Enhancing Optical and Thermal Stability of Blue-Emitting Perovskite Nanocrystals through Surface Passivation with Sulfonate or Sulfonic Acid Ligands.

This study aims to enhance the optical and thermal properties of cesium-based perovskite nanocrystals (NCs) through surface passivation with organic sulfonate (or sulfonic acid) ligands. Four different phenylated ligands, including sodium ß-styrenesulfonate (SbSS), sodium benzenesulfonate (SBS), sodium p-toluenesulfonate (SPTS), and 4-dodecylbenzenesulfonic acid (DBSA), were employed to modify blue-emitting CsPbBr1.5Cl1.5 perovskite NCs, resulting in improved size uniformity and surface functionalization. Transmission electron microscopy and X-ray photoelectron spectroscopy confirmed the successful anchoring of sulfonate or sulfonic acid ligands on the surface of perovskite NCs. Moreover, the photoluminescence quantum yield increased from 32% of the original perovskite NCs to 63% of the SPTS-modified ones due to effective surface passivation. Time-resolved photoluminescence decay measurements revealed extended PL lifetimes for ligand-modified NCs, indicative of reduced nonradiative recombination. Thermal stability studies demonstrated that the SPTS-modified NCs retained nearly 80% of the initial PL intensity when heated at 60 °C for 10 min, surpassing the performance of the original NCs. These findings emphasize the optical and thermal stability enhancement of cesium-based perovskite NCs through surface passivation with suitable sulfonate ligands.

Characteristics of multi-mode lasing in cesium lead bromide perovskite microwires with an isosceles right triangle cross-section.

The CsPbBr3 microwires with unique isosceles right triangle cross-sections are commonly observed via chemical vapor deposition method. In this work, we study the correlations between measured multi-mode lasing behaviors and the simulation of the mode patterns inside the triangular-rod microcavity. We confirm that lasing action with higher-order transverse modes can well sustain, even when these modes experience large optical loss due to the isosceles triangle cross-section. By comparing the experimental and simulation results, the higher-order transverse modes tend to show up prior to the fundamental transverse modes for wider microwires. We attribute this behavior to the nonuniform field distribution caused by the high absorption efficiency of CsPbBr3. We also elaborate on the difficulties to sustain the whispering gallery mode in the CsPbBr3 triangular-rod microcavity, which implies that the lateral dimension and geometry of the cavity should be considered carefully for the future design of low threshold wire-based laser devices.

One- and Two-Photon Excited Photoluminescence and Suppression of Thermal Quenching of CsSnBr3 Microsquare and Micropyramid.

Thermal photoluminescence (PL) quenching is fundamentally important for perovskite optoelectronic applications. Herein, we investigated PL characteristics of CsSnBr3 microsquares and micropyramids synthesized by chemical vapor deposition (CVD) and their PL quenching behavior at high temperature. These microstructures have favorable PL performances in ambient atmosphere. Under two-photon excitation, we observed whispering gallery modes (WGMs) in microsquares and amplified spontaneous emission (ASE) in micropyramids. Reversible PL losses due to thermal effect were observed for both samples. Monotonic blue shifts in PL emission upon temperature increase suggest a band gap widening associated with an emphanisis effect. Temperature-dependent spectral line width analysis reveals that a line width broadening is attributed to the dominant electron-longitudinal optical phonon interaction. The estimated activation energy of thermally assisted nonradiative recombination for CsSnBr3 microsquares and micropyramids is over 310 meV by the Arrhenius equation, which is higher than CsPbBr3. These results prove that CsSnBr3 exhibits better thermal stability than Pb-based perovskites.

Performance Comparison between the Nanoporous NiO x Layer and NiO x Thin Film for Inverted Perovskite Solar Cells with Long-Term Stability.

The development of hole-transport layers (HTLs) that elevate charge extraction, improve perovskite crystallinity, and decrease interfacial recombination is extremely important for enhancing the performance of inverted perovskite solar cells (PSCs). In this work, the nanoporous nickel oxide (NiO x ) layer as well as NiO x thin film was prepared via chemical bath deposition as the HTL. The sponge-like structure of the nanoporous NiO x helps to grow a pinhole-free perovskite film with a larger grain size compared to the NiO x thin film. The downshifted valence band of the nanoporous NiO x HTL can improve hole extraction from the perovskite absorbing layer. The device based on the nanoporous NiO x layer showed the highest efficiency of 13.43% and negligible hysteresis that was better than the one using the NiO x thin film as the HTL. Moreover, the PSCs sustained 80% of their initial efficiency after 50 days of storage. This study provides a powerful strategy to design PSCs with high efficiency and long-term stability for future production.

Synthesis of Red Cesium Lead Bromoiodide Nanocrystals Chelating Phenylated Phosphine Ligands with Enhanced Stability.

