• 한국진공학회:학술대회논문집
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• 한국진공학회 2013년도 제45회 하계 정기학술대회 초록집
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• pp.321.1-321.1
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• 2013

높은 광흡수 계수를 갖는 Cu(In,Ga)Se2(CIGS) 화합물 박막 소재는 고효율 태양전지 양산을 위해 가장 전도유망한 재료이나 상대적으로 매장량이 적은 In 및 Ga을 사용한다는 소재적 한계가 있다. Cu2ZnSnSe4(CZTSe) 혹은 Cu2ZnSnS4(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 0.8eV부터 1.5eV까지의 에너지 밴드갭을 갖는 것으로 알려져 있다. 본 연구에서는 열분해법으로 CZTS 나노 입자를 합성하였다. 용매로 Oleylamine을 사용하였는데, $260{\sim}340^{\circ}C$의 온도 범위에서 5시간 30분 동안 CZTS 나노입자를 합성하였고, $300^{\circ}C$에서 5시간 30분~9시간까지 합성하였다. 헥산을 이용하여 원심분리기와 초음파세척기로 용매인 Oleylamine을 제거하였고, 진공오븐에서 건조된 CZTS 분말의 FE-SEM (Field Emission Scanning Electron Microscope), XRD (X-Ray Diffraction), EDS (Energy Dispersive Spectroscopy) 분석 등을 통해 합성온도에 따른 구조적, 화학적 조성 변화를 조사하였다.

• 한국재료학회:학술대회논문집
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• 한국재료학회 2012년도 춘계학술발표대회
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• pp.99.1-99.1
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• 2012

The thin-film photovoltaic absorbers (CdTe and $Cu(In,Ga)Se_2$) can achieve solar conversion efficiencies of up to 20% and are now commercially available, but the presence of toxic (Cd,Se) and expensive elemental components (In, Te) is a real issue as the demand for photovoltaics rapidly increases. To overcome these limitations, there has been substantial interest in developing viable alternative materials, such as $Cu_2ZnSnS_4$ (CZTS) is an emerging solar absorber that is structurally similar to CIGS, but contains only earth abundant, non-toxic elements and has a near optimal direct band gap energy of 1.4 - 1.6 eV and a large absorption coefficient of ~104 $cm^{-1}$. The CZTS absorber layers are grown and investigated by various fabrication methods, such as thermal evaporation, e-beam evaporation with a post sulfurization, sputtering, non-vacuum sol-gel, pulsed laser, spray-pyrolysis method and electrodeposition technique. In the present work, we report an alternative aqueous chemical approach based on chemical bath deposition (CBD) method for large area deposition of CZTS thin films. Samples produced by our method were analyzed by scanning electron microscopy, X-ray diffraction, transmission electron microscopy, absorbance and photoluminescence. The results show that this inexpensive and relatively benign process produces thin films of CZTS exhibiting uniform composition, kesterite crystal structure, and some factors like triethanolamine, ammonia, temperature which strongly affect on the morphology of CZTS film.

• Current Applied Physics
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• 제18권12호
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• pp.1571-1576
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• 2018

Recent study shows that the main reason for limiting CZTS device performance lies in the low open circuit voltage, and crucial factor that could affect the $V_{oc}$ is secondary phases like ZnS existing in absorber layer and its interfaces. In this work, the $Cu_2ZnSnS_4$ thin film solar cells were prepared by sputtering CuSn and CuZn alloy targets. Through tuning the Zn/Sn ratios of the CZTS thin films, the crystal structure, morphology, chemical composition and phase purity of CZTS thin films were characterized by X-Ray Diffraction (XRD), scanning electron microscopy (SEM) equipped with an energy dispersive spectrometer (EDS) and Raman spectroscopy. The statistics data show that the CZTS solar cell with a ratio of Zn/Sn = 1.2 have the best power convention efficiency of 5.07%. After HCl etching process, the CZTS thin film solar cell with the highest efficiency 5.41% was obtained, which demonstrated that CZTS film solar cells with high efficiency could be developed by sputtering CuSn and CuZn alloy targets.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2016년도 제50회 동계 정기학술대회 초록집
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• pp.407.2-407.2
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• 2016

