Electrical transport properties of [(1 - x)succinonitrile:xpoly(ethylene oxide)]-LiCF3SO3-Co[tris-(2,2'-bipyridine)]3(TFSI)2-Co[tris-(2,2'-bipyridine)]3(TFSI)3 solid redox mediators.

A solid redox mediator (solid electrolyte) with an electrical conductivity (σ25°C) greater than 10-4 S cm-1 is an essential requirement for a dye-sensitized solar cell in the harsh weather of Gulf countries. This paper reports the electrical properties of solid redox mediators prepared using highly dissociable ionic salts: Co[tris-(2,2'-bipyridine)]3(TFSI)2, Co[tris-(2,2'-bipyridine)]3(TFSI)3, and LiCF3SO3 as a source of Co2+, Co3+, and Li+ ions, respectively, in a solid matrix: [(1 - x)succinonitrile:xpoly(ethylene oxide)], where x = 0, 0.5, and 1 in weight fraction. In the presence of large size of cations (Co2+ and Co3+) and large-sized and weakly-coordinated anions (TFSI- and CF3SO3-), only the succinonitrile-poly(ethylene oxide) blend (x = 0.5) resulted in highly conductive amorphous regions with σ25°C of 4.7 × 10-4 S cm-1 for EO/Li+ = 108.4 and 3.1 × 10-4 S cm-1 for EO/Li+ = 216.8. These values are slightly lower than 1.5 × 10-3 S cm-1 for x = 0 and higher than 6.3 × 10-7 S cm-1 for x = 1. Only blend-based electrolytes exhibited a downward curve in the log σ-T-1 plot, a low value of pseudo-activation energy (0.06 eV), a high degree of transparency, and high thermal stability, making it useful for device applications.

Electronic Structure and Optical Properties of Inorganic Pm3m and Pnma CsPbX3 (X = Cl, Br, I) Perovskite: A Theoretical Understanding from Density Functional Theory Calculations.

In this study, we investigated the optoelectronic properties of cubic (Pm3m) and orthorhombic (Pnma) CsPbX3 (X = I, Br, and Cl). We utilized the full potential linear augmented plane wave method, which is implemented in the WIEN2k code, to facilitate the investigation. Different exchange potentials were used to analyze the optoelectronic behavior using the available density functional theory methods. Our findings revealed that CsPbX3 perovskites display direct band gaps at the R and Г points for cubic (Pm3m) and orthorhombic (Pnma) structures, respectively. Among the exchange potentials, the mBJ-GGA method provided the most accurate results. These outcomes concurred with the experimental results. In both Pm3m and Pnma structures, interesting changes were observed when iodide (I) was replaced with bromine (Br) and then chlorine (Cl). The direct band gap at the R and Г points shifted to higher energy levels. Similarly, when I was replaced with Br and Cl, there was a noticeable decrease in the absorption coefficient, dielectric constants, refractive index, and reflectivity, in addition to a band gap shift to higher energy levels.

Surface Passivation for Promotes Bi-Excitonic Amplified Spontaneous Emission in CsPb(Br/Cl)3 Perovskite at Room Temperature.