Two new phosphine ligands, diphenylmethylphosphine (DPMP) and triphenylphosphine (TPP), were introduced onto cesium lead bromoiodide nanocrystals (CsPbBrI2 NCs) to improve air stability in the ambient atmosphere. Incorporating DPMP or TPP ligands can also enhance film-forming and optoelectronic properties of the CsPbBrI2 NCs. The results reveal that DPMP is a better ligand to stabilize the emission of CsPbBrI2 NCs than TPP after storage for 21 days. The increased carrier lifetime and photoluminescence quantum yield (PLQY) of perovskite NCs are due to the surface passivation by DPMP or TPP ligands, which reduces nonradiative recombination at the trap sites. The DPMP and TPP-treated CsPbBrI2 NCs were successfully utilized as red emitters for fabricating perovskite light-emitting diodes with enhanced performance and prolonged device lifetime relative to the pristine one.

Hemispherical Cesium Lead Bromide Perovskite Single-Mode Microlasers with High-Quality Factors and Strong Purcell Enhancement.

We realized a single-mode laser with an ultra-high quality factor in individual cesium lead bromide (CsPbBr3) perovskite micro-hemispheres fabricated by chemical vapor deposition. A series of lasing property analysis based on cavity size was reported under this material system. Due to good optical confinement capability of the whispering gallery resonant cavity and high optical gain of CsPbBr3 perovskite micro-hemispheres, single-mode lasing behavior was achieved with an ultra-high quality factor as large as 11,460 at room temperature. To study in detail the physical effects between lasing threshold and cavity, a set of cavity size dependence photoluminescence analyses were performed. We found that the lasing threshold increases while the cavity size decreases. Time-resolved PL analysis was conducted to confirm the relation between cavity size and lasing threshold. The larger cavity stands for longer PL lifetime and indicates easier-to-achieve carrier population inversion. Strong Purcell enhancement could be further investigated by the spontaneous emission coupling factor ß and internal quantum efficiency as a function of cavity size. A high ß-factor of 0.37 could be obtained from a 2.2 µm diameter hemisphere microcavity and a high Purcell factor of 14 in a 1.9 µm diameter hemisphere microcavity showing strong Purcell enhancement effect in our system.

Random lasing in cesium lead iodide (CsPbI3) thin films with no surface passivation.

We report the CsPbI3 random lasing at room temperature fabricated by a chemical deposition method. The CsPbI3 thin films with high crystalline quality have intense PL emission and easily achieve the lasing behavior with the Q-factor value over 7000. The lasing behavior of CsPbI3 thin films can be classified as random lasing by measuring lasing spectra at different collective angles. The fast Fourier transform analysis of the lasing spectra is employed to determine the effective cavity length. Most important of all, the lasing stability investigation shows the prolonged lasing stability over 4.8 X 105 laser shots in air.

High-Performance Perovskite-Based Light-Emitting Diodes from the Conversion of Amorphous Spin-Coated Lead Bromide with Phenethylamine Doping.

Large-grained and well-oriented methylammonium lead tribromide (MAPbBr3) perovskite was formed from the conversion of amorphous lead bromide (PbBr2) doped with phenethylamine (PEA). The addition of PEA ions (with an optimized molar ratio of 0.008%) to the PbBr2 solution assisted the formation of a smooth PEA-doped PbBr2 layer by spin-coating. Then, the PEA-doped PbBr2 thin film would convert into large-grained and well-oriented MAPbBr3 with the help of a solid-vapor reaction under a vaporized methylammonium bromide (MABr) and choline chloride (CC) atmosphere. Furthermore, both PEA and CC would passivate the defects of perovskite to improve the crystal quality of perovskite. By applying this perovskite layer in perovskite light-emitting diodes (PeLEDs), the maximum luminance and current efficiency of PeLEDs could reach 20,869 cd/m2 and 3.99 cd/A, respectively; these values are approximately five and three times larger than those of PeLEDs without PEA. The perovskite converted from spin-coated PbBr2 with a PEA dopant remarkably improved the luminance and current efficiency of its PeLEDs.

Enhanced ultraviolet electroluminescence from ZnO nanoparticles via decoration of partially oxidized Al layer.

We construct the ZnO-based superluminescent light-emitting diodes (SLEDs) by spin-coating ZnO nano-particles onto p-GaN/sapphire substrate. By inserting another thin Al layer to form an n-ZnO/Al/n-ZnO/p-GaN sandwich structured SLD, the intensities of the photoluminescence and electroluminescence were greatly enhanced, which can be attributed to the surface plasmon resonance of this Al layer. The tendency of the intensities of the entire electroluminescence spectra shows a super-linearly behavior with increasing the forward bias. Besides, the spectral bandwidth is narrowed down enormously owing to the achievement of the SLD. Furthermore, the interfacial emissions between ZnO/GaN are effectively suppressed by partially oxidizing the Al layer.

