Experimental proof is presented for a hitherto undetected solid-state reaction between the solar cell material Cu(2)ZnSn(S,Se)(4) (CZTS(e)) and the standard metallic back contact, molybdenum. Annealing experiments combined with Raman and transmission electron microscopy studies show that this aggressive reaction causes formation of MoS(2) and secondary phases at the CZTS|Mo interface during thermal processing. A reaction scheme is presented and discussed in the context of current state-of-the-art synthesis methods for CZTS(e). It is concluded that alternative back contacts will be important for future improvements in CZTS(e) quality.

Cu 2 ZnSnS 4 (CZTS) is a promising material for thin film solar cells based on sustainable resources. This paper explores some consequences of the chemical instability between CZTS and the standard Mo "back contact" layer used in the solar cell. Chemical passivation of the back contact interface using titanium nitride (TiN) diffusion barriers, combined with variations in the CZTS annealing process, enables us to isolate the effects of back contact chemistry on the electrical properties of the CZTS layer that result from the synthesis, as determined by measurements on completed solar cells. It is found that instability in the back contact is responsible for large current losses in the finished solar cell, which can be distinguished from other losses that arise from instabilities in the surface of the CZTS layer during annealing. The TiN-passivated back contact is an effective barrier to sulfur atoms and therefore prevents reactions between CZTS and Mo. However, it also results in a high series resistance and thus a reduced fill factor in the solar cell. The need for high chalcogen pressure during CZTS annealing can be linked to suppression of the back contact reactions and could potentially be avoided if better inert back contacts were to be developed.

Reducing absorber layer thickness below 500 nm in regular Cu(In,Ga)Se2 (CIGS) solar cells decreases cell efficiency considerably, as both short-circuit current and open-circuit voltage are reduced because of incomplete absorption and high Mo/CIGS rear interface recombination. In this work, an innovative rear cell design is developed to avoid both effects: a highly reflective rear surface passivation layer with nano-sized local point contact openings is employed to enhance rear internal reflection and decrease the rear surface recombination velocity significantly, as compared with a standard Mo/CIGS rear interface. The formation of nano-sphere shaped precipitates in chemical bath deposition of CdS is used to generate nano-sized point contact openings. Evaporation of MgF2 coated with a thin atomic layer deposited Al2O3 layer, or direct current magnetron sputtering of Al2O3 are used as rear surface passivation layers. Rear internal reflection is enhanced substantially by the increased thickness of the passivation layer, and also the rear surface recombination velocity is reduced at the Al2O3/CIGS rear interface. (MgF2/)Al2O3 rear surface passivated ultra-thin CIGS solar cells are fabricated, showing an increase in short circuit current and open circuit voltage compared to unpassivated reference cells with equivalent CIGS thickness. Accordingly, average solar cell efficiencies of 13.5% are realized for 385 nm thick CIGS absorber layers, compared with 9.1% efficiency for the corresponding unpassivated reference cells.

Recently, Cu(In,Ga)Se 2 (CIGS) solar cells have achieved 21% world-record efficiency, partly due to the introduction of a postdeposition potassium treatment to improve the front interface of CIGS absorber layers. However, as high-efficiency CIGS solar cells essentially require long diffusion lengths, the highly recombinative rear of these devices also deserves attention. In this paper, an Al 2 O 3 rear surface passivation layer with nanosized local point contacts is studied to reduce recombination at the standard Mo/CIGS rear interface. First, passivation layers with well-controlled grids of nanosized point openings are established by use of electron beam lithography. Next, rear-passivated CIGS solar cells with 240-nm-thick absorber layers are fabricated as study devices. These cells show an increase in open-circuit voltage (+57 mV), short-circuit current (+3.8 mA/cm 2 ), and fill factor [9.5% (abs.)], compared with corresponding unpassivated reference cells, mainly due to improvements in rear surface passivation and rear internal reflection. Finally, solar cell capacitance simulator (SCAPS) modeling is used to calculate the effect of reduced back contact recombination on high-efficiency solar cells with standard absorber layer thickness. The modeling shows that up to 50-mV increase in open-circuit voltage is anticipated. Index Terms-Al 2 O 3 , Cu(In,Ga)Se 2 , electron beam lithography, local point contacts, nanosized openings, passivation layer, passivated emitter and rear cell (PERC), rear internal reflection, rear surface recombination velocity, Si. I. INTRODUCTIONO VER the past two years, CIGS solar cells have taken a sudden leap in world record efficiency of 1%, from around 20% to 21% [1]. Before 2013, CIGS solar cell efficiency improvements were mainly due to enhancements in absorber material quality, and cell efficiencies were lingering around 20% for a few years-as achieved by National Renewable Energy Laboratory (NREL) and the Centre for Solar Energy and Hydrogen Research Baden-Württemberg (ZSW) [2]. However, in Manuscript

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The influence of the thickness of atomic layer deposited Zn 1Àx Sn x O y buffer layers and the presence of an intrinsic ZnO layer on the performance of Cu(In,Ga)Se 2 solar cells are investigated. The amorphous Zn 1Àx Sn x O y layer, with a [Sn]/([Sn] + [Zn]) composition of approximately 0.18, forms a conformal and in-depth uniform layer with an optical band gap of 3.3 eV. The short circuit current for cells with a Zn 1Àx Sn x O y layer are found to be higher than the short circuit current for CdS buffer reference cells and thickness independent. On the contrary, both the open circuit voltage and the fill factor values obtained are lower than the references and are thickness dependent. A high conversion efficiency of 18.0%, which is comparable with CdS references, is attained for a cell with a Zn 1Àx Sn x O y layer thickness of approximately 13 nm and with an i-ZnO layer.