Managing Multiple Halide-Related Defects for Efficient and Stable Inorganic Perovskite Solar Cells.

Halide-related surface defects on inorganic halide perovskite not only induce charge recombination but also severely limit the long-term stability of perovskite solar cells. Herein, adopting density functional theory calculation, we verify that iodine interstitials (Ii ) has a low formation energy similar to that of the iodine vacancy (VI ) and is also readily formed on the surface of all-inorganic perovskite, and it is regarded to function as an electron trap. We screen a specific 2,6-diaminopyridine (2,6-DAPy) passivator, which, with the aid of the combined effects from halogen-Npyridine and coordination bonds, not only successfully eliminates the Ii and dissociative I2 but also passivates the abundant VI . Furthermore, the two symmetric neighboring -NH2 groups interact with adjacent halides of the octahedral cluster by forming hydrogen bonds, which further promotes the adsorption of 2,6-DAPy molecules onto the perovskite surface. Such synergetic effects can significantly passivate harmful iodine-related defects and undercoordinated Pb2+ , prolong carrier lifetimes and facilitate the interfacial hole transfer. Consequently, these merits enhance the power-conversion efficiency (PCE) from 19.6 % to 21.8 %, the highest value for this type of solar cells, just as importantly, the 2,6-DAPy-treated CsPbI3-x Brx films show better environmental stability.

Flexible infrared photodetector based on indium antimonide nanowire arrays.

Narrow bandgap semiconductors like indium antimonide (InSb) are very suitable for high-performance room temperature infrared photodetectors, but the fragile nature of the wafer materials hinders their application as flexible/wearable devices. Here, we present a method to fabricate a photodetector device of assembled crystalline InSb nanowire (NW) arrays on a flexible substrate that balances high performance and flexibility, facilitating its application in wearable devices. The InSb NWs were synthesized by means of a vapor-liquid-solid technique, with gold nanoclusters as seeding particles. The morphological and crystal properties were investigated using scanning electron microscopy, x-ray diffraction and high-resolution transmission electron microscopy, which revealed the unique spike shape and high crystallinity with (111) and (220) planes of InSb NWs. The flexible infrared photodetector devices were fabricated by transferring the NWs onto transparent and stretchable polydimethylsiloxane substrate with pre-deposited gold electrodes. Current versus time measurement of the photodetector devices under light showed photoresponsivity and sensitivity to mid-infrared at bias as low as 0.1 V while attached to curved surfaces (suitable for skin implants). A high-performance NW device yielded efficient rise and decay times down to 1 s and short time lag for infrared detection. Based on dark current, calculated specific detectivity of the flexible photodetector was 1.4 × 1012Jones. The performance and durability render such devices promising for use as wearable infrared photodetectors.

Towards High Performance: Solution-Processed Perovskite Solar Cells with Cu-Doped CH3NH3PbI3.

Perovskite solar cells (PSCs) have demonstrated remarkable photovoltaic performance, positioning themselves as promising devices in the field. Theoretical calculations suggest that copper (Cu) can serve as an effective dopant, potentially occupying interstitial sites in the perovskite structure, thereby reducing the energy barrier and enhancing carrier extraction. Subsequent experimental investigations confirm that adding CuI as an additive to MAPbI3-based perovskite cells improves optoelectronic properties and overall device performance. Optimizing the amount of Cu (0.01 M) has been found to significantly enhance crystalline quality and grain size, leading to improved light absorption and suppressed carrier recombination. Consequently, the power conversion efficiency (PCE) of Cu-doped PSCs increased from 16.3% to 18.2%. However, excessive Cu doping (0.1 M) negatively impacts morphology, resulting in inferior optical properties and diminished device performance. Furthermore, Cu-doped PSCs exhibit higher stabilized power output (SPO) compared to pristine cells. This study underscores the substantial benefits of Cu doping for advancing the development of highly efficient PSCs.

