KR101279370B1 - PREPARATION METHOD OF CZTSe-BASED THIN FILM USING CO-EVAPORATION AND CZTSe-BASED THIN FILM PREPARED BY THE SAME - Google Patents
PREPARATION METHOD OF CZTSe-BASED THIN FILM USING CO-EVAPORATION AND CZTSe-BASED THIN FILM PREPARED BY THE SAME Download PDFInfo
- Publication number
- KR101279370B1 KR101279370B1 KR1020110140283A KR20110140283A KR101279370B1 KR 101279370 B1 KR101279370 B1 KR 101279370B1 KR 1020110140283 A KR1020110140283 A KR 1020110140283A KR 20110140283 A KR20110140283 A KR 20110140283A KR 101279370 B1 KR101279370 B1 KR 101279370B1
- Authority
- KR
- South Korea
- Prior art keywords
- thin film
- cztse
- based thin
- substrate temperature
- vacuum evaporation
- Prior art date
Links
- 239000010409 thin film Substances 0.000 title claims abstract description 67
- 238000010549 co-Evaporation Methods 0.000 title claims abstract description 5
- 238000002360 preparation method Methods 0.000 title 1
- 239000000758 substrate Substances 0.000 claims abstract description 56
- 238000000151 deposition Methods 0.000 claims abstract description 33
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 33
- 229910052718 tin Inorganic materials 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000001771 vacuum deposition Methods 0.000 claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 claims abstract description 16
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 15
- 230000008021 deposition Effects 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 229910052738 indium Inorganic materials 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 238000001704 evaporation Methods 0.000 description 8
- 230000004927 fusion Effects 0.000 description 8
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 6
- 238000007738 vacuum evaporation Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229910008772 Sn—Se Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 229910004613 CdTe Inorganic materials 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000011712 cell development Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
Images
Classifications
-
- 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
- H01L31/0256—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 the material
- H01L31/0264—Inorganic materials
- H01L31/0328—Inorganic materials including, apart from doping materials or other impurities, semiconductor materials provided for in two or more of groups H01L31/0272 - H01L31/032
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Physical Vapour Deposition (AREA)
Abstract
태양전지용 CZTSe계 박막의 제조방법 및 그 방법에 의해 제조된 CZTSe계 박막이 개시된다. 본 발명의 CZTSe계 박막의 제조방법은, (S1) Cu, Zn, Sn 및 Se을 동시진공증발법에 따라 기판에 증착하는 단계; 및 (S2) 감소된 기판 온도에서 Sn과 Se을 동시진공증발법에 따라 추가로 증착시키는 단계를 포함한다. 본 발명에 따르면, 고온의 기판 온도에서 Cu, In, Sn, Se를 동시진공증발법을 이용하여 증착한 후 그보다 낮은 기판 온도에서 Sn과 Se을 추가로 증착함으로써 높은 기판 온도에서의 열처리에 의한 Sn 손실을 최소화하고, 박막 내 원소 분포를 균일하게 하여 궁극적으로 에너지 변환효율이 높은 태양전지용 CZTSe계 박막을 제조할 수 있다. Disclosed are a method of manufacturing a CZTSe based thin film for a solar cell and a CZTSe based thin film manufactured by the method. Method for producing a CZTSe-based thin film of the present invention, (S1) depositing Cu, Zn, Sn and Se on a substrate by a co-vacuum evaporation method; And (S2) further depositing Sn and Se at a reduced substrate temperature by co-evaporation. According to the present invention, by depositing Cu, In, Sn, Se at a high substrate temperature by the co-vacuum evaporation method, and further by depositing Sn and Se at a lower substrate temperature Sn by heat treatment at a high substrate temperature Minimizing the loss and uniform element distribution in the thin film can ultimately produce a CZTSe-based thin film for solar cells with high energy conversion efficiency.
Description
본 발명은 동시진공증발을 이용한 태양전지용 CZTSe계 박막의 제조방법 및 그 방법에 의해 제조된 CZTSe계 박막에 관한 것으로, 더욱 상세하게는 고온의 기판 온도에서 Cu, In, Sn, Se를 동시진공증발법을 이용하여 증착한 후 그보다 낮은 기판 온도에서 Sn과 Se을 추가로 증착함으로써 동시진공증발 공정 중 발생하는 Sn 손실을 최소화하고, 박막 내 원소분포를 균일화할 수 있는 방법에 관한 것이다. The present invention relates to a method for manufacturing a CZTSe-based thin film for solar cells using co-vacuum evaporation, and to a CZTSe-based thin film prepared by the method, and more particularly to the simultaneous vacuum evaporation of Cu, In, Sn, Se at a high substrate temperature. The present invention relates to a method for minimizing Sn loss generated during the co-vacuum evaporation process and uniformizing element distribution in a thin film by further depositing Sn and Se at a lower substrate temperature after deposition using a method.
