Earth‐abundant and air‐stable Cu2BaSnS4−
Bandgap gradient is a proven approach for improving the open-circuit voltages (VOCs) in Cu(In,Ga)Se2and Cu(Zn,Sn)Se2thin-film solar cells, but has not been realized in Cd(Se,Te) thin-film solar cells, a leading thin-film solar cell technology in the photovoltaic market. Here, we demonstrate the realization of a bandgap gradient in Cd(Se,Te) thin-film solar cells by introducing a Cd(O,S,Se,Te) region with the same crystal structure of the absorber near the front junction. The formation of such a region is enabled by incorporating oxygenated CdS and CdSe layers. We show that the introduction of the bandgap gradient reduces the hole density in the front junction region and introduces a small spike in the band alignment between this and the absorber regions, effectively suppressing the nonradiative recombination therein and leading to improved VOCs in Cd(Se,Te) solar cells using commercial SnO2buffers. A champion device achieves an efficiency of 20.03% with a VOCof 0.863 V.more » « less
- NSF-PAR ID:
- Publisher / Repository:
- Nature Publishing Group
- Date Published:
- Journal Name:
- Nature Communications
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Earth‐abundant and air‐stable Cu2BaSnS4−
xSe x(CBTSSe) and related thin‐film absorbers are regarded as prospective options to meet the increasing demand for low‐cost solar cell deployment. Devices based on vacuum‐deposited CBTSSe absorbers have achieved record power conversion efficiency (PCE) of 5.2% based on a conventional device structure using CdS buffer and i‐ZnO/indium tin oxide (ITO) window layers, with open‐circuit voltage ( VOC) posing the major bottleneck for improving solar cell performance. The current study demonstrates a >20% improvement in VOC(from 0.62 to 0.75 V) and corresponding enhancement in PCE (from 5.1% to 6.2% without antireflection coating; to 6.5% with MgF2antireflection coating) for solution‐deposited CBTSSe solar cells. This performance improvement is realized by introducing an alternative successive ionic layer adsorption and reaction‐deposited Zn1− xCd xS buffer combined with sputtered Zn1− xMg xO/Al‐doped ZnO window/top contact layer, which offers lower electron affinities relative to the conventional CdS/i‐ZnO/ITO stack and better matching with the low electron affinity of CBTSSe. A combined experimental (temperature‐ and light intensity‐dependent VOCmeasurements) and device simulation (SCAPS‐1D) evaluation points to the importance of addressing relative band offsets for both the buffer and window layers relative to the absorber in mitigating interfacial recombination and optimizing CBTSSe solar cell performance.
Large-scale deployment of photovoltaic modules is required to power our renewable energy future. Kesterite, Cu2ZnSn(S, Se)4, is a p-type semiconductor absorber layer with a tunable bandgap consisting of earth abundant elements, and is seen as a potential ‘drop-in’ replacement to Cu(In,Ga)Se2in thin film solar cells. Currently, the record light-to-electrical power conversion efficiency (PCE) of kesterite-based devices is 12.6%, for which the absorber layer has been solution-processed. This efficiency must be increased if kesterite technology is to help power the future. Therefore two questions arise: what is the best way to synthesize the film? And how to improve the device efficiency? Here, we focus on the first question from a solution-based synthesis perspective. The main strategy is to mix all the elements together initially and coat them on a surface, followed by annealing in a reactive chalcogen atmosphere to react, grow grains and sinter the film. The main difference between the methods presented here is how easily the solvent, ligands, and anions are removed. Impurities impair the ability to achieve high performance (>∼10% PCE) in kesterite devices. Hydrazine routes offer the least impurities, but have environmental and safety concerns associated with hydrazine. Aprotic and protic based molecular inks are environmentally friendlier and less toxic, but they require the removal of organic and halogen species associated with the solvent and precursors, which is challenging but possible. Nanoparticle routes consisting of kesterite (or binary chalcogenides) particles require the removal of stabilizing ligands from their surfaces. Electrodeposited layers contain few impurities but are sometimes difficult to make compositionally uniform over large areas, and for metal deposited layers, they have to go through several solid-state reaction steps to form kesterite. Hence, each method has distinct advantages and disadvantages. We review the state-of-the art of each and provide perspective on the different strategies.
