KR20090131015A - Zno thin-film precursor, and preparation method of zno thin-film through chemical vapor deposition method using the same - Google Patents
Zno thin-film precursor, and preparation method of zno thin-film through chemical vapor deposition method using the same Download PDFInfo
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- 239000010409 thin film Substances 0.000 title claims abstract description 110
- 239000002243 precursor Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000005229 chemical vapour deposition Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 14
- JKUYRAMKJLMYLO-UHFFFAOYSA-N tert-butyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OC(C)(C)C JKUYRAMKJLMYLO-UHFFFAOYSA-N 0.000 claims abstract description 12
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 239000011592 zinc chloride Substances 0.000 claims abstract description 7
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 7
- -1 alkyl acetoacetate sodium Chemical compound 0.000 claims abstract description 5
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 5
- 239000011734 sodium Substances 0.000 claims abstract description 5
- JDPRRECMRPCSIF-UHFFFAOYSA-N ethyl 3-oxobutanoate;sodium Chemical group [Na].CCOC(=O)CC(C)=O JDPRRECMRPCSIF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 3
- 238000004519 manufacturing process Methods 0.000 claims description 40
- 239000011701 zinc Substances 0.000 claims description 37
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims description 12
- 238000000151 deposition Methods 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 7
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 10
- 238000000427 thin-film deposition Methods 0.000 abstract description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 175
- 239000011787 zinc oxide Substances 0.000 description 87
- 239000000203 mixture Substances 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 229910052725 zinc Inorganic materials 0.000 description 10
- 239000012535 impurity Substances 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000005240 physical vapour deposition Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000002076 thermal analysis method Methods 0.000 description 3
- 238000009834 vaporization Methods 0.000 description 3
- 230000008016 vaporization Effects 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- 241001085205 Prenanthella exigua Species 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910052798 chalcogen Inorganic materials 0.000 description 1
- 150000001787 chalcogens Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- UAKCMIIOSJFOTD-UHFFFAOYSA-M sodium;3-oxobutanoate Chemical compound [Na+].CC(=O)CC([O-])=O UAKCMIIOSJFOTD-UHFFFAOYSA-M 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
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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
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic System
- C07F3/06—Zinc 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/407—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
Description
본 발명은 화학기상증착법(Chemical Vapor Deposition, 이하, CVD라고 함)을 위한 ZnO 박막 제조용 전구체, 및 이를 이용한 ZnO 박막의 제조 방법에 관한 것이다. 구체적으로, 본 발명은 ZnO 박막 제조용 전구체로서TMEDA-Zn(에틸 아세토아세테이트)2 또는 TMEDA-Zn(3차-부틸 아세토아세테이트)2를 사용하여 ZnO 박막을 화학기상증착법으로 제조하는 방법에 관한 것이다. The present invention relates to a precursor for preparing a ZnO thin film for Chemical Vapor Deposition (hereinafter, referred to as CVD), and a method for producing a ZnO thin film using the same. Specifically, the present invention relates to a method for preparing a ZnO thin film by chemical vapor deposition using TMEDA-Zn (ethyl acetoacetate) 2 or TMEDA-Zn (tert-butyl acetoacetate) 2 as a precursor for preparing a ZnO thin film.
ZnO 박막은 반도체 분야 등 널리 산업분야에서 사용되나, 특히 그린 에너지라 불리는 태양전지의 상층의 n형 반도체 제조시 사용된다. 이러한 ZnO 박막은 태양전지의 핵심 소자인 윈도우 물질(window material)로 사용되며, 보다 나은 성능의 ZnO 박막을 달성하기 위해, 많은 연구가 진행 중 있다. 따라서, 신규한 ZnO의 박막 제조 기술이 태양전지 제작 공정의 핵심기술로 대두되고 있다. ZnO thin films are widely used in industrial fields such as semiconductor fields, but are particularly used in the manufacture of n-type semiconductors in upper layers of solar cells called green energy. The ZnO thin film is used as a window material, which is a core element of a solar cell, and many studies are underway to achieve better ZnO thin film. Therefore, a new ZnO thin film manufacturing technology is emerging as a core technology of the solar cell manufacturing process.
종래의 ZnO 박막의 제조 방법은 ZnO 박막의 특성을 이용하여, 고온에서 증기 화(Vaporization)를 시키는 증발법(Evaporation)을 이용하였다. 그러나 상기의 증발법은 간단하게 박막을 제조할 수 있는 반면에, 에너지가 많이 소요되어 효율이 떨어지고, 무엇보다도 증발 공정 도중 Zn과 O 원소의 공기 중 압력이 달라져 고순도의 양질의 ZnO 박막을 제조하기가 어려웠다. Conventional ZnO thin film manufacturing method using the evaporation (Vaporization) at a high temperature by using the characteristics of the ZnO thin film. However, while the above-mentioned evaporation method can produce a thin film simply, energy consumption is low and efficiency is low. Above all, during the evaporation process, the pressure of Zn and O elements in the air is changed to produce a high quality ZnO thin film of high purity. Was difficult.
