KR19990046683A - Organocuprous precursors for chemical deposition of copper - Google Patents
Organocuprous precursors for chemical deposition of copper Download PDFInfo
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- KR19990046683A KR19990046683A KR1019990013236A KR19990013236A KR19990046683A KR 19990046683 A KR19990046683 A KR 19990046683A KR 1019990013236 A KR1019990013236 A KR 1019990013236A KR 19990013236 A KR19990013236 A KR 19990013236A KR 19990046683 A KR19990046683 A KR 19990046683A
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- copper
- thin film
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- 239000010949 copper Substances 0.000 title claims abstract description 36
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000002243 precursor Substances 0.000 title abstract description 18
- 238000005234 chemical deposition Methods 0.000 title 1
- 238000000151 deposition Methods 0.000 claims abstract description 20
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- -1 copper (I) compound Chemical class 0.000 claims description 5
- 230000008016 vaporization Effects 0.000 claims description 2
- 230000008021 deposition Effects 0.000 abstract description 17
- 239000010409 thin film Substances 0.000 abstract description 17
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 12
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 abstract description 8
- 239000012691 Cu precursor Substances 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- PKXHXOTZMFCXSH-UHFFFAOYSA-N 3,3-dimethylbut-1-ene Chemical compound CC(C)(C)C=C PKXHXOTZMFCXSH-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- XWZIOMULOIOAOA-UHFFFAOYSA-N C(=C)[SiH3].[Cu+] Chemical compound C(=C)[SiH3].[Cu+] XWZIOMULOIOAOA-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- AASUFOVSZUIILF-UHFFFAOYSA-N diphenylmethanone;sodium Chemical compound [Na].C=1C=CC=CC=1C(=O)C1=CC=CC=C1 AASUFOVSZUIILF-UHFFFAOYSA-N 0.000 description 1
- GCSJLQSCSDMKTP-UHFFFAOYSA-N ethenyl(trimethyl)silane Chemical compound C[Si](C)(C)C=C GCSJLQSCSDMKTP-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- HYWCXWRMUZYRPH-UHFFFAOYSA-N trimethyl(prop-2-enyl)silane Chemical compound C[Si](C)(C)CC=C HYWCXWRMUZYRPH-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
- C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
-
- 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
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/08—Copper compounds
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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)
- Chemical Vapour Deposition (AREA)
- Electrodes Of Semiconductors (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Chemically Coating (AREA)
Abstract
본 발명은 구리 박막을 화학증착에 의해 형성할 때 유용하게 사용할 수 있는 하기 화학식 1의 유기 구리(I) 전구체에 관한 것으로, 본 발명에 따르는 유기 구리 전구체는 상온에서 액체로 존재하고 높은 증기압과 열안정성을 갖기 때문에 높은 증착속도로 구리를 화학증착시킬 수 있으며, 증착된 박막은 낮은 비저항치를 갖는다.The present invention relates to an organic copper (I) precursor of formula (1), which can be usefully used when forming a copper thin film by chemical vapor deposition, wherein the organic copper precursor according to the present invention exists as a liquid at room temperature and has high vapor pressure and heat. Because of its stability, it is possible to chemically deposit copper at a high deposition rate, and the deposited thin film has a low resistivity.
상기 식에서,Where
R1및 R3는 각각 독립적으로 C1-4알킬기이고,R 1 and R 3 are each independently a C 1-4 alkyl group,
R2는 수소 또는 C1-4알킬기이고,R 2 is hydrogen or a C 1-4 alkyl group,
R4 및 R5는 각각 독립적으로 CnF2n+1또는 CnH2n+1(n=0 내지 7)이다.R4 And R5Are each independently CnF2n + 1Or CnH2n + 1(n = 0 to 7).
Description
본 발명은 구리의 화학 증착에 유용한 유기 구리 (I) 전구체에 관한 것으로, 보다 상세하게는 반도체 공정 중 구리 배선 제조에 유용하게 활용할 수 있는 유기 구리(I) 전구체에 관한 것이다.FIELD OF THE INVENTION The present invention relates to organic copper (I) precursors useful for chemical vapor deposition of copper, and more particularly to organic copper (I) precursors that can be usefully employed in the manufacture of copper interconnects in semiconductor processes.
