• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2011년도 춘계학술대회 초록집
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• pp.106.1-106.1
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• 2011

The Cu(In,Ga)Se2 (CIGS) thin film solar cells have been achieved until almost 20% efficiency by NREL. These solar cells include chemically deposited CdS as buffer layer between CIGS absorber layer and ZnO window layer. Although CIGS solar cells with CdS buffer layer show excellent performance, the short wavelength response of CIGS solar cell is limited by narrow CdS band gap of about 2.42 eV. Taking into consideration the environmental aspect, the toxic Cd element should be replaced by a different material. Among Cd-free candidate materials, the CIGS thin film solar cells with ZnS buffer layer seem to be promising with 17.2%(module by showa shell K.K.), 18.6%(small area by NREL). However, ZnS/CIGS solar cells still show lower performance than CdS/CIGS solar cells. There are several reported reasons to reduce the efficiency of ZnS/CIGS solar cells. Nakada reported ZnS thin film had many defects such as stacking faults, pin-holes, so that crytallinity of ZnS thin film is poor, compared to CdS thin film. Additionally, it was known that the hetero-interface between ZnS and CIGS layer made unfavorable band alignment. The unfavorable band alignment hinders electron transport at the heteo-interface. In this study, we focused on growing defect-free ZnS thin film and for favorable band alignment of ZnS/CIGS, bandgap of ZnS and CIGS, valece band structure of ZnS/CIGS were modified. Finally, we verified the photovoltaic properties of ZnS/CIGS solar cells.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2006년도 춘계학술대회
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• pp.152-153
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• 2006

The new approach to buffer layer design for CIGS solar cells that permitted to reduce the buffer absorption losses in the short wavelength range and to overcome the disadvantages inherent to Cd-free CIGS solar cells was proposed. A chemical bath deposition method has been used to produce a high duality buffer layer that comprises thin film of CdS and Zn-based film. The double layer was grown on either ITO or CIGS substrates and its morphological, structural and optical properties were characterized. The Zn-based film was described as the ternary compound $ZnS_x(OH)_y$. The composition of the $ZnS_x(OH)_y$ layer was not uniform throughout its thickness. $ZnS_x(OH)_y$/CdS/substrate region was a highly intermixed region with gradually changing composition. The short wavelength cut-off of double layer was shifted to shorter wavelength (400nm) compared to that (520 nm) for the standard CdS by optimization of the double buffer design. The results show the way to improve the light energy collection efficiency of the nearly cadmium-free CIGS-based solar cells.

• 공업화학
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• 제25권6호
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• pp.577-580
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• 2014

CIGS 태양 전지용 cadmium (Cd)-free $In(OH)_xS_y$ 버퍼층을 화학적 용액성장법을 이용해서 형성시켰고 최적 반응시간을 파악하였다. 투과율 측정과 함께 이온집적빔 시스템으로 직접 박막을 관찰해서 박막성장 조건을 최적화 하였으며 X선 회절분석법과 X선 광전자 분광법, 주사현미경을 이용해서 박막의 특성을 파악하였다. 그 결과 $In(OH)_xS_y$ 버퍼층의 증착을 위한 최적 반응 시간은 온도 섭씨 $70^{\circ}$의 조건에서 20 min임을 확인하였으며, 이때의 버퍼층의 두께는 57 nm 가량이었고 밴드갭 에너지는 2.7 eV를 나타내었다. 아울러 molybdenum (Mo)층과 CIGS층 위에서 $In(OH)_xS_y$ 버퍼층을 형성시키는 경우에 XPS 피크의 차이는 볼 수 없었다.

