• Current Photovoltaic Research
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• 제7권1호
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• pp.1-8
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• 2019

The $Cu(In,Ga)Se_2$ (CIGS) thin film obtained by two-step process (metal deposition and Se annealing) has a rough surface morphology and many voids at the CIGS/Mo interface. To solve the problem a precursor that contains Se was employer by depositing a (In,Se)/(Cu,Ga) stacked layer. We devised a two-step annealing (vacuum pre-annealing and Se annealing) for the precursor because direct annealing of the precursor in Se environment resulted in the small grains with unwanted demarcation between stacked layers. After vacuum pre-annealing up to $500^{\circ}C$ the CIGS film consisted of CIGS phase and secondary phases including $In_4Se_3$, InSe, and $Cu_9(In,Ga)_4$. The secondary phases were completely converted to CIGS phase by a subsequent Se annealing. A void-free CIGS/Mo interface was obtained by the two-step annealing process. Especially, the CIGS film prepared by vacuum annealing $450^{\circ}C$ and subsequent Se annealing $550^{\circ}C$ showed a densely-packed grains with smooth surface, well-aligned bamboo grains on the top of the film, little voids in the film, and also little voids at the CIGS/Mo interface. The smooth surface enhanced the cell performance due to the increase of shunt resistance.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2011년도 제41회 하계 정기 학술대회 초록집
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• pp.218-218
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• 2011

The CIGS Solar Cells have the highest conversion efficiency in the film-type solar cells. They consist of p-type CuInSe2 film and n-type ZnO film. The CdS films are used as buffer layer in the CIGS solar cells since remarkable difference in the lattice constant and energy band gap of two films. The CdS films are toxic and make harmful circumstances. The CdS films deposition process need wet process. In this works, we design and make the hitter and lamp reflection part in the sputtering system for the ZnS films deposition as buffer layer, not using wet process. Film thickness, SEM, and AFM are measured for the uniformity valuation of the ZnS films. We conclude the optimum deposition temperature for the films uniformity less than 1.6%. The ZnS films deposited by the sputtering system are more dense and uniform than the CdS films deposited by the Chemical Bath Deposition Method(CBD) for the CIGS Solar Cells.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2006년도 춘계학술대회
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• pp.222-224
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• 2006

A non-vacuum process for $Cu(In,Ga)Se_2$ (CIGS) thin film solar cells from nanoparticle precursors was described in this work CIGS nanoparticle precursors was prepared by a low temperature colloidal route by reacting the starting materials $(CuI,\;InI_3,\;GaI_3\;and\;Na_2Se)$ in organic solvents, by which fine CIGS nanoparticles of about 20nm in diameter were obtained. The nanoparticle precursors were mixed with organic binder material for the rheology of the mixture to be adjusted for the doctor blade method. After depositing the mixture of CIGS with binder on Mo/glass substrate, the samples were preheated on the hot plate in air to evaporate remaining solvents ud to burn the organic binder material. Subsequently, the resultant (porous) CIGS/Mo/glass simple was selenized in a two-zone Rapid Thermal Process (RTP) furnace in order to get a solar ceil applicable dense CIGS absorber layer. Complete solar cell structure was obtained by depositing. The other layers including CdS buffer layer, ZnO window layer and Al electrodes by conventional methods. The resultant solar cell showed a conversion efficiency of 0.5%.

• 한국재료학회:학술대회논문집
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• 한국재료학회 2012년도 춘계학술발표대회
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• pp.92-92
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• 2012

Chalcopyrite-type Cu(In,Ga)Se2 (CIGS) is one of the most attractive compound semiconductor materials for thin film solar cells. Among various approaches to prepare the CIGS thin film, the powder process offers an extremely simple and materials-efficient method. Here, we present the mechano-chemical synthesis of CIGS compound powders and their use as an ink material for screen-printing. During the synthesis process, milling time and speed were varied in the range of 10~600 min and 100~300 rpm, respectively. Both phase evolution and powder characteristics were carefully monitored by X-ray diffraction (XRD) method, scanning electron microscope (SEM) observation, and particle size analysis by scanning mobility particle spectrometer (SMPS) and aerodynamic particle sizer (APS). We found the optimal milling condition as 200 rpm for 120 min but also found that a monolithic phase of CIGS powders without severe particle aggregation was difficult to be obtained by the mechano-chemical milling alone. Therefore, the optimized milling condition was combined with an adequate heat-treatment (300oC for 60 min) to provide the monolithic CIGS powder of a single phase with affordable particle characteristics for the preparation of CIGS thin film. The powder was used to prepare an ink for screen printing with which dense CIGS thin films were fabricated under the controlled selenization. The morphology and electrical properties of the thin films were analyzed by SEM images and hall measurement, respectively.

