CN113423862A - 金属膜形成用前驱体组合物、利用上述前驱体组合物的金属膜形成方法以及包含上述金属膜的半导体元件 - Google Patents
金属膜形成用前驱体组合物、利用上述前驱体组合物的金属膜形成方法以及包含上述金属膜的半导体元件 Download PDFInfo
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- CN113423862A CN113423862A CN201980079464.7A CN201980079464A CN113423862A CN 113423862 A CN113423862 A CN 113423862A CN 201980079464 A CN201980079464 A CN 201980079464A CN 113423862 A CN113423862 A CN 113423862A
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- 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
- C23C16/405—Oxides of refractory metals or yttrium
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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
- C07F17/00—Metallocenes
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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
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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
- 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
- C23C16/448—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 generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
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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
- C23C16/455—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]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
- C23C16/45529—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations specially adapted for making a layer stack of alternating different compositions or gradient compositions
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Abstract
本发明涉及一种金属膜形成用前驱体组合物,其特征在于:包括以化学式1至化学式3中的任意一个表示的锆化合物以及以化学式4至化学式6中的某一个表示的铪化合物。
Description
技术领域
本发明涉及一种金属膜形成用前驱体组合物、利用上述前驱体组合物的金属膜形成方法以及包含上述金属膜的半导体元件,尤其涉及一种在原子层沉积(ALD)或化学气相沉积(CVD)工程中使用的含有锆或铪的金属膜形成用前驱体组合物、利用上述前驱体组合物的金属膜形成方法以及包含上述金属膜的半导体元件。
背景技术
作为原子层沉积(ALD)或化学气相沉积(CVD)工程用的前驱体,目前已经开发使用多种形态的有机金属化合物。在通过适用如上所述的沉积功能而制造如动态随机存取存储器(DRAM)、电容器等半导体元件时主要使用的材料为氧化硅,但是最近因为要求高介电常数(high-k)的电气特性,正在利用铪或锆氧化物替代原有的氧化硅制造薄膜。
为了制造出如上所述的薄膜,需要选定适合于工程的前驱体并进行优化。例如,在大韩民国公开专利公报第10-2012-0093165号中作为前驱体适用化学式为ML(NR7R8)3的铪或锆化合物,已经确认上述前驱体作为包含环戊二烯基配体的化合物,是一种适合于薄膜形成工程的物质。
在上述先行技术中,通过分别适用锆化合物以及铪化合物而制造出含锆薄膜以及含铪薄膜,但是并没有公开通过对上述锆化合物以及铪化合物进行并用而制造含锆-铪薄膜的方法。
此外,在美国专利公报第8,962,078号中公开了一种作为铪前驱体的环戊二烯铪化合物以及作为锆前驱体的环戊二烯锆,但是在上述先行技术中也没用公开通过对锆化合物以及铪化合物进行并用而制造含锆-铪薄膜的方法。
此外,大韩民国公开专利公报第10-2017-0016748号涉及一种使用互不相同的第1源物质以及第2源物质形成物质膜的方法,作为上述源物质记载有如CpZr(NMe2)3、Hf(O-t-Bu)4、Hf(NEt2)4、Hf(NEtMe)4、Hf(NMe2)4、TDMAH等,包括与锆化合物以及铪化合物的并用相关的暗示,但是并没有具体公开制造含锆-铪薄膜的方法。
发明内容
技术问题
本发明的目的在于解决如上所述的现有技术中存在的问题而提供一种用于制造呈现出高介电常数(high-k)特性的含锆-铪薄膜的含有锆化合物以及铪化合物的前驱体组合物。
此外,本发明的目的在于提供一种通过包含可以对上述化合物中的1种或多种进行稀释或溶解的溶剂,可以通过气化移送到腔室内部的用于制造含锆-铪薄膜的前驱体组合物。
技术方案
为了达成如上所述的目的,适用本发明的金属膜形成用前驱体组合物,其特征在于:包括以下述化学式1至化学式3中的任意一个表示的锆化合物以及以下述化学式4至化学式6中的任意一个表示的铪化合物。
【化学式1】
【化学式2】
【化学式3】
【化学式4】
【化学式5】
【化学式6】
(在上述化学式1至化学式6中,R1至R5分别是独立的氢原子或C1-C6的烷基,L是Si或C1-C3的连接基,X1至X3是C1至C5的烷基或-NR6R7或-OR8或包含或不包含取代基的环戊二烯基,此时,R6至R8分别是独立的C1-C6的烷基。)
此时,上述金属膜形成用前驱体组合物还可以追加包含溶剂,而作为上述溶剂,可以使用C1-C16的饱和或不饱和烃、酮、醚、甘醇二甲醚、酯、四氢呋喃、叔胺中的任意一个或多个。
此外,上述溶剂相对于上述金属膜形成用前驱体组合物的总重量可以包含0.1至99重量%。
此外,上述锆化合物以及铪化合物可以按照0.1:99.9至99.9:0.1的重量比进行混合。
适用本发明的金属膜形成方法,其特征在于,包括:利用上述金属膜形成用前驱体组合物在基板上沉积形成金属膜的步骤。
此时,上述金属膜形成用前驱体组合物还可以追加包含溶剂,而上述溶剂相对于上述金属膜形成用前驱体组合物的总重量可以包含0.1至99重量%。
此外,上述金属膜可以通过原子层沉积法(Atomic Layer Deposition)、化学气相沉积法(Chemical Vapor Deposition)或蒸发法(Evaporation)中的任意一个方法进行沉积。
此外,还可以追加包括用于将上述金属膜形成用前驱体组合物供应到上述基板中的前驱体组合物传递步骤,此时,上述前驱体组合物传递步骤可以是利用蒸汽压力的挥发移送法、直接液体注入法(Direct Liquid Injection)或液体移送法(Liquid DeliverySystem)中的任意一个。
此外,上述沉积可以包括:将基板配置在腔室内部的步骤;将上述金属膜形成用前驱体组合物供应到上述腔室内部的步骤;向上述腔室内部供应反应性气体或反应性气体的等离子体的步骤;以及,在上述腔室内部通过热处理、等离子体处理以及光照射中的任意一个或多个方法进行处理的步骤。
