• Journal of Powder Materials
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• v.20 no.4
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• pp.245-252
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• 2013

This study attempted to manufacture a Cu-Ga coating layer via the cold spray process and to investigate the applicability of the layer as a sputtering target material. In addition, changes made to the microstructure and properties of the layer due to annealing heat treatment were evaluated, compared, and analyzed. The results showed that coating layers with a thickness of 520 mm could be manufactured via the cold spray process under optimal conditions. With the Cu-Ga coating layer, the ${\alpha}$-Cu and $Cu_3Ga$ were found to exist inside the layer regardless of annealing heat treatment. The microstructure that was minute and inhomogeneous prior to thermal treatment changed to homogeneous and dense with a more clear division of phases. A sputtering test was actually conducted using the sputtering target Cu-Ga coating layer (~2 mm thickness) that was additionally manufactured via the cold-spray coating process. Consequently, this test result confirmed that the cold sprayed Cu-Ga coating layer may be applied as a sputtering target material.

• Journal of Powder Materials
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• v.23 no.1
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• pp.21-25
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• 2016

The microstructural properties and electrical characteristics of sputtering films deposited with a Cu-Ga target are analyzed. The Cu-Ga target is prepared using the cold spray process and shows generally uniform composition distributions, as suggested by secondary ion mass spectrometer (SIMS) data. Characteristics of the sputtered Cu-Ga films are investigated at three positions (top, center and bottom) of the Cu-Ga target by X-ray diffraction (XRD), SIMS, 4-point probe and transmission electron microscopy (TEM) analysis methods. The results show that the Cu-Ga films are composed of hexagonal and unknown phases, and they have similar distributions of composition and resistivity at the top, center, and bottom regions of the Cu-Ga target. It demonstrates that these films have uniform properties regardless of the position on the Cu-Ga target. In conclusion, the cold spray process is expected to be a useful method for preparing sputter targets.

• ETRI Journal
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• v.34 no.5
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• pp.779-782
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• 2012

$CuIn_{1-x}Ga_xSe_2$ (CIGS) thin films are grown on Mo/soda lime glass using a reactive sputtering process in which a Se cracker is used to deliver reactive Se molecules. The Cu and $(In_{0.7}Ga_{0.3})_2Se_3$ targets are simultaneously sputtered under the delivery of reactive Se. The effects of Se flux on film composition are investigated. The Cu/(In+Ga) composition ratio increases as the Se flux increases at a plasma power of less than 30 W for the Cu target. The (112) crystal orientation becomes dominant, and crystal grain size is larger with Se flux. The power conversion efficiency of a solar cell fabricated using an 800-nm CIGS film is 8.5%.

• 한국신재생에너지학회:학술대회논문집
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• 2011.11a
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• pp.52.1-52.1
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• 2011

최근에 에너지 자원의 고갈이 다가오는 상황에서 태양전지 분야가 주목받고 있으며 이에 대한 시장이 급격하게 확대되고 있다. 그러나 현재의 태양전지는 주를 이루고있는 실리콘태양전지의 경우 원재료 수급이 불안정하여 가격 변동이 심하다. 따라서 이를 대체할 2세대 태양전지인 박막형 태양전지의 연구가 활발히 이루어지고 있다. 박막형 태양전지 중에서도 주목받고 있는 것은 Cu(In,Ga)$Se_2$(CIGS)박막 태양전지이다. CIGS는 Ga의 농도에 따라 1.02~1.68eV의 다양한 에너지 밴드갭을 갖는 직접천이형 반도체 물질이다. 또한 $1{\times}10^5cm^{-1}$의 높은 광흡수계수를 가지고 있으며, $450{\sim}590^{\circ}C$의 고온공정에서도 매우 안정하여 열화현상이 거의 보이지 않아 박막형 광흡수층 재료로서 적합하다. 흡수층을 제조하는 방법은 여러 가지가 있지만, 본 연구에서는 균일성이 뛰어나고 원료사용효율이 높은 sputtering 방법을 사용하였다. 그리고 결정화하기위해서 유독기체를 사용하는 셀.렌.화. (selenization) 방법 대신 전자빔을 조사하는 방법을 채택하였다. sputtering을 통한 CIGS precursor을 제조하기위해 2~3개의 화합물target을 사용하는데, 대표적인 방법으로 동시에 sputtering하는 co-sputtering 방법과 각각의 단일 층을 쌓아 제조하는 stack형으로 분류된다. 본 연구는 CIGS precursor를 제조하기 앞서 CuGa 단일 층만을 제조하여 공정조건에 따른 박막을 제조하였다. 제조된 CuGa 단일층은 전자빔 처리에 따른 영향을 알아보기 위해 전자빔의 세기와 공정시간을 달리하여 특성을 알아보았다. 실험에서는 Cu:75wt%,Ga:25wt% 조성의 target을 사용하여 공정 압력을 각각 10~1mTorr로 변화시키며 실험을 실시하였으며 공정 power는 50W, 70W, 100W로 변화 시키며 실험을 실시하였다. 이때 실험의 초기진공은 turbo-molecular pump를 이용하여 $1{\times}10^{-6}torr$ 이하로 하였으며, Target과 기판사이의 거리는 모두 같은 조건으로 고정하여 실험을 실시하였다. 박막의 균일성을 증가시키기 위하여 5 rpm의 속도로 기판을 회전하였으며 기판 온도는 가열하지 않고 상온에서 전구체를 증착하였다. 그 후 전자빔의 세기를 고정 시킨 후 전자빔 조사 시간을 조절하여 전자빔 조사 전후의 특성을 각각 분석하였다. 전기적특성은 Hall effect, 4-point probe, 구조적 특성은 SEM,EDS, XRD, XRF 를 이용하여 분석하였다.