최근 심각한 환경오염 문제와 화석 에너지 고갈로 차세대 청정에너지 개발에 대한 중요성이 증대되고 있다. 그 중에서도 태양전지는 태양 에너지를 직접 전기 에너지로 전환시키는 장치로서, 공해가 적고, 자원이 무한적이며 반영구적인 수명을 가지고 있어 미래 에너지 문제를 해결할 수 있는 에너지원으로 기대되고 있다.Recently, serious environmental pollution problem and depletion of fossil energy are increasing importance for next generation clean energy development. Among them, solar cells are devices that convert solar energy directly into electrical energy, and are expected to be an energy source that can solve future energy problems because it has fewer pollution, has endless resources, and has a semi-permanent lifetime.
태양전지는 광흡수층으로 사용되는 물질에 따라서 다양한 종류로 구분되며, 현재 가장 많이 사용되는 것은 실리콘을 이용한 실리콘 태양전지이다. 그러나 최근 실리콘의 공급부족으로 가격이 급등하면서 박막형 태양전지에 대한 관심이 증가하고 있다. 박막형 태양전지는 얇은 두께로 제작되므로 재료의 소모량이 적고, 무게가 가볍기 때문에 활용범위가 넓다. 이러한 박막형 태양전지의 재료로서, 비정질 실리콘과 CdTe, CIS계(CuInSe2, CuIn1-xGaxSe2, CuIn1-xGaxS2 등) 반도체 화합물이 있다.Solar cells are classified into various types according to materials used as light absorption layers, and at present, the most commonly used are silicon solar cells using silicon. However, as prices have soared recently due to a shortage of silicon, interest in thin-film solar cells is increasing. Thin-film solar cells are manufactured with a thin thickness, so the materials are consumed less and the weight is lighter, so the application range is wide. Examples of such thin film solar cells include amorphous silicon, CdTe, and CIS-based semiconductor compounds (CuInSe 2 , CuIn 1-x Ga x Se 2 , CuIn 1-x Ga x S 2, etc.).
높은 광흡수 계수를 갖는 Cu(In,Ga)Se2(CIGS) 화합물 박막 소재는 고효율 태양전지 양산을 위해 가장 전도유망한 재료이나 상대적으로 매장량이 적은 In 및 Ga을 사용한다는 소재적 한계가 있다. Cu2ZnSnSe4(CZTSe) 또는 Cu2ZnSnS4(CZTS)와 같은 Cu-Zn-Sn-Se계 화합물 반도체는 CIGS 내 희소원소인 In과 Ga이 범용원소인 Zn 및 Sn으로 대체된 소재로서 미래형 저가 태양전지 개발을 위해 활발히 연구되고 있는데, 그 화합물 조합에 따라 0.8 eV부터 1.5 eV까지의 에너지 밴드갭을 갖는 것으로 알려져 있다. Cu (In, Ga) Se 2 (CIGS) compound thin film material with high light absorption coefficient is the most promising material for mass production of high efficiency solar cell, but there is a material limitation that In and Ga use relatively small reserves. Cu-Zn-Sn-Se compound semiconductors, such as Cu 2 ZnSnSe 4 (CZTSe) or Cu 2 ZnSnS 4 (CZTS), are materials in which In and Ga, which are rare elements in CIGS, are replaced by Zn and Sn, which are universal elements Actively researched for solar cell development, it is known to have an energy bandgap from 0.8 eV to 1.5 eV depending on the compound combination.
현재까지 스퍼터링법에 기반한 2단계 공정에 의해 3.2%의 CZTSe 및 6.7%의 CZTS 태양전지 효율 달성이 보고된바 있으며(문헌 [Appl. Phys. Express 1, 2008, 041201, H. Katagiri et al.; Prog. Photovolt: Res. Appl. 2009; 17: 315-319, G. Zoppi et al.] 등 참고), 최근 비진공 방식을 이용하여 제조된 Cu2ZnSn(S,Se)4(CZTSSe) 태양전지가 9.6%의 변환효율을 생산하여 세계 최고기록을 갱신한바 있다(문헌 [Adv. Mater. 22, 2010, 1, T.K. Todorov et al.] 등 참고). 반면, 동시진공증발법에 의한 Cu-Zn-Sn-Se계 연구는 박막 조성 조절이 상대적으로 용이하다는 장점에도 불구하고, 상대적으로 공개된 연구결과의 양이 적으며 그 효율에 대한 보고는 특히 미미하다.To date, a two-step process based on sputtering has been reported to achieve 3.2% CZTSe and 6.7% CZTS solar cell efficiency (Appl. Phys. Express 1, 2008, 041201, H. Katagiri et al .; .. Prog Photovolt: Res Appl 2009 ; 17:.. 315-319, G. Zoppi et al] , such as reference), recent non-vacuum system made using the Cu 2 ZnSn (S, Se) 4 (CZTSSe) solar cell Has updated its world record by producing a conversion efficiency of 9.6% (see Adv. Mater. 22, 2010, 1, TK Todorov et al.). On the other hand, the Cu-Zn-Sn-Se system study by the simultaneous vacuum evaporation method has a relatively small amount of research results, Do.
