Uma V. Ghorpade

A Simple Aqueous Precursor Solution Processing of Earth-Abundant Cu2SnS3 Absorbers for Thin-Film Solar Cells

A simple and eco-friendly method of solution processing of Cu2SnS3 (CTS) absorbers using an aqueous precursor solution is presented. The precursor solution was prepared by mixing metal salts into a mixture of water and ethanol (5:1) with monoethanolamine as an additive at room temperature. Nearly carbon-free CTS films were formed by multispin coating the precursor solution and heat treating in air followed by rapid thermal annealing in S vapor atmosphere at various temperatures. Exploring the role of the annealing temperature in the phase, composition, and morphological evolution is essential for obtaining highly efficient CTS-based thin film solar cells (TFSCs). Investigations of CTS absorber layers annealed at various temperatures revealed that the annealing temperature plays an important role in further improving device properties and efficiency. A substantial improvement in device efficiency occurred only at the critical annealing temperature, which produces a compact and void-free microstructure with large grains and high crystallinity as a pure-phase absorber layer. Finally, at an annealing temperature of 600 °C, the CTS thin film exhibited structural, compositional, and microstructural isotropy by yielding a reproducible power conversion efficiency of 1.80%. Interestingly, CTS TFSCs exhibited good stability when stored in an air atmosphere without encapsulation at room temperature for 3 months, whereas the performance degraded slightly when subjected to accelerated aging at 80 °C for 100 h under normal laboratory conditions.

A facile and green synthesis of colloidal Cu2ZnSnS4 nanocrystals and their application in highly efficient solar water splitting

The development of solution-processable routes as well as compounds consisting of earth abundant elements is highly desirable to reduce the fabrication cost. Recently, kesterite Cu2ZnSnS4 (CZTS) nanocrystals (NCs) have attracted great attention for photoelectrochemical (PEC) water splitting owing to their suitable low-cost, earth-abundancy and suitable band gap energy. However, the environmentally benign synthesis of high-quality CZTS NCs without toxic solvents remains elusive. Here, a green chemistry approach employing vegetable oil as a non-toxic solvent for the synthesis of monodisperse and size-tunable CZTS NCs is introduced for the first time. Additionally, the relationship between the abnormal size behavior of the CZTS NCs and the degree of decomposition in the vegetable oil using electrospray ionization mass spectrometry (ESI-MS) measurements is elucidated for the first time. As a conceptual strategy, a ternary abundant compound based heterojunction nanostructure for efficient solar water splitting by introducing CZTS NCs onto 5 nm Zn(O,S) passivated layer/hydrothermally grown TiO2 nanorod arrays (TNRs) is designed and developed. Remarkably, this ternary CZTS NCs/Zn(O,S)/TNR photoelectrode shows a photocurrent density as high as 15.05 mA cm−2 at 1.23 V (vs. the NHE), which is the highest ever for previously reported CZTS NC-based photoelectrodes. The reasons for the enhanced PEC performance are discussed in detail based on different PEC characterizations. More importantly, this work reflects the sophistication of eco-friendly solution phase synthesized CZTS NCs without using any toxic chemicals as an earth abundant sensitizer and constitute a new paradigm towards the enhanced PEC performance with quantum dot based hetero-nanostructures.

Towards environmentally benign approaches for the synthesis of CZTSSe nanocrystals by a hot injection method

With the earths abundance of kesterite, recent progress in chalcogenide based Cu2ZnSn(Sx,Se1-x)4 (CZTSSe) thin films has drawn prime attention in thin film solar cells (TFSCs) research and development. This review is focused on the current developments in the synthesis of CZTS nanocrystals (NCs) using a hot injection (HI) technique and provides comprehensive discussions on the current status of CZTSSe TFSCs. This article begins with a description of the advantages of nanoparticulate based thin films, and then introduces the basics of this technique and the corresponding growth mechanism is also discussed. A brief overview further addresses a series of investigations on the developments in the HI based CZTSSe NCs using different solvents in terms of their high toxicity to environmentally benign materials. A variety of recipes and techniques for the NCs ink formulation and thereby the preparation of absorber layers using NC inks are outlined, respectively. The deposition of precursor thin films, post-deposition processes such as sulfurization or selenization treatments and the fabrication of CZTSSe NCs based solar cells and their performances are discussed. Finally, we discussed concluding remarks and the perspectives for further developments in the existing research on CZTSSe based nanoparticulate (NP) TFSCs towards future green technology.

