Evaluating Pb-based and Pb-free Halide Perovskites for Solar-Cell Applications: A Simulation Study.

Metal halide Pb-based and Pb-free perovskite crystal structures are an essential class of optoelectronic materials due to their significant optoelectronic properties, optical absorption and tuneable emission spectrum properties. However, the most efficient optoelectronic devices were based on the Pb as a monovalent cation, but its toxicity is a significant hurdle for commercial device applications. Thus, replacing the toxic Pb with Pb-free alternatives (such as tin (Sn)) for diverse photovoltaic and optoelectronic applications is essential. Moreover, replacing the volatile methylammonium (MA) with cesium (Cs) leads to the development of an efficient perovskite absorber layer with improved optical & thermal stability and stabilized photoconversion efficiency. This paper discusses the correlation between the experimental and theoretical work for the Pb-based and Pb-free perovskites synthesised using the hot-injection method at different temperatures. Here, simulation is also carried out using the help of SCAPS-1D software to study the effect of various parameters of CsSnI3 and CsPbI3 layers on solar cell performance. This experimental and theoretical comparative study of the Hot-injection method synthesised CsPbI3 and CsSnI3 perovskites is rarely investigated for optoelectronic applications.

Experimental and Theoretical Investigations of MAPbX3 -Based Perovskites (X=Cl, Br, I) for Photovoltaic Applications.

This work mainly focuses on synthesizing and evaluating the efficiency of methylammonium lead halide-based perovskite (MAPbX3 ; X=Cl, Br, I) solar cells. We used the colloidal Hot-injection method (HIM) to synthesize MAPbX3 (X=Cl, Br, I) perovskites using the specific precursors and organic solvents under ambient conditions. We studied the structural, morphological and optical properties of MAPbX3 perovskites using XRD, FESEM, TEM, UV-Vis, PL and TRPL (time-resolved photoluminescence) characterization techniques. The particle size and morphology of these perovskites vary with respect to the halide variation. The MAPbI3 perovskite possesses a low band gap and low carrier lifetime but delivers the highest PCE among other halide perovskite samples, making it a promising candidate for solar cell technology. To further enrich the investigations, the conversion efficiency of the MAPbX3 perovskites has been evaluated through extensive device simulations. Here, the optical constants, band gap energy and carrier lifetime of MAPbX3 were used for simulating three different perovskite solar cells, namely I, Cl or Br halide-based perovskite solar cells. MAPbI3 , MAPbBr3 and MAPbCl3 absorber layer-based devices showed ~13.7 %, 6.9 % and 5.0 % conversion efficiency. The correlation between the experimental and SCAPS simulation data for HIM-synthesized MAPBX3 -based perovskites has been reported for the first time.

Experimental analysis of methylammonium and Formamidinium-based halide perovskite properties for optoelectronic applications.

Nowadays, the toxicity of lead in metal-halide perovskites is the most precarious obstruction in the commercialization of perovskite-based optoelectronic devices. However, Pb-free metal halide perovskites as environment-friendly materials because of their exceptional properties, such as band-gap tunability, narrow emission spectra, low toxicity and easy solution-processability, are potential candidates for optoelectronic applications. Recently, literature reported the poor structural stability and low-emission intensity of Bi-based perovskite NCs. Still, this paper focuses on the fabrication of Formamidinium (FA)-based Bi mixed halide and Methylammonium(MA)-based Bi-pure halide perovskites using Ligand-Assisted Reprecipitation Technique (LARP) technique. XRD diffraction patterns of FA-based perovskites were slightly broad, signifying the nanocrystalline form and limited size of perovskite nanocrystals. While the XRD diffraction patterns of MA3Bi2X9 (X = Cl/Br/I) perovskites were narrow, signifying the amorphous nature and larger size of perovskite nanocrystals. The peak positions were varied in MA-based bismuth halide perovskites with respect to the halide variation from Br to Cl to I ions. The optical study shows the variation in band gap and average lifetime with respect to halide variation leading to enhanced optical properties for device applications. The band-gap of FA3Bi2BrxCl1-x & FA3Bi2IxCl1-x perovskites was calculated to be around 3.7 & 3.8 eV, respectively, while in MA-halide perovskites the band-gap was calculated to be 2.8 eV, 3.1 eV & 3.4 eV with respect to halide variation from I to Cl to Br in perovskite samples using Tauc's plot respectively. Moreover, simulation is carried out using the SCAPS-1D software to study the various parameters in MA & FA-based Bi-pure or mixed halide perovskites. Here, we discussed the variation in efficiency with respect to the thickness variation from 100 to 500 nm for MA3Bi2I9 halide perovskites. These MA3Bi2I9 halide perovskites show minimum efficiency of 4.65 % at 100 nm thickness, while the perovskite sample exhibits maximum efficiency of 10.32 % at 500 nm thickness. Thus, the results stated that the thickness of absorber layers directly affects the device characteristics for optoelectronic applications.

