KR20240104681A - Surface protector of thin film and deposition method of thin film using the same - Google Patents
Surface protector of thin film and deposition method of thin film using the same Download PDFInfo
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- 239000010409 thin film Substances 0.000 title claims description 165
- 238000000151 deposition Methods 0.000 title description 19
- 230000001012 protector Effects 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims description 77
- 238000000034 method Methods 0.000 claims description 66
- 230000008569 process Effects 0.000 claims description 55
- 230000002401 inhibitory effect Effects 0.000 claims description 51
- 239000000758 substrate Substances 0.000 claims description 30
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 239000002243 precursor Substances 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 18
- 230000009036 growth inhibition Effects 0.000 claims description 16
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 15
- 238000010926 purge Methods 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 5
- 229910052710 silicon Inorganic materials 0.000 abstract description 5
- 239000010703 silicon Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- ASLHVQCNFUOEEN-UHFFFAOYSA-N dioxomolybdenum;dihydrochloride Chemical compound Cl.Cl.O=[Mo]=O ASLHVQCNFUOEEN-UHFFFAOYSA-N 0.000 abstract 2
- BQBYSLAFGRVJME-UHFFFAOYSA-L molybdenum(2+);dichloride Chemical compound Cl[Mo]Cl BQBYSLAFGRVJME-UHFFFAOYSA-L 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 238000000859 sublimation Methods 0.000 abstract 1
- 230000008022 sublimation Effects 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 25
- 238000004458 analytical method Methods 0.000 description 12
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 9
- 230000008859 change Effects 0.000 description 9
- 230000008021 deposition Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- MXVFWIHIMKGTFU-UHFFFAOYSA-N C1=CC=CC1[Hf] Chemical compound C1=CC=CC1[Hf] MXVFWIHIMKGTFU-UHFFFAOYSA-N 0.000 description 8
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(iv) oxide Chemical compound O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000000231 atomic layer deposition Methods 0.000 description 7
- 238000000427 thin-film deposition Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229910000449 hafnium oxide Inorganic materials 0.000 description 6
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 6
- 229910052814 silicon oxide Inorganic materials 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical compound C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000005137 deposition process Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 238000000572 ellipsometry Methods 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- -1 methyl-tertiary butyl Chemical group 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C23C16/04—Coating on selected surface areas, e.g. using masks
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
- C23C16/45534—Use of auxiliary reactants other than used for contributing to the composition of the main film, e.g. catalysts, activators or scavengers
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
본 발명은 고순도의 이염화이산화몰리브덴 및 이의 제조방법에 관한 것으로서, 상기 이염화이산화몰리브덴은 불순물 중 실리콘(Si)의 함량이 400 중량ppm 이하인 것을 특징으로 하며, 승화정제 공정을 포함하여 제조됨으로써 고순도 이염화이산화몰리브덴을 수득할 수 있다.The present invention relates to high purity molybdenum dichloride dioxide and a method for producing the same. The molybdenum dichloride dioxide is characterized in that the content of silicon (Si) among impurities is 400 ppm by weight or less, and is manufactured including a sublimation purification process to provide high purity. Molybdenum dichloride can be obtained.
Description
본 발명은 박막 성장 억제용 화합물 및 이를 이용한 박막 형성 방법에 관한 것으로서, 더욱 상세하게는, 고온 증착 공정에 적합한 특성을 가지며, 박막 성장 억제를 통해 박막 증착 두께를 제어하여서 단차 피복성을 향상시키고 공정 부산물을 저감시킬 수 있는 공정에 적합한 박막 성장 억제용 화합물 및 이를 이용한 박막 형성 방법에 관한 것이다.The present invention relates to a compound for inhibiting thin film growth and a method of forming a thin film using the same. More specifically, the present invention relates to a compound for inhibiting thin film growth and a method of forming a thin film using the same. More specifically, it has properties suitable for a high temperature deposition process and improves step coverage by controlling the thickness of thin film deposition through inhibiting thin film growth and improving step coverage during the process. It relates to a compound for inhibiting thin film growth suitable for a process capable of reducing by-products and a method of forming a thin film using the same.
최근에 금속, 금속 산화물, 금속 질화물 등의 박막을 형성하는 방법으로 원자층증착법(ALD)이 많이 적용되고 있다. ALD 공정은 통상의 화학기상증착(CVD) 공정에 비해 단차 피복성을 개선하고 공정 부산물을 저감시킬 수 있는 장점이 있으나, 반도체 공정이 미세화되면서 고품질의 박막을 제조할 수 있는 공정이 개발되고 있다.Recently, atomic layer deposition (ALD) has been widely used as a method of forming thin films of metals, metal oxides, and metal nitrides. The ALD process has the advantage of improving step coverage and reducing process by-products compared to a typical chemical vapor deposition (CVD) process, but as semiconductor processes are becoming more refined, processes that can produce high-quality thin films are being developed.
이러한 개선된 공정을 위하여 박막 형성 공정을 수행할 때 박막 성장을 억제할 수 있는 화합물을 사용하여 표면과 반응시켜 증착 회피 영역에 증착 억제층을 형성하는 표면 제어를 통해 박막 두께 제어, 박막 증착 위치 조절이 가능하여 고품질의 박막을 제조할 수 있게 된다.For this improved process, when performing the thin film formation process, a compound capable of inhibiting thin film growth is used to react with the surface to form a deposition inhibition layer in the deposition avoidance area, controlling the thin film thickness and controlling the thin film deposition position through surface control. This makes it possible to manufacture high-quality thin films.
이러한 박막 성장 억제용 화합물로는 실리콘 함유 박막의 경우 불소 가스를 적용하고 있으나, 다양한 박막 형성 공정에 대응할 수 있는 신규 화합물도 개발되고 있다. Fluorine gas is used as a compound for suppressing thin film growth in the case of silicon-containing thin films, but new compounds that can respond to various thin film formation processes are also being developed.
