• 한국재료학회지
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• 제23권6호
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• pp.304-308
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• 2013

The effect of a sputter deposition sequence of Cu, Zn, and Sn metal layers on the properties of $Cu_2ZnSnS_4$ (CZTS) was systematically studied for solar cell applications. The set of Cu/Sn/Zn/Cu multi metal films was deposited on a Mo/$SiO_2$/Si wafer using dc sputtering. CZTS films were prepared through a sulfurization process of the Cu/Sn/Zn/Cu metal layers at $500^{\circ}C$ in a $H_2S$ gas environment. $H_2S$ (0.1%) gas of 200 standard cubic centimeters per minute was supplied in the cold-wall sulfurization reactor. The metal film prepared by one-cycle deposition of Cu(360 nm)/Sn(400 nm)/Zn(400 nm)/Cu(440 nm) had a relatively rough surface due to a well-developed columnar structure growth. A dense and smooth metal surface was achieved for two- or three-cycle deposition of Cu/Sn/Zn/Cu, in which each metal layer thickness was decreased to 200 nm. Moreover, the three-cycle deposition sample showed the best CZTS kesterite structures after 5 hr sulfurization treatment. The two- and three-cycle Cu/Sn/Zn/Cu samples showed high-efficient photoluminescence (PL) spectra after a 3 hr sulfurization treatment, wheres the one-cycle sample yielded poor PL efficiency. The PL spectra of the three-cycle sample showed a broad peak in the range of 700-1000 nm, peaked at 870 nm (1.425 eV). This result is in good agreement with the reported bandgap energy of CZTS.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2010년도 제39회 하계학술대회 초록집
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• pp.25-25
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• 2010

Cu(In, Ga)$Se_2$ (CIGS), $CuInS_2$ (CIS) 등의 Se, S계 화합물 박막 소재를 활용한 태양전지는 높은 광흡수 계수, 상대적으로 높은 효율, 화학적 안정성, 도시적인 미관 등으로 인하여 최근 부각되고 있다. 하지만 CIGS, CIS 등의 Se, S계 박막 소재는 상대적으로 매장량이 적은(희유 원소) In, Ga을 사용하고 있는 약점이 있으며 특히 In의 경우는 LCD Display에 사용되는 ITO 필름으로 인해 가격이 상승하고 있다. 따라서 결정질 실리콘 태양전지의 경험에서와 같이 생산량의 급증에서 기인하는 소재 부족 문제를 미연에 방지하고 안정적인 성장을 이루기 위해서는 희유 원소인 In과 Ga을 저가 범용원소로 대체 하는 기술을 추가적으로 개발해야 한다. $Cu_2ZnSnS_4$ (CZTS) 박막 태양전지는 Se, S계 태양전지에서 III 족 원소인 In, Ga을 II-IV 원소인 Zn와 Sn으로 대체하는 기술로 기존의 CIGS계 태양전지가 보유하고 있는 장점을 유지하면서 저가 태양전지를 구현할 수 있는 대체 물질로 최근 많은 관심을 받고 있다. CZTS 박막 태양전지 관련 세계 기술동향 조사에 따르면, 최근 2008년에 일본 Nagaoka 대학의 Katagiri 그룹에서 스퍼터를 이용하여 제조한 CZTS 박막 태양전지의 최고 효율이 6.77%가 됨을 보고하였고, 2010년 초에는 IBM에서 스핀코팅법을 이용하여 제조한 CZT(S, Se) 박막 태양전지의 효율을 9.66%까지 올릴 수 있음을 Advanced Materials에 보고하였다. 본 발표에서는 우선 CZTS 박막태양전지 제조 및 특성 분석 관련 개요 및 세계 기술 개발 동향 분석 결과를 설명할 것이다. 또한 본 실험실, 에너지 기술 연구원 및 KIST, 영남대 등 국내에서 진행되고 있는 CZTS 관련 기술 개발 현황에 대하여 설명할 것이다.

• 한국재료학회지
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• 제22권5호
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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.