Modifying Surface Termination by Bidentate Chelating Strategy Enables 13.77% Efficient Kesterite Solar Cells.

Surfaces display discontinuities in the kesterite-based polycrystalline films can produce large defect densities, including strained and dangling bonds. These physical defects tend to introduce electronic defects and surface states, which can greatly promote nonradiative recombination of electron-hole pairs and damage device performance. Here, an effective chelation strategy is reported to suppress these harmful physical defects related to unterminated Cu, Zn, and Sn sites by modifying the surface of Cu2ZnSn(S,Se)4 (CZTSSe) films with sodium diethyldithiocarbamate (NaDDTC). The conjoint theoretical calculations and experimental results reveal that the NaDDTC molecules can be coordinate to surface metal sites of CZTSSe films via robust bidentate chelating interactions, effectively reducing surface undercoordinated defects and passivating the electron trap states. Consequently, the solar cell efficiency of the NaDDTC-treated device is increased to as high as 13.77% under 100 mW cm-2 illumination, with significant improvement in fill factor and open-circuit voltage. This surface chelation strategy provides strong surface termination and defect passivation for further development and application of kesterite-based photovoltaics.

Heterointerface Design of Perovskite Single Crystals for High-Performance X-Ray Imaging.

Metal halide perovskite single crystals (MHP-SCs) are known for their facile fabrication into large sizes using inexpensive solution methods. Owing to their combination of large mobility-lifetime products and strong X-ray absorption, they are considered promising materials for efficient X-ray detection. However, they suffer from large dark currents and severe ion migration, which limit their sensitivity and stability in critical X-ray detection applications. Herein, a heterointerface design is proposed to reduce both the dark current and ion migration by forming a heterojunction. In addition, the carrier transport performance is significantly improved using heterointerface engineering by designing a gradient band structure in the SCs. The SC heterojunction detectors exhibit a high sensitivity of 3.98 × 105 µC Gyair -1 cm-2 with a low detection limit of 12.2 nGyair s-1 and a high spatial resolution of 10.2 lp mm-1 during imaging. These values are among the highest reported for state-of-the-art MHP X-ray detectors. Moreover, the detectors show excellent stability under continuous X-ray irradiation and maintainclear X-ray imaging after 240 d. This study provides novel insights into the design and fabrication of X-ray detectors with high detection efficiency and stability, which are beneficial for developing inexpensive, high-resolution X-ray imaging equipment.

Elaboration of Silicon Nanostructures with Vapor-Phase Silver Assisted Chemical Etching: Correlation between Structural and Optical Properties.

Based on the widely used wet metal-assisted electroless etching, we develop in this work a novel vapor-phase silver-assisted chemical etching (VP-Ag-ACE) suitable for the elaboration of highly doped p-silicon (Si) nanostructures with strong, visible, and multi-peak photoluminescence (PL) emissions. The lateral and vertical etching rates (LER and VER) were discussed based on the etching mechanism of the VP-Ag-ACE. The antireflective suitability of the vapor-etched layer has been evaluated by a reflectivity measurement and exhibits reflectivity values lower than 3%. The PL emission at both room and low temperatures emissions were deeply discussed and correlated with the structural properties of the Si morphologies and their surface states based on the FTIR results.

Interlayer-Spacing Engineering of Lead-Free Perovskite Single Crystal for High-Performance X-Ray Imaging.