따라서 최근 ZnO 박막 제조 방법으로, 물리증착법(physical vapor deposition; PVD), 전통 화학적인 방법을 이용한 용액성장법(CBD), 및 전기화학을 이용한 일종의 도금방법인 전착법 등 다양한 방법이 보고되고 있다. Therefore, as a method of manufacturing a ZnO thin film, various methods such as physical vapor deposition (PVD), solution growth method (CBD) using traditional chemical methods, and electrodeposition, which is a kind of plating method using electrochemistry, have been reported.
이러한 ZnO 박막 제조 방법은 물리증착법(PVD)과 진공증발증착법과 같이 상변형을 이용한 물리적인 방법과, 용액성장법, 전착법과 같이 화학적 반응이 수반되는 화학적인 방법 등 크게 2가지로 구분할 수 있다. The ZnO thin film manufacturing method can be classified into two types: physical methods using phase deformation, such as physical vapor deposition (PVD) and vacuum evaporation, and chemical methods involving chemical reactions such as solution growth and electrodeposition.
그러나 상기 두 가지 방법 모두 특정한 조성비를 갖는 ZnO 박막의 제공을 위해서는 다양한 공정 조건 인자를 요구한다. 예를 들면, 증기압을 맞추고, 용액의 농도비를 유지하는 것과 같은 복잡한 조절 과정이 필요하게 된다. However, both methods require various process condition factors to provide a ZnO thin film having a specific composition ratio. For example, complex control procedures such as adjusting the vapor pressure and maintaining the concentration ratio of the solution are required.
뿐만 아니라, 이러한 ZnO 박막의 제조 방법은 제조비용이 비교적 저렴하고, 제조설비가 간편하다는 장점이 있으나, ZnO 박막의 특성상 Zn와 O의 조성 조절이 어렵고, 또한 불순물 제거가 어렵다. 또한 불순물 없는 고순도 ZnO 박막 제조를 위해서는, ZnO 박막 증착 후 손실 원소의 보충과 상 형성을 위해 고온에서 열처리하는 등 후공정을 필요로 하는 단점들이 있다. In addition, the manufacturing method of the ZnO thin film has an advantage that the manufacturing cost is relatively low, and the manufacturing equipment is simple, but the composition of the ZnO thin film is difficult to control the composition of the ZnO and difficult to remove impurities. In addition, in order to manufacture a high purity ZnO thin film without impurities, there are disadvantages that require a post-process such as heat treatment at high temperature for replenishment of lossy elements and phase formation after deposition of the ZnO thin film.
이와 같은 종래의 ZnO 박막의 증착 방법의 문제점을 해결하고자 많은 연구가 수행되었으며, 그 대표적인 해결 방법이 화학기상증착법(CVD)이다. 이 화학기상증 착법(CVD)은 제조된 박막이 균일하고 선택적 증착이 가능하며, 일정한 조성을 갖는 전구체를 이용한다면 단일 조성의 박막을 손쉬운 공정을 통해 재현성 있게 제공할 수 있다는 장점이 있어 금속전극, 금속산화물 등의 반도체 제조 공정에서 널리 이용되고 있다. Many studies have been conducted to solve the problems of the conventional deposition method of the ZnO thin film, and the typical solution is chemical vapor deposition (CVD). Chemical Vapor Deposition (CVD) has the advantage that the thin film produced can be uniformly and selectively deposited, and if a precursor having a constant composition is used, a thin film of a single composition can be provided reproducibly through an easy process. It is widely used in semiconductor manufacturing processes, such as an oxide.
그러나 ZnO 박막 제조시 화학기상증착법을 이용하기 위해서는 무엇보다 Zn과 O 원소가 필요한 특정 조성비를 이루고 있으면서 열적 특성이 좋은 전구체를 개발하는 것이 중요하다. 이를 위해서 모든 성분이 특정한 조성비로 이루어진 ZnO 화합물의 화학기상증착법용 단일 유기 금속 전구체(Single Organometallic Precursor)가 필요하게 된다. However, in order to use chemical vapor deposition in the production of ZnO thin films, it is important to develop precursors having good thermal properties while achieving a specific composition ratio requiring Zn and O elements. For this purpose, a single organometallic precursor for chemical vapor deposition of ZnO compounds having a specific composition ratio is required.
이러한 단일 유기 금속 전구체는 Zn과 O의 여러 조성비에 대하여 안정한 화학착물을 형성할 뿐만 아니라, 낮은 온도에서 적절한 휘발 특성이 있어야 하며, 상대적으로 낮은 분해온도가 요구되고, 기화과정에서는 비교적 열에 안정해야 하고, 분해 후 쉽게 ZnO를 형성할 수 있어야 한다. These single organometallic precursors not only form stable chemical complexes for various composition ratios of Zn and O, but also have adequate volatilization at low temperatures, require relatively low decomposition temperatures, and must be relatively thermally stable during vaporization. After decomposition, it should be easy to form ZnO.