• 한국재료학회지
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• 제21권8호
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• pp.461-467
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• 2011

Cu(In, Ga)$Se_2$ (CIGS) precursor films were electrodeposited on Mo/glass substrates in acidic solutions containing $Cu^{2+}$, $In^{3+}$, $Ga^{3+}$, and $Se^{4+}$ ions at -0.6 V (SCE) and pH. 1.8. In order to induce recrystallization, the electrodeposited $Cu_{1.00}In_{0.81}Ga_{0.09}Se_{2.08}$ (25.0 at.% Cu + 20.2 at.% In + 2.2 at.% Ga + 52.0 at.% Se) precursor films were annealed under a high Se gas atmosphere for 15, 30, 45, and 60 min, respectively, at $500^{\circ}C$. The Se amount in the film increased from 52 at.% to 62 at.%, whereas the In amount in the film decreased from 20.8 at.% to 9.1 at.% as the annealing time increased from 0 (asdeposited state) to 60 min. These results were attributed to the Se introduced from the furnace atmosphere and reacted with the In present in the precursor films, resulting in the formation of the volatile $In_2Se$. CIGS precursor grains with a cauliflower shape grew as larger grains with the $CuSe_2$ and/or $Cu_{2-x}Se$ faceted phases as the annealing times increased. These faceted phases resulted in rough surface morphologies of the CIGS films. Furthermore, the CIGS layers were not dense because the empty spaces between the grains were not removed via annealing. Uniform thicknesses of the $MoSe_2$ layers occurred at the 45 and 60 min annealing time. This implies that there was a stable reaction between the Mo back electrode and the Se diffused through the CIGS film. The results obtained in the present research were sufficiently different from comparable studies where the recrystallization annealing was performed under an atmosphere of Ar gas only or a low Se gas pressure.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2009년도 춘계학술대회 논문집
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• pp.19-22
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• 2009

A non-vacuum process for fabrication of $CuIn_xGa_{1-x}Se_2$ (CIGS) absorber layer from the corresponing Cu, In, Ga solution precursors was described. Cu, In, Ga precursor solution was prepared by a room temperature colloidal route by reacting the starting materials $Cu(NO_3)_2$, $InCl_3$, $Ga(NO_3)$ and methanol. The Cu, In, Ga precursor solution was mixed with ethylcellulose as organic binder material for the rheology of the mixture to be adjusted for the doctor blade method. After depositing the mixture of Cu, In, Ga solution with binder on Mo/glass substrate, the samples were preheated on the hot plate in air to evaporate remaining solvents and to burn the organic binder material. Subsequently, the resultant CIG/Mo/glass sample was selenized in Se evaporation in order to get a solar cell applicable dense CIGS absorber layer. The CIGS absorber layer selenized at $530^{\circ}C$ substrate temperature for 1h with various metal organic ratio.

• 한국진공학회지
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• 제21권3호
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• pp.142-150
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• 2012

