KR20180034285A - Manufacturing method of thin film solar cell light absorber with controlled selenium and sulfer ration and thin film solar cell comprising therof - Google Patents
Manufacturing method of thin film solar cell light absorber with controlled selenium and sulfer ration and thin film solar cell comprising therof Download PDFInfo
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- 239000011669 selenium Substances 0.000 title claims abstract description 91
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 51
- 239000010409 thin film Substances 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title abstract description 15
- 239000006096 absorbing agent Substances 0.000 title description 3
- 238000000034 method Methods 0.000 claims abstract description 75
- 230000008569 process Effects 0.000 claims abstract description 52
- 238000010438 heat treatment Methods 0.000 claims abstract description 46
- 239000007789 gas Substances 0.000 claims abstract description 39
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 35
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 28
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 239000011593 sulfur Substances 0.000 claims abstract description 26
- 125000003748 selenium group Chemical group *[Se]* 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 238000002347 injection Methods 0.000 claims abstract description 12
- 239000007924 injection Substances 0.000 claims abstract description 12
- 238000005987 sulfurization reaction Methods 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims description 34
- 239000002184 metal Substances 0.000 claims description 34
- 239000002243 precursor Substances 0.000 claims description 32
- 150000002736 metal compounds Chemical class 0.000 claims description 11
- 229910052738 indium Inorganic materials 0.000 claims description 6
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229940065287 selenium compound Drugs 0.000 claims description 5
- 150000003343 selenium compounds Chemical class 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 238000009834 vaporization Methods 0.000 claims description 5
- 230000008016 vaporization Effects 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 4
- 239000007769 metal material Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910005543 GaSe Inorganic materials 0.000 claims description 3
- 240000002329 Inga feuillei Species 0.000 claims description 3
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 3
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 claims description 3
- 230000002250 progressing effect Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- 238000010926 purge Methods 0.000 abstract description 5
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 20
- 239000000758 substrate Substances 0.000 description 19
- 239000010949 copper Substances 0.000 description 14
- 239000011135 tin Substances 0.000 description 9
- 230000031700 light absorption Effects 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000004544 sputter deposition Methods 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000002250 absorbent Substances 0.000 description 4
- 230000002745 absorbent Effects 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 229910052733 gallium Inorganic materials 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000005361 soda-lime glass Substances 0.000 description 4
- 231100000331 toxic Toxicity 0.000 description 4
- 230000002588 toxic effect Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 229910000058 selane Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910016001 MoSe Inorganic materials 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910052798 chalcogen Inorganic materials 0.000 description 2
- -1 chalcogenide compound Chemical class 0.000 description 2
- 150000001787 chalcogens Chemical class 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005486 sulfidation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005289 physical deposition Methods 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- VIDTVPHHDGRGAF-UHFFFAOYSA-N selenium sulfide Chemical compound [Se]=S VIDTVPHHDGRGAF-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 238000000427 thin-film deposition Methods 0.000 description 1
- DZXKSFDSPBRJPS-UHFFFAOYSA-N tin(2+);sulfide Chemical compound [S-2].[Sn+2] DZXKSFDSPBRJPS-UHFFFAOYSA-N 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 231100000925 very toxic Toxicity 0.000 description 1
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- H01L31/042—PV modules or arrays of single PV cells
- H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
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- 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
- H01L31/03923—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 including AIBIIICVI compound materials, e.g. CIS, CIGS
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Abstract
Description
본 발명은 셀렌 금속을 이용한 셀렌화 열처리와 황화수소 가스를 이용한 황화 열처리의 연속 처리 공정으로 광흡수층 내의 셀렌 및 황의 조성이 조절된 박막 태양전지의 광흡수층 제조방법 및 상기 방법으로 제조된 광흡수층을 포함하는 박막 태양전지에 관한 것이다.The present invention relates to a method of manufacturing a light absorbing layer of a thin film solar cell in which the composition of selenium and sulfur in a light absorbing layer is controlled by a continuous process of selenization heat treatment using selenium metal and sulfiding heat treatment using hydrogen sulfide gas and a light absorbing layer To a thin film solar cell.
CIGS는 구리(Cu)-인듐(In)-갈륨(Ga)-셀레늄(Se)의 4원소로 이루어진 칼코제나이드 계 화합물 반도체로써 태양전지 흡수층으로 많은 연구가 진행되었다. 이 소재는 직접천이 반도체 화합물이기 때문에 태양광 에너지 전환 효율이 좋으며, Al, S 등의 원소를 첨가 도핑함으로써 에너지 갭을 1.0 ~ 2.7 eV까지 광대역으로 변환할 수 있어 광변환 효율을 더욱 향상시킬 수 있다고 알려져 있다. CIGS는 3원소(ternary) 반도체 CuInSe2(CIS)에 갈륨(Ga) 원소를 In으로 치환하여 도핑함으로써 효율을 증가시킨 것이다. 이 소재의 광흡수 계수는 105cm-1로서 광흡수 소재 중 가장 높아 고효율 태양전지를 만들 수 있다. 또한, 환경 안정성과 방사선에 대한 소재의 저항력도 매우 강하다. 두께 1~ 2 um의 박막으로도 고효율 태양전지 제조가 가능하며, 또한 장기적으로 전기, 광학적 안정성이 매우 우수한 특성을 보이고 있어 태양전지의 광흡수층으로 매우 이상적인 박막이다. 이에 따라 현재 사용되고 있는 고가의 결정질 실리콘 태양전지를 대체하여 태양광 발전의 경제성 및 환경 친화적 저가 고효율 태양전지 재료로 활발히 연구되어 지고 있다.CIGS is a chalcogenide compound semiconductor composed of four elements of copper (Cu) - indium (In) - gallium (Ga) - selenium (Se) Since this material is a direct transition semiconductor compound, it has good solar energy conversion efficiency. By adding doping elements such as Al and S, it is possible to convert the energy gap to a wide band from 1.0 to 2.7 eV, It is known. CIGS is an increase in efficiency by doping a ternary semiconductor CuInSe 2 (CIS) with a gallium (Ga) element substituted with In. The light absorption coefficient of this material is 10 5 cm -1, which is the highest among the light absorbing materials, so that a high efficiency solar cell can be produced. In addition, the environmental stability and the resistance of the material to radiation are also very strong. It is possible to fabricate high-efficiency solar cells with a thickness of 1 ~ 2 μm, and has excellent electrical and optical stability over the long term, making it a very ideal thin film for the light absorption layer of solar cells. As a result, it has been actively researched as an economical and environment friendly low cost and high efficiency solar cell material of solar power generation in place of the expensive crystalline silicon solar cell currently used.