Surface engineering of colloidal quaternary chalcogenide Cu2ZnSnS4 nanocrystals: a potential low-cost photocatalyst for water remediation.

Colloidal route synthesis of quaternary compound CZTS (Cu2ZnSnS4) has been anticipated with an inimitable combination of coordinating ligands and solvents using the hot injection technique. CZTS is recognized as one of the worthiest materials for photo-voltaic/catalytic applications due to its exclusive properties (viz., non-toxic, economical, direct bandgap, high absorbance coefficient, etc.). This paper demonstrates the formation of crystalline, single-phased, monodispersed, and electrically passivated CZTS nanoparticles using a distinctive combination of ligands viz. oleic acid (OA)-trioctylphosphine (TOP) and butylamine (BA)-trioctylphosphine (TOP). Detailed optical, structural, and electrochemical studies were done for all CZTS nanoparticles, and the most efficient composition was found using ligands butylamine and TOP. CZTS nanocrystals were rendered hydrophilic via surface-ligand engineering, which was used for photocatalysis studies of organic pollutants. Malachite green (MG) and rhodamine 6G (Rh) for water remediation have great commercial prospects. The unique selling proposition of this work is the rapid synthesis time (~ 45 min) of colloidal CZTS nanocrystals, cost-effective ligand-exchange process, and negligible material wastage (~ 200 µl per 10 ml of pollutant) during photocatalytic experiments.

Visible-light driven noble metal (Au, Ag) permeated multicomponent Cu2ZnSnS4 nanocrystals: A potential low-cost photocatalyst for textile effluents and heavy metal removal.

An exemplary vision to understand the fundamental role of metal-doped multi-components system such as Au/Ag doped CZTS (Cu2ZnSnS4) nanocrystals encourages the non-vacuum approach for the best performing photocatalyst. Hydrophilic nanoparticles (Au/Ag and CZTS) are allowed to amalgamate under NTP atmosphere, eradicating the prerequisite for high-end equipment. The potential of Au and Ag-doped CZTS nanoparticles was speculated using various optical and structural characterizations. The absorption range of CZTS nanoparticles lies in the visible range, while Au/Ag doping slightly red-shifts the absorption range, considered the desirable state for photocatalysis. The synthesized nanoparticles are highly monodispersed with ∼15-35 nm particle size for Ag, Au, and CZTS. Photocatalysis is a discernible scheme for treating wastewater containing dyes, textile effluents, chemicals, and heavy metals. Here, we strive to use these ex-situ synthesized nanomaterials as photocatalysts, where the real textile waste (collected from industrial outlets), dyes, and heavy metal (chromium (VI)) have been photo-reduced after scrutinizing the finest combination of Ag or Au doped CZTS. Au-CZTS shows superior catalytic activity with an efficiency of 99.7% with a rate constant of 0.2 min-1 (while Ag-CZTS shows 90% efficiency with a rate constant of 0.07 min-1); hence, used for real textile waste and heavy metal (Chromium VI) photo-reduction. The maximum efficiency achieved for textile-1, textile-2, and Cr (VI) reductions is 80%, 70%, and 97%, respectively. The nanocrystals are highly stable and recyclable, tested for 15 repeated cycles. These studies pave the way for developing cost-effective, environmentally-friendly, durable, and selective semiconductor-metal (Au/Ag) hybrid heterostructures as visible-light-driven photocatalysts for wastewater remediation.

Dye Sensitized Solar Cells (DSSCs) Electrolytes and Natural Photo-Sensitizers: A Review.

Dye-sensitized solar cells (DSSCs) have become the subject matter of significant interest for the research and due to their urge in the field of energy conservation. The safe supply of energy is welfare of human life. However, as an unattainable power-energy conservation source, also depletion of fossil fuels is an unfortunate mandate and, definitely it is imminent. To encounter this critical issue of energy, non-conventional sources of energy have gained lots of attention, especially solar energy because it's a device that converts light-energy directly to electrical-energy without harming the environment. DSSCs provides a reliable and a cheap alternative for different kinds of Photovoltaics. The spectacle realization of Dye-sensitized-solar-cell is typically relying on photosensitizer (Dye), electrolyte and metal oxide semiconductor. A natural dye has become most credible alternative for such expensive and rare inorganic/chemical sensitizers, due to its lower cost, easy fabrication, eco-friendly and abundance of raw material. Also, DSSC has easily implemented technology with significant efficiency. This review paper enlightens the emergence, operation/fabrication, components and development of DSSCs using natural photo-sensitizers and factors that affect the stability.

