KR20160046019A - Manufacturing method of polycrystalline p-type cigs thin film - Google Patents
Manufacturing method of polycrystalline p-type cigs thin film Download PDFInfo
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- 239000010409 thin film Substances 0.000 title claims abstract description 53
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 40
- 239000006185 dispersion Substances 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 41
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical compound [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 239000000758 substrate Substances 0.000 claims description 15
- 229910021617 Indium monochloride Inorganic materials 0.000 claims description 11
- 239000012153 distilled water Substances 0.000 claims description 11
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 8
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 5
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- 239000002245 particle Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- 239000007921 spray Substances 0.000 abstract description 16
- 231100000053 low toxicity Toxicity 0.000 abstract description 4
- 239000011669 selenium Substances 0.000 description 15
- 239000004065 semiconductor Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
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- 238000000576 coating method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000007764 slot die coating Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000009718 spray deposition Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- 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
- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
- H01L31/06—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers
- H01L31/072—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type
- H01L31/0749—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar cells
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- H—ELECTRICITY
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E10/541—CuInSe2 material PV cells
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Abstract
Description
본 발명은 태양전지용 CIGS(Cu(In,Ga)Se2) 박막의 제조방법에 관한 것으로, 보다 상세하게는, 스프레이 증착을 위한 CIGS 전구체 수용성 분산용액의 제조방법 및 셀렌화 열처리 공정을 통한 CIGS 박막의 제조방법에 관한 것이다. The present invention relates to a method for producing a CIGS (Cu (In, Ga) Se 2 ) thin film for a solar cell, and more particularly, to a method for producing a CIGS precursor water-soluble dispersion solution for spray deposition and a CIGS thin film And a method for producing the same.
태양 전지(Solar Cell)는 반도체의 성질을 이용하여 빛 에너지를 전기 에너지로 변환시키는 장치이다. 태양 전지는 시계나 계산기 등 휴대용 전자기기의 전원으로부터 넓은 개활지에 설치된 산업용 발전설비까지 폭넓게 이용된다. 또한, 최근 친환경 대체 에너지의 필요성이 증가함에 따라 태양 전지에 대한 관심이 고조되고 있다.Solar cell is a device that converts light energy into electrical energy using the properties of semiconductor. Solar cells are used extensively, from power sources for portable electronic devices such as watches and calculators to industrial power generation facilities installed in a wide open space. In addition, as the need for environmentally friendly alternative energy has increased, interest in solar cells is increasing.
태양 전지의 구조 및 원리를 간단히 설명하면, 태양 전지는 P(positive)형 반도체와 N(nagative)형 반도체를 접합시킨 PN접합 구조를 하고 있으며, 이러한 태양 전지에 태양광이 입사되면, 입사된 태양광이 가지고 있는 에너지에 의해 상기 반도체 내에서 정공(hole) 및 전자(electron)가 발생하고, 이때, PN접합에서 발생한 전기장에 의해서 상기 정공은 P형 반도체 쪽으로 이동하고 상기 전자는 N형 반도체 쪽으로 이동하게 되어 전위가 발생된다.The structure and principle of a solar cell will be briefly described. A solar cell has a PN junction structure in which a P (positive) semiconductor and an N (nagative) semiconductor are bonded. When solar light is incident on the solar cell, Holes and electrons are generated in the semiconductor due to the energy of light. At this time, the holes move toward the P-type semiconductor due to the electric field generated at the PN junction, and the electrons move toward the N-type semiconductor So that a potential is generated.
이와 같은 태양 전지는 기판형 태양 전지와 박막형 태양 전지로 구분할 수 있다. 상기 기판형 태양 전지는 실리콘과 같은 반도체물질 자체를 기판으로 이용하여 태양 전지를 제조한 것이고, 상기 박막형 태양 전지는 유리 등과 같은 기판 상에 박막의 형태로 반도체 층을 형성하여 태양 전지를 제조한 것이다.Such a solar cell can be classified into a substrate type solar cell and a thin film solar cell. The substrate type solar cell is a solar cell manufactured using a semiconductor material itself such as silicon as a substrate. The thin film type solar cell is manufactured by forming a semiconductor layer in the form of a thin film on a substrate such as glass .
상기 박막형 태양전지는 광흡수층을 구성하는 재료를 기준으로 Si 박막형 태양전지와 화합물 박막형 태양전지로 나눌 수 있고, 그 중 화합물 박막형 태양전지는 다시 Ⅱ-Ⅵ 태양전지, I-Ⅲ-Ⅵ(CIGS) 태양전지 등으로 분류할 수 있다.The thin film type solar cell can be divided into a Si thin film type solar cell and a compound thin film type solar cell based on the material constituting the light absorbing layer. The compound thin film type solar cell is divided into a II-VI solar cell, I-III-VI (CIGS) Solar cells and so on.
