Ultrathin Cu(In,Ga)Se2 solar cells are a promising way to reduce costs and to increase the electrical performance of thin film solar cells. An optical lithography process that can produce sub‐micrometer contacts in a SiO2 passivation layer at the CIGS rear contact is developed in this work. Furthermore, an optimization of the patterning dimensions reveals constrains over the features sizes. High passivation areas of the rear contact are needed to passivate the CIGS interface so that high performing solar cells can be obtained. However, these dimensions should not be achieved by using long distances between the contacts as they lead to poor electrical performance due to poor carrier extraction. This study expands the choice of passivation materials already known for ultrathin solar cells and its fabrication techniques.

In this work, Metal-Insulator-Semiconductor (MIS) structures were fabricated in order to study different types of insulators, namely, aluminum oxide (Al2O3), silicon nitride (Si3Nx) and silicon oxide (SiOx) to be used as passivation layers in Cu(In,Ga)Se2 (CIGS) thin film solar cells. The investigated stacks consisted of SLG/Mo/CIGS/insulator/Al. Raman scattering and Photoluminescence measurements were done to verify the insulator deposition influence on the CIGS surface. In order to study the electrical properties of the CIGS-insulator interface, capacitance vs. conductance and voltage (C-G-V) measurements were done to estimate the number and polarity of fixed insulator charges (Qf). The density of interface defects (Dit) was estimated from capacitance vs. conductance and frequency (C-G-f) measurements. This study evidences that the deposition of the insulators at high temperatures (300 ºC) and the use of sputtering technique cause surface modification on the CIGS surface. We found that, by varying the SiOx deposition parameters, it is possible to have opposite charges inside the insulator, which would allow its use in different device architectures. The material with lower Dit values was Al2O3 when deposited by sputtering.

Currently, one of the main limitations in ultrathin Cu(In,Ga)Se2 (CIGS) solar cells are the optical losses, since the absorber layer is thinner than the light optical path. Hence, light management, including rear optical reflection and light trapping is needed. In this work we focus on increasing the rear optical reflection. For this, a novel structure based on having a metal interlayer in between the Mo rear contact and the rear passivation layer is presented. In total, eight different metallic interlayers are compared. For the whole series, the passivation layer is aluminum oxide (Al2O3). The interlayers are used to enhance the reflectivity of the rear contact and thereby increasing the amount of light reflected back into the absorber. In order to understand the effects of the interlayer in the solar cell performance both from optical and/or electrical point of view, optical simulations were performed together with fabrication and electrical measurements. Optical simulations results are compared with current density-voltage (J-V) behavior and external quantum efficiency (EQE) measurements. A detailed comparison between all the interlayers is done, in order to identify the material with the greatest potential to be used as rear reflective layer for ultrathin CIGS solar cells and to establish fabrication challenges. The Ti-W alloy is a promising rear reflective layer since it provides solar cells with light to power conversion efficiency values of 9.9 %, which is 2.2 % (abs) higher than the passivated ultrathin sample and 3.7 % (abs) higher than the unpassivated ultrathin reference sample.

The effects of introducing a passivation layer at the rear of ultrathin Copper Indium Gallium di-Selenide Cu(In,Ga)Se2 (CIGS) solar cells is studied. Point contact structures have been created on 25 nm Al2O3 layer using e-beam lithography. Reference solar cells with ultrathin CIGS layers provide devices with average values of light to power conversion efficiency of 8.1 % while for passivated cells values reached 9.5 %. Electronic properties of passivated cells have been studied before, but the influence of growing the CIGS on Al2O3 with point contacts was still unknown from a structural and morphological point of view. Scanning Electron Microscopy, X-ray Diffraction and Raman spectroscopy measurements were performed. These measurements revealed no significant morphological or structural differences in the CIGS layer for the passivated samples compared with reference samples. These results are in agreement with the similar values of carrier density (~8x1016 cm-3) and depletion region (~160 nm) extracted using electrical measurements. A detailed comparison between both sample types in terms of current-voltage, external quantum efficiency and photoluminescence measurements show very different optoelectronic behaviour which is indicative of a successful passivation. SCAPS simulations are done to explain the observed results in view of passivation of the rear interface.

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A novel architecture that comprises rear interface passivation and increased rear optical reflection is presented with the following advantages: i) an enhanced optical reflection is achieved by depositing a metallic layer over the Mo rear contact; ii) the addition of a sputtered Al2O3 layer improves the interface quality with CIGS; and, iii) the rear-openings are refilled with Mo to maintain the optimal ohmic electrical contact as generally observed from the growth of CIGS on Mo. Hence, a decoupling between the electrical function and the optical function of the substrate is achieved. We present in detail the manufacturing procedure of such type of architectures together with its benefits and caveats. A preliminary electrical analysis of resulting solar cells showing a proof-of-concept of the architecture is presented and discussed.

In this work, it is presented a procedure to grow single phase Cu 12 Sb 4 S 13 and Cu 3 SbS 4 thin films consisting on the annealing of simultaneously sputtered metal precursors fllowed by a annealing treatment in a sulphur atmosphere. The selection of the ternary phase which is intended to grow is performed by adjusting the sulfur evaporation temperature in chalcogenization process. It is shown that for a sulphur evaporation temperature of 140 • C the predominant phase is Cu 12 Sb 4 S 13 and for 180 • C the predominant phase is Cu 3 SbS 4 . In order to ensure precursor composition homogeneity, the Cu-Sb metallic precursors are deposited simultaneously by rf magnetron sputtering using adjustable segmented targets. The morphological characterization of the films was made by scanning electron microscopy and the composition was analysed by energy dispersive spectroscopy. The structural analysis and phase identification were performed by X-ray diffraction and Raman scattering. The optical properties were studied through spectrophotometry on films deposited directly on bare glass.

Numerical simulations of AZO/Zn1−xGexO/Cu2O solar cell are performed in order to model for the first time the impact of the germanium composition of the ZnGeO buffer layer on the photovoltaic conversion efficiency. The physical parameters of the model are chosen with special care to match literature experimental measurements or are interpolated using the values from binary metal oxides in the case of the new Zn1−xGexO compound. The solar cell model accuracy is then confirmed thanks to the comparison of its predictions with measurements from the literature that were done on experimental devices obtained by thermal oxidation. This validation of the AZO/Zn1−xGexO/Cu2O model then allows to study the impact of the use of the low cost, environmental friendly and industrially compatible spray pyrolysis process on the solar cell efficiency. To that aim, the Cu2O absorber layer parameters are adjusted to typical values obtained by the spray pyrolysis process by selecting state of the art experimental data. The analysis of the impact of the absorber layer thickness, the carrier mobility, the defect and doping concentration on the solar cell performances allows to draw guidelines for ZnGeO/Cu2O thin film photovoltaic device realization through spray pyrolysis.