• Proceedings of the Materials Research Society of Korea Conference
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• 2011.10a
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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.

• Proceedings of the Korean Vacuum Society Conference
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• 2010.08a
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• pp.166-166
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• 2010

Recently, TFTs based on amorphous oxide semiconductors (AOSs) such as ZnO, InZnO, ZnSnO, GaZnO, TiOx, InGaZnO(IGZO), SnGaZnO, etc. have been attracting a grate deal of attention as potential alternatives to existing TFT technology to meet emerging technological demands where Si-based or organic electronics cannot provide a solution. Since, in 2003, Masuda et al. and Nomura et al. have reported on transparent TFTs using ZnO and IGZO as active layers, respectively, much efforts have been devoted to develop oxide TFTs using aforementioned amorphous oxide semiconductors as their active layers. In this thesis, I report on the performance of thin-film transistors using amorphous indium gallium zinc oxides for an active channel layer at room temperature. $SiO_2$ was employed as the gate dielectric oxide. The amorphous indium gallium zinc oxides were deposited by RF magnetron sputtering. The carrier concentration of amorphous indium gallium zinc oxide was controlled by oxygen pressure in the sputtering ambient. Devices are realized that display a threshold voltage of 1.5V and an on/off ration of > $10^9$ operated as an n-type enhancement mode with saturation mobility with $9.06\;cm^2/V{\cdot}s$. The devices show optical transmittance above 80% in the visible range. In conclusion, the fabrication and characterization of thin-film transistors using amorphous indium gallium zinc oxides for an active channel layer were reported. The operation of the devices was an n-type enhancement mode with good saturation characteristics.

• Applied Chemistry for Engineering
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• v.26 no.5
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• pp.526-532
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• 2015

Solar cells with other alternative energies are being importantly recognized related with post-2020 climate change regime formation. In a point of view of materials, solar cells are classified to organic and inorganic solar cells which can provide a plant-scale electricity. In particular, recent studies about compound semiconductor solar cells, such as III-V tandem solar cells, chalcopyrite-series CIGSSe solar cells, and kesterite-series CZTSSe solar cells were rapidly accelerated. In this report, we introduce a research trend and technical issues for the compound semiconductor solar cells.

• Proceedings of the Korean Vacuum Society Conference
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• 2014.02a
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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.

• Proceedings of the Materials Research Society of Korea Conference
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• 2012.05a
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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.

• Proceedings of the Korean Institute of Surface Engineering Conference
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• 2014.11a
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• pp.252-253
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• 2014

비정질 ITZO 박막은 ITZO(In:Sn:Zn= 8:1:1, 6:2:2, 4:3:3, 2:4:4) 타겟을 이용하여 상온에서 RF 마그네트론 스퍼터링 법으로 제조 되었다. ITZO 박막의 물성을 알아보기 위하여 조성별, 산소 분압별 및 열처리에 따른 박막의 구조적, 전기적, 광학적 특성을 분석하였다. 박막 실험 결과를 바탕으로 ITZO(4:3:3) 박막을 채널 층으로 이용하여 성공적으로 박막 트랜지스터를 제작 하였다.

• 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.

• Proceedings of the Korean Vacuum Society Conference
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• 2014.02a
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• pp.335-335
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• 2014