In recent years, Cu2ZnSn(S,Se)4(CZTSSe) materials have enabled important progress in associated thin‐film photovoltaic (PV) technology, while avoiding scarce and/or toxic metals; however, cationic disorder and associated band tailing fundamentally limit device performance. Cu2BaSnS4(CBTS) has recently been proposed as a prospective alternative large bandgap (~2 eV), environmentally friendly PV material, with ~2% power conversion efficiency (PCE) already demonstrated in corresponding devices. In this study, a two‐step process (i.e., precursor sputter deposition followed by successive sulfurization/selenization) yields high‐quality nominally pinhole‐free films with large (>1 µm) grains of selenium‐incorporated (
x= 3) Cu2BaSnS4− xSe x(CBTSSe) for high‐efficiency PV devices. By incorporating Se in the sulfide film, absorber layers with 1.55 eV bandgap, ideal for single‐junction PV, have been achieved within the CBTSSe trigonal structural family. The abrupt transition in quantum efficiency data for wavelengths above the absorption edge, coupled with a strong sharp photoluminescence feature, confirms the relative absence of band tailing in CBTSSe compared to CZTSSe. For the first time, by combining bandgap tuning with an air‐annealing step, a CBTSSe‐based PV device with 5.2% PCE (total area 0.425 cm2) is reported, >2.5× better than the previous champion pure sulfide device. These results suggest substantial promise for the emerging Se‐rich Cu2BaSnS4– xSe xfamily for high‐efficiency and earth‐abundant PV.
The large open‐circuit voltage deficit (
Voc,def) is the key issue that limits kesterite (Cu2ZnSn(S,Se)4, [CZTSSe]) solar cell performance. Substitution of Cu+by larger ionic Ag+((Ag,Cu)2ZnSn(S,Se)4, [ACZTSSe]) is one strategy to reduce Cu–Zn disorder and improve kesterite Voc. However, the so far reported ACZTSSe solar cell has not demonstrated lower Voc,defthan the world record device, indicating that some intrinsic defect properties cannot be mitigated using current approaches. Here, incorporation of Ag into kesterite through a dimethyl sulfoxide (DMSO) solution that can facilitate direct phase transformation grain growth and produce a uniform and less defective kesterite absorber is reported. The same coordination chemistry of Ag+and Cu+in the DMSO solution results in the same reaction path of ACZTSSe to CZTSSe, resulting in significant suppression of CuZndefects, its defect cluster [2CuZn + SnZn], and deep level defect CuSn. A champion device with an efficiency of 12.5% (active area efficiency 13.5% without antireflection coating) and a record low Voc,def(64.2% Shockley–Queisser limit) is achieved from ACZTSSe with 5% Ag content.
We fabricate and characterize methylammonium lead halide perovskite film as a novel back contact to CdTe thin‐film solar cells. We apply ~0.75 μm perovskite film at the interface of CdCl2‐activated and Cu‐doped CdTe surface and complete the device with Au back contact. We use Cu/Au back contact as a reference to compare results with novel back contact. Our investigation shows that incorporation of thin layer of perovskite film before the back contact metal reduces back contact barrier effect and improves fill factor (FF) and open‐circuit voltage (VOC) of the solar cells. Our low temperature JV results prove that thin‐film perovskite is a very necessary component in CdTe solar cells to reduce back contact barrier, to minimize interface or surface recombination, to improve collection efficiencies, and to increase the efficiency of solar cells. Our best device shows 7% increase in VOCto 0.875 V and ~7% increase in FF with the highest FF of 81%, and solar cell's efficiency finally increases by 10% with the use of MAPb(I1‐xBrx)3as an interface layer.