그런데, O와 Zn의 박막 제조에 있어서, Zn과 O의 상호인력이 강하게 작용하므로 박막을 만들기 전에 쉽게 ZnO으로 분해되고 그로 인해서 원하는 곳에 ZnO 박막을 쉽게 만들 수 없다는 것이 가장 큰 문제가 되고 있다. However, in the production of the thin film of O and Zn, the mutual attraction between Zn and O is strongly acted, so that it is easily decomposed into ZnO before the thin film is made, and therefore, the ZnO thin film cannot be easily made where desired.
또한 안정한 ZnO전구체를 제조한 경우에도 종래의 경우 너무 높은 온도에서 ZnO가 증착되어서 그 적용이나 응용이 어려웠다. 예를 들어 기존의 전구체를 이용한 ZnO 박막의 제조법은 500℃ 또는 600℃ 이상에서 증착이 가능했으나, 이 온도에 서는 태양전지의 흡수층인 CuIn1 - xGaxS2 또는 CuIn1 - xGaxSe2와 완충층인 CdS, In2S3의 박막에 구조적인 변화 또는 파괴가 일어나, 목적하는 태양 전지의 기능과 효율을 달성할 수 없었다. In addition, even when a stable ZnO precursor is manufactured, ZnO is deposited at too high a temperature in the related art, and thus application or application thereof is difficult. For example, the ZnO thin film manufacturing method using a precursor can be deposited at 500 ° C or 600 ° C or higher, but at this temperature, CuIn 1 - x Ga x S 2 or CuIn 1 - x Ga x Se Structural change or breakdown occurred in the thin films of 2 and the buffer layers CdS and In 2 S 3 , and thus the function and efficiency of the desired solar cell could not be achieved.
상기와 같은 종래 기술의 문제점을 해결하기 위해, 본 발명은 Zn과 O의 조성비가 일정하고 500℃ 이하의 낮은 온도에서도 화학 증착이 가능하며, 녹는점, 기화율, 분해온도, 열분해 후 잔존 불순물 여부 등과 같이 우수한 열적 특성을 나타내는 하기 화학식 1의 구조를 갖는 전구체 화합물을 제공하고자 한다. In order to solve the problems of the prior art as described above, the present invention has a constant composition ratio of Zn and O and is capable of chemical vapor deposition even at a low temperature of less than 500 ℃, melting point, vaporization rate, decomposition temperature, residual impurities after pyrolysis It is to provide a precursor compound having a structure of formula (1) exhibiting excellent thermal properties, such as.
[화학식 1][Formula 1]
(상기 식에서, R은 C1 내지 C4의 직쇄 또는 분쇄의 알킬기이다) (Wherein R is a C 1 to C 4 straight or pulverized alkyl group)
또한, 본 발명은 상기 화학식 1의 구조를 갖는 전구체 화합물의 제조 방법을 제공하고자 한다. In addition, the present invention is to provide a method for producing a precursor compound having the structure of Formula 1.
또한, 본 발명은 상기 화학식 1의 구조를 갖는 전구체 화합물을 이용하여 Zn과 O의 조성이 1:1인 ZnO 박막의 제조방법을 제공하고자 한다. In addition, the present invention is to provide a method for producing a ZnO thin film having a composition of Zn and O 1: 1 using a precursor compound having the structure of Formula 1.
위와 같은 과제를 해결하기 위한 본 발명의 한 특징에 따른 ZnO 박막 제조용 전구체는 하기 화학식 1의 구조를 가진다. The precursor for preparing a ZnO thin film according to one feature of the present invention for solving the above problems has a structure of formula (1).
[화학식 1][Formula 1]
(상기 식에서, R은 C1 내지 C4의 직쇄 또는 분쇄의 알킬기이다)(Wherein R is a C 1 to C 4 straight or pulverized alkyl group)
여기서, 상기 ZnO 박막 제조용 전구체는 TMEDA-Zn(에틸 아세토아세테이트)2 또는 TMEDA-Zn(3차-부틸 아세토아세테이트)2 일 수 있다. Here, the precursor for preparing the ZnO thin film may be TMEDA-Zn (ethyl acetoacetate) 2 or TMEDA-Zn (tert-butyl acetoacetate) 2 .
본 발명의 또 다른 특징에 따른 상기 화학식 1의 구조의 ZnO 박막 제조용 전구체의 제조 방법은 1) 테트라메틸에틸렌디아민을 염화아연과 반응시키는 단계; 및 2) 상기 단계 1)의 반응 결과물을 알킬아세토아세테이트 소듐과 반응시키는 단계;를 포함한다. According to another aspect of the present invention, a method of preparing a precursor for preparing a ZnO thin film having a structure of Chemical Formula 1 includes the steps of: 1) reacting tetramethylethylenediamine with zinc chloride; And 2) reacting the reaction product of step 1) with alkylacetoacetate sodium.
