• Proceedings of the Materials Research Society of Korea Conference
• /
• 2012.05a
• /
• pp.99.1-99.1
• /
• 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.

• Korean Journal of Materials Research
• /
• v.30 no.10
• /
• pp.566-572
• /
• 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.

• Korean Journal of Materials Research
• /
• v.31 no.11
• /
• pp.619-625
• /
• 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.

• The Journal of the Korea institute of electronic communication sciences
• /
• v.16 no.2
• /
• pp.233-240
• /
• 2021

For the production of neodymium-doped zinc sulfide thin films in various amounts, zinc sulfide and neodymium were simultaneously deposited using an RF magnetron sputtering equipment to form a thin films, and rapid thermal annealing was performed at 400℃ for 30 minutes as a post-treatment process. The structure, shape, and optical properties of ZnS thin films having various neodymium doping contents (0.35at.%, 1.31at.%, 1.82at.% and 1.90at.%) were studied. The X-ray diffraction pattern was grown to a (111) cubic structure in all thin films. The surface and structural morphology of the thin films due to the neodymium doping content was explained through SEM and AFM images. Only elements of Zn, S, and Nd that do not contain other impurities were identified through EDAX. The transmittance and band gap of the prepared thin films were confirmed using the UV-vis spectrum.

• Proceedings of the Korean Vacuum Society Conference
• /
• 2011.08a
• /
• pp.53-53
• /
• 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.

• Proceedings of the Materials Research Society of Korea Conference
• /
• 2012.05a
• /
• pp.65-65
• /
• 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
• /
• 2016.02a
• /
• pp.405-405
• /
• 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 Korean institute of surface engineering
• /
• v.51 no.2
• /
• pp.116-125
• /
• 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
• /
• v.45 no.3
• /
• pp.183-188
• /
• 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.

• Proceedings of the Korean Vacuum Society Conference
• /
• 2013.02a
• /
• pp.363-363
• /
• 2013

태양광 발전산업에서 현재 주류인 결정 실리콘 태양전지의 변환효율은 꾸준히 향상되고 있으나, 태양전지의 가격이 매년 서서히 하강되고 있는 실정에서 결정질 실리콘 가격의 상승 등으로 부가가치 창출에 어려움이 있으며, 생산 원가를 낮출 수 있는 태양전지 제조기술로는 2 세대 태양전지로 불리는 박막형이 현재의 대안이며, 특히 에너지 변환 효율과 생산 원가에서 장점이 있는 것이 CIGS 박막 태양전지로 판단된다. 화합물반도체 베이스인 CIGS 박막태양전지는 연구실에서는 세계적으로 20.3% 높은 효율을 보고하고 있으며, 모듈급에서도 13% 효율로 생산이 시작되고 있다. 국내에서도 연구실 규모 뿐만 아니라 대면적(모듈급) CIGS 박막태양전지 증착용 장비, 제조공정 등의 기술개발이 진행되고 있다. CIGSe2를 광흡수층으로 하는 CIGSe2 박막 태양전지의 구조는 여러 층의 단위박막(하부전극, 광흡수층, 버퍼층, 상부투명전극)을 순차적으로 형성시켜 만든다. 이중에 소다라임유리를 기판으로 하는 하부전극은 Mo 재료를 스퍼터링 방법으로 증착하여 주로 사용한다. 하부전극은 우수한 전기적 특성이 요구되며, 주상조직으로 성장하여야 하며, 고온 안정성 확보를 위하여 기판과의 밀착성이 좋아야하고 또한 레이저 패턴시 기판에서 잘 떨어져야 하는 특성을 동시에 가져야 한다. 본 연구에서는 대면적 CIGSe2 박막태양전지에서 요구되는 하부전극 Mo 박막의 제작과 그 특성에 대해 평가하고, 최종적으로 대면적 CIGSe2 박막태양전지 공정에 적용 그 결과를 논하고자 한다.