Over the past several years, transparent conducting oxides have been extensively studied in order to replace indium tin oxide (ITO). Here we report on fluorine doped zinc tin oxide (FZTO) films deposited on glass substrates by radio-frequency (RF) magnetron sputtering using a 30 wt% ZnO with 70 wt% SnO2 ceramic targets. The F-doping was carried out by introducing a mixed gas of pure Ar, CF4, and O2 forming gas into the sputtering chamber while sputtering ZTO target. Annealing temperature affects the structural, electrical and optical properties of FZTO thin films. All the as-deposited FZTO films grown at room temperature are found to be amorphous because of the immiscibility of SnO2 and ZnO. Even after the as-deposited FZTO films were annealed from $300{\sim}500^{\circ}C$, there were no significant changes. However, when the sample is annealed temperature up to $600^{\circ}C$, two distinct diffraction peaks appear in XRD spectra at $2{\Theta}=34.0^{\circ}$ and $52.02^{\circ}$, respectively, which correspond to the (101) and (211) planes of rutile phase SnO2. FZTO thin film annealed at $600^{\circ}C$ resulted in decrease of resistivity $5.47{\times}10^{-3}{\Omega}cm$, carrier concentration ~1019 cm-3, mobility~20 cm2 V-1s-1 and increase of optical band gap from 3.41 to 3.60 eV with increasing the annealing temperatures and well explained by Burstein-Moss effect. Change of work function with the annealing temperature was obtained by ultraviolet photoemission spectroscopy. The increase of annealing temperature leads to increase of work function from ${\phi}=3.80eV$ (as-deposited FZTO) to ${\phi}=4.10eV$ ($600^{\circ}C$ annealed FZTO) which are quite smaller than 4.62 eV for Al-ZnO and 4.74 eV for SnO2. Through X-ray photoelectron spectroscopy, incorporation of F atoms was found at around the binding energy of 684.28 eV in the as-deposited and annealed FZTO up to 400oC, but can't be observed in the annealed FZTO at 500oC. This result indicates that F atoms in FZTO films are loosely bound or probably located in the interstitial sites instead of substitutional sites and thus easily diffused into the vacuum from the films by thermal annealing. The optical transmittance of FZTO films was higher than 80% in all specimens and 2-3% higher than ZTO films. FZTO is a possible potential transparent conducting oxide (TCO) alternative for application in optoelectronics.

• 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.

• Proceedings of the Korean Vacuum Society Conference
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• 2012.02a
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• pp.400-400
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• 2012

산화물 반도체는 넓은 에너지갭을 가지고 높은 이동성과 높은 투명성을 가지기 때문에 초고 속 박막 트랜지스터(Thin film transistor; TFT)에 많이 응용되고 있다. 그러나 ZnO 및 $In_2O_3$ 산화물 반도체를 박막트랜지스터에 사용할 경우 소자가 불안정하여 전기적 성질이 저하되고 문턱전압의 이동이 일어난다. TFT에 사용되는 산화물 반도체로는 GaInZnO, ZrInZnO, HfInZnO 및 GaSnZnO의 전기적 특성에 관한 연구가 많이 되었다. 그러나 titanium-indium-zinc-oxide (TIZO) TFT에 대한 연구는 비교적 적게 수행 되었다. 본 연구에서는 TFTs의 안정성을 향상하기 위하여 TFT의 채널로 사용되는 TiInZnO를 형성하는데 간단한 제조 공정과 낮은 비용의 용액 증착방법을 사용하였다. 졸-겔 전해액은 Titanium (IV) isopropoxide $[Ti(OCH(CH_3)_2)_4]$, 0.1 M Zinc acetate dihydrate $[Zn(CH_3COO)_2{\cdot}2H_2O]$ 그리고 indium nitrate hydrate $[In(NO_3)_3{\cdot}xH_2O]$을 2-methoxyethanol의 용액에 합성하였다. $70^{\circ}C$에서 한 시간 동안 혼합 하였다. Ti의 몰 비율은 10%, 20% 및 40% 로 각각 달리하여 제작하였다. $SiO_2$층 위에 2,500 rpm 속도로 25초 동안 스핀 코팅하여 TFT를 제작하였다. TIZO 박막에 대한 X-선 광전자 스펙트럼 관측 결과는 Ti 몰 비율이 증가함에 따라 Ti 2p1/2피크의 세기가 증가함을 보여주었다. TiZO 박막에 Ti 원자를 첨가하면 $O^{2-}$ 이온이 감소하기 때문에 전하의 농도가 변화하였다. 전하 농도의 변화는 TiZO 채널을 사용하여 제작한 TFT의 문턱전압을 양 방향으로 이동 하였으며 off-전류를 감소하였다. TiZO 채널을 사용하여 제작한 TFT의 드레인 전류-게이트 전압 특성은 on/off비율이 $0.21{\times}107$ 만큼 크며 이것은 TFT 소자로서 우수한 성능을 보여주고 있다.