• 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.

• 한국재료학회:학술대회논문집
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• 한국재료학회 2012년도 춘계학술발표대회
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• pp.99.1-99.1
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• 2012

The thin-film photovoltaic absorbers (CdTe and $Cu(In,Ga)Se_2$) can achieve solar conversion efficiencies of up to 20% and are now commercially available, but the presence of toxic (Cd,Se) and expensive elemental components (In, Te) is a real issue as the demand for photovoltaics rapidly increases. To overcome these limitations, there has been substantial interest in developing viable alternative materials, such as $Cu_2ZnSnS_4$ (CZTS) is an emerging solar absorber that is structurally similar to CIGS, but contains only earth abundant, non-toxic elements and has a near optimal direct band gap energy of 1.4 - 1.6 eV and a large absorption coefficient of ~104 $cm^{-1}$. The CZTS absorber layers are grown and investigated by various fabrication methods, such as thermal evaporation, e-beam evaporation with a post sulfurization, sputtering, non-vacuum sol-gel, pulsed laser, spray-pyrolysis method and electrodeposition technique. In the present work, we report an alternative aqueous chemical approach based on chemical bath deposition (CBD) method for large area deposition of CZTS thin films. Samples produced by our method were analyzed by scanning electron microscopy, X-ray diffraction, transmission electron microscopy, absorbance and photoluminescence. The results show that this inexpensive and relatively benign process produces thin films of CZTS exhibiting uniform composition, kesterite crystal structure, and some factors like triethanolamine, ammonia, temperature which strongly affect on the morphology of CZTS film.

• 한국재료학회지
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• 제30권10호
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• pp.566-572
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• 2020

In the recent years, thin film solar cells (TFSCs) have emerged as a viable replacement for crystalline silicon solar cells and offer a variety of choices, particularly in terms of synthesis processes and substrates (rigid or flexible, metal or insulator). Among the thin-film absorber materials, SnS has great potential for the manufacturing of low-cost TFSCs due to its suitable optical and electrical properties, non-toxic nature, and earth abundancy. However, the efficiency of SnS-based solar cells is found to be in the range of 1 ~ 4 % and remains far below those of CdTe-, CIGS-, and CZTSSe-based TFSCs. Aside from the improvement in the physical properties of absorber layer, enormous efforts have been focused on the development of suitable buffer layer for SnS-based solar cells. Herein, we investigate the device performance of SnS-based TFSCs by introducing double buffer layers, in which CdS is applied as first buffer layer and ZnMgO films is employed as second buffer layer. The effect of the composition ratio (Mg/(Mg+Zn)) of RF sputtered ZnMgO films on the device performance is studied. The structural and optical properties of ZnMgO films with various Mg/(Mg+Zn) ratios are also analyzed systemically. The fabricated SnS-based TFSCs with device structure of SLG/Mo/SnS/CdS/ZnMgO/AZO/Al exhibit a highest cell efficiency of 1.84 % along with open-circuit voltage of 0.302 V, short-circuit current density of 13.55 mA cm^-2, and fill factor of 0.45 with an optimum Mg/(Mg + Zn) ratio of 0.02.

• 한국재료학회지
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• 제31권11호
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• pp.619-625
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• 2021

Cu₂ZnSn(S,Se)₄ (CZTSSe) based thin-film solar cells have attracted growing attention because of their earth-abundant and non-toxic elements. However, because of their large open-circuit voltage (V_oc)-deficit, CZTSSe solar cells exhibit poor device performance compared to well-established Cu(In,Ga)(S,Se)₂ (CIGS) and CdTe based solar cells. One of the main causes of this large V_oc-deficit is poor absorber properties for example, high band tailing properties, defects, secondary phases, carrier recombination, etc. In particular, the fabrication of absorbers using physical methods results in poor surface morphology, such as pin-holes and voids. To overcome this problem and form large and homogeneous CZTSSe grains, CZTSSe based absorber layers are prepared by a sputtering technique with different RTA conditions. The temperature is varied from 510 ℃ to 540 ℃ during the rapid thermal annealing (RTA) process. Further, CZTSSe thin films are examined with X-ray diffraction, X-ray fluorescence, Raman spectroscopy, IPCE, Energy dispersive spectroscopy and Scanning electron microscopy techniques. The present work shows that Cu-based secondary phase formation can be suppressed in the CZTSSe absorber layer at an optimum RTA condition.