상기 CIGS 태양전지는 구리(Cu), 인듐(In), 갈륨(Ga), 및 셀레늄(Se)의 4가지 원소가 합쳐져서 구성되는 화합물을 광흡수층으로 이용한 것이다. 이러한 CIGS 태양전지는 직접천이형 에너지 밴드갭을 가지고 있고, 광흡수계가 매우 높으며, 전기 광학적 안정성이 매우 우수한 특성을 가지고 있어, 수 마이크로 미터 두께의 박막으로도 고효율의 태양전지 제조가 가능하고 제조 비용 또한 저렴하므로 현재 사용되고 있는 고가의 결정질 실리콘 태양전지를 대체할 차세대 태양 전지 재료로 부각되고 있는 추세에 있다. 이러한 이유로, 최근 저비용으로 고효율의 CIGS 태양전지를 제조하기 위한 연구가 활발히 진행되고 있다.The CIGS solar cell uses a compound composed of four elements of copper (Cu), indium (In), gallium (Ga), and selenium (Se) as a light absorbing layer. Such a CIGS solar cell has a direct transition type energy bandgap, a very high absorption coefficient and a very excellent electro-optical stability. Thus, it is possible to manufacture a high efficiency solar cell even with a thin film of a few micrometers thick, It is also in the trend of becoming a next-generation solar cell material to replace expensive crystalline silicon solar cell which is currently used. For this reason, research for manufacturing a CIGS solar cell with high efficiency at low cost has been actively conducted recently.
저비용 CIGS 태양전지를 실현하기 위해서는 CIGS 흡수층 제조시 비진공 용액공정을 이용하여 제조 단가를 낮추어야 한다. 이 경우, 용액공정을 위한 CIGS 전구체의 제조가 선행되어야 하며, CIGS 전구체는 나노 잉크, 나노 입자, 분산용액 등의 형태로 제조된다. 이렇게 제조된 CIGS 전구체를 이용하여 스크린 프린팅, 스핀 코팅, 스프레이 증착 방법 등을 이용해 CIGS 박막을 형성한다.In order to realize a low-cost CIGS solar cell, the manufacturing cost should be lowered by using a non-vacuum solution process when manufacturing the CIGS absorption layer. In this case, the preparation of the CIGS precursor for the solution process should be preceded, and the CIGS precursor is prepared in the form of nano ink, nanoparticles, dispersion solution and the like. The CIGS precursor thus prepared is screen-printed, spin-coated, and spray-deposited to form a CIGS thin film.
스프레이 공정을 이용한 저비용 CIGS 태양전지 제작에 있어서, 종래 기술인 US 7,838,403호는 유기용매나 하이드라진 용매를 사용하는 방법을 제시하고 있으나, 독성이 강한 유기용매 및 하이드라진 용매를 사용함으로써 유독성의 용매 흄(fume)이 직접적으로 생성되어 이를 제거하기 위한 설비를 따로 마련해야 하는 단점이 있다.In the production of a low cost CIGS solar cell using a spray process, prior art US 7,838,403 discloses a method of using an organic solvent or a hydrazine solvent. However, by using an organic solvent and a hydrazine solvent having high toxicity, a toxic solvent fume And it is necessary to separately prepare a facility for removing it.
또한, 종래 기술인 한국공개특허 10-2012-0046673호는 레이저 유도 붕괴 분광법을 이용하여 CIGS 박막의 물질 분포 상태를 실시간으로 측정할 수 있는 장치가 구비된 CIGS 박막 태양전지 제조 공정 시스템에 관한 것으로, CIGS 박막 태양전지를 생산하면서 동시에 생산되는 CIGS 박막 태양전지의 품질을 관리할 수 있는 제조 공정 시스템을 제시하고 있으나, CIGS 박막의 조성 균일성을 확보할 수 있는 셀렌화 공정 조건의 조절 방법에 대해서는 언급하고 있지 않다. In addition, Korean Unexamined Patent Publication No. 10-2012-0046673 discloses a CIGS thin film solar cell manufacturing system equipped with a device capable of real-time measurement of a material distribution state of a CIGS thin film using laser induced decay spectroscopy, A manufacturing process system capable of managing the quality of the CIGS thin film solar cell produced simultaneously with the production of the thin film solar cell is proposed. However, a method of controlling the selenization process condition to secure the composition uniformity of the CIGS thin film is mentioned It is not.
이에, 본 발명은 독성이 적은 CIGS 전구체 수용성 분산용액을 저비용 스프레이 공정에 사용함으로써 제조 단가가 낮고 친환경적인 CIGS 박막의 제조방법을 제공하는 한편, 최적화된 셀렌화 공정을 통해 균일한 다결정 그레인(grain)을 갖는 CIGS 박막의 제조방법을 제공하는 것을 목적으로 한다.Accordingly, the present invention provides a method for producing a CIGS thin film which is low in production cost and is environmentally friendly by using a water-soluble CIGS precursor dispersion solution having low toxicity in a low-cost spraying process, and a method for producing a uniform polycrystalline grain by an optimized selenization process, And a method for producing the CIGS thin film.