동시진공증발법에 의한 Cu-Zn-Sn-Se계 박막 형성시 기판 온도에 따른 EDS 원소 조성 분석 그래프를 도 1에 나타내었다. 도 1에 따르면, 4가지 원소를 동시에 증발시켜 증착하는 종래의 CZTSe 제조방법을 이용할 때, Sn의 손실은 200℃ 내지 400℃에서는 크지 않지만, 400℃ 이상에서 급속히 발생하여 박막 성장에 요구되는 고온의 기판 온도를 Cu-Zn-Sn-Se계 박막 제조공정에 적용하는데 어려움이 있다. 이와 같은 Sn 손실은 동시진공증발공정 중 Sn이 Se와 만나 증발되고 증착되지 못하는 것에 기인하며, 결과적으로 상분리 및 두께 감소의 원인이 되어 태양전지 박막으로 사용시 에너지 변환효율이 저하될 수 있다. 따라서, Sn 손실에 따른 에너지 변환효율의 저하를 최소화하기 위해 동시진공증발 공정의 단계를 최적화할 필요성이 존재한다. 1 shows a graph of an EDS element composition analysis according to substrate temperature when forming a Cu-Zn-Sn-Se based thin film by a co-vacuum evaporation method. According to Figure 1, when using the conventional CZTSe manufacturing method of evaporating and depositing four elements at the same time, the loss of Sn is not large at 200 ℃ to 400 ℃, but occurs rapidly at 400 ℃ or more of the high temperature required for thin film growth It is difficult to apply the substrate temperature to the Cu-Zn-Sn-Se based thin film manufacturing process. The Sn loss is attributed to Sn being evaporated and not being deposited during the simultaneous vacuum evaporation process. As a result, phase separation and thickness decrease are caused, and energy conversion efficiency may be lowered when the thin film is used as a solar cell thin film. Therefore, there is a need to optimize the steps of the simultaneous vacuum evaporation process to minimize the degradation of the energy conversion efficiency due to Sn loss.
본 발명의 목적은 태양전지용 CZTSe계 박막의 제조방법에 있어서, 고온의 기판 온도에서 Cu, In, Sn, Se를 동시진공증발법을 이용하여 증착한 후 그보다 낮은 기판 온도에서 Sn과 Se을 추가로 증착함으로써 높은 기판 온도에서의 열처리에 의한 Sn 손실을 최소화하고, 박막 내 원소 분포를 균일하게 하여 궁극적으로 에너지 변환효율이 높은 태양전지용 CZTSe계 박막의 제조방법을 제공하는 데 있다. An object of the present invention is a method for manufacturing a CZTSe-based thin film for solar cells, by depositing Cu, In, Sn, Se at the substrate temperature of high temperature using a co-vacuum evaporation method and further added Sn and Se at a lower substrate temperature The present invention provides a method for manufacturing a CZTSe-based thin film for solar cells, which minimizes Sn loss due to heat treatment at a high substrate temperature and uniformly distributes elements in the thin film, thereby ultimately increasing energy conversion efficiency.
상기 목적을 달성하기 위해, 본 발명은 In order to achieve the above object,
(S1) Cu, Zn, Sn 및 Se을 동시진공증발법에 따라 기판에 증착하는 단계; 및 (S2) 감소된 기판 온도에서 Sn과 Se을 동시진공증발법에 따라 추가로 증착시키는 단계를 포함하는 태양전지용 CZTSe계 박막의 제조방법을 제공한다.(S1) depositing Cu, Zn, Sn and Se on the substrate by a co-vacuum evaporation method; And (S2) provides a method for producing a CZTSe-based thin film for solar cells comprising the step of further depositing Sn and Se at a reduced substrate temperature by the co-evaporation method.
본 발명의 S1 단계의 증착은 450∼600℃의 기판 온도에서 수행할 수 있다. Deposition of step S1 of the present invention can be carried out at a substrate temperature of 450 ~ 600 ℃.
본 발명의 S2 단계의 증착은 250∼400℃의 기판 온도에서 수행할 수 있다. Deposition of the step S2 of the present invention can be carried out at a substrate temperature of 250 ~ 400 ℃.
