KR101367827B1 - Hafnium compound, hafnium thin film-forming material and method for forming hafnium thin film - Google Patents

Hafnium compound, hafnium thin film-forming material and method for forming hafnium thin film Download PDF

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KR101367827B1
KR101367827B1 KR1020087008011A KR20087008011A KR101367827B1 KR 101367827 B1 KR101367827 B1 KR 101367827B1 KR 1020087008011 A KR1020087008011 A KR 1020087008011A KR 20087008011 A KR20087008011 A KR 20087008011A KR 101367827 B1 KR101367827 B1 KR 101367827B1
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hafnium
thin film
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다다아키 히라키
사토루 미하시
기요시 다즈케
아키히토 쓰바키타니
김병수
유승호
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솔브레인 주식회사
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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
    • 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 System
    • 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

Abstract

상온에서 액체이며 그리고 안정성이 높아 원료의 안정공급을 할 수 있어 고품질의 하프늄계 박막을 안정되게 형성할 수 있는 기술을 제공한다. 하기의 일반식[I]로 나타내는 화합물인 하프늄계 박막형성재료이다.It is liquid at room temperature and has high stability, so that stable supply of raw materials can be provided to provide a technology for stably forming high quality hafnium-based thin films. It is a hafnium-based thin film forming material which is a compound represented by the following general formula [I].

일반식[I]Formula [I]

LHf(NR1R2)3 LHf (NR 1 R 2 ) 3

(단, L은, 시클로펜타디에닐기 또는 치환 시클로펜타디에닐기, R1, R2는 알킬기이며, R1과 R2는 서로 달라고 좋고 같아도 좋다.)(Wherein L is a cyclopentadienyl group or a substituted cyclopentadienyl group, R 1 and R 2 are alkyl groups, and R 1 and R 2 may be different from each other or may be the same.)

Description

하프늄계 화합물, 하프늄계 박막형성재료 및 하프늄계 박막형성방법{HAFNIUM COMPOUND, HAFNIUM THIN FILM-FORMING MATERIAL AND METHOD FOR FORMING HAFNIUM THIN FILM}Hafnium-based compounds, hafnium-based thin film forming materials and hafnium-based thin film forming methods

본 발명은 하프늄계 박막형성기술에 관한 것이다.The present invention relates to a hafnium-based thin film formation technology.

테트라할로겐화하프늄(tetrahalogen化hafnium) 또는 테트라키스(디알킬아미노)하프늄(tetrakis(dialkylamino)hafnium) 또는 테트라키스(알콕시)하프늄(tetrakis(alkoxy)hafnium) 또는 테트라키스(β-디케톤)하프늄(tetrakis(β-diketone)hafnium)을 사용하여, 화학기상 성장방법(化學氣相成長方法) 혹은 원자층제어 성장방법(原子層制御成長方法)에 의하여 하프늄계 박막(薄膜)을 형성하는 것이 제안되어 있다.Tetrahalogenated hafnium or tetrakis (dialkylamino) hafnium or tetrakis (alkoxy) hafnium or tetrakis (β-diketone) hafnium It is proposed to form a hafnium-based thin film using (β-diketone) hafnium) by a chemical vapor growth method or an atomic layer controlled growth method. .

그런데 하프늄계 박막의 형성에 있어서는, 상기 화합물을 기화(氣化)시킬 필요가 있다. 그리고 기화를 위하여 상기 화합물은 가열된다.By the way, in formation of a hafnium-based thin film, it is necessary to vaporize the compound. And the compound is heated for vaporization.

그러나 테트라할로겐화하프늄이나 테트라키스(β-디케톤)하프늄은 고체이다. 이 때문에 기화가 곤란하여 안정된 가스 공급을 하는 것이 어렵다. 즉 원료의 안정공급이 어렵기 때문에 고품질의 하프늄계 박막을 안정되게 형성할 수 없다.However, tetrahalogenated hafnium and tetrakis (β-diketone) hafnium are solid. For this reason, vaporization is difficult and it is difficult to supply stable gas. In other words, it is difficult to stably supply high-quality hafnium-based thin films because it is difficult to stably supply raw materials.

테트라키스(디알킬아미노)하프늄은 열안정성(熱安定性)이 낮다. 따라서 가열해서 기화했을 때에 분해된다. 이 때문에 안정된 가스 공급을 하기 어렵다. 즉 원료의 안정공급이 어렵기 때문에 고품질의 하프늄계 박막을 안정되게 형성할 수 없다.Tetrakis (dialkylamino) hafnium has low thermal stability. Therefore, it decomposes when heated and vaporized. For this reason, it is difficult to supply stable gas. In other words, it is difficult to stably supply high-quality hafnium-based thin films because it is difficult to stably supply raw materials.

테트라키스(알콕시)하프늄도 안정성이 나쁘다. 예를 들면 보존하고 있는 것만으로도 분해되어 버린다. 이 때문에 안정된 가스 공급을 하기 어렵다. 즉 원료의 안정공급이 어렵기 때문에 고품질의 하프늄계 박막을 안정되게 형성할 수 없다.Tetrakis (alkoxy) hafnium also has poor stability. For example, it will decompose just to preserve. For this reason, it is difficult to supply stable gas. In other words, it is difficult to stably supply high-quality hafnium-based thin films because it is difficult to stably supply raw materials.

특허문헌1 : 일본국 공개특허공보 특개2005-298467Patent Document 1: Japanese Patent Application Laid-Open No. 2005-298467

특허문헌2 : 일본국 공개특허공보 특개2005-294421Patent Document 2: Japanese Patent Application Laid-Open No. 2005-294421

특허문헌3 : 일본국 공개특허공보 특개2004-137223Patent Document 3: Japanese Patent Application Laid-Open No. 2004-137223

특허문헌4 : 일본국 공개특허공보 특개2004-137222Patent Document 4: Japanese Patent Application Laid-Open No. 2004-137222

[발명이 이루고자 하는 기술적 과제][Technical problem to be achieved]

따라서 본 발명이 해결하고자 하는 과제는, 상기의 문제점을 해결하는 것이다. 특히, 상온에서 액체이며 그리고 안정성이 높고 원료의 안정공급이 이루어져, 고품질의 하프늄계 박막을 안정되게 형성할 수 있는 기술을 제공하는 것이다.Accordingly, the problem to be solved by the present invention is to solve the above problems. In particular, it is a liquid at room temperature, high stability and stable supply of raw materials to provide a technology capable of stably forming a high quality hafnium-based thin film.

[발명의 구성][Configuration of Invention]

상기 과제를 해결하기 위한 예의 검토를 하던 중에 LHf(NR1R2)3으로 표현되는 화합물은, 안정성이 높고 그리고 기화도 용이해서, 화학기상 성장방법이나 원자층제어 성장방법에 의하여 고품질의 하프늄계 박막을 형성할 수 있는 것을 찾아내기에 이르렀다.The compound represented by LHf (NR 1 R 2 ) 3 is highly stable and easy to vaporize during the study for solving the above-mentioned problems. Therefore, a high-quality hafnium-based compound is used by a chemical vapor growth method or an atomic layer controlled growth method. It came to find what can form a thin film.

상기 견해를 기초로 하여 본 발명을 달성하였다.The present invention has been accomplished based on the above viewpoint.

즉 상기의 과제는, 하기의 일반식[I]로 나타내는 것을 특징으로 하는 화합물에 의하여 해결된다.That is, the said subject is solved by the compound characterized by following General formula [I].

특히, 일반식[I]에 있어서의 L이 시클로펜타디에닐기, 메틸시클로펜타디에닐기 또는 에틸시클로펜타디에닐기이며, R1, R2가 메틸기 또는 에틸기인 것을 특징으로 하는 화합물에 의하여 해결된다.In particular, L in general formula [I] is a cyclopentadienyl group, a methylcyclopentadienyl group, or an ethylcyclopentadienyl group, and R <1> , R <2> is a methyl group or an ethyl group, It solves by the compound characterized by the above-mentioned.

