• Current Photovoltaic Research
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• v.7 no.1
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• pp.1-8
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• 2019

The $Cu(In,Ga)Se_2$ (CIGS) thin film obtained by two-step process (metal deposition and Se annealing) has a rough surface morphology and many voids at the CIGS/Mo interface. To solve the problem a precursor that contains Se was employer by depositing a (In,Se)/(Cu,Ga) stacked layer. We devised a two-step annealing (vacuum pre-annealing and Se annealing) for the precursor because direct annealing of the precursor in Se environment resulted in the small grains with unwanted demarcation between stacked layers. After vacuum pre-annealing up to $500^{\circ}C$ the CIGS film consisted of CIGS phase and secondary phases including $In_4Se_3$, InSe, and $Cu_9(In,Ga)_4$. The secondary phases were completely converted to CIGS phase by a subsequent Se annealing. A void-free CIGS/Mo interface was obtained by the two-step annealing process. Especially, the CIGS film prepared by vacuum annealing $450^{\circ}C$ and subsequent Se annealing $550^{\circ}C$ showed a densely-packed grains with smooth surface, well-aligned bamboo grains on the top of the film, little voids in the film, and also little voids at the CIGS/Mo interface. The smooth surface enhanced the cell performance due to the increase of shunt resistance.

• Proceedings of the Korean Vacuum Society Conference
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• 2011.08a
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• pp.218-218
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• 2011

The CIGS Solar Cells have the highest conversion efficiency in the film-type solar cells. They consist of p-type CuInSe2 film and n-type ZnO film. The CdS films are used as buffer layer in the CIGS solar cells since remarkable difference in the lattice constant and energy band gap of two films. The CdS films are toxic and make harmful circumstances. The CdS films deposition process need wet process. In this works, we design and make the hitter and lamp reflection part in the sputtering system for the ZnS films deposition as buffer layer, not using wet process. Film thickness, SEM, and AFM are measured for the uniformity valuation of the ZnS films. We conclude the optimum deposition temperature for the films uniformity less than 1.6%. The ZnS films deposited by the sputtering system are more dense and uniform than the CdS films deposited by the Chemical Bath Deposition Method(CBD) for the CIGS Solar Cells.

• 한국신재생에너지학회:학술대회논문집
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• 2006.06a
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• pp.222-224
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• 2006

A non-vacuum process for $Cu(In,Ga)Se_2$ (CIGS) thin film solar cells from nanoparticle precursors was described in this work CIGS nanoparticle precursors was prepared by a low temperature colloidal route by reacting the starting materials $(CuI,\;InI_3,\;GaI_3\;and\;Na_2Se)$ in organic solvents, by which fine CIGS nanoparticles of about 20nm in diameter were obtained. The nanoparticle precursors were mixed with organic binder material for the rheology of the mixture to be adjusted for the doctor blade method. After depositing the mixture of CIGS with binder on Mo/glass substrate, the samples were preheated on the hot plate in air to evaporate remaining solvents ud to burn the organic binder material. Subsequently, the resultant (porous) CIGS/Mo/glass simple was selenized in a two-zone Rapid Thermal Process (RTP) furnace in order to get a solar ceil applicable dense CIGS absorber layer. Complete solar cell structure was obtained by depositing. The other layers including CdS buffer layer, ZnO window layer and Al electrodes by conventional methods. The resultant solar cell showed a conversion efficiency of 0.5%.

• Proceedings of the Materials Research Society of Korea Conference
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• 2012.05a
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• pp.92-92
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• 2012

Chalcopyrite-type Cu(In,Ga)Se2 (CIGS) is one of the most attractive compound semiconductor materials for thin film solar cells. Among various approaches to prepare the CIGS thin film, the powder process offers an extremely simple and materials-efficient method. Here, we present the mechano-chemical synthesis of CIGS compound powders and their use as an ink material for screen-printing. During the synthesis process, milling time and speed were varied in the range of 10~600 min and 100~300 rpm, respectively. Both phase evolution and powder characteristics were carefully monitored by X-ray diffraction (XRD) method, scanning electron microscope (SEM) observation, and particle size analysis by scanning mobility particle spectrometer (SMPS) and aerodynamic particle sizer (APS). We found the optimal milling condition as 200 rpm for 120 min but also found that a monolithic phase of CIGS powders without severe particle aggregation was difficult to be obtained by the mechano-chemical milling alone. Therefore, the optimized milling condition was combined with an adequate heat-treatment (300oC for 60 min) to provide the monolithic CIGS powder of a single phase with affordable particle characteristics for the preparation of CIGS thin film. The powder was used to prepare an ink for screen printing with which dense CIGS thin films were fabricated under the controlled selenization. The morphology and electrical properties of the thin films were analyzed by SEM images and hall measurement, respectively.