예를 들어, 대한민국 공개특허공보 10-2022-0136073호에서는 아세트산메틸(methyl acetate), 아세트산에틸(ethyl acetate), 프로피온산메틸(methyl propionate) 및 프로피온산에틸(ethyl propionate)과 같은 아세트산 화합물을 사용하여 박막 성장 억제층을 형성하고 있다. 또한, 대한민국 공개특허공보 10-2022-0136072호에서는 증착체와 배위 결합할 수 있는 금속 알콕사이드를 이용하고 있으며, 대한민국 공개특허공보 10-2021-0046235호, 대한민국 공개특허공보 10-2021-0027069호 등에서는 할로겐 화합물을 이용하여 박막 성장 억제층을 형성하고 있다.For example, in Korean Patent Publication No. 10-2022-0136073, acetic acid compounds such as methyl acetate, ethyl acetate, methyl propionate, and ethyl propionate are used to form thin films. It forms a growth inhibitory layer. In addition, in Korean Patent Publication No. 10-2022-0136072, a metal alkoxide capable of coordinating with the vapor deposit is used, and in Korean Patent Publication No. 10-2021-0046235, Korean Patent Publication No. 10-2021-0027069, etc. is forming a thin film growth inhibition layer using a halogen compound.
이러한 박막 성장 억제용 화합물을 적용하면 ALD 공정을 통해 고품질의 박막을 형성할 수 있으나, 고온 증착 공정에서는 증착체와 화합물의 안정적 결합이 어려워 사용이 제한적인 문제점이 있다.Applying such thin film growth inhibition compounds can form high-quality thin films through the ALD process, but there is a problem in that their use is limited due to the difficulty in stable bonding of the deposited body and the compound in the high-temperature deposition process.
본 발명은 상기와 같은 종래기술을 감안하여 안출된 것으로, 고온 박막 형성 공정에서 박막 성장 억제층을 형성하여 박막의 성장 두께를 제어하고 고품질의 박막을 형성할 수 있도록 하는 박막 성장 억제용 화합물 및 이를 이용한 박막 형성 방법을 제공하는 것을 그 목적으로 한다.The present invention was developed in consideration of the above-described prior art, and includes a compound for inhibiting thin film growth that forms a thin film growth inhibiting layer in a high-temperature thin film forming process to control the growth thickness of the thin film and form a high-quality thin film, and the same. The purpose is to provide a thin film formation method using the present invention.
상기와 같은 목적을 달성하기 위한 본 발명의 박막 성장 억제용 화합물은 기판의 표면에 금속 함유 전구체 및 반응성 가스를 도입하여 박막을 형성 공정에서, 상기 기판의 표면에 형성된 증착체와 결합하여 박막 성장을 억제하는 화합물로서, 분해온도가 300℃ 이상이며, 상기 증착체와 배위 결합하는 배위결합형 또는 상기 증착체와 반응하는 반응형 박막 성장 억제용 화합물인 것을 특징으로 한다.In order to achieve the above object, the compound for inhibiting thin film growth of the present invention combines with the deposit formed on the surface of the substrate in the process of forming a thin film by introducing a metal-containing precursor and a reactive gas to the surface of the substrate to promote thin film growth. The inhibitory compound has a decomposition temperature of 300°C or higher and is characterized as being a coordination type that coordinates with the deposited body or a reactive thin film growth inhibiting compound that reacts with the deposited body.
이때, 상기 배위결합형 박막 성장 억제용 화합물은 화학식 1 또는 2로 표시되는 화합물일 수 있다.At this time, the compound for inhibiting the growth of a coordination type thin film may be a compound represented by Formula 1 or 2.
[화학식 1][Formula 1]
[화학식 2][Formula 2]
상기 화학식 1 및 2에서 R1 내지 R2는 각각 독립적으로 C1 내지 C6의 직쇄형, 분지형, 또는 고리형 탄화수소이며, R3 내지 R5는 각각 독립적으로 수소원자, C1 내지 C3의 직쇄형, 분지형, 또는 고리형 탄화수소이며, 화학식 2에서 n, m은 각각 독립적으로 1 내지 3 중 어느 하나의 정수이다.In Formulas 1 and 2, R 1 to R 2 are each independently a C 1 to C 6 straight-chain, branched, or cyclic hydrocarbon, and R 3 to R 5 are each independently a hydrogen atom, C 1 to C 3 It is a straight-chain, branched, or cyclic hydrocarbon, and in Formula 2, n and m are each independently an integer of 1 to 3.
또한, 상기 반응형 박막 성장 억제용 화합물은 화학식 3, 4 또는 5로 표시되는 화합물일 수 있다.Additionally, the compound for inhibiting the growth of a reactive thin film may be a compound represented by Formula 3, 4, or 5.
[화학식 3][Formula 3]
[화학식 4][Formula 4]
[화학식 5][Formula 5]
상기 화학식 3에서 R1 내지 R2는 각각 독립적으로 C1 내지 C3의 직쇄형, 분지형, 또는 고리형 탄화수소이며, R3 내지 R4는 각각 독립적으로 수소원자, C1 내지 C3의 직쇄형, 분지형, 또는 고리형 탄화수소이며, n은 1 내지 3 중 어느 하나의 정수이며, 상기 화학식 4 및 5에서 R1 내지 R2는 각각 독립적으로 C1 내지 C3의 직쇄형, 분지형, 또는 고리형 탄화수소이다.In Formula 3, R 1 to R 2 are each independently a straight-chain, branched, or cyclic hydrocarbon of C 1 to C 3 , and R 3 to R 4 are each independently a hydrogen atom or a straight hydrocarbon of C 1 to C 3 . It is a chain, branched, or cyclic hydrocarbon, n is any integer of 1 to 3, and in Formulas 4 and 5, R 1 to R 2 are each independently C 1 to C 3 straight chain, branched, Or it is a cyclic hydrocarbon.
또한, 본 발명의 박막 형성 방법은 챔버 내에 기판을 위치시키는 단계, 상기 챔버 내에 상기 박막 성장 억제용 화합물을 공급하는 단계, 상기 챔버 내부를 퍼징하고 금속 전구체를 공급하는 단계, 상기 챔버 내부를 퍼징하고 반응성 기체를 공급하는 단계를 포함하는 것을 특징으로 한다.In addition, the thin film forming method of the present invention includes the steps of placing a substrate in a chamber, supplying a compound for inhibiting thin film growth in the chamber, purging the inside of the chamber and supplying a metal precursor, purging the inside of the chamber, and It is characterized by comprising the step of supplying a reactive gas.