최근 반도체 기술 발전은 디바이스의 소형화를 통해 보다 향상된 기술을 추구함으로써 지속적으로 이루어져 왔으며, 이에 적합한 박막 재료와 공정 기술에 대한 연구가 활발히 진행되고 있다. 다양한 연구 방향 중 가장 각광을 받고 있는 공정은 유기금속 화학증착법 (MOCVD=metal organic chemical vapor deposition)에 의한 구리 박막 제조이다. 그 이유는 화학증착법을 사용할 경우 물리적증착법(PVD=physical vapor deposition) 보다 층덮힘(step coverage) 및 개구충전(hole filling) 특성이 뛰어나 미세 패턴 제조가 유리하고, 구리 배선을 사용하는 경우 기존의 금속 배선으로 쓰이는 알루미늄 배선 보다 비저항이 낮고 전류 밀도를 10 배 이상 높일 수 있어 고속 동작이 가능할 뿐 아니라 전자이동(electromigration)에 대한 내성이 강해 수명도 길어지며, 칩 크기도 같은 성능의 기존의 칩 보다 65% 정도나 줄일 수 있는 장점이 있기 때문이다. 또한, 구리 배선은 전력 소모량을 크게 줄일 수 있고 다층 배선 제품에서 제조 비용을 현재 보다 약 30 % 정도 줄일 수 있는 장점을 가진다.Recently, the development of semiconductor technology has been continuously made by pursuing improved technology through miniaturization of devices, and research on suitable thin film materials and process technologies is being actively conducted. Among the various research directions, the most popular process is the production of copper thin film by MOCVD (metal organic chemical vapor deposition). The reason for this is that the chemical vapor deposition method has better step coverage and hole filling characteristics than the physical vapor deposition (PVD = physical vapor deposition) method, so it is advantageous to manufacture a fine pattern. It has a lower resistivity and 10 times higher current density than aluminum wiring, which enables high-speed operation and long life due to its strong resistance to electromigration. This is because there is an advantage that can be reduced by about%. In addition, copper wiring has the advantage of significantly reducing power consumption and reducing manufacturing costs by about 30% in current multilayer wiring products.
구리 배선 제조에 사용하기 위한 유기 구리 전구체의 합성에 대한 연구가 활발하기는 하나, 아직 뚜렷하게 좋은 물성을 나타내는 전구체는 없다고 할 수 있다. 구리 박막은, 이전에는 Cu(II)(hfac)2(여기서, hfac는 헥사플루오로아세틸아세토네이트를 나타냄)와 같은 유기 구리 전구체를 사용하여 제조되어 왔다. 그러나, 상기 Cu(II) 전구체를 사용하는 CVD 방법은 높은 증착 온도를 필요로할 뿐만 아니라 생성된 Cu 박막이 여러가지 불순물로 오염되는 경우가 많았다.Although research on the synthesis of organic copper precursors for use in the manufacture of copper interconnects is active, there is no precursor showing a markedly good physical property. Copper thin films have previously been produced using organic copper precursors such as Cu (II) (hfac) 2 , where hfac represents hexafluoroacetylacetonate. However, the CVD method using the Cu (II) precursor not only requires a high deposition temperature, but also the resulting Cu thin film is often contaminated with various impurities.
지금까지 알려진 CVD 용 유리 구리(I) 전구체의 예로는, (hfac)Cu(I)(비닐트리메틸실란(VTMS)) 및 (hfac)Cu(I)(알릴트리메틸실란(ATMS))이 있으며, 이들을 저온 CVD 공정에 사용하여 전도성 기판 표면에 구리 박막을 증착시키는 방법이 노르만(Norman) 등의 미국 특허 제5,085,731호에 기재되어 있다. 그러나 상기 구리(I) 비닐실란 전구체를 사용한 CVD 공정에 의해 형성되는 구리 박막은 아직 충분치못한 물성을 갖는다.Examples of glass copper (I) precursors for CVD known to date include (hfac) Cu (I) (vinyltrimethylsilane (VTMS)) and (hfac) Cu (I) (allyltrimethylsilane (ATMS)). A method of depositing a thin copper film on a conductive substrate surface for use in low temperature CVD processes is described in US Pat. No. 5,085,731 to Norman et al. However, the copper thin film formed by the CVD process using the copper (I) vinylsilane precursor still has insufficient physical properties.