• Journal of Radiation Protection and Research
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• 제45권1호
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• pp.35-44
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• 2020

Background: Cadmium zinc telluride (CZT) is a promising material because of a high detection efficiency, good energy resolution, and operability at room temperature. However, the cost of CZT dramatically increases as its size increases. In this study, to achieve a large effective volume with relatively low cost, an array structure comprised of individual virtual Frisch-grid CZT detectors was proposed. Materials and Methods: The prototype consisted of 2 × 2 CZTs, a holder, anode and cathode printed circuit boards (PCBs), and an application-specific integrated circuit (ASIC). CZTs were used and the non-contacting shielding electrode method was applied for virtual Frisch-grid effect. An ASIC was used, and the holder and the PCBs were fabricated. In the current system, because the CZTs formed a common cathode, a total of 5 channels were assigned for data processing. Results and Discussion: An experiment using ¹³⁷Cs at room temperature was conducted for 10 minutes. Energy and timing information was acquired and the depth of interaction was calculated by the timing difference between the signals of both electrodes. Based on obtained three-dimensional position information, the energy correction was carried out, and as a result the energy spectra showed the improvements. In addition, a Compton image was reconstructed using the iterative method. Conclusion: The virtual Frisch-grid CZT detector based on the array structure was developed and the energy spectra and the Compton image were successfully acquired.

• Korean Chemical Engineering Research
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• 제55권1호
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• pp.93-98
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• 2017

본 실험에서는 $Cu_2ZnSnS_4$(CZTS) 태양전지의 흡수층 상부에 다양한 조성을 갖는 $Zn(O_x,S_{1-x})$ 버퍼층을 적용하여 특성 변화를 살펴보았다. $Zn(O_{0.76},S_{0.24})$, $Zn(O_{0.56},S_{0.44})$, $Zn(O_{0.33},S_{0.67})$ 그리고 $Zn(O_{0.17},S_{0.83})$의 4가지 단일막의 경우, 전자-정공의 재결합 억제에 유리한 밴드갭 구조를 나타내는 $Zn(O_{0.76},S_{0.24})$ 버퍼층을 소자에 적용했다. $Zn(O_{0.76},S_{0.24})$ 버퍼층을 소자에 적용 시, 흡수층으로부터 S가 버퍼층으로 확산되어 소자 내에서의 버퍼층은 $Zn(O_{0.7},S_{0.3})$의 조성을 나타냈다. CdS 버퍼층의 $E_V$보다 낮은 에너지 준위를 갖는 $Zn(O_{0.7},S_{0.3})$ 버퍼층은 전자-정공 재결합을 효과적으로 억제하기 때문에 CZTS 태양전지의 $J_{SC}$와 $V_{OC}$ 특성을 향상시켰다. 이를 통해 CdS 버퍼층이 적용된 CZTS 태양전지의 효율인 2.75%가 $Zn(O_{0.7},S_{0.3})$ 버퍼층 적용을 통해 4.86%로 향상되었다.

• 한국태양광발전학회지
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• 제2권2호
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• pp.8-20
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• 2016

• 한국재료학회:학술대회논문집
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• 한국재료학회 2012년도 춘계학술발표대회
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• pp.98.2-98.2
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• 2012

Thin film solar cells are growing up in the market due to their high efficiency and low cost. Especially CdTe and $CuInGaSe_2$ based solar cells are leading the other cells, but due to the limited percentage of the elements present in our earth's crust like Tellurium, Indium and Gallium, the price of the solar cells will increase rapidly. Copper Zinc Tin Sulfide (CZTS) and Copper Zinc Tin Selenide (CZTSe) semiconductor (having a kesterite crystal structure) are getting attention for its solar cell application as the absorber layer. CZTS and CZTSe have almost the same crystal structure with more environmentally friendly elements. Various authors have reported growth and characterization of CZTSe films and solar cells with efficiencies about 3.2% to 8.9%. In this study, a novel method to prepare CZTSe has been proposed based on selenization of stacked Copper Selenide ($Cu_2Se$), Tin Selenide ($SnSe_2$) and Zinc Selenide (Zinc Selenide) in six possible stacking combinations. Depositions were carried out through RF magnetron sputtering. Selenization of all the samples was performed in Close Space Sublimation (CSS) in vacuum at different temperatures for three minutes. Characterization of each sample has been performed in Field Emission SEM, XRD, Raman spectroscopy, EDS and Auger. In this study, the properties and results of $Cu_2ZnSnSe_4$ thin films grown by selenization will be presented.

