KR102739002B1 - novel tungsten precursor compound comprising silicon - Google Patents
novel tungsten precursor compound comprising siliconDownload PDFInfo
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- KR102739002B1 KR102739002B1KR1020190098590AKR20190098590AKR102739002B1KR 102739002 B1KR102739002 B1KR 102739002B1KR 1020190098590 AKR1020190098590 AKR 1020190098590AKR 20190098590 AKR20190098590 AKR 20190098590AKR 102739002 B1KR102739002 B1KR 102739002B1
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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
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
Translated fromKoreanDescription
Translated fromKorean본 발명은 실리콘을 포함하는 신규 텅스텐 전구체 화합물에 관한 것으로, 보다 상세하게는 텅스텐 함유 박막증착용 전구체로 유용한 실리콘을 포함하는 텅스텐 화합물, 이의 제조방법, 이를 포함하는 텅스텐함유 박막증착용 조성물 및 이를 이용하는 텅스텐함유 박막의 제조방법에 관한 것이다.The present invention relates to a novel tungsten precursor compound containing silicon, and more specifically, to a tungsten compound containing silicon useful as a precursor for tungsten-containing thin film deposition, a method for producing the same, a composition for tungsten-containing thin film deposition containing the same, and a method for producing a tungsten-containing thin film using the same.
반도체 산업에서의 신기술 및 재료의 개발이 이루어짐에 따라 반도체 집적회로와 같은 소자의 미세화, 고신뢰화, 고속화, 고기능화, 고집적화 등이 가능해졌다.As new technologies and materials are developed in the semiconductor industry, miniaturization, high reliability, high speed, high functionality, and high integration of devices such as semiconductor integrated circuits have become possible.
이와 더불어 집적회로의 박막을 형성하기위한 전구체에 요구되는 특성도 변화되어 왔다. 일반적으로 전구체에 요구되는 특성은 증기압이 높고 열 안정성이 우수하며 증착 챔버로의 이송이 쉬운 기체 또는 액체상의 화합물이어야 하고, 나아가 제조되는 박막의 종류에 따라 사용되는 반응 가스들과의 반응성도 우수해야한다.In addition, the characteristics required for precursors for forming thin films of integrated circuits have also changed. In general, the characteristics required for precursors are that they should be gaseous or liquid compounds with high vapor pressure, excellent thermal stability, and easy transport to the deposition chamber, and furthermore, they should have excellent reactivity with the reaction gases used depending on the type of thin film being manufactured.
한편 텅스텐 박막은 반도체 소자의 제조 공정에 있어서 다양하게 사용되고 있다. 구체적으로, 텅스텐, 특히 텅스텐 질화물(W-N)은 저항성이 비교적 낮고, 우수한 접착성을 가질 뿐만 아니라, 우수한 확산 방지막 성질을 갖고 있기 때문에, 기존의 Ti/TiN을 대체할 수 있는 소재로 많은 관심을 받고 있다.Meanwhile, tungsten thin films are being used in various ways in the manufacturing process of semiconductor devices. Specifically, tungsten, especially tungsten nitride (W-N), has relatively low resistivity, excellent adhesiveness, and excellent diffusion barrier properties, so it is receiving much attention as a material that can replace existing Ti/TiN.
일례로 구리(Cu)의 확산 방지막으로 질화 텅스텐(WN)막, 금속과 금속층을 연결해 주는 접전 재료(contact material)로 텅스텐 금속막 등이 있다. 이와 같은 텅스텐 막을 얻기위해 육불화텅스텐(WF6)과 반응 가스(NH3 및 H2)를 사용하여 CVD 방법으로 증착을 하여왔다. 그러나 육불화텅스텐과 반응 가스의 반응 부산물로 HF 및 HF salt 가 발생되어 기판에 결함을 유도하는 단점을 가진다. 이러한 단점을 극복하기 위한 많은 텅스텐 전구체들이 제안되어왔다. 일례로 텅스텐 헥사카르보닐(Tungsten hexacrbonyl, W(CO)6)이 제안되었으나, 텅스텐 헥사카르보닐은 고체 소스로 증착 챔버로의 이송이 용이하지 않으며 CO기에 의한 독성으로 박막형성용 전구체로 사용하기 어려운 단점을 가진다.For example, there is a tungsten nitride (WN) film as a diffusion barrier for copper (Cu), and a tungsten metal film as a contact material connecting metal and metal layers. In order to obtain such a tungsten film, deposition has been performed using tungsten hexafluoride (WF6 ) and reaction gases (NH3 and H2 ) by the CVD method. However, HF and HF salt are generated as reaction byproducts of tungsten hexafluoride and the reaction gas, which has the disadvantage of inducing defects in the substrate. Many tungsten precursors have been proposed to overcome this disadvantage. For example, tungsten hexacarbonyl (W(CO)6 ) has been proposed, but tungsten hexacarbonyl has the disadvantages of being difficult to transport to the deposition chamber as a solid source and being difficult to use as a precursor for forming a thin film due to toxicity caused by CO radicals.
더구나 텅스텐 질화막의 경우 육불화텅스텐을 전구체로 사용하여 텅스텐 금속막을 형성한 후 형성된 텅스텐 금속막을 다시 질화시키는 별도의 단계가 필요함으로 공정이 복잡한 문제점을 가진다.Moreover, in the case of a tungsten nitride film, the process is complicated because a separate step is required to form a tungsten metal film using tungsten hexafluoride as a precursor and then nitriding the formed tungsten metal film again.
따라서 박막 전구체로서 향상된 특성을 가지는 동시에 간단한 공정으로 다양한 텅스텐막을 형성할 수 있는 텅스텐 전구체의 개발이 여전히 요구되고 있다.Therefore, there is still a need for the development of a tungsten precursor that has improved properties as a thin film precursor and can form various tungsten films through a simple process.
본 발명은 텅스텐함유 박막의 제조가 가능한 전구체로 실리콘을 포함하는 신규한 텅스텐 화합물 및 이의 제조방법을 제공한다.The present invention provides a novel tungsten compound including silicon as a precursor capable of producing a tungsten-containing thin film and a method for producing the same.
또한 본 발명은 본 발명의 실리콘을 포함하는 텅스텐 화합물을 포함하는 텅스텐함유 박막증착용 조성물을 제공한다.The present invention also provides a composition for deposition of a tungsten-containing thin film comprising a tungsten compound including the silicon of the present invention.
또한 본 발명은 본 발명의 텅스텐함유 박막증착용 조성물을 이용하는 텅스텐함유 박막의 제조방법을 제공한다.In addition, the present invention provides a method for manufacturing a tungsten-containing thin film using the tungsten-containing thin film deposition composition of the present invention.
본 발명은 열안정성 및 휘발성이 우수하여 텅스텐함유 박막의 전구체로 매우 유용한 실리콘을 포함하는 텅스텐 화합물을 제공하는 것으로, 본 발명의 텅스텐 화합물은 하기 화학식 1로 표시된다.The present invention provides a tungsten compound containing silicon, which is very useful as a precursor of a tungsten-containing thin film due to its excellent thermal stability and volatility. The tungsten compound of the present invention is represented by the following chemical formula 1.