이러한 목적 달성을 위해, 본 발명은 증류수를 용매로 사용하는 CIGS 전구체 수용성 분산용액의 제조방법을 제공하고, 이렇게 제조된 분산용액을 이용하는 최적화된 스프레이 공정을 통한 CIGS 전구체 박막의 제조방법을 제공하며, 열처리 후 냉각하는 동안에도 Se를 공급하는 셀렌화 열처리 공정이 사용되는 다결정성 p-타입 CIGS 박막의 제조방법을 제공한다.The present invention provides a method for preparing a CIGS precursor aqueous dispersion solution using distilled water as a solvent and a method for producing a CIGS precursor thin film through an optimized spray process using the dispersion solution thus prepared, There is provided a method for producing a polycrystalline p-type CIGS thin film using a selenization heat treatment process for supplying Se even during cooling after heat treatment.
본 발명에 의할 경우 스프레이 공정에 적합한 저 독성의 CIGS 분산용액의 제공함으로써 저비용의 태양전지용 CIGS 박막의 제작이 가능하며, 최적화된 셀렌화 공정을 통해 균일한 다결정 그레인이 형성된 CIGS 박막의 제조가 가능하다.According to the present invention, a low-cost CIGS thin film for a solar cell can be manufactured by providing a low-toxicity CIGS dispersion solution suitable for a spray process, and a CIGS thin film having uniform polycrystalline grains can be manufactured through an optimized selenization process Do.
도 1은 본 발명의 실시예 1 내지 3에 따른 CIGS 전구체 수용성 분산용액의 제조 과정을 나타낸 모식도이다.
도 2는 본 발명의 실시예 4에 따라 CIGS 전구체 수용성 분산용액을 기판에 증착하는데 사용되는 스프레이 공정의 모식도이다.
도 3은 본 발명의 실시예 4에 따라 제조된 CIGS 전구체 박막의 SEM(Scanning Electron Microscope) 단면 사진 (a) 및 AFM(Atomic Force Microscope) 표면 사진 (b)이다.
도 4는 본 발명의 실시예 4에 따라 제조된 CIGS 전구체 박막의 EDS(Energy Disoersive Spectroscopy) 분석 결과를 나타낸 도면이다.
도 5는 본 발명의 실시예 4에 따라 제조된 CIGS 전구체 박막의 XRD(X-Ray Diffraction) 분석 결과를 나타낸 도면이다.
도 6은 본 발명의 실시예 5에 따른 열처리 조건을 나타낸 도면이다.
도 7은 본 발명의 실시예 5에 따라 냉각하면서 Se를 공급했을 때의 CIGS 박막의 SEM 단면 사진 (a) 및 냉각시 Se를 공급하지 않았을 때의 CIGS 박막의 SEM 단면 사진 (b)이다.BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view showing a process for producing a CIGS precursor water-soluble dispersion solution according to Examples 1 to 3 of the present invention. FIG.
2 is a schematic diagram of a spray process used to deposit a CIGS precursor aqueous dispersion solution on a substrate according to Example 4 of the present invention.
3 is a SEM (Scanning Electron Microscope) sectional view (a) and an AFM (Atomic Force Microscope) surface photograph (b) of a CIGS precursor thin film prepared according to Example 4 of the present invention.
4 is a graph showing the results of EDS (Energy Dispersive Spectroscopy) analysis of a CIGS precursor thin film prepared according to Example 4 of the present invention.
5 is a graph showing XRD (X-Ray Diffraction) analysis results of a CIGS precursor thin film prepared according to Example 4 of the present invention.
6 is a view showing a heat treatment condition according to
7 is a SEM cross-sectional photograph (a) of a CIGS thin film when Se is supplied while cooling according to Example 5 of the present invention, and a SEM cross-sectional photograph (b) of a CIGS thin film when Se is not supplied during cooling.
이하, 본 발명을 상세히 설명하기로 한다. 다만, 본 발명은 다양한 형태로 변경되어 구현될 수 있으며, 여기에서 설명하는 구현예에 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail. However, it should be understood that the present invention may be embodied in many other specific forms without departing from the spirit or essential characteristics thereof.