여기서, 상기 ZnO 박막 제조용 전구체는 TMEDA-Zn(에틸 아세토아세테이트)2 또는 TMEDA-Zn(3차-부틸 아세토아세테이트)2 일 수 있다. Here, the precursor for preparing the ZnO thin film may be TMEDA-Zn (ethyl acetoacetate) 2 or TMEDA-Zn (tert-butyl acetoacetate) 2 .
본 발명의 또 다른 특징에 따른 ZnO 박막 제조 방법은 상기 화학식 1의 구조의 ZnO 박막 제조용 전구체를 이용하여 화학기상증착법에 따라 ZnO 박막을 형성한다. ZnO thin film manufacturing method according to another feature of the present invention to form a ZnO thin film by chemical vapor deposition using a precursor for preparing a ZnO thin film of the structure of Formula 1.
여기서, 상기 ZnO 박막 제조용 전구체는 TMEDA-Zn(에틸 아세토아세테이트)2 또는 TMEDA-Zn(3차-부틸 아세토아세테이트)2 일 수 있다. Here, the precursor for preparing the ZnO thin film may be TMEDA-Zn (ethyl acetoacetate) 2 or TMEDA-Zn (tert-butyl acetoacetate) 2 .
그리고, 상기 ZnO 의 증착 온도가 390~450 ℃ 범위일 수 있다. And, the deposition temperature of the ZnO may be in the range of 390 ~ 450 ℃.
그리고, 상기 ZnO 박막 제조용 전구체가 아르곤 분위기 상태에서 버블러 온도 100 ℃ 내지 120℃에서 1 시간 동안 증착될 수 있다. The ZnO thin film precursor may be deposited at an bubbler temperature of 100 ° C. to 120 ° C. for 1 hour in an argon atmosphere.
또한, 본 발명의 또 다른 특징에 따른 태양 전지는 상기 ZnO 박막 제조 방법에 따라 ZnO 박막이 제조된다. In addition, in the solar cell according to another feature of the present invention, a ZnO thin film is manufactured according to the ZnO thin film manufacturing method.
본 발명에서는 앞서 개시한 화학식 1의 구조의 신규한 ZnO 박막 제조용 전구체 화합물을 제공한다. The present invention provides a novel precursor compound for preparing a ZnO thin film of the structure of formula (1) described above.
또한, 본 발명에서는 화학식 1의 구조의 신규한 ZnO 박막 제조용 전구체 화합물을 이용하여 ZnO 박막 증착 공정을 500℃ 이하의 낮은 온도에서도 수행할 수 있다. In addition, in the present invention, the ZnO thin film deposition process may be performed at a low temperature of 500 ° C. or less by using the novel precursor compound for preparing a ZnO thin film having the structure of Formula 1.
또한, 본 발명에 의한 화학식 1의 구조의 신규한 ZnO 박막 제조용 전구체 화합물을 이용하면, ZnO 박막 제조용 전구체의 열적 특성이 우수하여 ZnO으로 쉽게 분해되지 않아 원하는 곳에 ZnO 박막을 형성할 수 있다. In addition, when using the precursor compound for producing a ZnO thin film of the structure of the formula (1) according to the present invention, the thermal properties of the ZnO thin film manufacturing precursor is excellent, it is not easily decomposed into ZnO can form a ZnO thin film where desired.
본 발명의 화학식 1의 구조의 신규한 ZnO 박막 제조용 전구체 화합물은 종래의 ZnO 박막 제조용 전구체 화합물과는 달리, 그 구조에 불소와 같이 ZnO 박막에서 불순물로 기능할 수 있는 관능기를 포함하고 있지 않으므로, 본 발명의 화학식 1 구조의 신규한 ZnO 박막 제조용 전구체 화합물을 사용하여 형성된 ZnO 박막은 불소 와 같은 불순물을 포함하고 있지 않다. 따라서, 이러한 불소를 제거하기 위한 추가 공정이 필요 없다. 이러한 추가 공정은 높은 온도 조건을 요구하는 것이 일반적이므로, 종래의 ZnO 박막 제조용 전구체 화합물은 태양 전지 제조에 이용될 수 없으나, 본 발명의 ZnO 박막 제조용 전구체 화합물은 이와 같은 불순물 제거 공정을 요구하지 않으므로 태양전지에 특히 바람직하게 사용될 수 있다. Unlike the precursor compound for preparing a ZnO thin film, the novel precursor compound for preparing a ZnO thin film of the structure of Formula 1 of the present invention does not include a functional group capable of functioning as an impurity in a ZnO thin film, such as fluorine, in the structure. The ZnO thin film formed using the novel precursor compound for preparing a ZnO thin film having the structure of Formula 1 of the present invention does not contain impurities such as fluorine. Thus, no additional process for removing this fluorine is necessary. Since such additional processes generally require high temperature conditions, conventional precursor compounds for preparing ZnO thin films cannot be used in solar cell manufacture, but precursor compounds for preparing ZnO thin films of the present invention do not require such an impurity removal process. It may be used particularly preferably in a battery.