따라서, 본 발명에서는 열적으로 안정하며 상온에서 액체로 존재하여 구리의 저온 화학증착에 특히 적합하면서도 높은 증착 속도로 구리 박막을 형성할 수 있는 액상 유기 구리(I) 전구체를 제공하는데 그 목적이 있다.Accordingly, an object of the present invention is to provide a liquid organic copper (I) precursor that is thermally stable and is a liquid at room temperature, which is particularly suitable for low temperature chemical vapor deposition of copper, and can form a thin copper film at a high deposition rate.
도 1은 본 발명 및 종래 기술에 따른 구리 전구체 이용시의 증착 온도 변화에 따른 구리 증착 속도 변화를 나타내는 그래프이고,1 is a graph showing a change in copper deposition rate with a change in deposition temperature when using a copper precursor according to the present invention and the prior art,
도 2는 본 발명의 구리 전구체 이용시, 증착 온도 변화에 따른 박막의 비저항치의 변화를 나타내는 그래프이다.2 is a graph showing the change in the specific resistance of the thin film according to the deposition temperature change when using the copper precursor of the present invention.
본 발명에서는 상기 목적을 달성하기 위해 하기 화학식 1의 유기 구리(I) 화합물을 제공한다:The present invention provides an organic copper (I) compound of formula 1 to achieve the above object:
화학식 1Formula 1
상기 식에서,Where
R1및 R3는 각각 독립적으로 C1-4알킬기이고,R 1 and R 3 are each independently a C 1-4 alkyl group,
R2는 수소 또는 C1-4알킬기이고,R 2 is hydrogen or a C 1-4 alkyl group,
R4 및 R5는 각각 독립적으로 CnF2n+1또는 CnH2n+1(n=0 내지 7)이다.R4 And R5Are each independently CnF2n + 1Or CnH2n + 1(n = 0 to 7).
이하, 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명의 상기 화학식 1의 유기 구리(I) 화합물중 가장 대표적인 것은 하기 화학식 2의 화합물이다:The most representative of the organic copper (I) compound of Formula 1 of the present invention is a compound of Formula 2:
상기 화학식 2의 화합물((hfac)Cu(I)(DMB))은 유기 용매, 예를 들면 에테르 또는 디클로로메탄의 존재하에서 1,1,1,5,5,5-헥사플루오로-2,4-펜탄디온(Hhfac), 3,3-디메틸-1-부텐(DMB) 및 산화구리(I)(Cu2O)를 반응시켜 제조할 수 있다. 상기 반응은 Hhfac:DMB:산화구리를 바람직하게는 약 2:2:1의 몰비로 사용하고, 0 내지 20 ℃의 온도 및 대략 1기압의 압력에서 30 내지 60분간 반응시킴으로써 수행할 수 있다.The compound of Formula 2 ((hfac) Cu (I) (DMB)) is 1,1,1,5,5,5-hexafluoro-2,4 in the presence of an organic solvent such as ether or dichloromethane. It can be prepared by reacting -pentanedione (Hhfac), 3,3-dimethyl-1-butene (DMB) and copper oxide (I) (Cu 2 O). The reaction can be carried out by using Hhfac: DMB: copper oxide, preferably in a molar ratio of about 2: 2: 1, and reacting for 30 to 60 minutes at a temperature of 0 to 20 ° C. and a pressure of approximately 1 atmosphere.
상기 반응물들은 시판하는 것을 구입하여 사용할 수 있다.The reactants may be purchased commercially available.
본 발명에 따른 유기 구리(I) 화합물은 열적으로 안정하고 상온 내지 60 ℃ 범위 온도의 버블러(bubbler)에서 기화시킬 수 있으므로 구리 박막의 화학 증착에 편리하게 사용할 수 있다. 본 발명의 유기 구리(I) 전구체는 직접 액체 주입 시스템에 의해 주입될 수도 있다.The organic copper (I) compound according to the present invention can be conveniently used for chemical vapor deposition of a copper thin film because it is thermally stable and can be vaporized in a bubbler at a temperature ranging from room temperature to 60 ° C. The organic copper (I) precursor of the present invention may be implanted by a direct liquid injection system.