此时,上述反应性气体可以是水蒸气(H2O)、氧气(O2)、臭氧(O3)、过氧化氢(H2O2)、氢气(H2)、氨气(NH3)、一氧化氮(NO)一氧化二氮(N2O)、二氧化氮(NO2)、肼(N2H4)以及硅烷(SiH4)中的任意一个或多个,上述反应性气体的等离子体可以是射频(RF)等离子体、直流(DC)等离子体或远程(Remote)等离子体中的任意一个。
此外,上述腔室内部的沉积温度可以是250至400℃。
此外,上述锆化合物以及铪化合物可以按照0.1:99.9至99.9:0.1的重量比进行混合。
适用本发明的半导体元件,其特征在于:包括利用上述金属膜形成方法制造的金属膜;而适用本发明的晶体管,其特征在于:作为包括利用上述金属膜形成方法制造的金属膜的晶体管,上述金属膜构成上述晶体管的栅极绝缘层。
技术效果
因为适用本发明的前驱体组合物中含有锆化合物以及铪化合物,因此可以呈现出适合于制造具有高介电常数(high-k)特性的含锆-铪薄膜的特性。
此外,通过包含可以对上述化合物中的1中或多种进行稀释或溶解的溶剂,即使是高粘度的液状组合物或固体状态的化合物也可以通过气化而移送到腔室内部的效果。
此外,通过适用上述前驱体组合物,可以制造呈现出高介电常数(high-k)特性的多种半导体元件用薄膜。
附图说明
图1是对将适用本发明的金属薄膜沉积用前驱体组合物适用于介电体薄膜中的电容器的截面图进行图示的概念图。
图2是化合物1、化合物4以及由化合物1以及化合物4构成的组合物的核磁共振(NMR)分析结果。
图3是化合物2、化合物4以及由化合物2以及化合物4构成的组合物的核磁共振(NMR)分析结果。
图4是化合物3、化合物4以及由化合物3以及化合物4构成的组合物的核磁共振(NMR)分析结果。
图5是化合物1、化合物5以及由化合物1以及化合物5构成的组合物的核磁共振(NMR)分析结果。
图6是化合物2、化合物5以及由化合物2以及化合物5构成的组合物的核磁共振(NMR)分析结果。
图7是化合物3、化合物5以及由化合物3以及化合物5构成的组合物的核磁共振(NMR)分析结果。
图8是适用比较例以及实施例的锆前驱体、铪前驱体以及锆/铪前驱体组合物的热重分析结果。
图9是利用适用比较例以及实施例的锆前驱体、铪前驱体以及锆/铪前驱体组合物进行沉积的薄膜的X-线反射测定结果。
图10是利用适用比较例以及实施例的锆前驱体、铪前驱体以及锆/铪前驱体组合物进行沉积的薄膜的X-线光电分光测定结果。
图11是利用适用比较例以及实施例的锆前驱体、铪前驱体以及锆/铪前驱体组合物进行沉积的薄膜的电化学-循环伏安法(C-V)分析结果。
具体实施方式
接下来,将对本发明进行更为详细的说明。在本说明书以及权利要求书中所使用的术语或单词不应限定于通常的或词典上的含义做出解释,而是应该立足于发明人为了以最佳的方式对自己的发明进行说明而可以适当地对术语的概念做出定义的原则,以符合本发明之技术思想的含义以及概念做出解释。
适用本发明的金属膜形成用前驱体组合物,其特征在于:包括以下述化学式1至化学式3中的任意一个表示的锆化合物以及以下述化学式4至化学式6中的任意一个表示的铪化合物。
【化学式1】
【化学式2】
【化学式3】
【化学式4】
【化学式5】
【化学式6】
(在上述化学式1至化学式6中,R1至R5分别是独立的氢原子或C1-C6的烷基,L是Si或C1-C3的连接基,X1至X3是C1至C5的烷基或-NR6R7或-OR8或包含或不包含取代基的环戊二烯基,此时,R6至R8分别是独立的C1-C6的烷基。)
以上述化学式1表示的锆化合物作为含有1个环戊二烯基的化合物,可以代表性地以如下所述的物质作为例示,但是并不限定于此。
可以以CpZr(NMe2)3、[MeCp]Zr(NMe2)3、[(Me)2Cp]Zr(NMe2)3、[(Me)3Cp]Zr(NMe2)3、[(Me)4Cp]Zr(NMe2)3、[(Me)5Cp]Zr(NMe2)3、[EtCp]Zr(NMe2)3、[(Et)2Cp]Zr(NMe2)3、[(Et)3Cp]Zr(NMe2)3、[(Et)4Cp]Zr(NMe2)3、[(Et)5Cp]Zr(NMe2)3、[nPrCp]Zr(NMe2)3、[(nPr)2Cp]Zr(NMe2)3、[(nPr)3Cp]Zr(NMe2)3、[(nPr)4Cp]Zr(NMe2)3、[(nPr)5Cp]Zr(NMe2)3、[iPrCp]Zr(NMe2)3、[(iPr)2Cp]Zr(NMe2)3、[(iPr)3Cp]Zr(NMe2)3、[(iPr)4Cp]Zr(NMe2)3、[(iPr)5Cp]Zr(NMe2)3、[nBuCp]Zr(NMe2)3、[(nBu)2Cp]Zr(NMe2)3、[(nBu)3Cp]Zr(NMe2)3、[(nBu)4Cp]Zr(NMe2)3、[(nBu)5Cp]Zr(NMe2)3、[tBuCp]Zr(NMe2)3、[(tBu)2Cp]Zr(NMe2)3、[(tBu)3Cp]Zr(NMe2)3、[(tBu)4Cp]Zr(NMe2)3、[(tBu)5Cp]Zr(NMe2)3、[(Me)(Et)Cp]Zr(NMe2)3、[(Me)(Et)2Cp]Zr(NMe2)3、[(Me)(Et)3Cp]Zr(NMe2)3、[(Me)(Et)4Cp]Zr(NMe2)3、[(Me)2(Et)Cp]Zr(NMe2)3、[(Me)2(Et)2Cp]Zr(NMe2)3、[(Me)3(Et)Cp]Zr(NMe2)3、[(Me)3(Et)2Cp]Zr(NMe2)3、[(Me)(nPr)Cp]Zr(NMe2)3、[(Me)(nPr)2Cp]Zr(NMe2)3、[(Me)(nPr)3Cp]Zr(NMe2)3、[(Me)(nPr)4Cp]Zr(NMe2)3、[(Me)2(nPr)Cp]Zr(NMe2)3、[(Me)2(nPr)2Cp]Zr(NMe2)3、[(Me)3(nPr)Cp]Zr(NMe2)3、[(Me)3(nPr)2Cp]Zr(NMe2)3、[(Me)(iPr)Cp]Zr(NMe2)3、[(Me)(iPr)2Cp]Zr(NMe2)3、[(Me)(iPr)3Cp]Zr(NMe2)3、[(Me)(iPr)4Cp]Zr(NMe2)3、[(Me)2(iPr)Cp]Zr(NMe2)3、[(Me)2(iPr)2Cp]Zr(NMe2)3、[(Me)3(iPr)Cp]Zr(NMe2)3、[(Me)3(iPr)2Cp]Zr(NMe2)3、[(Me)(tBu)Cp]Zr(NMe2)3、[(Me)(tBu)2Cp]Zr(NMe2)3、[(Me)(tBu)3Cp]Zr(NMe2)3、[(Me)(tBu)4Cp]Zr(NMe2)3、[(Me)2(tBu)Cp]Zr(NMe2)3、[(Me)2(tBu)2Cp]Zr(NMe2)3、[(Me)3(tBu)Cp]Zr(NMe2)3、[(Me)3(tBu)2Cp]Zr(NMe2)3中的任意一个或多个化合物为例。
此外,以上述化学式2表示的锆化合物作为含有2个环戊二烯基的化合物,可以代表性地以如下所述的物质作为例示,但是并不限定于此。
可以以[Cp]2Zr(NMe2)2、[MeCp]2Zr(NMe2)2、[(Me)2Cp]2Zr(NMe2)2、[(Me)3Cp]2Zr(NMe2)2、[(Me)4Cp]2Zr(NMe2)2、[(Me)5Cp]2Zr(NMe2)2、[EtCp]2Zr(NMe2)2、[(Et)2Cp]2Zr(NMe2)2、[(Et)3Cp]2Zr(NMe2)2、[(Et)4Cp]2Zr(NMe2)2、[(Et)5Cp]2Zr(NMe2)2、[nPrCp]2Zr(NMe2)2、[(nPr)2Cp]2Zr(NMe2)2、[(nPr)3Cp]2Zr(NMe2)2、[(nPr)4Cp]2Zr(NMe2)2、[(nPr)5Cp]2Zr(NMe2)2、[iPrCp]2Zr(NMe2)2、[(iPr)2Cp]2Zr(NMe2)2、[(iPr)3Cp]2Zr(NMe2)2、[(iPr)4Cp]2Zr(NMe2)2、[(iPr)5Cp]2Zr(NMe2)2、[nBuCp]2Zr(NMe2)2、[(nBu)2Cp]2Zr(NMe2)2、[(nBu)3Cp]2Zr(NMe2)2、[(nBu)4Cp]2Zr(NMe2)2、[(nBu)5Cp]2Zr(NMe2)2、[tBuCp]2Zr(NMe2)2、[(tBu)2Cp]2Zr(NMe2)2、[(tBu)3Cp]2Zr(NMe2)2、[(tBu)4Cp]2Zr(NMe2)2、[(tBu)5Cp]2Zr(NMe2)2、[(Me)(Et)Cp]2Zr(NMe2)2、[(Me)(Et)2Cp]2Zr(NMe2)2、[(Me)(Et)3Cp]2Zr(NMe2)2、[(Me)