[화학식 1][Chemical Formula 1]
(상기 화학식 1에서,(In the above chemical formula 1,
R1및 R2는 서로 독립적으로 (C1-C10)알킬이며,R1 and R2 are independently (C1-C10) alkyl,
R3은 (C1-C10)알킬, 모노(C1-C10)알킬아미노 또는 디(C1-C10)알킬아미노이며, R3의 알킬은 실릴, 모노(C1-C10)알킬실릴 또는 디(C1-C10)알킬실릴로 더 치환될 수 있으며;R3 is (C1-C10)alkyl, mono(C1-C10)alkylamino or di(C1-C10)alkylamino, and the alkyl of R3 may be further substituted with silyl, mono(C1-C10)alkylsilyl or di(C1-C10)alkylsilyl;
R4 내지 R8은 서로 독립적으로 수소 또는 (C1-C10)알킬이며;R4 to R8 are each independently hydrogen or (C1-C10) alkyl;
n은 1 내지 5의 정수이다.)n is an integer from 1 to 5.)
바람직하게 본 발명의 상기 화학식 1에서 R1 및 R2는 서로 독립적으로 (C1-C4)알킬이며, R3은 실릴(C1-C4)알킬, 모노(C1-C4)알킬실릴로 치환된 (C1-C4)알킬, 디(C1-C4)알킬실릴로 치환된 (C1-C4)알킬, 모노(C1-C4)알킬아미노 또는 디(C1-C4)알킬아미노이며; R4 내지 R8은 서로 독립적으로 수소 또는 (C1-C4)알킬이며; n은 1 내지 3의 정수일 수 있다.Preferably, in the chemical formula 1 of the present invention, R1 and R2 are each independently (C1-C4) alkyl, R3 is (C1-C4) silyl, (C1-C4) alkyl substituted with mono (C1-C4) alkylsilyl, (C1-C4) alkyl substituted with di (C1-C4) alkylsilyl, mono (C1-C4) alkylamino or di (C1-C4) alkylamino; R4 to R8 are each independently hydrogen or (C1-C4) alkyl; n may be an integer of 1 to 3.
양질의 박막을 형성하기위한 측면에서 바람직하게 본 발명의 상기 화학식 1은 하기 화학식 2로 표시될 수 있다.In terms of forming a high-quality thin film, the chemical formula 1 of the present invention can preferably be represented by the following chemical formula 2.
[화학식 2][Chemical formula 2]
(상기 화학식 2에서(In the above chemical formula 2
R11은 (C1-C10)알킬이며,R11 is (C1-C10) alkyl,
R3은 (C1-C10)알킬, 모노(C1-C10)알킬아미노 또는 디(C1-C10)알킬아미노이며, R3의 알킬은 실릴, 모노(C1-C10)알킬실릴 또는 디(C1-C10)알킬실릴로 더 치환될 수 있으며;R3 is (C1-C10)alkyl, mono(C1-C10)alkylamino or di(C1-C10)alkylamino, and the alkyl of R3 may be further substituted with silyl, mono(C1-C10)alkylsilyl or di(C1-C10)alkylsilyl;
R4 내지 R8은 서로 독립적으로 수소 또는 (C1-C10)알킬이며;R4 to R8 are each independently hydrogen or (C1-C10) alkyl;
n은 1 내지 5의 정수이다.)n is an integer from 1 to 5.)
본 발명의 일 실시예에 따른 화학식 2에서 R11은 (C1-C4)알킬이며, R3은 디(C1-C4)알킬아미노이며; R4 내지 R8은 서로 독립적으로 수소 또는 (C1-C4)알킬이며; n은 1 내지 3의 정수일 수 있다.In chemical formula 2 according to one embodiment of the present invention, R11 is (C1-C4) alkyl, R3 is di(C1-C4) alkylamino; R4 to R8 are each independently hydrogen or (C1-C4) alkyl; and n can be an integer of 1 to 3.
구체적으로 본 발명의 일 실시예에 따른 텅스텐 화합물은 하기 화합물에서 선택되는 것일 수 있으나, 이에 한정이 있는 것은 아니다.Specifically, the tungsten compound according to one embodiment of the present invention may be selected from the following compounds, but is not limited thereto.
또한 본 발명은 본 발명의 텅스텐 화합물의 제조방법을 제공하는 것으로, 본 발명의 텅스텐 화합물의 제조방법은 하기 화학식 3의 화합물과 하기 화학식 4의 화합물을 반응시켜 하기 화학식 2의 화합물을 제조하는 단계를 포함한다.In addition, the present invention provides a method for producing a tungsten compound of the present invention, wherein the method for producing a tungsten compound of the present invention includes a step of reacting a compound of the following chemical formula 3 with a compound of the following chemical formula 4 to produce a compound of the following chemical formula 2.
[화학식 2][Chemical formula 2]
[화학식 3][Chemical Formula 3]
[화학식 4][Chemical Formula 4]
(상기 화학식 2 내지 4에서,(In the above chemical formulas 2 to 4,
R11은 (C1-C10)알킬이며,R11 is (C1-C10) alkyl,
R3은 (C1-C10)알킬, 모노(C1-C10)알킬아미노 또는 디(C1-C10)알킬아미노이며, R3의 알킬은 실릴(C1-C4)알킬, 모노(C1-C10)알킬실릴 또는 디(C1-C10)알킬실릴로 더 치환될 수 있으며;R3 is (C1-C10)alkyl, mono(C1-C10)alkylamino or di(C1-C10)alkylamino, and the alkyl of R3 may be further substituted with silyl(C1-C4)alkyl, mono(C1-C10)alkylsilyl or di(C1-C10)alkylsilyl;
R4 내지 R8은 서로 독립적으로 수소 또는 (C1-C10)알킬이며;R4 to R8 are each independently hydrogen or (C1-C10) alkyl;
n은 1 내지 5의 정수이며,n is an integer from 1 to 5,
X는 할로겐이다.)X is a halogen.)
또한 본 발명은 하기 화학식 1-1로 표시되는 텅스텐 화합물을 포함하는 박막증착용 조성물을 제공한다.In addition, the present invention provides a composition for thin film deposition comprising a tungsten compound represented by the following chemical formula 1-1.
[화학식 1-1][Chemical Formula 1-1]
(상기 화학식 1-1에서,(In the above chemical formula 1-1,
R1및 R2는 서로 독립적으로 (C1-C10)알킬이며,R1 and R2 are independently (C1-C10) alkyl,
R3은 (C1-C10)알킬, 모노(C1-C10)알킬아미노 또는 디(C1-C10)알킬아미노이며, R3의 알킬은 실릴, 모노(C1-C10)알킬실릴, 디(C1-C10)알킬실릴또는 트리(C1-C10)알킬실릴로 더 치환될 수 있으며;;R3 is (C1-C10)alkyl, mono(C1-C10)alkylamino or di(C1-C10)alkylamino, and the alkyl of R3 may be further substituted with silyl, mono(C1-C10)alkylsilyl, di(C1-C10)alkylsilyl or tri(C1-C10)alkylsilyl;;
R4 내지 R8은 서로 독립적으로 수소 또는 (C1-C10)알킬이며;R4 to R8 are each independently hydrogen or (C1-C10) alkyl;
n은 1 내지 5의 정수이다.)n is an integer from 1 to 5.)