하프늄계 박막을 형성하기 위한 재료로서,As a material for forming a hafnium-based thin film,

하기의 일반식[I]로 나타내는 화합물인 것을 특징으로 하는 하프늄계 박막형성재료에 의하여 해결된다.It is solved by the hafnium-based thin film forming material, which is a compound represented by the following general formula [I].

하프늄계 박막을 형성하기 위한 재료로서,As a material for forming a hafnium-based thin film,

하기의 일반식[I]으로 나타내는 화합물과,The compound represented by the following general formula [I],

상기 화합물이 용해되는 용매를 함유하는 것을Containing a solvent in which the compound is dissolved

특징으로 하는 하프늄계 박막형성재료에 의하여 해결된다.This is solved by the hafnium-based thin film forming material.

일반식[I]Formula [I]

LHf(NR1R2)3 LHf (NR 1 R 2 ) 3

(단, L은, 시클로펜타디에닐기 또는 치환 시클로펜타디에닐기, R1, R2는 알킬기이며, R1과 R2는 서로 달라고 좋고 같아도 좋다.)(Wherein L is a cyclopentadienyl group or a substituted cyclopentadienyl group, R 1 and R 2 are alkyl groups, and R 1 and R 2 may be different from each other or may be the same.)

특히, 상기한 하프늄계 박막형성재료로서, 상기 일반식[I]에 있어서의 L이 시클로펜타디에닐기 혹은 메틸시클로펜타디에닐기 또는 에틸시클로펜타디에닐기이며, 또한 R1, R2가 메틸기 또는 에틸기인 것을 특징으로 하는 하프늄계 박막형성재료에 의하여 해결된다.In particular, as the hafnium-based thin film forming material, L in the general formula [I] is a cyclopentadienyl group, a methylcyclopentadienyl group or an ethylcyclopentadienyl group, and R 1 , R 2 are a methyl group or an ethyl group. It is solved by a hafnium-based thin film forming material characterized in that.

그 중에서도, 상기 일반식[I]의 화합물이 CpHf(NMe2)3, (MeCp)Hf(NMe2)3, (EtCp)Hf(NMe2)3, CpHf(NMeEt)3〔Cp=시클로펜타디에닐기, MeCp=메틸시클로펜타디에닐기, EtCp=에틸시클로펜타디에닐기, Me=메틸기, Et=에틸기〕인 것을 특징으로 하는 하프늄계 박막형성재료에 의하여 해결된다.Especially, the compound of the general formula [I] is CpHf (NMe 2 ) 3 , (MeCp) Hf (NMe 2 ) 3 , (EtCp) Hf (NMe 2 ) 3 , CpHf (NMeEt) 3 [Cp = cyclopentadier It is solved by a hafnium-based thin film forming material, wherein a nil group, MeCp = methylcyclopentadienyl group, EtCp = ethylcyclopentadienyl group, Me = methyl group, and Et = ethyl group.

상기한 하프늄계 박막형성재료로서, 용매가, 탄소수5∼40(특히, 15 이하)의 탄화수소계 화합물 및 탄소수2∼40(특히, 20 이하)의 아민계 화합물의 군 중에서 선택되는 1개 또는 두 개 이상의 화합물인 하프늄계 박막형성재료에 의하여 해결된다.As the hafnium-based thin film forming material, one or two solvents are selected from the group of a hydrocarbon compound having 5 to 40 carbon atoms (especially 15 or less) and an amine compound having 2 to 40 carbon atoms (especially 20 or less). It is solved by hafnium-based thin film forming material which is more than one compound.

상기의 하프늄계 박막형성재료는, 특히 화학기상 성장방법 또는 원자층제어 성장방법에 의하여 하프늄계 박막을 형성하기 위한 재료이다.The hafnium-based thin film forming material is a material for forming a hafnium-based thin film, in particular, by a chemical vapor growth method or an atomic layer controlled growth method.

상기의 과제는, 상기 하프늄계 박막형성재료를 사용해서 화학기상 성장방법에 의하여 기판 상에 하프늄계 박막을 형성하는 것을 특징으로 하는 하프늄계 박막형성방법에 의하여 해결된다.The above object is solved by the hafnium-based thin film forming method, wherein the hafnium-based thin film forming material is used to form a hafnium-based thin film on a substrate by a chemical vapor deposition method.

상기의 과제는, 상기 하프늄계 박막형성재료를 사용해서 원자층제어 성장방법에 의하여 기판 상에 하프늄계 박막을 형성하는 것을 특징으로 하는 하프늄계 박막형성방법에 의하여 해결된다.The above object is solved by the hafnium-based thin film forming method, wherein the hafnium-based thin film forming material is used to form a hafnium-based thin film on a substrate by an atomic layer controlled growth method.

[발명의 효과][Effects of the Invention]

본 발명에 의하면, 하프늄계 박막을 양호하게 형성할 수 있다. 즉, 하프늄계 박막을 형성하기 위한 원료가 안정성이 높고 또한 기화하기 쉽기 때문에, 원료의 안정공급이 이루어져 고품질의 하프늄계 박막이 안정되게 형성된다.According to the present invention, a hafnium-based thin film can be formed satisfactorily. That is, since the raw material for forming the hafnium-based thin film is high in stability and easy to vaporize, a stable supply of the raw material is made, and a high-quality hafnium-based thin film is formed stably.

도1은, CpHf(NMe2)3의 NMR스펙트럼이다.1 is an NMR spectrum of CpHf (NMe 2 ) 3 .

도2는, CVD 장치의 개략도이다.2 is a schematic diagram of a CVD apparatus.

도3은, (MeCp)Hf(NMe2)3의 NMR스펙트럼이다.3 is an NMR spectrum of (MeCp) Hf (NMe 2 ) 3 .

도4는, (EtCp)Hf(NMe2)3의 NMR스펙트럼이다.4 is an NMR spectrum of (EtCp) Hf (NMe 2 ) 3 .

도5는, CpHf(NMeEt)3의 NMR스펙트럼이다.5 is an NMR spectrum of CpHf (NMeEt) 3 .

도6은, (MeCp)Hf(NMe2)3의 TG-DTA 차트이다.6 is a TG-DTA chart of (MeCp) Hf (NMe 2 ) 3 .

*도면의 주요부분에 대한 부호의 설명*Description of the Related Art [0002]

1 용기 2 기화기1 vessel 2 vaporizers

3 가열기 4 기판3 burners 4 substrates

5 분해반응로 6 가열기5 cracking furnace 6 burner

7 진공펌프7 vacuum pump

본 발명의 신규화합물은 하기의 일반식[I]로 나타내는 화합물이다. 특히, 하기의 일반식[I]에 있어서의 L이 시클로펜타디에닐기(cyclopentadienyl group), 메틸시클로펜타디에닐기(methylcyclopentadienyl group) 또는 에틸시클로펜타디에닐기(ethylcyclopentadienyl group)이며, R1, R2가 메틸기(methyl group) 또는 에틸기(ethyl group)인 화합물이다. 그 중에서도, CpHf(NMe2)3, (MeCp)Hf(NMe2)3, (EtCp)Hf(NMe2)3, CpHf(NMeEt)3이다.The novel compound of the present invention is a compound represented by the following general formula [I]. In particular, L in the following general formula [I] is a cyclopentadienyl group, a methylcyclopentadienyl group, or an ethylcyclopentadienyl group, an ethylcyclopentadienyl group, R <1> , R <2> is It is a compound which is a methyl group or an ethyl group. Among them, CpHf (NMe 2 ) 3 , (MeCp) Hf (NMe 2 ) 3 , (EtCp) Hf (NMe 2 ) 3 , and CpHf (NMeEt) 3 .