Cu2ZnSnS4 (CZTS) 박막은 낮은 가격과 유리한 특성을 가지므로서 차세대 박막 태양전지에서 이상적인 흡수층 물질 중 하나로 여겨지고 있다. 우리는 CZTS 박막 태양전지를 합성하는 데 있어서 Zn와 ZnS를 전구체에 사용하여 이에 따른 특성 차이를 연구하였다. 열처리 한 박막은 Zn와 ZnS를 사용하였을 때 특성 차이를 조사하기 위하여 여러 분석을 진행하였다. CZTS 박막의 미세구조와 조성 분포, 전기적 특성을 살펴보았다. Zn를 사용한 CZTS 박막은 큰 입자크기와 더 적은 영역에서 Zn가 집중되어 있는 층을 가진다. CZTS와 Mo 경계인 이 영역에 ZnS 2차상이 존재함을 의미하며 Zn 타겟을 사용하였을 때 더 낮은 Zn 조성을 가지는 것을 확인하였고 이는 결과적으로 접합 특성의 향상을 가져온다. 제작 된 CZTS 태양 전지 소자에서 이러한 이유로 Zn를 사용하였을 때 5.06%로 ZnS를 사용하였을 때에 비하여 더 높은 효율을 얻을 수 있었다.

• Current Photovoltaic Research
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• 제1권2호
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• pp.82-89
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• 2013

$Cu_2ZnSnS_4$ thin film have been fabricated by rapid thermal annealing of dc-sputtered metal precursor with Cu/ZnSn/Cu stack in sulfur ambient. A CZTS film with a good uniformity was formed at $560^{\circ}C$ in 6 min. $Cu_2SnS_3$ and $Cu_3SnS_4$ secondary phases were present at $540^{\circ}C$ and a trace amount of $Cu_2SnS_3$ secondary phase was present at $560^{\circ}C$. Single-phase large-grained CZTS film with rough surface was formed at $560^{\circ}C$. Solar cell with best efficiency of 4.7% ($V_{oc}=632mV$, $j_{sc}=15.8mA/cm^2$, FF = 47.13%) for an area of $0.44cm^2$ was obtained for the CZTS absorber grown at $560^{\circ}C$ for 6 min. The existence of second phase at lower-temperature annealing and rough surface at higher-temperature annealing caused the degradation of cell performance. Also poor back contact by void formation deteriorated cell performance. The fill factor was below 0.5; it should be increased by minimizing voids at the CZTS/Mo interface. Our results suggest that CZTS absorbers can be grown by rapid thermal annealing of metallic precursors in sulfur ambient for short process times ranging in minutes.

• Nuclear Engineering and Technology
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• 제55권8호
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• pp.2797-2801
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• 2023

CdZnTeSe (CZTS) has attracted attention for applications in X- and gamma-ray detectors owing to its improved properties compared to those of CdZnTe (CZT). In this study, we grew and processed single crystals of CZT and CZTS using the Bridgeman method to confirm the feasibility of using a dosimeter for high-energy X-rays in radiotherapy. We evaluated their linearity and precision using the coefficient of determination (R²) and relative standard deviation (RSD). CZTS showed sufficient RSD values lower than 1.5% of the standard for X-ray dosimetry, whereas CZT's RSD values increased dramatically under some conditions. CZTS exhibited an R² value of 0.9968 at 500 V/cm, whereas CZT has an R² value of 0.9373 under the same conditions. The X-ray response of CZTS maintains its pulse shape at various dose rates, and its properties are improved by adding selenium to the CdTe matrix to lower the defect density and sub-grain boundaries. Thus, we validated that CZTS shows a better response than CZT to high-energy X-rays used for radiotherapy. Further, the applicability of an onboard imager, a high-energy X-ray (>6 MV) image, is presented. The proposed methodology and results can guide future advances in X-ray dose detection.