또한, 본 발명은 Cu, Zn, Sn 및 Se을 동시진공증발법에 따라 기판에 증착하고, 감소된 기판 온도에서 Sn과 Se을 동시진공증발법에 따라 추가로 증착시켜 제조한 태양전지용 CZTSe계 박막을 제공한다.In addition, the present invention is a CZTSe-based thin film for solar cells prepared by depositing Cu, Zn, Sn and Se on the substrate by the co-vacuum evaporation method, and further depositing Sn and Se by the co-vacuum evaporation method at a reduced substrate temperature To provide.
또한, 본 발명은 Cu, Zn, Sn 및 Se을 동시진공증발법에 따라 기판에 증착하고, 감소된 기판 온도에서 Sn과 Se을 동시진공증발법에 따라 추가로 증착시켜 제조한 태양전지용 CZTSe계 박막을 포함하는 태양전지를 제공한다.In addition, the present invention is a CZTSe-based thin film for solar cells prepared by depositing Cu, Zn, Sn and Se on the substrate by the co-vacuum evaporation method, and further depositing Sn and Se by the co-vacuum evaporation method at a reduced substrate temperature It provides a solar cell comprising a.
본 발명에 따르면, 고온의 기판 온도에서 Cu, Zn, Sn, Se를 동시진공증발법을 이용하여 증착한 후 그보다 낮은 기판 온도에서 Sn과 Se을 추가로 증착함으로써 높은 기판 온도에서의 열처리에 의한 Sn 손실을 최소화하고, 박막 내 원소 분포를 균일하게 하여 궁극적으로 에너지 변환효율이 높은 태양전지용 CZTSe계 박막을 제조할 수 있다. According to the present invention, by depositing Cu, Zn, Sn, Se at a high substrate temperature by the co-vacuum evaporation method, and further by depositing Sn and Se at a lower substrate temperature Sn by heat treatment at a high substrate temperature Minimizing the loss and uniform element distribution in the thin film can ultimately produce a CZTSe-based thin film for solar cells with high energy conversion efficiency.
도 1은 CZTSe계 박막 형성시 기판온도에 따른 EDS 원소 조성 분석 그래프이다.
도 2는 본 발명의 실시예에 따른 공정상 온도 및 시간 프로파일 곡선이다.
도 3은 본 발명의 비교예에 따른 공정상 온도 및 시간 프로파일 곡선이다.
도 4는 본 발명의 실시예에 따라 제조된 CZTSe계 박막의 AES 곡선이다.
도 5는 본 발명의 비교예에 따라 제조된 CZTSe계 박막의 AES 곡선이다.
도 6은 본 발명의 실시예에 따라 제조된 CZTSe계 박막의 XRD 분석 그래프이다.
도 7은 본 발명의 비교예에 따라 제조된 CZTSe계 박막의 XRD 분석 그래프이다.1 is a graph illustrating an EDS element composition according to substrate temperature when forming a CZTSe-based thin film.
2 is a process temperature and time profile curve in accordance with an embodiment of the present invention.
3 is a process temperature and time profile curve according to a comparative example of the present invention.
4 is an AES curve of a CZTSe-based thin film manufactured according to an embodiment of the present invention.
5 is an AES curve of a CZTSe-based thin film prepared according to a comparative example of the present invention.
6 is an XRD analysis graph of a CZTSe-based thin film prepared according to an embodiment of the present invention.
7 is an XRD analysis graph of a CZTSe-based thin film prepared according to a comparative example of the present invention.
이하 본 발명의 태양전지용 CZTSe계 박막의 제조방법을 상세히 설명한다.Hereinafter, a method of manufacturing the CZTSe-based thin film for solar cells of the present invention will be described in detail.
본 발명의 태양전지용 CZTSe계 박막의 제조방법은 총 두 단계로 나누어 볼 수 있다.
The manufacturing method of the CZTSe-based thin film for solar cells of the present invention can be divided into a total of two steps.
먼저, Cu, Zn, Sn 및 Se을 동시진공증발법에 따라 기판에 증착한다(S1 단계).First, Cu, Zn, Sn and Se are deposited on the substrate by a co-vacuum evaporation method (step S1).
동시진공증발법은 화합물 박막을 제조하기 위하여 진공 하에서 여러 원소를 동시에 증발시켜 증착하는 방법으로 구체적인 장치 및 수행 방법은 본 기술 분야의 통상의 기술자에게 널리 알려져 있다. 구체적으로는, 진공 하에서 기판 온도를 일정하게 유지하여 Cu, Zn, Sn, Se 원소를 함유하는 각각의 증발기구를 동시에 가열하여 증발 증착시켜 기판상에 전구체 박막을 형성할 수 있다. 이때 증발기구는 에퓨젼 셀(effusion cell) 등을 사용할 수 있다. 이때 증착되는 박막의 원하는 조성 및 두께는 각 원소의 증착율 및 증착시간을 조절하여 얻을 수 있다.Simultaneous vacuum evaporation is a method of evaporating and depositing several elements at the same time under vacuum to prepare a compound thin film. Detailed apparatus and method are well known to those skilled in the art. Specifically, the substrate temperature may be kept constant under vacuum, and the evaporation mechanisms containing Cu, Zn, Sn, and Se elements may be simultaneously heated to evaporate to form a precursor thin film on the substrate. In this case, the evaporation mechanism may use an fusion cell. At this time, the desired composition and thickness of the deposited thin film can be obtained by adjusting the deposition rate and deposition time of each element.