일반식[I]Formula [I]

LHf(NR1R2)3 LHf (NR 1 R 2 ) 3

(단, L은, 시클로펜타디에닐기 또는 치환 시클로펜타디에닐기(substituted cyclopentadienyl group), R1, R2는 알킬기(alkyl group)이며, R1과 R2는 서로 달라고 좋고 같아도 좋다.)(Wherein L is a cyclopentadienyl group or a substituted cyclopentadienyl group, R 1 and R 2 are alkyl groups, and R 1 and R 2 may be different or the same.)

상기 화합물은, 특히 하프늄계 박막형성재료로서 사용된다. 그 중에서도, 화학기상 성장방법이나 원자층제어 성장방법에 의하여 하프늄계 박막을 형성하기 위한 재료로서 사용된다. 상기 일반식[I]로 나타내는 화합물이 하프늄계 박막형성재료로서 사용될 경우에, 그 화합물은, 단독 또는 그 화합물이 용해되는 용매의 혼합물의 형태로 사용되는 것이 바람직하다. 즉 용액(용질(일반식[I]) + 용매)형태인 것이다. 용매는, 바람직하게는 탄소수5∼40(특히, 5∼15)의 탄화수소계 화합물 및 탄소수2∼40(특히, 2∼20)의 아민계 화합물의 군(群) 중으로부터 선택되는 1개 또는 두 개 이상의 화합물이다. 그 중에서도 바람직한 것은, 탄화수소계의 용매에서는, 예를 들면 노르말데칸(n-decane), 노르말헵탄(n-heptane), 노르말헥산(n-hexane), 테트라데칸, 크실렌(xylene), 톨루엔(toluene)을 들 수 있고, 또 아민계의 용매에서는, 예를 들면 트리에틸아민, 비스(트리메틸시릴)아민, 디에틸아민, 피리딘을 들 수 있다. 용매의 양은, 일반식[I]로 나타내는 화합물100질량부에 대하여 용매가 1∼10000질량부, 특히 100∼2000질량부가 바람직하다. 즉 이러한 용매를 사용함으로써 재료의 공급이 원활하게 이루어진다. 한편, CpHf(NMe2)3, (MeCp)Hf(NMe2)3, (EtCp)Hf(NMe2)3, CpHf(NMeEt)3 등의 화합물이 가장 바람직한 것은, 이들 등의 화합물에 의하여 형성된 하프늄계 박막의 막질이 우수했기 때문이다.The said compound is used especially as a hafnium type thin film formation material. Among them, it is used as a material for forming a hafnium-based thin film by a chemical vapor growth method or an atomic layer controlled growth method. When the compound represented by the general formula [I] is used as a hafnium-based thin film forming material, the compound is preferably used in the form of a mixture of a solvent in which the compound is dissolved. That is, in the form of a solution (solute (general formula [I]) + solvent). The solvent is preferably one or two selected from the group of a hydrocarbon compound having 5 to 40 carbon atoms (particularly 5 to 15) and an amine compound having 2 to 40 carbon atoms (particularly 2 to 20). Or more compounds. Among them, preferred hydrocarbon solvents include, for example, normal decane (n-decane), normal heptane (n-heptane), normal hexane (n-hexane), tetradecane, xylene and toluene. Examples of the amine solvent include triethylamine, bis (trimethylsilyl) amine, diethylamine, and pyridine. As for the quantity of a solvent, 1-10000 mass parts of solvents are especially preferable 100-2000 mass parts with respect to 100 mass parts of compounds represented by General formula [I]. In other words, by using such a solvent, the supply of materials is smooth. On the other hand, compounds such as CpHf (NMe 2 ) 3 , (MeCp) Hf (NMe 2 ) 3 , (EtCp) Hf (NMe 2 ) 3 , CpHf (NMeEt) 3, and the like are most preferable, hafnium formed by such compounds. This is because the film quality of the system thin film is excellent.

본 발명의 하프늄계 박막형성방법은, 상기한 하프늄계 박막형성재료(상기 일반식[I]로 나타내는 화합물 또는 상기 일반식[I]로 나타내는 화합물을 포함하는 용액)를 사용하여, 화학기상 성장방법에 의하여 기판 상에 하프늄계 박막을 형성하는 방법이다. 또는 상기한 하프늄계 박막형성재료(상기 일반식[I]로 나타내는 화합물 또는 상기 일반식[I]로 나타내는 화합물을 포함하는 용액)를 사용하여, 원자층제어 성장방법에 의하여 기판 상에 하프늄계 박막을 형성하는 방법이다.The hafnium-based thin film forming method of the present invention is a chemical vapor growth method using the hafnium-based thin film forming material (a solution containing the compound represented by the general formula [I] or the compound represented by the general formula [I]). To form a hafnium-based thin film on a substrate. Or using the hafnium-based thin film forming material (a solution containing the compound represented by the general formula [I] or the compound represented by the general formula [I]) on the substrate by an atomic layer controlled growth method. How to form.

한편 본 발명에 있어서, 하프늄계 박막으로는, Hf막 이외에도 예를 들면 산화하프늄 막이 있다. 이러한 막은, 본 발명의 하프늄계 박막형성재료를 성막(成膜)함에 있어서 산화제의 환경하에서 함으로써 얻어진다. 또 오존 가스를 병용함으로써도 얻어진다. 그리고 성막시의 환경(가스)에 의하여 하프늄계 박막의 조성이 적당하게 결정된다. 예를 들면 질화 분위기 하에서 성막이 이루어지면, 질화하프늄 박막을 형성할 수 있다.In the present invention, the hafnium-based thin film includes, for example, a hafnium oxide film in addition to the Hf film. Such a film is obtained by forming an hafnium-based thin film forming material of the present invention under an oxidizing agent environment. It is also obtained by using ozone gas in combination. The composition of the hafnium-based thin film is appropriately determined by the environment (gas) at the time of film formation. For example, when the film is formed in a nitride atmosphere, a hafnium nitride thin film can be formed.

이하, 구체적 실시예를 들어서 설명한다.Hereinafter, specific examples will be described.

실시예1Example 1

〔신규 화합물 CpHf(NMe2)3의 합성〕[Synthesis of New Compound CpHf (NMe 2 ) 3 ]

29g의 테트라키스(디메틸아미노)하프늄과, 5.3g의 시클로펜타디엔을 70mL의 벤젠 중에 질소 분위기 하에 두고, 1시간에 걸쳐 교반(攪拌)하였다. 이 용액을 2시간에 걸쳐 가열 환류(還流)시킨 후에, 벤젠을 감압 증류 제거(distilled off)하였다. 남은 황색 액체를 70∼80℃에서 0.1Torr의 감압 증류하여, 25g의 황색 액체를 얻었다.29 g of tetrakis (dimethylamino) hafnium and 5.3 g of cyclopentadiene were placed in 70 mL of benzene under a nitrogen atmosphere and stirred for 1 hour. After the solution was heated to reflux over 2 hours, benzene was distilled off under reduced pressure. The remaining yellow liquid was distilled under reduced pressure of 0.1 Torr at 70 to 80 ° C. to obtain 25 g of a yellow liquid.

이 황색 액체는, 비등점이 75℃/0.2Torr의 액체이었다.This yellow liquid had a liquid having a boiling point of 75 ° C./0.2 Torr.

또 NMR로 측정한 결과, 스펙트럼은 이하의 공명선(共鳴線)을 나타냈다.Moreover, as a result of measurement by NMR, the spectrum showed the following resonance lines.

