Facile Approach for Metallic Precursor Engineering for Efficient Kesterite Thin-Film Solar Cells.

Kesterite-based Cu2ZnSn(S,Se)4 (CZTSSe) thin-film solar cells (TFSCs) are a promising candidate for low-cost, clean energy production owing to their environmental friendliness and the earth-abundant nature of their constituents. However, the advancement of kesterite TFSCs has been impeded by abundant defects and poor microstructure, limiting their performance potential. In this study, we present efficient Ag-alloyed CZTSSe TFSCs enabled by a facile metallic precursor engineering approach. The positioning of the Ag nanolayer in the metallic stacked precursor proves crucial in expediting the formation of Cu-Sn metal alloys during the alloying process. Specifically, Ag-included metallic precursors promote the growth of larger grains and a denser microstructure in CZTSSe thin films compared to those without Ag. Moreover, the improved uniformity of Ag, facilitated by the evaporation deposition technique, significantly suppresses the formation of detrimental defects and related defect clusters. This suppression effectively reduces nonradiative recombination, resulting in enhanced performance in kesterite TFSCs. This study not only introduces a metallic precursor engineering strategy for efficient kesterite-based TFSCs but also accelerates the development of microstructure evolution from metallic stacked precursors to metal chalcogenide compounds.

Achieving Low VOC-deficit Characteristics in Cu2ZnSn(S,Se)4 Solar Cells through Improved Carrier Separation.

Kesterite-based thin-film solar cells (TFSCs) have recently gained significant attention in the photovoltaic (PV) sector for their elemental earth abundance and low toxicity. An inclusive study from the past reveals basic knowledge about the grain boundary (GB) and grain interior (GI) interface. However, the compositional dependency of the surface potential within GBs and GIs remains unclear. The present work provides insights into the surface potential of the bulk and GB interfaces. The tin (Sn) composition is sensitive to the absorber morphology, and therefore, it significantly impacts absorber and device properties. The absorber morphology improves with the formation of larger grains as the Sn content increases. Additionally, the presence of Sn(S,Se)2 and increased [ZnCu + VCu] A-type defect cluster density are observed, validated through Raman analysis. The secondary ion mass spectroscopy analysis reveals the altered distribution of sulfur (S) and sodium (Na) with higher near-surface accumulation. The synergistic outcome of the increased density of defects and the accumulation of S near the interface provides a larger GB and GI difference and expedites carrier separation improvement. Consequently, at an optimum compositional ratio of Cu/(Zn+Sn) = ∼0.6, the power conversion efficiency (PCE) is significantly improved from 6.42 to 11.04% with a record open-circuit voltage (VOC) deficit of 537 mV.

A Facile Process for Partial Ag Substitution in Kesterite Cu2ZnSn(S,Se)4 Solar Cells Enabling a Device Efficiency of over 12.

A cation substitution in Cu2ZnSn(S,Se)4 (CZTSSe) offers a viable strategy to reduce the open-circuit voltage (Voc)-deficit by altering the characteristics of band-tail states, antisite defects, and related defect clusters. Herein, we report a facile single process, i.e., simply introducing a thin Ag layer on a metallic precursor, to effectively improve the device characteristics and performances in kesterite (Agx,Cu1-x)2ZnSn(Sy,Se1-y)4 (ACZTSSe) solar cells. Probing into the relationship between the external quantum efficiency derivative (dEQE/dλ) and device performances revealed the Voc-deficit characteristics in the ACZTSSe solar cells as a function of Cu and Ag contents. The fabricated champion ACZTSSe solar cell device showed an efficiency of 12.07% and a record low Voc-deficit of 561 mV. Thorough investigations into the mechanism underpinning the improved performance in the ACZTSSe device further revealed the improved band-tailing characteristic, effective minority carrier lifetime, and diode factors as well as reduced antisite defects and related defect clusters as compared to the CZTSSe device. This study demonstrates the feasibility of effectively suppressing antisite defects, related defect clusters, and band-tailing characteristics by simply introducing a thin Ag layer on a metallic precursor in the kesterite solar cells, which in turn effectively reduces the Voc-deficit.

Flexible High-Efficiency CZTSSe Solar Cells on Diverse Flexible Substrates via an Adhesive-Bonding Transfer Method.