또한, 상기 박막 형성 방법의 ALD 윈도우는 350 내지 400℃일 수 있다.Additionally, the ALD window of the thin film forming method may be 350 to 400°C.
본 발명에 따른 박막 성장 억제용 화합물은 고온 박막 형성 공정에 적용할 수 있으며, 박막 성장 억제층을 형성하여 박막의 성장 두께를 제어하고 고품질의 박막을 형성하는 효과를 나타낸다.The compound for inhibiting thin film growth according to the present invention can be applied to a high-temperature thin film forming process, and forms a thin film growth inhibiting layer to control the growth thickness of the thin film and form a high-quality thin film.
도 1은 배위결합형 박막 성장 억제용 화합물(a) 및 반응형 박막 성장 억제용 화합물(b)이 기판 표면에서 증착체와 반응하는 과정을 도시한 개념도이다.
도 2는 CpHf을 이용한 HfO2 박막 증착 시 C-2-4를 350℃(a), 370℃(b), 및 400℃(c) 조건에서의 공급 시간(feeding time) 변화에 따른 HfO2 박막 증착 두께 변화를 측정한 결과이다.
도 3은 CpHf을 이용한 HfO2 박막 증착 시 C-2-4를 350℃(a), 370℃(b), 및 400℃(c) 조건에서의 적용한 퍼지 시간(purge time) 변화에 따른 HfO2 박막 증착 두께 변화를 측정한 결과이다.
도 4는 CpHf을 이용한 HfO2 박막 증착시 C-2-4를 350℃(a), 400℃(b) 조건에서 적용하여 증착한 HfO2 박막의 XPS 분석 결과이다.
도 5는 CpHf을 이용한 HfO2 박막 증착시 R-1-2를 350℃(a), 370℃(b), 및 400℃(c) 조건에서의 적용한 공급 시간(feeding time) 변화에 따른 HfO2 박막 증착 두께 변화를 측정한 결과이다.
도 6은 CpHf을 이용한 HfO2 박막 증착시 R-1-2를 350℃(a), 400℃(b) 조건에서 적용하여 증착 한 HfO2 박막의 XPS 분석 결과이다.
도 7은 CpHf을 이용한 HfO2 박막 증착시 R-1-1을 350℃(a), 400℃(b) 조건에서 적용하여 증착 한 HfO2 박막의 XPS 분석 결과이다.
도 8는 TMA을 이용한 Al2O3 박막 증착시 C-2-4, R-1-1, R-1-2를 350℃ 0.02Torr 조건에서 적용에 따른 Al2O3 박막 증착 두께 변화를 측정한 결과이다.
도 9은 TMA을 이용한 Al2O3 박막 증착시 R-1-2를 350℃ 조건에서의 적용한 공급 시간(feeding time) 변화에 따른 Al2O3 박막 증착 두께 변화를 측정한 결과이다.
도 10은 CpHf을 이용한 HfO2 박막 증착시 C-2-7을 350℃(a), 400℃(b) 조건에서 적용하여 증착 한 HfO2 박막의 XPS 분석 결과이다.Figure 1 is a conceptual diagram showing the process in which a compound for inhibiting the growth of a coordination type thin film (a) and a compound for inhibiting the growth of a reactive thin film (b) react with a deposited body on the surface of a substrate.
Figure 2 shows the HfO 2 thin film according to the change in feeding time of C-2-4 at 350°C (a), 370°C (b), and 400°C (c) conditions when depositing the HfO 2 thin film using CpHf. This is the result of measuring the change in deposition thickness.
Figure 3 shows HfO 2 according to the change in purge time applied to C-2-4 under conditions of 350°C (a), 370°C (b), and 400°C (c) when depositing a HfO 2 thin film using CpHf. This is the result of measuring the change in thin film deposition thickness.
Figure 4 shows the XPS analysis results of the HfO 2 thin film deposited by applying C-2-4 at 350°C (a) and 400°C (b) when depositing the HfO 2 thin film using CpHf.
Figure 5 shows HfO 2 according to the change in feeding time applied to R-1-2 under conditions of 350°C (a), 370°C (b), and 400°C (c) when depositing a HfO 2 thin film using CpHf. This is the result of measuring the change in thin film deposition thickness.
Figure 6 shows the XPS analysis results of the HfO 2 thin film deposited by applying R-1-2 under conditions of 350°C (a) and 400°C (b) when depositing the HfO 2 thin film using CpHf.
Figure 7 shows the XPS analysis results of the HfO 2 thin film deposited by applying R-1-1 at 350°C (a) and 400°C (b) when depositing the HfO 2 thin film using CpHf.
Figure 8 measures the change in Al 2 O 3 thin film deposition thickness according to application of C-2-4, R-1-1, and R-1-2 at 350°C and 0.02 Torr when depositing Al 2 O 3 thin film using TMA. It is a result.
Figure 9 shows the results of measuring the change in Al 2 O 3 thin film deposition thickness according to the change in feeding time when R-1-2 was applied at 350°C when depositing Al 2 O 3 thin film using TMA.
Figure 10 shows the XPS analysis results of the HfO 2 thin film deposited by applying C-2-7 under conditions of 350°C (a) and 400°C (b) when depositing the HfO 2 thin film using CpHf.
이하 본 발명을 보다 상세히 설명한다. 본 명세서 및 청구범위에 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.Hereinafter, the present invention will be described in more detail. Terms or words used in this specification and claims should not be construed as limited to their common or dictionary meanings, and the inventor may appropriately define the concept of terms in order to explain his or her invention in the best way. It must be interpreted with meaning and concept consistent with the technical idea of the present invention based on the principle that it is.