본 발명은 CIGS 전구체 분산용액을 제조하는 단계 (A), CIGS 전구체 분산용액을 기판에 증착시켜 CIGS 전구체 박막을 형성하는 단계 (B) 및 셀렌화 열처리하는 단계 (C)를 포함하는 다결정성 p-타입 CIGS 박막의 제조방법에 관한 것이며, 특히, 상기 셀렌화 열처리가 승온, 가열 및 냉각 단계로 이루어지고, 승온, 가열 및 냉각 단계 동안 Se가 공급되는 다결정성 p-타입 CIGS 박막의 제조방법에 관한 것이다.The present invention relates to a method for preparing a polycrystalline p-type precursor solution, comprising the steps of (A) preparing a CIGS precursor dispersion solution, (B) forming a CIGS precursor thin film by depositing a CIGS precursor dispersion solution on a substrate, and (C) Type CIGS thin film in which the selenization heat treatment is performed by heating, heating and cooling steps, and Se is supplied during the heating, heating and cooling steps, and more particularly, to a method for producing a polycrystalline p- will be.
이하에서는 각 단계별로 구체적으로 살펴보도록 한다.Hereinafter, each step will be described in detail.
단계 (A): Step (A): CIGSCIGS 전구체 분산용액의 제조 Preparation of precursor dispersion solution
본 발명의 일 측면에서, 상기 CIGS 전구체 분산용액을 제조하는 단계는 하기의 단계들을 포함할 수 있다.In one aspect of the present invention, the step of preparing the CIGS precursor dispersion solution may include the following steps.
(a) SeC(NH2)2 및 GaCl3에 증류수를 첨가하여 SeC(NH2)2:GaCl3 수용액을 제조한 후 교반하는 단계;(a) adding distilled water to SeC (NH 2 ) 2 and GaCl 3 to produce SeC (NH 2 ) 2 : GaCl 3 Preparing an aqueous solution and stirring;
(b) 상기 교반된 SeC(NH2)2:GaCl3 수용액을 필터링한 후 InCl3 용액과 혼합하여 SeC(NH2)2:GaCl3:InCl3 수용액을 제조하는 단계; 및(b) (NH 2) of the stirring SeC 2: 3 GaCl SeC (NH 2) was mixed with InCl 3 solution and then filtering the aqueous solution 2, comprising the steps of: preparing the aqueous solution of InCl 3;: 3 GaCl And
(c) 상기 제조된 SeC(NH2)2:GaCl3:InCl3 수용액에 증류수를 첨가한 후 CuCl2 수용액과 혼합하여 CIGS 전구체 분산용액을 제조하는 단계.(c) adding distilled water to the prepared SeC (NH 2 ) 2 : GaCl 3 : InCl 3 aqueous solution, and then mixing with an aqueous CuCl 2 solution to prepare a CIGS precursor dispersion solution.
상기 단계 (a)에서, SeC(NH2)2:GaCl3 수용액의 제조는 질소 분위기 하에서 이루어질 수 있으며, SeC(NH2)2에 GaCl3을 넣은 후 증류수를 첨가하는 방식으로 제조될 수 있다.In step (a), SeC (NH 2 ) 2 : GaCl 3 The aqueous solution may be prepared in a nitrogen atmosphere, or may be prepared by adding GaCl 3 to SeC (NH 2 ) 2 and then adding distilled water.
본 발명의 일 측면에서, 상기 단계 (b)의 필터링(filtering)은 PTFE 필터를 사용하여 수행하는 것이 바람직하다. 이러한 필터링를 통해 SeC(NH2)2:GaCl3 수용액 중 SeC(NH2)2에 존재하는 유기 성분과 단계 (c)에서 혼합되는 CuCl2와의 급격한 응집을 방지할 수 있다. 필터링을 거치지 않는 경우, SeC(NH2)2에 존재하는 유기 성분과 CuCl2와의 급격한 응집이 발생하여 CIGS 분산용액의 입자 크기가 커질 수 있다. 이 경우, 스프레이 공정에서 사용되는 분사 노즐이 막힐 가능성이 있다. In one aspect of the present invention, the filtering in step (b) is preferably performed using a PTFE filter. Through this filtering, SeC (NH 2 ) 2 : GaCl 3 It is possible to prevent the rapid aggregation of the organic component present in SeC (NH 2 ) 2 in aqueous solution and CuCl 2 mixed in step (c). Without filtering, rapid aggregation of CuCl 2 with organic components present in SeC (NH 2 ) 2 may occur and the particle size of the CIGS dispersion solution may increase. In this case, the spray nozzle used in the spray process may be clogged.