본 단계에서의 증착시 기판 온도는 450 내지 600℃를 유지하며, 증착되는 Cu, Zn, Sn, Se 각각의 양은 원하는 조성에 따라 증발기구, 즉, 에퓨젼 셀의 온도 변화를 통한 증착율 조절로써 가능하다. 증착시간은 에퓨젼 셀의 온도를 변화시켜 단축 또는 연장시킬 수 있으나, 10분 내지 60분 범위에서 수행하는 것이 바람직하다.
Substrate temperature is maintained at 450 to 600 ℃ during deposition in this step, and the amount of Cu, Zn, Sn, Se to be deposited is possible by controlling the deposition rate through the evaporation mechanism, that is, the temperature of the fusion cell according to the desired composition Do. The deposition time may be shortened or extended by changing the temperature of the fusion cell, but is preferably performed in the range of 10 minutes to 60 minutes.
다음으로, 감소된 기판 온도에서 Sn과 Se을 동시진공증발법에 따라 S1에서 증착된 박막에 추가로 증착시켜 CZTSe계 박막을 제조한다(S2 단계).Next, at a reduced substrate temperature, Sn and Se are further deposited on the thin film deposited in S1 by the co-evaporation method to prepare a CZTSe-based thin film (step S2).
본 단계의 기술적 핵심은 S1 단계 수행 후 기판 온도를 감소시킨 후 S1 단계에서보다 낮은 기판 온도에서 Sn과 Se의 추가 증착을 수행하는 것이다. 기판 온도의 감소는 Se 분위기 또는 Se+Sn 분위기 하에서 수행될 수도 있고, 어떠한 원소의 공급 없이 수행될 수도 있으며, 특별한 분위기에 한정되지 않는다. 낮은 기판 온도에서의 추가 증착은 고온의 기판 온도에서의 형성된 전구체 박막 내 손실된 Sn을 보충시키는 역할을 한다. 구체적으로는, Se을 함유하는 증발기구와 Sn을 함유하는 증발기구를 동시에 가열하여 진공증발시켜 Se와 Sn을 추가로 증착시킨 후 냉각하여 제조할 수 있다. 상기 증발기구는 에퓨전셀일 수 있다. The technical core of this step is to reduce the substrate temperature after performing step S1 and then perform further deposition of Sn and Se at a lower substrate temperature than in step S1. Reduction of the substrate temperature may be performed under an Se atmosphere or a Se + Sn atmosphere, may be performed without supply of any element, and is not limited to a special atmosphere. Further deposition at low substrate temperatures serves to compensate for the lost Sn in the formed precursor thin film at high substrate temperatures. Specifically, the evaporation apparatus containing Se and the evaporation apparatus containing Sn may be simultaneously heated and vacuum evaporated to further deposit Se and Sn and then cool them. The evaporation mechanism may be an fusion cell.
본 단계에서의 추가 증착시 기판 온도는 250∼400℃를 유지하며, 증착시간은 에퓨젼 셀의 온도를 변화시켜 단축 또는 연장시킬 수 있으나, S1 단계와 동일한 에퓨젼 셀의 온도에서 5분 내지 40분 범위에서 수행하는 것이 바람직하다. The substrate temperature is maintained at 250 to 400 ° C. during the further deposition in this step, and the deposition time can be shortened or extended by changing the temperature of the fusion cell, but 5 to 40 minutes at the same temperature of the fusion cell as in the step S1. Preference is given to performing in minutes.
CZTSe계 박막 성장에는 고온의 기판 온도가 필수적이며, 기판 온도가 높을수록 결정립이 큰 양질의 박막을 얻을 수 있다. 기존의 동시진공증발법에 의한 CZTSe계 박막 제조에서는 기판 온도를 상승시킬수록 Sn 손실량이 증가하여 에너지 변환 효율이 낮아지게 되어 결과적으로는 특정 온도 이상으로는 기판 온도를 상승시킬 수 없었다. 그러나 손실된 Sn을 추가 보충하는 단계를 도입하여 Sn 손실량을 최소화한 본 발명에 따르면 CZTSe계 박막 성장에 필요한 고온의 기판 온도를 공정에 적용할 수 있는 효과가 있다.