일반적인 박막 형성 공정은 기판의 표면에 금속 함유 전구체 및 반응성 가스를 도입하여 박막을 형성하게 되며, 상기 금속 함유 전구체가 기판에 흡착한 후 상기 반응성 가스와 반응함으로써 기판 상에 박막을 형성하게 된다. 이 과정에서 기판 상에 금속 함유 전구체의 의한 증착체나 표면에 흡착한 금속과 반응성 가스의 반응에 의한 증착체가 형성되는데, 본 발명의 박막 성장 억제용 화합물은 상기 박막 형성 공정 중에서 상기 기판의 표면에 형성된 증착체와 결합하여 박막 성장을 억제하는 화합물이다. 본 발명의 박막 성장 억제용 화합물은 분해온도가 300℃ 이상으로 고온 박막 형성 공정에 사용할 수 있다. A typical thin film formation process forms a thin film by introducing a metal-containing precursor and a reactive gas to the surface of a substrate, and the metal-containing precursor adsorbs to the substrate and reacts with the reactive gas to form a thin film on the substrate. In this process, a deposit is formed on the substrate by a metal-containing precursor or by a reaction between a metal adsorbed on the surface and a reactive gas. The compound for inhibiting thin film growth of the present invention is formed on the surface of the substrate during the thin film formation process. It is a compound that binds to the deposited material and inhibits thin film growth. The compound for inhibiting thin film growth of the present invention has a decomposition temperature of 300°C or higher and can be used in a high temperature thin film forming process.
상기 박막 성장 억제용 화합물은 상기 증착체와 배위 결합하는 배위결합형 또는 상기 증착체와 반응하는 반응형 박막 성장 억제용 화합물일 수 있다. 도 1을 참조하여 상기 박막 성장 억제용 화합물을 설명하면, 배위결합형 화합물은 도 1(a)와 같이 기판 상에 흡착한 금속과 배위 결합을 형성하여 박막 성장 억제층을 형성하게 되는데, 박막 성장 억제용 화합물의 크기로 인해 충분한 차단 효과를 나타낼 수 있다. 또한, 반응형 박막 성장 억제용 화합물은 도 1(b)에서와 같이 기판에 흡착된 금속과 결합한 산소 원자와 반응하여 결합을 형성하는데, 예를 들어, 기판 표면에 흡착한 금속 수산화물의 수산기와 반응함으로써 상기와 같은 산소-화합물 결합을 형성할 수 있다. 이는 고온의 오존(O3) 분위기 하에서 차단 효과를 저감시킬 수도 있지만, 일반적인 고온 공정에서 유효하게 적용될 수 있다.The thin film growth inhibiting compound may be a coordination type that coordinates with the deposited body or a reactive thin film growth inhibiting compound that reacts with the deposited body. When explaining the thin film growth inhibition compound with reference to FIG. 1, the coordination compound forms a coordination bond with the metal adsorbed on the substrate as shown in FIG. 1(a) to form a thin film growth inhibition layer. Due to the size of the inhibitory compound, it can exhibit sufficient blocking effect. In addition, the reactive thin film growth inhibition compound reacts with the oxygen atom bonded to the metal adsorbed on the substrate to form a bond, as shown in Figure 1(b). For example, it reacts with the hydroxyl group of the metal hydroxide adsorbed on the substrate surface. By doing so, the oxygen-compound bond as described above can be formed. This may reduce the blocking effect under a high temperature ozone (O 3 ) atmosphere, but can be effectively applied in general high temperature processes.
상기 배위결합형 박막 성장 억제용 화합물은 화학식 1 또는 2로 표시되는 화합물일 수 있다.The compound for inhibiting the growth of a coordination-type thin film may be a compound represented by Formula 1 or 2.
[화학식 1][Formula 1]
[화학식 2][Formula 2]
상기 화학식 1 및 2에서 R1 내지 R2는 각각 독립적으로 C1 내지 C6의 직쇄형, 분지형, 또는 고리형 탄화수소이며, R3 내지 R5는 각각 독립적으로 수소원자, C1 내지 C3의 직쇄형, 분지형, 또는 고리형 탄화수소이며, 화학식 2에서 n, m은 각각 독립적으로 1 내지 3 중 어느 하나의 정수이다.In Formulas 1 and 2, R 1 to R 2 are each independently a C 1 to C 6 straight-chain, branched, or cyclic hydrocarbon, and R 3 to R 5 are each independently a hydrogen atom, C 1 to C 3 It is a straight-chain, branched, or cyclic hydrocarbon, and in Formula 2, n and m are each independently an integer of 1 to 3.
또한, 상기 반응형 박막 성장 억제용 화합물은 화학식 3, 4 또는 5로 표시되는 화합물일 수 있다.Additionally, the compound for inhibiting the growth of a reactive thin film may be a compound represented by Formula 3, 4, or 5.
상기 화합물은 산소 원자를 포함하는 화학구조를 가지며 상기 산소 원자와 기판 표면에 흡착한 금속 원자 사이에 배위 결합을 형성함으로써 결합 상태를 형성할 수 있게 된다.The compound has a chemical structure containing an oxygen atom and can form a bonded state by forming a coordination bond between the oxygen atom and the metal atom adsorbed on the surface of the substrate.
상기 화학식 1 및 2로 표시되는 화합물의 예시적 화합물로는 표 1과 같은 화합물을 들 수 있다.Exemplary compounds of the compounds represented by Formulas 1 and 2 include those shown in Table 1.
표 1의 화합물은 끓는점(b.p.)가 증착 온도에 비해 낮아 기화하여 기판 상에 공급할 수 있으며, 증착체와는 배위 결합을 형성할 수 있으므로 효과적인 박막 성장 억제층을 형성할 수 있다.The compounds in Table 1 have a boiling point (b.p.) lower than the deposition temperature, so they can be vaporized and supplied on the substrate, and can form coordination bonds with the deposited body, forming an effective thin film growth inhibition layer.
또한, 상기 반응형 박막 성장 억제용 화합물은 화학식 3, 4 또는 5로 표시되는 화합물일 수 있다.Additionally, the compound for inhibiting the growth of a reactive thin film may be a compound represented by Formula 3, 4, or 5.
[화학식 3][Formula 3]
[화학식 4][Formula 4]
[화학식 5][Formula 5]
상기 화학식 3에서 R1 내지 R2는 각각 독립적으로 C1 내지 C3의 직쇄형, 분지형, 또는 고리형 탄화수소이며, R3 내지 R4는 각각 독립적으로 수소원자, C1 내지 C3의 직쇄형, 분지형, 또는 고리형 탄화수소이며, n은 1 내지 3 중 어느 하나의 정수이며, 상기 화학식 4 및 5에서 R1 내지 R2는 각각 독립적으로 C1 내지 C3의 직쇄형, 분지형, 또는 고리형 탄화수소이다.In Formula 3, R 1 to R 2 are each independently a straight-chain, branched, or cyclic hydrocarbon of C 1 to C 3 , and R 3 to R 4 are each independently a hydrogen atom or a straight hydrocarbon of C 1 to C 3 . It is a chain, branched, or cyclic hydrocarbon, n is any integer of 1 to 3, and in Formulas 4 and 5, R 1 to R 2 are each independently C 1 to C 3 straight chain, branched, Or it is a cyclic hydrocarbon.