Facile, Room Temperature, Electroless Deposited (Fe1− x ,Mn x )OOH Nanosheets as Advanced Catalysts: The Role of Mn Incorporation

Herein, bimetallic iron (Fe)-manganese (Mn) oxyhydroxide ((Fe1-x, Mnx )OOH, FeMnOOH) nanosheets on fluorine-doped tin oxide conducting substrates and on semiconductor photoanodes are synthesized by a facile, room temperature, electroless deposition method as catalysts for both electrochemical and photo-electrochemical (PEC) water splitting, respectively. Surprisingly, Mn-doped FeOOH can significantly modulate the nanosheet morphology to increase the active surface area, boost more active sites, and augment the intrinsic activity by tuning the electronic structure of FeOOH. Due to the 2D nanosheet architecture, the optimized FeMnOOH exhibits superior electrochemical activity and outstanding durability for the oxygen evolution reaction with a low overpotential of 246 mV at 10 mA cm-2 and 414 mV at 100 mA cm-2 , and long-term stability for 40 h without decay, which is comparable to the best electrocatalysts for water oxidation reported in the literature. By integrating with semiconductor photoanodes (such as α-Fe2 O3 nanorod (NR) arrays), bimetallic FeMnOOH catalysts achieve solar-driven water splitting with a significantly enhanced PEC performance (3.36 mA cm-2 at 1.23 V vs reversible hydrogen electrode (RHE)) with outstanding long-term stability (≈8 h) compared to that of the bare Fe2 O3 NR (0.92 mA cm-2 at 1.23 V vs RHE).

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.

Eutectic solvent-mediated selective synthesis of Cu–Sb–S-based nanocrystals: combined experimental and theoretical studies toward highly efficient water splitting

Recently, emerging Cu–Sb–S-based compounds have been identified as an attractive candidate for photovoltaic (PV) applications because of their high natural abundance, eco-friendly features and typical phase-dependent characteristics. Herein, a simple eutectic solvent-mediated (choline chloride/ethylene glycol) synthetic approach for newly debuted Cu–Sb–S-based nanocrystals (NCs) with phase-selective properties is presented. This combination of material and preparation method may promote the exchange of carriers by avoiding a steric hindrance for a facile charge transport encountered in NCs prepared using amines, thiols, hydrazines and phosphine oxide solvents. A temperature-dependent study of an ethaline-based deep eutectic solvent (DES) is conducted to elucidate the characteristics of associated chemical shifts and vibrations and to determine changes in hydrogen bonding interactions using structural and thermal analytical techniques. The results suggest that ethaline is a strong candidate as a greener solvent for the synthesis of NCs at relatively low temperatures. The electronic structures of all four Cu–Sb–S phases—Cu3SbS4, CuSbS2, Cu3SbS3, and Cu12Sb4S13—were simulated using the Vienna ab initio Simulation (VASP) code, projector augmented-wave (PAW) potentials and the hybrid functional method (HSE 06) and using density functional theory for combined theoretical and experimental studies. Discrepancies between the experimental and theoretical bandgap values of 0.29, 0.18, 0.12 and 0.16 eV were observed for Cu3SbS4, CuSbS2, Cu3SbS3 and Cu12Sb4S13 compounds, respectively. A photoelectrochemical (PEC) water reduction system with a Mo/photoelectrode/CdS/Pt/electrolyte configuration generated a cathodic photocurrent of −1.28 and −2.72 mA cm−2 for Cu3SbS4 and CuSbS2 electrodes, respectively, at 0 V versus the reversible hydrogen electrode (VRHE) under AM 1.5 G illumination, demonstrating the great potential of NCs prepared via eutectic solvent-mediated synthesis. This is the first successful attempt to apply eutectic solvent-mediated Cu–Sb–S NCs for solar driven H2 production. These outcomes suggest that designing proper functional materials through the application of greener synthesis strategies can improve water-splitting performance and would help meet the perpetual technological need for greener methods.