Perovskite-type lead halides exhibit promising performances in optoelectronic applications, for which lasers are one of the most promising applications. Although the bulk structure has some advantages, perovskite has additional advantages at the nanoscale owing to its high crystallinity given by a lower trap density. Although the nanoscale can produce efficient light emission, its comparatively poor chemical and colloidal stability limits further development of devices based on this material. Nevertheless, bulk perovskites are promising as optical amplifiers. There has been some developmental progress in the study of optical response and amplified spontaneous emission (ASE) as a benchmark for perovskite bulk phase laser applications. Therefore, to achieve high photoluminescence quantum yields (PLQYs) and large optical gains, material development is essential. One of the aspects in which these goals can be achieved is the incorporation of a bulk structure of high-quality crystallization films based on inorganic perovskite, such as cesium lead halide (CsPb(Br/Cl)3), in polymethyl methacrylate (PMMA) polymer and encapsulation with the optimal thickness of the polymer to achieve complete surface coverage, prevent degradation, surface states, and surface defects, and suppress emission at depth. Sequential evaporation of the perovskite precursors using a single-source thermal evaporation technique (TET) effectively deposited two layers. The PL and ASEs of the bare and modified films with a thickness of 400 nm PMMA were demonstrated. The encapsulation layer maintained the quantum yield of the perovskite layer in the air for more than two years while providing added optical gain compared to the bare film. Under a picosecond pulse laser, the PL wavelength of single excitons and ASE wavelength associated with the stimulated decay of bi-excitons were achieved. The two ASE bands were highly correlated and competed with each other; they were classified as exciton and bi-exciton recombination, respectively. According to the ASE results, bi-exciton emission could be observed in an ultrastable CsPb(Br/Cl)3 film modified by PMMA with a very low excitation energy density of 110 µJ/cm2. Compared with the bare film, the ASE threshold was lowered by approximately 5%. A bi-exciton has a binding energy (26.78 meV) smaller than the binding energy of the exciton (70.20 meV).

Successful Growth of TiO2 Nanocrystals with {001} Facets for Solar Cells.

The growth of nanocrystals (NCs) from metal oxide-based substrates with exposed high-energy facets is of particular importance for many important applications, such as solar cells as photoanodes due to the high reactivity of these facets. The hydrothermal method remains a current trend for the synthesis of metal oxide nanostructures in general and titanium dioxide (TiO2) in particular since the calcination of the resulting powder after the completion of the hydrothermal method no longer requires a high temperature. This work aims to use a rapid hydrothermal method to synthesize numerous TiO2-NCs, namely, TiO2 nanosheets (TiO2-NSs), TiO2 nanorods (TiO2-NRs), and nanoparticles (TiO2-NPs). In these ideas, a simple non-aqueous one-pot solvothermal method was employed to prepare TiO2-NSs using tetrabutyl titanate Ti(OBu)4 as a precursor and hydrofluoric acid (HF) as a morphology control agent. Ti(OBu)4 alone was subjected to alcoholysis in ethanol, yielding only pure nanoparticles (TiO2-NPs). Subsequently, in this work, the hazardous chemical HF was replaced by sodium fluoride (NaF) as a means of controlling morphology to produce TiO2-NRs. The latter method was required for the growth of high purity brookite TiO2 NRs structure, the most difficult TiO2 polymorph to synthesize. The fabricated components are then morphologically evaluated using equipment, such as transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), electron diffraction (SAED), and X-ray diffraction (XRD). In the results, the TEM image of the developed NCs shows the presence of TiO2-NSs with an average side length of about 20-30 nm and a thickness of 5-7 nm. In addition, the image TEM shows TiO2-NRs with diameters between 10 and 20 nm and lengths between 80 and 100 nm, together with crystals of smaller size. The phase of the crystals is good, confirmed by XRD. The anatase structure, typical of TiO2-NS and TiO2-NPs, and the high-purity brookite-TiO2-NRs structure, were evident in the produced nanocrystals, according to XRD. SAED patterns confirm that the synthesis of high quality single crystalline TiO2-NSs and TiO2-NRs with the exposed {001} facets are the exposed facets, which have the upper and lower dominant facets, high reactivity, high surface energy, and high surface area. TiO2-NSs and TiO2-NRs could be grown, corresponding to about 80% and 85% of the {001} outer surface area in the nanocrystal, respectively.

Structural, Thermal, and Electrical Properties of Poly(Ethylene Oxide)-Tetramethyl Succinonitrile Blend for Redox Mediators.