본 발명은 화학기상증착법으로 ZnO 박막 제조 시에 ZnO 박막의 전구체로 사용되는 하기 화학식 1로 표시되는 유기금속 화합물인 ZnO 박막 제조용 전구체를 제공한다. The present invention provides a precursor for preparing a ZnO thin film, which is an organometallic compound represented by the following Chemical Formula 1, used as a precursor of a ZnO thin film when the ZnO thin film is manufactured by chemical vapor deposition.
[화학식 1][Formula 1]
(상기 식에서, R은 C1 내지 C4의 직쇄 또는 분쇄의 알킬기이다)(Wherein R is a C 1 to C 4 straight or branched alkyl group)
상기 화학식 1로 표시되는 본 발명의 ZnO 박막 제조용 전구체는 아래 반응식 1로 표시되는 바와 같이 테트라메틸에틸렌디아민(tetramethyl ethylene diamine)과 염화아연(ZnCl2), 그리고 알킬 아세토아세테이트 소듐(alkyl acetoacetate sodium)을 이용하여 합성된다. The precursor for preparing a ZnO thin film of the present invention represented by Chemical Formula 1 includes tetramethyl ethylene diamine, zinc chloride (ZnCl 2 ), and alkyl acetoacetate sodium as shown in Scheme 1 below. Synthesized using.
(상기 반응식 1에서, R은 C1 내지 C4의 직쇄 또는 분쇄의 알킬기이다)) (In the above Reaction Scheme 1, R is a C 1 to C 4 linear or pulverized alkyl group))
여기서, 염화아연 대신에 Zn(acetate)2 또는 ZnNO3를 사용할 수 있으며, 알킬 아세토아세테이트 소듐으로는 에틸 아세토아세테이트 소듐 또는 3차 부틸 아세토아세테이트 소듐이 바람직하게 사용된다. Here, Zn (acetate) 2 or ZnNO 3 may be used instead of zinc chloride, and ethyl acetoacetate sodium or tertiary butyl acetoacetate sodium is preferably used as alkyl acetoacetate sodium.
따라서, 본 발명의 상기 화학식 1의 ZnO 박막 제조용 전구체로는 TMEDA-Zn(에틸 아세토아세테이트)2 또는 TMEDA-Zn(3차-부틸 아세토아세테이트)2가 바람직하게 사용된다. Therefore, as a precursor for preparing a ZnO thin film of Chemical Formula 1 of the present invention, TMEDA-Zn (ethyl acetoacetate) 2 or TMEDA-Zn (tert-butyl acetoacetate) 2 is preferably used.
이하, 실시예를 통하여, 본 발명의 ZnO 박막 제조용 전구체의 제조 방법 및 ZnO 박막의 제조방법을 구체적으로 살펴보나, 본 발명이 이에 제한되는 것은 아니다. Hereinafter, the method of manufacturing the precursor for manufacturing the ZnO thin film and the method of manufacturing the ZnO thin film according to the present invention will be described in detail, but the present invention is not limited thereto.
실시예Example 1 : One : TMEDATMEDA -- ZnZn (에틸 (ethyl 아세토아세테이트Acetoacetate )) 22 의 합성Synthesis of
200 ㎖ 슈링크 플라스크에 용매로 에틸에테르(ethyl ether) 50 ㎖를 넣고 염화아연(ZnCl2) 0.2몰을 용해시키고, 테트라메틸에틸렌디아민(tetramethyl ethylene diamine; TMEDA) 0. 2 몰을 첨가하였다. 50 ml of ethyl ether was added to a 200 ml shrink flask, 0.2 mol of zinc chloride (ZnCl 2 ) was dissolved, and 0.2 mol of tetramethyl ethylene diamine (TMEDA) was added thereto.
그 결과, 바로 생성되는 매우 밝은 하얀색 침전물인 0.2 몰의 TMEDA-ZnCl2을 글라스필터를 이용하여 분리 수득하였다. 아세톤 50 ㎖ 용매에 앞서 수득된 TMEDA-ZnCl2을 녹이고 에틸 아세토아세테이트 소듐(ethyl acetoacetate sodium) 0.4몰을 용해시킨 후, 30분 동안 반응시켰다. 그 후, 염화나트륨을 제거하고 재결정하여 목적하는 0. 16 몰의TMEDA-Zn(에틸 아세토아세테이트)2를 수득하였다. As a result, 0.2 mole of TMEDA-ZnCl 2 , which is a very bright white precipitate, produced immediately, was separated and obtained using a glass filter. TMEDA-ZnCl 2 obtained above was dissolved in 50 ml of acetone, 0.4 mol of ethyl acetoacetate sodium was dissolved, and then reacted for 30 minutes. Thereafter, sodium chloride was removed and recrystallized to obtain the desired 16. 16 moles of TMEDA-Zn (ethyl acetoacetate) 2 .