1H-NMR(C6D6) : 3.0(s, 18H), 6.0(s, 5H) 1 H-NMR (C 6 D 6 ): 3.0 (s, 18H), 6.0 (s, 5H)

한편, 도1은 시클로펜타디에닐트리스(디메틸아미노)하프늄의 NMR 스펙트럼이다.1 is an NMR spectrum of cyclopentadienyl tris (dimethylamino) hafnium.

그리고 상기 반응형태 및 NMR 스펙트럼으로부터, 얻어진 황색 액체는 시클로펜타디에닐트리스(디메틸아미노)하프늄[CpHf(NMe2)3]인 것을 알았다.From the reaction mode and the NMR spectrum, the obtained yellow liquid was found to be cyclopentadienyltris (dimethylamino) hafnium [CpHf (NMe 2 ) 3 ].

다음에 150g의 CpHf(NMe2)3을 용기 중에 넣어서 100℃로 가열하고 또한 아르곤가스(캐리어가스(carrier gas))를 500ml/분의 비율로 공급했다. 기화한 CpHf(NMe2)3은, 캐리어 가스와 함께 가열 배관(가열온도는 100℃, 120℃, 150℃)을 거쳐 회수장치로 회수되었다. 한편 이 때에, 장치 내는 진공으로 배기되어 있다.Next, 150 g of CpHf (NMe 2 ) 3 was placed in a container and heated to 100 ° C, and argon gas (carrier gas) was supplied at a rate of 500 ml / min. The vaporized CpHf (NMe 2 ) 3 was recovered with the carrier gas through a heating pipe (heating temperatures of 100 ° C., 120 ° C. and 150 ° C.) to a recovery device. At this time, the inside of the apparatus is evacuated by vacuum.

이렇게 하여 회수된 CpHf(NMe2)3의 NMR 스펙트럼을 측정하고, 각 온 도에 있어서의 분해물량(分解物 量)을 확인했다. 그 결과, 100℃, 120℃ 및 150℃의 모든 온도에 있어서, 분해물량은 0이었다. 즉, CpHf(NMe2)3은 안정성이 높은 것이라는 것을 알았다.The NMR spectrum of CpHf (NMe 2 ) 3 recovered in this way was measured, and the amount of decomposition products at each temperature was confirmed. As a result, the decomposition product amount was 0 at all the temperatures of 100 ° C, 120 ° C and 150 ° C. That is, it turned out that CpHf (NMe 2 ) 3 has high stability.

또 CpHf(NMe2)3의 TG-DTA를 측정한 바, 기화율은 88.6%이었다. 즉, 높은 기화율이기 때문에 기화하기 쉬운 재료이며 Hf계 박막을 형성하는데도 적합한 재료인 것을 알았다.In addition, the TG-DTA of CpHf (NMe 2 ) 3 was measured, and the vaporization rate was 88.6%. That is, it was found that it is a material that is easy to vaporize because of its high vaporization rate, and is a material suitable for forming an Hf-based thin film.

〔Hf계 박막의 형성〕[Formation of Hf-based thin film]

도2는, Hf계 박막을 성막하기 위한 장치의 개략도이다.2 is a schematic diagram of an apparatus for forming an Hf-based thin film.

도2에서 1은 용기, 2는 기화기, 3은 가열기, 4는 기판, 5는 분해반응로, 6은 가열기, 7은 진공펌프이다.In Fig. 2, 1 is a vessel, 2 is a vaporizer, 3 is a heater, 4 is a substrate, 5 is a decomposition reaction, 6 is a heater, and 7 is a vacuum pump.

그리고 도2의 장치를 사용해서 기판5 상에 Hf계 박막을 제작하였다.Then, an Hf-based thin film was produced on the substrate 5 using the apparatus of FIG.

즉 용기1 내에 CpHf(NMe2)3을 넣고, 질소 가스(압송 가스)를 0.1g/분의 비율로 공급했다. 압송된 CpHf(NMe2)3은 기화기2에서 기화되어 분해반응로5로 유도되었다. 기화기2 및 배관은 가열기6으로 120∼130℃로 가온(加溫)되어 있다. 한편 이 때에 장치 내는 진공으로 배기되어 있다. 또 기판4는 400℃로 가열되어 있다. 그 결과, 기판4 상에 막이 형성되었다.That is, CpHf (NMe 2 ) 3 was put in the container 1 and nitrogen gas (pressure gas) was supplied at a rate of 0.1 g / min. The pressurized CpHf (NMe 2 ) 3 was vaporized in the vaporizer 2 to be introduced into the decomposition reactor 5. The vaporizer | carburetor 2 and piping are heated at 120-130 degreeC with the heater 6. At this time, the inside of the apparatus is evacuated by vacuum. In addition, the board | substrate 4 is heated at 400 degreeC. As a result, a film was formed on the substrate 4.

상기한 바와 같이 하여 형성된 막은, 면내(面內) 균일성이 우수한 것이었다. 또 ICP-MS로 조사한 결과, Hf박막인 것이 확인되었다.The film formed as mentioned above was excellent in in-plane uniformity. Moreover, as a result of irradiation with ICP-MS, it was confirmed that it was Hf thin film.

실시예2Example 2

〔신규 화합물 (MeCp)Hf(NMe2)3의 합성〕Synthesis of New Compound (MeCp) Hf (NMe 2 ) 3 ]

10g의 테트라키스(디메틸아미노)하프늄과, 2g의 메틸시클로펜타디엔을 35mL의 벤젠 중에 질소분위기 하에 두고, 1시간에 걸쳐 교반하였다. 이 용액을 2시간에 걸쳐 가열 환류시킨 후에 벤젠을 감압 증류 제거하였다. 남은 황색 액체를 70∼80℃에서 0.1Torr의 감압 증류하여, 11g의 황색 액체를 얻었다.10 g of tetrakis (dimethylamino) hafnium and 2 g of methylcyclopentadiene were placed in 35 mL of benzene under nitrogen atmosphere and stirred over 1 hour. The solution was heated to reflux over 2 hours, and then benzene was distilled off under reduced pressure. The remaining yellow liquid was distilled under reduced pressure of 0.1 Torr at 70-80 degreeC, and 11 g of yellow liquids were obtained.

이 황색 액체는, 비등점이 72℃/0.1Torr인 액체이었다.This yellow liquid was a liquid having a boiling point of 72 ° C./0.1 Torr.

또 NMR로 측정한 결과, 스펙트럼은 이하의 공명선을 나타냈다.Moreover, as a result of measurement by NMR, the spectrum showed the following resonance lines.

1H-NMR(C6D6) : 2.1(s, 3H), 3.0(s, 18H), 5.8(m, 2H), 5.9(m, 2H) 1 H-NMR (C 6 D 6 ): 2.1 (s, 3H), 3.0 (s, 18H), 5.8 (m, 2H), 5.9 (m, 2H)

한편, 도3은 메틸시클로펜타디에닐트리스(디메틸아미노)하프늄의 NMR 스펙트럼이다.3 is an NMR spectrum of methylcyclopentadienyltris (dimethylamino) hafnium.

그리고 상기 반응형태 및 NMR 스펙트럼으로부터, 얻어진 황색 액체는 메틸시클로펜타디에닐트리스(디메틸아미노)하프늄[(MeCp)Hf(NMe2)3]인 것을 알았다.From the reaction mode and the NMR spectrum, the obtained yellow liquid was found to be methylcyclopentadienyltris (dimethylamino) hafnium [(MeCp) Hf (NMe 2 ) 3 ].