An all-solid−state dye-sensitized solar cell is one of the non-fossil fuel-based electrochemical devices for electricity generation in a high-temperature region. This device utilizes a redox mediator, which is a fast ion-conducting solid polymer electrolyte (SPE). The SPE makes the device economical, thinner, and safer in high-temperature regions. The SPE generally has a form of matrix−plasticizer−redox salts. Succinonitrile (SN) is generally employed as a plasticizer for reducing the crystallinity of poly(ethylene oxide), abbreviated as PEO, a common polymeric matrix. In the present paper, the structural and thermal properties of tetramethyl succinonitrile (TMSN) were compared with SN for its application as a solid plasticizer. TMSN and SN both are plastic crystals. TMSN has four methyl groups by replacing the hydrogen of the SN, resulting in higher molecular weight, solid−solid phase transition temperature, and melting temperature. We thoroughly studied the structural, thermal, and electrical properties of the [(1−x)PEO: xTMSN] blend for utilizing it as a matrix, where x = 0−0.25 in mole fraction. The FT-IR spectra and XRD patterns of the blends exhibited PEO-alike up to x = 0.15 mole and TMSN-alike for x > 0.15 mole. Differential scanning calorimetry revealed formation of a eutectic phase from x = 0.1 mole and phase separation from x = 0.15 mole. The blends with x = 0.1−0.15 mole had a low value of PEO crystallinity. Thermogravimetric analysis showed thermal stability of the blends up to 75 °C. The blends exhibited electrical conductivity, σ25°C more than 10−9 S cm−1, and Arrhenius behavior (activation energy, ~0.8 eV) in a temperature region, 25−50 °C.

Amplified Spontaneous Emission from Thermally Evaporated High-Quality Thin Films of CsPb(Br1-xYx)3 (Y = I, Cl) Perovskites.

As a wavelength-tunable lasing material, perovskites are now generating a lot of scientific attention. Conventional solution-processed CsPbX3 perovskite films sometimes suffer unavoidable pinhole defects and poor surface morphology, severely limiting their performance on amplified spontaneous emission (ASE) and lasing application. Herein, a thermal evaporation approach is explored in our work to achieve a uniform and high-coverage CsPb(Br1-xYx)3 (Y = I, Cl) perovskites polycrystalline thin film. The ASE of these films was studied using a picosecond laser system. The ASE profile increases rapidly over the narrow peak in relation to the laser pump intensity, confirming the development of stimulated emission. ASE began when the energy density threshold was reached and ranged between 25 and 170 µJ/cm2 per pulse for perovskite materials when replacing I with Br and then Cl. This work emphasizes the notable optical properties of high-quality perovskite thin films, leading to possible accessible uses in optoelectronic applications.

Electrical Transport, Structural, Optical and Thermal Properties of [(1-x)Succinonitrile: xPEO]-LiTFSI-Co(bpy)3(TFSI)2-Co(bpy)3(TFSI)3 Solid Redox Mediators.

The solar cell has been considered one of the safest modes for electricity generation. In a dye-sensitized solar cell, a commonly used iodide/triiodide redox mediator inhibits back-electron transfer reactions, regenerates dyes, and reduces triiodide into iodide. The use of iodide/triiodide redox, however, imposes several problems and hence needs to be replaced by alternative redox. This paper reports the first Co2+/Co3+ solid redox mediators, prepared using [(1−x)succinonitrile: xPEO] as a matrix and LiTFSI, Co(bpy)3(TFSI)2, and Co(bpy)3(TFSI)3 as sources of ions. The electrolytes are referred to as SN_E (x = 0), Blend 1_E (x = 0.5 with the ethereal oxygen of the PEO-to-lithium ion molar ratio (EO/Li+) of 113), Blend 2_E (x = 0.5; EO/Li+ = 226), and PEO_E (x = 1; EO/Li+ = 226), which achieved electrical conductivity of 2.1 × 10−3, 4.3 × 10−4, 7.2 × 10−4, and 9.7 × 10−7 S cm−1, respectively at 25 °C. Only the blend-based polymer electrolytes exhibited the Vogel-Tamman-Fulcher-type behavior (vitreous nature) with a required low pseudo-activation energy (0.05 eV), thermal stability up to 125 °C, and transparency in UV-A, visible, and near-infrared regions. FT-IR spectroscopy demonstrated the interaction between salt and matrix in the following order: SN_E < Blend 2_E < Blend 1_E << PEO_E. The results were compared with those of acetonitrile-based liquid electrolyte, ACN_E.