본 발명의 일 측면에서, 상기 단계 (c)에서, SeC(NH2)2:GaCl3:InCl3 수용액에 증류수를 첨가한 후의 용액의 농도가 0.20M 이하인 것이 바람직하다. 이는 CuCl2가 고농도 수용액에서 SeC(NH2)2와 응집하기 때문에 분산용액을 형성하지 못하게 되고, 이러한 응집은 수용액의 농도가 약 0.20M 이상인 경우에 주로 발생하기 때문이다. 이 때문에, 상기 단계 (c)에서는, SeC(NH2)2:GaCl3:InCl3 수용액에 증류수를 첨가하여 용액의 농도를 0.20M 이하로 조절한 후에 CuCl2 수용액을 첨가하는 것이 바람직하다.In one aspect of the present invention, in the step (c), the concentration of the solution after adding distilled water to the aqueous solution of SeC (NH 2 ) 2 : GaCl 3 : InCl 3 is preferably 0.20 M or less. This is because CuCl 2 can not form a dispersion solution because it coagulates with SeC (NH 2 ) 2 in a high concentration aqueous solution, and this aggregation occurs mainly when the concentration of aqueous solution is about 0.20 M or more. Therefore, in step (c), it is preferable to add distilled water to the aqueous solution of SeC (NH 2 ) 2 : GaCl 3 : InCl 3 to adjust the concentration of the solution to 0.20 M or less, followed by the addition of the aqueous solution of CuCl 2 .
또한, 본 발명의 일 측면에서, 상기 단계 (c)에서 제조된 CIGS 전구체 수용성 분산용액의 입자 크기는 0.3 mm 이내인 것이 바람직하다. 이는, 분산용액의 입자 크기가 0.3 mm를 초과할 경우에 스프레이 공정 시 사용되는 스프레이 노즐이 막힐 우려가 있기 때문이다.In one aspect of the present invention, the particle size of the CIGS precursor aqueous dispersion solution prepared in step (c) is preferably within 0.3 mm. This is because spray nozzles used in the spraying process may clog when the particle size of the dispersion solution exceeds 0.3 mm.
단계 (B): Step (B): CIGSCIGS 전구체 박막의 제조 Preparation of precursor thin films
본 발명은 상기 단계 (a) 내지 (c)를 거쳐 제조된 CIGS 전구체 수용성 분산용액을 기판에 증착시켜 CIGS 전구체 박막을 형성하는 단계를 포함하는, 다결정성 p-타입 CIGS 박막의 제조방법을 제공한다.The present invention provides a method for producing a polycrystalline p-type CIGS thin film comprising depositing a CIGS precursor aqueous dispersion solution prepared through the steps (a) to (c) on a substrate to form a CIGS precursor thin film .
일 측면에서, 상기 기판은 몰리브덴이 증착된 유리기판이 사용될 수 있으며, 운반 기체(carrier gas)로서 고순도의 질소가 사용될 수 있다. 또한, 상기 CIGS 전구체 수용성 분산용액은 중력식으로 공급될 수 있다.In one aspect, the substrate may be a glass substrate on which molybdenum is deposited, and nitrogen of high purity may be used as a carrier gas. In addition, the CIGS precursor water-soluble dispersion solution may be gravity-fed.
일 측면에서, 상기 증착은 스핀 코팅(spin coating), 딥 코팅(dip coating), 스프레이 코팅(spray coating), 닥터 블레이드코팅(Dr. blade coating), 롤코팅(roll coating), 바 코팅(bar coating), 그래비에 코팅(gravier coating), 슬롯다이코팅(slot-die coating) 중 적어도 어느 하나의 방법으로 코팅할 수 있으나, 이에 한정된 것은 아니다. 특히, 스프레이 코팅 방법을 사용하여 수행되는 것이 바람직하다. 스프레이 코팅 방법을 사용할 경우, 스프레이와 기판 사이의 거리는 약 25 cm 정도인 것이 바람직하다.In one aspect, the deposition can be accomplished by any suitable method including spin coating, dip coating, spray coating, Dr. blade coating, roll coating, bar coating, ), Gravure coating, and slot-die coating. However, the present invention is not limited thereto. Particularly, it is preferable to be carried out using a spray coating method. When using a spray coating method, the distance between the spray and the substrate is preferably about 25 cm.
단계 (C): Step (C): 다결정성Polycrystalline p- p- 타입type CIGSCIGS 박막의 제조 Manufacture of thin films
본 발명은 상기 단계 (B)를 통해 형성된 CIGS 전구체 박막을 셀렌화 열처리하는 단계를 포함하는, 다결정성 p-타입 CIGS 박막의 제조방법을 제공한다.The present invention provides a method for producing a polycrystalline p-type CIGS thin film comprising a step of subjecting a CIGS precursor thin film formed through the step (B) to a selenization heat treatment.