High temperature substrate temperature is essential for CZTSe-based thin film growth, and the higher the substrate temperature, the higher the size of the crystal grains. In the conventional CZTSe-based thin film manufacturing by the simultaneous vacuum evaporation method, the Sn loss amount increases as the substrate temperature is increased, resulting in low energy conversion efficiency. As a result, the substrate temperature cannot be raised above a specific temperature. However, according to the present invention, which minimizes Sn loss by introducing a supplemental step of supplementing lost Sn, there is an effect of applying a high temperature substrate temperature required for CZTSe-based thin film growth to a process.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범주 및 기술사상 범위 내에서 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.
실시예 Example
먼저, 소다라임 유리기판에 DC 스퍼터링 방법으로 몰리브덴 후면 전극을 약 1㎛의 두께로 증착하였다. 상기 유리기판상에 Cu, Zn, Sn, Se을 동시진공증발법으로 500℃의 기판온도에서 60분간 증착하여 전구체 박막을 형성한 후, Se 분위기 하에서 기판 온도를 370℃로 내리고 Sn, Se을 30분간 더 증착하였다. 이때, 각각의 에퓨젼 셀의 온도는 Cu 1380℃, Zn 335℃, Sn 1480℃, Se 210℃로 하였다.
First, a molybdenum back electrode was deposited on a soda-lime glass substrate with a thickness of about 1 μm by DC sputtering. Cu, Zn, Sn, Se were deposited on the glass substrate for 60 minutes at a substrate temperature of 500 ° C. by a simultaneous vacuum evaporation method to form a precursor thin film, and then the substrate temperature was lowered to 370 ° C. under a Se atmosphere, and Sn and Se were kept for 30 minutes. Further deposition. At this time, the temperature of each fusion cell was made into Cu 1380 degreeC, Zn 335 degreeC, Sn 1480 degreeC, and Se 210 degreeC.
실시예에 따른 CZTSe계 박막의 제조공정상 온도 및 시간 프로파일 곡선은 도 2에 나타낸 바와 같다.
Temperature and time profile curves during the manufacturing process of the CZTSe-based thin film according to the embodiment are shown in FIG. 2.
비교예Comparative example
상기 실시예 1과 동일한 기판을 준비하여, Cu, Zn, Sn, Se을 동시진공증발법으로 500℃의 기판에서 60분간 증착하여 박막 생성과 동시에 열처리가 이루어지게 하였다. 이때 각각의 에퓨젼 셀의 온도는 Cu 1480℃, Zn 335℃, Sn 1480℃, Se 210℃로 하였다.
The same substrate as in Example 1 was prepared, and Cu, Zn, Sn, and Se were deposited on a substrate at 500 ° C. for 60 minutes by a co-vacuum evaporation method so that heat treatment was performed simultaneously with thin film generation. At this time, the temperature of each fusion cell was Cu 1480 ° C, Zn 335 ° C, Sn 1480 ° C, Se 210 ° C.
비교예에 따른 CZTSe계 박막의 제조공정상 온도 및 시간 프로파일 곡선은 도 3에 나타낸 바와 같다.
Temperature and time profile curves during the manufacturing process of the CZTSe-based thin film according to the comparative example are shown in FIG. 3.
시험예 1: CZTSe계 박막 조성의 EDS 및 AES 분석Test Example 1 Analysis of EDS and AES of CZTSe-based Thin Film Composition
상기 실시예 및 비교예에 따라 제조된 CZTSe계 박막의 조성을 EDS(Energy Dispersive Spectroscopy) 및 AES(Auger Electron Spectroscopy)에 의해 분석하였다. 이에 따른 EDS 분석결과를 하기 표 1에 나타내었으며, AES 분석 곡선을 도 4(실시예) 및 도 5(비교예)에 나타내었다.
The composition of the CZTSe-based thin films prepared according to the Examples and Comparative Examples was analyzed by Energy Dispersive Spectroscopy (EDS) and Auger Electron Spectroscopy (AES). The results of the EDS analysis are shown in Table 1 below, and the AES analysis curves are shown in FIGS. 4 (Example) and 5 (Comparative Example).
상기 표 1 및 도 4 및 도 5에 따르면, 비교예에서는 상분리에 의해 원소의 조성이 박막 내에서 균일하지 못할 뿐 아니라, Sn이 손실된 것을 확인할 수 있었다. 이에 반해, 실시예에서는 박막 내 원소의 조성이 표면거리에 관계없이 비교적 균일하게 나타났으며, Sn 또한 박막 내 존재하여 비교적 균일한 조성을 갖는 것을 확인할 수 있었다. 따라서 본 발명의 CZTSe계 박막의 제조방법은 결정성장이 충분히 이루어지도록 높은 온도에서 박막을 형성하면서도, 이에 의해 Sn이 손실되는 것을 최소화할 수 있음을 알 수 있다.