Tetramethyl Succinonitrile as a Solid Plasticizer in a Poly(ethylene oxide)8 -LiI-I2 Solid Polymer Electrolyte.

Dye-sensitized solar cell (DSSC) is a promising alternative to the commercially available amorphous silicon-based solar cell because of several advantageous properties. A DSSC with a fast ion conducting solid polymer electrolyte is required for the arid atmosphere of Gulf countries. In this work, a new matrix, poly(ethylene oxide)-tetramethyl succinonitrile blend to synthesize a blend-LiI-I2 solid polymer electrolyte for the DSSC application has been proposed. The tetramethyl succinonitrile is a member of plastic crystal with a solid-solid phase transition temperature (Tpc ) of ≈71 °C and melting temperature (Tm ) of ≈170.5 °C. Its molar fraction, 0.1-0.15 is sufficient enough for synthesizing a polymer electrolyte with electrical conductivity of >10-4 S cm-1 at room temperature. This electrolyte shows Vogel-Tamman-Fulcher type behavior with a low value (≈0.083 eV) of pseudo-activation energy for easy ion transport. The results of Fourier-transform infrared spectroscopy, X-ray diffractometry, and differential scanning calorimetry studies reveal the plasticizing effect of tetramethyl succinonitrile to form an amorphous phase. This electrolyte results in a ≈661% gain in short-circuit current density and thereby a ≈552% gain in the cell efficiency (≈3.5%) with respect to the DSSC prepared with the tetramethyl succinonitrile-free electrolyte.

Density Functional Theory Analysis of Structural, Electronic, and Optical Properties of Mixed-Halide Orthorhombic Inorganic Perovskites.

Inorganic metal-halide perovskites hold a lot of promise for solar cells, light-emitting diodes, and lasers. A thorough investigation of their optoelectronic properties is ongoing. In this study, the accurate modified Becke Johnson generalized gradient approximation (mBJ-GGA) method without/with spin orbital coupling (SOC) implemented in the WIEN2k code was used to investigate the effect of mixed I/Br and Br/Cl on the electronic and optical properties of orthorhombic CsPb(I1-x Br x )3 and CsPb(Br1-x Cl x )3 perovskites, while the Perdew-Burke-Ernzerhof generalized gradient approximation (PBE-GGA) method was used to investigate their structural properties. The calculated band gap (E g) using the mBJ-GGA method was in good agreement with the experimental values reported, and it increased clearly from 1.983 eV for CsPbI3 to 2.420 and 3.325 eV for CsPbBr3 and CsPbCl3, respectively. The corrected mBJ + SOC E g value is 1.850 eV for CsPbI3, which increased to 2.480 and 3.130 eV for CsPbBr3 and CsPbCl3, respectively. The calculated photoabsorption coefficients show a blue shift in absorption, indicating that these perovskites are suitable for optical and optoelectronic devices.

Enhancement of Light Amplification of CsPbBr3 Perovskite Quantum Dot Films via Surface Encapsulation by PMMA Polymer.