CIGS (CIS)를 광흡수층으로 하는 태양전지 구조의 제작은 다양한 증착 방법으로 진행할 수 있으며, 실리콘 계열과 달리 고가의 장비 사용하지 않는 용액 시스템으로도 제작이 가능하며, 물리적 및 화학적 증착 방법 역시 쉽게 접근 할 수 있다.The fabrication of the solar cell structure using CIGS (CIS) as the light absorbing layer can be performed by various deposition methods. Unlike the silicon type, it is possible to fabricate a solution system that does not use expensive equipment, and the physical and chemical deposition methods are easily accessible can do.
CIGS 태양전지 계열의 기판 재료로는 유리 기판을 사용하는데, 이외에 알루미나와 같은 세라믹 기판 및 스텐레스 스틸과 같은 금속 재료의 기판도 사용하여 제작하고 있다. 유리기판은 코르닝(Corning) 유리 기판이 있지만 값이 비싸 사용에 어려움이 있어 가격이 낮은 소다라임 유리를 많이 사용하고 있다. 그 밖에 폴리이미드 기판이 있지만 CIGS 계열의 박막 증착 공정 온도 조건으로 사용하기에는 어려움이 있다. 소다라임 유리를 기판으로 사용하는 경우에는 유리의 불순물인 Na 이온이 Mo 후면 전극층 위로 디퓨젼되어 CIGS 흡수층으로 확산되어 지는데 이때 흡수층의 결정성이 향상되고 표면이 개선되며, 정공의 밀도가 높아져서 fill factor 와 개방전압이 높아져 효율 특성이 향상된다고 알려져 있다.The CIGS solar cell substrate is made of a glass substrate. In addition, a ceramic substrate such as alumina and a substrate made of a metal material such as stainless steel are also used. Although the glass substrate is a Corning glass substrate, it is expensive, which makes it difficult to use, so that a low cost soda lime glass is used. In addition, there are polyimide substrates, but it is difficult to use it as a temperature condition of the CIGS type thin film deposition process. When soda lime glass is used as a substrate, Na ions, which are impurities of glass, are diffused onto the Mo back electrode layer and diffused into the CIGS absorption layer. At this time, the crystallinity of the absorption layer is improved and the surface is improved. And the open-circuit voltage is increased to improve the efficiency characteristics.
또한, 광흡수층은 초기 삼원화합물인 CIS 태양전지에 대한 연구가 활발히 진행되었으나, 에너지 밴드갭이 1 eV 로 낮아 높은 단락전류는 확보할 수 있으나 개방전압이 낮아 효율 확보 측면에서는 어려움을 보였다. 이에 따라 물질 첨가를 통한 밴드갭 조절로 효율을 높이고자 하였고 연구가 진행된 물질이 사원계 화합물인 CIGS 이다. CISe에서 In 일부를 Ga으로 대체하여 밴드갭을 적정수준인 1.5 eV까지 올렸으며 Ga을 조절하여 CIGS 화합물의 밴드갭을 조절하는 연구가 많이 진행되고 있으나, 아직까지 효과가 우수한 기술이 개발되지 못하고 있는 실정이다. In addition, studies on CIS solar cell, which is an early trivalent compound, have been actively carried out. However, since the energy bandgap is as low as 1 eV, a short circuit current can be secured, but the open circuit voltage is low. Therefore, we tried to increase the efficiency by controlling the bandgap through the addition of materials. The studied material is CIGS, which is an empirical compound. In CISe, a part of In has been replaced with Ga to increase the band gap to an appropriate level of 1.5 eV. There have been many studies to control the bandgap of CIGS compound by controlling Ga, but a technique with excellent effect has not yet been developed It is true.
또한, CIGS 광흡수층의 일반적인 제조 공정은 스퍼터링 공정을 통하여 전구체를 형성한 후, 열처리하여 흡수층을 제작하는 2-단계 공정으로 진행되고 이 공정에 대부분 수소 셀렌(H2Se)를 사용하는데, H2Se 가스는 매우 독성이며, 재료 및 운용 비용이 높기 때문에 공정에 제약이 많다.In addition, the general manufacturing process of the CIGS light absorbing layer is a two-step process in which a precursor is formed through a sputtering process and then heat-treated to form an absorbing layer. In this process, hydrogen selenide (H2Se) It is toxic, and there are many process restrictions because of high material and operation cost.
2-단계 공정을 이용하여 제작한 CIGS 흡수층은 Mo 계면쪽 Ga 원소 축척 문제가 발생하는데, 이러한 문제를 해결하고자 단계적 열처리를 적용하여 H2S 가스를 마지막에 주입하는 SAS(Sulfurization after selenization) 공정 기술을 적용하고 있다.The CIGS absorption layer produced by the two-step process causes a Ga scale problem in the Mo interface. To solve this problem, the Sulfurization after selenization (SAS) process, in which H2S gas is injected at the end by applying a stepwise heat treatment, is applied .
또한, CIGS 화합물 태양전지는 In, Ga 재료가 고가라는 단점으로 인하여, In, Ga을 Zn, Sn으로 대체함으로써 새로운 태양전지를 제작하는 연구가 진행되고 있는데, CZTS 태양전지는 Zn 와 Sn이 자연적으로 매장량이 매우 풍부한 원소이고, 상대적으로 값싸며, 유해성이 낮기 때문에 친환경적인 흡수층 물질로 평가받고 있다. 또한, CZTSe 나 CZTSSe 제작은 CZT 및 CZTS 의 전구체를 셀렌화 열처리 공정을 통하여 제조되고 있다. 셀렌화 열처리 공정을 통한 CZTSe 박막은 높은 흡광계수로 인하여 태양전지로서의 특성이 우수하다는 장점을 가지고 있지만, 낮은 밴드갭 특성으로 인하여 태양전지 개방전압이 낮은 문제점이 있다. 그리고 황화 열처리 공정을 통한 CZTS 박막은 높은 밴드갭 특성을 가지나, 자체의 높은 저항 특성 및 낮은 케리어 수명으로 인하여 전류특성이 낮은 문제점이 있다.In addition, due to the disadvantage that CIGS compound solar cells are expensive in In and Ga materials, researches are being made to fabricate new solar cells by replacing In, Ga with Zn and Sn. CZTS solar cells, The deposits are highly abundant, relatively inexpensive, and low in toxicity, making them an eco-friendly absorbent material. In addition, CZTSe and CZTSSe are manufactured by the selenization heat treatment process of precursors of CZT and CZTS. The CZTSe thin film through the selenization annealing process has an advantage that it has excellent characteristics as a solar cell due to its high extinction coefficient, but has a problem that the open cell voltage of the solar cell is low due to low bandgap characteristics. The CZTS thin film through the sulfidation heat treatment process has a high bandgap characteristic, but has a low current characteristic due to its high resistance characteristic and low carrier lifetime.