According to Table 1 and FIGS. 4 and 5, in Comparative Examples, the composition of the elements was not uniform in the thin film due to phase separation, and it was confirmed that Sn was lost. On the contrary, in the examples, the composition of the elements in the thin film appeared relatively uniform regardless of the surface distance, and it was confirmed that Sn also existed in the thin film and had a relatively uniform composition. Therefore, it can be seen that the method of manufacturing the CZTSe-based thin film of the present invention can form a thin film at a high temperature such that crystal growth is sufficiently performed, thereby minimizing the loss of Sn.
시험예 2: CZTSe계 박막의 XRD에 의한 결정구조 분석Test Example 2 Analysis of Crystal Structure by XRD of CZTSe Thin Film
상기 실시예 및 비교예에 따라 제조된 CZTSe계 박막을 XRD(X-Ray Diffraction)분석하여 도 6(실시예) 및 도 7(비교예)에 각각 나타내었다. 도 6 및 도 7에 따르면, 실시예에 따라 제조된 박막은 CZTSe 구조의 패턴으로 나타났으나, 비교예에 따라 제조된 박막은 Sn이 손실되었을 뿐 아니라, CuxSe 및 ZnSe으로 상분리가 일어난 것을 확인할 수 있었다.
X-ray diffraction (XRD) analysis of the CZTSe-based thin films prepared according to the Examples and Comparative Examples are shown in FIGS. 6 (Example) and 7 (Comparative Example), respectively. 6 and 7, the thin film prepared according to the embodiment was found to have a pattern of a CZTSe structure, but the thin film prepared according to the comparative example not only lost Sn, but also phase-separated with Cu x Se and ZnSe. I could confirm it.
상기 시험예 1 및 시험예 2에 따르면, 본 발명의 CZTSe계 박막의 제조방법은 결정성장이 충분히 이루어지도록 높은 온도에서 박막을 형성하면서도, 이에 의해 Sn이 손실되는 것을 최소화할 수 있고, 박막 내 상분리가 일어나는 것을 방지하여 균일한 박막 내 조성을 구현할 수 있는 것을 알 수 있다.
According to Test Example 1 and Test Example 2, the CZTSe-based thin film manufacturing method of the present invention can form a thin film at a high temperature to sufficiently crystallize, thereby minimizing the loss of Sn, phase separation in the thin film It can be seen that it is possible to implement a composition in a uniform thin film by preventing the occurrence of.
Claims (5)
(S2) 감소된 기판 온도에서 Sn과 Se을 동시진공증발법에 따라 추가로 증착시키는 단계를 포함하는 태양전지용 CZTSe계 박막의 제조방법.(S1) depositing Cu, Zn, Sn and Se on the substrate by a co-vacuum evaporation method; And
(S2) A method of manufacturing a CZTSe-based thin film for a solar cell comprising the step of further depositing Sn and Se at a reduced substrate temperature by a co-evaporation method.
상기 S1 단계의 증착은 450∼600℃의 기판 온도에서 수행하는 것을 특징으로 하는 태양전지용 CZTSe계 박막의 제조방법.The method according to claim 1,
The deposition of the step S1 is a method of manufacturing a CZTSe-based thin film for solar cells, characterized in that performed at a substrate temperature of 450 ~ 600 ℃.