Photonic devices based on perovskite materials are considered promising alternatives for a wide range of these devices in the future because of their broad bandgaps and ability to contribute to light amplification. The current study investigates the possibility of improving the light amplification characteristics of CsPbBr3 perovskite quantum dot (PQD) films using the surface encapsulation technique. To further amplify emission within a perovskite layer, CsPbBr3 PQD films were sandwiched between two transparent layers of poly(methyl methacrylate) (PMMA) to create a highly flexible PMMA/PQD/PMMA waveguide film configuration. The prepared perovskite film, primed with a polymer layer coating, shows a marked improvement in both emission efficiency and amplified spontaneous emission (ASE)/laser threshold compared with bare perovskite films on glass substrates. Additionally, significantly improved photoluminescence (PL) and long decay lifetime were observed. Consequently, under pulse pumping in a picosecond duration, ASE with a reduction in ASE threshold of ~1.2 and 1.4 times the optical pumping threshold was observed for PQDs of films whose upper face was encapsulated and embedded within a cavity comprising two PMMA reflectors, respectively. Moreover, the exposure stability under laser pumping was greatly improved after adding the polymer coating to the top face of the perovskite film. Finally, this process improved the emission and PL in addition to enhancements in exposure stability. These results were ascribed in part to the passivation of defects in the perovskite top surface, accounting for the higher PL intensity, the slower PL relaxation, and for about 14 % of the ASE threshold decrease.

Achieving Optical Gain of the CsPbBr3 Perovskite Quantum Dots and Influence of the Variable Stripe Length Method.

High-quality inorganic cesium lead halide perovskite quantum dot (CsPbBr3 PQD) thin films were successfully deposited directly from a powdered source and used as an active laser medium following the examination of their distinctive surface and structural properties. To determine the suitability of the CsPbBr3 PQDs as an active laser medium, amplified spontaneous emission (ASE) and optical gain properties were investigated under picosecond pulse excitation using the variable stripe length (VSL) method. The thin film of CsPbBr3 PQDs has exhibited a sufficient value of the optical absorption coefficient of ∼0.86 × 105 cm-1 near the band edge and a direct band gap energy E g ∼2.38 eV. The samples showed enhanced emission, and ASE was successfully recorded at a low threshold. The light emitted from the edge was observed near 2.40 and 2.33 eV for the stimulated emission (SE) and ASE regimes, respectively. The nonradiative decay contributes excitons dominant over biexcitons in the sample edge emission above the ASE threshold, making it practical for CsPbBr3 PQDs to be used as optical gain media without undergoing repeated SE processes above the threshold over long periods. A high value of the optical gain coefficient was recorded at 346 cm-1.

Single-Source Thermal Evaporation Growth and the Tuning Surface Passivation Layer Thickness Effect in Enhanced Amplified Spontaneous Emission Properties of CsPb(Br0.5Cl0.5)3 Perovskite Films.

High-quality inorganic cesium lead halide perovskite CsPb(Br0.5Cl0.5)3 thin films were successfully achieved through evaporation of the precursors and deposition sequentially by a single-source thermal evaporation system. The different melting points of the precursors were enabled us to evaporate precursors one by one in one trip. The resulting films through its fabrication were smooth and pinhole-free. Furthermore, this technique enabled complete surface coverage by high-quality perovskite crystallization and more moisture stability oppositely of that produce by solution-processed. Then the perovskite films were encapsulated by evaporated a polymethyl methacrylate (PMMA) polymer as a specialized surface passivation approach with various thicknesses. The blue emission, high photoluminescence quantum yield (PLQY), stable, and low threshold of amplified spontaneous emission (ASE) properties of CsPb(Br0.5Cl0.5)3 films in the bulk structure at room temperature were achieved. The effects of the surface-passivation layer and its thickness on the optical response were examined. Detailed analysis of the dependence of ASE properties on the surface passivation layer thickness was performed, and it was determined this achieves performance optimization. The ASE characteristics of bare perovskite thin film were influenced by the incorporation of the PMMA with various thicknesses. The improvement to the surface layer of perovskite thin films compared to that of the bare perovskite thin film was attributed to the combination of thermal evaporation deposition and surface encapsulation. The best results were achieved when using a low PMMA thickness up to 100 nm and reducing the ASE threshold by ~11 µJ/cm2 when compared with free-encapsulation and by ~13 µJ/cm2 when encapsulation occurs at 200 nm or thicker. Compared to the bare CsPb(Br0.5Cl0.5)3, ASE reduced 1.1 times when the PMMA thickness was 100 nm.