또한, 양산화 공정에서 사용하는 셀렌화 열처리 공정은 일반적으로 H2Se 가스를 사용하지만 H2Se는 매우 독성 가스이며 고가인 문제점이 있다. 반면 순수 Se 금속을 이용한 셀렌화 공정은 저가이며, 과량 사용시 단락 전류의 증가 등의 장점이 있다. 하지만 과량을 사용하게 되면 공정 후 잔유물이 생겨 제거 및 셀렌-황화 동시 열처리가 어려우며, 후면 전극 층의 MoSe2 층 두께가 증가하여, S 처리 시 소자의 직렬 저항 증가를 일으킨다. In addition, the selenization heat treatment process used in the mass production process generally uses H 2 Se gas, but H 2 Se is a very toxic gas and expensive. On the other hand, the selenization process using pure Se metal is inexpensive and has advantages such as an increase in short circuit current in an excessive use. However, if excess amount is used, it is difficult to remove and remove selenium-sulphide by simultaneous heat treatment due to the residue after the process, and the thickness of the MoSe 2 layer of the rear electrode layer is increased, which causes an increase in series resistance of the device during S treatment.
또한, 과량을 사용하게 되면 공정 후 잔유물이 생겨 제거하기가 어려운 단점이 있으나, 태양전지 소자 측면에서 순수 Se 금속을 과량 사용 시 단락 전류의 증가 등의 장점이 있으며, 후면전극 층의 MoSe2 층 두께가 증가한다.In addition, there is a disadvantage in that excessive use may result in residue after the process. However, there is an advantage such as an increase in short circuit current when the pure Se metal is excessively used on the side of the solar cell element, and the MoSe 2 layer thickness .
CZTS 계의 밴드갭은 S 와 Se 비율의 양으로 조절이 가능하지만 현재까지 S와 Se 의 비율 조절은 열처리 공정 전 주입한 칼코젠 소스 S/Se 비에 따라 제조된 흡수층에서 S/Se 이 달라지는 실험이 대부분으로, 순수 금속 셀렌을 이용한 셀렌화 공정을 통한 효율이 우수한 CZTSSe 광흡수층의 제조를 위해 광흡수층의 밴드갭을 조절할 수 있는 새로운 기술개발이 필요한 실정이다.The bandgap of the CZTS system can be controlled by the amount of S and Se, but until now, the ratio of S to Se is controlled by the S / Se ratio of the absorbed layer prepared according to the S / Se ratio of chalcogen source before the heat treatment In order to manufacture CZTSSe light absorbing layer with high efficiency through the selenization process using pure metal selenium, it is necessary to develop a new technique for controlling the band gap of the light absorbing layer.
이에 본 발명은 순수 셀렌 금속을 이용하여 셀렌화 공정 후 황화 열처리를 수행하여 광흡수층 내의 Se 및 S를 조절함으로써 매우 독성이며 고가인 H2Se 가스를 사용하지 않고도 광흡수층의 밴드갭을 조절할 수 있는 방법을 확립함으로써 본 발명을 완성하였다.Therefore, the present invention can control the bandgap of the light absorption layer without using highly toxic and expensive H2Se gas by controlling the Se and S in the light absorption layer by performing the sulphiding heat treatment after the selenization process using pure selenium metal Thereby completing the present invention.
따라서 본 발명의 목적은 광흡수층 내의 셀렌(Se) 및 황(S)의 조성이 조절된 박막 태양전지의 광흡수층 제조방법을 제공하는 것이다.Accordingly, an object of the present invention is to provide a method of manufacturing a light absorbing layer of a thin film solar cell in which the composition of selenium (Se) and sulfur (S) in a light absorbing layer is controlled.
본 발명의 다른 목적은 본 발명의 방법으로 제조된 황(S)/셀렌(Se)의 조성비가 0.05~0.20인 광흡수층을 포함하는 박막 태양전지를 제공하는 것이다.Another object of the present invention is to provide a thin film solar cell comprising a light absorbing layer having a composition ratio of sulfur (S) / selenium (Se) produced by the method of the present invention is 0.05 to 0.20.
따라서 본 발명은, 후면 전극층 상에 금속, 금속 황 또는 금속 셀렌을 포함하는 금속 화합물 전구체를 증착하는 단계; 순수 셀렌 금속을 이용하여 셀렌(Se)화 공정을 진행하는 단계; 셀렌화 공정 후 잔유 셀렌 물질 및 기화 가스를 제거(purge) 하는 단계; 및 황화 수소(H2S) 가스 주입 및 황화 열처리를 순차적으로 진행하는 단계를 포함하는, 광흡수층 내의 셀렌(Se) 및 황(S)의 조성이 조절된 박막 태양전지의 광흡수층 제조방법을 제공한다. Accordingly, the present invention provides a method of manufacturing a thin film transistor, comprising: depositing a metal compound precursor including a metal, metal sulfur or metal selenium on a rear electrode layer; Conducting a selenization (Se) process using pure selenium metal; Purifying the residual selenium material and the vaporized gas after the selenization process; (S) and sulfur (S) in a light absorbing layer, which comprises sequentially injecting hydrogen sulfide (H 2 S) gas and sulfurizing heat treatment.
본 발명의 일실시예에 따르면, 상기 금속 화합물 전구체는 Cu, Zn, Sn 또는 In의 순수 금속 물질; CuGa 또는 CuIn의 금속 합금 물질; CuS, ZnS 또는 SnS 의 금속 황화 물질; CuSe, ZnSe, SnSe, InGaSe, GaSe 또는 InSe 의 금속 셀렌 화합물; 및 CuSSe, ZnSSe 또는 SnSSe 의 금속 황화 셀렌 화합물;로 이루어진 군 중에서 선택되는 것일 수 있다.According to an embodiment of the present invention, the metal compound precursor may be a pure metal material of Cu, Zn, Sn or In; A metal alloy material of CuGa or CuIn; Metal sulfides of CuS, ZnS or SnS; Metal selenium compounds of CuSe, ZnSe, SnSe, InGaSe, GaSe or InSe; And a metal sulfide selenium compound of CuSSe, ZnSSe or SnSSe.
본 발명의 일실시예에 따르면, 셀렌화 공정은 상기 금속 전구체 화합물의 휘발을 억제하기 위하여 500 Torr ~ 750 Torr의 압력에서 수행하는 것일 수 있다. According to one embodiment of the present invention, the selenization process may be performed at a pressure of 500 Torr to 750 Torr to suppress the volatilization of the metal precursor compound.