바람직하게 본 발명의 일 실시예에 따른 화학식 1-1에서 R1 및 R2는 서로 독립적으로 (C1-C4)알킬이며, R3은 실릴(C1-C4)알킬, 모노(C1-C4)알킬실릴로 치환된 (C1-C4)알킬, 디(C1-C4)알킬실릴로 치환된 (C1-C4)알킬, 트리(C1-C4)알킬실릴로 치환된 (C1-C4)알킬, 모노(C1-C4)알킬아미노 또는 디(C1-C4)알킬아미노이며; R4 내지 R8은 서로 독립적으로 수소 또는 (C1-C4)알킬이며; n은 1 내지 3의 정수일 수 있다.Preferably, in the chemical formula 1-1 according to one embodiment of the present invention, R1 and R2 are each independently (C1-C4) alkyl, R3 is (C1-C4) silyl, (C1-C4) alkyl substituted with mono (C1-C4) alkylsilyl, (C1-C4) alkyl substituted with di (C1-C4) alkylsilyl, (C1-C4) alkyl substituted with tri (C1-C4) alkylsilyl, mono (C1-C4) alkylamino or di (C1-C4) alkylamino; R4 to R8 are each independently hydrogen or (C1-C4) alkyl; n may be an integer from 1 to 3.
또한 본 발명은 본 발명의 텅스텐함유 박막증착용 조성물을 이용하여 텅스텐함유 박막을 형성하는 방법을 제공한다.In addition, the present invention provides a method for forming a tungsten-containing thin film using the tungsten-containing thin film deposition composition of the present invention.
본 발명의 일 실시예에 따른 박막은 유기금속 화학기상 증착법, 원자층 증착법공정, 저압 기상 증착법, 플라즈마 강화 기상 증착법 또는 플라즈마 강화 원자층 증착법에 의해 수행되는 것일 수 있다.The thin film according to one embodiment of the present invention may be formed by a metalorganic chemical vapor deposition method, an atomic layer deposition process, a low pressure vapor deposition method, a plasma enhanced vapor deposition method, or a plasma enhanced atomic layer deposition method.
본 발명의 실리콘을 포함하는 텅스텐 화합물은 텅스텐함유 박막의 전구체로 우수한 열안정성 및 휘발성을 가짐으로써 양질의 텅스텐함유 박막을 제조할 수 있다.The tungsten compound including silicon of the present invention has excellent thermal stability and volatility as a precursor of a tungsten-containing thin film, thereby enabling the production of a high-quality tungsten-containing thin film.
또한 본 발명의 실리콘을 포함하는 텅스텐 화합물은 상온에서 액체로 취급이 매우 용이하며, 저장안정성이 매우 높다.In addition, the tungsten compound including silicon of the present invention is very easy to handle as a liquid at room temperature and has very high storage stability.
또한 본 발명의 실리콘을 포함하는 텅스텐 화합물은 화합물 내 질소를 포함함으로써 별도의 금속박막의 질화단계가 필요치 않아 간단한 공정으로 텅스텐 질화막을 제조할 수 있다.In addition, the tungsten compound including silicon of the present invention contains nitrogen in the compound, so a separate nitriding step of a metal thin film is not required, and thus a tungsten nitride film can be manufactured through a simple process.
따라서 본 발명의 텅스텐함유 박막증착용 조성물은 본 발명의 실리콘을 포함하는 텅스텐 화합물을 전구체로 사용함으로써 다양한 공정으로 양질의 박막을 제조할 수 있다.Therefore, the tungsten-containing thin film deposition composition of the present invention can produce a high-quality thin film through various processes by using the tungsten compound including silicon of the present invention as a precursor.
도 1은 본 발명의 실시예 1에서 제조된 본 발명의 텅스텐 화합물 및 BTBMW의 TGA 분석 결과를 나타낸 그래프이다.Figure 1 is a graph showing the results of TGA analysis of the tungsten compound of the present invention and BTBMW manufactured in Example 1 of the present invention.
본 발명에 기재된 "알킬"은 탄소수 1 내지 10, 바람직하게 탄소수 1 내지 6, 보다 바람직하게 탄소수 1 내지 4를 가진 포화된 직쇄상 또는 분지상의 비-고리(cyclic) 탄화수소를 의미한다. "저급 알킬"은 탄소수가 1 내지 4인 직쇄상 또는 분지상 알킬을 의미한다. 대표적인 포화 직쇄상 알킬은 -메틸, -에틸, -n-프로필, -n-부틸, -n-펜틸, -n-헥실, -n-헵틸, -n-옥틸, -n-노닐 과 -n-데실을 포함하고, 반면에 포화 분지상 알킬은 -이소프로필, -sec-부틸, -이소부틸, -tert-부틸, 이소펜틸, 2-메틸헥실, 3-메틸부틸, 2-메틸펜틸, 3-메틸펜틸, 4-메틸펜틸, 2-메틸헥실, 3-메틸헥실, 2-메틸펜틸, 3-메틸펜틸, 4-메틸펜틸, 2-메틸헥실, 3-메틸헥실, 4-메틸헥실, 5- 메틸헥실, 2,3-디메틸부틸, 2,3-디메틸펜틸, 2,4-디메틸펜틸, 2,3-디메틸헥실, 2,4-디메틸헥실, 2,5-디메틸헥실, 2,2-디메틸펜틸, 2,2-디메틸헥실, 3,3-디메틸펜틸, 3,3-디메틸헥실, 4,4-디메틸헥실, 2-에틸펜틸, 3-에틸펜틸, 2-데틸헥실, 3-에틸헥실, 4-에틸헥실, 2-메틸-2-에틸펜틸, 2-메틸-3-에틸펜틸, 2-메틸-4-에틸펜틸, 2-메틸-2-에틸헥실, 2-메틸-3-에틸헥실, 2-메틸-4-에틸헥실, 2,2-디에틸펜틸, 3,3-디에틸헥실, 2,2-디에틸헥실, 및 3,3-디에틸헥실을 포함한다."Alkyl" as used herein means a saturated straight-chain or branched non-cyclic hydrocarbon having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms. "Lower alkyl" means a straight-chain or branched alkyl having 1 to 4 carbon atoms. Representative saturated straight-chain alkyls include -methyl, -ethyl, -n-propyl, -n-butyl, -n-pentyl, -n-hexyl, -n-heptyl, -n-octyl, -n-nonyl and -n-decyl, whereas saturated branched alkyls include -isopropyl, -sec-butyl, -isobutyl, -tert-butyl, isopentyl, 2-methylhexyl, 3-methylbutyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylhexyl, 3-methylhexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 2,3-dimethylbutyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 2,3-dimethylhexyl, 2,4-Dimethylhexyl, 2,5-dimethylhexyl, 2,2-dimethylpentyl, 2,2-dimethylhexyl, 3,3-dimethylpentyl, 3,3-dimethylhexyl, 4,4-dimethylhexyl, 2-ethylpentyl, 3-ethylpentyl, 2-deethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 2-methyl-2-ethylpentyl, 2-methyl-3-ethylpentyl, 2-methyl-4-ethylpentyl, 2-methyl-2-ethylhexyl, 2-methyl-3-ethylhexyl, 2-methyl-4-ethylhexyl, 2,2-diethylpentyl, 3,3-diethylhexyl, 2,2-diethylhexyl, and 3,3-diethylhexyl.