Ultra-Stable Polycrystalline CsPbBr3 Perovskite-Polymer Composite Thin Disk for Light-Emitting Applications.

Organic-inorganic halide organometal perovskites have demonstrated very promising performance in optoelectronic applications, but their relatively poor chemical and colloidal stability hampers the further improvement of devices based on these materials. Perovskite material engineering is crucial for achieving high photoluminescence quantum yields (PLQYs) and long stability. Herein, these goals are attained by incorporating bulk-structure CsPbBr3, which prevents colloidal degradation, into polymethyl methacrylate (PMMA) polymer in thin-disk form. This technology can potentially realize future disk lasers with no optical and structural contributions from the polymer. The polycrystalline CsPbBr3 perovskite particles were simply obtained by using a mechanical processing technique. The CsPbBr3 was then incorporated into the PMMA polymer using a solution blending method. The polymer enhanced the PLQYs by removing the surface trap states and increasing the water resistance and stability under ambient conditions. In our experimental investigation, the CsPbBr3/PMMA composites were extraordinarily stable and remained strongly luminescent after water immersion for three months and air exposure for over one year, maintaining 80% of their initial photoluminescence intensity. The CsPbBr3/PMMA thin disk produced amplified spontaneous emission for a long time in air and for more than two weeks in water.

Fabrication of Thin Films from Powdered Cesium Lead Bromide (CsPbBr3) Perovskite Quantum Dots for Coherent Green Light Emission.

High-quality thin films were obtained directly by spin-coating glass substrates with suspensions of powdered cesium lead bromide (CsPbBr3) perovskite quantum dots (PQDs). The structural properties of the films were characterized via transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD) analysis, and atomic force microscopy (AFM). The crystal structure of the CsPbBr3 PQDs was unique. The optical behavior of the CsPbBr3 PQDs, including absorption and emission, was then investigated to determine the absorption coefficient and band gap of the material. The CsPbBr3 PQDs were evaluated as active lasing media and irradiated with a pulsed laser under ambient conditions. The PQDs were laser-active when subjected to optical pumping for pulse durations of 70-80 ps at 15 Hz. Amplified spontaneous emission (ASE) by the CsPbBr3 PQD thin films was observed, and a narrow ASE band (∼5 nm) was generated at a low threshold energy of 22.25 µJ cm-2. The estimated ASE threshold carrier density (n th) was ∼7.06 × 1018 cm-3. Band-gap renormalization (BGR) was indicated by an ASE red shift and a BGR constant of ∼27.10 × 10-8 eV. A large optical absorption coefficient, photoluminescence (PL), and a substantial optical gain indicated that the CsPbBr3 PQD thin films could be embedded in a wide variety of cavity resonators to fabricate unique on-chip coherent light sources.

Structural, Electronic, and Optical Properties of CsPb(Br1-xClx)3 Perovskite: First-Principles Study with PBE-GGA and mBJ-GGA Methods.

The effect of halide composition on the structural, electronic, and optical properties of CsPb(Br1-xClx)3 perovskite was investigated in this study. When the chloride (Cl) content of x was increased, the unit cell volume decreased with a linear function. Theoretical X-ray diffraction analyses showed that the peak (at 2θ = 30.4°) shifts to a larger angle (at 2θ = 31.9°) when the average fraction of the incorporated Cl increased. The energy bandgap (Eg) was observed to increase with the increase in Cl concentration. For x = 0.00, 0.25, 0.33, 0.50, 0.66, 0.75, and 1.00, the Eg values calculated using the Perdew-Burke-Ernzerhof potential were between 1.53 and 1.93 eV, while those calculated using the modified Becke-Johnson generalized gradient approximation (mBJ-GGA) potential were between 2.23 and 2.90 eV. The Eg calculated using the mBJ-GGA method best matched the experimental values reported. The effective masses decreased with a concentration increase of Cl to 0.33 and then increased with a further increase in the concentration of Cl. Calculated photoabsorption coefficients show a blue shift of absorption at higher Cl content. The calculations indicate that CsPb(Br1-xClx)3 perovskite could be used in optical and optoelectronic devices by partly replacing bromide with chloride.

