• 한국신재생에너지학회:학술대회논문집
• /
• 2010.06a
• /
• pp.85.2-85.2
• /
• 2010

$Cu_2ZnSnSe_4$ (CZTSe) is one of candidate to alternate $Cu(In,Ga)Se_2$ as solar absorber material for solar cell. The expensive elements of In and Ga are replaced by Zn and Sn, respectively to lower the material cost. In this study we fabricated CZTSe thin film by selenization of single precursor layer consisted metallic constituent. Precursor compositions ratio were selected to have Cu-poor and Zn-rich content and prepared by RF magnetron sputtering. Thermal processing was applied to introduce selenium into as-deposited films at temperatures ranging from 350 to 500 for time up to 120 minutes. Single precursor films showed amorphous structure and consist of individual elements of Cu, Zn, and Sn. It was confirmed by XRD analysis that synthesis of CZTSe compound is occurred from lower temperature process, although concurrently additional phases such as binary cooper selenides are also existed. The quality of CZTSe crystal was improved as temperature increased. We also investigated the optical and electrical properties of as-selenized CZTSe as well.

• Journal of Sensor Science and Technology
• /
• v.13 no.2
• /
• pp.157-167
• /
• 2004

A stoichiometric mixture of evaporating materials for $CuAlSe_{2}$ single crystal thin films was prepared from horizontal electric furnace. To obtain the single crystal thin films, $CuAlSe_{2}$ 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 $680^{\circ}C$ and $410^{\circ}C$, 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 $CuAlSe_{2}$ single crystal thin films measured with Hall effect by van der Pauw method are $9.24{\times}10^{16}cm^{-3}$ and $295cm^{2}/V{\codt}s$ at 293 K, respectively. The temperature dependence of the energy band gap of the $CuAlSe_{2}$ obtained from the absorption spectra was well described by the Varshni's relation, $E_{g}(T)$ = 2.8382 eV - ($8.68{\circ}10^{-4}$ eV/K)$T^{2}$/(T + 155 K). The crystal field and the spin-orbit splitting energies for the valence band of the $CuAlSe_{2}$ have been estimated to be 0.2026 eV and 0.2165 eV at 10 K, respectively, by means of the photocurrent spectra and the Hopfield quasicubic model. These results indicate that the splitting of the ${\Delta}so$ definitely exists in the ${\Gamma}_{5}$ states of the valence band of the $CuAlSe_{2}$. The three photocurrent peaks observed at 10 K are ascribed to the $A_{1-}$, $B_{1-}$, and $C_{1-}$ exciton peaks for n = 1.

• Laser Solutions
• /
• v.17 no.4
• /
• pp.7-13
• /
• 2014

In this work, the application of laser induced breakdown spectroscopy (LIBS) for the composition analysis of thin $Cu(In,Ga)Se_2$ (CIGS) solar cell films ($1-2{\mu}m$ thickness) is reported. For the ablation of CIGS films, femtosecond (fs) laser (wavelength = 343nm, pulse width = 500fs) and nanosecond (ns) laser (wavelength = 266nm, pulse width = 5ns) were used under atmospheric environment. The emission spectra were detected with an intensified charge coupled device (ICCD) spectrometer and multichannel CCD spectrometer for fs-LIBS and ns-LIBS, respectively. The calibration curves for fs-LIBS and ns-LIBS intensity ratios of Ga/Cu, In/Cu, and Ga/In were generated with respect to the concentration ratios measured by inductively coupled plasma optical emission spectrometry (ICP-OES).

• Current Photovoltaic Research
• /
• v.1 no.1
• /
• pp.38-43
• /
• 2013

$Cu(In,Ga)_3Se_5$ is a candidate material for the top cell of $Cu(In,Ga)Se_2$ tandem cells. This phase is often found at the surface of the $Cu(In,Ga)Se_2$ film during $Cu(In,Ga)Se_2$ cell fabrication, and plays a positive role in $Cu(In,Ga)Se_2$ cell performance. However, the exact properties of the $Cu(In,Ga)_3Se_5$ film have not been extensively studied yet. In this work, $Cu(In,Ga)_3Se_5$ films were fabricated on Mo-coated soda-lime glass substrates by a three-stage co-evaporation process. The Cu content in the film was controlled by varying the deposition time of each stage. X-ray diffraction and Raman spectroscopy analyses showed that, even though the stoichiometric Cu/(In+Ga) ratio is 0.25, $Cu(In,Ga)_3Se_5$ is easily formed in a wide range of Cu content as long as the Cu/(In+Ga) ratio is held below 0.5. The optical band gap of $Cu_{0.3}(In_{0.65}Ga_{0.35})_3Se_5$ composition was found to be 1.35eV. As the Cu/(In+Ga) ratio was decreased further below 0.5, the grain size became smaller and the band gap increased. Unlike the $Cu(In,Ga)Se_2$ solar cell, an external supply of Na with $Na_2S$ deposition further increased the cell efficiency of the $Cu(In,Ga)_3Se_5$ solar cell, indicating that more Na is necessary, in addition to the Na supply from the soda lime glass, to suppress deep level defects in the $Cu(In,Ga)_3Se_5$ film. The cell efficiency of $CdS/Cu(In,Ga)_3Se_5$ was improved from 8.8 to 11.2% by incorporating Na with $Na_2S$ deposition on the CIGS film. The fill factor was significantly improved by the Na incorporation, due to a decrease of deep-level defects.