일 측면에서, 상기 셀렌화 열처리는 스프레이 공정을 통해 형성된 CIGS 전구체 박막에 Se를 지속적으로 공급하면서 열처리하는 것을 의미하며, 상기 Se는 승온, 가열 및 냉각 단계에서 150 Å/분 내지 200 Å/분으로 공급될 수 있다. 보다 바람직하게는, 상기 Se는 승온, 가열 및 냉각 단계에서 180 Å/분으로 공급될 수 있다. 특히, 냉각하는 단계에서 Se를 지속적으로 공급하는 경우, 도 7a와 같이 다결정성 CIGS 박막의 균일한 그레인(grain) 형성에 크게 도움을 주는 것을 확인할 수 있는데, 이는 CIGS 박막 내 존재하는 Se원소의 외부 확산을 막아주어 CIGS 조성 및 결정 구조가 유지되기 때문이다.In one aspect, the selenization heat treatment refers to heat treatment while continuously supplying Se to a CIGS precursor thin film formed through a spraying process, and the Se is heated at a temperature of 150 Å / min to 200 Å / min Can be supplied. More preferably, the Se can be supplied at a heating rate of 180 A / min in the heating, heating and cooling stages. Particularly, when Se is continuously supplied in the cooling step, it can be confirmed that the continuous supply of Se greatly contributes to the formation of uniform grains of the polycrystalline CIGS thin film as shown in FIG. 7A, And the CIGS composition and crystal structure are maintained.
본 발명의 일 측면에서, 상기 승온, 가열 각각 30분 내지 60분 동안 이루어질 수 있고 냉각 단계는 자연 냉각으로 이루어질 수 있다. 특히, 상기 승온, 가열 및 냉각 단계는 각각 30분 내지 40분 동안 이루어지는 것이 바람직하다. 가장 바람직하게는, 상기 승온, 가열 및 냉각 단계는 각각 30분 동안 이루어지는 것이 바람직하다.In one aspect of the present invention, the heating and heating may be performed for 30 minutes to 60 minutes each, and the cooling step may be performed by natural cooling. In particular, the heating, heating, and cooling steps are preferably performed for 30 minutes to 40 minutes, respectively. Most preferably, the heating, heating and cooling steps are each performed for 30 minutes.
본 발명의 일 측면에서, 상기 셀렌화 열처리시의 승온 속도는 15℃/분 내지 20℃/분이고, 냉각 속도는 1℃/분 내지 10℃/분 일 수 있다. 특히, 상기 셀렌화 열처리시의 승온 속도가 18.5℃/분이고, 냉각 속도가 자연 냉각인 것이 바람직하다.In one aspect of the present invention, the temperature raising rate during the selenization heat treatment may be 15 ° C / min to 20 ° C / min and the cooling rate may be 1 ° C / min to 10 ° C / min. Particularly, it is preferable that the rate of temperature rise during the selenization heat treatment is 18.5 ° C / min and the cooling rate is naturally cooled.
본 발명의 일 측면에서, 상기 셀렌화 열처리시 가열 단계에서의 온도는 550℃ 내지 600℃로 유지될 수 있다. 특히, 셀렌화 열처리시 가열 단계에서의 온도는 580℃ 내지 590℃로 유지되는 것이 바람직하다.In one aspect of the present invention, the temperature in the heating step in the selenization heat treatment may be maintained at 550 ° C to 600 ° C. In particular, it is preferable that the temperature in the heating step in the selenization heat treatment is maintained at 580 캜 to 590 캜.
다른 측면에서, 본 발명은 상기 단계 (A) 내지 (C)를 포함하는 방법에 따라 제조된 다결정성 p-타입 CIGS 박막에 관한 것이다.In another aspect, the present invention relates to a polycrystalline p-type CIGS thin film prepared according to a method comprising the above steps (A) to (C).
이하에서는, 첨부된 도면과 함께 실시예를 통하여 본 발명을 보다 상세하게 설명한다. 그러나 하기의 실시예는 본 발명의 내용을 구체화하기 위한 것일 뿐 실시예에 의해 본 발명이 한정되는 것은 아니다.
Hereinafter, the present invention will be described in more detail by way of examples with reference to the accompanying drawings. However, the following examples are intended only to illustrate the present invention and are not intended to limit the scope of the present invention.
실시예Example
실시예Example 1. One. SeCSeC (( NHNH 22 )) 22 :: GaClGaCl 33 수용액의 제조Preparation of aqueous solution
도 1에서 나타낸 바와 같이, 질소 분위기 하에서 SeC(NH2)2에 0.06M의 GaCl3를 넣고 증류수를 첨가하였다. 이어서, 실온에서 1000 rpm으로 20분 동안 교반하였다. As shown in FIG. 1, 0.06M GaCl 3 was added to SeC (NH 2 ) 2 under a nitrogen atmosphere, and distilled water was added. Subsequently, the mixture was stirred at room temperature for 20 minutes at 1000 rpm.
실시예Example 2. 2. InClInCl 33 의 첨가Addition of
도 1에서 나타낸 바와 같이, SeC(NH2)2:GaCl3 수용액을 0.45 ㎛ PTFE 필터로 필터링하였다. 다음으로, 0.30M의 InCl3 용액에 필터링된 SeC(NH2)2:GaCl3 수용액을 혼합하였다. As also shown in the 1, SeC (NH 2) 2: 3 GaCl The aqueous solution was filtered with a 0.45 탆 PTFE filter. Next, SeC (NH 2) filtered the InCl 3 solution of 0.30M 2: 3 GaCl Aqueous solution.
