• Current Photovoltaic Research
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• 제3권3호
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• pp.75-79
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• 2015

Recently, $Cu_2ZnSn(S_xSe_{1-x})_4$ (CZTSSe) has been received a tremendous attraction as light absorber material in thin film solar cells (TFSCs), because of its earth abundance, inexpensive and non-toxic constituents and versatile material characteristics. Kesterite CZTSSe thin films were synthesized by sulfo-selenization of sputtered Cu/Sn/Zn stacked metallic precursors. The sulfo-selenization of Cu/Sn/Zn stacked metallic precursor thin films has been carried out in a graphite box using rapid thermal annealing (RTA) technique. Annealing process was done under sulfur and selenium vapor pressure using Ar gas at $520^{\circ}C$ for 10 min. The effect of tuning Se/(S+Se) precursor composition ratio on the properties of CZTSSe films has been investigated. The XRD, Raman, FE-SEM and XRF results indicate that the properties of sulfo-selenized CZTSSe thin films strongly depends on the Se/(S+Se) composition ratio. In particular, the CZTSSe TFSCs with Se/(S+Se) = 0.37 exhibits the best power conversion efficiency of 4.83% with $V_{oc}$ of 467 mV, $J_{sc}$ of $18.962mA/cm^2$ and FF of 54%. The systematic changes observed with increasing Se/(S+Se) ratio have been discussed in detail.

• Current Photovoltaic Research
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• 제3권2호
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• pp.54-60
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• 2015

ZnSnO thin films were deposited by atomic layer deposition (ALD) process using diethyl zinc ($Zn(C_2H_5)_2$) and tetrakis (dimethylamino) tin ($Sn(C_2H_6N)_4$) as metal precursors and water vapor as a reactant. ALD process has several advantages over other deposition methods such as precise thickness control, good conformality, and good uniformity for large area. The composition of ZnSnO thin films was controlled by varying the ratio of ZnO and $SnO_2$ ALD cycles. The ALD ZnSnO film was an amorphous state. The band gap of ZnSnO thin films increased as the Sn content increased. The CIGS solar cell using ZnSnO buffer layer showed about 18% energy conversion efficiency. With such a high efficiency with the ALD ZnSnO buffer and no light soaking effect, AlD ZnSnO buffer mighty be a good candidate to replace Zn(S,O) buffer in CIGSsolar cells.

• 한국재료학회지
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• 제28권10호
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• pp.564-569
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• 2018

$Cu_2ZnSn(S,Se)_4$ (CZTSSe) films were prepared on Mo coated soda lime glass substrates by sulfo-selenization of sputtered stacked Zn-Sn-Cu(CZT) precursor films. The precursor was dried in a capped state with aqueous NaOH solution. The CZT precursor films were sulfo-selenized in the S + Se vapor atmosphere. Sodium was doped during the sulfo-selenization treatment. The effect of sodium doping on the structural and electrical properties of the CZTSSe thin films were studied using FE-SEM(field-emission scanning electron microscopy), XRD(X-ray diffraction), XRF(X-ray fluorescence spectroscopy), dark current, SIMS(secondary ion mass spectrometry), conversion efficiency. The XRD, XRF, FE-SEM, Dark current, SIMS and cell efficiency results indicated that the properties of sulfo-selenized CZTSSe thin films were strongly related to the sodium doping. Further detailed analysis and discussion for effect of sodium doping on the properties CZTSSe thin films will be discussed.

• Current Photovoltaic Research
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• 제1권2호
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• pp.109-114
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• 2013

$Cu_2ZnSnS_4$ (CZTS) nanoparticles were synthesized by a solvothermal method using copper (II) acetate, zinc acetate, tin chloride, and sulfur in diethylenetriamine solvent. Binary sulfide particles such as CuS, ZnS, SnS, and $SnS_2$ were obtained at $180^{\circ}C$; single-phase CZTS nanoparticles were obtained at $280^{\circ}C$. CZTS nanoparticles with spherical shape and grain size of 40 to 60 nm were obtained at $280^{\circ}C$. In the middle of 180 and $280^{\circ}C$, CZTS and ZnS phases were found. The time variation of reaction at $280^{\circ}C$ revealed that an amorphous state formed first instead of binary phases and then the amorphous phase was converted to crystalline CZTS state; it is different reaction path way from conventional solid-state reaction path of which binary phases react to form CZTS. CZTS films deposited and annealed from single-phase nanoparticles showed porous microstructure and poor adhesion. This indicates that a combination of CZTS and other flux phase is necessary to have a dense film for device fabrication.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2014년도 제46회 동계 정기학술대회 초록집
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• pp.472.1-472.1
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• 2014