• Korean Journal of Materials Research
• /
• v.22 no.5
• /
• pp.259-273
• /
• 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 KIEE Conference
• /
• 1998.07d
• /
• pp.1264-1267
• /
• 1998

$Cu(In_xGa_{1-x})Se_2$ thin films were prepared and characterized with various Ga contents. As the Ga content increased, the grain size of CIGS film became smaller. The 2 $\theta$ values in XRD patterns were shifted to larger values and the overlapped peaks were splitted. The energy bandgap increased from 1.04 to 1.67 eV and the resistivity decreased. The solar cell fabricated with ZnO/CdS/$Cu(In_{0.7}Ga_{0.3})Se_2/Mo$ structure yielded an efficeincy of 14.48% with an acitive area of 0.18 $cm^2$. The efficiency decreased with further increase of Ga content.

• Current Photovoltaic Research
• /
• v.7 no.4
• /
• pp.103-110
• /
• 2019

Cu(In,Ga)₃Se₅ (β-CIGS) has a band gap of 1.35 eV, which is an optimum value for high solar-energy conversion efficiency. The effects of Cu and Ga content on the cell performance were investigated previously. However, the effect of Se content on the cell performance is not well understood yet. In this work, β-CIGS films were fabricated by three-stage co-evaporation of elemental sources with various Se fluxes at the third stage instead of at all stages. The average composition of five samples was Cu_1.05(In_0.59,Ga_0.41)3Se_y, where the stoichiometric y value is 5.03 and the stoichiometric Se/metal (Se/M) ratio is 1.24. We varied the Se/metal ratio in a range from 1.18 to 1.28. We found that the best efficiency was achieved when the Se/M ratio was 1.24, which is exactly the stoichiometric value where the CIGS grains on the CIGS surface were tightly connected and faceted. With the optimum Se/M ratio, we were able to enhance the cell efficiency of a β-CIGS solar cell from 9.6% to 12.0% by employing a Na₂S post deposition treatment. Our results indicate that Na₂S post deposition treatment is very effective to enhance the cell efficiency to a level on par with that in α-CIGS cell.

• 한국신재생에너지학회:학술대회논문집
• /
• 2011.11a
• /
• pp.53.1-53.1
• /
• 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 Institute of Electrical and Electronic Material Engineers Conference
• /
• 2001.11a
• /
• pp.167-170
• /
• 2001

The stochiometric mix of evaporating materials for the CdGa$_2$Se$_4$ single crystal thin films was prepared from horizontal furnace. To obtain the single crystal thin films, CdGa$_2$Se$_4$ mixed crystal was deposited on thoroughly etched semi-insulating GaAs(100) substrate by the Hot Wall Epitaxy (HWE) system. The source and substrate temperature were 630$^{\circ}C$ and 420$^{\circ}C$, respectively. The crystalline structure of single crystal thin films was investigated by the photoluminescence and double crystal X-ray diffraction (DCXD). The carrier density and mobility of CdGa$_2$Se$_4$ single crystal thin films measured from Hall erect by van der Pauw method are 8.27x10$\^$17/ cm$\^$-3/, 345 $\textrm{cm}^2$/V$.$s at 293 K, respectively. From the Photocurrent spectrum by illumination of perpendicular light on the c-axis of the CuInSe$_2$ single crystal thin film, we have found that the values of spin orbit splitting ΔSo and the crystal field splitting ΔCr were 106.5 meV and 418.9 meV at 10 K, respectively. From the photoluminescence measurement on CdGa$_2$Se$_4$ single crystal thin film, we observed free excition (E$\_$X/) existing only high quality crystal and neutral bound exiciton (D$\^$0/,X) having very strong peak intensity. Then, the full-width-at-half-maximum(FWHM) and binding energy of neutral donor bound excision were 8 meV and 13.7 meV, respectivity. By Haynes rule, an activation energy of impurity was 137 meV,

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
• /
• 2002.05c
• /
• pp.108-111
• /
• 2002

CIGS film has been fabricated on soda-lime glass, which is coated with Mo film. by multi-source evaporation process. The films has been prepared with thickness of 1.0 ${\mu}m$, 1.75${\mu}m$, 2.0${\mu}m$, 2.3${\mu}m$, and 3.0${\mu}m$. X-ray diffraction analysis with film thickness shows that CIGS films exhibit a strong (112) preferred orientation. Furthermore. CIGS films exhibited distinctly decreasing the full width of half-maximum and (112) preferred peak with film thickness. Also, The film's microstructure, such as the preferred orientation, the full width at half-maximum(FWHM), and the interplanar spacing were examined by X-ray diffraction. The preparation condition and the characteristics of the unit layers were as followings ; Mo back contact DC sputter, CIGS absorber layer : three-stage coevaporation, CdS buffer layer : chemical bath deposition, ZnO window layer : RF sputtering, $MgF_2$ antireflectance : E-gun evaporation