다음에, 150g의 (MeCp)Hf(NMe2)3을 용기 중에 넣어서 100℃로 가열하고 또한 아르곤가스(캐리어가스)를 500ml/분의 비율로 공급했다. 기화한 (MeCp)Hf(NMe2)3은, 캐리어가스와 함께 가열 배관(가열온도는 100℃, 120℃, 150℃)을 거쳐 회수장치로 회수되었다. 한편 이 때에 장치 내는 진공으로 배기되어 있다.Next, 150 g of (MeCp) Hf (NMe 2 ) 3 was placed in a container and heated to 100 ° C, and argon gas (carrier gas) was supplied at a rate of 500 ml / min. The vaporized (MeCp) Hf (NMe 2 ) 3 was recovered with the carrier gas through a heating pipe (heating temperatures of 100 ° C., 120 ° C. and 150 ° C.) to a recovery device. At this time, the inside of the apparatus is evacuated by vacuum.

이렇게 하여 회수된 (MeCp)Hf(NMe2)3의 NMR 스펙트럼을 측정하고, 각 온도에 있어서의 분해물량을 확인하였다. 그 결과, 100℃, 120℃ 및 150℃의 모든 온도에 있어서, 분해 물량은 0이었다. 즉, (MeCp)Hf(NMe2)3은 안정성이 높은 것을 알았다.The NMR spectrum of (MeCp) Hf (NMe 2 ) 3 recovered in this way was measured, and the amount of decomposition products at each temperature was confirmed. As a result, the decomposition | disassembly quantity was 0 in all the temperature of 100 degreeC, 120 degreeC, and 150 degreeC. That is, it was found that (MeCp) Hf (NMe 2 ) 3 had high stability.

또 (MeCp)Hf(NMe2)3의 TG-DTA를 측정한 바, 기화율이 97.3% 이었다. 즉 높은 기화율이기 때문에 기화하기 쉬운 재료이며, Hf계 박막을 형성하는데도 적합한 재료인 것을 알았다. 한편, 도6은 (MeCp)Hf(NMe2)3의 TG-DTA 차트이다.Moreover, the vaporization rate was 97.3% when the TG-DTA of (MeCp) Hf (NMe 2 ) 3 was measured. That is, it was found that it is a material that is easy to vaporize because of its high vaporization rate, and is a material suitable for forming an Hf-based thin film. 6 is a TG-DTA chart of (MeCp) Hf (NMe 2 ) 3 .

〔Hf계 박막의 형성〕[Formation of Hf-based thin film]

실시예1에 있어서, CpHf(NMe2)3의 대신에 (MeCp)Hf(NMe2)3을 사용해서 마찬가지로 하여 기판4 상에 막을 형성하였다.In Example 1, a film was formed on the substrate 4 in the same manner using (MeCp) Hf (NMe 2 ) 3 instead of CpHf (NMe 2 ) 3 .

이렇게 하여 얻어진 막은, 면내 균일성이 우수한 것이었다. 또 ICP-MS로 조사한 결과, Hf 박막인 것이 확인되었다.The film thus obtained was excellent in in-plane uniformity. Moreover, as a result of irradiation with ICP-MS, it was confirmed that it was an Hf thin film.

실시예3Example 3

〔신규 화합물 (EtCp)Hf(NMe2)3의 합성〕Synthesis of New Compound (EtCp) Hf (NMe 2 ) 3 ]

25g의 테트라키스(디메틸아미노)하프늄과, 7g의 에틸시클로펜타디엔을 60mL의 벤젠 중에 질소분위기 하에 두고, 1시간에 걸쳐 교반하였다. 이 용액을 2시간에 걸쳐 가열 환류시킨 후에 벤젠을 감압 증류 제거하였다. 남은 황색 액체를 70∼80℃에서 0.1Torr의 감압 증류하고, 19g의 황색 액체를 얻었다.25 g of tetrakis (dimethylamino) hafnium and 7 g of ethylcyclopentadiene were placed in 60 mL of benzene under a nitrogen atmosphere and stirred over 1 hour. The solution was heated to reflux over 2 hours, and then benzene was distilled off under reduced pressure. The remaining yellow liquid was distilled under reduced pressure of 0.1 Torr at 70-80 degreeC, and 19 g of yellow liquids were obtained.

이 황색 액체는, 비등점이 78℃/0.2Torr인 액체이었다.This yellow liquid was a liquid having a boiling point of 78 ° C./0.2 Torr.

또 NMR로 측정한 결과, 스펙트럼은 이하의 공명선을 나타냈다.Moreover, as a result of measurement by NMR, the spectrum showed the following resonance lines.

1H-NMR(C6D6) : 1.1(t, 3H), 2.5(q, 2H), 3.0(s, 18H), 5.9(m, 2H), 6.0(m, 2H) 1 H-NMR (C 6 D 6 ): 1.1 (t, 3H), 2.5 (q, 2H), 3.0 (s, 18H), 5.9 (m, 2H), 6.0 (m, 2H)

한편, 도4는 에틸시클로펜타디에닐트리스(디메틸아미노)하프늄의 NMR 스펙트럼이다.4 is an NMR spectrum of ethylcyclopentadienyltris (dimethylamino) hafnium.

그리고 상기 반응형태 및 NMR 스펙트럼으로부터, 얻어진 황색 액체는 에틸시클로펜타디에닐트리스(디메틸아미노)하프늄[(EtCp)Hf(NMe2)3]인 것을 알았다.From the reaction mode and the NMR spectrum, the obtained yellow liquid was found to be ethylcyclopentadienyltris (dimethylamino) hafnium [(EtCp) Hf (NMe 2 ) 3 ].

다음에 150g의 (EtCp)Hf(NMe2)3을 용기 중에 넣어서 100℃로 가열하고 또한 아르곤가스(캐리어가스)를 500ml/분의 비율로 공급했다. 기화한 (EtCp)Hf(NMe2)3은, 캐리어가스와 함께 가열 배관(가열온도는 100℃, 120℃, 150℃)을 거쳐 회수장치로 회수되었다. 한편 이 때에 장치 내는 진공으로 배기되어 있다.Next, 150 g of (EtCp) Hf (NMe 2 ) 3 was placed in a container, heated to 100 ° C, and argon gas (carrier gas) was supplied at a rate of 500 ml / min. The vaporized (EtCp) Hf (NMe 2 ) 3 was recovered with the carrier gas through a heating pipe (heating temperatures of 100 ° C., 120 ° C. and 150 ° C.) to a recovery device. At this time, the inside of the apparatus is evacuated by vacuum.

이렇게 하여 회수된 (EtCp)Hf(NMe2)3의 NMR 스펙트럼을 측정하고, 각 온도에 있어서의 분해물량을 확인하였다. 그 결과, 100℃, 120℃ 및 150℃의 모든 온도에 있어서, 분해 물량은 0이었다. 즉, (EtCp)Hf(NMe2)3은 안정성이 높은 것을 알았다.The NMR spectrum of (EtCp) Hf (NMe 2 ) 3 recovered in this way was measured, and the amount of decomposition products at each temperature was confirmed. As a result, the decomposition | disassembly quantity was 0 in all the temperature of 100 degreeC, 120 degreeC, and 150 degreeC. That is, it was found that (EtCp) Hf (NMe 2 ) 3 had high stability.

또 (EtCp)Hf(NMe2)3의 TG-DTA를 측정한 바, 기화율은 94.8%이었다. 즉, 높은 기화율이기 때문에 기화하기 쉬운 재료이며, Hf계 박막을 형성하는데 적합한 재료인 것을 알았다.In addition, the TG-DTA of (EtCp) Hf (NMe 2 ) 3 was measured and found to have a vaporization rate of 94.8%. That is, it was found that it is a material that is easy to vaporize because of its high vaporization rate, and is a material suitable for forming an Hf-based thin film.

〔Hf계 박막의 형성〕[Formation of Hf-based thin film]

실시예1에 있어서, CpHf(NMe2)3의 대신에 (EtCp)Hf(NMe2)3을 사용해서 마찬가지로 하여 기판4 상에 막을 형성하였다.In Example 1, a film was formed on the substrate 4 in the same manner using (EtCp) Hf (NMe 2 ) 3 instead of CpHf (NMe 2 ) 3 .