(Et)4Cp]2Zr(NMe2)2、[(Me)2(Et)Cp]2Zr(NMe2)2、[(Me)2(Et)2Cp]2Zr(NMe2)2、[(Me)3(Et)Cp]2Zr(NMe2)2、[(Me)3(Et)2Cp]2Zr(NMe2)2、[(Me)(nPr)Cp]2Zr(NMe2)2、[(Me)(nPr)2Cp]2Zr(NMe2)2、[(Me)(nPr)3Cp]2Zr(NMe2)2、[(Me)(nPr)4Cp]2Zr(NMe2)2、[(Me)2(nPr)Cp]2Zr(NMe2)2、[(Me)2(nPr)2Cp]2Zr(NMe2)2、[(Me)3(nPr)Cp]2Zr(NMe2)2、[(Me)3(nPr)2Cp]2Zr(NMe2)2、[(Me)(iPr)Cp]2Zr(NMe2)2、[(Me)(iPr)2Cp]2Zr(NMe2)2、[(Me)(iPr)3Cp]2Zr(NMe2)2、[(Me)(iPr)4Cp]2Zr(NMe2)2、[(Me)2(iPr)Cp]2Zr(NMe2)2、[(Me)2(iPr)2Cp]2Zr(NMe2)2、[(Me)3(iPr)Cp]2Zr(NMe2)2、[(Me)3(iPr)2Cp]2Zr(NMe2)2、[(Me)(tBu)Cp]2Zr(NMe2)2、[(Me)(tBu)2Cp]2Zr(NMe2)2、[(Me)(tBu)3Cp]2Zr(NMe2)2、[(Me)(tBu)4Cp]2Zr(NMe2)2、[(Me)2(tBu)Cp]2Zr(NMe2)2、[(Me)2(tBu)2Cp]2Zr(NMe2)2、[(Me)3(tBu)Cp]2Zr(NMe2)2、[(Me)3(tBu)2Cp]2Zr(NMe2)2中的任意一个或多个化合物为例。
此外,以上述化学式3表示的锆化合物作为在环戊二烯基与金属原子之间利用连接基形成桥(bridge)的结构的化合物,可以代表性地以如下所述的物质作为例示,但是并不限定于此。
可以使用Zr[CpCH2NMe](NMe2)2、Zr[Cp(CH2)2NMe](NMe2)2、Zr[Cp(CH2)3NMe](NMe2)2、Zr[Cp(CH2)4NMe](NMe2)2、Zr[Cp(CH2)5NMe](NMe2)2、Zr[CpCH2NMe](Cp)(NMe2)、Zr[Cp(CH2)2NMe](Cp)(NMe2)、Zr[Cp(CH2)3NMe](Cp)(NMe2)、Zr[Cp(CH2)4NMe](Cp)(NMe2)、Zr[Cp(CH2)5NMe](Cp)(NMe2)、Zr[(CpMe)CH2NMe](NMe2)2、Zr[(CpMe)(CH2)2NMe](NMe2)2、Zr[(CpMe)(CH2)3NMe](NMe2)2、Zr[(CpMe)(CH2)4NMe](NMe2)2、Zr[(CpMe)(CH2)5NMe](NMe2)2、Zr[(CpMe)CH2NMe](Cp)(NMe2)、Zr[(CpMe)(CH2)2NMe](Cp)(NMe2)、Zr[(CpMe)(CH2)3NMe](Cp)(NMe2)、Zr[(CpMe)(CH2)4NMe](Cp)(NMe2)、Zr[(CpMe)(CH2)5NMe](Cp)(NMe2)、Zr[CpCH2NMe](CpMe)(NMe2)、Zr[Cp(CH2)2NMe](CpMe)(NMe2)、Zr[Cp(CH2)3NMe](CpMe)(NMe2)、Zr[Cp(CH2)4NMe](CpMe)(NMe2)、Zr[Cp(CH2)5NMe](CpMe)(NMe2)、Zr[(CpMe2)CH2NMe](NMe2)2、Zr[(CpMe2)(CH2)2NMe](NMe2)2、Zr[(CpMe2)(CH2)3NMe](NMe2)2、Zr[(CpMe2)(CH2)4NMe](NMe2)2、Zr[(CpMe2)(CH2)5NMe](NMe2)2、Zr[(CpMe2)CH2NMe](Cp)(NMe2)、Zr[(CpMe2)(CH2)2NMe](Cp)(NMe2)、Zr[(CpMe2)(CH2)3NMe](Cp)(NMe2)、Zr[(CpMe2)(CH2)4NMe](Cp)(NMe2)、Zr[(CpMe2)(CH2)5NMe](Cp)(NMe2)、Zr[CpCH2NMe](CpMe2)(NMe2)、Zr[Cp(CH2)2NMe](CpMe2)(NMe2)、Zr[Cp(CH2)3NMe](CpMe2)(NMe2)、Zr[Cp(CH2)4NMe](CpMe2)(NMe2)、Zr[Cp(CH2)5NMe](CpMe2)(NMe2)、Zr[(CpMe3)CH2NMe](NMe2)2、Zr[(CpMe3)(CH2)2NMe](NMe2)2、Zr[(CpMe3)(CH2)3NMe](NMe2)2、Zr[(CpMe3)(CH2)4NMe](NMe2)2、Zr[(CpMe3)(CH2)5NMe](NMe2)2、Zr[(CpMe3)CH2NMe](Cp)(NMe2)、Zr[(CpMe3)(CH2)2NMe](Cp)(NMe2)、Zr[(CpMe3)(CH2)3NMe](Cp)(NMe2)、Zr[(CpMe3)(CH2)4NMe](Cp)(NMe2)、Zr[(CpMe3)(CH2)5NMe](Cp)(NMe2)、Zr[CpCH2NMe](CpMe3)(NMe2)、Zr[Cp(CH2)3NMe](CpMe3)(NMe2)、Zr[Cp(CH2)3NMe](CpMe3)(NMe2)、Zr[Cp(CH2)4NMe](CpMe3)(NMe2)、Zr[Cp(CH2)5NMe](CpMe3)(NMe2)、Zr[CpCH2NMe](CpMe4)(NMe2)、Zr[Cp(CH2)3NMe](CpMe4)(NMe2)、Zr[Cp(CH2)3NMe](CpMe4)(NMe2)、Zr[Cp(CH2)4NMe](CpMe4)(NMe2)、Zr[Cp(CH2)5NMe](CpMe4)(NMe2)Zr[(CpEt)CH2NMe](NMe2)2、Zr[(CpEt)(CH2)2NMe](NMe2)2、Zr[(CpEt)(CH2)3NMe](NMe2)2、Zr[(CpEt)(CH2)4NMe](NMe2)2、Zr[(CpEt)(CH2)5NMe](NMe2)2、Zr[CpCH2NMe](CpEt)(NMe2)、Zr[Cp(CH2)2NMe](CpEt)(NMe2)、Zr[Cp(CH2)3NMe](CpEt)(NMe2)、Zr[Cp(CH2)4NMe](CpEt)(NMe2)、Zr[Cp(CH2)5NMe](CpEt)(NMe2)、Zr[(CpMeEt)CH2NMe](NMe2)2、Zr[(CpMeEt)(CH2)2NMe](NMe2)2、Zr[(CpMeEt)(CH2)3NMe](NMe2)2、Zr[(CpMeEt)(CH2)4NMe](NMe2)2、Zr[(CpMeEt)(CH2)5NMe](NMe2)2、Zr[CpCH2NMe](CpMeEt)(NMe2)、Zr[Cp(CH2)2NMe](CpMeEt)(NMe2)、Zr[Cp(CH2)3NMe](CpMeEt)(NMe2)、Zr[Cp(CH2)4NMe](CpMeEt)(NMe2)、Zr[Cp(CH2)5NMe](CpMeEt)(NMe2)、Zr[(CpMePr)CH2NMe](NMe2)2、Zr[(CpMePr)(CH2)2NMe](NMe2)2、Zr[(CpMePr)(CH2)3NMe](NMe2)2、Zr[(CpMePr)(CH2)4NMe](NMe2)2、Zr[(CpMePr)(CH2)5NMe](NMe2)2、Zr[(CpiPr)CH2NMe](NMe2)2、Zr[(Cpi-PrEt)(CH2)2NMe](NMe2)2、Zr[(CpiPrEt)(CH2)3NMe](NMe2)2、Zr[(CpiPrEt)(CH2)4NMe](NMe2)2、Zr[(CpiPrEt)(CH2)5NMe](NMe2)2中的任意一个或多个化合物。
此外,以上述化学式4表示的铪化合物作为含有1个环戊二烯基的化合物,可以代表性地以如下所述的物质作为例示,但是并不限定于此。