Capabilities of time-resolved X-ray excited optical luminescence of the Taiwan Photon Source 23A X-ray nanoprobe beamline.

Time-resolved X-ray excited optical luminescence (TR-XEOL) was developed successfully for the 23A X-ray nanoprobe beamline located at the Taiwan Photon Source (TPS). The advantages of the TR-XEOL facility include (i) a nano-focused X-ray beam (<60 nm) with excellent spatial resolution and (ii) a streak camera that can simultaneously record the XEOL spectrum and decay time. Three time spans, including normal (30 ps to 2 ns), hybrid (30 ps to 310 ns) and single (30 ps to 1.72 µs) bunch modes, are available at the TPS, which can fulfil different experimental conditions involving samples with various lifetimes. It is anticipated that TR-XEOL at the TPS X-ray nanoprobe could provide great characterization capabilities for investigating the dynamics of photonic materials.

Defect induced ferromagnetic ordering in epitaxial Zn0.95Mn0.05O films on sapphire (0 0 0 1).

We report the influence of Mn dopant on magnetic properties of Zn0.95Mn0.05O (ZMO)/Al2O3(0 0 0 1) hetero-epitaxial systems grown by using pulsed-laser deposition. The room temperature (RT) intrinsic ferromagnetic (FM) ordering verified by superconducting quantum interference device magnetometer and x-ray magnetic circular dichroism spectrum of Mn L 2,3 edges is ascribed to the substitutional Mn atoms in the Zn site of ZnO. Mn in ZMO has a tetrahedral local symmetry instead of the octahedral symmetry of MnO, after verifying the absence of the Mn-related impurities or clusters in ZMO epitaxial film by Mn K-edge and Zn K-edge x-ray absorption spectroscopy spectrum, as well as the analysis of long-range structural ordering on Renninger scan of forbidden (0 0 0 5) reflection in x-ray diffraction, transmission electron microscopy and Raman spectrum. Comparison of x-ray absorption spectra of ZMO with those of ZnO epilayers at O K-, Zn K-, and L 3-edges indicates that the substitution of the Zn site with Mn enhances the charge-transfer (CT) transition and the presence of Zn vacancies (VZn) also dominate the photoluminescence (PL) spectrum, implying that the formation of numerous VZn defects plays an important role in activating FM interactions. The strong CT effect and the existence of high-density VZn suggest that the intrinsic RT FM ordering of insulating ZMO is a result of the formation of the bound magnetic polarons (BMPs) that interact with each other via intermediate magnetic impurities.

Phonon confinement and size effect in Raman spectra of ZnO nanoparticles.

We study Raman spectra of ZnO nanoparticles of 5-12 nm size in the whole range of the first-order phonon bands. We apply the 3D phonon confinement model (PCM) for the interpretation of the observed Raman spectra. It is found that PCM is well applicable to the acoustic modes as well as to the optical ones, despite the fact that PCM has been thought not to be suitable for acoustic phonons. We show that the asymptotic behavior of PCM for the small-size limit is more consistent with the observation than that of the elastic sphere model (ESM). Furthermore, PCM gives detailed information on the complex size-dependent shapes of the phonon bands.

Investigation of Cavity Enhanced XEOL of a Single ZnO Microrod by Using Multifunctional Hard X-ray Nanoprobe.

The multifunctional hard X-ray nanoprobe at Taiwan Photon Source (TPS) exhibits the excellent ability to simultaneously characterize the X-ray absorption, X-ray excited optical luminescence (XEOL) as well as the dynamics of XEOL of materials. Combining the scanning electron microscope (SEM) into the TPS 23A end-station, we can easily and quickly measure the optical properties to map out the morphology of a ZnO microrod. A special phenomenon has been observed that the oscillations in the XEOL associated with the confinement of the optical photons in the single ZnO microrod shows dramatical increase while the X-ray excitation energy is set across the Zn K-edge. Besides having the nano-scale spatial resolution, the synchrotron source also gives a good temporal domain measurement to investigate the luminescence dynamic process. The decay lifetimes of different emission wavelengths and can be simultaneously obtained from the streak image. Besides, SEM can provide the cathodoluminescence (CL) to be a complementary method to analyze the emission properties of materials, we anticipate that the X-ray nanoprobe will open new avenues with great characterization ability for developing nano/microsized optoelectronic devices.

Selective-area growth of single-crystal wurtzite GaN nanorods on SiOx/Si(001) substrates by reactive magnetron sputter epitaxy exhibiting single-mode lasing.