실시예Example 2: 2: TMEDATMEDA -- ZnZn (3차-부틸 (Tert-butyl 아세토아세테이트Acetoacetate )) 2 2 의 합성 Synthesis of
200 ㎖ 슈링크 플라스크에 용매로 에틸에테르 50 ㎖를 넣고 염화아연 0.2몰을 용해시키고, 테트라메틸에틸렌디아민 0. 2 몰을 첨가하였다. 50 ml of ethyl ether was added to a 200 ml shrink flask, 0.2 mol of zinc chloride was dissolved, and 0.2 mol of tetramethylethylenediamine was added thereto.
그 결과, 바로 생성되는 매우 밝은 하얀색 침전물인 0.2 몰의 TMEDA-ZnCl2을 글라스필터를 이용하여 분리 수득하였다. 아세톤 50 ㎖ 용매에 앞서 수득된 TMEDA-ZnCl2을 녹이고 3차 부틸 아세토아세테이트 소듐(tert-butly acetoacetate sodium) 0.4몰을 용해시킨 후, 30분 동안 반응을 시켰다. 그 후, 염화나트륨을 제거하고 재결정하여 목적하는 0.1 몰의 TMEDA-Zn(3차-부틸 아세토아세테이트)2 을 수득하였다. As a result, 0.2 mole of TMEDA-ZnCl 2 , which is a very bright white precipitate, produced immediately, was separated and obtained using a glass filter. TMEDA-ZnCl 2 obtained above was dissolved in 50 ml of acetone, 0.4 mol of tert-butly acetoacetate sodium was dissolved, and then reacted for 30 minutes. Thereafter, sodium chloride was removed and recrystallized to obtain the desired 0.1 mol of TMEDA-Zn (tert-butyl acetoacetate) 2 .
실험예Experimental Example : : ZnOZnO 박막 제조용 전구체 특성 측정 Measurement of precursor properties for thin film production
실시예 1 및 2 에서 합성한 ZnO 박막 제조용 전구체들에 각각 NMR(핵자기공명분석법), FT-IR(적외선 분광분석법), MASS(질량분석법) 및 원소분석법을 수행하였으며, 그 결과를 하기 표 1에 나타내었다. NMR (nuclear magnetic resonance analysis), FT-IR (infrared spectroscopy), MASS (mass spectrometry) and elemental analysis were performed on the precursors for preparing the ZnO thin film synthesized in Examples 1 and 2, and the results are shown in Table 1 below. Shown in
* : eacac = 에틸 아세토아세테이트(ethly acetoacetate) *: eacac = ethyl acetoacetate
**:tbac = 3차 부틸 아세토아세테이트(tert-butly acetoacetate) **: tbac = tert-butly acetoacetate
***:MASS(질량분석) = DIP-FAB-mass ***: MASS = DIP-FAB-mass
****:FT-IR(적외선 분광분석) = KBr 펠렛 ****: FT-IR (infrared spectroscopy) = KBr pellet
한편, 상기 실시예 1 및 2에서 제조된 ZnO 박막 제조용 전구체들을 열분석기(Thermal Analysis)를 이용하여 전구체의 상압에서의 녹는점 및 분해온도를 측정하였다. 그 결과를 하기 표 2 에 나타내었다. Meanwhile, the precursors for preparing the ZnO thin films prepared in Examples 1 and 2 were measured using a thermal analysis (Thermal Analysis) to measure the melting point and decomposition temperature of the precursor at atmospheric pressure. The results are shown in Table 2 below.
*: 공기 및 열 안정성 : 녹는점보다 높은 온도에서 2일 이상 유지 여부 *: Air and Thermal Stability: Whether to be kept for 2 days or more above the melting point
**: 녹는점, 분해온도 : 열분석(Thermal Analysis) 분석 결과 **: melting point, decomposition temperature: Thermal Analysis
상기 표 2에서 볼 수 있는 바와 같이, 실시예 1 및 2에서 제조된 ZnO 박막 제조용 전구체들은 둘 다 녹는점보다 높은 온도에서 2일 이상 유지되므로, 공기 및 열 안정성이 우수하였다. 그리고, 분해 온도가 상대적으로 낮아 전구체의 요구 특성을 잘 충족하는 것을 확인하였다. 또한, 녹는점과 분해 온도 사이에서 승화로 보이는 상변화를 일으키므로, 낮은 온도에서 우수한 휘발 특성을 가짐을 확인하였다. As can be seen in Table 2, the precursors for preparing the ZnO thin film prepared in Examples 1 and 2 were both maintained for two days or more at a temperature higher than the melting point, it was excellent in air and thermal stability. In addition, it was confirmed that the decomposition temperature was relatively low to satisfy the required characteristics of the precursor. In addition, it was confirmed that the phase change that appears as a sublimation between the melting point and decomposition temperature, has excellent volatilization characteristics at low temperatures.
또한, 실시예 1 및 2에 의해 제조된 ZnO 박막 제조용 전구체는 ZnO 박막 형성시 가장 중요한 아연과 산소 원소의 조성비를 1:1로 유지시킬 수 있다는 점에서 아주 유용하게 작용할 수 있다. In addition, the precursors for manufacturing the ZnO thin film prepared in Examples 1 and 2 can be very useful in that the composition ratio of zinc and oxygen elements, which are most important in forming the ZnO thin film, can be maintained at 1: 1.