可以以CpHf(NMe2)3、[MeCp]Hf(NMe2)3、[(Me)2Cp]Hf(NMe2)3、[(Me)3Cp]Hf(NMe2)3、[(Me)4Cp]Hf(NMe2)3、[(Me)5Cp]Hf(NMe2)3、[EtCp]Hf(NMe2)3、[(Et)2Cp]Hf(NMe2)3、[(Et)3Cp]Hf(NMe2)3、[(Et)4Cp]Hf(NMe2)3、[(Et)5Cp]Hf(NMe2)3、[nPrCp]Hf(NMe2)3、[(nPr)2Cp]Hf(NMe2)3、[(nPr)3Cp]Hf(NMe2)3、[(nPr)4Cp]Hf(NMe2)3、[(nPr)5Cp]Hf(NMe2)3、[iPrCp]Hf(NMe2)3、[(iPr)2Cp]Hf(NMe2)3、[(iPr)3Cp]Hf(NMe2)3、[(iPr)4Cp]Hf(NMe2)3、[(iPr)5Cp]Hf(NMe2)3、[nBuCp]Hf(NMe2)3、[(nBu)2Cp]Hf(NMe2)3、[(nBu)3Cp]Hf(NMe2)3、[(nBu)4Cp]Hf(NMe2)3、[(nBu)5Cp]Hf(NMe2)3、[tBuCp]Hf(NMe2)3、[(tBu)2Cp]Hf(NMe2)3、[(tBu)3Cp]Hf(NMe2)3、[(tBu)4Cp]Hf(NMe2)3、[(tBu)5Cp]Hf(NMe2)3、[(Me)(Et)Cp]Hf(NMe2)3、[(Me)(Et)2Cp]Hf(NMe2)3、[(Me)(Et)3Cp]Hf(NMe2)3、[(Me)(Et)4Cp]Hf(NMe2)3、[(Me)2(Et)Cp]Hf(NMe2)3、[(Me)2(Et)2Cp]Hf(NMe2)3、[(Me)3(Et)Cp]Hf(NMe2)3、[(Me)3(Et)2Cp]Hf(NMe2)3、[(Me)(nPr)Cp]Hf(NMe2)3、[(Me)(nPr)2Cp]Hf(NMe2)3、[(Me)(nPr)3Cp]Hf(NMe2)3、[(Me)(nPr)4Cp]Hf(NMe2)3、[(Me)2(nPr)Cp]Hf(NMe2)3、[(Me)2(nPr)2Cp]Hf(NMe2)3、[(Me)3(nPr)Cp]Hf(NMe2)3、[(Me)3(nPr)2Cp]Hf(NMe2)3、[(Me)(iPr)Cp]Hf(NMe2)3、[(Me)(iPr)2Cp]Hf(NMe2)3、[(Me)(iPr)3Cp]Hf(NMe2)3、[(Me)(iPr)4Cp]Hf(NMe2)3、[(Me)2(iPr)Cp]Hf(NMe2)3、[(Me)2(iPr)2Cp]Hf(NMe2)3、[(Me)3(iPr)Cp]Hf(NMe2)3、[(Me)3(iPr)2Cp]Hf(NMe2)3、[(Me)(tBu)Cp]Hf(NMe2)3、[(Me)(tBu)2Cp]Hf(NMe2)3、[(Me)(tBu)3Cp]Hf(NMe2)3、[(Me)(tBu)4Cp]Hf(NMe2)3、[(Me)2(tBu)Cp]Hf(NMe2)3、[(Me)2(tBu)2Cp]Hf(NMe2)3、[(Me)3(tBu)Cp]Hf(NMe2)3、[(Me)3(tBu)2Cp]Hf(NMe2)3中的任意一个或多个化合物为例。
此外,以上述化学式5表示的铪化合物作为含有2个环戊二烯基的化合物,可以代表性地以如下所述的物质作为例示,但是并不限定于此。
可以以[Cp]2Hf(NMe2)2、[MeCp]2Hf(NMe2)2、[(Me)2Cp]2Hf(NMe2)2、[(Me)3Cp]2Hf(NMe2)2、[(Me)4Cp]2Hf(NMe2)2、[(Me)5Cp]2Hf(NMe2)2、[EtCp]2Hf(NMe2)2、[(Et)2Cp]2Hf(NMe2)2、[(Et)3Cp]2Hf(NMe2)2、[(Et)4Cp]2Hf(NMe2)2、[(Et)5Cp]2Hf(NMe2)2、[nPrCp]2Hf(NMe2)2、[(nPr)2Cp]2Hf(NMe2)2、[(nPr)3Cp]2Hf(NMe2)2、[(nPr)4Cp]2Hf(NMe2)2、[(nPr)5Cp]2Hf(NMe2)2、[iPrCp]2Hf(NMe2)2、[(iPr)2Cp]2Hf(NMe2)2、[(iPr)3Cp]2Hf(NMe2)2、[(iPr)4Cp]2Hf(NMe2)2、[(iPr)5Cp]2Hf(NMe2)2、[nBuCp]2Hf(NMe2)2、[(nBu)2Cp]2Hf(NMe2)2、[(nBu)3Cp]2Hf(NMe2)2、[(nBu)4Cp]2Hf(NMe2)2、[(nBu)5Cp]2Hf(NMe2)2、[tBuCp]2Hf(NMe2)2、[(tBu)2Cp]2Hf(NMe2)2、[(tBu)3Cp]2Hf(NMe2)2、[(tBu)4Cp]2Hf(NMe2)2、[(tBu)5Cp]2Hf(NMe2)2、[(Me)(Et)Cp]2Hf(NMe2)2、[(Me)(Et)2Cp]2Hf(NMe2)2、[(Me)(Et)3Cp]2Hf(NMe2)2、[(Me)(Et)4Cp]2Hf(NMe2)2、[(Me)2(Et)Cp]2Hf(NMe2)2、[(Me)2(Et)2Cp]2Hf(NMe2)2、[(Me)3(Et)Cp]2Hf(NMe2)2、[(Me)3(Et)2Cp]2Hf(NMe2)2、[(Me)(nPr)Cp]2Hf(NMe2)2、[(Me)(nPr)2Cp]2Hf(NMe2)2、[(Me)(nPr)3Cp]2Hf(NMe2)2、[(Me)(nPr)4Cp]2Hf(NMe2)2、[(Me)2(nPr)Cp]2Hf(NMe2)2、[(Me)2(nPr)2Cp]2Hf(NMe2)2、[(Me)3(nPr)Cp]2Hf(NMe2)2、[(Me)3(nPr)2Cp]2Hf(NMe2)2、[(Me)(iPr)Cp]2Hf(NMe2)2、[(Me)(iPr)2Cp]2Hf(NMe2)2、[(Me)(iPr)3Cp]2Hf(NMe2)2、[(Me)(iPr)4Cp]2Hf(NMe2)2、[(Me)2(iPr)Cp]2Hf(NMe2)2、[(Me)2(iPr)2Cp]2Hf(NMe2)2、[(Me)3(iPr)Cp]2Hf(NMe2)2、[(Me)3(iPr)2Cp]2Hf(NMe2)2、[(Me)(tBu)Cp]2Hf(NMe2)2、[(Me)(tBu)2Cp]2Hf(NMe2)2、[(Me)(tBu)3Cp]2Hf(NMe2)2、[(Me)(tBu)4Cp]2Hf(NMe2)2、[(Me)2(tBu)Cp]2Hf(NMe2)2、[(Me)2(tBu)2Cp]2Hf(NMe2)2、[(Me)3(tBu)Cp]2Hf(NMe2)2、[(Me)3(tBu)2Cp]2Hf(NMe2)2中的任意一个或多个为例。
此外,以上述化学式6表示的铪化合物作为在环戊二烯基与金属原子之间利用连接基形成桥(bridge)的结构的化合物,可以代表性地以如下所述的物质作为例示,但是并不限定于此。
可以使用Hf[CpCH2NMe](NMe2)2、Hf[Cp(CH2)2NMe](NMe2)2、Hf[Cp(CH2)3NMe](NMe2)2、Hf[Cp(CH2)4NMe](NMe2)2、Hf[Cp(CH2)5NMe](NMe2)2、Hf[CpCH2NMe](Cp)(NMe2)、Hf[Cp(CH2)2NMe](Cp)(NMe2)、Hf[Cp(CH2)3NMe](Cp)(NMe2)、Hf[Cp(CH2)4NMe](Cp)(NMe2)、Hf[Cp(CH2)5NMe](Cp)(NMe2)、Hf[(CpMe)CH2NMe](NMe2)2、Hf[(CpMe)(CH2)2NMe](NMe2)2、Hf[(CpMe)(CH2)3NMe](NMe2)2、Hf[(CpMe)(CH2)4NMe](NMe2)2、Hf[(CpMe)(CH2)5NMe](NMe2)2、Hf[(CpMe)CH2NMe](Cp)(NMe2)、Hf[(CpMe)(CH2)2NMe](Cp)(NMe2)、Hf[(CpMe)(CH2)3NMe](Cp)(NMe2)、Hf[(CpMe)(CH2)4NMe](Cp)(NMe2)、Hf[(CpMe)(CH2)5NMe](Cp)(NMe2)、Hf[CpCH2NMe](CpMe)(NMe2)、Hf[Cp(CH2)2NMe](CpMe)(NMe2)、Hf[Cp(CH2)3NMe](CpMe)(NMe2)、Hf[Cp(CH2)4NMe](CpMe)(NMe2)、Hf[Cp(CH2)5NMe](CpMe)(NMe2)、Hf[(CpMe2)CH2NMe](NMe2)2、Hf[(CpMe2)(CH2)2NMe](NMe2)2、Hf[(CpMe2)(CH2)3NMe](NMe2)2、Hf[(CpMe2)(CH2)4NMe](NMe2)2、Hf[(CpMe2)(CH2)5NMe](NMe2)2、Hf[(CpMe2)CH2NMe](Cp)(NMe2)、Hf[(CpMe2)(CH2)2NMe](Cp)(NMe2)、Hf[(CpMe2)(CH2)3NMe](Cp)(NMe2)、Hf[(CpMe2)(CH2)4NMe](Cp)(NMe