• Current Photovoltaic Research
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• v.5 no.4
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• pp.135-139
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• 2017

We fabricated two different transparent conducting oxide thin films of ZnO doped with Ga ($Ga_2O_3$ 0.9 wt%) as well as Al ($Al_2O_3$ 2.1 wt%) (GAZO) and ZnO doped only with Al ($Al_2O_3$ 3 wt%) (AZO). It was investigated how it affects the moisture resistance of the transparent electrode. In addition, $Cu(In,Ga)Se_2$ thin film solar cells with two transparent oxides as front electrodes were fabricated, and the correlation between humidity resistance of transparent electrodes and device performance of solar cells was examined. When both transparent electrodes were exposed to high temperature distilled water, they showed a rapid increase in sheet resistance and a decrease in the fill factor of the solar cell. However, AZO showed a drastic decrease in efficiency at the beginning of exposure, while GAZO showed that the deterioration of efficiency occurred over a long period of time and that the long term moisture resistance of GAZO was better.

• Journal of Ceramic Processing Research
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• v.13 no.spc1
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• pp.140-144
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• 2012

Ga-doped ZnO (GZO) was a limit of application on the photovoltaic devices such as CIGS, CdTe and DSSC requiring high process temperature, because it's electrical resistivity is unstable above 300 ℃ at atmosphere. Therefore, ZTO (zinc tin oxide) was introduced in order to improve permeability and thermal stability of GZO film. The resistivity of GZO (300 nm) single layer increased remarkably from 1.8 × 10-3Ωcm to 5.5 × 10-1Ωcm, when GZO was post-annealed at 400 ℃ in air atmosphere. In the case of the ZTO (150 nm)/GZO (150 nm) double layer, resistivity showed relatively small change from 3.1 × 10-3Ωcm (RT) to 1.2 × 10-2Ωcm (400 ℃), which showed good agreement with change of carrier density. This result means that ZTO upper layer act as a barrier for oxygen at high temperature. Also ZTO (150 nm)/GZO (150 nm) double layer showed lower WVTR compared to GZO (300 nm) single layer. Because ZTO has lower WVTR compared to GZO, ZTO thin film acts as a barrier by preventing oxygen and water molecules to penetrate on top of GZO thin film.

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

• Proceedings of the Korean Vacuum Society Conference
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• 2012.02a
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• pp.291-291
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• 2012

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 2세대 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 규모뿐만 아니라 대면적(모듈급) CIGS 박막 태양전지 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 하부전극은 Mo 재료을 스퍼터링 방법으로 증착하여 주로 사용한다. 하부전극은 0.24 Ohm/cm2 정도의 전기적 특성이 요구되며, 주상조직으로 성장하여야 하며, 고온 안정성 확보를 위하여 기판과의 밀착성이 좋아야하고 또한 레이저 패턴시 기판에서 잘 떨어져야 하는 특성을 동시에 가져야 한다. 그리고 CIGSe2의 광흡수층 제조시 셀렌화 공정에서 100 nm 이하의 MoSe2 두께를 갖도록 해야하며, 이는 CIGSe2 박막태양전지의 Rs 값을 줄여 Ohmic 접촉을 향상시키는데 기여한다. 본 연구에서는 CIGSe2 박막태양전지에서 요구되는 하부 전극 Mo 박막의 제작과 CIGSe2 박막태양전지 전체공정에 적용후의 MoSe2/Mo 박막특성에 대해서 연구결과들을 논하고자 한다. (본 연구는 경북그린에너지프론티어기업발굴육성사업 연구지원금으로 이루어졌음).

• Proceedings of the Korean Vacuum Society Conference
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• 2013.02a
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• pp.458-458
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• 2013

We investigated a study on the thermal degradation of boron doped zinc-oxide (BZO) layer which used as a transparent conducting layer on the Cu (In1-xGax) Se2 (CIGS) based thin film solar cells. Devices were annealed under the temperature of $100^{\circ}C$ or 100 hours and then Hall measurement was carried out to characterize the parameters of mobility (${\mu}Hall$), resistivity (${\rho}$), conductivity (${\sigma}$) and sheet resistance (Rsh). The initial values of ${\mu}Hall$, ${\rho}$, ${\sigma}$ and Rsh were $29.3cm^2$/$V{\cdot}s$, $2.1{\times}10^{-3}{\Omega}{\cdot}cm$, $476.4{\Omega}^{-1}{\cdot}cm^{-1}$ and $19.1{\Omega}$/${\Box}$ respectively. After the annealing process, the values were $4.5cm^2$/$V{\cdot}s$, $12.8{\times}10^{-3}{\Omega}{\cdot}cm$, $77.9{\Omega}^{-1}{\cdot}cm^{-1}$ and $116.6{\Omega}$/${\Box}$ respectively. We observed that ${\mu}Hall$ and ${\sigma}$ were decreased, and ${\rho}$ and Rsh were increased. In this study, BZO layer plays an important role of conducting path for electrons generated by incident light onthe CIGS absorption layer. Therefore, the degradation of BZO layer characterized by the parameters of ${\mu}Hall$, ${\rho}$, ${\sigma}$ and Rsh, affect to the cell efficiency.