• Journal of the Korean institute of surface engineering
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• v.46 no.2
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• pp.75-79
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• 2013

A one-step route was developed to fabricate $Cu(In,Ga)Se_2$ (CIGS) thin films by radio frequency (RF) magnetron sputtering from a single quaternary $CuIn_{0.75}Ga_{0.25}Se_2$ target. The effects of the substrate temperatures on the structural and electrical properties of the CIGS layers were investigated by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), energy dispersive X-ray spectroscopy (EDS) and Hall effect measurements. All the deposited films showed a preferential orientation along the (112) direction. The films deposited at $300^{\circ}C$ and $400^{\circ}C$ revealed that chalcopyrite main (112) peak and weak prominent peaks of (220)/(204) and (312)/(116), indicating polycrystalline structures. The element ratio of the deposited film at $300^{\circ}C$ were almost the same as the near-optimum value. The carrier concentration of the films decreased with increasing substrate temperatures.

• Journal of Powder Materials
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• v.18 no.6
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• pp.552-561
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• 2011

This study attempted to manufacture a Cu-15 at.%Ga coating layer via the cold spray process and investigated the effect of heat treatment environment on the properties of cold sprayed coating material. Three kinds of heat treatment environments, $5%H_2$+argon, pure argon, and vacuum were used in this study. Annealing treatments were conducted at $200{\sim}800^{\circ}C$/1 hr. With the cold sprayed coating layer, pure ${\alpha}$-Cu and small amounts of $Ga_2O_3$ were detected in the XRD, EDS, EPMA analyses. Porosity significantly decreased and hardness also decreased with increasing annealing temperature. The inhomogeneous dendritic microstructure of cold sprayed coating material changed to the homogeneous and dense one (microstructural evolution) with annealing heat treatment. Oxides near the interface of particles could be reduced by heat treatment especially in vacuum and argon environments. Vacuum environment during heat treatment was suggested to be most effective one to improve the densification and purification properties of cold sprayed Cu-15 at.%Ga coating material.

• Journal of the Korean institute of surface engineering
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• v.46 no.1
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• pp.16-21
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• 2013

CIGS (Cu-In-Ga-Se) films were deposited on the Mo coated soda lime glass (Mo/SLG) by RF magnetron sputtering using a single sintered target with different chemical compositions. Heat treatment of the CIGS films were carried out under three different conditions, 1step ($350^{\circ}C$ for 2 hour and $550^{\circ}C$ for 2 hour) and 2step ($350^{\circ}C$ for 1 hour and $550^{\circ}C$ for 1 hour). In the case of CIGS films post-annealed on 2step method, grain size remarkably increased compared to other methods, indicating that chemical composition [Cu/(Ga+In) = 1] of CIGS films was same as CIGS target. After heat treatment by 2step method, band gap energy of the CIGS film deposited at RF 80 W showed 1.4 eV which is broadly similar to identical band gap energy (1.2 eV) of CIGS film prepared by evaporation method. Therefore, 2step heat treatment method could be expected to low temperature process.

