烷锑、烷基二甲硅烷锑、氨基二甲硅烷锑和它们的混合物。
3、权利要求1的方法，其中甲硅烷锑前驱体选自：
其中R2-10独立地为氢原子，具有1到10个碳原子的直链、支链、或环状的烷基基团或链烯基基团，或者芳香基团；R1独立地为氢原子，具有2到10个碳原子的直链、支链、或环状的烷基基团或链烯基基团，或者芳香基团；R11和R12独立地为具有1到10个碳原子的直链、支链、或环状的烷基基团或链烯基基团，或者芳香基团。
4、权利要求1的方法，其中所述甲硅烷锑前驱体是三(三甲基甲硅烷)锑。
5、权利要求1的方法，其中使用具有如下通式的氨基锗作为锗的来源：
其中R1和R2独立地为具有1到10个碳原子的直链、支链、或环状的烷基基团。
6、权利要求1的方法，其中使用具有如下通式的甲硅烷碲作为碲的来源：
其中R1、R2、R3、R4、R5和R6独立地为氢原子，具有1到10个碳原子的含有或不含双键的直链、支链、或环状的烷基基团，或者芳香基团。
7、权利要求1的方法，其中所述甲硅烷锑前驱体沉积后与具有通式ROH的醇接触，其中R是具有1到10个碳原子的直链、支链、或环状的的烷基基团，或者芳香基团。
8、一种制造锗—锑—碲合金膜的方法，其使用选自原子层沉积和化学气相沉积的工艺，其中甲硅烷锑前驱体被用作所述合金膜的锑的来源，其中所述甲硅烷锑选自：
其中R2-10独立地为氢原子，具有1到10个碳原子的直链、支链、或环状的烷基基团或链烯基基团，或者芳香基团；R1独立地为氢原子，具有2到10个碳原子的直链、支链、或环状的烷基基团或链烯基基团，或者芳香基团；R11和R12独立地为具有1到10个碳原子的直链、支链、或环状的烷基基团或链烯基基团，或者芳香基团；其中所述锗前驱体是具有如下通式的氨基锗：
其中R1和R2独立地为具有1到10个碳原子的直链、支链、或环状的烷基基团；其中所述碲前驱体是甲硅烷碲，其选自：
其中R1、R2、R3、R4、R5和R6独立选自氢原子，具有1到10个碳原子的含有或不含双键的直链、支链、或环状的烷基基团，或者芳香基团。
9、一种具有选自下述通式结构的物质组成：
其中R2-10独立地为氢原子，具有1到10个碳原子的直链、支链、或环状的烷基基团或链烯基基团，或者芳香族基团；R1独立地为氢原子，具有2到10个碳原子的直链、支链、或环状的烷基基团或链烯基基团，或者芳香族基团；R11和R12独立地为具有1到10个碳原子的直链、支链、或环状的烷基基团或链烯基基团，或者芳香基团；如果结构(A)中，R1-9中的一个是苯基，那么在承载苯基的该硅原子上的剩余的R1-9不能全是甲基；如果结构(A)中R1-9中的任一个是C1-3或苯基，那么不是所有的R1-9全都相同。
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| CN101495672B (zh) | 2006-11-02 | 2011-12-07 | 高级技术材料公司 | 对于金属薄膜的cvd/ald有用的锑及锗复合物 |
| TWI471449B (zh) * | 2007-09-17 | 2015-02-01 | Air Liquide | 用於ｇｓｔ膜沈積之碲前驅物 |
| JP5650880B2 (ja) * | 2007-10-31 | 2015-01-07 | アドバンスド テクノロジー マテリアルズ，インコーポレイテッド | 非晶質Ｇｅ／Ｔｅ蒸着方法 |
| US7960205B2 (en) * | 2007-11-27 | 2011-06-14 | Air Products And Chemicals, Inc. | Tellurium precursors for GST films in an ALD or CVD process |
| EP2279285B1 (en) | 2008-04-25 | 2015-02-11 | ASM International N.V. | Synthesis and use of precursors for ald of tellurium and selenium thin films |
-
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
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- 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
- 2012-10-02 JP JP2012220284A patent/JP5778648B2/ja not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102687243A (zh) * | 2009-10-26 | 2012-09-19 | Asm国际公司 | 用于含va族元素的薄膜ald的前体的合成和使用 |
| CN102687243B (zh) * | 2009-10-26 | 2016-05-11 | Asm国际公司 | 用于含va族元素的薄膜ald的前体的合成和使用 |
| CN103590017A (zh) * | 2012-08-13 | 2014-02-19 | 气体产品与化学公司 | 在ald/cvd工艺中用于gst薄膜的前体 |
| CN103590017B (zh) * | 2012-08-13 | 2016-08-17 | 气体产品与化学公司 | 在ald/cvd工艺中用于gst薄膜的前体 |
| CN104099578A (zh) * | 2013-04-11 | 2014-10-15 | 气体产品与化学公司 | 制备多组分膜的方法 |
| CN110592554A (zh) * | 2013-06-26 | 2019-12-20 | 应用材料公司 | 沉积金属合金膜的方法 |
| CN106068335A (zh) * | 2014-03-04 | 2016-11-02 | 皮考逊公司 | 锗或氧化锗的原子层沉积 |
| CN104341355A (zh) * | 2014-10-22 | 2015-02-11 | 江南大学 | 用于相变存储材料的氨基嘧啶Ge(Ⅱ)前质体及其制备方法 |
| US10199234B2 (en) | 2015-10-02 | 2019-02-05 | Asm Ip Holding B.V. | Methods of forming metal silicides |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2013060663A (ja) | 2013-04-04 |
| TWI382104B (zh) | 2013-01-11 |
| JP5778648B2 (ja) | 2015-09-16 |
| US20090191330A1 (en) | 2009-07-30 |
| US8318252B2 (en) | 2012-11-27 |
| JP2009215645A (ja) | 2009-09-24 |
| EP2083096A1 (en) | 2009-07-29 |
| JP5350819B2 (ja) | 2013-11-27 |
| EP2083096B1 (en) | 2013-01-02 |
| TW200934885A (en) | 2009-08-16 |
| KR20090082873A (ko) | 2009-07-31 |
| KR101068013B1 (ko) | 2011-09-26 |
| CN101497999B (zh) | 2012-08-08 |
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