본 명세서에서 "C1-C10"와 같이 기재된 경우, 이는 탄소수가 1 내지 10개임을 의미한다. 예를 들어, C1-C4알킬은 탄소 수가 1 내지 4인 알킬을 의미한다. 구체적인 일례로 메틸(methyl), 에틸(ethyl), 프로필(propyl), 이소프로필(iso-propyl), 부틸(butyl), 이소부틸(iso-butyl) 또는 tert-부틸(tert-butyl)일 수 있다.When it is described as "C1-C10" in this specification, it means that it has 1 to 10 carbon atoms. For example, C1-C4 alkyl means alkyl having 1 to 4 carbon atoms. Specific examples thereof include methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, or tert-butyl.
본 명세서에 기재된 "할로겐"은 플루오린, 클로린, 브로민 또는 아이오딘을 의미한다.“Halogen” as used herein means fluorine, chlorine, bromine or iodine.
본 명세서에서 기재된 "모노알킬아미노"는 -NHCH3, -NHCH2CH3, -NH(CH2)2CH3, -NH(CH2)3CH3, -NH(CH2)4CH3, -NH(CH2)5CH3, 및 이와 유사한 것을 포함하는, -NH(알킬)을 의미하며, 여기에서 알킬은 위에서 정의된 것과 같다.The term "monoalkylamino" as used herein means -NH(alkyl), including -NHCH3 , -NHCH2 CH3 , -NH(CH2 )2 CH3 , -NH(CH2 )3 CH3 , -NH(CH2 )4 CH3 , -NH(CH2 )5 CH3 , and the like, wherein alkyl is as defined above.
본 명세서에서 기재된 "디알킬아미노"는 -N(CH3)2, -N(CH2CH3)2, -N((CH2)2CH3)2, -N(CH3)(CH2CH3), 및 이와 유사한 것을 포함하는 -N(알킬)(알킬)을 의미하며, 여기에서 각 알킬은 서로 독립적으로 위에서 정의된 알킬이다.As used herein, "dialkylamino" means -N(alkyl)(alkyl),including -N(CH3 )2 , -N(CH2 CH3 )2 , -N((CH2 )2 CH3 ) 2 , -N(CH3 )(CH2 CH3 ), and the like, wherein each alkyl is independently an alkyl as defined above.
본 명세서에서 기재된 “실리콘을 포함하는”의 기재는 "실릴기를 가지는"과 동일한 의미로 “실릴기”는 특별한 기재가 없는 한 실릴, 모노알킬실릴, 디알킬실릴 및 트리알킬실릴을 모두 포함하는 것을 의미하며, 여기에서 알킬은 위에서 정의된 것과 같다.The term “comprising silicone” as used herein is synonymous with “having a silyl group,” and “silyl group” unless otherwise specified includes silyl, monoalkylsilyl, dialkylsilyl, and trialkylsilyl, where alkyl is as defined above.
본 명세서에서 기재된 "실릴"은 -SiH3을 의미한다.As used herein, “silyl” means -SiH3 .
본 명세서에서 기재된 "모노알킬실릴"은 -SiH2CH3, -SiH2CH2CH3, -SiH2(CH2)3CH3, -SiH2(CH2)4CH3, -SiH2(CH2)5CH3, 및 이와 유사한 것을 포함하는, -SiH2(알킬)을 의미하며, 여기에서 알킬은 위에서 정의된 것과 같다.As used herein, "monoalkylsilyl" means -SiH2 CH3 , -SiH2 CH2 CH3 , -SiH2 (CH2 )3 CH3 , -SiH2 (CH2 )4CH3 , -SiH2 (CH2 )5 CH3 , and the like, wherein alkyl is as defined above.
본 명세서에서 기재된 "디알킬실릴"은 -Si(H)(CH3)(CH3), -Si(H)(CH2CH3)CH3, -Si(H)((CH2)3)(CH3), -Si(H)((CH2)4CH3)(CH3), -Si(H)(CH2CH3)(CH2CH3), 및 이와 유사한 것을 포함하는, -Si(H)(알킬)(알킬)을 의미하며, 여기에서 각 알킬은 서로 독립적으로 위에서 정의된 알킬이다.As used herein, "dialkylsilyl" means -Si(H)(CH3 )(CH3 ), -Si(H)(CH2 CH3 )CH3 , -Si(H)((CH2 )3 )(CH3 ), -Si(H)((CH2 )4 CH3 )(CH3 ), -Si(H)(CH2 CH3 )(CH2 CH3 ), and the like, -Si(H)(alkyl)(alkyl), wherein each alkyl is independently an alkyl as defined above.
본 명세서에서 기재된 "트리알킬실릴"은 -Si(CH3)(CH3)(CH3), -Si(CH3)(CH2CH3)(CH3), -Si(CH3)((CH2)3)(CH3), -Si(CH3)((CH2)4CH3)(CH3), -Si(CH3)(CH2CH3)(CH2CH3), 및 이와 유사한 것을 포함하는, -Si(알킬)(알킬)(알킬)을 의미하며, 여기에서 각 알킬은 서로 독립적으로 위에서 정의된 알킬이다.As used herein, "trialkylsilyl" means -Si(CH3 )(CH3 )(CH3 ), -Si(CH3 )(CH2 CH3 )(CH3 ), -Si(CH3 )((CH2 )3 )(CH3 ), -Si(CH3 )((CH2 )4 CH3 )(CH3 ), -Si(CH3 )(CH2 CH3 )(CH2 CH3 ), and the like, -Si(alkyl)(alkyl)(alkyl), wherein each alkyl is independently an alkyl as defined above.
본 발명은 텅스텐함유 박막의 전구체로 매우 유용한 실리콘을 포함하는 텅스텐 화합물을 제공하는 것으로, 본 발명의 실리콘을 포함하는 텅스텐 화합물은 하기 화학식 1로 표시된다.The present invention provides a tungsten compound including silicon, which is very useful as a precursor of a tungsten-containing thin film. The tungsten compound including silicon of the present invention is represented by the following chemical formula 1.
[화학식 1][Chemical Formula 1]
(상기 화학식 1에서,(In the above chemical formula 1,
R1및 R2는 서로 독립적으로 (C1-C10)알킬이며,R1 and R2 are independently (C1-C10) alkyl,
R3은 (C1-C10)알킬, 모노(C1-C10)알킬아미노 또는 디(C1-C10)알킬아미노이며, R3의 알킬은 실릴, 모노(C1-C10)알킬실릴 또는 디(C1-C10)알킬실릴로 더 치환될 수 있으며;R3 is (C1-C10)alkyl, mono(C1-C10)alkylamino or di(C1-C10)alkylamino, and the alkyl of R3 may be further substituted with silyl, mono(C1-C10)alkylsilyl or di(C1-C10)alkylsilyl;
R4 내지 R8은 서로 독립적으로 수소 또는 (C1-C10)알킬이며;R4 to R8 are each independently hydrogen or (C1-C10) alkyl;
n은 1 내지 5의 정수이다.)n is an integer from 1 to 5.)
본 발명의 일 실시예에 따른 화학식 1의 실리콘을 포함하는 텅스텐 화합물은 텅스텐이 반드시 하나 이상의 실릴알킬기를 가짐으로써 열안정성이 현저하게 향상되는 동시에 휘발성이 높아 양질의 박막을 제조할 수 있다.A tungsten compound containing silicon of chemical formula 1 according to one embodiment of the present invention has significantly improved thermal stability and high volatility since tungsten necessarily has at least one silylalkyl group, thereby enabling the production of a high-quality thin film.