본 발명의 일실시예에 따르면, 금속 셀렌의 무게는 셀렌(Se)화 공정을 위한 열처리 챔버 부피 300 cm3 당 0.05 ~ 0.5 g으로 사용하는 것일 수 있다.According to one embodiment of the present invention, the weight of the metal selenium may be 0.05 to 0.5 g per 300 cm 3 of the heat treatment chamber volume for the selenization (Se) process.
본 발명의 일실시예에 따르면, 셀렌화 공정 후 잔유 셀렌 물질 및 기화 가스 제거는 150~300 Torr에서 수행하는 것일 수 있다. According to one embodiment of the present invention, the residual selenium material and the degassing gas removal after the selenization process may be performed at 150 to 300 Torr.
본 발명의 일실시예에 따르면, 황화 수소 가스 주입 후, 황화 열처리는 500~1000 Torr에서 수행하는 것일 수 있다.According to one embodiment of the present invention, after the hydrogen sulfide gas injection, the sulfurization heat treatment may be performed at 500 to 1000 Torr.
본 발명의 일실시예에 따르면, 황화 수소(H2S) 가스 주입은 100 sccm ~ 2000 sccm의 양으로 주입하는 것일 수 있다.According to one embodiment of the present invention, hydrogen sulfide (H2S) gas injection may be performed in an amount of 100 sccm to 2000 sccm.
본 발명의 일실시예에 따르면, 상기 셀렌(Se) 및 황(S)의 조성은 S/Se가 0.05~0.20의 비율을 갖는 것일 수 있다.According to an embodiment of the present invention, the composition of selenium (Se) and sulfur (S) may have a ratio of S / Se of 0.05 to 0.20.
또한 본 발명은 본 발명의 방법으로 제조된 황(S)/셀렌(Se)의 조성비가 0.05~0.20인 광흡수층을 포함하는 박막 태양전지를 제공한다.The present invention also provides a thin film solar cell comprising a light absorption layer having a composition ratio of sulfur (S) / selenium (Se) of 0.05 to 0.20 produced by the method of the present invention.
본 발명의 일실시예에 따르면, 상기 태양전지는 Cu2InGa(S,Se)4 또는 Cu2ZnSn(S,Se)4 기반의 5원계 화합물 박막 태양전지일 수 있다.According to an embodiment of the present invention, the solar cell may be a quaternary compound thin film solar cell based on Cu 2 InGa (S, Se) 4 or Cu 2 ZnSn (S, Se) 4 .
본 발명의 광흡수층 내의 셀렌(Se) 및 황(S)의 조성이 조절된 박막 태양전지의 광흡수층 제조방법은 순수 셀렌 금속을 이용하여 셀렌화 공정 후 황화 열처리를 수행함으로써 광흡수층 내의 셀렌 및 황의 함량을 효과적으로 조절할 수 있는 장점이 있고, 이러한 본 발명의 방법은 매우 독성이며 고가인 H2Se 가스를 사용하지 않고도 효과적으로 광흡수층의 밴드갭을 조절할 수 있는 효과가 있다.The method of manufacturing a light absorbing layer of a thin film solar cell in which the composition of selenium (Se) and sulfur (S) is controlled in the light absorbing layer of the present invention is characterized by performing sulphiding heat treatment after selenization using pure selenium metal, The method can effectively control the band gap of the light absorption layer without using the highly toxic and expensive H2Se gas.
도 1은 본 발명의 열처리 전의 금속 전구체 구조를 나타낸 모식도이다.
도 2는 열처리 장비 내에 안착 되는 구조물을 나타낸 모식도이다.
도 3은 본 발명의 일실시예에서 실시한 열처리 공정의 온도 프로파일 그래프를 나타낸 것이다.
도 4는 본 발명의 일실시예에서 열처리 한 박막으로 제조한 태양전지 소자에 대한 EQE 특성 분석 결과를 나타낸 그래프이다.BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing the structure of a metal precursor before heat treatment of the present invention. Fig.
Fig. 2 is a schematic view showing a structure that is seated in a heat treatment equipment.
FIG. 3 is a graph showing a temperature profile of a heat treatment process performed in an embodiment of the present invention.
4 is a graph showing the results of analysis of EQE characteristics for a solar cell device fabricated from a thin film heat-treated in an embodiment of the present invention.
본 발명은 광흡수층 내의 셀렌(Se) 및 황(S)의 조성이 조절된 박막 태양전지의 광흡수층을 제조하는 새로운 방법을 제공함에 특징이 있다.The present invention is characterized by providing a novel method of manufacturing a light absorbing layer of a thin film solar cell in which the composition of selenium (Se) and sulfur (S) in a light absorbing layer is controlled.
본 발명에 따른 광흡수층 내의 셀렌 및 황의 조성이 조절된 광흡수층은, 후면 전극층 상에 금속, 금속 황 또는 금속 셀렌을 포함하는 금속 화합물 전구체를 증착하는 단계; 순수 셀렌 금속을 이용하여 셀렌(Se)화 공정을 진행하는 단계; 셀렌화 공정 후 잔유 셀렌 물질 및 기화 가스를 제거(purge) 하는 단계; 및 황화 수소(H2S) 가스 주입 및 황화 열처리를 순차적으로 진행하는 단계를 포함한다.The light absorbing layer in which the composition of selenium and sulfur in the light absorbing layer according to the present invention is adjusted includes a step of depositing a metal compound precursor including a metal, metal sulfur or metal selenium on the rear electrode layer; Conducting a selenization (Se) process using pure selenium metal; Purifying the residual selenium material and the vaporized gas after the selenization process; And a step of sequentially injecting a hydrogen sulfide (H2S) gas and a sulfurizing heat treatment.
특히 본 발명은 순수 셀렌 금속을 이용하여 셀렌화 공정 후 황화 열처리를 수행함으로써 광흡수층 내의 셀렌 및 황의 함량을 효과적으로 조절할 수 있는 방법을 제공함으로써, 종래 사용되던 매우 독성이며 고가인 H2Se 가스를 사용하지 않고도 효과적으로 광흡수층의 밴드갭을 조절할 수 있다.In particular, the present invention provides a method of effectively controlling the content of selenium and sulfur in the light absorbing layer by performing a sulphiding heat treatment after the selenization process using pure selenium metal, and thus, without using a conventionally used highly toxic and expensive H2Se gas The bandgap of the light absorption layer can be effectively controlled.
