• Proceedings of the Korean Vacuum Society Conference
• /
• 2010.08a
• /
• pp.298-299
• /
• 2010

Cu(In, Ga)Se2 (CIGS) 박막 태양전지는 Soda lime glass/Mo/CIGS/CdS/ZnO/ITO/Al 의 구조를 가지고 있다. CIGS 화합물은 direct bandgap 구조를 하고 있으며, 광흡수율이 다른 어떤 물질들 보다 뛰어나 박막으로도 충분히 태양광을 흡수할 수 있다. 또한 Ga의 도핑 농도에 따른 밴드갭 조절도 가능하다. 이러한 성질들로 인해 현재 박막태양전지로서 20.1%의 최고효율을 가지고 있다.[1] CIGS 박막 태양전지에서 p-CIGS layer와 스퍼터링으로 증착되는 n-ZnO layer사이의 buffer 층으로 chemical bath deposition (CBD)-CdS 박막을 주로 사용한다. CBD-CdS 박막은 n-ZnO 스퍼터로 증착 시킬 때, CIGS 층의 손상을 최소화하고, 이 두 층 사이에서의 격자상수와 밴드갭의 차이를 줄여주어 CIGS 박막태양전지의 효율을 증가 시키는 역할을 한다. 하지만, Cd (카드뮴)의 심각한 독성과 낮은 밴드갭(2.4eV)으로 인해 CIGS 층에서의 광흡수율을 줄여, CdS를 대체할 새로운 buffer 층의 필요성이 대두되었다.[2] 그 대안으로 ZnS, Zn(O, S, OH), (Zn, Mg)O, In2S3 같은 물질이 연구되고 있다. 현재 CBD-ZnS를 buffer 층으로 사용한 CIGS 박막태양전지의 효율은 최고 18.6%로 CBD-CdS의 최고효율보다는 약 1.5% 낮지만, ZnS가 높은 밴드갭(3.7~3.8eV)과 Cd-free 물질이라는 점에서 CdS를 대체할 물질로 각광받고 있다. 본 연구에서는 기존의 CdS 박막을 제조하는 방법과 같은 방법인 CBD를 이용하여 ZnS 박막을 제조하였다. ZnS 박막을 제조하기 위해서는 Zinc sulfate, Thiourea, 암모니아가 사용된다. 암모니아의 mol 농도에 따른 CBD-ZnS/CIGS 박막태양전지의 효율 변화를 관찰하기 위해 암모니아의 mol 농도는 1 mol, 2 mol, 3 mol, 4 mol, 5 mol, 6 mol, 그 이상의 과량을 사용하여 실험하였다. 실험 결과, 암모니아농도 5 mol에서 효율 13.82%를 확인할 수 있었다. 최고효율을 보인 조건인 암모니아 농도가 5 mol 일 때, Voc는 0.602V, Jsc는 33.109mA/cm2, FF는 69.4%를 나타내었다.

• Proceedings of the Korean Vacuum Society Conference
• /
• 2016.02a
• /
• pp.431-431
• /
• 2016

Typical Cu(In,Ga)Se2 (CIGS)-based solar cells have a buffer layer between CIGS absorber layer and transparent ZnO front electrode, which plays an important role in improving the cell performance. Among various buffer materials, chemical bath deposition (CBD)-ZnS is being steadily studied to alternative to conventional CdS and the efficiency of CBD-ZnS/CIGS solar cell shows the comparable values with that of CdS/CIGS solar cell. The intriguing thing is that reversible changes occur after exposure to illumination due to the metastable defect states in completed ZnS/CIGS solar cell, which induces an improvement of solar cell performance. Thus, it implies that the understanding of metastable defects in CBD-ZnS/CIGS solar cell is important issue. In this study, we fabricate the ITO/i-ZnO/CBD-ZnS/CIGS/Mo/SLG solar cells by controlling the NH4OH mole concentration (from 2 M to 3.5 M) of CBD-ZnS buffer layer and observe their conversion efficiency with and without light soaking for 1 hr. From the results, NH4OH mole concentration and light exposure can significantly affect the CBD-ZnS/CIGS solar cell performance. In order to investigate that which layer can contain metastable defect states to influence on solar cell performance, impedance spectroscopy and capacitance profiling technique with exposure to illumination have been applied to CBD-ZnS/CIGS solar cell. These techniques give a very useful information on the density of states within the bandgap of CIGS, free carriers density, and light-induced metastable effects. Here, we present the rearranged charge distribution after exposure to illumination and suggest the origin of the metastable defect states in CBD-ZnS/CIGS solar cell.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
• /
• v.31 no.3
• /
• pp.177-181
• /
• 2018

We prepared ZnS thin films via chemical bath deposition (CBD) in an aqueous solution of ammonia ($NH_3$) and hydrazine ($N_2H_4$). The composition ratio of hydrazine used was 0%, 17%, 22%, 29%, or 50%. We investigated the effects of hydrazine and ammonia on the growth, and the structural and optical properties of ZnS in terms of surface uniformity, voids, and grain size. We found that during the growth of ZnS films, hydrazine was very effective for improving the surface morphology and layer uniformity with fast layer formation, while it had no effect on the bandgap energy, $E_g$.