• Korean Journal of Materials Research
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• v.21 no.8
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• pp.461-467
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• 2011

Cu(In, Ga)$Se_2$ (CIGS) precursor films were electrodeposited on Mo/glass substrates in acidic solutions containing $Cu^{2+}$, $In^{3+}$, $Ga^{3+}$, and $Se^{4+}$ ions at -0.6 V (SCE) and pH. 1.8. In order to induce recrystallization, the electrodeposited $Cu_{1.00}In_{0.81}Ga_{0.09}Se_{2.08}$ (25.0 at.% Cu + 20.2 at.% In + 2.2 at.% Ga + 52.0 at.% Se) precursor films were annealed under a high Se gas atmosphere for 15, 30, 45, and 60 min, respectively, at $500^{\circ}C$. The Se amount in the film increased from 52 at.% to 62 at.%, whereas the In amount in the film decreased from 20.8 at.% to 9.1 at.% as the annealing time increased from 0 (asdeposited state) to 60 min. These results were attributed to the Se introduced from the furnace atmosphere and reacted with the In present in the precursor films, resulting in the formation of the volatile $In_2Se$. CIGS precursor grains with a cauliflower shape grew as larger grains with the $CuSe_2$ and/or $Cu_{2-x}Se$ faceted phases as the annealing times increased. These faceted phases resulted in rough surface morphologies of the CIGS films. Furthermore, the CIGS layers were not dense because the empty spaces between the grains were not removed via annealing. Uniform thicknesses of the $MoSe_2$ layers occurred at the 45 and 60 min annealing time. This implies that there was a stable reaction between the Mo back electrode and the Se diffused through the CIGS film. The results obtained in the present research were sufficiently different from comparable studies where the recrystallization annealing was performed under an atmosphere of Ar gas only or a low Se gas pressure.

• 한국신재생에너지학회:학술대회논문집
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• 2009.06a
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• pp.19-22
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• 2009

A non-vacuum process for fabrication of $CuIn_xGa_{1-x}Se_2$ (CIGS) absorber layer from the corresponing Cu, In, Ga solution precursors was described. Cu, In, Ga precursor solution was prepared by a room temperature colloidal route by reacting the starting materials $Cu(NO_3)_2$, $InCl_3$, $Ga(NO_3)$ and methanol. The Cu, In, Ga precursor solution was mixed with ethylcellulose as organic binder material for the rheology of the mixture to be adjusted for the doctor blade method. After depositing the mixture of Cu, In, Ga solution with binder on Mo/glass substrate, the samples were preheated on the hot plate in air to evaporate remaining solvents and to burn the organic binder material. Subsequently, the resultant CIG/Mo/glass sample was selenized in Se evaporation in order to get a solar cell applicable dense CIGS absorber layer. The CIGS absorber layer selenized at $530^{\circ}C$ substrate temperature for 1h with various metal organic ratio.

• Journal of the Korean Vacuum Society
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• v.21 no.3
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• pp.142-150
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• 2012

In this Study, Mo back electrode were deposited as the functions of various working pressure, deposition time and plasma per-treatment on sodalime glass (SLG) for application to CIGS thin film solar cell using by DC sputtering method, and were analyzed Mo change to $MoSe_2$ layer through selenization processes. And finally Mo back electrode characteristics were evaluated as application to CIGS device after Al/AZO/ZnO/CdS/CIGS/Mo/SLG fabrication. Mo films fabricated as a function of the working pressure from 1.3 to 4.9mTorr are that physical thickness changed to increase from 1.24 to 1.27 ${\mu}m$ and electrical characteristics of sheet resistance changed to increase from 0.195 to 0.242 ${\Omega}/sq$ as according to the higher working pressure. We could find out that Mo film have more dense in lower working pressure because positive Ar ions have higher energy in lower pressure when ions impact to Mo target, and have dominated (100) columnar structure without working pressure. Also Mo films fabricated as a function of the deposition time are that physical thickness changed to increase from 0.15 to 1.24 ${\mu}m$ and electrical characteristics of sheet resistance changed to decrease from 2.75 to 0.195 ${\Omega}/sq$ as according to the increasing of deposition time. This is reasonable because more thick metal film have better electrical characteristics. We investigated Mo change to $MoSe_2$ layer through selenization processes after Se/Mo/SLG fabrication as a function of the selenization time from 5 to 40 minutes. $MoSe_2$ thickness were changed to increase as according to the increasing of selenization time. We could find out that we have to control $MoSe_2$ thickness to get ohmic contact characteristics as controlling of proper selenization time. And we fabricated and evaluated CIGS thin film solar cell device as Al/AZO/ZnO/CdS/CIGS/Mo/SLG structures depend on Mo thickness 1.2 ${\mu}m$ and 0.6 ${\mu}m$. The efficiency of CIGS device with 0.6 ${\mu}m$ Mo thickness is batter as 9.46% because Na ion of SLG can move to CIGS layer more faster through thin Mo layer. The adhesion characteristics of Mo back electrode on SLG were improved better as plasma pre-treatment on SLG substrate before Mo deposition. And we could expect better efficiency of CIGS thin film solar cell as controlling of Mo thickness and $MoSe_2$ thickness depend on Na effect and selenization time.

• 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.