Lead-free A3 Bi2 I9 -type perovskites are demonstrated as a class of promising semiconductors for high-performance X-ray detection due to their high bulk resistivity and strong X-ray absorption, as well as reduced ion migration. However, due to their long interlamellar distance along their c-axis, their limited carrier transport along the vertical direction is a bottleneck for their detection sensitivity. Herein, a new A-site cation of aminoguanidinium (AG) with all-NH2 terminals is designed to shorten the interlayer spacing by forming more and stronger NH···I hydrogen bonds. The prepared large AG3 Bi2 I9 single crystals (SCs) render shorter interlamellar distance for a larger mobility-lifetime product of 7.94 × 10-3  cm2  V-1 , which is three times higher than the value measured on the best MA3 Bi2 I9 SC (2.87 × 10-3  cm2  V-1 ). Therefore, the X-ray detectors fabricated on the AG3 Bi2 I9 SC exhibit high sensitivity of 5791 uC Gy-1  cm-2 , a low detection limit of 2.6 nGy s-1, and a short response time of 690 µs, all of which are far better than those of the state-of-the-art MA3 Bi2 I9 SC detectors. The combination of high sensitivity and high stability enables astonishingly high spatial resolution (8.7 lp mm-1 ) X-ray imaging. This work will facilitate the development of low-cost and high-performance lead-free X-ray detectors.

Tailored Cysteine-Derived Molecular Structures toward Efficient and Stable Inorganic Perovskite Solar Cells.

Surface-defect-triggered non-radiative charge recombination and poor stability have become the main roadblock to continued improvement in inorganic perovskite solar cells (PSCs). Herein, the main culprits are identified on the inorganic perovskite surface by first-principles calculations, and to purposefully design a brand-new passivator, Boc-S-4-methoxy-benzyl-l-cysteine (BMBC), whose multiple Lewis-based functional groups (NH, S and CO) to suppress halide vacancies and coordinate with undercoordinated Pb2+ through typical Lewis baseacid reactions. The tailored electron-donating methoxyl group (CH3 O-) can cause an increased electron density on the benzene ring, which strengthens the interaction with undercoordinated Pb2+ via electrostatic interactions. This BMBC passivation can reduce the surface trap density, enlarge grains, prolong the charge lifetime, and cause a more suitable energy-level alignment. In addition, the hydrophobic tert-butyl in butoxycarbonyl (Boc-) group ensures that BMBC is uniformly covered and prevents harmful aggregation through steric repulsion at the perovskite/hole-transporting layer (HTL) interface, thus providing a hydrophobic umbrella to resist moisture invasion. Consequently, the combination of the above increases the efficiency of CsPbI3-x Brx PSC from 18.6% to 21.8%, the highest efficiency for this type of inorganic metal halide PSCs so far, as far as it is known. Moreover, the device exhibits higher environmental and thermal stability.

MNOS stack for reliable, low optical loss, Cu based CMOS plasmonic devices.

We study the electro optical properties of a Metal-Nitride-Oxide-Silicon (MNOS) stack for a use in CMOS compatible plasmonic active devices. We show that the insertion of an ultrathin stoichiometric Si(3)N(4) layer in a MOS stack lead to an increase in the electrical reliability of a copper gate MNOS capacitance from 50 to 95% thanks to a diffusion barrier effect, while preserving the low optical losses brought by the use of copper as the plasmon supporting metal. An experimental investigation is undertaken at a wafer scale using some CMOS standard processes of the LETI foundry. Optical transmission measurments conducted in a MNOS channel waveguide configuration coupled to standard silicon photonics circuitry confirms the very low optical losses (0.39 dB.µm(-1)), in good agreement with predictions using ellipsometric optical constants of Cu.

Perovskite Quantum Dots in Solar Cells.

Perovskite quantum dots (PQDs) have captured a host of researchers' attention due to their unique properties, which have been introduced to lots of optoelectronics areas, such as light-emitting diodes, lasers, photodetectors, and solar cells. Herein, the authors aim at reviewing the achievements of PQDs applied to solar cells in recent years. The engineering concerning surface ligands, additives, and hybrid composition for PQDSCs is outlined first, followed by analyzing the reasons of undesired performance of PQDSCs. Subsequently, a novel overview that PQDs are utilized to improve the photovoltaic performance of various kinds of solar cells, is provided. Finally, this review is summarized and some challenges and perspectives concerning PQDs are also discussed.