하기에서는 본 발명에 따른 광흡수층 내의 셀렌(Se) 및 황(S)의 조성이 조절된 박막 태양전지의 광흡수층 제조방법에 대해 구체적으로 설명하며, 본 발명의 방법으로 제조된 열처리 전의 금속 전구체의 구조는 도 1에 나타내었다. Hereinafter, a method for manufacturing a light absorbing layer of a thin film solar cell in which the composition of selenium (Se) and sulfur (S) in a light absorbing layer according to the present invention is controlled will be described in detail. The metal precursor The structure is shown in Fig.
본 발명에 따른 태양전지의 광흡수층 제조를 위해 먼저, 후면 전극층 상에 금속, 금속 황 또는 금속 셀렌을 포함하는 금속 화합물 전구체를 증착한다.In order to manufacture a light absorbing layer of a solar cell according to the present invention, a metal compound precursor including a metal, metal sulfur or metal selenium is deposited on a rear electrode layer.
후면 전극층은 기판 상에 형성된 것으로, 상기 기판은 고온에서 사용 가능한 기판이라면 모두 가능하며, 이에 제한되지는 않지만, 소다 라임(soda-lime) 유리 , 웨이퍼(wafer) 또는 퀄츠 기판을 사용할 수 있다. The back electrode layer is formed on the substrate. The substrate may be any substrate that can be used at high temperatures, and a soda-lime glass, a wafer, or a QUALZ substrate may be used, although not limited thereto.
상기 기판은 상기 기판은 먼저 아세톤, 메탄올, 2차 증류수를 이용하여 순차적으로 세척하며, 바람직하게는 초음파를 함께 이용하여 깨끗하게 세척한다.The substrate is washed sequentially with acetone, methanol, and secondary distilled water, and then cleaned with ultrasound.
세척된 기판 위에 후면 전극층을 형성하며, 상기 후면 전극은 몰리브덴 전극을 사용할 수 있다. A rear electrode layer is formed on the cleaned substrate, and the rear electrode may be a molybdenum electrode.
상기 후면 전극층 상에 금속, 금속 황 또는 금속 셀렌을 포함하는 금속 화합물 전구체의 증착은 스퍼터링 방법, 증발 방식 또는 용액 공정 방식 모두 사용 가능하며, 본 발명의 일실시예에서는 스퍼터링 방법으로 증착하였다. The metal compound precursor including metal, metal sulfur or metal selenium on the rear electrode layer can be deposited by a sputtering method, an evaporation method, or a solution processing method. In one embodiment of the present invention, the metal compound precursor is deposited by a sputtering method.
또한 상기 금속 화합물 전구체는 Cu, Zn, Sn 또는 In의 순수 금속 물질; CuGa 또는 CuIn의 금속 합금 물질; CuS, ZnS 또는 SnS 의 금속 황화 물질; CuSe, ZnSe, SnSe, InGaSe, GaSe 또는 InSe 의 금속 셀렌 화합물; 및 CuSSe, ZnSSe 또는 SnSSe 의 금속 황화 셀렌 화합물;로 이루어진 군 중에서 선택된 하나 이상의 조합을 적층 구조 형태로 증착할 수 있다.The metal compound precursor may be a pure metal material of Cu, Zn, Sn or In; A metal alloy material of CuGa or CuIn; Metal sulfides of CuS, ZnS or SnS; Metal selenium compounds of CuSe, ZnSe, SnSe, InGaSe, GaSe or InSe; And a metal sulphide selenide compound of CuSSe, ZnSSe or SnSSe can be deposited in the form of a laminate structure.
바람직하게는 순수 금속의 Cu, Zn 및 Sn 타겟을 이용하여 증착할 수 있으며, 금속 화합물 전구체의 순서는 열처리 후의 조성비 및 균일도를 고려하여 Cu/Sn/Zn/Mo의 순서를 갖는 적층 구조 증착할 수 있다. The order of the metal compound precursors can be deposited in the order of Cu / Sn / Zn / Mo, considering the composition ratio and uniformity after the heat treatment. have.
다음으로, 순수 셀렌 금속을 이용하여 셀렌(Se)화 공정을 진행하는데, 이때 상기 셀렌화 공정은 도 2의 열처리 장비를 이용하여 수행할 수 있다. 도 2에 기재된 열처리 장비 내에 삽입되는 구조물은 기판 서셉터용 트레이와 셀렌 금속 기화용 트레이 및 기화 가스의 밀폐용 플랭크 기구를 포함하도록 구성되어 있다. Next, the pure selenium metal is used to carry out the selenization (Se) process, wherein the selenization process can be performed using the heat treatment equipment of FIG. The structure to be inserted into the heat treatment equipment described in FIG. 2 is configured to include a tray for a substrate susceptor, a tray for selenium metal vaporization, and a flank mechanism for sealing a vaporized gas.
셀렌화 공정은 앞서 증착된 금속 화합물 전구체를 열처리 장비에 넣고 진행하며, 셀렌화를 위한 셀렌 금속은 전구체 하단에 안착시켜 수행하며, 이때 상기 셀렌 금속은 열처리 챔버 부피 300 cm3 당 0.05 ~ 0.5 g으로 사용한다.The selenization process is carried out by placing the previously deposited metal compound precursor in a heat treatment equipment and placing the selenium metal for selenization at the bottom of the precursor, wherein the selenium metal is in the range of 0.05 to 0.5 g per 300 cm 3 of the heat treatment chamber volume use.
셀렌 금속과 전구체를 열처리 장비 내에 안착 후, 열처리 공정 단계는 도 3에 나타낸 바와 같다. 즉, 열처리 공정은 총 3단계의 온도 스텝을 통해 수행할 수 있는데, 1번째 단계(A)의 온도 설정은 전구체의 합금을 위한 단계로서, 300℃± 30℃의 온도 범위에서 5~30분 동안 수행한다. 2번째 단계는 전구체의 셀렌화 열처리 단계로서, 전구체의 셀렌화 단계는 온도 B 지점이 끝날 때까지 진행되며, 430 ℃ ± 10 ℃의 온도 범위에서 5~30분 동안 동안 수행한다. 이와 같이 본 발명에 따른 셀렌화 열처리 공정이 수행되는 동안에는 어떠한 가스도 공급되지 않은 상태에서 진행한다.After placing the selenium metal and the precursor in the heat treatment equipment, the heat treatment process steps are as shown in Fig. That is, the heat treatment process can be carried out through a total of three temperature steps. The temperature setting of the first step (A) is a step for the precursor alloy and is performed at a temperature range of 300 ° C ± 30 ° C for 5 to 30 minutes . The second step is a selenization heat treatment step of the precursor. The selenization step of the precursor is carried out until the end of the temperature B, and the temperature is in the range of 430 ° C ± 10 ° C for 5 to 30 minutes. Thus, while the selenization heat treatment process according to the present invention is performed, no gas is supplied.
