• Proceedings of the Materials Research Society of Korea Conference
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• 2003.11a
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• pp.154-154
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• 2003

A stoichiometric mixture of evaporating materials for CuGaSe2 single crystal thin films was prepared from horizontal electric furnace. Using extrapolation method of X-ray diffraction patterns for the polycrystal CuGaSe2, it was found tetragonal structure whose lattice constant at and co were 5.615 ${\AA}$ and 11.025 ${\AA}$, respectively. To obtain the single crystal thin films, CuGaSe2 mixed crystal was deposited on thoroughly etched semi-insulating GaAs(100) substrate by the hot wall epitaxy (MWE) system. The source and substrate temperatures were Slot and 450$^{\circ}C$, respectively. The crystalline structure of the single crystal thin films was investigated by the photoluminescence and double crystal X-ray diffraction (UXD). The carrier density and mobility of CuGaSe2 single crystal thin films measured with Hall effect by van der Pauw method are 5.0l${\times}$10$\^$17/ cm$\^$-3/ and 245 $\textrm{cm}^2$/V$.$s at 293K, respectively. The temperature dependence of the energy band gap of the CuGaSe2 obtained from the absorption spectra was well described by the Varshni's relation, Eg(T) = 1.7998 eV - (8.7489${\times}$10$\^$-4/ eV/K)T$^2$/(T + 335 K. After the as-grown CuGaSe2 single crystal thin films was annealed in Cu-, Se-, and Ca-atmospheres, the origin of point defects of CuGaSe2 single crystal thin films has been investigated by the photoluminescence(PL) at 10 K The native defects of V$\_$CU/, V$\_$Se/, Cu$\_$int/, and Se$\_$int/ obtained by PL measurements were classified as a donors or accepters type. And we concluded that the heat-treatment in the Cu-atmosphere converted CuGaSe2 single crystal thin films to an optical n-type. Also, we confirmed that Ga in CuGaSe2/GaAs did not form the native defects because Ga in CuGaSe2 single crystal thin films existed in the form of stable bonds.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.24 no.9
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• pp.755-759
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• 2011

$Cu(In_{1-x},Ga_x)Se_2$ thin films have been considered as an effective absorber material for high efficient solar cells. In this paper, the CIGS thin films with varied Ga content were prepared using a co-evaporation process of three stage. We carry out structure and electrical optical property on the thin film in varied Ga content. CIGS thin films have been characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM), energy-dispersive spectroscopy(EDS), four-point probe measurement, and the Hall measurement. To optimize Ga contents, Ga/(In+Ga) ratio were changed from 0.13 to 0.72. At this time the carrier concentrations were varied from $1.22{\times}10^{11}\;cm^{-3}$ to $5.07{\times}10^{16}\;cm^{-3}$, and electrical resistivity were varied from $1.11{\times}10^0\;{\Omega}-cm$ to $1.08{\times}10^2\;{\Omega}-cm$. A strong <220/204> orientation and a lager grain size were obtained at a Ga/(In+Ga) of 0.3. We were able to achieve conversion efficiency as high as 15.95% with a Ga/(In+Ga) of 0.3.

• 한국신재생에너지학회:학술대회논문집
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• 2007.06a
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• pp.339-342
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• 2007

$Cu(In_{1-x}Ga_{x})Se_2$(CIGS)는 매우 큰 광흡수계수를 가지고 있으므로 박막형 태양전지의 광흡수층 재료로서 많은 연구가 진행되고 있다. 박막이 태양전지의 광흡수층으로 이용되기 위해서는 큰 결정크기와 평탄한 표면, 적당한 전기적 특성을 가져야 한다. 이러한 특성들은 CIGS 박막의 조성에 큰 영향을 받고 있는 것으로 보고되고 있다. 본 연구에서는 동시증발법을 이용하여 Cu/(In+Ga) 비를 0.9로 고정한 후 Ga 조성(Ga/(In+Ga)의 비 : 0.32, 0.49, 0.69, 0.8, 1)을 변화시켜 Wide band gap CIGS 박막태양전지를 만들었다. 기판은 soda line glass를 사용하였고 뒷면 전극으로는 Mo를 스퍼터링법으로 증착하였다. 또한 버퍼층으로는 기존에 쓰이고 있는 CdS를 CBD(Chemical Bath Deposition)법으로 층착시켰으며, 윈도우층으로는 i-ZnO/n-ZnO를 스파터링 법으로 층착하였다. 그리고 앞면전극으로는 Al을 E-beam 으로 증착하였다. 분석은 XRD, SEM, QE로 분석하였다. 위 실험에서 얻은 결과로는 Ga/(In+Ga)비가 증가할수록 Cu(In,Ga)Se2 박막은 회절 peak들이 큰 회절각으로 이동하였고, 이것은 Ga 원자와 In 원자의 원자반경의 차이에서 기인된 것으로 사료된다. 또한 Ga 조성이 증가할수록 단파장 쪽으로 이동하는 것을 볼 수 있으며, Voc가 증가하다가 에너지 밴드캡이 1.62 eV 이상에서는 Voc가 감소하는 것을 볼 수 있는데 이것은 Ga 조성이 증가할수록 에너지 밴드캡이 커지면서 defect level 이 존재하기 때문인 것으로 사료된다. Ga/(In+Ga)비가 1일 때의 변환효율은 8.5 %이고， Voc : 0.74 (V), Jsc : 17.2 ($mA/cm^{2}$), F.F : 66.6(%) 이다.