본 발명의 화합물을 전구체로 사용하여 화학증착법에 의해 기판 상에 구리박막을 증착시키는 공정은 통상의 방법으로, 예를 들면 본 발명의 전구체 화합물을 기화시킨 다음 생성된 기체를 운반 기체와 함께 가열된 기판에 도입함으로써 달성할 수 있다. 화학 증착시 운반 기체로는 아르곤과 같은 불활성기체를 사용하며, 기판으로는 백금, 실리카, TiN 기판 등을 사용할 수 있다.The process of depositing a copper thin film on a substrate by chemical vapor deposition using the compound of the present invention as a precursor is carried out in a conventional manner, for example, by vaporizing the precursor compound of the present invention and then heating the resulting gas with a carrier gas. It can achieve by introducing into a board | substrate. In chemical vapor deposition, an inert gas such as argon may be used as a carrier gas, and a platinum, silica, or TiN substrate may be used as the substrate.
이하, 실시예를 참조로 본 발명을 보다 상세히 설명하며, 본 발명이 이에 국한되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.
실시예 1: 유기 구리(I) 전구체((hfac)Cu(I)(DMB))의 합성Example 1 Synthesis of Organic Copper (I) Precursor ((hfac) Cu (I) (DMB))
Cu2O 0.5 g (3.5mmol)와 MgSO40.84g (7.0mmol)를 포함하고 있는 쉴렝크 (Schlenk) 플라스크에 에테르 30 ml를 넣고, 3,3-디메틸-1-부텐 0.59 g (7.0 mmol)을 천천히 가하였다. 에테르 용매는 아르곤 기류하에서 나트륨 벤조페논으로부터 증류하여 사용하였다. 생성된 붉은색 현탁액을 30분간 교반한 후 0 ℃로 냉각하였다. 여기에 Hhfac 1.46 g (7.0mmol)이 녹아있는 에테르 용액을 캐뉼라를 이용하여 천천히 가하고 30분 정도 상온에서 교반하였다. 이때 용액의 색이 초록색으로 변하였다. 이 용액을 셀라이트(CelliteR)에 통과시켜 거른 다음 진공하에서 용매를 제거하여 초록색 액체 형태의 화합물 1.12 g을 얻었다. 수율은 90%였고,1H NMR로서 화합물을 확인하였으며, 그 결과는 다음과 같다.30 ml of ether was added to a Schlenk flask containing 0.5 g (3.5 mmol) of Cu 2 O and 0.84 g (7.0 mmol) of MgSO 4 , and 0.59 g (7.0 mmol) of 3,3-dimethyl-1-butene Was added slowly. The ether solvent was used distilled from sodium benzophenone under argon stream. The resulting red suspension was stirred for 30 minutes and then cooled to 0 ° C. An ether solution containing 1.46 g (7.0 mmol) of Hhfac was slowly added thereto using a cannula and stirred at room temperature for about 30 minutes. At this time the color of the solution turned green. The solution was passed through Celite (Cellite R ), and then the solvent was removed in vacuo to yield 1.12 g of a compound in the form of a green liquid. The yield was 90%, the compound was confirmed by 1 H NMR, the results are as follows.