상기와 같이 셀렌화 공정이 끝나면, 셀렌의 기화 가스와 잔유물인 셀렌 금속을 제거하기 위하여 2번째 단계에서 공정압력을 300 Torr 이하인 (150)~(300)Torr로 설정하여 퍼지 단계를 수행한다. 이때 불황성 가스인 아르곤을 주입하여 셀렌의 기화 가스와 잔유물인 셀렌 금속을 보다 쉽게 제거한다. 2단계의 퍼지 공정이 끝나면 H2S 가스를 주입하여 흡수층의 황화 열처리를 진행하는 단계를 수행하는데(C), 이때의 공정 압력은 황화 수소 가스 주입 시점부터 500 Torr 이상, 바람직하게는 700~1000 Torr으로 설정하여 수행한다. 황화수소 가스 주입량은 100 sccm ~ 2000 sccm 까지 주입한다. After the selenization process is completed, the purging step is performed by setting the process pressure to (150) to (300) Torr, which is lower than 300 Torr, in the second step in order to remove the selenium vapor and the selenium metal as a residue. At this time, argon, which is a non-flammable gas, is injected to more easily remove the vaporized gas of selenium and the selenium metal as a residue. When the purge step of the second step is completed, a step of performing the heat treatment of sulfiding of the absorbing layer by injecting H 2 S gas is performed (C). The process pressure at this time is 500 Torr or more, preferably 700 to 1000 Torr. The amount of hydrogen sulfide gas injected is from 100 sccm to 2000 sccm.
이와 같이 황화 수소 가스 주입과 황화 열처리를 순차적으로 수행하여, 광흡수층 내의 셀렌(Se) 및 황(S)의 조성이 조절된 박막 태양전지의 광흡수층을 제조한다.Thus, a light absorbing layer of a thin film solar cell in which the composition of selenium (Se) and sulfur (S) in the light absorbing layer is controlled by sequentially injecting hydrogen sulphide gas and performing heat treatment of sulphide.
즉, 본 발명에서 제공하는 열처리 공정은, 제1단계로 셀렌화 공정이며, 제2단계로 금속 셀렌 제거 및 셀렌 기화 제거 공정이고, 제3단계는 황화 수소를 공급하여 광흡수층 내에 황을 공급하는 단계로 구성되는 것이다. That is, the heat treatment process provided by the present invention is a selenization process in a first step, a metal selenium removal and a selenium vaporization removal process in a second step, and a third step in which sulfur is supplied into the light absorption layer by supplying hydrogen sulfide .
나아가 본 발명의 일실시예에서는 황화 수소 주입량에 따른 제조된 흡수층의 특성에 변화를 주는지 확인하기 위해, 500, 1000, 2000 sccm의 양으로 황화 수소를 주입하여 제조한 흡수층 내의 S/Se 조성비를 분석한 결과, S/Se가 0.05~0.20의 비율을 갖는 것으로 나타났고, 황화 수소의 주입량에 비례하여 S/Se 조성비가 증가하는 것으로 나타나, 본 발명에서 제공하는 간단한 방법으로 S/Se 조성비 조절을 통한 밴드갭 조절이 가능함을 알 수 있었다.Further, in order to confirm whether the characteristics of the absorbing layer produced according to the hydrogen sulfide injection amount are changed, S / Se composition ratio in the absorbing layer prepared by injecting hydrogen sulfide in an amount of 500, 1000, 2000 sccm is analyzed As a result, it was found that S / Se ratio was in the range of 0.05 to 0.20, and the S / Se composition ratio was increased in proportion to the amount of hydrogen sulfide injected. As a result, the S / Se composition ratio Band gap can be controlled.
또한 본 발명자들은 상기 본 발명의 방법으로 제조된 광흡수층을 이용하여 박막 태양전지를 제조하고, 태양전지의 특성(성능)을 분석하였는데, 그 결과, 황화수소 가스 공급량이 증가할수록 밴드갭이 증가하는 것을 확인할 수 있었다.The inventors of the present invention fabricated a thin film solar cell using the light absorbing layer manufactured by the method of the present invention and analyzed the characteristics (performance) of the solar cell. As a result, it was found that the bandgap increases as the hydrogen sulfide gas supply amount increases I could confirm.
그러므로 본 발명은 상기 본 발명의 방법으로 제조된 황(S)/셀렌(Se)의 조성비가 0.05~0.20인 광흡수층을 포함하는 박막 태양전지를 제공한다.Therefore, the present invention provides a thin film solar cell comprising a light absorbing layer having a composition ratio of sulfur (S) / selenium (Se) produced by the method of the present invention is 0.05 to 0.20.
특히 본 발명에 따른 상기 박막 태양전지는 Cu2InGa(S,Se)4 또는 Cu2ZnSn(S,Se)4 기반의 5원계 화합물 박막 태양전지일 수 있다. In particular, the thin film solar cell according to the present invention may be a pentasic compound thin film solar cell based on Cu 2 InGa (S, Se) 4 or Cu 2 ZnSn (S, Se) 4 .
이상 본 발명에서 제공하는 광흡수층 내의 셀렌(Se) 및 황(S)의 조성이 조절된 박막 태양전지의 광흡수층 제조는 순수한 금속 셀렌에 열이 전달되도록 하여 기화된 가스를 이용하여 금속 화합물을 성장시킬 수 있는 효과를 가지며, 이러한 간단한 방법 만으로도 광흡수층 내의 S/Se의 조성비를 조절할 수 있어, 태양전지의 효율 향상에 기여할 수 있다. The light absorbing layer of the thin film solar cell having the controlled composition of selenium (Se) and sulfur (S) in the light absorbing layer provided in the present invention can transmit heat to the pure metal selenium, This simple method can control the composition ratio of S / Se in the light absorbing layer and contribute to the improvement of the efficiency of the solar cell.
이하에서 첨부된 도면을 참조하여 본 발명의 실시 예를 상세히 설명하며, 본 발명을 기술함에 있어서, 관련된 기술은 반도체 기술 분야에서 통상적인 지식을 가진 자에게 충분히 이해되도록 제공함에 목적이 있다.DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS In the following, embodiments of the present invention will be described in detail with reference to the accompanying drawings. In describing the present invention, it is an object of the present invention to provide a related art to a person having ordinary skill in the semiconductor technology.