뿐만 아니라 ZnO 박막 제조용 전구체 내에서 아연과 산소의 조성비를 1:4로 유지시킬 수 있으며, 그에 따라 ZnO 박막 제조시 그 성장 속도를 최대로 할 수 있다. In addition, the composition ratio of zinc and oxygen in the precursor for manufacturing the ZnO thin film can be maintained at 1: 4, thereby maximizing its growth rate when manufacturing the ZnO thin film.
따라서 본 실시예 1 및 2에 의해 제조된 새로운 ZnO 박막 제조용 전구체는 아연과 산소원소의 조성비가 1:1인 ZnO 박막을 효율적으로 제조할 수 있는 우수한 전구체이다.Therefore, the new ZnO thin film precursors prepared according to Examples 1 and 2 are excellent precursors that can efficiently prepare ZnO thin films having a composition ratio of zinc and oxygen element of 1: 1.
실시예Example 3: 3: ZnOZnO 박막의 제조 Manufacture of thin film
상기의 실시예 1에서 수득된 0.1 g TMEDA-Zn(에틸 아세토아세테이트)2를 사용하여 도 1과 같은 CVD 장치로 ZnO 박막을 제조하였다. The ZnO thin film was prepared by the CVD apparatus as shown in FIG. 1 using 0.1 g TMEDA-Zn (ethyl acetoacetate) 2 obtained in Example 1 above.
CVD 장치는 아르곤 분위기 하에서 전구체 용 버블러 온도를 120 ℃로 유지하고, 증착 기판(substrate) 온도를 CIGS(CulnGaSe2) 형태의 반도체 태양전지의 최적온도인 390℃, 410℃, 430 ℃, 및 450 ℃ 범위로 조절하고, CVD 챔버는 5 mtorr로 감압한 후, 실시예 1에서 수득된 TMEDA-Zn(에틸 아세토아세테이트)2를 1 시간 동안 실리콘(100) 위에 200~2000㎚ 두께로 증착하였다. The CVD apparatus maintains the bubbler temperature for the precursor at 120 ° C. under an argon atmosphere, and the deposition substrate temperature is 390 ° C., 410 ° C., 430 ° C., and 450 ° C., which is an optimum temperature for a semiconductor solar cell in the form of CIGS (CulnGaSe 2). After adjusting to the range, the CVD chamber was decompressed to 5 mtorr, and then TMEDA-Zn (ethyl acetoacetate) 2 obtained in Example 1 was deposited on the
제조된 ZnO 박막은 도 2의 XRD(X-Ray Diffraction) 결과로부터 불순물이 전혀 없는 고순도로 형성되었음을 확인하였고, 도 3 및 4의 전자현미경 사진을 통하여 박막 내 입자 크기가 70~80nm로 균일하게 제조되었음을 확인하였다. The prepared ZnO thin film was confirmed to be formed in high purity without any impurities from the XRD (X-Ray Diffraction) result of FIG. It was confirmed.
구체적으로, 도 2로부터, 증착 기판(substrate) 온도가 390℃, 410℃, 430℃ 및 450℃인 경우, ZnO의 피크를 확인할 수 있다. 그로부터, 증착된 ZnO 박막이 불순물이 전혀 없는 고순도의 ZnO 단일상 박막임을 확인하였고, 증착 기판의 온도가 증가함에 따라 결정성이 좋아지고, 박막의 두께가 두꺼워짐을 확인할 수 있었다. Specifically, from FIG. 2, when the substrate temperature is 390 ° C., 410 ° C., 430 ° C. and 450 ° C., the peak of ZnO may be confirmed. From this, it was confirmed that the deposited ZnO thin film was a ZnO single-phase thin film of high purity without any impurities, and as the temperature of the deposition substrate was increased, the crystallinity was improved and the thickness of the thin film was increased.
도 3 및 도 4는 증착 기판(substrate) 온도가 410℃에서 증착한 ZnO 박막에 대한 전자 주사 현미경 사진을 나타낸다. 3 and 4 show electron scanning micrographs of a ZnO thin film deposited at a deposition substrate temperature of 410 ° C.
구체적으로, 도 3 및 4는 각각 실시예 3을 통해 증착된 ZnO 박막에 대한 정면과 측면의 전자 주사 현미경 사진이다. 도 3 및 4에서 보는 바와 같이 증착된 각각의 박막은 어떠한 불순물도 없고, 전 영역에 걸쳐서 균일하게 박막이 증착되었음을 알 수 있다. Specifically, FIGS. 3 and 4 are electron scanning micrographs of the front and side surfaces of the ZnO thin film deposited through Example 3, respectively. As shown in FIGS. 3 and 4, each of the deposited thin films was free of any impurities, and the thin films were uniformly deposited over the entire region.