구체적으로 본 발명의 일 실시예에 따른 화학식 1의 실리콘을 포함하는 텅스텐 화합물은 중심금속인 텅스텐에 비스(이미도)기를 가지는 동시에 하나 이상의 실릴알킬기를 가짐으로써 박막증착용 전구체의 특성을 향상시킨다.Specifically, a tungsten compound containing silicon of chemical formula 1 according to one embodiment of the present invention has a bis(imido) group on tungsten as a central metal and at least one silylalkyl group, thereby improving the properties of a precursor for thin film deposition.
뿐만 아니라 본 발명의 일 실시예에 따른 화학식 1의 텅스텐 화합물은 상온에서 액체로 존재하여 취급이 용이하며 높은 열안정성으로 인해 저장안정성 또한 우수하다.In addition, the tungsten compound of chemical formula 1 according to one embodiment of the present invention exists as a liquid at room temperature, making it easy to handle, and also has excellent storage stability due to its high thermal stability.
바람직하게 본 발명의 일 실시예에 따른 상기 화학식 1에서 R1 및 R2는 서로 독립적으로 (C1-C4)알킬이며, R3은 실릴(C1-C4)알킬, 모노(C1-C4)알킬실릴로 치환된 (C1-C4)알킬, 디(C1-C4)알킬실릴로 치환된 (C1-C4)알킬, 모노(C1-C4)알킬아미노 또는 디(C1-C4)알킬아미노이며; R4 내지 R8은 서로 독립적으로 수소 또는 (C1-C4)알킬이며; n은 1 내지 3의 정수일 수 있다.Preferably, in the chemical formula 1 according to one embodiment of the present invention, R1 and R2 are each independently (C1-C4) alkyl, R3 is (C1-C4) silyl, (C1-C4) alkyl substituted with mono (C1-C4) alkylsilyl, (C1-C4) alkyl substituted with di (C1-C4) alkylsilyl, mono (C1-C4) alkylamino or di (C1-C4) alkylamino; R4 to R8 are each independently hydrogen or (C1-C4) alkyl; n may be an integer from 1 to 3.
향상된 열안정성 및 휘발성을 가지기위한 측면에서 바람직하게 본 발명의 일 실시예에 따른 화학식 1은 하기 화학식 2로 표시될 수 있다.In terms of having improved thermal stability and volatility, chemical formula 1 according to one embodiment of the present invention may be preferably represented by the following chemical formula 2.
[화학식 2][Chemical formula 2]
(상기 화학식 2에서(In the above chemical formula 2
R11은 (C1-C10)알킬이며,R11 is (C1-C10) alkyl,
R3은 (C1-C10)알킬, 모노(C1-C10)알킬아미노 또는 디(C1-C10)알킬아미노이며, R3의 알킬은 실릴, 모노(C1-C10)알킬실릴 또는 디(C1-C10)알킬실릴로 더 치환될 수 있으며;R3 is (C1-C10)alkyl, mono(C1-C10)alkylamino or di(C1-C10)alkylamino, and the alkyl of R3 may be further substituted with silyl, mono(C1-C10)alkylsilyl or di(C1-C10)alkylsilyl;
R4 내지 R8은 서로 독립적으로 수소 또는 (C1-C10)알킬이며;R4 to R8 are each independently hydrogen or (C1-C10) alkyl;
n은 1 내지 5의 정수이다.)n is an integer from 1 to 5.)
보다 좋기로는 본 발명의 일 실시예에 따른 화학식 2에서 R11은 (C1-C4)알킬이며, R3은 디(C1-C4)알킬아미노이며; R4 내지 R8은 서로 독립적으로 수소 또는 (C1-C4)알킬이며; n은 1 내지 3의 정수일 수 있으며, 더욱 좋기로는 R11은 tert-부틸이며, R3은 디(C1-C4)알킬아미노이며; R4 및 R5는 수소이며; R6 내지 R8은 서로 독립적으로 수소 또는 (C1-C4)알킬이며; n은 1 내지 3의 정수일 수 있다.More preferably, in the chemical formula 2 according to one embodiment of the present invention, R11 is (C1-C4) alkyl, R3 is di (C1-C4) alkylamino; R4 to R8 are each independently hydrogen or (C1-C4) alkyl; n may be an integer from 1 to 3, and even more preferably, R11 is tert-butyl, R3 is di (C1-C4) alkylamino; R4 and R5 are hydrogen; R6 to R8 are each independently hydrogen or (C1-C4) alkyl; and n may be an integer from 1 to 3.
구체적으로 본 발명의 일 실시예에 따른 텅스텐 화합물은 하기 화합물에서 선택될 수 있으나, 이에 한정이 있는 것은 아니다.Specifically, the tungsten compound according to one embodiment of the present invention may be selected from the following compounds, but is not limited thereto.
또한 본 발명은 본 발명의 텅스텐 화합물을 제조하는 방법을 제공한다.The present invention also provides a method for producing the tungsten compound of the present invention.
본 발명의 실리콘을 포함하는 텅스텐 화합물의 제조방법은 하기 화학식 3과 화학식 4의 화합물을 반응시켜 하기 화학식 2의 화합물을 제조하는 단계;를 포함한다.The method for producing a tungsten compound including silicon of the present invention includes the step of reacting compounds of the following chemical formulas 3 and 4 to produce a compound of the following chemical formula 2.
[화학식 2][Chemical formula 2]
[화학식 3][Chemical Formula 3]
[화학식 4][Chemical Formula 4]
(상기 화학식 2 내지 4에서,(In the above chemical formulas 2 to 4,
R11은 (C1-C10)알킬이며,R11 is (C1-C10) alkyl,
R3은 (C1-C10)알킬, 모노(C1-C10)알킬아미노 또는 디(C1-C10)알킬아미노이며, R3의 알킬은 실릴, 모노(C1-C10)알킬실릴 또는 디(C1-C10)알킬실릴로 더 치환될 수 있으며;R3 is (C1-C10)alkyl, mono(C1-C10)alkylamino or di(C1-C10)alkylamino, and the alkyl of R3 may be further substituted with silyl, mono(C1-C10)alkylsilyl or di(C1-C10)alkylsilyl;
R4 내지 R8은 서로 독립적으로 수소 또는 (C1-C10)알킬이며;R4 to R8 are each independently hydrogen or (C1-C10) alkyl;
n은 1 내지 5의 정수이며;n is an integer from 1 to 5;
X는 할로겐이다.)X is a halogen.)
본 발명의 텅스텐 화합물의 제조방법은 일례로 상기와 같은 방법으로 제조될 수 있으나, 이외에 당업자가 인식할 수 있는 범위내에서 가능한 방법이라면 모두 가능하다.The method for producing the tungsten compound of the present invention can be produced by, for example, the method described above, but any other method that is possible within the scope recognized by those skilled in the art is also possible.
본 발명의 일 실시예에 따른 상기 화학식 4의 화합물은 화학식 3의 화합물, 1몰에 대하여 1.00 내지 5.00몰로 사용될 수 있으며, 바람직하게 1.0 내지 2.0몰로 사용될 수 있다.According to one embodiment of the present invention, the compound of chemical formula 4 can be used in an amount of 1.00 to 5.00 moles per mole of the compound of chemical formula 3, and preferably, can be used in an amount of 1.0 to 2.0 moles.
