• Proceedings of the Korean Vacuum Society Conference
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• 2011.08a
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• pp.53-53
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• 2011

This paper describes results for surface and bulk characterization of the most promising thin film solar cell material for high performance devices, (Ag,Cu) (In,Ga) Se2 (ACIGS). This material in particular exhibits a range of exotic behaviors. The surface and general materials science of the material also has direct implications for the operation of solar cells based upon it. Some of the techniques and results described will include scanning probe (AFM, STM, KPFM) measurements of epitaxial films of different surface orientations, photoelectron spectroscopy and inverse photoemission, Auger electron spectroscopy, and more. Bulk measurements are included as support for the surface measurements such as cathodoluminescence imaging around grain boundaries and showing surface recombination effects, and transmission electron microscopy to verify the surface growth behaviors to be equilibrium rather than kinetic phenomena. The results show that the polar close packed surface of CIGS is the lowest energy surface by far. This surface is expected to be reconstructed to eliminate the surface charge. However, the AgInSe2 compound has yielded excellent atomic-resolution images of the surface with no evidence of surface reconstruction. Similar imaging of CuInSe2 has proven more difficult and no atomic resolution images have been obtained, although current imaging tunneling spectroscopy images show electronic structure variations on the atomic scale. A discussion of the reasons why this may be the case is given. The surface composition and grain boundary compositions match the bulk chemistry exactly in as-grow films. However, the deposition of the heterojunction forming the device alters this chemistry, leading to a strongly n-type surface. This also directly explains unpinning of the Fermi level and the operation of the resulting devices when heterojunctions are formed with the CIGS. These results are linked to device performance through simulation of the characteristic operating behaviors of the cells using models developed in my laboratory.

• Journal of the Korea Convergence Society
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• v.13 no.3
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• pp.197-202
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• 2022

The CZTS solar cell is a thin film solar cell using an absorption layer composed of Cu, Zn, Sn, Se, and S, and is cheaper than a CIGS solar cell using In and Ga and more eco-friendly than a perovskite and CdTe solar cell using Pb and Cd. In this study, we conducted a bending test for flexible CZTS solar cells. Experiments were conducted in the direction of inner benidng with compressive stress and outer bending with tensile stress, and during the number of bending 1,000 times with a radius of curvature of 50 mmR, the efficiency of the solar cell decreased by up to 12.7%, and the biggest cause of efficiency reduction in both directions was a large decrease in parallel resistance.

• Korean Journal of Materials Research
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• v.32 no.11
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• pp.481-488
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• 2022

The Cu₂ZnSn(S_xSe_1-x)₄ (CZTSSe) absorbers are promising thin film solar cells (TFSCs) materials, to replace existing Cu(In,Ga)Se₂ (CIGS) and CdTe photovoltaic technology. However, the best reported efficiency for a CZTSSe device, of 13.6 %, is still too low for commercial use. Recently, partially replacing the Zn²⁺ element with a Cd²⁺element has attracting attention as one of the promising strategies for improving the photovoltaic characteristics of the CZTSSe TFSCs. Cd²⁺ elements are known to improve the grain size of the CZTSSe absorber thin films and improve optoelectronic properties by suppressing potential defects, causing short-circuit current (J_sc) loss. In this study, the structural, compositional, and morphological characteristics of CZTSSe and CZCTSSe thin films were investigated using X-ray diffraction (XRD), X-ray fluorescence spectrometer (XRF), and Field-emission scanning electron microscopy (FE-SEM), respectively. The FE-SEM images revealed that the grain size improved with increasing Cd²⁺ alloying in the CZTSSe thin films. Moreover, there was a slight decrease in small grain distribution as well as voids near the CZTSSe/Mo interface after Cd²⁺ alloying. The solar cells prepared using the most promising CZTSSe absorber thin films with Cd²⁺ alloying (8 min. 30 sec.) exhibited a power conversion efficiency (PCE) of 9.33 %, J_sc of 34.0 mA/cm², and fill factor (FF) of 62.7 %, respectively.