상기 화학식 3 내지 5로 표시되는 화합물의 예시적 화합물로는 표 2와 같은 화합물을 들 수 있다.Exemplary compounds of the formulas 3 to 5 include those shown in Table 2.
표 2의 화합물 또한 기화하여 기판 상에 공급할 수 있으며, 증착체와는 화학적으로 결합을 형성할 수 있으므로 효과적인 박막 성장 억제층을 형성할 수 있다.The compounds in Table 2 can also be vaporized and supplied on the substrate, and can form a chemical bond with the deposited material, forming an effective thin film growth inhibition layer.
상기 박막 성장 억제용 화합물을 적용한 박막 형성 방법은 챔버 내에 기판을 위치시키는 단계, 상기 챔버 내에 상기 박막 성장 억제용 화합물을 공급하는 단계, 상기 챔버 내부를 퍼징하고 금속 전구체를 공급하는 단계, 상기 챔버 내부를 퍼징하고 반응성 기체를 공급하는 단계를 포함하는 것일 수 있다.A method of forming a thin film using the compound for inhibiting thin film growth includes placing a substrate in a chamber, supplying the compound for inhibiting thin film growth into the chamber, purging the inside of the chamber and supplying a metal precursor, and supplying a metal precursor to the inside of the chamber. It may include purging and supplying a reactive gas.
즉, 박막 성장 억제용 화합물을 박막 형성용 금속 함유 전구체를 기판 표면에 흡착시키기 전에 먼저 흡착시켜 기판 표면을 보호할 수 있는데, 이 경우, 박막 형성 시 반응성 가스와 반응하여 발생되는 공정 부산물이 상기 박막 성장 억제용 화합물과 함께 제거됨으로써 기판의 부식이나 열화를 방지하고 사이클당 박막 성장률을 적절히 낮추어 단차 피복성 및 박막 두께의 균일성을 개선시킬 수 있게 된다. 또한, 원하는 두께의 박막을 증착하기 위해서 저감된 증착률에 따른 사이클당 박막 성장률을 감안하여 박막 형성 공정의 단위 사이클을 적절하게 선택하여서 수행할 수 있다.In other words, the substrate surface can be protected by first adsorbing the compound for inhibiting thin film growth before adsorbing the metal-containing precursor for forming the thin film to the surface of the substrate. In this case, the process by-products generated by reacting with the reactive gas during the formation of the thin film are the thin film. By being removed along with the growth inhibition compound, corrosion or deterioration of the substrate can be prevented and the thin film growth rate per cycle can be appropriately lowered to improve step coverage and thin film thickness uniformity. In addition, in order to deposit a thin film of a desired thickness, the unit cycle of the thin film formation process can be appropriately selected and performed by taking into account the thin film growth rate per cycle according to the reduced deposition rate.
상기와 같은 공정을 통해 제조되는 박막은 300℃ 이상, 바람직하게는 350℃ 이상의 고온 공정을 통해 제조되는데, 본 발명의 박막 형성 방법을 적용하는 ALD 공정에서는 ALD 윈도우는 300 내지 450℃, 바람직하게는 300 내지 450℃인 조건에서 공정을 수행할 수 있다.The thin film manufactured through the above process is manufactured through a high temperature process of 300°C or higher, preferably 350°C or higher. In the ALD process applying the thin film forming method of the present invention, the ALD window is 300 to 450°C, preferably The process can be performed under conditions of 300 to 450°C.
상기 박막 형성 공정을 위한 기판으로는 유리, 실리콘, 실리콘 산화물, 실리콘 질화막 등의 실리콘 함유 박막 및 급속 산화막, 금속 질화막 등의 금속 함유 박막을 사용할 수 있고, 실리콘 또는 실리콘 산화물의 반도체용 기판을 사용할 수 있다. 또한, 상기 박막을 형성하는 금속으로는 2족, 3족, 4족, 5족, 6족, 7족, 또는 8족 금속을 적용할 수 있다.As a substrate for the thin film formation process, silicon-containing thin films such as glass, silicon, silicon oxide, and silicon nitride films and metal-containing thin films such as rapid oxidation films and metal nitride films can be used, and silicon or silicon oxide semiconductor substrates can be used. there is. Additionally, the metal forming the thin film may be a Group 2, 3, 4, 5, 6, 7, or 8 metal.
이하, 실시예를 통하여 본 발명의 박막 성장 억제용 화합물을 공정에 적용할 때의 효과를 설명한다.Hereinafter, the effect of applying the compound for inhibiting thin film growth of the present invention to a process will be explained through examples.
[공정예 1][Process Example 1]
박막 성장 억제용 화합물로 에틸렌글리콜디에틸에테르(C-2-4)를 사용하여 박막 형성 공정을 수행하였다. 박막 형성용 전구체로는 사이클로펜타디에닐 하프늄(CpHf)을 사용하였으며 반응성 가스로는 오존을 사용하였다. 증착 온도는 300℃ 이상이며, 산화실리콘(SiO2) 기판 상에 하프늄 산화물 박막을 형성하되 50사이클 공정을 수행하였다.A thin film formation process was performed using ethylene glycol diethyl ether (C-2-4) as a compound for inhibiting thin film growth. Cyclopentadienyl hafnium (CpHf) was used as a precursor for thin film formation, and ozone was used as a reactive gas. The deposition temperature was above 300°C, and a 50-cycle process was performed to form a hafnium oxide thin film on a silicon oxide (SiO 2 ) substrate.
