• The Journal of the Korea institute of electronic communication sciences
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• v.15 no.4
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• pp.665-670
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• 2020

Buffer layer in CIGS thin-film solar cells improves energy conversion efficiency through band alignment between the absorption layer and the window layer. ZnS is a non-toxic II-VI compound semiconductor with direct-transition band gaps and n-conductivity as well as with excellent lattice matching for CIGS absorbent layers. In this study, the structural and optical properties of ZnS thin films, deposited by RF magnetron sputtering method and subsequently performed by the rapid thermal annealing treatment, were investigated for the buffer layer. The zincblende cubic structures along (111), (220), and (311) were shown in all specimens. The rapid thermal annealed specimens at the relatively low temperatures were polycrystalline structure with the wurtzite hexagonal structures along (002). Rapid thermal annealing at high temperatures changed the polycrystalline structure to the single crystal of the zincblende cubic structures. Through the chemical analysis, the zincblende cubic structure was obtained in the specimen with the ratio of Zn/S near stoichiometry. ZnS thin film showed the shifted absorption edge towards the lower wavelength as annealing temperature increased, and the mean optical transmittance in the visible light range increased to 80.40% under 500℃ conditions.

• Proceedings of the Materials Research Society of Korea Conference
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• 2012.05a
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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.

• Proceedings of the Korean Vacuum Society Conference
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• 2016.02a
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• pp.405-405
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• 2016

CIGS 박막 태양전지에서 완충층으로 사용되는 ZnS는 단파장 영역에서 높은 투과도와 CIGS 계면과의 좋은 접착을 가지고 친환경적이며 3.74eV의 에너지 밴드갭을 가지고 있기 때문에 CdS를 사용했을 때 보다 더 넓은 에너지 영역의 광자를 p-n 접합 경계 영역으로 통과 시킬 수 있고 Cd-free 물질이라는 점에서 기존의 CdS 완충층의 대체 물질로 각광 받고 있다. 본 연구에서는 CIGS 박막에 화학습식공정 방법을 이용하여 최적화된 ZnS 박막의 증착 조건을 찾기 위해 실험 변수인 시약의 농도, 실험온도, 열처리 조건 등의 다양한 변화를 통해 실험을 진행하였고, 박막의 갈라짐과 pin-hole 현상을 개선하고 균일한 막을 제조하기 위해 구연산 나트륨 농도에 따른 ZnS 박막의 특성을 연구하였다. 본 실험 결과로서 실험변수인 황산아연의 농도 0.15M, 암모니아는 0.3M, 티오요소 1M, 공정 온도 $80^{\circ}C$의 최적화 된 조건에서 가장 좋은 품질의 ZnS 박막을 제조하였지만, ZnS 박막의 열처리 후 산소의 양이 줄어감에 따라 박막의 표면이 갈라지고 pin-hole 현상이 발생하는 것을 확인할 수 있었다. 박막의 품질을 개선하기 위해 구연산 나트륨을 첨가하여 실험한 결과 구연산 나트륨의 0.05M의 농도에서는 박막 표면에 90nm의 갈라짐의 크기와 pin-hole 현상이 남아있는 것을 확인하였고, 농도가 높아질수록 점차 크기가 줄어들면서 0.4M에서는 갈라짐이 거의 없는 표면과 pin-hole 현상도 없어지는 것을 확인하였고, 약 144nm의 박막 두께와 3.8eV의 에너지 밴드갭을 가지고, 약 81%의 높은 광투과율을 갖는 고품질의 ZnS 박막을 제작할 수 있었다.

• Journal of the Korea Institute of Information and Communication Engineering
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• v.14 no.7
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• pp.1647-1652
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• 2010

A CdS film has been used as a window layer in CdTe and Cu(In,Ga)$Se_2$ thin films solar cell. Partial substitution of Zn for Cd increases the photocurrent and the open-circuit voltage by providing a match in the electron affinities of the two materials and the higher band gap. In this paper, CdZnS/CdTe and CdS/CdTe heterojunctions were fabricated and the electrical characteristics were investigated. Current-voltage-temperature measurements showed that the current transport for CdS/CdTe heterojunction was controlled by both tunneling and interface recombination. However, CdZnS/CdTe heterojunction displayed different current transport mechanism with the operating temperature. For above room temperature, the current transport of device was generation/recombination in the depletion region and was the leakage current and/or tunneling in the range below room temperature.