• 한국재료학회지
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• 제28권12호
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• pp.748-757
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• 2018

Inorganic semiconductor compounds, e.g., CIGS and CZTS, are promising materials for thin film solar cells because of their high light absorption coefficient and stability. Research on thin film solar cells using this compound has made remarkable progress in the last two decades. Vacuum-based processes, e.g., co-evaporation and sputtering, are well established to obtain high-efficiency CIGS and/or CZTS thin film solar cells with over 20 % of power conversion. However, because the vacuum-based processes need high cost equipment, they pose technological barriers to producing low-cost and large area photovoltaic cells. Recently, non-vacuum based processes, for example the solution/nanoparticle precursor process, the electrodeposition method, or the polymer-capped precursors process, have been intensively studied to reduce capital expenditure. Lately, over 17 % of energy conversion efficiency has been reported by solution precursors methods in CIGS solar cells. This article reviews the status of non-vacuum techniques that are used to fabricate CIGS and CZTS thin films solar cells.

• Journal of Electrochemical Science and Technology
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• 제9권4호
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• pp.308-319
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• 2018

Single step electrodeposition of $Cu_2ZnSnS_4$ (CZTS) for solar cell applications was studied using an aqueous thiocyanate based electrolyte. The sodium thiocyanate complexing agent was found to decrease the difference in the deposition potential of the elements. X-ray diffraction analysis of the samples indicates the formation of kesterite phase CZTS. UV-vis studies reveal the band gap of the deposits to be in the range of 1.2 - 1.5 eV. The thickness of the deposit was found to decrease with increase in pH of the electrolyte. Nearly stoichiometric composition was obtained for CZTS films coated at pH 2 and 2.5. I-V characterization of the film with indium tin oxide (ITO) substrate in the presence and the absence of light source indicate that the resistance decrease significantly in the presence of light indicating suitability of the deposits for solar cell applications. Results of electrochemical impedance spectroscopic studies reveal that the cathodic process for sulfur reduction is the slowest among all the elements.

• 한국재료학회:학술대회논문집
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• 한국재료학회 2011년도 추계학술발표대회
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• pp.35.1-35.1
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• 2011

New photovoltaic (PV) materials and manufacturing approaches are needed for meeting the demand for lower-cost solar cells. The prototypal thin-film photovoltaic absorbers (CdTe and $Cu(In,Ga)Se_2$) can achieve solar conversion efficiencies of up to 20% and are now commercially available, but the presence of toxic (Cd,Se) and expensive elemental components (In, Te) is a real issue as the demand for photovoltaics rapidly increases. To overcome these limitations, there has been substantial interest in developing viable alternative materials, such as $Cu_2ZnSnS_4$ (CZTS) is an emerging solar absorber that is structurally similar to CIGS, but contains only earth abundant, non-toxic elements and has a near optimal direct band gap energy of 1.4~1.6 ev and a large absorption coefficient of ${\sim}10^4\;cm^{-1}$. The CZTS absorber layers are grown and investigated by various fabrication methods, such as thermal evaporation, e-beam evaporation with a post sulfurization, sputtering, non-vacuum sol-gel, pulsed laser, spray-pyrolysis method and electrodeposition technique. In the present work, we report an alternative method for large area deposition of CZTS thin films that is potentially high throughput and inexpensive when used to produce monolithically integrated solar panel modules. Specifically, we have developed an aqueous chemical approach based on chemical bath deposition (CBD) with a subsequent sulfurization heat treatment. Samples produced by our method were analyzed by scanning electron microscopy, X-ray diffraction, transmission electron microscopy, absorbance and photoluminescence. The results show that this inexpensive and relatively benign process produces thin films of CZTS exhibiting uniform composition, kesterite crystal structure, and good optical properties. A preliminary solar cell device was fabricated to demonstrate rectifying and photovoltaic behavior.

• 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.