• Proceedings of the Korean Vacuum Society Conference
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• 2011.08a
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• pp.375-375
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• 2011

Cu(In1-xGax)Se2 (CIGS)박막증착법 중 금속 전구체의 셀렌화 공정법은 다른 제조 방법에 비해 대면적 생산에 유리하고, 비교적 공정 과정이 간단하다는 장점이 있다. 이 제조 방법은 금속 전구체를 만든 후에 셀렌화 공정을 하게 된다. 셀렌화 공정은 대부분 H2Se 가스를 사용하지만 유독성으로 사용하는데 주의해야 한다. 본 실험은 H2Se를 사용하지 않고 Se원료를 주입하기 위해 Se cracker를 사용했고 금속 전구체 증착과 셀렌화를 동시에 하는 반응성 스퍼터링 후 열처리 법을 이용하여 CIGS 박막을 증착 했다. CIGS의 박막의 Cu/[In+Ga], Ga/[In+Ga]비를 변화시켜 특성변화를 관찰했다. Cu/[In+Ga]비가 감소할수록 CIGS의 결정방향인 (112) 이 우세하게 발달했고 Ga/[In+Ga]비가 증가할수록 CIGS의 결정면 사이의 값이 작아지기 때문에 CIGS peak의 2-Theta 값이 증가하게 된다. CIGS 박막 태양전지의 구조는 Al/Ni/ITO/i-ZnO/CdS/CIGS/Mo/glass 제작했다. CIGS박막의 조성비가 Cu/[In+Ga]=0.84, Ga/[In+Ga]=0.24인 박막태양전지에서 개방전압 0.48 V, 단락전류밀도 33.54 mA/cm2, 충실도 54.20% 그리고 변환효율 8.63%를 얻었다.

• Proceedings of the Korean Vacuum Society Conference
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• 2013.08a
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• pp.314.2-314.2
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• 2013

CIGS 박막의 물성은 조성에 크게 영향을 받으며, 특히 박막 내 Cu/(In+Ga) 비는 매우 중요한 변수로서 태양전지 특성에 영향을 주게 된다. Cu(In1-xGax)Se2 박막의 전하농도 및 반도체로의 성격을 가장 명확하게 결정하는 조성비는 Cu/(In+Ga) 비이다. 태양전지와 같은 소자로 작용하기 위해서는 Cu/(In+Ga) 비가 1보다 작아야 한다. 고효율의 태양전지는 Cu/(In+Ga)조성이 0.85~0.95로 slightly Cu-poor가 되어야 만들어진다. 본 연구에서는 Cu조성에 따른 CIGS 박막의 구조적, 전기적 특성과 CIGS 태양전지 효율 특성에 관하여 연구하였다. 미세구조 분석결과 Cu 조성이 증가함에 따라 큰 결정립을 가지며 결정립의 성장이 고르게 되어 접합 형성을 좋게 하는 경향을 보였다. X선 회절 분석결과, Cu 함유량 비율이 증가하면서 <112>의 우선배향성에서 <220/204>으로 변화하였다. 그러나, Cu/(In+Ga) 비율이 1이상이 첨가됨에 따라 우선배향은 다시 <112>로 변화함을 알 수 있었다. EDX 분석결과 Ga/(In+Ga) 0.31, Cu/(In+Ga) 0.86의 비율일 때, Carrier density $1.49{\times}1016$ cm-3을 나타내었다. CIGS의 태양전지의 효율 측정결과 Voc=596mV, Jsc=37.84mA/cm2, FF=72.96%로 ${\eta}$=16.47%를 달성하였다.

