ZnO thin films are of considerable interest because they can be customized by various coating technologies to have high electrical conductivity and high visible light transmittance. Therefore, ZnO thin films can be applied to various optoelectronic device applications such as transparent conducting thin films, solar cells and displays. In this study, ZnO rod and thin films are fabricated using aqueous chemical bath deposition (CBD), which is a low-cost method at low temperatures, and environmentally friendly. To investigate the structural, electrical and optical properties of ZnO for the presence of citrate ion, which can significantly affect crystal form of ZnO, various amounts of the citrate ion are added to the aqueous CBD ZnO reaction bath. As a result, ZnO crystals show a nanorod form without citrate, but a continuous thin film when citrate is above a certain concentration. In addition, as the citrate concentration increases, the electrical conductivity of the ZnO thin films increases, and is almost unchanged above a certain citrate concentration. Cu(In,Ga)Se2 (CIGS) solar cell substrates are used to evaluate whether aqueous CBD ZnO thin films can be applicable to real devices. The performance of aqueous CBD ZnO thin films shows performance similar to that of a sputter-deposited ZnO:Al thin film as top transparent electrodes of CIGS solar cells.

Silver nanowire (AgNW) networks have been adopted as a front electrode in Cu(In,Ga)Se2 (CIGS) thin film solar cells due to their low cost and compatibility with the solution process. When an AgNW network is applied to a CIGS thin film solar cell, reflection loss can increase because the CdS layer, with a relatively high refractive index (n ~ 2.5 at 550 nm), is exposed to air. To resolve the issue, we apply solution-processed ZnO nanorods to the AgNW network as an anti-reflective coating. To obtain high performance of the optical and electrical properties of the ZnO nanorod and AgNW network composite, we optimize the process parameters – the spin coating of AgNWs and the concentration of zinc nitrate and hexamethylene tetramine (HMT – to fabricate ZnO nanorods. We verify that 10 mM of zinc nitrate and HMT show the lowest reflectance and 10% cell efficiency increase when applied to CIGS thin film solar cells.

To realize high-performance thin film solar cells, we prepared CIGS by the co-evaporation technique on both sodalime and Corning glass substrates. The structural and efficient properties were investigated by varying the thickness of the Mo:Na layer, where the total thickness of the back contact was fixed at 1μm. As a result, when the Mo:Na thickness was 300 nm on soda-lime glass, the measured Na content was 0.28 %, the surface morphology was a plate-like compact structure, and the crystallinity by XRD showed a strong peak of (112) preferential orientation together with relatively intense (220) and (204) peaks as the secondary phases influenced crystal formation. In addition, the substrates on soda-lime glass effected the lowest surface roughness of 2.76 nm and the highest carrier density and short circuit current. Through the optimization of the Mo:Na layer, a solar conversion efficiency of 11.34% was achieved. When using the Corning glass, a rather low conversion efficiency of 9.59% was obtained. To determine the effects of the concentration of sodium and in order to develop a highefficiency solar cells, a very small amount of sodium was added to the soda lime glass substrate.

A high-quality CIGS film with a selenization process needs to be developed for low-cost and large-scale production. In this study, we used Cu2In3, CuGa and Cu2Se sputter targets for the deposition of a precursor. The precursor deposited by sputtering was selenized in Se vapor. The precursor layer deposited by the co-sputtering of Cu2In3, CuGa and Cu2Se showed a uniform distribution of Cu, In, Ga, and Se throughout the layer with Cu, In, CuIn, CuGa and Cu2Se phases. After selenization at 550˚C for 30 min, the CIGS film showed a double-layer microstructure with a large-grained top layer and a small-grained bottom layer. In the AES depth profile, In was found to have accumulated near the surface while Cu had accumulated in the middle of the CIGS film. By adding a Cu-In-Ga interlayer between the co-sputtered precursor layer and the Mo film and adding a thin Cu2Se layer onto the co-sputtered precursor layer, large CIGS grains throughout the film were produced. However, the Cu accumulated in the middle of CIGS film in this case as well. By supplying In, Ga and Se to the CIGS film, a uniform distribution of Cu, In, Ga and Se was achieved in the middle of the CIGS film.