Recent Developments in Upscalable Printing Techniques for Perovskite Solar Cells.

Just over a decade, perovskite solar cells (PSCs) have been emerged as a next-generation photovoltaic technology due to their skyrocketing power conversion efficiency (PCE), low cost, and easy manufacturing techniques compared to Si solar cells. Several methods and procedures have been developed to fabricate high-quality perovskite films to improve the scalability and commercialize PSCs. Recently, several printing technologies such as blade-coating, slot-die coating, spray coating, flexographic printing, gravure printing, screen printing, and inkjet printing have been found to be very effective in controlling film formation and improving the PCE of over 21%. This review summarizes the intensive research efforts given for these printing techniques to scale up the perovskite films as well as the hole transport layer (HTL), the electron transport layer (ETL), and electrodes for PSCs. In the end, this review presents a description of the future research scope to overcome the challenges being faced in the printing techniques for the commercialization of PSCs.

Effect of Solvent Residue in the Thin-Film Fabrication on Perovskite Solar Cell Performance.

Organic-inorganic Pb-based halide perovskite photoelectrical materials, especially perovskite solar cells (PSCs), have attracted attention due to the significant efforts in improving the power conversion efficiency (PCE) to above 25%. However, the stability issue of the PSCs restricts their further development for commercialization. Strategies are designed to keep moisture and oxygen out of the perovskite films, such as additive, surface passivation, and solvent engineering; however, usually, the corrosion of active films by the residual solvent is mostly ignored. Solvent residue is the paramount factor influencing the stability of the perovskite film prepared by the solution method, and most solvents can be easily absorbed and accelerate the perovskite film decomposition. Here, we studied the residual solvent effect on two kinds of perovskite films obtained by different annealing processes: hot air annealing and hot bench annealing. Several detection techniques were used to study the performance of two different annealing methods, including time-of-flight secondary ion mass spectrometry (ToF-SIMS), thermogravimetric analysis (TGA), and field-emission scanning electron microscopy (FESEM). The perovskite film obtained by hot air annealing shows less residual solvent and better device performance than the hot bench annealing method. This method is expected to provide insight into reducing solvent residue to improve the stability of the PSCs, especially for future commercialization.

Wide-Bandgap Organic-Inorganic Lead Halide Perovskite Solar Cells.

Under the groundswell of calls for the industrialization of perovskite solar cells (PSCs), wide-bandgap (>1.7 eV) mixed halide perovskites are equally or more appealing in comparison with typical bandgap perovskites when the former's various potential applications are taken into account. In this review, the progress of wide-bandgap organic-inorganic hybrid PSCs-concentrating on the compositional space, optimization strategies, and device performance-are summarized and the issues of phase segregation and voltage loss are assessed. Then, the diverse applications of wide-bandgap PSCs in semitransparent devices, indoor photovoltaics, and various multijunction tandem devices are discussed and their challenges and perspectives are evaluated. Finally, the authors conclude with an outlook for the future development of wide-bandgap PSCs.

Highly Efficient and Stable CsPbTh3 (Th = I, Br, Cl) Perovskite Solar Cells by Combinational Passivation Strategy.

The distorted lead iodide octahedra of all-inorganic perovskite based on triple halide-mixed CsPb(I2.85 Br0.149 Cl0.001 ) framework have made a tremendous breakthrough in its black phase stability and photovoltaic efficiency. However, their performance still suffers from severe ion migration, trap-induced nonradiative recombination, and black phase instability due to lower tolerance factor and high total energy. Here, a combinational passivation strategy to suppress ion migration and reduce traps both on the surface and in the bulk of the CsPhTh3 perovskite film is developed, resulting in improved power conversion efficiency (PCE) to as high as 19.37%. The involvement of guanidinium (GA) into the CsPhTh3 perovskite bulk film and glycocyamine (GCA) passivation on the perovskite surface and grain boundary synergistically enlarge the tolerance factor and suppress the trap state density. In addition, the acetate anion as a nucleating agent significantly improves the thermodynamic stability of GA-doped CsPbTh3 film through the slight distortion of PbI6 octahedra. The decreased nonradiative recombination loss translates to a high fill factor of 82.1% and open-circuit voltage (VOC ) of 1.17 V. Furthermore, bare CsPbTh3 perovskite solar cells without any encapsulation retain 80% of its initial PCE value after being stored for one month under ambient conditions.