Triplet Energy Transfer Mechanism of Ternary Organic Hybrid Thin Films of PFO/MEH-PPV/CsPbBr3 Perovskite Quantum Dots.

The triplet energy transfer mechanism of novel poly(9,9-di-n-octylflourenyl-2,7-diyl) (PFO)/poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV)/CsPbBr3 perovskite quantum dot (PQD) hybrid thin films was comprehensively investigated. The concentrations of PFO and MEH-PPV in all the specimens were fixed, while the PQD content was varied with various weight ratios and premixed by a solution blending method before it was spin-coated onto glass substrates. The triplet non-radiative Förster resonance energy transfers (FRETs) in the PFO/MEH-PPV/PQDs ternary blend, the dual FRET from PFO to both PQDs and MEH-PPV, and the secondary FRET from PQDs to MEH-PPV were observed. The values of the Förster radius (Ro) of FRET from PFO to MEH-PPV in the presence of various PQD contents (Case I) increased from 92.3 to 104.7 Å, and they decreased gradually from 68.0 to 39.5 Å for FRET from PFO to PQDs in the presence of MEH-PPV (Case II). These Ro values in both cases confirmed the dominance of FRET in ternary hybrid thin films. Upon increasing the PQD content, the distance between the donor and acceptor molecules (RDA) and the conjugation length (Aπ) in both cases gradually decreased. The small values of Ro, RDA, and Aπ with a decrease in the energy transfer lifetime (τET) due to an increase in the PQD contents in both Cases I and II confirmed the efficient FRET in the hybrid. To prevent intermolecular transfer in PFO, the concentrations of MEH-PPV (Case I) and PQDs (Case II) should be decreased to a range of 0.57-0.39 mM and increased in the range of 1.42-7.25 mM.

Reducing Amplified Spontaneous Emission Threshold in CsPbBr3 Quantum Dot Films by Controlling TiO2 Compact Layer.

Amplified spontaneous emission (ASE) threshold in CsPbBr3 quantum dot films is systematically reduced by introducing high quality TiO2 compact layer grown by atomic-layer deposition. Uniform and pinhole-free TiO2 films of thickness 10, 20 and 50 nm are used as a substrates for CsPbBr3 quantum dot films to enhance amplified spontaneous emission performance. The reduction is attributed indirectly to the improved morphology of TiO2 compact layer and subsequently CsPbBr3 active layer as grown on better quality substrates. This is quantified by the reduced roughness of the obtained films to less than 5 nm with 50 nm TiO2 substrate. Considering the used growth method for the quantum dot film, the improved substrate morphology maintains better the structure of the used quantum dots in the precursor solution. This results in better absorption and hence lower threshold of ASE. Besides that, the improved film quality results further in reducing light scattering and hence additional slight optical enhancement. The work demonstrates a potential venue to reduce the amplified spontaneous emission threshold of quantum dot films and therefore enhanced their optical performance.

Density Functional Study of Cubic, Tetragonal, and Orthorhombic CsPbBr3 Perovskite.