1H-NMR(CDCl3, ppm) δ 6.12(s, 1H), 5.38(m, 1H), 4.30(dd, 2H), 1.15(s, 6H) 1 H-NMR (CDCl 3 , ppm) δ 6.12 (s, 1H), 5.38 (m, 1H), 4.30 (dd, 2H), 1.15 (s, 6H)
실시예 2: 구리 박막의 증착 및 물성 시험Example 2: Deposition and Properties of Copper Thin Films
실시예 1에서 합성된 화합물 및 선행 문헌인 미국 특허 제5,085,731호에 개시된 (hfac)Cu(I)(VTMS) 및 (hfac)Cu(I)(ATMS)를 전구체로 사용하여, 45 ℃의 버블러에서 기화시킨 다음, 화학증착법에 의해 증착온도를 변화시키면서 TiN기판 위에 구리박막을 증착시켰다. 이때 기화된 구리 전구체의 운반 기체로는 아르곤을 50 sccm의 유량으로 사용하였고, 화학증착시의 증착실 전체 압력은 0.3 mmHg로 일정하게 유지하였다. 이때의 증착 온도 변화에 따른 증착 속도와 증착된 박막의 비저항치를 도 1에 나타내었다.Bubbler at 45 ° C. using the compound synthesized in Example 1 and (hfac) Cu (I) (VTMS) and (hfac) Cu (I) (ATMS) disclosed in U.S. Patent No. 5,085,731, as precursors After evaporating at, the copper thin film was deposited on the TiN substrate while the deposition temperature was changed by chemical vapor deposition. At this time, argon was used as a carrier gas of the vaporized copper precursor at a flow rate of 50 sccm, and the total pressure of the deposition chamber during chemical vapor deposition was kept constant at 0.3 mmHg. The deposition rate and the resistivity of the deposited thin film according to the deposition temperature change are shown in FIG. 1.
도 1로부터 알 수 있듯이, 본 발명에 따른 전구체를 사용하는 경우 구리 박막은 100 ℃의 증착온도에서부터 증착이 되기 시작하여 175 ℃까지 증착 속도가 급격히 증가하다가 그 이상의 온도에서는 거의 증가가 완만하게 나타났다. 이러한 구리 증착속도는 선행 문헌에 개시된 전구체를 이용하는 경우에 비해 5 내지 7 배 정도 높았다.As can be seen from Figure 1, in the case of using the precursor according to the present invention, the copper thin film starts to be deposited at a deposition temperature of 100 ℃, the deposition rate is rapidly increased to 175 ℃, the increase was almost steadily above that temperature. This copper deposition rate was about 5 to 7 times higher than when using the precursors disclosed in the prior literature.
또한, 도 2는 본 발명에 따른 전구체를 사용하여 증착된 구리 박막의 증착 온도에 따른 구리 박막 비저항치를 나타낸 그래프로서, 증착이 시작되는 초기 온도(100 내지 125 ℃)에서는 비저항치가 다소 높지만, 150 내지 250 ℃ 범위의 온도에서의 비저항치는 벌크 구리의 값(1.67 μΩ·cm)과 비슷하게 됨을 알 수 있다.In addition, Figure 2 is a graph showing the resistivity of the copper thin film according to the deposition temperature of the copper thin film deposited using the precursor according to the present invention, although the resistivity is somewhat higher at the initial temperature (100 to 125 ℃) when the deposition is started, 150 to It can be seen that the specific resistance at temperatures in the range of 250 ° C. is similar to that of bulk copper (1.67 μ67 · cm).
본 발명에 따르는 액상 유기 구리(I) 전구체는 상온에서 높은 증기압을 갖고 열안정성이 우수하여 높은 증착속도로 비저항치가 낮은 구리 박막을 화학 증착법에 의해 형성할 수 있다.The liquid organic copper (I) precursor according to the present invention has a high vapor pressure at room temperature and is excellent in thermal stability, thereby forming a copper thin film having a low resistivity at a high deposition rate by chemical vapor deposition.