본 발명의 일 실시예에 따른 화학식 2로 표시되는 텅스텐 화합물의 제조방법에 사용되는 용매는 바람직하게 n-헥산, 클로로벤젠, 톨루엔, 다이클로로에탄(DCE), 다이옥산, 디에틸에테르 및 디클로로메테인(MC)에서 선택되는 하나(단독용매) 또는 둘이상의 혼합용매가 사용될 수 있으며, 보다 바람직하게 수율 등의 반응효율을 높이기위한 측면에서 에테르 또는 디에틸에테르 용매 하에서 화학식 2의 화합물을 제조하는 단계는 낮은 온도(-78℃이하)에서 화합물 4를 천천히 첨가한 후 상온(18 내지 30℃)에서 수행될 수 있으며, 바람직하게는 20 내지 25℃에서 8 내지 24시간동안 수행될 수 있다.The solvent used in the method for producing a tungsten compound represented by chemical formula 2 according to one embodiment of the present invention is preferably one (single solvent) or a mixed solvent of two or more selected from n-hexane, chlorobenzene, toluene, dichloroethane (DCE), dioxane, diethyl ether and dichloromethane (MC), and more preferably, in order to increase the reaction efficiency such as the yield, the step of producing the compound of chemical formula 2 in the presence of an ether or diethyl ether solvent may be performed at room temperature (18 to 30°C) after slowly adding compound 4 at a low temperature (-78°C or lower), and preferably, may be performed at 20 to 25°C for 8 to 24 hours.
또한 본 발명은 하기 화학식 1-1로 표시되는 실리콘을 포함하는 텅스텐 화합물을 포함하는 박막증착용 조성물을 제공한다.In addition, the present invention provides a composition for thin film deposition comprising a tungsten compound including silicon represented by the following chemical formula 1-1.
[화학식 1-1][Chemical Formula 1-1]
(상기 화학식 1-1에서,(In the above chemical formula 1-1,
R1및 R2는 서로 독립적으로 (C1-C10)알킬이며,R1 and R2 are independently (C1-C10) alkyl,
R3은 (C1-C10)알킬, 모노(C1-C10)알킬아미노 또는 디(C1-C10)알킬아미노이며, R3의 알킬은 실릴, 모노(C1-C10)알킬실릴, 디(C1-C10)알킬실릴또는 트리(C1-C10)알킬실릴로 더 치환될 수 있으며;R3 is (C1-C10)alkyl, mono(C1-C10)alkylamino or di(C1-C10)alkylamino, and the alkyl of R3 may be further substituted with silyl, mono(C1-C10)alkylsilyl, di(C1-C10)alkylsilyl or tri(C1-C10)alkylsilyl;
R4 내지 R8은 서로 독립적으로 수소 또는 (C1-C10)알킬이며;R4 to R8 are each independently hydrogen or (C1-C10) alkyl;
n은 1 내지 5의 정수이다.)n is an integer from 1 to 5.)
본 발명의 일 실시예에 다른 텅스텐함유 박막증착용 조성물은 화학식 1-1로 표시되는 실리콘을 포함하는 텅스텐 화합물을 포함함으로써 양질의 박막을 다양한 증착방법으로 용이하게 제조할 수 있다.In another embodiment of the present invention, a tungsten-containing thin film deposition composition comprises a tungsten compound including silicon represented by the chemical formula 1-1, thereby enabling easy production of a high-quality thin film by various deposition methods.
바람직하게 본 발명의 일 실시예에 따른 화학식 1-1에서 R1 및 R2는 서로 독립적으로 (C1-C4)알킬이며, R3은 실릴(C1-C4)알킬, 모노(C1-C4)알킬실릴로 치환된 (C1-C4)알킬, 디(C1-C4)알킬실릴로 치환된 (C1-C4)알킬, 트리(C1-C4)알킬실릴로 치환된 (C1-C4)알킬, 모노(C1-C4)알킬아미노 또는 디(C1-C4)알킬아미노이며; R4 내지 R8은 서로 독립적으로 수소 또는 (C1-C4)알킬이며; n은 1 내지 3의 정수일 수 있다.Preferably, in the chemical formula 1-1 according to one embodiment of the present invention, R1 and R2 are each independently (C1-C4) alkyl, R3 is (C1-C4) silyl, (C1-C4) alkyl substituted with mono (C1-C4) alkylsilyl, (C1-C4) alkyl substituted with di (C1-C4) alkylsilyl, (C1-C4) alkyl substituted with tri (C1-C4) alkylsilyl, mono (C1-C4) alkylamino or di (C1-C4) alkylamino; R4 to R8 are each independently hydrogen or (C1-C4) alkyl; n may be an integer from 1 to 3.
또한 본 발명은 본 발명의 박막증착용 조성물을 이용하는 박막의 제조방법을 제공한다.In addition, the present invention provides a method for manufacturing a thin film using the thin film deposition composition of the present invention.
본 발명의 텅스텐함유 박막은 통상적인 방법으로 제조될 수 있으며, 일례로 유기금속 화학기상 증착법(MOCVD), 원자층 증착법(ALD) 공정, 저압 기상 증착법(LPCVD), 플라즈마 강화 기상 증착법 (PECVD) 또는 플라즈마 강화 원자층 증착법(PEALD)등을 들 수 있다.The tungsten-containing thin film of the present invention can be manufactured by a conventional method, and examples thereof include metalorganic chemical vapor deposition (MOCVD), atomic layer deposition (ALD) process, low pressure chemical vapor deposition (LPCVD), plasma enhanced chemical vapor deposition (PECVD), or plasma enhanced atomic layer deposition (PEALD).
본 발명의 텅스텐함유 박막은 본 발명의 텅스텐 화합물을 이용하여 제조되며, 한정이 있는 것은 아니나 바람직하게 텅스텐질화막일 수 있다.The tungsten-containing thin film of the present invention is manufactured using the tungsten compound of the present invention, and is preferably a tungsten nitride film, although there is no limitation thereto.
본 발명의 텅스텐함유 박막의 제조방법은 높은 휘발성과 높은 열적 안정성을 가지는 본 발명의 텅스텐 화합물을 전구체로 사용하여 제조됨으로써 제조된 텅스텐함유 박막은 물리적, 전기적, 화학적 특성이 극히 우수하다.The method for manufacturing a tungsten-containing thin film of the present invention is performed by using the tungsten compound of the present invention, which has high volatility and high thermal stability, as a precursor, so that the manufactured tungsten-containing thin film has extremely excellent physical, electrical, and chemical properties.
본 발명의 텅스텐함유 박막의 제조방법에서 본 발명의 텅스텐 화합물의 주입온도는 상온(25) 내지 120 ℃일 수 있으며, 본 발명의 텅스텐 화합물의 높은 휘발성으로 인해 텅스텐 화합물이 증착될 기판의 온도는 100 내지 450 ℃, 챔버내부 압력은 0.1 내지 10 torr일 수 있다.In the method for manufacturing a tungsten-containing thin film of the present invention, the injection temperature of the tungsten compound of the present invention may be room temperature (25) to 120°C, and due to the high volatility of the tungsten compound of the present invention, the temperature of the substrate on which the tungsten compound is to be deposited may be 100 to 450°C, and the pressure inside the chamber may be 0.1 to 10 torr.