• 한국신재생에너지학회:학술대회논문집
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• 2011.11a
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• pp.53.1-53.1
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• 2011

현재 태양전지시장에서 비중이 많은 실리콘 태양전지는 높은 효율에 비해 제조 단가가 비싸다는 단점을 가지고 있다. 이에 비해 칼코파라이트 구조의 $CuInSe_2$ (CIS)계 화합물은 직접 천이형 반도체로서 높은 광흡수 계수($1{\times}105cm-{\acute{e}1$)와 밴드갭 조절의 용이성 및 열적 안정성 등으로 인해 고효율 박막 태양전지용 광흡수층 재료로 많은 관심을 끌고 있다. CIS 계 물질에 속하는 Cu(InGa)$Se_2$ (CIGS) 태양전지의 경우 양산화에 sputtering방식사용하고 Showa Shell에서는 대면적 CIGS 모듈 효율 13.4%를 달성한 바 있다. 현재 CIGS는 열처리하는 방법으로 selenization 공정을 사용하는데 이 공정은 유독한 $H_2Se$ gas를 이용해야 한다는 점과 긴 시간 동안 열처리를 해야 하는 단점을 가지고 있다. 따라서 이러한 단점을 보완하기 위해 본 연구에서는 전자빔을 사용하여 후속 공정을 실시하였다. 전자빔을 사용할 경우 낮은 온도에서 precursor를 처리하며 짧은 시간에 공정이 끝난다는 장점이 있다. 본 연구에서는 sodalime glass위에 조성비(Cu 60.87% Se 38.66%)인 Cu_2Se$ target(4.002"${\times}0.123$") 을 DC sputter를 이용하여 DC power를 50W,100W를 주고 Working pressure를 20,15,10,5,3,1mtorr로 조절하여 증착하였다. 전자빔의 세기 조건을 3Kv, Rf power 200W, Ar 7sccm로 전자빔 조사 시간을 1,2,3,4,5min으로 늘려가며 최적화 실험 하였고 최적화된 조건으로 $Cu_2Se$ target에 조사 하였다. 박막의 특성평가는 전자빔 조사 전/후에 대해 XRD, SEM, XRF, Hall measurement, UV-VIS을 이용하여 분석평가를 하였다. 이 실험은 $Cu_2Se$상이 자라는 특성과 표면 상태에 따라 CIGS박막을 증착하였을 때 나타나는 효율 변화를 알아 보기위한 초기 공정 실험이다.

• Proceedings of the Korean Vacuum Society Conference
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• 2012.02a
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• pp.382-382
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• 2012

CIGS thin films have received great attention as a promising material for solar cells due to their high absorption coefficient, appropriate bandgap, long-term stability, and low cost production. CIGS thin films are deposited by various methods such as co-evaporation, sputtering, spray pyrolysis and electro-deposition. The deposition technique is one of the most important processes in preparing CIGS thin film solar cells. Among these methods, co-evaporation is one of the best technique for obtaining high quality and stoichiometric CIGS films. However, co-evaporation method is known to be unsuitable for commercialization. The sputtering is known to be very effective and feasible process for mass production. In this study, CIGS thin films have prepared by rf magnetron sputtering using a $Cu(In_{1-x}Ga_x)Se_2$ single quaternary target without post deposition selenization. This process has been examined by the effects of deposition parameters on the structural and compositional properties of the films. In addition, we will explore the influences of substrate temperature and additional annealing treatment after deposition on the characteristics of CIGS thin films. The thickness of CIGS films will be measured by Tencor-P1 profiler. The crystalline properties and surface morphology of the films will be analyzed using X-ray diffraction and scanning electron microscopy, respectively. The optical properties of the films will be determined by UV-Visible spectroscopy. Electrical properties of the films will be measured using van der Pauw geometry and Hall effect measurement at room temperature using indium ohmic contacts.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2007.06a
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• pp.48-48
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• 2007

P-type transparent conducting $CuGaO_2$ thin films have been prepared by DC/RF sputtering using Quartz(0001) and sapphire(0001) substrates. The target was fabricated by heating a stoichiometric mixture of CuO and $Ga_2O_3$ at 1373K for 12h under $N_2$ atmosphere. The film were deposited under mixture gas of Ar and $O_2(Ar:O_2=4:1)$ during 10~30min. and the as-deposited films were annealed at 1123K and $N_2$ atmosphere. Room temperature conductivity and the activation energy of the sintered body in the temperature range of 223K ~ 423K were 0 004S/cm, 1.9eV, respectively. XRD revealed that all of the as-deposited films were amorphous. Heating of the films deposited on Quartz substrates above 1123K resulted in crystallization with a second phase of $CuSiO_3$, which was assumed owing to reaction with Quartz substrate. The single phase of $CuGaO_2$ was obtained at the film deposited on the sapphire substrates. The transmittance after annealing of DC- and RF-sputtered films were 55~75% at 550nm. From the transmittance and reflectance measurement. the direct band gap of the DC/RF-sputtered films were 3.63eV and 3.57eV. and there was little difference between DC and RF sputtered films.