타원편광반사법(ellipsometry)을 이용하여 기판 상의 하프늄 산화물 박막의 두께를 측정한 결과 도 2(a)와 같이 박막 성장 억제용 화합물을 공급하지 않은 경우 박막 두께가 350℃에서 43Å이었다. C-2-4 박막 성장 억제용 화합물을 각각 350℃, 370℃, 400℃에서 공급시간 1초, 3초, 5초로 박막 형성 공정을 수행하였으며, 1초에서부터 약 39% GPC 감소율로 안정화되었다(도 2). As a result of measuring the thickness of the hafnium oxide thin film on the substrate using ellipsometry, the thin film thickness was 43 Å at 350°C when a compound for inhibiting thin film growth was not supplied, as shown in FIG. 2(a). The thin film formation process was performed with the C-2-4 thin film growth inhibition compound at 350°C, 370°C, and 400°C, respectively, with supply times of 1 second, 3 seconds, and 5 seconds, and stabilized at a GPC reduction rate of about 39% from 1 second ( Figure 2).
또한, C-2-4 박막 성장 억제용 화합물을 각각 350℃, 370℃, 400℃에서 박막 성장 억제용 화합물의 퍼지 시간을 30초, 60초, 90초로 박막 형성 공정을 수행하였으며, 박막 성자 억제용 화합물의 퍼지 30초에서부터 약 41% GPC 감소율로 안정화되었다(도 3).In addition, the thin film formation process was performed with the C-2-4 thin film growth inhibition compound at 350℃, 370℃, and 400℃, respectively, with purge times of 30 seconds, 60 seconds, and 90 seconds, and thin film growth inhibition was performed. From 30 seconds of purge of the compound, the GPC reduction rate stabilized at about 41% (Figure 3).
또한, 박막 형성용 전구체로는 사이클로펜타디에닐 하프늄(CpHf)과 반응성 가스로는 오존, 박막 성장 억제용 화합물로 에틸렌글리콜디에틸에테르(C-2-4)을 사용하여 형성한 박막의 불순물 조성을 확인하기 위하여 350℃, 400℃ 공정조건에서 실험 박막을 XPS를 사용하여 조성분석을 진행하였다. 분석 결과, 도 4와 같이 350℃, 400℃ 박막에서 하프늄다이옥사이드가 형성이 되었으며, 질소와 탄소 원소는 검출되지 않았다.In addition, the impurity composition of the thin film formed using cyclopentadienyl hafnium (CpHf) as a precursor for thin film formation, ozone as a reactive gas, and ethylene glycol diethyl ether (C-2-4) as a compound for inhibiting thin film growth was confirmed. To this end, composition analysis was performed using XPS on the experimental thin films under process conditions of 350°C and 400°C. As a result of the analysis, as shown in Figure 4, hafnium dioxide was formed in the thin film at 350°C and 400°C, and nitrogen and carbon elements were not detected.
[공정예 2] [Process Example 2]
박막 성장 억제용 화합물로 디메틸카보네이트(R-1-2)를 사용하여 박막 형성 공정을 수행하였다. 박막 형성용 전구체로는 사이클로펜타디에닐 하프늄(CpHf)을 사용하였으며 반응성 가스로는 오존을 사용하였다. 증착 온도는 300℃ 이상이며, 산화실리콘(SiO2) 기판 상에 하프늄 산화물 박막을 형성하되 50사이클 공정을 수행하였다.A thin film formation process was performed using dimethyl carbonate (R-1-2) as a compound for inhibiting thin film growth. Cyclopentadienyl hafnium (CpHf) was used as a precursor for thin film formation, and ozone was used as a reactive gas. The deposition temperature was above 300°C, and a 50-cycle process was performed to form a hafnium oxide thin film on a silicon oxide (SiO 2 ) substrate.
타원편광반사법(ellipsometry)을 이용하여 기판 상의 하프늄 산화물 박막의 두께를 측정한 결과 도 5(a)와 같이 박막 성장 억제용 화합물을 공급하지 않은 경우 박막 두께가 350℃에서 44Å이었다. R-1-2 박막 성장 억제용 화합물을 각각 350℃, 370℃, 400℃에서 공급시간 1초, 3초, 5초, 10초로 박막 형성 공정을 수행하였으며, 350℃, 370℃, 400℃ 공정온도에서 1초부터 약 63%의 GPC 감소율이 확인되었다(도 5),As a result of measuring the thickness of the hafnium oxide thin film on the substrate using ellipsometry, the thin film thickness was 44 Å at 350°C when a compound for inhibiting thin film growth was not supplied, as shown in FIG. 5(a). The thin film formation process was performed with the R-1-2 thin film growth inhibition compound at 350℃, 370℃, and 400℃ with supply times of 1 second, 3 seconds, 5 seconds, and 10 seconds, respectively, and the 350℃, 370℃, and 400℃ processes. A GPC reduction rate of approximately 63% was confirmed from 1 second at temperature (Figure 5).
또한, 박막 형성용 전구체로는 사이클로펜타디에닐 하프늄(CpHf)과 반응성 가스로는 오존, 박막 성장 억제용 화합물로 디메틸카보네이트(R-1-2)을 사용하여 형성한 박막의 불순물 조성을 확인하기 위하여 350℃, 400℃ 공정조건에서 실험 박막을 XPS를 사용하여 조성분석을 진행하였다. 분석 결과 도 6과 같이 350℃, 400℃ 박막에서 하프늄다이옥사이드가 형성이 되었으며, 질소와 탄소 원소는 검출되지 않았다.In addition, to confirm the impurity composition of the thin film formed using cyclopentadienyl hafnium (CpHf) as a precursor for thin film formation, ozone as a reactive gas, and dimethyl carbonate (R-1-2) as a compound for inhibiting thin film growth, 350 Composition analysis of the experimental thin films was performed using XPS under process conditions of ℃ and 400℃. As a result of the analysis, as shown in Figure 6, hafnium dioxide was formed in the thin film at 350°C and 400°C, and nitrogen and carbon elements were not detected.
[공정예 3][Process Example 3]
박막 성장 억제용 화합물로 2,3-다이하이드로피란(R-1-1)를 사용하여 박막 형성 공정을 수행하였다. 박막 형성용 전구체로는 사이클로펜타디에닐 하프늄(CpHf)을 사용하였으며 반응성 가스로는 오존을 사용하였다. 증착 온도는 300℃ 이상이며, 산화실리콘(SiO2) 기판 상에 하프늄 산화물 박막을 형성하되 50사이클 공정을 수행하였다. A thin film formation process was performed using 2,3-dihydropyran (R-1-1) as a compound for inhibiting thin film growth. Cyclopentadienyl hafnium (CpHf) was used as a precursor for thin film formation, and ozone was used as a reactive gas. The deposition temperature was above 300°C, and a 50-cycle process was performed to form a hafnium oxide thin film on a silicon oxide (SiO 2 ) substrate.