<실시예 1>≪ Example 1 >
본 발명의 화합물 박막 태양전지의 제조Preparation of the compound thin film solar cell of the present invention
먼저, 소다라임 유리 기판을 아세톤, 메탄올 및 2차 증류수를 이용하여 순차적으로 세척하였다. 기판 세척 후, 스퍼터링 방법으로 몰리브덴 후면 전극을 증착시켰다. 이후 상기 몰리브덴 후면 전극 상에 DC 스퍼터 증착법으로 25℃의 기판 온도에서 후면전극으로 사용되는 몰리브덴(Mo)을 증착후 아연(Zn),주석(Sn),구리(Cu), 순서로 증착되도록 금속 전구체층을 형성하였다. 즉 몰리브덴 후면 전극 상에 Zn, 그 위로 Sn,그 위로 Cu의 순서로 적층되도록 증착시켰다. First, the soda lime glass substrate was sequentially washed with acetone, methanol, and secondary distilled water. After the substrate was cleaned, a molybdenum back electrode was deposited by sputtering. Then, molybdenum (Mo) used as a back electrode is deposited on the molybdenum back electrode by a DC sputter deposition method at a substrate temperature of 25 DEG C, and then zinc (Zn), tin (Sn), and copper (Cu) Layer. That is, Zn on the molybdenum back electrode, Sn over it, and Cu over it in this order.
이후 열처리 장비를 이용하여 열처리 시켰는데, 셀렌 및 황화 열처리 공정은 상기와 같이 제작한 금속 전구체를 열처리 장비에 삽입시킨 후, 셀렌화를 위한 셀렌 금속이나 파우더 소스를 전구체 하단에 안착시켜 진행하였다. 이에 대한 개략도는 도 2에 나타내었다. 이때 셀렌 금속이나 파우더는 기화용 트레이 상에 약 0.35g이 안착되도록 하였고, 삽입되는 구조물의 부피는 약 300 cm3 이다.The selenium and sulphide heat treatment process was performed by inserting the prepared metal precursor into the heat treatment equipment and placing selenium metal or powder source for selenization at the bottom of the precursor. A schematic diagram thereof is shown in Fig. At this time, about 0.35 g of selenium metal or powder is deposited on the vaporization tray, and the volume of the inserted structure is about 300 cm 3 .
셀렌 금속과 전구체를 열처리 장비 내에 안착 후 열처리 공정을 수행하였는데, 총 3단계의 온도 단계를 통하여 셀렌-황화 열처리 공정을 수행하였다. 1번째 셀렌화 열처리 공정에서 도 3의 A 지점의 온도 설정은 전구체의 합금을 위한 단계로서 300 ℃±30 ℃온도에서 실행하였고, B 지점의 단계는 전구체의 셀렌화 열처리를 단계를 위한 것으로 전구체의 셀렌화 단계는 온도 B 지점이 끝날 때까지 진행하였다. B 지점의 온도 설정은 430 ℃±10 ℃ 조건에서 실행하였다. 셀렌화 공정이 끝난 후 0.35g 의 셀렌의 기화 가스와 잔유물인 셀렌 금속을 제거하기 위하여 2번째 단계에서 공정압력을 300 Torr 이하로 설정하여 퍼지(purge) 단계를 진행하였다. 이때 불활성 가스인 아르곤을 주입하여 보다 쉽게 제거할 수 있도록 하였다.Selenium metal and precursor were placed in a heat treatment equipment and heat treatment process was performed. Selenium - sulfurization heat treatment process was performed through three temperature steps. In the first selenization heat treatment step, the temperature setting at point A in FIG. 3 was performed at a temperature of 300 ° C ± 30 ° C for the precursor alloy, and the step at point B was for the selenization heat treatment of the precursor The selenization step was continued until the end of temperature B was reached. The temperature setting at point B was carried out at 430 ° C ± 10 ° C. After the selenization process, purge step was performed by setting the process pressure to 300 Torr or less in the second step in order to remove the vaporized gas of selenium of 0.35 g and the selenium metal which is the remnant. At this time, argon, which is an inert gas, is injected to make it easier to remove.
2단계 퍼지 공정이 끝나면 C 지점부터 H2S 가스를 주입하여 흡수층의 황화 열처리를 진행하였는데 C 지점의 공정 압력은 황화 수소 가스 주입 시점부터 700 Torr 이상으로 설정하여 진행하였다. 황화수소 가스 주입량은 각각 500, 1000, 2000 sccm의 양으로 주입하였다. At the end of the second stage purge process, H2S gas was injected from the C point to proceed with the heat treatment of the sulfidation of the absorption layer. The process pressure at the C point was set to 700 Torr or more from the injection point of the hydrogen sulfide gas. The amount of hydrogen sulfide gas injected was 500, 1000, and 2000 sccm, respectively.
이후, 상기 방법으로 제조된 흡수층 박막을 습식공정을 통하여 CdS 버퍼층을 약 50nm 두께로 증착시켰고, 제조된 흡수층 박막 위에 스퍼터링 공정을 이용하여 ZnO 50nm 와 Al-doped:ZnO (AZO) 300nm이 되도록 순차적으로 증착시켰으며, 이후 상기 박막 위에 알루미늄을 1㎛의 두께를 갖도록 증착시켜 본 발명에 따른 박막 태양전지를 제조하였다.Then, a CdS buffer layer was deposited to a thickness of about 50 nm through a wet process, and a ZnO layer and a Al-doped ZnO layer (AZO) were sequentially deposited to a thickness of about 50 nm on the absorber layer by sputtering. And then aluminum was deposited on the thin film so as to have a thickness of 1 탆 to prepare a thin film solar cell according to the present invention.
<실험예 1><Experimental Example 1>
황화수소 가스 주입량에 따른 흡수층 내의 S/Se 조성분석 Analysis of S / Se Composition in Absorbent Layer by Hydrogen Sulfide Gas Injection Amount
상기 실시예 1에서 황화수소 가스 주입량을 각기 달리하여 제조한 열처리 후의 CZTSSe 박막내의 조성비를 제작한 흡수층 표면에 대한 EDS 분석을 통해 확인하였다. 하기 표 1은 황화수소 가스 주입 조건을 나타낸 것이고, 표 2는 주입량에 따라 제조된 흡수층 내의 S/Se 조성비 분석 결과를 나타낸 것이다.The composition ratio of the CZTSSe thin film after heat treatment prepared by varying the injection amount of hydrogen sulfide gas in Example 1 was confirmed by EDS analysis on the surface of the absorbent layer. Table 1 below shows the hydrogen sulfide gas injection conditions, and Table 2 shows the S / Se composition ratio analysis results in the absorption layer produced according to the injection amount.
상기 표 2에 나타낸 바와 같이, 황화 수소 가스 공급량이 증가할수록 흡수층 내의 S/Se 가 상승하고 있는 것으로 나타났다. As shown in Table 2, S / Se in the absorbent layer was increased as the amount of hydrogen sulfide gas supplied increased.