2)、Hf[(CpMe2)(CH2)5NMe](Cp)(NMe2)、Hf[CpCH2NMe](CpMe2)(NMe2)、Hf[Cp(CH2)2NMe](CpMe2)(NMe2)、Hf[Cp(CH2)3NMe](CpMe2)(NMe2)、Hf[Cp(CH2)4NMe](CpMe2)(NMe2)、Hf[Cp(CH2)5NMe](CpMe2)(NMe2)、Hf[(CpMe3)CH2NMe](NMe2)2、Hf[(CpMe3)(CH2)2NMe](NMe2)2、Hf[(CpMe3)(CH2)3NMe](NMe2)2、Hf[(CpMe3)(CH2)4NMe](NMe2)2、Hf[(CpMe3)(CH2)5NMe](NMe2)2、Hf[(CpMe3)CH2NMe](Cp)(NMe2)、Hf[(CpMe3)(CH2)2NMe](Cp)(NMe2)、Hf[(CpMe3)(CH2)3NMe](Cp)(NMe2)、Hf[(CpMe3)(CH2)4NMe](Cp)(NMe2)、Hf[(CpMe3)(CH2)5NMe](Cp)(NMe2)、Hf[CpCH2NMe](CpMe3)(NMe2)、Hf[Cp(CH2)3NMe](CpMe3)(NMe2)、Hf[Cp(CH2)3NMe](CpMe3)(NMe2)、Hf[Cp(CH2)4NMe](CpMe3)(NMe2)、Hf[Cp(CH2)5NMe](CpMe3)(NMe2)、Hf[CpCH2NMe](CpMe4)(NMe2)、Hf[Cp(CH2)3NMe](CpMe4)(NMe2)、Hf[Cp(CH2)3NMe](CpMe4)(NMe2)、Hf[Cp(CH2)4NMe](CpMe4)(NMe2)、Hf[Cp(CH2)5NMe](CpMe4)(NMe2)Hf[(CpEt)CH2NMe](NMe2)2、Hf[(CpEt)(CH2)2NMe](NMe2)2、Hf[(CpEt)(CH2)3NMe](NMe2)2、Hf[(CpEt)(CH2)4NMe](NMe2)2、Hf[(CpEt)(CH2)5NMe](NMe2)2、Hf[CpCH2NMe](CpEt)(NMe2)、Hf[Cp(CH2)2NMe](CpEt)(NMe2)、Hf[Cp(CH2)3NMe](CpEt)(NMe2)、Hf[Cp(CH2)4NMe](CpEt)(NMe2)、Hf[Cp(CH2)5NMe](CpEt)(NMe2)、Hf[(CpMeEt)CH2NMe](NMe2)2、Hf[(CpMeEt)(CH2)2NMe](NMe2)2、Hf[(CpMeEt)(CH2)3NMe](NMe2)2、Hf[(CpMeEt)(CH2)4NMe](NMe2)2、Hf[(CpMeEt)(CH2)5NMe](NMe2)2、Hf[CpCH2NMe](CpMeEt)(NMe2)、Hf[Cp(CH2)2NMe](CpMeEt)(NMe2)、Hf[Cp(CH2)3NMe](CpMeEt)(NMe2)、Hf[Cp(CH2)4NMe](CpMeEt)(NMe2)、Hf[Cp(CH2)5NMe](CpMeEt)(NMe2)、Hf[(CpMePr)CH2NMe](NMe2)2、Hf[(CpMePr)(CH2)2NMe](NMe2)2、Hf[(CpMePr)(CH2)3NMe](NMe2)2、Hf[(CpMePr)(CH2)4NMe](NMe2)2、Hf[(CpMePr)(CH2)5NMe](NMe2)2、Hf[(CpiPr)CH2NMe](NMe2)2、Hf[(Cpi-PrEt)(CH2)2NMe](NMe2)2、Hf[(CpiPrEt)(CH2)3NMe](NMe2)2、Hf[(CpiPrEt)(CH2)4NMe](NMe2)2、Hf[(CpiPrEt)(CH2)5NMe](NMe2)2中的任意一个或多个化合物。
其中,上述化合物中的Cp为环戊二烯基,Me为甲基,Et为乙基,Pr为丙基,nPr为正丙基,iPr为异丙基,nBu为正丁基,tBu为t-丁基。
上述前驱体组合物可以包含溶剂,这是为了当上述化合物在室温条件下为粘度较高的液体状态或固体状态时通过对其进行稀释降低粘度或溶解而添加。此外,上述溶剂相对于上述金属膜形成用前驱体组合物的总重量可以包含0.1至99重量%,较佳地可以包含0.1至50重量%,更较佳地可以包含1至20重量%的范围。
通常,包含环戊二烯基的上述锆化合物以及铪化合物的粘度范围约为8.7至10cps左右,在对其进行混合的情况下的粘度值为9至10cps,大体上可以满足在薄膜制造工程中所要求的10cps以下,较佳地为5至9cps的粘度值,但是根据其结构有粘度值为10cps以上的化合物存在,而且在所适用的组合物上可能会导致粘度值过高的问题。因此,考虑到如上所述的组合物的粘度值,上述溶剂在上述含量范围内混合适当的量进行使用。
适用本发明的金属膜形成方法,其特征在于,包括:利用上述金属膜形成用前驱体组合物在基板上沉积形成金属膜的步骤。
此时,上述金属膜形成用前驱体组合物还可以追加包含溶剂,而且如上所述,相对于上述金属膜形成用前驱体组合物的总重量可以包含0.1至99重量%。
这是因为上述锆化合物以及铪化合物中的任意一个或上述之组合在室温条件下可能会是粘度较高的液体状态或固体状态,而在如上所述的情况下,上述溶剂的含量会根据粘度较高的液体状态的化合物的量或固体状态的化合物的量而发生变化。此外,上述锆化合物以及铪化合物的重量比可以是0.1:99.9至99.9:0.1,较佳地可以是1:80至80:1,更较佳地可以是30:70至70:30,上述比例可以根据所需要的金属膜的电气特性以及用途进行调节。
具体来讲,利用上述前驱体组合物的金属膜的制造方法,除了作为金属化合物使用上述的前驱体组合物之外,可以按照一般的通过沉积的金属膜的制造方法实施,具体来讲可以利用如化学沉积法(chemical vapor deposition,CVD)或原子层沉积法(atomiclayer deposition,ALD)、蒸发法(evaporation)等方法实施。例如,在沉积氧化钇或氮化钇薄膜的情况下,在原子层沉积法(ALD)中可以在250至400℃的沉积温度下将前驱体以及反应气体注入到腔室中,而在化学沉积法(CVD)或蒸发法中可以在上述温度下同时注入前驱体以及反应气体。
即,可以通过包括向位于反应器(腔室)内部的金属膜形成用基板上方供应上述前驱体组合物的步骤,以及向上述反应器内部供应反应性气体并实施从由热处理、等离子体处理以及光照射构成的组中选择的1种处理工程的步骤的制造方法进行制造。上述等离子体处理可以使用射频(RF)等离子体、直流(DC)等离子体、远程(Remote)等离子体等。
首先,将适用本发明的前驱体组合物供应到金属膜形成用基板上方。此时,作为上述金属膜形成用基板,可以不受限制地使用因为技术性作用而需要涂布金属膜的在半导体制造中所使用的任何基板。具体来讲,可以使用硅基板(Si)、二氧化硅基板(SiO2)、氮化硅基板(SiN)、氮氧化硅基板(SiON)、氮化钛基板(TiN)、氮化钽基板(TaN)、钨基板(W)或如铂基板(Pt)、钯基板(Pd)、铑基板(Rh)或金基板(Au)等贵金属基板。
在将上述金属膜形成用前驱体组合物供应到上述基板上的前驱体组合物传递步骤中,作为上述传递方法可以适用利用蒸汽压力将前驱体组合物或用于改善薄膜特性的有机溶剂的挥发气体移送到腔室内部的挥发移送法、直接注入液态的前驱体组合物的直接液体注入法(Direct Liquid Injection)或在将前驱体组合物溶解到有机溶剂中之后进行移送的液体移送法(LDS:Liquid Delivery System)。上述前驱体组合物的液体移送方法,可以通过利用液体搬运***(LDS:Liquid Delivery System)将液态的前驱体组合物通过气化器转化成气态之后移送到金属薄膜形成用基板上方的方式实施。
在采用将上述前驱体组合物溶解到有机溶剂之后进行移送的液体移送法时还可以追加包含溶剂,这种方式可以在因为作为上述前驱体组合物适用的化合物中的一部分或全部的粘度较高而难以在液体移送方式的气化器中得到充分气化的情况下使用。
例如,可以以沸点为130℃以下或30~130℃且常温即25℃下的密度为0.6g/cm3且蒸汽压力为70㎜Hg的叔胺或烷烃为例,在同时满足沸点、密度以及蒸汽压力条件的时可以提升膜形成组合物的粘度降低效果以及挥发性改善效果,因此可以形成均匀性以及阶梯覆盖特性得到改善的薄膜。
但是,除了如上所述的溶剂之外,只要可以在对锆以及铪化合物进行溶解的同时具有适合于液体移送法的程度的粘度以及溶解度,就可以通过使用C1-C16的饱和或不饱和烃、酮、醚、甘醇二甲醚、酯、四氢呋喃以及叔胺中的任意一个或多个的混合溶剂而适用于使用上述前驱体组合物的工程中。