실시예Example 3. 3. CuClCuCl 22 의 첨가 및 ≪ / RTI & CIGSCIGS 전구체 분산용액의 제조 Preparation of precursor dispersion solution
도 1에서 나타낸 바와 같이, 증류수를 첨가하여 용액의 농도를 0.20M 이하로 맞춘 후 CuCl2를 첨가하였다. 도 1에 최종 생성된 CIGS 전구체 수용성 분산용액을 나타내었으며, CIGS 분산용액이 옅은 노란색 (Pale yellow)을 띠고 있음을 확인할 수 있다.As shown in FIG. 1, distilled water was added to adjust the concentration of the solution to 0.20 M or less, and then CuCl 2 was added. FIG. 1 shows the CIGS precursor water-soluble dispersion solution finally produced, and it can be confirmed that the CIGS dispersion solution is pale yellow.
실시예Example 4. 스프레이 공정을 이용한 4. Using a spray process CIGSCIGS 전구체 박막의 제조 Preparation of precursor thin films
도 2에 나타낸 바와 같이, 스프레이 공정을 사용하여 CIGS 전구체 박막을 형성하였다. 이 때, 운반 기체로는 고순도 질소를 사용하고 중력식으로 CIGS 전구체 용액을 공급하였으며, 하기 표 1과 같은 스프레이 공정 조건을 사용하였다. As shown in Figure 2, a CIGS precursor film was formed using a spray process. At this time, high purity nitrogen was used as a carrier gas, and a CIGS precursor solution was gravity-fed, and the spray process conditions as shown in Table 1 below were used.
농도가 0.08M인 CIGS 전구체 용액을 사용하여 몰리브덴 증착된 유리기판 위에 스프레이 공정으로 증착시킨 CIGS 전구체 박막의 SEM 단면 사진 (a) 및 AFM 표면 사진 (b)을 도 3에 나타내었다. 표면의 Root Mean Square(RMS) 값은 17.2nm이었다. 또한, CIGS 전구체 박막의 EDS 분석 결과를 도 4에 나타내었고, 이를 통해, Se, Cu, In 및 Ga의 atomic percentage는 각각 48.24, 27.70, 19.22, 4.84 at%임을 확인할 수 있다. 도 5에는 XRD 분석 결과를 나타내었으며, (112), (220), (312)로 표시된 CIGS의 주요 피크를 확인할 수 있다. (A) and AFM surface photograph (b) of a CIGS precursor thin film deposited by a spray process on a molybdenum deposited glass substrate using a CIGS precursor solution having a concentration of 0.08M are shown in FIG. The Root Mean Square (RMS) value of the surface was 17.2 nm. The results of the EDS analysis of the CIGS precursor thin film are shown in FIG. 4, which shows that the atomic percentages of Se, Cu, In and Ga are 48.24, 27.70, 19.22 and 4.84 at%, respectively. FIG. 5 shows the results of XRD analysis, and the major peaks of CIGS indicated by (112), (220) and (312) can be confirmed.
실시예Example 5. 5. 다결정성Polycrystalline p- p- 타입type CIGSCIGS 박막의 제조 Manufacture of thin films
Se을 공급하며 열처리하는 셀렌화 열처리 공정을 통해 다결정성 p-타입 CIGS 박막을 형성하였다. 이러한 셀렌화 열처리 공정은 30분에 걸쳐 온도를 상승시키는 단계, 30분 동안 증착을 하는 단계 및 30분 동안 냉각하는 단계로 수행되었으며, 도 6에 시간에 따른 셀렌화 열처리 공정 조건을 나타내었다. 또한, 온도 상승 단계 및 증착하는 단계뿐만 아니라 냉각하는 단계에서도 Se를 공급하였을 때 결정이 균일하게 생성된 CIGS 박막의 SEM 단면 사진 (a) 및 냉각하는 단계에서 Se를 공급하지 않았을 때 결정이 불균일하게 생성된 CIGS 박막의 SEM 단면 사진 (b)을 도 7에 나타내었다.Se, and annealed to form a polycrystalline p-type CIGS thin film. This selenization heat treatment process was performed by raising the temperature over 30 minutes, performing the deposition for 30 minutes, and cooling for 30 minutes, and FIG. 6 shows the selenization heat treatment process according to time. In addition, the SEM cross-sectional photograph (a) of the CIGS thin film in which the crystals were uniformly formed when the Se was supplied as well as the temperature raising step and the deposition step, as well as the cooling step, The SEM cross-sectional photograph (b) of the resulting CIGS thin film is shown in FIG.