이렇게 하여 얻어진 막은, 면내 균일성이 우수한 것이었다. 또 ICP-MS로 조사한 결과, Hf 박막인 것이 확인되었다.The film thus obtained was excellent in in-plane uniformity. Moreover, as a result of irradiation with ICP-MS, it was confirmed that it was an Hf thin film.

실시예4Example 4

〔신규 화합물 CpHf(NMeEt)3의 합성〕[Synthesis of New Compound CpHf (NMeEt) 3 ]

63g의 테트라키스(메틸에틸아미노)하프늄과, 10g의 시클로펜타디엔을 140mL의 벤젠 중에 질소분위기 하에 두고, 1시간에 걸쳐 교반하였다. 이 용액을 2시간에 걸쳐 가열 환류시킨 후에 벤젠을 감압 증류 제거하였다. 남은 황색 액체를 80∼90℃에서 0.1Torr의 감압 증류하고, 36g의 황색 액체 를 얻었다.63 g of tetrakis (methylethylamino) hafnium and 10 g of cyclopentadiene were placed in 140 mL of benzene under a nitrogen atmosphere and stirred for 1 hour. The solution was heated to reflux over 2 hours, and then benzene was distilled off under reduced pressure. The remaining yellow liquid was distilled under reduced pressure of 0.1 Torr at 80-90 degreeC, and 36 g of yellow liquids were obtained.

이 황색 액체는, 비등점이 85℃/0.2Torr의 액체이었다.This yellow liquid had a boiling point of 85 ° C./0.2 Torr.

또 NMR로 측정한 결과, 스펙트럼은 이하의 공명선을 나타냈다.Moreover, as a result of measurement by NMR, the spectrum showed the following resonance lines.

1H-NMR(C6D6) : 1.0(t, 9H), 2.9(s, 9H), 3.2(q, 6H), 6.1(s, 5H) 1 H-NMR (C 6 D 6 ): 1.0 (t, 9H), 2.9 (s, 9H), 3.2 (q, 6H), 6.1 (s, 5H)

한편, 도5는 시클로펜타디에닐트리스(메틸에틸아미노)하프늄의 NMR 스펙트럼이다.5 is an NMR spectrum of cyclopentadienyl tris (methylethylamino) hafnium.

그리고 상기 반응형태 및 NMR 스펙트럼으로부터, 얻어진 황색 액체는 시클로펜타디에닐트리스(메틸에틸아미노)하프늄[CpHf(NMeEt)3]인 것이 판명되었다.From the reaction mode and the NMR spectrum, the obtained yellow liquid was found to be cyclopentadienyltris (methylethylamino) hafnium [CpHf (NMeEt) 3 ].

다음에 150g의 CpHf(NMeEt)3을 용기 중에 넣어서 100℃로 가열하고 또한 아르곤가스(캐리어가스)를 500ml/분의 비율로 공급했다. 기화한 CpHf(NMeEt)3은, 캐리어가스와 함께 가열 배관(가열온도는 100℃, 120℃, 150℃)을 거쳐 회수장치로 회수되었다. 한편 이 때에 장치 내는 진공으로 배기되어 있다.Next, 150 g of CpHf (NMeEt) 3 was placed in a container and heated to 100 ° C, and argon gas (carrier gas) was supplied at a rate of 500 ml / min. The vaporized CpHf (NMeEt) 3 was recovered with the carrier gas through a heating pipe (heating temperatures of 100 ° C, 120 ° C, and 150 ° C) to a recovery device. At this time, the inside of the apparatus is evacuated by vacuum.

이렇게 하여 회수된 CpHf(NMeEt)3의 NMR 스펙트럼을 측정하고, 각 온도에 있어서의 분해물량을 확인하였다. 그 결과, 100℃, 120℃ 및 150℃의 모든 온도에 있어서, 분해 물량은 0이었다. 즉 CpHf(NMeEt)3은 안정성이 높은 것이 판명되었다.In this way, the NMR spectrum of CpHf (NMeEt) 3 recovered was measured, and the amount of decomposition products at each temperature was confirmed. As a result, the decomposition | disassembly quantity was 0 in all the temperature of 100 degreeC, 120 degreeC, and 150 degreeC. In other words, CpHf (NMeEt) 3 was found to have high stability.

또 CpHf(NMeEt)3의 TG-DTA를 측정한 바, 기화율은 90.1%이었다. 즉, 높은 기화율이기 때문에 기화하기 쉬운 재료이며, Hf계 박막을 형성하는데 적합한 재료인 것이 판명되었다.In addition, the TG-DTA of CpHf (NMeEt) 3 was measured, and the vaporization rate was 90.1%. That is, it was proved that it is a material which is easy to vaporize because of high vaporization rate, and is a material suitable for forming an Hf-based thin film.

〔Hf계 박막의 형성〕[Formation of Hf-based thin film]

실시예1에 있어서, CpHf(NMe2)3의 대신에 CpHf(NMeEt)3을 사용해서 마찬가지로 하여 기판4 상에 막을 형성하였다.In Example 1, instead of CpHf (NMe 2 ) 3 , CpHf (NMeEt) 3 was used in the same manner to form a film on the substrate 4.

이렇게 하여 얻어진 막은, 면내 균일성이 우수한 것이었다. 또 ICP-MS로 조사한 결과, Hf 박막인 것이 확인되었다.The film thus obtained was excellent in in-plane uniformity. Moreover, as a result of irradiation with ICP-MS, it was confirmed that it was an Hf thin film.

실시예5Example 5

실시예1에 있어서, 성막에 있어서 용매로서 노르말데칸을 사용한 것 외에는 동일하게 하였다. 그 결과, 기판4 상에 박막이 형성되었다.In Example 1, it carried out similarly except having used normal decane as a solvent in film-forming. As a result, a thin film was formed on the substrate 4.

이렇게 하여 얻어진 막은, 면내 균일성이 우수한 것이었다. 또 ICP-MS로 조사한 결과, Hf 박막인 것이 확인되었다.The film thus obtained was excellent in in-plane uniformity. Moreover, as a result of irradiation with ICP-MS, it was confirmed that it was an Hf thin film.

실시예6Example 6

실시예1에 있어서는 화학기상 성장방법에 의하여 성막되었을 경우이지만, 실시예6에 있어서는 원자층제어 성장방법에 의하여 성막이 이루어졌다.In Example 1, the film was formed by the chemical vapor growth method. In Example 6, the film was formed by the atomic layer controlled growth method.

그 결과, 면내 균일성이 우수한 Hf 박막이 형성되어 있었다.As a result, the Hf thin film excellent in in-plane uniformity was formed.

실시예7Example 7

실시예2에 있어서는 화학기상 성장방법에 의하여 성막되었을 경우이지 만, 실시예7에 있어서는 원자층제어 성장방법에 의하여 성막이 이루어졌다.In Example 2, the film was formed by the chemical vapor growth method. In Example 7, the film was formed by the atomic layer controlled growth method.

그 결과, 면내 균일성이 우수한 Hf박막이 형성되어 있었다.As a result, the Hf thin film excellent in in-plane uniformity was formed.

실시예8Example 8

실시예3에 있어서는 화학기상 성장방법에 의하여 성막되었을 경우이지만, 실시예8에 있어서는 원자층제어 성장방법에 의하여 성막이 이루어졌다.In Example 3, the film was formed by the chemical vapor growth method. In Example 8, the film was formed by the atomic layer controlled growth method.

그 결과, 면내 균일성이 우수한 Hf 박막이 형성되어 있었다.As a result, the Hf thin film excellent in in-plane uniformity was formed.