• 한국태양에너지학회:학술대회논문집
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• 한국태양에너지학회 2012년도 춘계학술발표대회 논문집
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• pp.146-148
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• 2012

In our study, we have focused on optimizing good quality of ZnS buffer layer by chemical bath deposition (CBD) from a bath containing $ZnSO_4$, Thiourea and Ammonia in aqueous solution onto CIGS solar cells. The influence of deposition parameter such as pH, deposition temperature, stirring speed played a very important role on transmission, homogeneity, crystalline of ZnS buffer layer. The transmission spectrum showed a good transmission characteristic above 80% invisible spectral region. CIGS thin flim solar cell with ZnS buffer layer has been realized with the efficiency of 14.2%.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2009년도 춘계학술대회 논문집
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• pp.138-138
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• 2009

Recently, thin-film solar cells of Cu(In,Ga)$Se_2$(CIGS) have reached a high level of performance, which has resulted in a 19.9%-efficient device. These conventional devices were typically fabricated using chemical bath deposited CdS buffer layer between the CIGS absorber layer and ZnO window layer. However, the short wavelength response of CIGS solar cell is limited by narrow CdS band gap of about 2.42 eV. Taking into consideration the environmental aspect, the toxic Cd element should be replaced by a different material. It is why during last decades many efforts have been provided to achieve high efficiency Cd-free CIGS solar cells. In order to alternate CdS buffer layer, ZnS buffer layer is grown by using chemical bath deposition(CBD) technique. The thickness and chemical composition of ZnS buffer layer can be conveniently by varying the CBD processing parameters. The processing parameters were optimized to match band gap of ZnS films to the solar spectrum and exclude the creation of morphology defects. Optimized ZnS buffer layer showed higher optical transmittance than conventional thick-CdS buffer layer at the short wavelength below ~520 nm. Then, chemically deposited ZnS buffer layer was applied to CIGS solar cell as a alternative for the standard CdS/CIGS device configuration. This CIGS solar cells were characterized by current-voltage and quantum efficiency measurement.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2015년도 제49회 하계 정기학술대회 초록집
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• pp.257.1-257.1
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• 2015

Cu(In,Ga)Se2 (CIGS) 박막 태양 전지에서 buffer layer는 CIGS 흡수층과 TCO 사이의 밴드갭 차이에 대한 문제점과 lattice mismatch를 해결하기 위해 필수적이다. 흔히 buffer layer 물질로는 CdS가 가장 많이 사용되고 있으나 Cd의 독성에 관한 문제가 야기되고 있다. 따라서 ZnS(O, OH) buffer layer가 친환경 물질로 기존의 CdS 버퍼 층의 대체 물질로 각광 받고 있으며, 단파장 범위에서 높은 투과율로 인해 wide band gap의 Chalcopyrite 태양 전지에 응용되는 buffer layer로 많은 연구가 이루어지고 있다. 또한 buffer layer를 최적화 하여 carrier lifetime과 양자 효율이 증가시킬 수 있는 특성을 가지고 있다. 이 연구에서는 Cu(In,Ga)Se2 (CIGS) 박막에 화학습식공정 (CBD) 방법을 이용하여 최적화된 ZnS(O, OH)의 증착 조건을 찾고, 고품질의 buffer layer를 제조하기 위한 실험에 초점을 맞췄다. 또한, buffer layer의 막질을 개선하고 균일한 막을 제조하기 위해 processing parameters인 시약의 농도, 제조 시간 및 온도 등의 다양한 변화를 통해 실험을 진행하였다. 그 후 최적화된 ZnS(O, OH) buffer layer의 특성 분석을 위해 X-ray diffraction(XRD), photoluminescence (PL), scanning electron microscope (SEM) and GD-OES을 이용하였고, 이를 통해 제조된 CIGS 박막 태양전지는 light induced current-voltage (LIV) and external quantum efficiency (EQE)를 통해 특성 분석을 실시 하였다. 결과적으로, 제조된 ZnS(O, OH) buffer layer의 $ZnSO4{\cdot}7H2O$의 농도는 0.16 M, Thiourea는 0.5 M, NH4OH는 7.5 M, 그리고 반응 온도는 77.5 oC의 조건 하에 CIGS 기판 위에 균일하고 균열이 없는 ZnS(O, OH) 박막을 제조하였으며 이때 제조된 태양전지의 소자 특성은 Voc = 0.478 V, Jsc = 35.79 mA/cm2, FF = 47.77%, ${\eta}=8,18 %$이다.