Claims (10)
CIGS 전구체 분산용액을 기판에 증착시켜 CIGS 전구체 박막을 형성하는 단계; 및
셀렌화 열처리하는 단계를 포함하며,
상기 셀렌화 열처리는 승온, 가열 및 냉각 단계로 이루어지고, 승온, 가열 및 냉각 단계 동안 Se가 공급되는 것을 특징으로 하는, 다결정성 p-타입 CIGS 박막의 제조방법.Preparing a CIGS precursor dispersion solution;
Depositing a CIGS precursor dispersion solution on a substrate to form a CIGS precursor thin film; And
Selenizing heat treatment,
Wherein the selenization heat treatment comprises heating, heating and cooling steps, wherein Se is supplied during the heating, heating and cooling steps.
Se가 승온, 가열 및 냉각 단계에서 증착속도 150Å/분 내지 200Å/분으로 공급되는 것을 특징으로 하는, 다결정성 p-타입 CIGS 박막의 제조방법.The method according to claim 1,
Se is supplied at a deposition rate of 150 ANGSTROM / min to 200 ANGSTROM / min in a heating step, a heating step and a cooling step.
승온, 가열 및 냉각 단계가 각각 30분 내지 60분 동안 이루어지는 것을 특징으로 하는, 다결정성 p-타입 CIGS 박막의 제조방법.The method according to claim 1,
Wherein the heating, heating and cooling steps are performed for 30 minutes to 60 minutes, respectively.
셀렌화 열처리시의 승온 속도가 15℃/분 내지 20℃/분이고, 냉각 속도가 1℃/분 내지 10℃/분인 것을 특징으로 하는 다결정 p-타입 CIGS 박막의 제조방법.The method according to claim 1,
Wherein the rate of temperature rise during the selenization heat treatment is from 15 ° C / min to 20 ° C / min, and the cooling rate is from 1 ° C / min to 10 ° C / min.
셀렌화 열처리시의 가열 단계에서 온도가 550℃ 내지 600℃로 유지되는 것을 특징으로 하는, 다결정성 p-타입 CIGS 박막의 제조방법.5. The method according to any one of claims 1 to 4,
Characterized in that the temperature is maintained at 550 占 폚 to 600 占 폚 in the heating step during the selenization heat treatment.
상기 CIGS 전구체 분산용액을 제조하는 단계가
(a) SeC(NH2)2 및 GaCl3에 증류수를 첨가하여 SeC(NH2)2:GaCl3 수용액을 제조한 후 교반하는 단계;
(b) 상기 교반된 SeC(NH2)2:GaCl3 수용액을 필터링한 후 InCl3 용액과 혼합하여 SeC(NH2)2:GaCl3:InCl3 수용액을 제조하는 단계; 및
(c) 상기 제조된 SeC(NH2)2:GaCl3:InCl3 수용액에 증류수를 첨가한 후 CuCl2 수용액과 혼합하여 CIGS 전구체 분산용액을 제조하는 단계를 포함하는 것을 특징으로 하는, 다결정성 p-타입 CIGS 박막의 제조방법.5. The method according to any one of claims 1 to 4,
The step of preparing the CIGS precursor dispersion solution
(a) adding distilled water to SeC (NH 2 ) 2 and GaCl 3 to produce SeC (NH 2 ) 2 : GaCl 3 Preparing an aqueous solution and stirring;
(b) (NH 2) of the stirring SeC 2: 3 GaCl SeC (NH 2) was mixed with InCl 3 solution and then filtering the aqueous solution 2, comprising the steps of: preparing the aqueous solution of InCl 3;: 3 GaCl And
(c) adding distilled water to the prepared SeC (NH 2 ) 2 : GaCl 3 : InCl 3 aqueous solution and then mixing with an aqueous CuCl 2 solution to prepare a CIGS precursor dispersion solution. - Method of manufacturing type CIGS thin film.
상기 (c) 단계에서, SeC(NH2)2:GaCl3:InCl3 수용액에 증류수를 첨가한 후의 용액의 농도가 0.20M 이하인 것을 특징으로 하는, 다결정성 p-타입 CIGS 박막의 제조방법.The method according to claim 6,
Wherein the concentration of the solution after adding distilled water to an aqueous solution of SeC (NH 2 ) 2 : GaCl 3 : InCl 3 is 0.20 M or less in the step (c).
상기 (c) 단계에서 제조된 CIGS 전구체 분산용액의 입자 크기가 0.3 mm 이내인 것을 특징으로 하는, 다결정성 p-타입 CIGS 박막의 제조방법.The method according to claim 6,
Wherein the CIGS precursor dispersion solution prepared in step (c) has a particle size of 0.3 mm or less.
상기 증착이 스프레이-코팅(spray-coating) 방법을 사용하여 수행되는 것을 특징으로 하는, 다결정성 p-타입 CIGS 박막의 제조방법.The method according to claim 1,
Wherein the deposition is performed using a spray-coating method. ≪ RTI ID = 0.0 > 8. < / RTI >
A polycrystalline p-type CIGS thin film prepared according to the method of any one of claims 1 to 4.
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