실시예9Example 9

실시예4에 있어서는 화학기상 성장방법에 의하여 성막되었을 경우이지만, 실시예9에 있어서는 원자층제어 성장방법에 의하여 성막이 이루어졌다.In Example 4, the film was formed by the chemical vapor growth method. In Example 9, the film was formed by the atomic layer controlled growth method.

그 결과, 면내 균일성이 우수한 Hf 박막이 형성되어 있었다.As a result, the Hf thin film excellent in in-plane uniformity was formed.

실시예10Example 10

실시예1과 동일하게 하여, 이소프로필시클로펜타디에닐트리스(디메틸아미노)하프늄을 얻었다.In the same manner as in Example 1, isopropylcyclopentadienyltris (dimethylamino) hafnium was obtained.

그리고 이소프로필시클로펜타디에닐트리스(디메틸아미노)하프늄을 사용하고, 실시예1과 동일하게 하여 기판4 상에 막을 형성하였다.Then, using isopropylcyclopentadienyltris (dimethylamino) hafnium, a film was formed on the substrate 4 in the same manner as in Example 1.

이렇게 하여 얻어진 막은, 실시예1의 막과 비교하면 뒤떨어지지만 면내 균일성이 우수한 것이었다.The film thus obtained was inferior to that of Example 1 but was excellent in in-plane uniformity.

실시예11Example 11

실시예1과 동일하게 하여, 이소프로필시클로펜타디에닐트리스(메틸에틸아미노)하프늄을 얻었다.In the same manner as in Example 1, isopropylcyclopentadienyltris (methylethylamino) hafnium was obtained.

그리고 이소프로필시클로펜타디에닐트리스(메틸에틸아미노)하프늄을 사용하고, 실시예1과 동일하게 하여 기판4 상에 막을 형성하였다.Then, using isopropylcyclopentadienyltris (methylethylamino) hafnium, a film was formed on the substrate 4 in the same manner as in Example 1.

이렇게 하여 얻어진 막은, 실시예1의 막과 비교하면 뒤떨어지지만 면내 균일성이 우수한 것이었다.The film thus obtained was inferior to that of Example 1 but was excellent in in-plane uniformity.

실시예12Example 12

실시예1과 동일하게 하여, 에틸시클로펜타디에닐트리스(디에틸아미노)하프늄을 얻었다.In the same manner as in Example 1, ethylcyclopentadienyltris (diethylamino) hafnium was obtained.

그리고 에틸시클로펜타디에닐트리스(디에틸아미노)하프늄을 사용하고, 실시예1과 동일하게 하여 기판4 상에 막을 형성하였다.Ethylcyclopentadienyltris (diethylamino) hafnium was used in the same manner as in Example 1 to form a film on the substrate 4.

이렇게 하여 얻어진 막은, 실시예1의 막과 비교하면 뒤떨어지지만 면내 균일성이 우수한 것이었다.The film thus obtained was inferior to that of Example 1 but was excellent in in-plane uniformity.

실시예13Example 13

실시예1과 동일하게 하여, 이소프로필시클로펜타디에닐트리스(디에틸아미노)하프늄을 얻었다.In the same manner as in Example 1, isopropylcyclopentadienyltris (diethylamino) hafnium was obtained.

그리고 이소프로필시클로펜타디에닐트리스(디에틸아미노)하프늄을 사용하고, 실시예1과 동일하게 하여 기판4 상에 막을 형성하였다.Using isopropylcyclopentadienyltris (diethylamino) hafnium, a film was formed on the substrate 4 in the same manner as in Example 1.

이렇게 하여 얻어진 막은, 실시예1의 막과 비교하면 뒤떨어지지만 면내 균일성이 우수한 것이었다.The film thus obtained was inferior to that of Example 1 but was excellent in in-plane uniformity.

실시예14Example 14

실시예1과 동일하게 하여, 메틸시클로펜타디에닐트리스(메틸에틸아미노) 하프늄을 얻었다.In the same manner as in Example 1, methylcyclopentadienyltris (methylethylamino) hafnium was obtained.

그리고 메틸시클로펜타디에닐트리스(메틸에틸아미노)하프늄을 사용하고, 실시예1과 동일하게 하여 기판4 상에 막을 형성하였다.A film was formed on the substrate 4 in the same manner as in Example 1 using methylcyclopentadienyltris (methylethylamino) hafnium.

이렇게 하여 얻어진 막은, 면내 균일성이 우수한 것이었다. 또 ICP-MS로 조사한 바, Hf 박막인 것이 확인되었다.The film thus obtained was excellent in in-plane uniformity. Moreover, when irradiated with ICP-MS, it confirmed that it was a Hf thin film.

비교예1Comparative Example 1

실시예1에 있어서, CpHf(NMe2)3의 대신에, 테트라키스(메틸에틸아미노)하프늄을 사용한 것 외에는 동일하게 하여, 기판4 상에 막을 형성하였다.In Example 1, a film was formed on the substrate 4 in the same manner except that tetrakis (methylethylamino) hafnium was used instead of CpHf (NMe 2 ) 3 .

이렇게 하여 얻어진 막은, 실시예1과 비하여 면내 균일성이 뒤떨어지는 것이었다.The film obtained in this way was inferior to in-plane uniformity compared with Example 1.

비교예2Comparative Example 2

실시예1에 있어서, CpHf(NMe2)3의 대신에, 테트라키스(에톡시)하프늄을 사용한 것 외에는 동일하게 하여, 기판4 상에 막을 형성하였다.In Example 1, a film was formed on the substrate 4 in the same manner except that tetrakis (ethoxy) hafnium was used instead of CpHf (NMe 2 ) 3 .

이렇게 하여 얻어진 막은, 실시예1에 비하여 면내 균일성이 뒤떨어지는 것이었다.The film obtained in this way was inferior to in-plane uniformity compared with Example 1.

비교예3Comparative Example 3

실시예1에 있어서, CpHf(NMe2)3의 대신에, 테트라키스(β-디케톤)하프늄를 사용한 것 외에는 동일하게 하여, 기판4 상에 막을 형성하였다.In embodiment 1, instead of CpHf (NMe 2) 3, in the same manner except that hapeunyumreul tetrakis (β- diketone), and the film was formed on the substrate 4.

이렇게 하여 얻어진 막은, 실시예1에 비하여 면내 균일성이 뒤떨어 지는 것이었다.The film obtained in this way was inferior to in-plane uniformity compared with Example 1.

비교예4Comparative Example 4

실시예1에 있어서, CpHf(NMe2)3의 대신에, HfC14을 사용한 것 외에는 동일하게 하여, 기판4 상에 막을 형성하였다.In Example 1, a film was formed on the substrate 4 in the same manner as in the case of using HfC1 4 instead of CpHf (NMe 2 ) 3 .

이렇게 하여 얻어진 막은, 실시예1에 비하여 면내 균일성이 뒤떨어지는 것이었다.The film obtained in this way was inferior to in-plane uniformity compared with Example 1.

하프늄계 박막이 사용되는 분야, 예를 들면 반도체 분야 등에 있어서 특히 유용하다.It is especially useful in the field | area where a hafnium type thin film is used, for example, a semiconductor field.