• 한국재료학회:학술대회논문집
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• 한국재료학회 2011년도 춘계학술발표대회
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• pp.42.1-42.1
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• 2011

높은 광흡수 계수를 갖는Cu(In,Ga) $Se_2$ (CIGS) 화합물 박막 소재는 고효율 태양전지 양산을 위해 가장 전도유망한 재료이나 상대적으로 매장량이 적은 In 및 Ga을 사용한다는 소재적 한계가 있다. $Cu_2ZnSnSe_4$ (CZTSe) 혹은 $Cu_2ZnSnS_4$(CZTS)와 같은 Cu-Zn-Sn-Se계 화합물 반도체는 CIGS 내 희소원소인 In과 Ga이 범용원소인 Zn 및 Sn으로 대체된 소재로써 미래형 저가 태양전지 개발을 위해 활발히 연구되고 있는데, 그 화합물 조합에 따라 0.8 eV부터 1.5 eV까지의 에너지 밴드갭을 갖는 것으로 알려져 있다. 스퍼터링법에 기반한 2단계 공정에 의해 3.2%의 CZTSe 및 6.7%의 CZTS 태양전지 효율 달성이 보고된 바 있으며, 최근 비진공 방식을 이용하여 제조된 $Cu_2ZnSn(S,Se)_4$ (CZTSSe) 태양전지가 9.6%의 변환효율을 생산하여 세계 최고기록을 갱신한 바 있다. 반면, 동시진공증발법에 의한 Cu-Zn-Sn-Se계 연구는 박막 조성 조절이 상대적으로 용이하다는 장점에도 불구하고, 상대적으로 공개된 연구결과의 양이 적으며 그 효율에 대한 보고는 특히 미미하다. 본 연구에서는 동시진공증발법에 의한 CZTSe 박막 연구 결과를 바탕으로 Sn 손실을 최소화하기 위한 진공증발 공정을 최적화하였으며, 이를 통해 CZTSe 박막 태양전지를 제조하고 그 특성분석을 통해 5% 이상의 변환효율을 달성하였다.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2013년도 제45회 하계 정기학술대회 초록집
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• pp.97-97
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• 2013

Recently, Cu2ZnSn(S,Se)4 (CZTSS), 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 CZTSS-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 104 cm-1, and high theoretical conversion efficiency of 32.2% in thin film solar cells. Despite these promising characteristics, research into CZTSS 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%. I will briefly overview the recent technological development of CZTSS thin film solar cells and then introduce our research results mainly related to sputter based process. CZTSS thin film solar cells are prepared by sulfurization of stacked both metallic and sulfide precursors. Sulfurization process was performed in both furnace annealing system and rapid thermal processing system using S powder as well as 5% diluted H2S gas source at various annealing temperatures ranging from $520^{\circ}C$ to $580^{\circ}C$. Structural, optical, microstructural, and electrical properties of absorber layers were characterized using XRD, SEM, TEM, UV-Vis spectroscopy, Hall-measurement, TRPL, etc. The effects of processing parameters, such as composition ratio, sulfurization pressure, and sulfurization temperature on the properties of CZTSS absorber layers will be discussed in detail. CZTSS thin film solar cell fabricated using metallic precursors shows maximum cell efficiency of 6.9% with Jsc of 25.2 mA/cm2, Voc of 469 mV, and fill factor of 59.1% and CZTS thin film solar cell using sulfide precursors shows that of 4.5% with Jsc of 19.8 mA/cm2, Voc of 492 mV, and fill factor of 46.2%. In addition, other research activities in our lab related to the formation of CZTS absorber layers using solution based processes such as electro-deposition, chemical solution deposition, nano-particle formation will be introduced briefly.

• 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.