본 발명의 텅스텐함유 박막의 제조방법에서 사용되는 반응가스는 한정이 있는 것은 아니나, 수소(H2), 히드라진(N2H4), 오존(O3), 산소(O2), 물(H2O), 암모니아(NH3), 질소(N2), 실란(SiH4), 보란(BH3), 디보란(B2H6) 및 포스핀(PH3)에서 선택되는 하나 또는 하나이상의 혼합기체일 수 있다.The reaction gas used in the method for manufacturing a tungsten-containing thin film of the present invention is not limited, but may be one or a mixture of one or more gases selected from hydrogen (H2 ), hydrazine (N2 H4 ), ozone (O3 ), oxygen (O2 ), water (H2 O), ammonia (NH3 ), nitrogen (N2 ), silane (SiH4 ), borane (BH3 ), diborane (B2 H6 ), and phosphine (PH3 ).
이하, 실시예를 통하여 본 발명의 구성을 보다 구체적으로 설명하지만, 하기의 실시예들은 본 발명에 대한 이해를 돕기 위한 것으로서, 본 발명의 범위가 여기에 국한된 것은 아니다.Hereinafter, the composition of the present invention will be described more specifically through examples, but the following examples are intended to help understanding the present invention, and the scope of the present invention is not limited thereto.
[실시예 1] W(Nt-Bu)2N(CH3)2CH2TMS의 합성[Example 1] Synthesis of W(Nt-Bu)2 N(CH3 )2 CH2 TMS
250mL의 플라스크를 진공건조하여 N2분위기를 만들어 주고, 비스(tert-부틸이미도)비스(메틸아미도)텅스텐(BTBMW) 20g(48mmol)을 넣어주었다. 여기에 용매인 diethyl ether 90mL를 넣어 녹여 주었다. Acetone/dry ice bath를 이용하여 플라스크의 온도를 -78˚C까지 냉각 시킨 후 TMS-methylmagnesium chloride 48mL(48mmol)(1M in diethyl ether)를 천천히 넣어주었다. 그 후 상온까지 승온하여, 16시간 교반시켰다. 반응 종료 후 반응물을 celite filter를 진행 후 20mL diethyl ether로 씻어주고, 감압 농축하였다. 얻어진 잔류물을 증류 정제하여 W(Nt-Bu)2N(CH3)2CH2TMS, 16.3g(35.6mmol, 74%)을 얻었다(정제 조건 78℃/1.2torr).A 250 mL flask was vacuum-dried to create a N2 atmosphere, and 20 g (48 mmol) of bis(tert-butylimido)bis(methylamido)tungsten (BTBMW) was added. 90 mL of diethyl ether as a solvent was added and dissolved. The temperature of the flask was cooled to -78˚C using an acetone/dry ice bath, and 48 mL (48 mmol) of TMS-methylmagnesium chloride (1 M in diethyl ether) was slowly added. The temperature was then raised to room temperature and stirred for 16 hours. After the reaction was completed, the reactant was filtered through a celite filter, washed with 20 mL of diethyl ether, and concentrated under reduced pressure. The obtained residue was purified by distillation to obtain W(Nt-Bu)2 N(CH3 )2 CH2 TMS, 16.3 g (35.6 mmol, 74%) (purification conditions 78°C/1.2 torr).
1H NMR 400MHz(C6D6) δ 3.38(s, 6H), 1.37(s, 18H), 0.82(s, 2H), 0.23(s, 9H)1 H NMR 400MHz(C6 D6 )δ 3.38(s, 6H), 1.37(s, 18H), 0.82(s, 2H), 0.23(s, 9H)
[실시예 2] W(Nt-Bu)2(CH2TMS)2의 합성[Example 2] Synthesis of W(Nt-Bu)2 (CH2 TMS)2
250mL 플라스크를 진공건조하여 N2분위기를 만들어 주고, BTBMW 20g(48mmol)을 넣어주었다. 여기에 용매인 diethyl ether 90mL를 넣어 녹여 주었다. Acetone/dry ice bath를 이용하여 플라스크의 온도를 -78˚C까지 냉각 시킨 후 TMS-methylmagnesium chloride 96mL(96mmol)(1M in diethyl ether)를 천천히 넣어주었다. 그 후 상온까지 승온하여, 16시간 교반시켰다. 반응 종료후 반응물을 celite filter를 진행 후 20mL diethyl ether로 씻어주고, 감압 농축하였다. 농축된 조 생성물을 증류 정제하여 W(Nt-Bu)2(CH2TMS)2, 18.7g(37.5mmol, 78%)을 얻었다(정제 조건 89℃/1.3torr).A 250 mL flask was vacuum-dried to create an N2 atmosphere, and 20 g (48 mmol) of BTBMW was added. 90 mL of diethyl ether as a solvent was added and dissolved. The temperature of the flask was cooled to -78˚C using an acetone/dry ice bath, and 96 mL (96 mmol) of TMS-methylmagnesium chloride (1 M in diethyl ether) was slowly added. The temperature was then raised to room temperature and stirred for 16 hours. After the reaction was completed, the reactant was filtered through a celite filter, washed with 20 mL of diethyl ether, and concentrated under reduced pressure. The concentrated crude product was purified by distillation to obtain 18.7 g (37.5 mmol, 78%) of W(Nt-Bu)2 (CH2 TMS)2 (purification conditions 89℃/1.3 torr).
1H NMR 400MHz(C6D6) δ 1.43(s, 18H), 0.75(s, 4H), 0.21(s, 18H)1 H NMR 400MHz(C6 D6 )δ 1.43(s, 18H), 0.75(s, 4H), 0.21(s, 18H)
[실시예 3 및 비교예 1] 텅스텐 화합물의 물질 분석[Example 3 and Comparative Example 1] Material Analysis of Tungsten Compounds
상기 실시예 1에서 제조된 W(Nt-Bu)2N(CH3)2CH2TMS 및 비교예 1로 BTBMW의 열적 안정성 및 휘발성과 분해 온도를 측정하기 위해, 열무게 분석법(TGA)을 이용하였다(TGA 조건: 10℃/분의 속도로 500℃까지 가온 시키면서 1.5bar/분의 압력으로 아르곤 주입).In order to measure the thermal stability, volatility, and decomposition temperature of W(Nt-Bu)2 N(CH3 )2 CH2 TMS manufactured in Example 1 and BTBMW of Comparative Example 1, thermogravimetric analysis (TGA) was used (TGA conditions: heating to 500°C at a rate of 10°C/min while injecting argon at a pressure of 1.5 bar/min).
실시예 1에서 제조된 텅스텐 화합물은 97℃부근에서 질량 감소가 일어나기 시작하여 212℃에서 약99%의 질량 감소를, 191℃에서 T1/2을 확인할 수 있다.The tungsten compound manufactured in Example 1 begins to lose mass at around 97°C, and a mass loss of approximately 99% is confirmed at 212°C, and T1/2 is confirmed at 191°C.
이에 반해 비교예 1의 화합물(BTBMW)은 68℃부근에서 질량 감소가 일어나기 시작하여 182℃에서 약99%의 질량 감소를, 164℃에서 T1/2을 확인할 수 있다.In contrast, the compound (BTBMW) of Comparative Example 1 begins to lose mass around 68°C, and a mass loss of approximately 99% is observed at 182°C, and T1/2 is observed at 164°C.
따라서 본 발명의 실리콘을 포함하는 텅스텐 화합물이 실리콘을 포함하지 않은 텅스텐 화합물과 대비하여 현저하게 향상된 열안정성을 가짐을 알 수 있다.Therefore, it can be seen that the tungsten compound including silicon of the present invention has significantly improved thermal stability compared to a tungsten compound not including silicon.