Claims (20)

삭제delete 삭제delete 삭제delete 하프늄계 박막을 형성하기 위한 재료로서,As a material for forming a hafnium-based thin film, 하기의 일반식[I],The following general formula [I], 일반식[I]Formula [I] CpHf(NR1R2)3 Cp Hf (NR 1 R 2 ) 3 (단, Cp는 시클로펜타디에닐기(cyclopentadienyl group), R1, R2는 알킬기(alkyl group)이며, R1과 R2는 서로 달라고 좋고 같아도 좋다.)( Wherein Cp is a cyclopentadienyl group , R 1 and R 2 are alkyl groups, and R 1 and R 2 may be different or the same.) 로 나타내는 화합물인 것을 특징으로 하는 하프늄계 박막형성재료.A hafnium-based thin film forming material, characterized in that the compound. 제4항에 있어서,5. The method of claim 4, 상기 일반식[I]에 있어서의 R1, R2가 메틸기 또는 에틸기인 것을R 1 and R 2 in General Formula [I] being a methyl group or an ethyl group 특징으로 하프늄계 박막형성재료.Hafnium-based thin film forming material. 제4항에 있어서,5. The method of claim 4, 상기 일반식[I]로 나타내는 화합물이, CpHf(NMe2)3, CpHf(NMeEt)3(단, Cp=시클로펜타디에닐기, Me=메틸기, Et=에틸기)의 군 중에서 선택되는 어느 하나인 것을The compound represented by the general formula [I] is any one selected from the group of CpHf (NMe 2 ) 3 and CpHf (NMeEt) 3 (where Cp = cyclopentadienyl group, Me = methyl group, and Et = ethyl group). 특징으로 하는 하프늄계 박막형성재료.Hafnium-based thin film forming material characterized in that. 제4항에 있어서,5. The method of claim 4, 상기 일반식[I]로 나타내는 화합물 이외에, 상기 일반식[I]로 나타내는 화합물이 용해되는 용매를 함유하는 것을 특징으로 하는 하프늄계 박막형성재료.A hafnium-based thin film forming material, in addition to the compound represented by the general formula [I], contains a solvent in which the compound represented by the general formula [I] is dissolved. 제7항에 있어서,The method of claim 7, wherein 용매가, 탄소수5∼40의 탄화수소계 화합물 및 탄소수2∼40의 아민계 화합물의 군 중에서 선택되는 1개 또는 두 개 이상의 화합물인 것을 특징으로 하는 하프늄계 박막형성재료.A hafnium-based thin film forming material, wherein the solvent is one or two or more compounds selected from the group consisting of a C5-C40 hydrocarbon compound and a C2-C40 amine compound. 제4항에 있어서,5. The method of claim 4, 화학기상 성장방법에 의하여 하프늄계 박막을 형성하기 위한 재료인 것을 특징으로 하는 하프늄계 박막형성재료.A hafnium-based thin film forming material, characterized in that the material for forming a hafnium-based thin film by a chemical vapor growth method. 제4항에 있어서,5. The method of claim 4, 원자층제어 성장방법에 의하여 하프늄계 박막을 형성하기 위한 재료인 것을 특징으로 하는 하프늄계 박막형성재료.A hafnium-based thin film forming material, characterized in that it is a material for forming a hafnium-based thin film by an atomic layer controlled growth method. 화학기상 성장방법에 의하여 기판 상에 하프늄계 박막을 형성하는 방법으로서,As a method of forming a hafnium-based thin film on a substrate by a chemical vapor growth method, 하기의 일반식[I],The following general formula [I], 일반식[I]Formula [I] CpHf(NR1R2)3 Cp Hf (NR 1 R 2 ) 3 (단, Cp는 시클로펜타디에닐기, R1, R2는 알킬기이며, R1과 R2는 서로 달라고 좋고 같아도 좋다.)(However, Cp is a cyclopentadienyl group , R 1 , R 2 is an alkyl group, and R 1 and R 2 may be different from each other or may be the same.) 로 나타내는 화합물이 사용되는 것을 특징으로 하는 하프늄계 박막형성방법.A hafnium-based thin film forming method characterized by using a compound represented by. 제11항에 있어서,12. The method of claim 11, 상기 일반식[I]에 있어서의 R1, R2가 메틸기 또는 에틸기인 것을R 1 and R 2 in General Formula [I] being a methyl group or an ethyl group 특징으로 하는 하프늄계 박막형성방법.Hafnium-based thin film forming method characterized in that. 제11항에 있어서,12. The method of claim 11, 상기 일반식[I]로 나타내는 화합물이, CpHf(NMe2)3, CpHf(NMeEt)3(단, Cp=시클로펜타디에닐기, Me=메틸기, Et=에틸기)의 군 중에서 선택되는 어느 하나인 것을The compound represented by the general formula [I] is any one selected from the group of CpHf (NMe 2 ) 3 and CpHf (NMeEt) 3 (where Cp = cyclopentadienyl group, Me = methyl group, and Et = ethyl group). 특징으로 하는 하프늄계 박막형성방법.Hafnium-based thin film forming method characterized in that. 제11항에 있어서,12. The method of claim 11, 상기 일반식[I]로 나타내는 화합물이 용매 중에 용해된 용액으로서 사용되는 것을 특징으로 하는 하프늄계 박막형성방법.A hafnium-based thin film forming method, wherein the compound represented by the general formula [I] is used as a solution dissolved in a solvent. 제14항에 있어서,The method of claim 14, 용매가, 탄소수5∼40의 탄화수소계 화합물 및 탄소수2∼40의 아민계 화합물의 군의 중에서 선택되는 1개 또는 두 개 이상의 화합물인 것을 특징으로 하는 하프늄계 박막형성방법.A hafnium-based thin film forming method, wherein the solvent is one or two or more compounds selected from the group of a hydrocarbon compound having 5 to 40 carbon atoms and an amine compound having 2 to 40 carbon atoms. 원자층제어 성장방법에 의하여 기판 상에 하프늄계 박막을 형성하는 방법으로서,A method of forming a hafnium-based thin film on a substrate by an atomic layer controlled growth method, 하기의 일반식[I],The following general formula [I], 일반식[I]Formula [I] CpHf(NR1R2)3 Cp Hf (NR 1 R 2 ) 3 (단, Cp는 시클로펜타디에닐기, R1, R2는 알킬기이며, R1과 R2는 서로 달라고 좋고 같아도 좋다.)(However, Cp is a cyclopentadienyl group, R 1 , R 2 is an alkyl group, and R 1 and R 2 may be different from each other or may be the same.) 로 나타내는 화합물이 사용되는 것을 특징으로 하는 하프늄계 박막형성방법.A hafnium-based thin film forming method characterized by using a compound represented by. 제16항에 있어서,The method of claim 16, 상기 일반식[I]에 있어서의 R1, R2가 메틸기 또는 에틸기인 것을R 1 and R 2 in General Formula [I] being a methyl group or an ethyl group 특징으로 하는 하프늄계 박막형성방법.Hafnium-based thin film forming method characterized in that. 제16항에 있어서,The method of claim 16, 상기 일반식[I]로 나타내는 화합물이, CpHf(NMe2)3, CpHf(NMeEt)3(단, Cp=시클로펜타디에닐기, Me=메틸기, Et=에틸기)의 군 중에서 선택되는 어느 하나인 것을The compound represented by the general formula [I] is any one selected from the group of CpHf (NMe 2 ) 3 and CpHf (NMeEt) 3 (where Cp = cyclopentadienyl group, Me = methyl group, and Et = ethyl group). 특징으로 하는 하프늄계 박막형성방법.Hafnium-based thin film forming method characterized in that. 제16항에 있어서,The method of claim 16, 상기 일반식[I]로 나타내는 화합물이 용매 중에 용해된 용액으로서 사용되는 것을 특징으로 하는 하프늄계 박막형성방법.A hafnium-based thin film forming method, wherein the compound represented by the general formula [I] is used as a solution dissolved in a solvent. 제19항에 있어서,The method of claim 19, 용매가, 탄소수5∼40의 탄화수소계 화합물 및 탄소수2∼40의 아민계 화합물의 군 중에서 선택되는 1개 또는 두 개 이상의 화합물인 것을 특징으로 하는 하프늄계 박막형성방법.A hafnium-based thin film formation method, wherein the solvent is one or two or more compounds selected from the group consisting of a hydrocarbon compound of 5 to 40 carbon atoms and an amine compound of 2 to 40 carbon atoms.
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