作为一实施例,在相对于前驱体组合物的总重量包含1至99重量%的二甲基乙醇胺的情况下可以适用如上所述的液体移送法,因为在叔胺的含量不足1重量%时会导致薄膜的物性特性改善效果微乎其微的问题,而在超过99重量%时会因为前驱体的浓度过低而造成沉积速度的降低并进一步导致生产性下降的问题,因此在上述的范围内使用为宜。更具体来讲,上述前驱体组合物以90:10至10:90的重量比包含上述前驱体组合物以及溶剂为宜。在相对于前驱体组合物的叔胺的含量超出上述的重量比范围而过高或过低的情况下,可能会导致薄膜的均匀性以及阶梯覆盖改善效果降低的问题。
通过在如上所述的溶剂中包含呈现出较低的粘度以及高挥发性的溶剂,前驱体组合物可以呈现出改善的粘度以及挥发性,而且可以在形成基板时提升前驱体的基板吸附效率以及稳定性并缩短工程时间。此外,因为前驱体物质是在被溶剂稀释的状态下得到气化,因此可以以更加均匀地状态移送到沉积腔室内部并借此更加均匀地吸附到基板上,从而最终可以提升所沉积的薄膜的均匀性(uniformity)以及阶梯覆盖(step coverage)特性。此外,叔胺中的盈余不成键电子对可以提升前驱体物质在基板吸附过程中的稳定性,从而将在原子层沉积法(ALD)工程中的化学气相沉积(CVD)最小化。此外,除了如上所述的叔胺之外,在使用C1-C16的饱和或不饱和烃、酮、醚、甘醇二甲醚、酯、四氢呋喃等溶剂以及上述之组合时,不仅可以达成以液体移送为目的的适当的粘度调整效果,还可以提升分散性并借此达成电气特性的提升。
适用本发明的前驱体组合物含有锆化合物以及铪化合物,所以以此制造出的金属膜与一般的氧化锆薄膜相比可以大幅提升高介电常数(high K)特性。此外,因为是通过液体移送形成薄膜,因此锆以及铪的分散性极高,从而可以使得所沉积的薄膜呈现出整体均匀且优秀的电气特性,而且还可以达成降低漏电流值(leakage current)的效果。
此外,为了进一步改善在供应上述前驱体组合物时最终形成的金属膜上的电气特性即静电容量以及漏电流值,还可以根据需要作为第2金属前驱体供应包含从硅(Si)、钛(Ti)、锗(Ge)、锶(Sr)、铌(Nb)、呗(Ba)、铪(Hf)、钽(Ta)以及镧族原子选择的一种以上的金属(M")的金属前驱体。上述第2金属前驱体可以是包含上述金属的烷基酰胺化合物或烷氧基化合物。作为一实例,在上述金属为Si的情况下,作为第2金属前驱体可以使用如SiH(N(CH3)2)3、Si(N(C2H5)2)4、Si(N(C2H5)(CH3))4、Si(N(CH3)2)4、Si(OC4H9)4、Si(OC2H5)4、Si(OCH3)4、Si(OC(CH3)3)4等。
上述第2金属前驱体的供应可以利用与上述前驱体组合物的供应方法相同的方法实施,上述第2金属前驱体可以与上述前驱体组合物一起供应到薄膜形成用基板上方,或者也可以在完成前驱体组合物的供应之后依次供应。
如上所述的前驱体组合物以及选择性的第2金属前驱体,在为了与上述金属膜形成用基板进行接触而供应到反应腔室内部之前维持50至250℃的温度为宜,较佳地维持100至200℃的温度为宜。
此外,在前驱体组合物的供应步骤之后供应反应性气体之前,为了可以帮助上述前驱体组合物以及选择性的第2金属前驱体移动到基板上方,或者为了使得反应器内部具有适合于沉积的适当压力,或者为了将存在于腔室内部的杂质等排放到外部,可以实施向反应器内部吹扫如氩(Ar)、氮(N2)或氦(He)等惰性气体的工程。此时,惰性气体的吹扫以反应器内部压力达到1至5Torr的方式实施为宜。
在完成上述金属前驱体的供应之后,向反应器内部供应反应性气体,并在反应性气体存在的条件下实施从由热处理、等离子体处理以及光照射构成的组中选择的1种处理工程。
作为上述反应性气体,可以使用水蒸气(H2O)、氧气(O2)、臭氧(O3)、过氧化氢(H2O2)、氢气(H2)、氨气(NH3)、一氧化氮(NO)一氧化二氮(N2O)、二氧化氮(NO2)、肼(N2H4)以及硅烷(SiH4)中的任意一个或上述之混合物。在上述如水蒸气、氧气以及臭氧等氧化性气体存在的条件下实施时,可以形成金属氧化物薄膜,而在如氢气、氨气、肼以及硅烷等还原性气体存在的条件下实施时,可以形成金属单体或金属氮化物薄膜。
此外,上述热处理、等离子体处理或光照射处理工程是为了提供金属前驱体的沉积所需要的热能,可以按照通常的方法实施。较佳地,为了以充分的生长速度制造出具有所需要的物理性状态以及组成的金属薄膜,以反应器内部的基板的温度维持100至1,000℃,较佳地以维持250至400℃的状态实施上述处理工程为宜。
此外,在上述处理工程中与上述说明相同,为了可以帮助上述反应性气体移动到基板上方,或者为了使得反应器内部具有适合于沉积的适当压力,或者为了将存在于反应器内部的杂质或副产物等排放到外部,可以实施向反应器内部吹扫如氩(Ar)、氮(N2)或氦(He)等惰性气体的工程。
通过将如上所述的金属前驱体的投入、反应性气体的投入以及惰性气体的投入处理工程作为一个循环,并重复实施一个循环以上,可以形成含金属薄膜。
具体来讲,在作为反应性气体使用氧化性气体的情况下所制造出的含金属薄膜,可以包含下述化学式7的金属氧化物:
【化学式7】
(M1-aM"a)Ob
在上述化学式7中,a为0≤a<1,b为0<b≤2,M是从由Zr、Hf以及Ti构成的组中选择,M"衍生自第2金属前驱体,是从硅(Si)、钛(Ti)、锗(Ge)、锶(Sr)、铌(Nb)、钡(Ba)、铪(Hf)、钽(Ta)以及镧族原子选择。
如上所述的金属膜的制造方法,通过利用热稳定性优秀的金属前驱体,可以在沉积工程中在与目前相比更高的温度下实施沉积工程,而且不会造成因为前驱体的热分解而导致的颗粒污染或如碳等杂质污染,因此,通过适用本发明的制造方法形成的含金属薄膜可以适用于半导体元件中的高介电物质膜,尤其是半导体内存元件中的动态随机存取存储器(DRAM)、互补金属氧化物半导体(CMOS)等。
作为另一实施形态,提供一种利用上述金属膜的形成方法形成的金属膜以及包含上述薄膜的半导体元件。具体来讲,上述半导体元件可以是包含随机存取存储器(RAM)用金属绝缘体金属(MIM)的半导体元件。
此外,上述半导体元件除了在元件内的如随机存取存储器(RAM)等需要高介电特性的物质膜上包含适用本发明的含金属薄膜之外,与一般的半导体元件的构成相同。
即,在由下部电极、介电体薄膜以及上部电极依次层叠构成的电容器中,上述下部电极以及上部电极可以包含金属物质,而上述下部电极的形状可以采用如平板、圆筒形、柱形等多种形状,此时,作为上述介电体薄膜可以适用利用本发明的前驱体组合物形成的薄膜。
例如,上述介电体薄膜可以包含锆氧化物以及铪氧化物。此外,也可以通过对包含从锆氧化物以及铪氧化物中选择的至少2种氧化物的薄膜进行层叠或混合的方式形成。
通过在圆筒形或柱形的下部电极上按照如上所述的方法沉积介电体薄膜,还可以对上述介电体薄膜的结晶性、介电特性以及漏电流特性进行改善。
例如,如图1(a)、(b)所示,可以形成以AlxOy薄膜或YxOy薄膜等作为中心在两侧面沉积ZrxHfyOz薄膜,或如图1(b)至(e)所示,可以形成在AlxOy、ZrOx、HfOx的沉积薄膜上对上述ZrxHfyOz薄膜进行沉积的形态的多种介电体薄膜。
此外,还可以通过适用本发明的薄膜而制造出晶体管。上述晶体管形成于基板上,包括栅极绝缘层、栅极电极、源极区域以及漏极区域。栅极电极可以包含金属物质,而栅极绝缘层可以包含利用薄膜形成用组合物沉积的金属氧化物或金属氮化物薄膜。例如,栅极绝缘层可以包含锆氧化物以及铪氧化物。此外,上述栅极绝缘层也可以通过对从锆氧化物以及铪氧化物中选择的至少2种氧化物薄膜进行层叠或混合的方式形成。更具体来讲,可以将HfxOy或ZrxHfyOz薄膜作为上述栅极绝缘层适用。
接下来,将通过实施例对本发明的效果进行说明。
用于制造组合物的化合物如表1所示。
【表1】
<前驱体以及各个混合物的反应性确认以及物性确认>
为了对各个化合物之间的反应性进行确认,在对化合物直接进行混合之后对肉眼观察时的变化、核磁共振(HMR)测定上的变化以及反应性等进行了确认,同时根据需要对热重分析、粘度以及热稳定性等物性进行了确认。
对化合物1和化合物4以及上述之组合物的评估结果如表2所示。表2中的组成比为化合物1以及化合物4的重量比。
【表2】