상기에서는 본 발명의 바람직한 실시예에 대하여 설명하였지만, 본 발명은 이에 한정되는 것이 아니고 본 발명의 기술 사상 범위 내에서 여러 가지로 변형하여 실시하는 것이 가능하고 이 또한 첨부된 특허 청구 범위에 속하는 것은 당연하다. Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and various modifications can be made within the scope of the technical idea of the present invention, and it is obvious that the present invention belongs to the appended claims. Do.
앞서, 상세히 살펴본 바와 같이, 본 발명은 상기 화학식 1구조의 단일 전구 체를 사용하여 390~450℃ 온도 영역에서 고순도의 산화 아연(zinc oxide) 박막을 형성할 수 있는 방법을 제공한다. As described above in detail, the present invention provides a method of forming a zinc oxide thin film of high purity in the temperature range of 390 ~ 450 ℃ using a single precursor of the structure (1).
이와 같은 본 발명의 ZnO 박막 제조 방법은 대표적 차세대 화합물 반도체로서, 한국특허등록 공보 제789064호에 개시된 CuInS2박막과, 한국특허등록공보 제679640호에 개시된 13족과 칼코겐 원소(S, Se, Te)의 박막 In2S3 , In2Se3에 명시된 전구체들을 이용하여, CuIn1 -xGaxSe2, CuIn1 - xGaxS2/CdS또는 In2Se3/ZnO 구성 형태의 화합물 반도체 태양전지를 화학기상증착의 단일공정으로 만들 수 있게 한다. Such a ZnO thin film manufacturing method of the present invention is a representative next-generation compound semiconductor, CuInS 2 thin film disclosed in Korean Patent No. 790864, Group 13 and chalcogen elements (S, Se, Compounds in the form of CuIn 1- x Ga x Se 2, CuIn 1 - x Ga x S 2 / CdS or In 2 Se 3 / ZnO constituents, using the precursors specified in the thin films In 2 S 3 , In 2 Se 3 It can make semiconductor solar cell into a single process of chemical vapor deposition.
도 1은 본 발명의 ZnO 박막 제조용 CVD 장치의 구성을 개념적으로 도시한다. 1 conceptually shows the configuration of a CVD apparatus for producing a ZnO thin film of the present invention.
도 2는 본 발명의 ZnO 박막 제조 방법에 따라 제조된 ZnO 박막의 XRD 결과를 도시한다. Figure 2 shows the XRD results of the ZnO thin film prepared according to the ZnO thin film manufacturing method of the present invention.
도 3 및 도 4는 본 발명의 ZnO 박막 제조 방법에 따라 제조된 ZnO 박막에 대한 정면과 측면의 전자 주사 현미경 사진이다.3 and 4 are electron scanning micrographs of the front and side of the ZnO thin film prepared according to the ZnO thin film manufacturing method of the present invention.
Claims (10)
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| WO2012120918A1 (en) * | 2011-03-09 | 2012-09-13 | 株式会社Adeka | Zinc oxide film-forming composition, zinc oxide film production method, and zinc compound |
| WO2013129746A1 (en) * | 2012-02-27 | 2013-09-06 | 중앙대학교 산학협력단 | Tin sulfide precursor, thin film using tin sulfide precursor, and preparation method therefor |
| KR101540032B1 (en) * | 2012-02-27 | 2015-07-29 | 중앙대학교 산학협력단 | Precursor for preparing the SnS thin-film and manufacturing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2012120918A1 (en) * | 2011-03-09 | 2012-09-13 | 株式会社Adeka | Zinc oxide film-forming composition, zinc oxide film production method, and zinc compound |
| JP2012188510A (en) * | 2011-03-09 | 2012-10-04 | Adeka Corp | Zinc oxide film-forming composition, zinc oxide film production method and zinc compound |
| CN103415576A (en) * | 2011-03-09 | 2013-11-27 | 株式会社艾迪科 | Zinc oxide film-forming composition, zinc oxide film production method, and zinc compound |
| KR101507673B1 (en) * | 2011-03-09 | 2015-03-31 | 가부시키가이샤 아데카 | Zinc oxide film-forming composition, zinc oxide film production method, and zinc compound |
| EP2684917A4 (en) * | 2011-03-09 | 2015-04-29 | Adeka Corp | Zinc oxide film-forming composition, zinc oxide film production method, and zinc compound |
| US9133349B2 (en) | 2011-03-09 | 2015-09-15 | Adeka Corporation | Zinc oxide film-forming composition, zinc oxide film production method, and zinc compound |
| TWI548640B (en) * | 2011-03-09 | 2016-09-11 | Adeka Corp | A zinc oxide film forming composition, and a method for producing a zinc oxide film |
| WO2013129746A1 (en) * | 2012-02-27 | 2013-09-06 | 중앙대학교 산학협력단 | Tin sulfide precursor, thin film using tin sulfide precursor, and preparation method therefor |
| KR101540032B1 (en) * | 2012-02-27 | 2015-07-29 | 중앙대학교 산학협력단 | Precursor for preparing the SnS thin-film and manufacturing method thereof |
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