• Transactions on Electrical and Electronic Materials
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• v.6 no.5
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• pp.229-232
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• 2005

Direct characterization of band alignment at chemical bath deposition $(CBD)-CdS/Cu_{0.93}(In_{1-x}Ga_x)Se_2$ has been carried out by photoemission spectroscopy (PES) and inverse photoemission spectroscopy (IPES). Ar ion beam etching at the condition of the low ion kinetic energy of 400 eV yields a removal of surface contamination as well as successful development of intrinsic feature of each layer and the interfaces. Especially interior regions of the wide gap CIGS layers with a band gap of $1.4\~1.6\;eV$ were successfully exposed. IPES spectra revealed that conduction band offset (CBO) at the interface region over the wide gap CIGS of x = 0.60 and 0.75 was negative, where the conduction band minimum of CdS was lower than that of CIGS. It was also observed that an energy spacing between conduction band minimum (CBM) of CdS layer and valance band maximum (VBM) of $Cu_{0.93}(In_{0.25}Ga_{0.75})Se_2$ layer at interface region was no wider than that of the interface over the $Cu_{0.93}(In_{0.60}Ga_{0.40})Se_2$ layer.

• Korean Journal of Materials Research
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• v.22 no.5
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• pp.259-273
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• 2012

Chalcogenide-based semiconductors, such as $CuInSe_2$, $CuGaSe_2$, Cu(In,Ga)$Se_2$ (CIGS), and CdTe have attracted considerable interest as efficient materials in thin film solar cells (TFSCs). Currently, CIGS and CdTe TFSCs have demonstrated the highest power conversion efficiency (PCE) of over 11% in module production. However, commercialized CIGS and CdTe TFSCs have some limitations due to the scarcity of In, Ga, and Te and the environmental issues associated with Cd and Se. Recently, kesterite CZTS, which is one of the In- and Ga- free absorber materials, has been attracted considerable attention as a new candidate for use as an absorber material in thin film solar cells. The CZTS-based absorber material has outstanding characteristics such as band gap energy of 1.0 eV to 1.5 eV, high absorption coefficient on the order of $10^4cm^{-1}$, and high theoretical conversion efficiency of 32.2% in thin film solar cells. Despite these promising characteristics, research into CZTS-based thin film solar cells is still incomprehensive and related reports are quite few compared to those for CIGS thin film solar cells, which show high efficiency of over 20%. The recent development of kesterite-based CZTS thin film solar cells is summarized in this work. The new challenges for enhanced performance in CZTS thin films are examined and prospective issues are addressed as well.

• Proceedings of the Korean Vacuum Society Conference
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• 2012.02a
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• pp.585-585
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• 2012

$Cu(In_{1-x}Ga_x)Se_2$(CIGS) 박막 태양전지는 Chalcopyrite 계 박막 태양전지로 Cu, In, Ga, Se 각 원소의 조성을 적절히 조절하여 박막을 성장시킨다. 성장시킨 CIGS 박막은 광흡수계수가 $10^5cm^{-1}$로 다른 물질보다 뛰어나고 직접 천이형 반도체로서 얇은 두께로도 고효율의 박막 제작이 가능하다. CIGS 태양전지를 제조하는 방법은 3-stage 동시 증착법, 금속 전구체의 셀렌화 공정법, 전기 증착법 등이 있다. 그 중에 금속 전구체의 셀렌화 공정법은 다른 제조 방법에 비해 대면적 생산에 유리한 장점이 있다. 하지만 아직 상대적으로 3-stage 동시 증착법에 비해 낮은 에너지 변환 효율이 보고된다. 본 실험에서는 기존의 금속 전구체의 셀렌화 공정법과는 달리 전구체 증착과 셀렌화 공정을 동시에 하고, Se cracker를 통하여 Se 원료를 주입하는 방식인 반응성 스퍼터링 공정에서 reservoir zone의 온도 변화에 따른 특성을 분석하였다. Se cracker의 reservoir zone 온도가 증가할수록 Cu/(In+Ga) 비가 증가한다. CIGS 박막 태양전지의 구조는 Al/Ni/ITO/i-ZnO/CdS/CIGS/Mo/Soda lime glass이다. CIGS 박막의 조성비가 Cu/(In+Ga)=0.89, Ga/(In+Ga)=0.17인 박막 태양전지에서 개방전압 0.34 V, 단락전류밀도 $32.61mA/cm^2$, 충실도 56.2% 그리고 변환 효율 6.19%를 얻었다. 본 연구는 2011년도 지식경제부의 재원으로 한국에너지 기술평가원(KTEP)의 지원을 받아 수행한 연구 과제입니다(No.20093020010030).