Cu(In, Ga)Se2 (CIGS) precursor films were electrodeposited on Mo/glass substrates in acidic solutions containingCu2+, In3+, Ga3+, and Se4+ ions at −0.6V (SCE) and pH 1.8. In order to induce recrystallization, the electrodepositedCu1.00In0.81Ga0.09Se2.08 (25.0at.% Cu+20.2at.% In+2.2at.% Ga+52.0at.% Se) precursor films were annealed under a highSe gas atmosphere for 15, 30, 45, and 60 min, respectively, at 500oC. The Se amount in the film increased from 52at.% to62at.%, whereas the In amount in the film decreased from 20.8at.% to 9.1at.% as the annealing time increased from 0 (as-deposited state) to 60 min. These results were attributed to the Se introduced from the furnace atmosphere and reacted withthe In present in the precursor films, resulting in the formation of the volatile In2Se. CIGS precursor grains with a cauliflowershape grew as larger grains with the CuSe2 and/or Cu2-xSe faceted phases as the annealing times increased. These faceted phasesresulted in rough surface morphologies of the CIGS films. Furthermore, the CIGS layers were not dense because the emptyspaces between the grains were not removed via annealing. Uniform thicknesses of the MoSe2 layers occurred at the 45 and60 min annealing time. This implies that there was a stable reaction between the Mo back electrode and the Se diffused throughthe CIGS film. The results obtained in the present research were sufficiently different from comparable studies where therecrystallization annealing was performed under an atmosphere of Ar gas only or a low Se gas pressure.

Cu(In,Ga)Se2(CIGS) photovoltaic thin films were electrodeposited on Mo/glass substrates with an aqueous solution containing 2 mM CuCl2, 8 mM InCl3, 20 mM GaCl3 and 8mM H2SeO3 at the electrodeposition potential of -0.6 to -1.0 V(SCE) and pH of 1.8. The best chemical composition of Cu1.05In0.8Ga0.13Se2 was found to be achieved at -0.7 V(SCE). The precursor Cu-In-Ga-Se films were annealed for crystallization to chalcopyrite structure at temperatures of 100-500˚C under Ar gas atmosphere. The chemical compositions, microstructures, surface morphologies, and crystallographic structures of the annealed films were analyzed by EPMA, FE-SEM, AFM, and XRD, respectively. The precursor Cu-In-Ga-Se grains were grown sparsely on the Mo-back contact and also had very rough surfaces. However, after annealing treatment beginning at 200˚C, the empty spaces between grains were removed and the grains showed well developed columnar shapes with smooth surfaces. The precursor Cu-In-Ga-Se films were also annealed at the temperature of 500˚C for 60 min under Se gas atmosphere to suppress the Se volatilization. The Se amount on the CIGS film after selenization annealing increased above the Se amount of the electrodeposited state and the MoSe2 phase occurred, resulting from the diffusion of Se through the CIGS film and interaction with Mo back electrode. However, the selenization-annealed films showed higher crystallinity values than did the films annealed under Ar atmosphere with a chemical composition closer to that of the electrodeposited state.

The selenization process has been a promising method for low-cost and large-scale production of high quality CIGS film. However, there is the problem that most Ga in the CIGS film segregates near the Mo back contact. So the solar cell behaves like a CuInSe2 and lacks the increased open-circuit voltage. In this study we investigated the Ga distribution in CIGS films by using the Ga2Se3 layer. The Ga2Se3 layer was applied on the Cu-In-Ga metal layer to increase Ga content at the surface of CIGS films and to restrict Ga diffusion to the CIGS/Mo interface with Ga and Se bonding. The layer made by thermal evaporation was showed to an amorphous Ga2Se3 layer in the result of AES depth profile, XPS and XRD measurement. As the thickness of Ga2Se3 layer increased, a small-grained CIGS film was developed and phase seperation was showed using SEM and XRD respectively. Ga distributions in CIGS films were investigated by means of AES depth profile. As a result, the [Ga]/[In+Ga] ratio was 0.2 at the surface and 0.5 near the CIGS/Mo interface when the Ga2Se3 thickness was 220 nm, suggesting that the Ga2Se3 layer on the top of metal layer is one of the possible methods for Ga redistribution and open circuit voltage increase.

In high-efficiency Cu(In,Ga)Se2 solar cells, Na is doped into a Cu(In,Ga)Se2 light-absorbing layer from sodalime-glass substrate through Mo back-contact layer, resulting in an increase of device performance. However, this supply of sodium is limited when the process temperature is too low or when a substrate does not supply Na. This limitation can be overcome by supplying Na through external doping. For Na doping, an NaF interlayer was deposited on Mo/glass substrate. A Cu(In,Ga)Se2 absorber layer was deposited on the NaF interlayer by a three-stage co-evaporation process As the thickness of NaF interlayer increased, smaller grain sizes were obtained. The resistivity of the NaF-doped CIGS film was of the order of 103Ω·cm indicating that doping was not very effective. However, highest conversion efficiency of 14.2% was obtained when the NaF thickness was 25 nm, suggesting that Na doping using an NaF interlayer is one of the possible methods for external doping.