通过表2的结果可以确认,由化合物1以及化合物4构成的组合物在肉眼观察时没有颜色变化且没有生成沉淀物。此外,在核磁共振(NMR)测定结果中也没有观察到化学结构上的变化(图2)。因此,可以判定化合物1以及化合物4的组合物可以以稳定的状态使用。
此外,通过对化合物2以及化合物4、化合物3以及化合物4、化合物1以及化合物5、化合物2以及化合物5的核磁共振(NMR)测定结果中也可以确认组合物的制造不会导致化学结构上的变化(图3至图6)。
接下来,对化合物3和化合物5以及上述之组合物执行了评估,其结果如表3所示。表3中的组成比为化合物1以及化合物4的重量比。
【表3】
通过表3的结果可以确认,由化合物3以及化合物5构成的组合物在肉眼观察时没有颜色变化且没有生成沉淀物。此外,NMR分析结果没有观察到化学结构上的变化,因此可以判定上述由化合物3以及化合物5构成的组合物可以以稳定的状态使用(图7)。此外,通过热重分析(TGA)分析结果可以确认,即使是以组合物使用也不会对挥发特性造成影响,可以维持各个化合物在挥发温度范围内的挥发特性(图8)。
接下来,为了对不同溶剂含量下的物性进行评估,在对化合物1以及化合物4按照60:40的重量比进行混合的组合物中作为溶剂使用了辛烷(Octane)以及二甲基乙醇胺(DMEA,dimethylethylamine)。其结果如表4所示。
【表4】
参阅表4中的结果可以确认,即使是在通过向上述组合物添加溶剂进行稀释的情况下,在核磁共振(NMR)分析结果中没有观察到化学性的变化。借此可以确认,可以根据需要混合适当的溶剂进行使用,而且可以通过对溶剂的含量进行调节而将组合物调节成适合于在沉积工程中适用的适当的粘度。此外,通过热重分析(TGA)分析结果可以确认,即使是在向组合物添加溶剂的情况下也没有观察到显著的挥发特性的变化。
对上述组合物以及化合物1、化合物4进行热重分析(TGA)以及粘度分析的结果如表5所示。
【表5】
参阅表5中的结果可以确认,由化合物1以及化合物4构成的组合物呈现出基于组成比的热重分析(TGA)分析结果的稳定特性。即,即使是以组合物形态使用的情况下也不会对挥发特性造成影响,可以呈现出各个化合物的挥发温度范围内的挥发特性。此外,通过粘度测定结果可以确认,可以通过调节组成比而对粘度进行调节。此外,并没有发生因为混合的副作用而导致粘度增加的现象。
此外,对化合物1以及化合物4和上述之组合物执行了热稳定性分析,并对各个试料相对于初期纯度的纯度降低率进行了计算。其结果如表6所示。
【表6】
参阅表6中的结果可以确认,化合物1与化合物4相比热稳定性相对较差。但是,虽然在由化合物1以及化合物4构成的组合物中根据组成比具有一定的纯度降低率的差异,但是整体上纯度降低率有所下降。通过如上所述的结果可以确认,在以组合物形态适用时可以达成改善热稳定性的效果。即,因为热稳定性相对较高的化合物4可以对热稳定性相对较低的化合物1所受到的热能的一部分影响进行补偿,因此可以呈现出如上所述的效果。
此外,为了对不同溶剂以及组成的热稳定性进行确认,对以60:40的重量比含有化合物1以及化合物4的组合物执行了评估。其结果如表7所示。
【表7】
参阅表7中的结果,可以对在140以及160℃条件下与投入溶剂之前相比的基于溶剂的类型以及比例的组合物的纯度降低率进行确认。对于辛烷,虽然没有明确地呈现出基于溶剂含量的纯度降低率的改善效果,但是可以确认稳定性没有发生劣化而且可以为了粘度调节以及其他目的使用溶剂。
此外,对于二甲基乙醇胺(DMEA),呈现出了基于溶剂含量的纯度降低率的改善效果。据估计,这是因为在使用胺溶剂时可以借助于胺的不成键电子对使得前驱体的中心金属区域稳定化。通过如上所述的试验结果可以确认,可以通过在组合物上附加用于对上述组合物的沉积工程进行优化的多种溶剂而对组合物的物性进行调节。
此外,对化合物1至化合物5的不同组成的反应性进行评估的结果如表8所示。
【表8】
参阅表8中的结果可以确认,各个组合物在肉眼观察时没有颜色变化且没有生成沉淀物。此外,在核磁共振(NMR)分析结果中也没有观察到化学结构上的变化。因此,可以判定对化合物1至化合物5进行组合的组合物可以以稳定的状态使用。此外,通过热重分析(TGA)分析结果可以确认,即使是以组合物使用也不会对挥发特性造成影响,可以维持各个化合物在挥发温度范围内的挥发特性。
<锆氧化物薄膜以及铪氧化物薄膜和锆/铪氧化物薄膜的制造以及薄膜特性分析>
利用原子层沉积(Atomic Layer Deposition,ALD)装置实施了适用由化合物1以及化合物4构成的组合物的氧化物薄膜沉积工程。在试验中使用的基板为裸硅(bare Si)晶圆。通过将化合物1作为前驱体使用的工程(比较例1)制造出了Zr氧化物薄膜,并通过将化合物2作为前驱体使用的工程(比较例2)制造除了Hf氧化物薄膜。
此外,作为化合物1以及化合物4的组成比,将重量比为60:40的组合物(实施例1)、50:50的组合物(实施例2)、40:60的组合物(实施例3)、以及向按照50:50的重量比混合的化合物1以及化合物4的组合物混合5重量%的辛烷的组合物(实施例4)执行了沉积工程。
在用于形成Zr以及Hf单一氧化物的薄膜的原子层沉积(ALD)工程中以气泡形态(bubbler type)投入源,并将沉积温度设定为300℃。
此外,在沉积Zr/Hf复合氧化物薄膜的试验中以液体搬运***(LDS)方式实施了原子层沉积(ALD)工程,并将沉积温度设定为300℃。
对于如上所述的通过原子层沉积(ALD)工程制造出的Zr氧化物薄膜、Hf氧化物薄膜、Zr/Hf复合氧化物薄膜,对其单位生长速度(GPC)以及均匀度(Uniformity)进行了确认。其结果如表9所示。
【表9】
参阅表9中的结果可以确认,组合物与单一膜沉积相比呈现出了略高的单位生长速度。据估计,这是因为在沉积工程中可以借助于构成组合物的2种成分的相互补充效果,在种晶(seed)形成促进以及沉积步骤中促进表面反应面积。此外,对所制造出的Zr氧化物薄膜、Hf氧化物薄膜以及Zr/Hf氧化物薄膜的X-线反射测定(X-Ray Reflectivity,XRR)进行确认的结果以及密度如表10以及图9所示。
【表10】
参阅表10中的结果可以确认,使用化合物1的沉积工程与使用化合物4的沉积工程相比,其膜密度明显偏低。此外,在使用组合物的沉积工程中,与组合物的组成比的平均值相比呈现出了较高的模拟度。通过如上所述的结果可以确认,在使用组合物的沉积工程中所获取到的薄膜呈现出了足以制造出半导体元件的膜密度。
此外,对所通过薄膜形成工程制造出的Zr氧化物薄膜、Hf氧化物薄膜以及Zr/Hf氧化物薄膜的X-线光电分光法(X-Ray Photoelectron Spectroscopy,XPS)测定结果如表11以及图10所示。
【表11】
Zr(at%) | Hf(at%) | O(at%) | C(at%) | Cl(at%) | |
比较例1 | 37 | - | 62 | - | - |
比较例2 | - | 41 | 59 | - | - |
实施例1 | 23.8 | 15.2 | 60.8 | - | - |
实施例2 | 20.2 | 19.4 | 60.2 | - | - |
实施例3 | 16 | 24 | 59.8 | - | - |
实施例4 | 19.8 | 19.3 | 60.7 | - | - |
参阅表11中的结果可以确认,在使用Zr/Hf前驱体组合物的沉积工程中,组合物中的Zr以及Hf的比例与所制造出的薄膜的Zr以及Hf的组成一致。借此可以确认,可以通过对组合物的Zr/Hf比例进行调节而轻易地调节薄膜内的Zr/Hf浓度。此外,薄膜内的C、Cl等其他杂志的含量都在1at%以下的水准之内,借此可以确认在原子层沉积(ALD)工程中可以制造出没有杂志的纯净的薄膜。
此外,对所制造出的Zr氧化物薄膜、Hf氧化物薄膜以及Zr/Hf氧化物薄膜的电化学-循环伏安法(Cyclic Voltammetry,C-V)测定结果如表12以及图11所示。
【表12】
参阅表12可以确认,Zr氧化物薄膜的介电率为26左右,而Hf氧化物薄膜的介电率为25左右。关于此,在使用组合物制造出的薄膜中虽然根据其组成比略有不同,但是整体上呈现出了30以上的高介电率。尤其是,在组成比为40:60的情况(实施例3)下的介电率为35以上。借此可以确认,通过利用组合物对薄膜内的Zr以及Hf的组成比进行调节,可以有效地改善薄膜的整体介电率。
通过如上所述的较佳的实施形态对本发明进行了详细的说明,但是本发明并不限定于上述实施形态,具有本发明所属技术领域之一般知识的人员可以在不脱离本发明之精神的范围内进行各种变形以及变更。而如上所述的变形例以及变更例也应该解释为包含在本发明所附的权利要求书的范围之内。