Cu2ZnSn(S,Se)4 (CZTSSe) thin-film solar cells are showing great promise due to using earth-abundant and nontoxic materials and tuning the band gap through the amount of S and Se. Flexible high-efficiency CZTSSe solar cells are one of the outstanding research challenges because they currently require the use of thick glass substrates due to the high-temperature heat treatment process, and for this reason, few flexible CZTSSe solar cells have been reported. Furthermore, most researchers have used thin glass and metal substrates with little flexibility; the power conversion efficiency (PCE or η) values of the solar cells made with them have been slightly lower. To overcome these hurdles, we transferred high-efficiency CZTSSe solar cells formed on a soda-lime glass substrate to flexible substrates via an adhesive-bonding transfer method. Through this method, we were able to achieve the PCE of 5.8-7.1% on completely flexible substrates such as cloth, paper, and poly(ethylene terephthalate) (PET). In particular, we were able to produce a CZTSSe solar cell on a PET substrate with a PCE of 7.1%, which is the highest among fully flexible CZTSSe solar cells currently known to us. In addition, we deeply analyzed the PCE degradation of the flexible CZTSSe solar cell fabricated by the transfer method through a panoramic focused ion-beam image and nanoindentation. From the results of our work, we provide an insight into the possibility of making flexible high-efficiency CZTSSe solar cells using our transfer method.

8% Efficiency Cu2ZnSn(S,Se)4 (CZTSSe) Thin Film Solar Cells on Flexible and Lightweight Molybdenum Foil Substrates.

The use of flexible and highly conducting molybdenum (Mo) foil as a substrate offers several advantages such as a high thermal stability, smooth surface, and chemical inertness for the fabrication of high-efficiency thin film solar cells (TFSCs) by lowering the manufacturing costs. Here, we report a record preliminary efficiency of ∼8% for sputtered-grown Cu2ZnSn(S,Se)4 (CZTSSe) TFSCs on flexible and lightweight Mo foils. Careful studies were focused on identifying the role of preparative parameters such as annealing temperature, absorber composition, and post-preparative optimization to bridge the obtained record efficiency of ∼8% to a previous record efficiency of 7.04% for Na-incorporated CZTSSe sputter-based TFSCs. Interestingly, the preliminary record efficiency of ∼8% for our CZTSSe device grown via a scalable sputtering method was achieved by optimizing the absorber quality and post-preparative device optimization. While our preliminary results with a record efficiency demonstrate the potential of sputtering method, there is much scope for further improvement in the device efficiency by thoroughly understanding alkali element doping in the absorber layer.

Towards highly efficient and low-cost oxygen evolution reaction electrocatalysts: An effective method of electronic waste management by utilizing waste Cu cable wires.

Currently, electronic waste (e-waste) is the world's most challenging and rapidly growing problem in the waste stream. To develop an alternative way to use e-waste (waste copper (Cu) wires) to accelerate the oxygen evolution reaction (OER) of water electrolysis, the waste Cu wires are used as a low-cost current collector. We demonstrate a simple electrodeposition process to deposit nickel-iron hydroxide (NiFe LDH) nanosheets on self-supported copper hydroxide (Cu(OH)2/Cu) nanowires grown via chemical-oxidation on waste Cu wire. Benefiting from the efficient electron transport, high mass activity, and surface area this electrocatalyst exhibits an efficient OER performance with a low overpotential of 275 mV and 390 mV at 20 and 100 mA cm-2 respectively, with excellent stability. This work provides a promising pathway to recycle e-waste into value-added resources in various energy conversion applications.

Band Tail Engineering in Kesterite Cu2ZnSn(S,Se)4 Thin-Film Solar Cells with 11.8% Efficiency.

Herein, we report a facile process, i.e., controlling the initial chamber pressure during the postdeposition annealing, to effectively lower the band tail states in the synthesized CZTSSe thin films. Through detailed analysis of the external quantum efficiency derivative ( dEQE/ dλ) and low-temperature photoluminescence (LTPL) data, we find that the band tail states are significantly influenced by the initial annealing pressure. After carefully optimizing the deposition processes and device design, we are able to synthesize kesterite CZTSSe thin films with energy differences between inflection of d(EQE)/dλ and LTPL as small as 10 meV. These kesterite CZTSSe thin films enable the fabrication of solar cells with a champion efficiency of 11.8% with a low Voc deficit of 582 mV. The results suggest that controlling the annealing process is an effective approach to reduce the band tail in kesterite CZTSSe thin films.