Structural Modelling of Hybrid ZnO-CdSe Nano-Compounds Using X-ray Photoelectron Spectroscopy Depth-Profiling Technique.

In the present work, ZnO nanoparticles were synthesized using chemical route method. Composition ratio for Zn:O and various oxidation states were determined using XPS (X-ray photoelectron spectroscopy) technique. The 1 hr calcined ZnO nanoparticles were found to the best due to their monodispersed nature (size ˜20 nm) and high purity. These nanoparticles were then used for synthesizing ZnO-CdSe nano-compounds. These nanocrystals were integrated with CdSe qdots (synthesized using Hot-Injection technique) of varied size (5 nm and 8 nm) via MPA (mercaptopropionic acid) as a linker to develop hybrid nano-compounds for photoactive applications like Quantum Dot sensitized solar cells (QDSSC's) etc. Here, the main objective of the work was to explore the structure of hybrid nano-compounds. XPS-depth-profiling technique was used as an investigation technique for the compositional and structural analyses of ZnO-CdSe nano-compounds. The compositional structure was analyzed layer wise (obtained by etching at different time of sputtering) for the exact position of ZnO and CdSe nanoparticles. On the basis of above study utilizing depth profiling technique of XPS and TEM images, it was found that high quality of hybrid nano-compounds can be synthesized with smaller sized quantum dots, as compared to larger sized quantum dots because of unbounded phosphorus (P) and selenium (Se). Also, it confirms the role of linker that strengthens the binding of CdSe quantum dots on the surface of ZnO thus making it hard to separate the anchored, interstitial CdSe completely which paves the way for the development of stoichiometric, structurally and morphologically-stable ZnO-CdSe nano-compounds.

Self-Activated Green-Yellow Emitting Gd2CaZnO5 Phosphor for Efficient Ultra-Violet Light-Emitting Diodes.

A new self-activated green-yellow emitting Gd2CaZnO5 (GCZO) phosphor was synthesized using solid-state reaction method at high-temperature. XRD analysis confirmed the orthorhombic structure of the sample with the Pbnm space group. SEM micrographs reveal the irregular morphology with micron sized particles. Detailed photoluminescence (PL) analysis revealed that the excitation of the phosphor lies in the UV range (˜377 nm) with the related broad green-yellow emission centered at 530 nm. The broad band emission ranging from ˜450 nm to 650 nm can be attributed to the surface defects and oxygen vacancies. The calculated luminescence decay lifetime for the optimized phosphor was found to be 2.925 µs. Furthermore, the color-coordinate (x, y) were calculated and found to be (0.44, 0.45), which lies in the green-yellow (˜540 nm) region of the electromagnetic spectrum. The values of color coordinates and Color correlated temperature of 3289 K support the synthesized phosphor for the emission of warm white-light. These results perfectly established the suitability of this green-yellow emitting GCZO phosphor for Ultra-Violet Light-Emitting Diodes (LEDs) excited white-LED applications.

Charge Transport Properties of Hybrid Nanocomposites Based on Colloidal PbSe Quantum Dots in Poly(2-methoxy,5-(2'-ethylhexyloxy)-P-Phenylenevinylene (MEH-PPV) Matrix.

The synthesis of PbSe nanoparticles were carried out by colloidal route using lead acetate as starting material with Oleic acid/TOP as capping agents at the optimized growth temperature. The phase and surface analysis of oleic acid/TOP capped PbSe nanocrystallites were studied in detail in this article. Current-voltage characteristics of pristine and lead selenide quantum dots (PbSe QDs) incorporated in poly(2-methoxy,5-(2'-ethylhexyloxy)-p-phenylenevinylene (MEH-PPV) thin films have been studied at different temperatures (306-125 K) in hole only device configuration, i.e., ITO/poly(ethylene-dioxythiophene):polystyrenesulphonate (PEDOT:PSS)/MEH-PPV/Au and ITO/PEDOT:PSS/MEH-PPV:PbSe/Au. It has been found that the presence of PbSe QDs in MEH-PPV results in the modulation of the charge transport mechanism from dual conduction mechanism, i.e., trap and mobility model to only trap model. It signifies that the traps are becoming shallower due to reduction in trap density from 2×1017 to 1.2×1017 cm-3 as well as trap energy reduces from 74 meV to 62 meV on the incorporation of PbSe QDs.

Photoreduction of Dye with Noble Metal Gold Permeated with Metal Oxide Titania.