• Proceedings of the Korean Vacuum Society Conference
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• 2013.02a
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• pp.405-406
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• 2013

Ga-doped ZnO (GZO)는 $300^{\circ}C$ 이상의 온도에서는 전기적으로 불안정하기 때문에 CIGS, CdTe, DSC와 같은 태양전지의 높은 공정온도 때문에 사용이 제한적이다. ZTO thin film은 Al2O3, SiO2, TiO2, ZnO tihin film과 비교하여 산소 및 수분에 대하여 투과성이 상대적으로 낮은 것으로 알려져 있다. 따라서 GZO single layer에 비하여 ZTO-GZO multi-layer를 구성하여 TCO를 제작하면, 높은 공정온도에서도 사용 가능하다. 실제 제작된 GZO single layer (300 nm)에서 비저항이 $7.69{\times}10^{-4}{\Omega}{\cdot}cm$에서 $500^{\circ}C$에서 열처리 후 $7.76{\times}10^{-2}{\Omega}{\cdot}cm$으로 급격하게 상승한다. ZTO single layer (420 nm)는 as-grown에서는 측정 불가했지만, $400^{\circ}C$에서 열처리 후 $3.52{\times}10^{-1}{\Omega}{\cdot}cm$ $500^{\circ}C$에서 열처리 후 $4.10{\times}10^{-1}{\Omega}{\cdot}cm$으로 열처리에 따른 큰 변화가 없다. 또한 ZTO-GZO multi-layer (720 nm)의 경우 비저항이 $2.11{\times}10^{-3}{\Omega}{\cdot}cm$에서 $500^{\circ}C$에서 열처리 후 $3.67{\times}10^{-3}{\Omega}{\cdot}cm$으로 GZO에 비하여 상대적으로 변화폭이 작다. 또한 ZTO의 두께에 따른 영향을 확인하기 위하여 ZTO를 2 scan, 4 scan, 6 scan 공정 진행 및 $500^{\circ}C$에서 열처리 후 ZTO, ZTO-GZO thin film의 비저항을 측정하였다. ZTO의 경우 $3.34{\times}10^{-1}{\Omega}{\cdot}cm$ (2 scan), $3.62{\times}10^{-1}{\Omega}{\cdot}cm$ (4 scan), $4.1{\times}10^{-1}{\Omega}{\cdot}cm$ (6 scan)으로 큰 차이가 없으며, ZTO-GZO에서도 $3.73{\times}10^{-3}{\Omega}{\cdot}cm$ (2 scan), $3.42{\times}10^{-3}{\Omega}{\cdot}cm$ (4 scan), $3.67{\times}10^{-3}{\Omega}{\cdot}cm$ (6 scan)으로 큰 차이가 없음을 확인하였다. 염료감응 태양전지에 적용하여 기존에 사용되는 FTO대신에 ZTO-GZO를 사용하며, 가격적 측면, 성능적 측면에서 개선 가능할 것으로 생각된다.

• Proceedings of the Materials Research Society of Korea Conference
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• 2012.05a
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• pp.65-65
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• 2012

Copper zinc tin sulfide ($Cu_2ZnSnS_4$, CZTS) is a very promising material as a low cost absorber alternative to other chalcopyrite-type semiconductors based on Ga or In because of the abundant and economical elements. In addition, CZTS has a band-gap energy of 1.4~1.5eV and large absorption coefficient over ${\sim}10^4cm^{-1}$, which is similar to those of $Cu(In,Ga)Se_2$(CIGS) regarded as one of the most successful absorber materials for high efficient solar cell. Most previous works on the fabrication of CZTS thin films were based on the vacuum deposition such as thermal evaporation and RF magnetron sputtering. Although the vacuum deposition has been widely adopted, it is quite expensive and complicated. In this regard, the solution processes such as sol-gel method, nanocrystal dispersion and hybrid slurry method have been developed for easy and cost-effective fabrication of CZTS film. Among these methods, the hybrid slurry method is favorable to make high crystalline and dense absorber layer. However, this method has the demerit using the toxic and explosive hydrazine solvent, which has severe limitation for common use. With these considerations, it is highly desirable to develop a robust, easily scalable and relatively safe solution-based process for the fabrication of a high quality CZTS absorber layer. Here, we demonstrate the fabrication of a high quality CZTS absorber layer with a thickness of 1.5~2.0 ${\mu}m$ and micrometer-scaled grains using two different non-vacuum approaches. The first solution-processing approach includes air-stable non-toxic solvent-based inks in which the commercially available precursor nanoparticles are dispersed in ethanol. Our readily achievable air-stable precursor ink, without the involvement of complex particle synthesis, high toxic solvents, or organic additives, facilitates a convenient method to fabricate a high quality CZTS absorber layer with uniform surface composition and across the film depth when annealed at $530^{\circ}C$. The conversion efficiency and fill factor for the non-toxic ink based solar cells are 5.14% and 52.8%, respectively. The other method is based on the nanocrystal dispersions that are a key ingredient in the deposition of thermally annealed absorber layers. We report a facile synthetic method to produce phase-pure CZTS nanocrystals capped with less toxic and more easily removable ligands. The resulting CZTS nanoparticle dispersion enables us to fabricate uniform, crack-free absorber layer onto Mo-coated soda-lime glass at $500^{\circ}C$, which exhibits a robust and reproducible photovoltaic response. Our simple and less-toxic approach for the fabrication of CZTS layer, reported here, will be the first step in realizing the low-cost solution-processed CZTS solar cell with high efficiency.