상기 S2 단계의 증착은 250∼400℃의 기판 온도에서 수행하는 것을 특징으로 하는 태양전지용 CZTSe계 박막의 제조방법.The method according to claim 1,
The deposition of the step S2 is a method of manufacturing a CZTSe-based thin film for solar cells, characterized in that performed at a substrate temperature of 250 ~ 400 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020110140283A KR101279370B1 (en) | 2011-12-22 | 2011-12-22 | PREPARATION METHOD OF CZTSe-BASED THIN FILM USING CO-EVAPORATION AND CZTSe-BASED THIN FILM PREPARED BY THE SAME |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020110140283A KR101279370B1 (en) | 2011-12-22 | 2011-12-22 | PREPARATION METHOD OF CZTSe-BASED THIN FILM USING CO-EVAPORATION AND CZTSe-BASED THIN FILM PREPARED BY THE SAME |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20130072738A KR20130072738A (en) | 2013-07-02 |
| KR101279370B1 true KR101279370B1 (en) | 2013-07-04 |
Family
ID=48987348
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020110140283A KR101279370B1 (en) | 2011-12-22 | 2011-12-22 | PREPARATION METHOD OF CZTSe-BASED THIN FILM USING CO-EVAPORATION AND CZTSe-BASED THIN FILM PREPARED BY THE SAME |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR101279370B1 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3146612B2 (en) * | 1992-04-14 | 2001-03-19 | 松下電器産業株式会社 | Method for producing solid solution thin film and method for producing solar cell |
| KR101094326B1 (en) | 2009-12-15 | 2011-12-19 | 한국에너지기술연구원 | Cu-In-Zn-Sn-Se,S THIN FILM FOR SOLAR CELL AND PREPARATION METHOD THEREOF |
-
2011
- 2011-12-22 KR KR1020110140283A patent/KR101279370B1/en active IP Right Grant
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3146612B2 (en) * | 1992-04-14 | 2001-03-19 | 松下電器産業株式会社 | Method for producing solid solution thin film and method for producing solar cell |
| KR101094326B1 (en) | 2009-12-15 | 2011-12-19 | 한국에너지기술연구원 | Cu-In-Zn-Sn-Se,S THIN FILM FOR SOLAR CELL AND PREPARATION METHOD THEREOF |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20130072738A (en) | 2013-07-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7842534B2 (en) | Method for forming a compound semi-conductor thin-film | |
| US20150075620A1 (en) | Copper indium gallium selenide (cigs) thin films with composition controlled by co-sputtering | |
| EP2309548A2 (en) | Photoelectric conversion device, method for producing the same and solar battery | |
| KR101094326B1 (en) | Cu-In-Zn-Sn-Se,S THIN FILM FOR SOLAR CELL AND PREPARATION METHOD THEREOF | |
| WO2012055738A2 (en) | Thin film solar cell fabrication | |
| US20120180870A1 (en) | Photoelectric conversion device, method for producing the same, and solar battery | |
| KR101628312B1 (en) | PREPARATION METHOD OF CZTSSe-BASED THIN FILM SOLAR CELL AND CZTSSe-BASED THIN FILM SOLAR CELL PREPARED BY THE METHOD | |
| KR20130016528A (en) | Preparation method for czt(s,se) thin film and czt(s,se) thin film prepared the same | |
| Zeng et al. | Effect of S/(S+ Se) ratio during the annealing process on the performance of Cu2ZnSn (S, Se) 4 solar cells prepared by sputtering from a quaternary target | |
| Reyes-Figueroa et al. | Structural properties of In2Se3 precursor layers deposited by spray pyrolysis and physical vapor deposition for CuInSe2 thin-film solar cell applications | |
| US9112095B2 (en) | CIGS absorber formed by co-sputtered indium | |
| KR101734362B1 (en) | Forming method for acigs film at low temperature and manufacturing method for solar cell by using the forming method | |
| KR101279370B1 (en) | PREPARATION METHOD OF CZTSe-BASED THIN FILM USING CO-EVAPORATION AND CZTSe-BASED THIN FILM PREPARED BY THE SAME | |
| KR101358055B1 (en) | PREPARATION METHOD OF CZTSe THIN FILM AND CZTSe THIN FILM PREPARED THE SAME | |
| Liang et al. | Thermal induced structural evolution and performance of Cu2ZnSnSe4 thin films prepared by a simple route of ion-beam sputtering deposition | |
| US9601642B1 (en) | CZTSe-based thin film and method for preparing the same, and solar cell using the same | |
| US20130316490A1 (en) | Solar cell and solar cell production method | |
| KR20150023102A (en) | A solar cell comprising czts thin film with uniform composition and a method of manufacturing the same | |
| KR101388458B1 (en) | Preparation method for cigs thin film using rapid thermal processing | |
| Oliveira et al. | In-situ sol-gel synthesis and thin film deposition of Cu (In, Ga)(S, Se) 2 solar cells | |
| KR102057234B1 (en) | Preparation of CIGS thin film solar cell and CIGS thin film solar cell using the same | |
| US9472708B2 (en) | Method of fabricating copper indium gallium selenide (CIGS) thin film for solar cell using simplified co-vacuum evaporation and copper indium gallium selenide (CIGS) thin film for solar cell fabricated by the same | |
| KR101406704B1 (en) | FABRICATION METHOD OF CZTSe ABSORBER LAYERS BY CO-EVAPORATION PROCESS | |
| Palmiotti et al. | Homogeneous CuGaSe2 growth by the CuPRO process with In-Situ AgBr treatment | |
| Yamaguchi et al. | Preparation of Cu2ZnSnSe4 thin films by selenization of precursor evaporated from Cu2ZnSnSe4 compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20160610 Year of fee payment: 4 |
|
| FPAY | Annual fee payment |
Payment date: 20170324 Year of fee payment: 5 |
|
| FPAY | Annual fee payment |
Payment date: 20180416 Year of fee payment: 6 |
|
| FPAY | Annual fee payment |
Payment date: 20200309 Year of fee payment: 8 |