<실험예 2><Experimental Example 2>
황화수소 가스 주입량에 따른 제조된 태양전지의 특성분석Characterization of manufactured solar cell according to hydrogen sulfide gas injection amount
상기 실시예 1에서 황화수소 가스 주입량을 달리하여 제조한 각 태양전지의 특성을 당업계에 알려진 EQE 분석 방법을 통해 측정하였다.The characteristics of each solar cell prepared by varying the amount of hydrogen sulfide gas injected in Example 1 were measured by an EQE analysis method known in the art.
그 결과, 도 4에 나타낸 바와 같이, [Eln(1-EQE)]2를 통하여 밴드갭을 측정한 바에 의하면 황화수소 가스 공급량이 증가할수록 밴드갭이 증가하는 것을 알 수 있었다.As a result, as shown in FIG. 4, the band gap was measured through [Eln (1-EQE)] 2 , and it was found that the band gap was increased as the hydrogen sulfide gas supply amount was increased.
이제까지 본 발명에 대하여 그 바람직한 실시예들을 중심으로 살펴보았다. 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자는 본 발명이 본 발명의 본질적인 특성에서 벗어나지 않는 범위에서 변형된 형태로 구현될 수 있음을 이해할 수 있을 것이다. 그러므로 개시된 실시예들은 한정적인 관점이 아니라 설명적인 관점에서 고려되어야 한다. 본 발명의 범위는 전술한 설명이 아니라 특허청구범위에 나타나 있으며, 그와 동등한 범위 내에 있는 모든 차이점은 본 발명에 포함된 것으로 해석되어야 할 것이다.The present invention has been described with reference to the preferred embodiments. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the disclosed embodiments should be considered in an illustrative rather than a restrictive sense. The scope of the present invention is defined by the appended claims rather than by the foregoing description, and all differences within the scope of equivalents thereof should be construed as being included in the present invention.
100: 기판
101: Mo 후면 전극층
102: Zn 금속전구체 층
103: Sn 금속전구체 층
104: Cu 금속전구체 층
200 : 칼코젠 원소 안착 홀더
201 : 전구체 안착 홀더
202 : 플랭크
203 : 전구체
204 : 칼코젠 원소 (Se 금속 원소)100: substrate
101: Mo rear electrode layer
102: Zn metal precursor layer
103: Sn metal precursor layer
104: Cu metal precursor layer
200: Calcose elemental holder
201: Precursor seat holder
202: Flank
203: precursor
204: chalcogen element (Se metal element)
Claims (10)
순수 셀렌 금속을 이용하여 셀렌(Se)화 공정을 진행하는 단계;
셀렌화 공정 후 잔유 셀렌 금속 및 셀렌의 기화 가스를 제거(purge) 하는 단계; 및
황화 수소(H2S) 가스를 주입하고 황화 열처리를 순차적으로 진행하는 단계를 포함하는,
광흡수층 내의 셀렌(Se) 및 황(S)의 조성이 조절된 박막 태양전지의 광흡수층 제조방법. Depositing a metal compound precursor comprising a metal, metal sulfur or metal selenium on the back electrode layer;
Conducting a selenization (Se) process using pure selenium metal;
Purifying the residual selenium metal and selenium vaporization gas after the selenization process; And
Injecting hydrogen sulfide (H2S) gas and progressing the sulfurization heat treatment sequentially;
Wherein the composition of selenium (Se) and sulfur (S) in the light absorbing layer is controlled.
상기 금속 화합물 전구체는 Cu, Zn, Sn 또는 In의 순수 금속 물질; CuGa 또는 CuIn의 금속 합금 물질; CuS, ZnS 또는 SnS 의 금속 황화 물질; CuSe, ZnSe, SnSe, InGaSe, GaSe 또는 InSe 의 금속 셀렌 화합물; 및 CuSSe, ZnSSe 또는 SnSSe 의 금속 황화 셀렌 화합물;로 이루어진 군 중에서 선택되는 것을 특징으로 하는 방법. The method according to claim 1,
The metal compound precursor may be a pure metal material of Cu, Zn, Sn or In; A metal alloy material of CuGa or CuIn; Metal sulfides of CuS, ZnS or SnS; Metal selenium compounds of CuSe, ZnSe, SnSe, InGaSe, GaSe or InSe; And a metal sulphide selenium compound of CuSSe, ZnSSe or SnSSe.
셀렌화 공정은 상기 금속 전구체 화합물의 휘발을 억제하기 위하여 500 Torr ~ 750 Torr의 압력에서 수행하는 것을 특징으로 하는 방법.The method according to claim 1,
Wherein the selenization process is performed at a pressure of 500 Torr to 750 Torr to suppress the volatilization of the metal precursor compound.
금속 셀렌의 무게는 셀렌(Se)화 공정을 위한 열처리 챔버 부피 300 cm3 당 0.05 ~ 0.5 g으로 사용하는 것을 특징으로 하는 방법.The method according to claim 1,
Characterized in that the weight of the metal selenium is used in the range of 0.05 to 0.5 g per 300 cm < 3 > of volume of the heat treatment chamber for the selenization (Se) process.
셀렌화 공정 후 잔유 셀렌 금속 및 셀렌의 기화 가스 제거는 150~300 Torr에서 수행하는 것을 특징으로 하는 방법.The method according to claim 1,
Wherein the removal of the residual selenium metal and selenium vaporization after the selenization process is carried out at 150 to 300 Torr.
황화 수소 가스 주입 후, 황화 열처리는 500~1000 Torr에서 수행하는 것을 특징으로 하는 방법.The method according to claim 1,
Characterized in that, after the introduction of the hydrogen sulphide gas, the sulphidation heat treatment is carried out at 500 to 1000 Torr.
황화 수소(H2S) 가스 주입은 100 sccm ~ 2000 sccm의 양으로 주입하는 것을 특징으로 하는 방법.The method according to claim 1,
Wherein the hydrogen sulfide (H2S) gas injection is performed in an amount of 100 sccm to 2000 sccm.
상기 셀렌(Se) 및 황(S)의 조성은 S/Se가 0.05~0.20의 비율을 갖는 것을 특징으로 하는 방법. The method according to claim 1,
Wherein the composition of selenium (Se) and sulfur (S) has a S / Se ratio of 0.05 to 0.20.
상기 태양전지는 Cu2InGa(S,Se)4 또는 Cu2ZnSn(S,Se)4 기반의 5원계 화합물 박막 태양전지인 것을 특징으로 하는 박막 태양전지. 10. The method of claim 9,
Wherein the solar cell is a pentavalent compound thin film solar cell based on Cu 2 InGa (S, Se) 4 or Cu 2 ZnSn (S, Se) 4 .
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