Cobalt Iron Hydroxide as a Precious Metal-Free Bifunctional Electrocatalyst for Efficient Overall Water Splitting.

Highly efficient and stable electrocatalysts from inexpensive and earth-abundant elements are emerging materials in the overall water splitting process. Herein, cobalt iron hydroxide nanosheets are directly deposited on nickel foam by a simple and rapid electrodeposition method. The cobalt iron hydroxide (CoFe/NF) nanosheets not only allow good exposure of the highly active surface area but also facilitate the mass and charge transport capability. As an anode, the CoFe/NF electrocatalyst displays excellent oxygen evolution reaction catalytic activity with an overpotential of 220 mV at a current density of 10 mA cm-2 . As a cathode, it exhibits good performance in the hydrogen evolution reaction with an overpotential of 110 mV, reaching a current density of 10 mA cm-2 . When CoFe/NF electrodes are used as the anode and the cathode for water splitting, a low cell voltage of 1.64 V at 10 mA cm-2 and excellent stability for 50 h are observed. The present work demonstrates a possible pathway to develop a highly active and durable substitute for noble metal electrocatalysts for overall water splitting.

Chemically Deposited CdS Buffer/Kesterite Cu2ZnSnS4 Solar Cells: Relationship between CdS Thickness and Device Performance.

Earth-abundant, copper-zinc-tin-sulfide (CZTS), kesterite, is an attractive absorber material for thin-film solar cells (TFSCs). However, the open-circuit voltage deficit (Voc-deficit) resulting from a high recombination rate at the buffer/absorber interface is one of the major challenges that must be overcome to improve the performance of kesterite-based TFSCs. In this paper, we demonstrate the relationship between device parameters and performances for chemically deposited CdS buffer/CZTS-based heterojunction TFSCs as a function of buffer layer thickness, which could change the CdS/CZTS interface conditions such as conduction band or valence band offsets, to gain deeper insight and understanding about the Voc-deficit behavior from a high recombination rate at the CdS buffer/kesterite interface. Experimental results show that device parameters and performances are strongly dependent on the CdS buffer thickness. We postulate two meaningful consequences: (i) Device parameters were improved up to a CdS buffer thickness of 70 nm, whereas they deteriorated at a thicker CdS buffer layer. The Voc-deficit in the solar cells improved up to a CdS buffer thickness of 92 nm and then deteriorated at a thicker CdS buffer layer. (ii) The minimum values of the device parameters were obtained at 70 nm CdS thickness in the CZTS TFSCs. Finally, the highest conversion efficiency of 8.77% (Voc: 494 mV, Jsc: 34.54 mA/cm2, and FF: 51%) is obtained by applying a 70 nm thick CdS buffer to the Cu2ZnSn(S,Se)4 absorber layer.

Aqueous-Solution-Processed Cu2ZnSn(S,Se)4 Thin-Film Solar Cells via an Improved Successive Ion-Layer-Adsorption-Reaction Sequence.

A facile improved successive ionic-layer adsorption and reaction (SILAR) sequence is described for the fabrication of Cu2ZnSn(S,Se)4 (CZTSSe) thin-film solar cells (TFSCs) via the selenization of a precursor film. The precursor films were fabricated using a modified SILAR sequence to overcome compositional inhomogeneity due to different adsorptivities of the cations (Cu+, Sn4+, and Zn2+) in a single cationic bath. Rapid thermal annealing of the precursor films under S and Se vapor atmospheres led to the formation of carbon-free Cu2ZnSnS4 (CZTS) and CZTSSe absorber layers, respectively, with single large-grained layers. The best devices based on CZTS and CZTSSe absorber layers showed total area (∼0.30 cm2) power conversion efficiencies (PCEs) of 1.96 and 3.74%, respectively, which are notably the first-demonstrated efficiencies using a modified SILAR sequence. Detailed diode analyses of these solar cells revealed that a high shunt conductance (G sh), reverse saturation current density (J o), and ideality factor (n d) significantly affected the PCE, open-circuit voltage (V oc), and fill factor (FF), whereas the short-circuit current density (J sc) was dominated by the series resistance (R s) and G sh. However, the diode analyses combined with the compositional and interface microstructural analyses shed light on further improvements to the device efficiency. The facile layer-by-layer growth of the kesterite CZTS-based thin films in aqueous solution provides a great promise as an environmentally benign pathway to fabricate a variety of multielement-component compounds with high compositional homogeneities.