• 한국전자통신학회논문지
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• 제16권2호
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• pp.233-240
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• 2021

다양한 함량으로 네오디뮴이 도핑된 황화아연 박막제작은 RF 마그네트론 스퍼터링 장비를 이용하여 황화아연과 네오디뮴을 동시 증착하여 박막을 제작하였고, 후처리 공정으로 급속열처리를 400℃ 에서 30분간 실시하였다. 다양한 네오디뮴의 도핑 함량(0.35at.%, 1.31at.%, 1.82at.% 및 1.90at.%)을 갖는 ZnS 박막의 구조, 형태, 광학적 특성을 연구하였다. X-선 회절 패턴은 모든 박막에서 (111)방향의 큐빅 구조로 성장하였다. SEM 이미지와 AFM 이미지를 통해 네오디뮴 도핑 함량에 의한 박막의 표면 및 구조적 형태에 대하여 설명하였다. EDAX를 통해 다른 불순물이 포함되지 않은 Zn, S 및 Nd의 원소만을 확인하였다. UV-vis 스펙트럼을 이용하여 제작된 박막의 투과율과 밴드갭을 확인하였다.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2011년도 제41회 하계 정기 학술대회 초록집
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• pp.53-53
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• 2011

This paper describes results for surface and bulk characterization of the most promising thin film solar cell material for high performance devices, (Ag,Cu) (In,Ga) Se2 (ACIGS). This material in particular exhibits a range of exotic behaviors. The surface and general materials science of the material also has direct implications for the operation of solar cells based upon it. Some of the techniques and results described will include scanning probe (AFM, STM, KPFM) measurements of epitaxial films of different surface orientations, photoelectron spectroscopy and inverse photoemission, Auger electron spectroscopy, and more. Bulk measurements are included as support for the surface measurements such as cathodoluminescence imaging around grain boundaries and showing surface recombination effects, and transmission electron microscopy to verify the surface growth behaviors to be equilibrium rather than kinetic phenomena. The results show that the polar close packed surface of CIGS is the lowest energy surface by far. This surface is expected to be reconstructed to eliminate the surface charge. However, the AgInSe2 compound has yielded excellent atomic-resolution images of the surface with no evidence of surface reconstruction. Similar imaging of CuInSe2 has proven more difficult and no atomic resolution images have been obtained, although current imaging tunneling spectroscopy images show electronic structure variations on the atomic scale. A discussion of the reasons why this may be the case is given. The surface composition and grain boundary compositions match the bulk chemistry exactly in as-grow films. However, the deposition of the heterojunction forming the device alters this chemistry, leading to a strongly n-type surface. This also directly explains unpinning of the Fermi level and the operation of the resulting devices when heterojunctions are formed with the CIGS. These results are linked to device performance through simulation of the characteristic operating behaviors of the cells using models developed in my laboratory.

• 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.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2016년도 제50회 동계 정기학술대회 초록집
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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.

• 한국표면공학회지
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• 제51권2호
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• pp.116-125
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• 2018

Aluminum-doped zinc oxide (AZO) is a commonly used material for the front contact layer of chalcopyrite $CuInGaSe_2$ (CIGS) based thin film solar cells since it satisfies the requisite optical and electrical properties with low cost and abundant elemental availability. Low-resistivity and high-transmission front contacts have been developed for high-performance CIGS solar cells, and nearly meet the required performance. However, the durability of the cell especially for the corrosion resistance of AZO films has not been studied intensively. In this work, AZO films were prepared on Corning glass 7059 substrates by radio frequency magnetron sputtering depending on the hydrogen content. The electrical and optical properties and electrochemical corrosion resistance of the AZO films were evaluated as a function of the hydrogen content. With increasing hydrogen content to 6 wt%, the crystallinity, crystal size, and surface roughness of the films increased, and the resistivity decreased with increased carrier concentration, Hall mobility, oxygen vacancies, and $Zn(OH)_2$ binding on the AZO surface. At a hydrogen content of 6 wt%, the corrosion resistance was also relatively high with less columnar morphology, shallow pore channels, and lower grain boundary angles.

• Applied Microscopy
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• 제45권3호
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• pp.183-188
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• 2015

Due to the miniaturization of semiconductor devices, their crystal structure on the nanoscale must be analyzed. However, scanning electron microscope-electron backscatter diffraction (EBSD) has a limitation of resolution in nanoscale and high-resolution electron microscopy (HREM) can be used to analyze restrictive local structural information. In this study, three-dimensional (3D) automated crystal orientation and phase mapping using transmission electron microscopy (TEM) (3D TEM-EBSD) was used to identify the crystal structure relationship between an epitaxially grown CdS interfacial layer and a $Cu(In_xGa_{x-1})Se_2$ (CIGS) solar cell layer. The 3D TEM-EBSD technique clearly defined the crystal orientation and phase of the epitaxially grown layers, making it useful for establishing the growth mechanism of functional nano-materials.