Unassisted visible solar water splitting with efficient photoelectrodes sensitized by quantum dots synthesized via an environmentally friendly eutectic solvent-mediated approach

Deep eutectic solvents (DESs) based on choline chloride/ethylene glycol have been explored as synthetic media for recently introduced Cu–Sb–S based colloidal quantum dots (CQDs) decorated on NiO/fluorine-doped tin oxide (FTO) and TiO2/FTO photoelectrodes for unassisted solar water splitting for hydrogen generation. The feasibility of the use of an environmentally benign solvent-based synthetic process is demonstrated herein by preparing the earth-abundant Cu–Sb–S-based CQDs and utilizing them in a solar energy harvesting material for photoelectrochemical (PEC) water splitting while avoiding the use of sacrificial agents. The band alignment between CQDs and NiO or TiO2 clearly suggests that the CQD-modified NiO and TiO2 electrodes act as a potential photocathode (NiO/Cu3SbS4/ZnS) and photoanode (TiO2/CuSbS2/ZnS) with faradaic efficiencies of up to 74 and 86%, respectively, which allows us to construct an efficient PEC cell to split water at an overall solar-to-hydrogen (STH) efficiency of ∼0.28%. The tandem photoelectrode configuration in an unassisted mode of solar-driven water splitting based on a wire-linked system shows ∼0.97 mA cm−2 of current density, and can split water under zero-bias conditions. Enhancement of the PEC device by accelerating electron and hole transport and broadening the diffusion length using photosensitizer materials while avoiding typical recombination with a thin passivation layer was achieved. The charge transport mechanism through combining experimental results in half and overall water splitting reactions is proposed. The success of such efficient multi-layered heterojunction photoelectrodes is essential for the future development of green energy harvesting devices.

A facile, one-step electroless deposition of NiFeOOH nanosheets onto photoanodes for highly durable and efficient solar water oxidation

A low-cost, highly efficient and durable photoelectrochemical (PEC) water-splitting system can be realized through designing a hierarchical core/shell nanostructured photoanode entirely composed of Earth-abundant elements. Herein, we report the rational design of a core/shell nanostructured photoanode with a TiO2 nanorod (NR) array as the core and a highly active Earth-abundant NiFe oxyhydroxide ((Ni1−xFex)OOH, NiFeOOH) oxygen evolution catalyst (OEC) as the shell for PEC water oxidation. Specifically, the NiFeOOH nanosheets were prepared via a facile, one-step electroless deposition method for a short reaction time of 10 min at room temperature. The TiO2/NiFeOOH core/shell nanostructured photoanode exhibits an unprecedented enhancement in photocurrent density (3.85 mA cm−2 at 1.23 V vs. a reversible hydrogen electrode, (RHE)), no decay in photocurrent density over 24 h, and an obvious cathodic onset potential shift of 133 mV compared to the TiO2 NRs (0.73 mA cm−2 at 1.23 V vs. RHE). The electron transfer mechanism is discussed through electrochemical impedance spectroscopy studies and calculated band alignments via ultraviolet photoelectron spectroscopy characterization. This work not only suggests a simple, room temperature electroless strategy for integrating Earth-abundant catalysts with photoanodes, but also accelerates the development of rationally designed core/shell photoanodes for efficient and durable solar water oxidation.

Solution Processed Porous Fe2O3 Thin Films for Solar-Driven Water Splitting

We report facile solution processing of mesoporous hematite (α-Fe2O3) thin films for high efficiency solar-driven water splitting. Fe2O3 thin films were prepared on fluorine doped tin oxide(FTO) conducting substrates by spin coating of a precursor solution followed by annealing at 550 oC for 30 min. in air ambient. Specifically, the precursor solution was prepared by dissolving non-toxic FeCl3 as an Fe source in highly versatile dimethyl sulfoxide(DMSO) as a solvent. The as-deposited and annealed thin films were characterized for their morphological, structural and optical properties using field-emission scanning electron microscopy(FE-SEM), X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS) and UV-Vis absorption spectroscopy. The photoelectrochemical performance of the precursor (α-FeOOH) and annealed (α-Fe2O3) films were characterized and it was found that the α-Fe2O3 film exhibited an increased photocurrent density of ~0.78 mA/cm2 at 1.23 V vs. RHE, which is about 3.4 times higher than that of the α-FeOOH films (0.23 mA/cm2 at 1.23 V vs. RHE). The improved performance can be attributed to the improved crystallinity and porosity of α-Fe2O3 thin films after annealing treatment at higher temperatures. Detailed electrical characterization was further carried out to elucidate the enhanced PEC performance of α-Fe2O3 thin films.