박막 형성용 전구체로는 사이클로펜타디에닐 하프늄(CpHf)과 반응성 가스로는 오존, 박막 성장 억제용 화합물로 2,3-다이하이드로피란(R-1-1)을 사용하여 형성한 박막의 불순물 조성을 확인하기 위하여 350℃, 400℃ 공정조건에서 실험 박막을 XPS를 사용하여 조성 분석을 진행하였다. 분석 결과 도 7과 같이 350℃, 400℃ 박막에서 하프늄다이옥사이드가 형성이 되었으며, 질소와 탄소 원소는 검출되지 않았다.Confirm the impurity composition of the thin film formed using cyclopentadienyl hafnium (CpHf) as a precursor for thin film formation, ozone as a reactive gas, and 2,3-dihydropyran (R-1-1) as a compound for inhibiting thin film growth. To this end, composition analysis was performed using XPS on the experimental thin films under process conditions of 350°C and 400°C. As a result of the analysis, as shown in Figure 7, hafnium dioxide was formed in the thin film at 350°C and 400°C, and nitrogen and carbon elements were not detected.
[공정예 4] [Process Example 4]
박막 성장 억제용 화합물로 에틸렌글리콜디에틸에테르(C-2-4), 디메틸카보네이트(R-1-2), 2,3-다이하이드로피란(R-1-1) 박막 형성용 전구체로 트리메틸알루미늄(TMA)을 사용하여 증착 실험을 실시하였다. 350℃ 공정 온도에서 각 박막 성장 억제용 화합물의 따른 성장 억제를 도 8과 같이 확인하였다. Al2O3 박막을 형성함에 있어 성장 억제용 화합물로 디메틸카보네이트(R-1-2)는 약 45% GPC 감소율이 확인되었다.Compounds for inhibiting thin film growth include ethylene glycol diethyl ether (C-2-4), dimethyl carbonate (R-1-2), and 2,3-dihydropyran (R-1-1), and trimethyl aluminum as a precursor for thin film formation. Deposition experiments were performed using (TMA). The growth inhibition of each thin film growth inhibition compound at a process temperature of 350°C was confirmed as shown in FIG. 8. Dimethyl carbonate (R-1-2), a growth-inhibiting compound in forming an Al 2 O 3 thin film, was confirmed to have a GPC reduction rate of about 45%.
R-1-2 박막 성장 억제용 화합물을 도 9와 같이 각 350℃ 공정 온도에서 박막 성장 억제용 화합물의 공급 시간을 도 3과 같이 1초, 3초, 5초, 10초로 박막 형성 공정을 수행한 결과 1초에서부터 약 45% GPC 감소율로 안정화되었다. R-1-2 A thin film formation process was performed for supplying the compound for inhibiting thin film growth at a process temperature of 350°C as shown in FIG. 9 with supply times of 1 second, 3 seconds, 5 seconds, and 10 seconds as shown in FIG. 3. As a result, the GPC reduction rate was stabilized at about 45% from 1 second.
[공정예 5][Process Example 5]
박막 성장 억제용 화합물로 메틸터셔리부틸이서(C-2-7)를 사용하여 박막 형성 공정을 수행하였다. 박막 형성용 전구체로는 사이클로펜타디에닐 하프늄(CpHf)을 사용하였으며 반응성 가스로는 오존을 사용하였다. 350℃, 400℃ 온도 조건에서, 산화실리콘(SiO2) 기판 상에 하프늄 산화물 박막을 형성하되 50사이클 공정을 수행하였다.A thin film formation process was performed using methyl-tertiary butyl (C-2-7) as a compound for inhibiting thin film growth. Cyclopentadienyl hafnium (CpHf) was used as a precursor for thin film formation, and ozone was used as a reactive gas. Under temperature conditions of 350°C and 400°C, a 50-cycle process was performed to form a hafnium oxide thin film on a silicon oxide (SiO 2 ) substrate.
박막 형성용 전구체로는 사이클로펜타디에닐 하프늄(CpHf)과 반응성 가스로는 오존, 박막 성장 억제용 화합물로 메틸터셔리부틸이서(C-2-7)을 사용하여 형성한 박막의 불순물 조성을 확인하기 위하여 350℃, 400℃ 공정조건에서 실험 박막을 XPS를 사용하여 조성 분석을 진행하였다. 분석 결과 도 10과 같이 350℃, 400℃ 박막에서 하프늄다이옥사이드가 형성이 되었으며, 질소와 탄소 원소는 검출되지 않았다.To confirm the impurity composition of the thin film formed using cyclopentadienyl hafnium (CpHf) as a precursor for thin film formation, ozone as a reactive gas, and methyl tertiary butyl (C-2-7) as a compound for inhibiting thin film growth. Composition analysis of the experimental thin films was performed using XPS under process conditions of 350°C and 400°C. As a result of the analysis, as shown in Figure 10, hafnium dioxide was formed in the thin film at 350°C and 400°C, and nitrogen and carbon elements were not detected.
이러한 결과로부터 본 발명의 박막 성장 억제용 화합물은 고온 증착 공정에 적합한 특성을 가지며, 박막 성장 억제를 통해 박막 증착 두께를 제어하여서 단차 피복성을 향상시키고 공정 부산물을 저감시킬 수 있는 공정에 적합하여 고품질의 박막을 형성할 수 있음이 확인되었다.From these results, the compound for inhibiting thin film growth of the present invention has characteristics suitable for a high temperature deposition process, and is suitable for a process that can improve step coverage and reduce process by-products by controlling the thin film deposition thickness by inhibiting thin film growth, thereby producing high quality. It was confirmed that a thin film could be formed.
본 발명은 상술한 바와 같이 바람직한 실시형태를 들어 설명하였으나, 상기 실시형태들에 한정되지 아니하며 본 발명의 정신을 벗어나지 않는 범위 내에서 당해 발명이 속하는 기술분야에서 통상의 지식을 가진 자에 의해 다양한 변형과 변경이 가능하다. 그러한 변형예 및 변경예는 본 발명과 첨부된 특허청구범위의 범위 내에 속하는 것으로 보아야 한다.The present invention has been described with reference to preferred embodiments as described above, but is not limited to the above embodiments and may be modified in various ways by those skilled in the art without departing from the spirit of the invention. and can be changed. Such modifications and variations should be considered to fall within the scope of the present invention and the appended claims.