현재 Cu(In,Ga)Se2나 Cu2ZnSn(S,Se)4 (CZTSSe)계 박막태양전지의 버퍼층으로 가장 많이 사용되는 물질은 CdS이다. 하지만 Cd의 독성 문제로 인해 사용에 제약이 있고, CdS의 작은 밴드갭(~2.4 eV)으로 인해 단 파장 영역에서 광활성층의 빛 흡수를 저해하는 문제 때문에 새로운 대체 물질을 찾으려는 연구가 많이 이루어지고 있다. 이러한 관점에서, ZnS계 물질은 독성 원소인 Cd을 사용하지 않고, 3.6 eV 정도의 큰 밴드갭을 가지기 때문에, CdS 버퍼층을 대체하기 위한 물질로 관심을 받고 있다. ZnS계 버퍼층을 증착하는 위해 chemical bath deposition (CBD), molecular beam epitaxy (MBE), thermal evaporation, spray pyrolysis, sputtering, elecrtrodepostion 등의 다양한 공정이 사용될 수 있다. 본 연구에서는 상기의 다양한 공정 가운데, 공정 단가가 낮고, 대면적 공정에 용이한 CBD 공정을 이용하여 ZnS계 버퍼층을 증착하는 연구를 수행하였다. 용액의 조성, 농도, 공정 온도, 시간 등을 비롯한 다양한 공정 변수가 ZnS계 박막의 morphology, 조성, 결정성, 광학적 특성 등 다양한 특성에 미치는 영향이 체계적으로 연구되었다. 또한, 상기 ZnS계 버퍼층을 CZTSSe 박막태양전지에 적용하여 CdS를 성공적으로 대체할 수 있음을 확인하였다. 본 연구를 통하여 ZnS계 버퍼층이 향후 친환경적인 박막태양전지 제조에 활용될 수 있는 가능성을 확인할 수 있었다.

• 한국재료학회지
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• 제23권1호
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• pp.7-12
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• 2013

The $Cu_2ZnSnS_4$ (CZTS) thin film solar cell is a candidate next generation thin film solar cell. For the application of an absorption layer in solar cells, CZTS thin films were deposited by pulsed laser deposition (PLD) at substrate temperature of $300^{\circ}C$ without post annealing process. Deposition time was carefully adjusted as the main experimental variable. Regardless of deposition time, single phase CZTS thin films are obtained with no existence of secondary phases. Irregularly-shaped grains are densely formed on the surface of CZTS thin films. With increasing deposition time, the grain size increases and the thickness of the CZTS thin films increases from 0.16 to $1{\mu}m$. The variation of the surface morphology and thickness of the CZTS thin films depends on the deposition time. The stoichiometry of all CZTS thin films shows a Cu-rich and S-poor state. Sn content gradually increases as deposition time increases. Secondary ion mass spectrometry was carried out to evaluate the elemental depth distribution in CZTS thin films. The optimal deposition time to grow CZTS thin films is 150 min. In this study, we show the effect of deposition time on the structural properties of CZTS thin film deposited on soda lime glass (SLG) substrate using PLD. We present a comprehensive evaluation of CZTS thin films.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2013년도 제44회 동계 정기학술대회 초록집
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• pp.688-688
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• 2013