• Current Photovoltaic Research
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• v.3 no.2
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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.

• Proceedings of the KIEE Conference
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• 1998.07d
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• pp.1264-1267
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• 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.

• Proceedings of the Korean Vacuum Society Conference
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• 2011.02a
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• pp.410-410
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• 2011

Chalcopyrite계 화합물 $CuInGaSe_2$($CIGSe_2$)는 높은 광흡수율과 전기적 특성 및 안정성, 그리고 1.02~1.67 eV 범위의 최적의 에너지 밴드갭을 가져 박막태양전지용 광흡수층 재료로 많은 관심을 받고 있다. 일반적으로 $CIGSe_2$ 박막태양전지의 광흡수층을 형성하는 공정은 고효율 태양전지 제작이 가능한 진공공정을 이용한다. $CIGSe_2$ 광흡수층을 형성하는데 있어 진공 공정을 용액기반 공정으로 대처한다면 저비용으로 보다 간단하면서 효율적인 태양전지의 제조가 가능 할 것으로 기대된다. 본 연구에서는 $CIGSe_2$ 광흡수층을 2 단계에 걸쳐 제작하였다. 먼저 Cu, In, Ga 성분을 포함하는 용액을 이용하여 CIG 전구체막을 형성한 후, 다음 단계로 selenization 공정을 진행함으로써 $CIGSe_2$ 박막을 제작하였다. $CIGSe_2$의 결정 성장을 위하여 selenization 공정의 열처리 온도와 시간을 조절하여 CIG 전구체막과 Se 원소의 결합반응을 최적화할 수 있는 공정 조건을 확보하였으며 이를 통해 우수한 결정 및 전기적 특성을 갖는 $CIGSe_2$박막을 제조하였다. 제작된 $CIGSe_2$ 박막의 광전변환 효율을 측정하여 단위셀로서의 구현이 가능함을 확인하였으며 XRD, SEM, EDS, UV-visible을 통하여 $CIGSe_2$박막의 특성을 분석하였다.

• Journal of the Korean Solar Energy Society
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• v.31 no.1
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• pp.93-99
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• 2011

To guarantee more exact maximum power of solar cell module, it is absolutely required to have performance characteristics of various solar cells. Today, there are many types of solar simulator for large area measurement. But it is very opaque how to select the best one for various solar cell module like crystalline silicon solar cell, high efficiency solar cell, amorphous silicon thin film solar cell, CdTe and CIGS solar cell module. So, in this paper 4 types of photovoltaic module were selected to compare the electrical characteristics by changing light pulse duration time and voltage scan direction. Light pulse duration time was varied from 10msec to 800msec. And two types of voltage scan directions, Voc->Isc and Isc->Voc were selected. From this results, optimum measuring condition was suggested and electrical variation was analysed for each types of solar cell module. The detail description is specified as the following paper.

• Applied Microscopy
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• v.45 no.3
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• pp.183-188
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• 2015

Due to the miniaturization of semiconductor devices, their crystal structure on the nanoscale must be analyzed. However, scanning electron microscope-electron backscatter diffraction (EBSD) has a limitation of resolution in nanoscale and high-resolution electron microscopy (HREM) can be used to analyze restrictive local structural information. In this study, three-dimensional (3D) automated crystal orientation and phase mapping using transmission electron microscopy (TEM) (3D TEM-EBSD) was used to identify the crystal structure relationship between an epitaxially grown CdS interfacial layer and a $Cu(In_xGa_{x-1})Se_2$ (CIGS) solar cell layer. The 3D TEM-EBSD technique clearly defined the crystal orientation and phase of the epitaxially grown layers, making it useful for establishing the growth mechanism of functional nano-materials.