Cesium lead bromide (CsPbBr3) perovskite has recently gained significance owing to its rapidly increasing performance when used for light-emitting devices. In this study, we used density functional theory to determine the structural, electronic, and optical properties of the cubic, tetragonal, and orthorhombic temperature-dependent phases of CsPbBr3 perovskite using the full-potential linear augmented plane wave method. The electronic properties of CsPbBr3 perovskite have been investigated by evaluating their changes upon exerting spin-orbit coupling (SOC). The following exchange potentials were used: the local density approximation (LDA), Perdew-Burke-Ernzerhof generalized gradient approximation (PBE-GGA), Engel-Vosko GGA (EV-GGA), Perdew-Burke-Ernzerhof GGA revised for solids (PBEsol-GGA), modified Becke-Johnson GGA (mBJ-GGA), new modified Becke-Johnson GGA (nmBJ-GGA), and unmodified Becke-Johnson GGA (umBJ-GGA). Our band structure results indicated that the cubic, tetragonal, and orthorhombic phases have direct energy bandgaps. By including the SOC effect in the calculations, the bandgaps computed with mBJ-GGA and nmBJ-GGA were found to be in good agreement with the experimental results. Additionally, despite the large variations in their lattice constants, the three CsPbBr3 phases possessed similar optical properties. These results demonstrate a wide temperature range of operation for CsPbBr3.

Rapid Room-Temperature Synthesis of Mesoporous TiO2 Sub-Microspheres and Their Enhanced Light Harvesting in Dye-Sensitized Solar Cells.

Submicron sized mesoporous spheres of TiO2 have been a potential alternative to overcome the light scattering limitations of TiO2 nanoparticles in dye-sensitized solar cells (DSSCs). Currently available methods for the growth of mesoporous TiO2 sub-microspheres involve long and relatively high temperature multi-stage protocols. In this work, TiO2 mesoporous sub-microspheres composed of ~5 nm anatase nanocrystallites were successfully synthesized using a rapid one-pot room-temperature CTAB-based solvothermal synthesis. X-Ray Diffraction (XRD) showed that the grown structures have pure anatase phase. Transmission electron microscopy (TEM) revealed that by reducing the surfactant/precursor concentration ratio, the morphology could be tuned from monodispersed nanoparticles into sub-micron sized mesoporous beads with controllable sizes (50-200 nm) and with good monodispersity as well. The growth mechanism is explained in terms of the competition between homogeneous nucleation/growth events versus surface energy induced agglomeration in a non-micelle CTAB-based soft templating environment. Further, dye-sensitized solar cells (DSSCs) were fabricated using the synthesized samples and characterized for their current-voltage characteristics. Interestingly, the DSSC prepared with 200 nm TiO2 sub-microspheres, with reduced surface area, has shown close efficiency (5.65%) to that of DSSC based on monodispersed 20 nm nanoparticles (5.79%). The results show that light scattering caused by the agglomerated sub-micron spheres could compensate for the larger surface areas provided by monodispersed nanoparticles.

One step synthesis of NiO nanoparticles via solid-state thermal decomposition at low-temperature of novel aqua(2,9-dimethyl-1,10-phenanthroline)NiCl2 complex.

[NiCl2(C14H12N2)(H2O)] complex has been synthesized from nickel chloride hexahydrate (NiCl2·6H2O) and 2,9-dimethyl-1,10-phenanthroline (dmphen) as N,N-bidentate ligand. The synthesized complex was characterized by elemental analysis, infrared (IR) spectroscopy, ultraviolet-visible (UV-vis) spectroscopy and differential thermal/thermogravimetric analysis (TG/DTA). The complex was further confirmed by single crystal X-ray diffraction (XRD) as triclinic with space group P-1. The desired complex, subjected to thermal decomposition at low temperature of 400 °C in an open atmosphere, revealed a novel and facile synthesis of pure NiO nanoparticles with uniform spherical particle; the structure of the NiO nanoparticles product was elucidated on the basis of Fourier transform infrared (FT-IR), UV-vis spectroscopy, TG/DTA, XRD, scanning electron microscopy (SEM), energy-dispersive X-ray spectrometry (EDXS) and transmission electron microscopy (TEM).