Al-doped ZnO (AZO) thin films have attracted a lot of attention as a cheap transparent conducting oxide (TCO) material that can replace the expensive Sn-doped In2O3. In particular, AZO thin films are widely used as a window layer of chalcogenide-based thin film solar cells such as Cu(In,Ga)Se2 and Cu2ZnSnS4 (CZTS). Mostly important requirements for the window layer material of the thin film solar cells are the high transparency and the low sheet resistance, because they influence the light absorption by the activelayer and the electron collection from the active layer, respectively. In this study, we prepared the AZO thin films by RF magnetron sputtering using a ZnO/Al2O3 (98：2wt%) ceramic target, and the effect of the sputtering condition such as the working pressure, RF power, and the working distance on the optical, electrical, and crystallographic properties of the AZO thin films was investigated. The AZO thin films with optimized properties were used as a window layer of CZTS thin film solar cells. The CZTS active layers were prepared by the electrochemical deposition and the subsequent sulfurization process, which is also one of the cost-effective synthetic approaches. In addition, the solar cell properties of the CZTS thin film solar cells, such as the photocurrent density-voltage (J-V) characteristics and the external quantum efficiency (EQE) were investigated.

• 공업화학
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• 제8권5호
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• pp.804-810
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• 1997

실리콘의 모노머로 사용되고 있는 MCS 합성촉매계에 관한 연구를 수행하였다. 기존 3원촉매계(Cu/Zn/Sn)에 조촉매 Cd를 추가시킨 4원촉매계(CuCl/$ZnCl_2$/Sn/Cd)는 원료 규소와 염화메틸로부터 MCS를 합성하는 촉매로서 성능이 3원촉매계 보다 우수하였다. 4원촉매계는 조성이 혼합촉매/규소=5/95, Zn/Cu=0.1, Sn/Cu=0.001, Cd/Cu=0.001가 되도록 구성하고, 슬러리상태에서 혼합한 후 활성화된 접촉물질을 제조하여 MCS 합성에 사용하였을 때, 규소소모율 92%에서 평균선택도 92%, 규소소모율 40%에서 반응속도는 175(g-MCS/hr.kg-Si)이었다.

• 한국태양에너지학회:학술대회논문집
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• 한국태양에너지학회 2012년도 춘계학술발표대회 논문집
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• pp.400-403
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• 2012

$Cu_2ZnSnSe_4$(CZTSe) is emerged as a promising material for thin-film solar cells because of non-toxic, inexpensive and earth abundant more than $Cu(In,Ga)Se_2$ materials. For fabricating compound semiconductor thin-film solar cells, CdS is widely used for a buffer layer which fabricated by a chemical bath deposition method (CBD). Through the experiment, we controlled deposition temperature and mol ratio of solution conditions to find the proper grain 크기 and exact composition. The optimum CdS layers were characterized in terms of surface morphology by using a scanning electron microscope (SEM) and atomic force microscope (AFM). The optimized CdS layer process was applied on CZTSe thin-films. The thickness of buffer layer related with device performance of solar cells which controlled by deposition time. Local surface potential of CdS/CZTSe thin-films was investigated by Kelvin probe force microscopy (KPFM). From these results, we can deduce local electric properties with different thickness of buffer layer on CZTSe thin-films. Therefore, we investigated the effect of CdS buffer layer thickness on the CZTSe thin-films for decreasing device losses. From this study, we can suggest buffer layer thickness which contributes to efficiencies and device performance of CZTSe thin-film solar cells.

• 한국재료학회지
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• 제25권12호
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• pp.708-712
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• 2015

This study reports the effects of $H_2S$ gas concentration on the properties of $Cu_2ZnSnS_4(CZTS)$ thin films. Specifically, sulfurization process with low $H_2S$ concentrations of 0.05% and 0.1%, along with 5% $H_2S$ gas, was studied. CZTS films were directly synthesized on Mo/Si substrates by chemical bath deposition method using copper sulfate, zinc sulfate heptahydrate, tin chloride dihydrate, and sodium thiosulfate pentahydrate. Smooth CZTS films were grown on substrates at optimized chemical bath deposition condition. The CZTS films sulfurized at low $H_2S$ concentrations of 0.05 % and 0.1% showed very rough and porous film morphology, whereas the film sulfurized at 5% $H_2S$ yielded a very smooth and dense film morphology. The CZTS films were fully crystallized in kesterite crystal form when they were sulfurized at $500^{\circ}C$ for 1 h. The kesterite CZTS film showed a reasonably good room-temperature photoluminescence spectrum that peaked in a range of 1.4 eV to 1.5 eV, consistent with the optimal bandgap for CZTS solar cell applications.