• Proceedings of the Korean Vacuum Society Conference
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• 2016.02a
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• pp.305.2-305.2
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• 2016

Tin monosulfide (SnS) is one promising candidate absorber material which replace the current technology based on cadmium telluride (CdTe) and copper indium gallium sulfide selenide (CIGS) for its suitable optical band gap, high absorption coefficient, earth-abundant, non-toxic and cost-effective. During past years work, thin film solar cells based on SnS films had been improved to 4.36% certified efficiency. In this study, Tin monosul fide was obtained by atomic layer deposition (ALD) using the reaction of Tetrakis (dimethylamino) tin (TDMASn, [(CH3)2N]4Sn) and hydrogen sulfide (H2S) at low temperatures (100 to 200 oC). The direct optical band gap and strong optical absorption of SnS films were observed throughout the Ultraviolet visible spectroscopy (UV VIS), and the properties of SnS films were analyzed by sanning Electron Microscope (SEM) and X-Ray Diffraction (XRD).

• Proceedings of the Korean Vacuum Society Conference
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• 2013.02a
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• pp.434-436
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• 2013

Ga-doped ZnO (GZO) was substitutes of the SnO2:F films on soda lime glass substrate in the photovoltaic devices such as CIGS, CdTe and DSSC due to good properties and low cost. However, it was reported that the electrical resistivity of GZO is unstable above $300^{\circ}C$ in air atmosphere. To improve thermal stability of GZO thin films at high temperature above $300^{\circ}C$ an $TiO_2$ thin film was deposited on the top of GZO thin films as a barrier layer by Pulsed Laser Deposition (PLD) method. $TiO_2$ thin films were deposited at various thicknesses from 25 nm to 100 nm. Subsequently, these films were annealed at temperature of $300^{\circ}C$, $400^{\circ}C$, $500^{\circ}C$ in air atmosphere for 20 min. The XRD measurement results showed all the films had a preferentially oriented ( 0 0 2 ) peak, and the intensity of ( 0 0 2 ) peak nearly did not change both GZO (300 nm) single layer and $TiO_2$ (50 nm)/GZO (300 nm) double layer. The resistivity of GZO (300 nm) single layer increased from $7.6{\times}10^{-4}{\Omega}m$ (RT) to $7.7{\times}10^{-2}{\Omega}m$ ($500^{\circ}C$). However, in the case of the $TiO_2$ (50 nm)/GZO (300 nm) double layer, resistivity showed small change from $7.9{\times}10^{-4}{\Omega}m$ (RT) to $5.2{\times}10^{-3}{\Omega}m$ ($500^{\circ}C$). Meanwhile, the average transmittance of all the films exceeded 80% in the visible spectrum, which suggests that these films will be suitable for photovoltaic devices.

• Korean Journal of Materials Research
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• v.20 no.12
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• pp.661-668
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• 2010

Cu(In,Ga)$Se_2$(CIGS) photovoltaic thin films were electrodeposited on Mo/glass substrates with an aqueous solution containing 2 mM $CuCl_2$, 8 mM $InCl_3$, 20 mM $GaCl_3$ and 8mM $H_2SeO_3$ at the electrodeposition potential of -0.6 to -1.0 V(SCE) and pH of 1.8. The best chemical composition of $Cu_{1.05}In_{0.8}Ga_{0.13}Se_2$ was found to be achieved at -0.7 V(SCE). The precursor Cu-In-Ga-Se films were annealed for crystallization to chalcopyrite structure at temperatures of 100-$500^{\circ}C$ under Ar gas atmosphere. The chemical compositions, microstructures, surface morphologies, and crystallographic structures of the annealed films were analyzed by EPMA, FE-SEM, AFM, and XRD, respectively. The precursor Cu-In-Ga-Se grains were grown sparsely on the Mo-back contact and also had very rough surfaces. However, after annealing treatment beginning at $200^{\circ}C$, the empty spaces between grains were removed and the grains showed well developed columnar shapes with smooth surfaces. The precursor Cu-In-Ga-Se films were also annealed at the temperature of $500^{\circ}C$ for 60 min under Se gas atmosphere to suppress the Se volatilization. The Se amount on the CIGS film after selenization annealing increased above the Se amount of the electrodeposited state and the $MoSe_2$ phase occurred, resulting from the diffusion of Se through the CIGS film and interaction with Mo back electrode. However, the selenization-annealed films showed higher crystallinity values than did the films annealed under Ar atmosphere with a chemical composition closer to that of the electrodeposited state.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.30 no.10
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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.

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