Claims (16)
2.根据权利要求1所述的金属膜形成用前驱体组合物,其特征在于:
还追加包含溶剂。
3.根据权利要求2所述的金属膜形成用前驱体组合物,其特征在于:
上述溶剂为C1-C16的饱和或不饱和烃、酮、醚、甘醇二甲醚、酯、四氢呋喃、叔胺中的任意一个或多个。
4.根据权利要求2所述的金属膜形成用前驱体组合物,其特征在于:
上述溶剂相对于上述金属膜形成用前驱体组合物的总重量包含0.1至99重量%。
5.根据权利要求1所述的金属膜形成用前驱体组合物,其特征在于:
上述锆化合物以及铪化合物是按照0.1:99.9至99.9:0.1的重量比进行混合。
6.一种金属膜的形成方法,其特征在于,包括:
利用根据权利要求1所述的金属膜形成用前驱体组合物在基板上沉积金属膜的步骤。
7.根据权利要求6所述的金属膜形成方法,其特征在于:
上述金属膜形成用前驱体组合物还追加包含溶剂。
8.根据权利要求6所述的金属膜形成方法,其特征在于:
上述溶剂相对于上述金属膜形成用前驱体组合物的总重量包含0.1至99重量%。
9.根据权利要求6或权利要求7所述的金属膜形成方法,其特征在于:
上述金属膜是通过原子层沉积法、化学气相沉积法或蒸发法中的任意一个方法进行沉积。
10.根据权利要求6或权利要求7所述的金属膜形成方法,其特征在于:
还追加包括将上述金属膜形成用前驱体组合物供应到上述基板上的前驱体组合物传递步骤;
上述前驱体组合物传递步骤是利用蒸汽压力的挥发移送法、直接液体注入法或液体移送法中的任意一个。
11.根据权利要求6或权利要求7所述的金属膜形成方法,其特征在于:
上述沉积,包括:
将基板配置在腔室内部的步骤;
将上述金属膜形成用前驱体组合物供应到上述腔室内部的步骤;
向上述腔室内部供应反应性气体或反应性气体的等离子体的步骤;以及,
在上述腔室内部通过热处理、等离子体处理以及光照射中的任意一个或多个方法进行处理的步骤。
12.根据权利要求11所述的金属膜形成方法,其特征在于:
上述反应性气体是水蒸气、氧气、臭氧、过氧化氢、氢气、氨气、一氧化氮、一氧化二氮、二氧化氮、肼以及硅烷中的任意一个或多个,上述反应性气体的等离子体可以是射频等离子体、直流等离子体或远程等离子体中的任意一个。
13.根据权利要求11所述的金属膜形成方法,其特征在于:
上述腔室内部的沉积温度为250至400℃。
14.根据权利要求6或权利要求7所述的金属膜形成方法,其特征在于:
上述锆化合物以及铪化合物是按照0.1:99.9至99.9:0.1的重量比进行混合。
15.一种半导体元件,其特征在于:
包括根据权利要求6或权利要求7所述的金属膜形成方法制造的金属膜。
16.一种晶体管,其特征在于:
作为包括根据权利要求5或权利要求6所述的金属膜形成方法制造的金属膜的晶体管,
上述金属膜构成上述晶体管的栅极绝缘层。
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6984591B1 (en) * | 2000-04-20 | 2006-01-10 | International Business Machines Corporation | Precursor source mixtures |
US20110183527A1 (en) * | 2009-08-18 | 2011-07-28 | Youn-Joung Cho | Precursor Composition, Methods of Forming a Layer, Methods of Forming a Gate Structure and Methods of Forming a Capacitor |
WO2013150920A1 (ja) * | 2012-04-05 | 2013-10-10 | 東京エレクトロン株式会社 | 半導体デバイスの製造方法及び基板処理システム |
KR20140078534A (ko) * | 2012-12-17 | 2014-06-25 | 솔브레인씨그마알드리치 유한회사 | 금속 전구체 및 이를 이용하여 제조된 금속 함유 박막 |
CN103930431A (zh) * | 2011-03-15 | 2014-07-16 | 株式会社Mecharonics | 新型第4b族金属有机化合物及其制备 |
KR20160000392A (ko) * | 2014-06-24 | 2016-01-04 | 솔브레인씨그마알드리치 유한회사 | 박막 형성용 조성물 |
CN106062242A (zh) * | 2014-02-26 | 2016-10-26 | 株式会社Eugene科技材料 | 用于形成含锆膜的前驱体组合物以及用其形成含锆膜的方法 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008128141A2 (en) | 2007-04-12 | 2008-10-23 | Advanced Technology Materials, Inc. | Zirconium, hafnuim, titanium, and silicon precursors for ald/cvd |
EP2464652A4 (en) | 2009-08-14 | 2013-01-09 | Air Liquide | HAFNIUM AND ZIRCONIUM-CONTAINING PRECEDENTS AND METHOD OF USE THEREOF |
US8962078B2 (en) | 2012-06-22 | 2015-02-24 | Tokyo Electron Limited | Method for depositing dielectric films |
KR102358566B1 (ko) | 2015-08-04 | 2022-02-04 | 삼성전자주식회사 | 물질막 형성 방법 |
-
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Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6984591B1 (en) * | 2000-04-20 | 2006-01-10 | International Business Machines Corporation | Precursor source mixtures |
US20110183527A1 (en) * | 2009-08-18 | 2011-07-28 | Youn-Joung Cho | Precursor Composition, Methods of Forming a Layer, Methods of Forming a Gate Structure and Methods of Forming a Capacitor |
CN103930431A (zh) * | 2011-03-15 | 2014-07-16 | 株式会社Mecharonics | 新型第4b族金属有机化合物及其制备 |
WO2013150920A1 (ja) * | 2012-04-05 | 2013-10-10 | 東京エレクトロン株式会社 | 半導体デバイスの製造方法及び基板処理システム |
US20150017813A1 (en) * | 2012-04-05 | 2015-01-15 | Tokyo Electron Limited | Semiconductor Device Manufacturing Method and Substrate Treatment System |
KR20140078534A (ko) * | 2012-12-17 | 2014-06-25 | 솔브레인씨그마알드리치 유한회사 | 금속 전구체 및 이를 이용하여 제조된 금속 함유 박막 |
CN106062242A (zh) * | 2014-02-26 | 2016-10-26 | 株式会社Eugene科技材料 | 用于形成含锆膜的前驱体组合物以及用其形成含锆膜的方法 |
KR20160000392A (ko) * | 2014-06-24 | 2016-01-04 | 솔브레인씨그마알드리치 유한회사 | 박막 형성용 조성물 |
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