Claims (3)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019990013236A KR100298125B1 (en) | 1999-04-15 | 1999-04-15 | Organocuprous precursors for chemical deposition of copper |
| JP2000612535A JP2002542397A (en) | 1999-04-15 | 1999-12-07 | Organocopper (I) precursor for chemical vapor deposition of copper thin films |
| PCT/KR1999/000743 WO2000063461A1 (en) | 1999-04-15 | 1999-12-07 | Novel organocuprous precursors for chemical vapor deposition of a copper film |
| CNB998026484A CN1194117C (en) | 1999-04-15 | 1999-12-07 | Organocuprous precursors for chemical vapor deposition of copper film |
| EP99959960A EP1102872A4 (en) | 1999-04-15 | 1999-12-07 | Novel organocuprous precursors for chemical vapor deposition of a copper film |
| RU2000118774/04A RU2181725C2 (en) | 1999-04-15 | 1999-12-07 | Copper (i)-organic compounds and method of copper film precipitation by their using |
| TW088122014A TW524881B (en) | 1999-04-15 | 1999-12-15 | An organocuprous compound and a process for depositing a copper film on a substrate |
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| KR1019990013236A KR100298125B1 (en) | 1999-04-15 | 1999-04-15 | Organocuprous precursors for chemical deposition of copper |
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| EP (1) | EP1102872A4 (en) |
| JP (1) | JP2002542397A (en) |
| KR (1) | KR100298125B1 (en) |
| CN (1) | CN1194117C (en) |
| RU (1) | RU2181725C2 (en) |
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| KR100347838B1 (en) * | 2000-03-07 | 2002-08-07 | 학교법인 포항공과대학교 | Process for improving the thermal stability of liquid organocuprous precursors |
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| UA78180C2 (en) * | 1997-10-03 | 2007-03-15 | Меріаль | Porcine circovirus, vaccines and diagnostic reagents |
| KR100358045B1 (en) * | 1999-12-22 | 2002-10-25 | 주식회사 하이닉스반도체 | Method of forming a copper wiring in a semiconductor device |
| KR100338112B1 (en) * | 1999-12-22 | 2002-05-24 | 박종섭 | Method of forming a copper wiring in a semiconductor device |
| DE10228050A1 (en) * | 2002-06-24 | 2004-01-15 | Merck Patent Gmbh | Dikupfer (I) oxolate complexes as precursor substances for metallic copper deposition |
| DE10319454A1 (en) * | 2003-04-29 | 2004-11-18 | Merck Patent Gmbh | Dikupfer (I) oxalate complexes as a precursor for metallic copper deposition |
| EP1811059B1 (en) * | 2004-09-27 | 2012-10-31 | Ulvac, Inc. | Process for formation of copper-containing film |
| DE102009023952A1 (en) | 2009-06-04 | 2010-12-09 | DüRR DENTAL AG | Method for determining tooth color of e.g. dental prosthesis, involves providing difference between color values of images and tooth color pattern as measurement for correlating colors of tooth region and tooth color pattern |
| CN103298971B (en) * | 2010-11-17 | 2015-07-08 | Up化学株式会社 | Diazadiene-based metal compound, method for preparing same and method for forming a thin film using same |
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| US5144049A (en) * | 1991-02-04 | 1992-09-01 | Air Products And Chemicals, Inc. | Volatile liquid precursors for the chemical vapor deposition of copper |
| US5187300A (en) * | 1991-02-04 | 1993-02-16 | Air Products And Chemicals, Inc. | Volatile precursors for copper CVD |
| US5358743A (en) * | 1992-11-24 | 1994-10-25 | University Of New Mexico | Selective and blanket chemical vapor deposition of Cu from (β-diketonate)Cu(L)n by silica surface modification |
| JP3282392B2 (en) * | 1994-08-10 | 2002-05-13 | 三菱マテリアル株式会社 | Organocopper compounds for copper thin film formation by metalorganic chemical vapor deposition with high vapor pressure |
| US5744192A (en) * | 1996-11-08 | 1998-04-28 | Sharp Microelectronics Technology, Inc. | Method of using water vapor to increase the conductivity of cooper desposited with cu(hfac)TMVS |
| US6090963A (en) * | 1998-11-10 | 2000-07-18 | Sharp Laboratories Of America, Inc. | Alkene ligand precursor and synthesis method |
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| KR100347838B1 (en) * | 2000-03-07 | 2002-08-07 | 학교법인 포항공과대학교 | Process for improving the thermal stability of liquid organocuprous precursors |
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| TW524881B (en) | 2003-03-21 |
| CN1290309A (en) | 2001-04-04 |
| CN1194117C (en) | 2005-03-23 |
| KR100298125B1 (en) | 2001-09-13 |
| EP1102872A4 (en) | 2008-04-30 |
| RU2181725C2 (en) | 2002-04-27 |
| JP2002542397A (en) | 2002-12-10 |
| EP1102872A1 (en) | 2001-05-30 |
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