Photoactive degradation of textile malachite green (MG), methylene blue (MB) dyes has been permeated on metal oxide TiO2 nanoparticles under sunlight. Semiconductor photocatalysis is a promising method for removal of toxic chemicals from wastewater produced by industry. Due to tunable bandgap, TiO2 among various semiconductor studied mostly. Large band gap (UV active) and recombination of exciton in TiO2 less active in photo degradation. Noble metals such as gold nanoparticles deposited on TiO2 surface increased the optical activity and to shift optical response to visible region. Degradation detail has been carried out by characterisation such as XRD, UV-Vis, PL, TEM, and SEM for MG and MB textile dyes under sunlight irradiation. UV-visible absorption spectra and PL spectra shows that photo-response of as prepared sample is extended from UV to visible region. PL intensity decreases with increases in concentration of Au nanoparticles, decreases in intensity in optical spectra of Au-TiO2 composites shows that charge transfer process dominates. Au-TiO2 plays an essential role in enhancing photocatalytical activity. Decolorization optimization depends on catalyst concentration, Dye concentration, light intensity and, irradiation time.

Magneto-Opto Electronic Applications of Conductive and Room Temperature Ferromagnetic (Al, Mn) Co-Doped ZnO Particles with Visible Emission.

The Mn, Al co-doped ZnO samples were synthesized using solid-state reaction method and were annealed in furnace at 300 °C, 600 °C and 900°C temperature. All the samples prepared were investigated in detail for analysis of their structural, morphological, optical, magnetic and electrical behavior. The XRD data confirmed the hexagonal wurtzite structure of pristine, Mn doped and Al, Mn co-doped ZnO. For morphological investigation SEM and TEM techniques were employed. The PL properties of the ZnO:Mn, Al sample revealed emission in the blue region (415-438 nm). Furthermore, IV studies were carried out to examine the conductivity of the ZnO:Mn, Al samples and maximum conductivity was found in the sample with 5% Al doping and annealing temperature 600 °C. The magnetic measurements revealed room temperature ferromagnetic behavior in the optimized ZnO:Mn, Al sample annealed at 600 °C which indicates its suitability for Magneto-Opto Electronic Applications.

An electrochemical biosensor based on novel butylamine capped CZTS nanoparticles immobilized by uricase for uric acid detection.

Quaternary chalcopyrite, i.e., Cu2ZnSnS4 (CZTS) nanoparticles films have been proposed as a novel matrix system for enzyme-based electrochemical biosensors providing a non-toxic, low-cost alternative for the fabrication of bioelectrodes. The easy tuneability of the band gap of CZTS by varying the cation ratio and size of nanoparticles facilitate to impart desirable electrical properties in the material. Butylamine capped spherical CZTS nanoparticles of size 15-16 nm and band gap 2.65 eV have been synthesized by colloidal hot injection technique. The films of CZTS onto ITO substrates are deposited using dip coating technique, and uricase enzyme have been immobilized onto CZTS films using EDC-NHS binding chemistry. Electrochemical analyses of this bioelectrode revealed that the uricase/CZTS/ITO/glass electrode exhibits good linearity over a wide range of 0-700 µM uric acid concentration with a limit of detection (LOD) of 0.066 µM. The low value of 0.13 × 10-4 M of Michaelis-Menten constant (Km) indicate the enhanced affinity of immobilized enzyme (uricase) towards uric acid. Thus, the present report confirms the promising application of the p-type CZTS thin film matrix for the realization of an electrochemical biosensor.

An insight into the mechanism of charge-transfer of hybrid polymer:ternary/quaternary chalcopyrite colloidal nanocrystals.

In this work, we have demonstrated the structural and optoelectronic properties of the surface of ternary/quaternary (CISe/CIGSe/CZTSe) chalcopyrite nanocrystallites passivated by tri-n-octylphosphine-oxide (TOPO) and tri-n-octylphosphine (TOP) and compared their charge transfer characteristics in the respective polymer: chalcopyrite nanocomposites by dispersing them in poly(3-hexylthiophene) polymer. It has been found that CZTSe nanocrystallites due to their high crystallinity and well-ordered 3-dimensional network in its pristine form exhibit a higher steric- and photo-stability, resistance against coagulation and homogeneity compared to the CISe and CIGSe counterparts. Moreover, CZTSe nanocrystallites display efficient photoluminescence quenching as evident from the high value of the Stern-Volmer quenching constant (K SV) and eventually higher charge transfer efficiency in their respective polymer P3HT:CZTSe composites. We modelled the dependency of the charge transfer from the donor and the charge separation mechanism across the donor-acceptor interface from the extent of crystallinity of the chalcopyrite semiconductors (CISe/CIGSe/CZTSe). Quaternary CZTSe chalcopyrites with their high crystallinity and controlled morphology in conjunction with regioregular P3HT polymer is an attractive candidate for hybrid solar cells applications.