• Transactions on Electrical and Electronic Materials
• /
• v.5 no.1
• /
• pp.1-6
• /
• 2004

Zinc sulfide is a semiconductor with wide band gap and high refractive index and hence promising material to be used as ARC on commercial silicon solar cells. Uniform deposition of zinc sulfide (ZnS) by using chemical bath deposition (CBD) method over a large area of silicon surface is an emerging field of research because ZnS film can be used as a low cost antireflection coating (ARC). The main problem of the CBD bath process is the huge amount of precipitation that occurs during heterogeneous reaction leading to hamper the rate of deposition as well as uniformity and chemical stoichiometry of deposited film. Molar concentration of thiorea plays an important role in varying the percentage of reflectance and refractive index of as-deposited CBD ZnS film. Desirable rate of film deposition (19.6 ${\AA}$ / min), film uniformity (Std. dev. < 1.8), high value of refractive index (2.35), low reflectance (0.655) have been achieved with proper optimization of ZnS bath. Decrease in refractive index of CBD ZnS film due to high temperature treatment in air ambiance has been pointed out in this paper. Solar cells of conversion efficiency 13.8 ％ have been successfully achieved with a large area (103 mm ${\times}$ 103 mm) mono-crystalline silicon wafers by using CBD ZnS antireflection coating in this modified approach.

• Proceedings of the Korean Vacuum Society Conference
• /
• 2014.02a
• /
• pp.472.1-472.1
• /
• 2014

현재 Cu(In,Ga)Se2나 Cu2ZnSn(S,Se)4 (CZTSSe)계 박막태양전지의 버퍼층으로 가장 많이 사용되는 물질은 CdS이다. 하지만 Cd의 독성 문제로 인해 사용에 제약이 있고, CdS의 작은 밴드갭(~2.4 eV)으로 인해 단 파장 영역에서 광활성층의 빛 흡수를 저해하는 문제 때문에 새로운 대체 물질을 찾으려는 연구가 많이 이루어지고 있다. 이러한 관점에서, ZnS계 물질은 독성 원소인 Cd을 사용하지 않고, 3.6 eV 정도의 큰 밴드갭을 가지기 때문에, CdS 버퍼층을 대체하기 위한 물질로 관심을 받고 있다. ZnS계 버퍼층을 증착하는 위해 chemical bath deposition (CBD), molecular beam epitaxy (MBE), thermal evaporation, spray pyrolysis, sputtering, elecrtrodepostion 등의 다양한 공정이 사용될 수 있다. 본 연구에서는 상기의 다양한 공정 가운데, 공정 단가가 낮고, 대면적 공정에 용이한 CBD 공정을 이용하여 ZnS계 버퍼층을 증착하는 연구를 수행하였다. 용액의 조성, 농도, 공정 온도, 시간 등을 비롯한 다양한 공정 변수가 ZnS계 박막의 morphology, 조성, 결정성, 광학적 특성 등 다양한 특성에 미치는 영향이 체계적으로 연구되었다. 또한, 상기 ZnS계 버퍼층을 CZTSSe 박막태양전지에 적용하여 CdS를 성공적으로 대체할 수 있음을 확인하였다. 본 연구를 통하여 ZnS계 버퍼층이 향후 친환경적인 박막태양전지 제조에 활용될 수 있는 가능성을 확인할 수 있었다.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
• /
• v.30 no.10
• /
• pp.625-630
• /
• 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.

• Proceedings of the Materials Research Society of Korea Conference
• /
• 2010.05a
• /
• pp.35.1-35.1
• /
• 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.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
• /
• v.14 no.2
• /
• pp.104-110
• /
• 2001

Structural, optical and electrical properties of Cd$_{1-x}$ Zn$_{x}$S films deposited by chemical bath deposition(CBD), which is a very attractive method for low-cost and large-area solar cells, are presented. Especially, in order to control more effectively the zinc component of the films, zinc acetate, which was used as the zinc source, was added in the reaction solution after preheating the reaction solution and the pH of the reaction solution decreased with increasing the concentration of zinc acetate. The films prepared after preheating and pH control had larger zinc component and higher optical band gap. The crystal structures of Cd$_{1-x}$ Zn$_{x}$S films was a wurtzite type with a preferential orientation of the (002) plane and the lattice constants of the films changed from the value for CdS to those for ZnS with increasing the mole ratio of the zinc acetate. The minimum lattice mismatch between Cd$_{1-x}$ Zn$_{x}$S and CdTe were 2.7% at the mole ratio of (ZnAc$_2$)/(CdAc$_2$+ZnAc$_2$)=0.4. As the more zinc substituted for Cd in the films, the optical transmittance improved, while the absorption edge shifted toward a shorterwavelength. the photoconductivity of the films was higher than the dark conductivity, while the ratio of those increased with increasing the mole ratio of zinc acetate. acetate.

• Proceedings of the Korean Vacuum Society Conference
• /
• 2015.08a
• /
• pp.257.1-257.1
• /
• 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.

• 한국신재생에너지학회:학술대회논문집
• /
• 2009.06a
• /
• pp.138-138
• /
• 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.