Claims (5)
상기 박막 성장 억제용 화합물은 분해온도가 300℃ 이상이며, 상기 증착체와 배위결합하는 배위결합형 또는 상기 증착체와 반응하는 반응형 박막 성장 억제용 화합물인 것을 특징으로 하는 박막 성장 억제용 화합물.
In the process of forming a thin film by introducing a metal-containing precursor and a reactive gas to the surface of a substrate, a thin film growth inhibition compound that binds to the deposit formed on the surface of the substrate to inhibit thin film growth,
The compound for inhibiting thin film growth has a decomposition temperature of 300°C or higher, and is a compound for inhibiting thin film growth, which is a coordination type that coordinates with the deposit or a reactive compound for inhibiting thin film growth that reacts with the deposit.
상기 배위결합형 박막 성장 억제용 화합물은 화학식 1 또는 2로 표시되는 화합물인 것을 특징으로 하는 박막 성장 억제용 화합물.
[화학식 1]
[화학식 2]
상기 화학식 1 및 2에서 R1 내지 R2는 각각 독립적으로 C1 내지 C6의 직쇄형, 분지형, 또는 고리형 탄화수소이며, R3 내지 R5는 각각 독립적으로 수소원자, C1 내지 C3의 직쇄형, 분지형, 또는 고리형 탄화수소이며, 화학식 2에서 n, m은 각각 독립적으로 1 내지 3 중 어느 하나의 정수이다.
In claim 1,
The coordination-type thin film growth inhibitory compound is a compound for thin film growth inhibition, characterized in that it is a compound represented by Formula 1 or 2.
[Formula 1]
[Formula 2]
In Formulas 1 and 2, R 1 to R 2 are each independently a C 1 to C 6 straight-chain, branched, or cyclic hydrocarbon, and R 3 to R 5 are each independently a hydrogen atom, C 1 to C 3 It is a straight-chain, branched, or cyclic hydrocarbon, and in Formula 2, n and m are each independently an integer of 1 to 3.
상기 반응형 박막 성장 억제용 화합물은 화학식 3, 4 또는 5로 표시되는 화합물인 것을 특징으로 하는 박막 성장 억제용 화합물.
[화학식 3]
[화학식 4]
[화학식 5]
상기 화학식 3에서 R1 내지 R2는 각각 독립적으로 C1 내지 C3의 직쇄형, 분지형, 또는 고리형 탄화수소이며, R3 내지 R4는 각각 독립적으로 수소원자, C1 내지 C3의 직쇄형, 분지형, 또는 고리형 탄화수소이며, n은 1 내지 3 중 어느 하나의 정수이며,
상기 화학식 4 및 5에서 R1 내지 R2는 각각 독립적으로 C1 내지 C3의 직쇄형, 분지형, 또는 고리형 탄화수소이다.
In claim 1,
The compound for inhibiting thin film growth is a compound represented by Formula 3, 4 or 5.
[Formula 3]
[Formula 4]
[Formula 5]
In Formula 3, R 1 to R 2 are each independently a straight-chain, branched, or cyclic hydrocarbon of C 1 to C 3 , and R 3 to R 4 are each independently a hydrogen atom or a straight hydrocarbon of C 1 to C 3 . It is a chain, branched, or cyclic hydrocarbon, and n is any integer from 1 to 3,
In Formulas 4 and 5, R 1 to R 2 are each independently a C 1 to C 3 straight-chain, branched, or cyclic hydrocarbon.
상기 챔버 내에 청구항 1에 따른 박막 성장 억제용 화합물을 공급하는 단계;
상기 챔버 내부를 퍼징하고 금속 전구체를 공급하는 단계;
상기 챔버 내부를 퍼징하고 반응성 기체를 공급하는 단계;
를 포함하는 것을 특징으로 하는 박막 형성 방법.
Positioning the substrate within the chamber;
Supplying a compound for inhibiting thin film growth according to claim 1 into the chamber;
Purging the inside of the chamber and supplying a metal precursor;
Purging the inside of the chamber and supplying a reactive gas;
A thin film forming method comprising:
상기 박막 형성 방법의 ALD 윈도우는 350 내지 400℃인 것을 특징으로 하는 박막 형성 방법.
In claim 4,
The ALD window of the thin film forming method is 350 to 400°C.
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| PCT/KR2023/021059 WO2024144069A1 (en) | 2022-12-28 | 2023-12-20 | Compound for inhibiting growth of thin film and thin film forming method using same |
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| KR20210027069A (en) | 2019-08-29 | 2021-03-10 | 솔브레인 주식회사 | Growth inhibitor for forming thin film, method for forming thin film and semiconductor substrate prepared therefrom |
| KR20210046235A (en) | 2019-10-18 | 2021-04-28 | 솔브레인 주식회사 | Growth inhibitor for forming thin film, method for forming thin film and semiconductor substrate prepared therefrom |
| KR20220136072A (en) | 2021-03-31 | 2022-10-07 | 오션브릿지 주식회사 | Growth inhibitor for forming thin film for and deposition method for preparing film using the same |
| KR20220136073A (en) | 2021-03-31 | 2022-10-07 | 오션브릿지 주식회사 | Growth inhibitor for forming thin film for and deposition method for preparing film using the same |
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| KR20210027069A (en) | 2019-08-29 | 2021-03-10 | 솔브레인 주식회사 | Growth inhibitor for forming thin film, method for forming thin film and semiconductor substrate prepared therefrom |
| KR20210046235A (en) | 2019-10-18 | 2021-04-28 | 솔브레인 주식회사 | Growth inhibitor for forming thin film, method for forming thin film and semiconductor substrate prepared therefrom |
| KR20220136072A (en) | 2021-03-31 | 2022-10-07 | 오션브릿지 주식회사 | Growth inhibitor for forming thin film for and deposition method for preparing film using the same |
| KR20220136073A (en) | 2021-03-31 | 2022-10-07 | 오션브릿지 주식회사 | Growth inhibitor for forming thin film for and deposition method for preparing film using the same |
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