In(Ga)N Nanostructures and Devices Grown by Molecular Beam Epitaxy and Metal-Assisted Photochemical Etching.

This review summarizes the recent research on nitride nanostructures and their applications. We cover recent advances in the synthesis and growth of porous structures and low-dimensional nitride nanostructures via metal-assisted photochemical etching and molecular beam epitaxy. The growth of nitride materials on various substrates, which improves their crystal quality, doping efficiency, and flexibility of tuning performance, is discussed in detail. Furthermore, the recent development of In(Ga)N nanostructure applications (light-emitting diodes, lasers, and gas sensors) is presented. Finally, the challenges and directions in this field are addressed.

Optical Properties and First-Principles Study of CH3NH3PbBr3 Perovskite Structures.

Solution-processed organic-inorganic hybrid perovskites have attracted attention as light-harvesting materials for solar cells and photonic applications. The present study focuses on cubic single crystals and microstructures of CH3NH3PbBr3 perovskite fabricated by a one-step solution-based self-assembly method. It is seen that, in addition to the nucleation from the precursor solution, crystallization occurs when the solution is supersaturated, followed by the formation of a small nucleus of CH3NH3PbBr3 that self-assembles into bigger hollow cubes. A three-dimensional (3D) fluorescence microscopy investigation of hollow cubes confirmed the formation of hollow plates on the bottom; then, the growth starts from the perimeter and propagates to the center of the cube. Furthermore, the growth in the (001) direction follows a layer-by-layer growth model to form a complete cube, confirmed by scanning electronic microscopy (SEM) observations. Two-dimensional (2D)-3D fluorescence microscopy and photoluminescence (PL) measurements confirm a peak emission at 535 nm. To get more insights into the structural and optical properties, density functional theory (DFT) simulations were conducted. The electronic and optical properties calculated by DFT are in agreement with the obtained experimental values. The density-of-state (DOS) calculations revealed that the valence band maximum (VBM) consists of states contributed by Br and Pb, which agrees with the X-ray photoelectron spectroscopy valence band (XPS VB) measurements.

Cubes, squares, and books: a simple transition metal/bridging ligand combination can lead to a surprising range of structural types with the same metal/ligand proportions.

Reaction of two structurally related bridging ligands L(26Py) and L(13Ph), in which two bidentate chelating pyrazolyl-pyridine units are connected to either a 2,6-pyridine-diyl or 1,3-benzene-diyl central group via methylene spacers, with first-row transition metal dications, results in a surprising variety of structures. The commonest is that of an octanuclear coordination cage [M(8)L(12)]X(16) [M = Co(II) or Zn(II); X = perchlorate or tetrafluoroborate] in which a metal ion is located at each of the eight vertices of an approximate cube, and one bis-bidentate bridging ligand spans each edge. The arrangement of fac and mer tris-chelate metal centers around the inversion center results in approximate (non-crystallographic) S(6) symmetry. Another structural type observed in the solid state is a hexanuclear complex [Co(6)(L(13Ph))(9)](ClO(4))(12) in which the six metal ions are in a rectangular array (two rows of three), folded about the central Co-Co vector like a partially open book, with each metal-metal edge containing one bridging ligand apart from the two outermost metal-metal edges which are spanned by a pair of bridging ligands in a double helical array. The final structural type we observed is a tetranuclear square [Ni(4)(L(26Py))(6)](BF(4))(8), with the four Ni-Ni edges spanned alternately by one and two bridging ligand such that it effectively consists of two dinuclear double helicates cross-linked by additional bridging ligands. A balance between the "cube" and "book" forms, which varied from compound to compound, was observed in solution in many cases by (1)H NMR and ES mass spectrometry studies.