• Journal of the Korean Solar Energy Society
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• v.23 no.2
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• pp.59-70
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• 2003

A stoichiometric mixture of evaporating materials for $CuGaSe_2$ single crystal thin films was prepared from horizontal electric furnace. Using extrapolation method of X-ray diffraction patterns for the polycrystal $CuGaSe_2$, it was found tetragonal structure whose lattice constant $a_0$ and $c_0$ were $5.615{\AA}$ and $11.025{\AA}$, respectively. To obtain the single crystal thin films, $CuGaSe_2$ mixed crystal was deposited on thoroughly etched semi-insulating GaAs(100) substrate by the hot wall epitaxy (HWE) system. The source and substrate temperatures were $610^{\circ}C$ and $450^{\circ}C$, respectively. The crystalline structure of the single crystal thin films was investigated by the photoluminescence and double crystal X-ray diffraction (DCXD). The carrier density and mobility of $CuGaSe_2$ single crystal thin films measured with Hall effect by van der Pauw method are $5.01\times10^{17}cm^{-3}$ and $245cm^2/V{\cdot}s$ at 293K. respectively. The temperature dependence of the energy band gap of the $CuGaSe_2$ obtained from the absorption spectra was well described by the Varshni's relation, $E_g$(T)=1.7998 eV-($8.7489\times10^{-4}$ eV/K)$T^2$/(T+335K). After the as-grown $CuGaSe_2$ single crystal thin films was annealed in Cu-, Se-, and Ga-atmospheres, the origin of point defects of $CuGaSe_2$ single crystal thin films has been investigated by the photoluminescence(PL) at 10 K. The native defects of $V_{CU},\;V_{Se},\;Cu_{int}$ and $Se_{int}$ obtained by PL measurements were classified as a donors or acceptors type. And we concluded that the heat-treatment in the Cu-atmosphere converted $CuGaSe_2$ single crystal thin films to an optical n-type. Also, we confirmed that Ga in $CuGaSe_2$/GaAs did not form the native defects because Ga in $CuGaSe_2$ single crystal thin films existed in the form of stable bonds.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2003.07a
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• pp.352-356
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• 2003

A stoichiometric mixture of evaporating materials for $CuGaSe_2$ single crystal am films was prepared from horizontal electric furnace. Using extrapolation method of X-ray diffraction patterns for the polycrystal $CuGaSe_2$, it was found tetragonal structure whose lattice constant $a_0$ and $c_0$ were $5.615\;{\AA}\;and\;11.025\;{\AA}$, respectively. To obtain the single crystal thin films, $CuGaSe_2$ mixed crystal was deposited on thoroughly etched semi-insulating GaAs(100) substrate by the hot wall epitaxy (HWE) system. The source and substrate temperatures were $610^{\circ}C$ and $450^{\circ}C$, respectively, The crystalline structure of the single crystal thin films was investigated by the photoluminescence and double crystal X-ray diffraction (DCXD). The carrier density and mobility of $CuGaSe_2$ single crystal thin films measured with Hall effect by van der Pauw method are $9.24{\times}10^{16}\;cm^{-3}$ and $295\;cm^2/V{\cdot}s$ at 293 K, respectively. The temperature dependence of the energy band gap of the $CuGaSe_2$ obtained from the absorption spectra was well described by the Varshni's relation, $E_g(T)\;:\;1.7998\;eV\;-\;(8.7489\;{\times}\;10^{-4}\;eV/K)T^2(T\;+\;335\;K)$. After the as-grown $CuGaSe_2$ single crystal thin films was annealed in Cu-, Se-, and Ga-atmospheres, the origin of point defects of $CuGaSe_2$ single crystal thin films has been investigated by the photoluminescence(PL) at 10 K. The native defects of $V_{CU}$, $V_{Se}$, $CU_{int}$, and $Se_{int}$, obtained by PL measurements were classified as a donors or accepters type. And we concluded that the heat-treatment in the Cu-atmosphere converted $CuGaSe_2$ single crystal thin films to an optical n-type. Also, we confirmed that Ga in $CuGaSe_2/GaAs$ did not form the native defects because Ga in $CuGaSe_2$ single crystal thin films existed in the form of stable bonds.