Claims (10)
Translated fromKorean[화학식 1]
(상기 화학식 1에서,
R1및 R2는 서로 독립적으로 (C1-C10)알킬이며,
R3은 모노(C1-C10)알킬아미노 또는 디(C1-C10)알킬아미노이며;
R4 내지 R8은 서로 독립적으로 수소 또는 (C1-C10)알킬이며;
n은 1 내지 5의 정수이다.)A tungsten compound represented by the following chemical formula 1:
[Chemical Formula 1]
(In the above chemical formula 1,
R1 and R2 are independently (C1-C10) alkyl,
R3 is mono(C1-C10)alkylamino or di(C1-C10)alkylamino;
R4 to R8 are each independently hydrogen or (C1-C10) alkyl;
n is an integer from 1 to 5.)
상기 화학식 1에서, R1 및 R2는 서로 독립적으로 (C1-C4)알킬이며, R3은 모노(C1-C4)알킬아미노 또는 디(C1-C4)알킬아미노이며;
R4 내지 R8은 서로 독립적으로 수소 또는 (C1-C4)알킬이며;
n은 1 내지 3의 정수인 텅스텐 화합물.In paragraph 1,
In the above chemical formula 1, R1 and R2 are independently (C1-C4) alkyl, and R3 is mono(C1-C4) alkylamino or di(C1-C4) alkylamino;
R4 to R8 are each independently hydrogen or (C1-C4) alkyl;
Tungsten compound where n is an integer from 1 to 3.
상기 화학식 1은 하기 화학식 2로 표시되는 텅스텐 화합물:
[화학식 2]
(상기 화학식 2에서
R11은 (C1-C10)알킬이며,
R3은 모노(C1-C10)알킬아미노 또는 디(C1-C10)알킬아미노이며;
R4 내지 R8은 서로 독립적으로 수소 또는 (C1-C10)알킬이며;
n은 1 내지 5의 정수이다.)In paragraph 1,
The above chemical formula 1 is a tungsten compound represented by the following chemical formula 2:
[Chemical formula 2]
(In the above chemical formula 2
R11 is (C1-C10) alkyl,
R3 is mono(C1-C10)alkylamino or di(C1-C10)alkylamino;
R4 to R8 are each independently hydrogen or (C1-C10) alkyl;
n is an integer from 1 to 5.)
상기 화학식 2에서 R11은 (C1-C4)알킬이며, R3은 디(C1-C4)알킬아미노이며; R4 내지 R8은 서로 독립적으로 수소 또는 (C1-C4)알킬이며; n은 1 내지 3의 정수인 텅스텐 화합물.In the third paragraph,
A tungsten compound wherein in the above chemical formula 2, R11 is (C1-C4) alkyl, R3 is di(C1-C4) alkylamino; R4 to R8 are each independently hydrogen or (C1-C4) alkyl; and n is an integer from 1 to 3.
상기 텅스텐 화합물은 하기 화합물에서 선택되는 텅스텐 화합물.
The above tungsten compound is a tungsten compound selected from the following compounds.
[화학식 2]
[화학식 3]
[화학식 4]
(상기 화학식 2 내지 4에서,
R11은 (C1-C10)알킬이며,
R3은 (C1-C10)알킬, 모노(C1-C10)알킬아미노 또는 디(C1-C10)알킬아미노이며, R3의 알킬은 실릴, 모노(C1-C10)알킬실릴 또는 디(C1-C10)알킬실릴로 더 치환될 수 있으며;
R4 내지 R8은 서로 독립적으로 수소 또는 (C1-C10)알킬이며;
n은 1 내지 5의 정수이며;
X는 할로겐이다.) A method for producing a tungsten compound, comprising the step of reacting a compound of the following chemical formula 3 with a compound of the following chemical formula 4 to produce a compound of the following chemical formula 2.
[Chemical formula 2]
[Chemical Formula 3]
[Chemical Formula 4]
(In the above chemical formulas 2 to 4,
R11 is (C1-C10) alkyl,
R3 is (C1-C10)alkyl, mono(C1-C10)alkylamino or di(C1-C10)alkylamino, and the alkyl of R3 may be further substituted with silyl, mono(C1-C10)alkylsilyl or di(C1-C10)alkylsilyl;
R4 to R8 are each independently hydrogen or (C1-C10) alkyl;
n is an integer from 1 to 5;
X is a halogen.)
[화학식 1-1]
(상기 화학식 1-1에서,
R1및 R2는 서로 독립적으로 (C1-C10)알킬이며,
R3은 (C1-C10)알킬, 모노(C1-C10)알킬아미노 또는 디(C1-C10)알킬아미노이며, R3의 알킬은 실릴, 모노(C1-C10)알킬실릴, 디(C1-C10)알킬실릴 또는 트리(C1-C10)알킬실릴로 더 치환될 수 있으며;
R4 내지 R8은 서로 독립적으로 수소 또는 (C1-C10)알킬이며;
n은 1 내지 5의 정수이다.) A composition for thin film deposition comprising a tungsten compound represented by the following chemical formula 1-1.
[Chemical Formula 1-1]
(In the above chemical formula 1-1,
R1 and R2 are independently (C1-C10) alkyl,
R3 is (C1-C10)alkyl, mono(C1-C10)alkylamino or di(C1-C10)alkylamino, and the alkyl of R3 may be further substituted with silyl, mono(C1-C10)alkylsilyl, di(C1-C10)alkylsilyl or tri(C1-C10)alkylsilyl;
R4 to R8 are each independently hydrogen or (C1-C10) alkyl;
n is an integer from 1 to 5.)
상기 화학식 1-1에서, R1 및 R2는 서로 독립적으로 (C1-C4)알킬이며, R3은 실릴(C1-C4)알킬, 모노(C1-C4)알킬실릴로 치환된 (C1-C4)알킬, 디(C1-C4)알킬실릴로 치환된 (C1-C4)알킬, 트리(C1-C4)알킬실릴로 치환된 (C1-C4)알킬, 모노(C1-C4)알킬아미노 또는 디(C1-C4)알킬아미노이며;
R4 내지 R8은 서로 독립적으로 수소 또는 (C1-C4)알킬이며;
n은 1 내지 3의 정수인 박막증착용 조성물.In Article 7,
In the above chemical formula 1-1, R1 and R2 are each independently (C1-C4) alkyl, R3 is (C1-C4) silyl, (C1-C4) alkyl substituted with mono(C1-C4) alkylsilyl, (C1-C4) alkyl substituted with di(C1-C4) alkylsilyl, (C1-C4) alkyl substituted with tri(C1-C4) alkylsilyl, mono(C1-C4) alkylamino or di(C1-C4) alkylamino;
R4 to R8 are each independently hydrogen or (C1-C4) alkyl;
A composition for thin film deposition, wherein n is an integer from 1 to 3.
상기 박막은 유기금속 화학기상 증착법, 원자층 증착법공정, 저압 기상 증착법, 플라즈마 강화 기상 증착법 또는 플라즈마 강화 원자층 증착법에 의해 수행되는 것인 방법.In Article 9,
A method wherein the above thin film is formed by organic metal chemical vapor deposition, atomic layer deposition, low pressure vapor deposition, plasma enhanced vapor deposition or plasma enhanced atomic layer deposition.
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