CIGS 박막 태양전지 기판소재인 소다라임유리 표면에 플라즈마 전처리 후 DC 마그네트론 스퍼터링 방법으로 Mo 박막을 제조하였다. 증착압력과 증착시간 변화에 따른 Mo 박막의 물리적, 전기적 특성을 분석하였고, 셀렌화 처리 조건에 따른 $MoSe_2$ 생성 여부와 경향성을 연구하였으며, Mo 박막 두께에 따른 AZO/i-ZnO/CdS/CIGS/Mo/SLG 구조의 태양전지를 제조하여 그 특성을 분석 및 평가하였다. 증착압력이 4.9 mTorr에서 1.3 mTorr로 감소할수록 치밀하고 결정입자 사이의 공극이 적고, 증착속도가 감소하고 전기저항도가 낮은 Mo 박막이 증착되었다. 증착온도가 상온에서 $200^{\circ}C$로 증가할수록 Mo 박막은 치밀한 구조를 가지고 결정성은 향상되어 면저항이 낮게 나타났다. 셀렌화 시간이 길어질수록 Mo 박막 층은 줄어들고, $MoSe_2$ 층 생성두께가 커지는 것을 알 수 있었고, 열처리로 인해 결정화 되면서 전체 박막의 두께가 줄어들었으며, $MoSe_2$ 층의 배양성은 c축이 Mo 표면과 수직 방향으로 성장된 것을 알 수 있었다. Mo 박막의 두께가 1.2 ${\mu}m$와 0.6 ${\mu}m$인 AZO/i-ZnO/CdS/CIGS/Mo/SLG 구조로 이루어진 CIGS 박막 태양전지를 제조하였다. Mo 박막의 두께가 1.2 ${\mu}m$일 때 보다 0.6 ${\mu}m$일 때 CIGS 박막 태양전지의 변환 효율은 9.46%로 비교적 우수한 특성을 나타났다. CIGS 박막 태양전지에서 하부전극인 Mo 박막 특성은 유리기판 및 광흡수 층과의 계면 형성 따라 큰 영향을 미친다는 것을 알 수 있었고, 유리기판의 플라즈마 처리와 Mo 박막의 두께조절로 Na 효과 및 $MoSe_2$층 형성 제어함으로써 CIGS 박막 태양전지의 특성 개선에 효과를 가질 수 있었다.

• 한국재료학회:학술대회논문집
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• 한국재료학회 2012년도 춘계학술발표대회
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• pp.65-65
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• 2012

Copper zinc tin sulfide ($Cu_2ZnSnS_4$, CZTS) is a very promising material as a low cost absorber alternative to other chalcopyrite-type semiconductors based on Ga or In because of the abundant and economical elements. In addition, CZTS has a band-gap energy of 1.4~1.5eV and large absorption coefficient over ${\sim}10^4cm^{-1}$, which is similar to those of $Cu(In,Ga)Se_2$(CIGS) regarded as one of the most successful absorber materials for high efficient solar cell. Most previous works on the fabrication of CZTS thin films were based on the vacuum deposition such as thermal evaporation and RF magnetron sputtering. Although the vacuum deposition has been widely adopted, it is quite expensive and complicated. In this regard, the solution processes such as sol-gel method, nanocrystal dispersion and hybrid slurry method have been developed for easy and cost-effective fabrication of CZTS film. Among these methods, the hybrid slurry method is favorable to make high crystalline and dense absorber layer. However, this method has the demerit using the toxic and explosive hydrazine solvent, which has severe limitation for common use. With these considerations, it is highly desirable to develop a robust, easily scalable and relatively safe solution-based process for the fabrication of a high quality CZTS absorber layer. Here, we demonstrate the fabrication of a high quality CZTS absorber layer with a thickness of 1.5~2.0 ${\mu}m$ and micrometer-scaled grains using two different non-vacuum approaches. The first solution-processing approach includes air-stable non-toxic solvent-based inks in which the commercially available precursor nanoparticles are dispersed in ethanol. Our readily achievable air-stable precursor ink, without the involvement of complex particle synthesis, high toxic solvents, or organic additives, facilitates a convenient method to fabricate a high quality CZTS absorber layer with uniform surface composition and across the film depth when annealed at $530^{\circ}C$. The conversion efficiency and fill factor for the non-toxic ink based solar cells are 5.14% and 52.8%, respectively. The other method is based on the nanocrystal dispersions that are a key ingredient in the deposition of thermally annealed absorber layers. We report a facile synthetic method to produce phase-pure CZTS nanocrystals capped with less toxic and more easily removable ligands. The resulting CZTS nanoparticle dispersion enables us to fabricate uniform, crack-free absorber layer onto Mo-coated soda-lime glass at $500^{\circ}C$, which exhibits a robust and reproducible photovoltaic response. Our simple and less-toxic approach for the fabrication of CZTS layer, reported here, will be the first step in realizing the low-cost solution-processed CZTS solar cell with high efficiency.