• 한국전기전자재료학회논문지
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• 제30권10호
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• pp.625-630
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• 2017

ZnS was chemically deposited as a buffer layer alternative to CdS, for use as a Cd-free buffer layer in $Cu(In_{1-x}Ga_x)Se_2$ (CIGS) solar cells. The deposition of a thin film of ZnS was carried out by chemical bath deposition, following which the structural and optical properties of the ZnS layer were studied. For the experiments, zinc sulfate hepta-hydrate ($ZnSO_4{\cdot}7H_2O$), thiourea ($SC(NH_2)_2$), and ammonia ($NH_4OH$) were used as the reacting agents. The mole concentrations of $ZnSO_4$ and $SC(NH_2)_2$ were fixed at 0.03 M and 0.8 M, respectively, while that of ammonia, which acts as a complexing agent, was varied from 0.3 M to 3.5 M. By varying the mole concentration of ammonia, optimal values for parameters like optical transmission, deposition rate, and surface morphology were determined. For the fixed mole concentrations of $0.03M\;ZnSO_4{\cdot}7H_2O$ and $0.8M\;SC(NH_2)_2$, it was established that 3.0 M of ammonia could provide optimal values of the deposition rate (5.5 nm/min), average optical transmittance (81%), and energy band gap (3.81 eV), rendering the chemically deposited ZnS suitable for use as a Cd-free buffer layer in CIGS solar cells.

• 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.

• Current Photovoltaic Research
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• 제9권3호
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• pp.96-105
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• 2021

Even though above 22% efficiencies have been reported in Cd-free Cu(In,Ga)Se₂ (CIGS) solar cell with Zn-containing buffers, the efficiencies with Zn-containing buffers, in general, are well below 20%. One of the reasons is Zn diffusion from the Zn-containing buffer layer to CIGS film during buffer growth. To avoid the degradation, it is necessary to prevent the diffusion of Zn atoms from Zn-containing buffer to CIGS film. For the purpose, we characterized an In₂Se₃ film as a possible diffusion barrier layer because In₂Se₃ has no Zn component. It was found that an In₂Se₃ layer grown at 300℃ was very effective in preventing Zn diffusion from a Zn-containing buffer. Also, the In₂Se₃ had a large potential barrier in the valence band at the In₂Se₃/CIGS interface. Therefore, In₂Se₃ passivation has the potential to achieve a super-high efficiency in CIGS solar cells that employ Cd-free ALD processed buffers containing Zn.

• 한국재료학회:학술대회논문집
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• 한국재료학회 2010년도 춘계학술발표대회
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• pp.35.1-35.1
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• 2010

The Cu(In,Ga)Se2(CIGS) thin film solar cells have been achieved until almost 20% efficiency by NREL. These solar cells include chemically deposited CdS as buffer layer between CIGS absorber layer and ZnO window layer. Although CIGS solar cells with CdS buffer layer show excellent performance, many groups made hard efforts to overcome its disadvantages in terms of high absorption of short wavelength, Cd hazardous element. Among Cd-free candidate materials, the CIGS thin film solar cells with Zn compound buffer layer seem to be promising with 15.2%(module by showa shell K.K.), 18.6%(small area by NREL). However, few groups were successful to report high-efficiency CIGS solar cells with Zn compound buffer layer, compared to be known how to fabricate these solar cells. Each group's chemical bah deposition (CBD) condition is seriously different. It may mean that it is not fully understood to grow high quality Zn compound thin film on the CIGS using CBD. In this study, we focused to clarify growth mechanism of chemically deposited Zn compound thin film on the CIGS, especially. Additionally, we tried to characterize junction properties with unfavorable issues, that is, slow growth rate, imperfect film coverage and minimize these issues. Early works reported that film deposition rate increased with reagent concentration and film covered whole rough CIGS surface. But they did not mention well how film growth of zinc compound evolves homogeneously or heterogeneously and what kinds of defects exist within film that can cause low solar performance. We observed sufficient correlation between growth quality and concentration of NH3 as complex agent. When NH3 concentration increased, thickness of zinc compound increased with dominant heterogeneous growth for high quality film. But the large amounts of NH3 in the solution made many particles of zinc hydroxide due to hydroxide ions. The zinc hydroxides bonded weakly to the CIGS surface have been removed at rinsing after CBD.