Twofold Porosity and Surface Functionalization Effect on Pt-Porous GaN for High-Performance H2-Gas Sensors at Room Temperature.

The achievement of H2 detection, up to 25 ppm, at room temperature using sulfur-treated, platinum (Pt)-decorated porous GaN is reported in this study. This achievement is attributed to the large lateral pore size, Pt catalyst, and surface treatment using organic sulfide. The performance of H2-gas sensors is studied as a function of the operating temperature by providing an adsorption activation energy of 22 meV at 30 ppm H2, confirming the higher sensitivity of the sulfide-treated Pt-porous GaN sensor. Furthermore, the sensing response of the sulfide-treated Pt-porous GaN gas sensor increases with the increase in porosity (surface-to-volume ratio) and pore radii. Using the Knudsen diffusion-surface reaction equation, the H2 gas concentration profile is simulated and fitted within the porous GaN layer, revealing that H2 diffusion is limited by small pore radii because of its low diffusion rate. The simulated gas sensor responses to H2 versus the pore diameter show the same trend as observed for the experimental data. The sulfide-treated Pt-porous GaN sensor achieves ultrasensitive H2 detection at room temperature for 125 nm pore radii.

Scandium effect on the luminescence of Er-Sc silicates prepared from multi-nanolayer films.

Polycrystalline Er-Sc silicates (Er x Sc2-x Si2O7 and Er x Sc2-x SiO5) were fabricated using multilayer nanostructured films of Er2O3/SiO2/Sc2O3 deposited on SiO2/Si substrates by RF sputtering and thermal annealing at high temperature. The films were characterized by synchrotron radiation grazing incidence X-ray diffraction, cross-sectional transmission electron microscopy, energy-dispersive X-ray spectroscopy, and micro-photoluminescence measurements. The Er-Sc silicate phase Er x Sc2-x Si2O7 is the dominant film, and Er and Sc are homogeneously distributed after thermal treatment because of the excess of oxygen from SiO2 interlayers. The Er concentration of 6.7 × 10(21) atoms/cm(3) was achieved due to the presence of Sc that dilutes the Er concentration and generates concentration quenching. During silicate formation, the erbium diffusion coefficient in the silicate phase is estimated to be 1 × 10(-15) cm(2)/s at 1,250°C. The dominant Er x Sc2 - x Si2O7 layer shows a room-temperature photoluminescence peak at 1,537 nm with the full width at half maximum (FWHM) of 1.6 nm. The peak emission shift compared to that of the Y-Er silicate (where Y and Er have almost the same ionic radii) and the narrow FWHM are due to the small ionic radii of Sc(3+) which enhance the crystal field strength affecting the optical properties of Er(3+) ions located at the well-defined lattice sites of the Sc silicate. The Er-Sc silicate with narrow FWHM opens a promising way to prepare photonic crystal light-emitting devices.

On the phenomenon of large photoluminescence red shift in GaN nanoparticles.

We report on the observation of broad photoluminescence wavelength tunability from n-type gallium nitride nanoparticles (GaN NPs) fabricated using the ultraviolet metal-assisted electroless etching method. Transmission and scanning electron microscopy measurements performed on the nanoparticles revealed large size dispersion ranging from 10 to 100 nm. Nanoparticles with broad tunable emission wavelength from 362 to 440 nm have been achieved by exciting the samples using the excitation power-dependent method. We attribute this large wavelength tunability to the localized potential fluctuations present within the GaN matrix and to vacancy-related surface states. Our results show that GaN NPs fabricated using this technique are promising for tunable-color-temperature white light-emitting diode applications.