Selective-area growth (SAG) of single-crystal wurtzite GaN nanorods (NRs) directly onto Si(001) substrates with un-etched native SiOx amorphous layer, assisted by a patterning TiNx mask fabricated by nanosphere lithography (NSL), has been realized by reactive magnetron sputter epitaxy (MSE). The GaN NRs were grown vertically to the substrate surface with the growth direction along c-axis in the well-defined nano-opening areas. A 5-step structural and morphological evolution of the SAG NRs observed at different sputtering times depicts a comprehensive growth model, listed in sequence as: formation of a polycrystalline wetting layer, predominating c-axis oriented nucleation, coarsening and coalescence of multi-islands, single NR evolution, and finally quasi-equilibrium crystal shape formation. Room-temperature cathodoluminescence spectroscopy shows a strong GaN bandedge emission with a uniform luminescence across the NRs, indicating that the SAG NRs are grown with high quality and purity. In addition, single-longitudinal-mode lasing, attributed to well-faceted NR geometry forming a Fabry-Pérot cavity, was achieved by optical pumping, paving a way for fabricating high-performance laser optoelectronics using MSE.

Improvement of photoluminescence and lasing properties in ZnO submicron spheres by elimination of surface-trapped state.

We report on the enhancement of photoluminescence and laser action behaviors of ZnO submicron spheres fabricated by a sol-gel process. As annealing temperature increases, intense ultraviolet excitonic emission at room temperature can be observed. Upon pulsed excitations, the lasing threshold gradually decreases as annealed temperature increases, which is consistent with the results of the ratio of surface-trapped exciton to donor-bound exciton emissions at low temperature. X-ray photoelectron spectroscopy confirmed that adsorbed OH bonds played a critical role in trapping species of exciton at the ZnO surface. The superior optical properties of high-annealing ZnO mainly result from the elimination of a surface-trapped state.

Ultraviolet/blue light-emitting diodes based on single horizontal ZnO microrod/GaN heterojunction.

We report electroluminescence (EL) from single horizontal ZnO microrod (MR) and p-GaN heterojunction light-emitting diodes under forward and reverse bias. EL spectra were composed of two blue emissions centered at 431 and 490 nm under forward biases, but were dominated by a ultraviolet (UV) emission located at 380 nm from n-ZnO MR under high reverse biases. Light-output-current characteristic of the UV emission reveals that the rate of radiative recombination is faster than that of the nonradiative recombination. Highly efficient ZnO excitonic recombination at reverse bias is caused by electrons tunneling from deep-level states near the n-ZnO/p-GaN interface to the conduction band in n-ZnO.

Optoelectrical characteristics of green light-emitting diodes containing thick InGaN wells with digitally grown InN/GaN.

Compared with conventionally grown thin InGaN wells, thick InGaN wells with digitally grown InN/GaN exhibit superior optical properties. The activation energy (48 meV) of thick InGaN wells (generated by digital InN/GaN growth from temperature-dependent integrated photoluminescence intensity) is larger than the activation energy (25 meV) of conventionally grown thin InGaN wells. Moreover, thick InGaN wells with digitally grown InN/GaN exhibit a smaller σ value (the degree of localization effects) of 19 meV than that of conventionally grown thin InGaN wells (23 meV). Compared with green light-emitting diodes (LEDs) with conventional thin InGaN wells, the improvement in 20-A/cm² output power for LEDs containing thick InGaN wells with digitally grown InN/GaN is approximately 23%.

Enhanced optical confinement and lasing characteristics of individual urchin-like ZnO microstructures prepared by oxidation of metallic Zn.

We prepared urchin-like micron-sized ZnO cavities with high optical quality by oxidizing metallic Zn and proposed the mechanism that resulted in the growth of the urchin-like microstructures. The photoluminescence spectra of the ZnO microstructures had a predominant excitonic emission at room temperature. The lasing properties of the urchin-like ZnO microstructures were investigated systematically through excitation power- and size-dependent photoluminescence measurements. The results showed that a low lasing threshold with high quality factors could be achieved because of the high reflectivity of the optical reflectors formed by the tapered nanowires. The unique optical characteristics may facilitate the development of high-efficiency random lasers.

p-type Mesoscopic nickel oxide/organometallic perovskite heterojunction solar cells.

In this article, we present a new paradigm for organometallic hybrid perovskite solar cell using NiO inorganic metal oxide nanocrystalline as p-type electrode material and realized the first mesoscopic NiO/perovskite/[6,6]-phenyl C61-butyric acid methyl ester (PC61BM) heterojunction photovoltaic device. The photo-induced transient absorption spectroscopy results verified that the architecture is an effective p-type sensitized junction, which is the first inorganic p-type, metal oxide contact material for perovskite-based solar cell. Power conversion efficiency of 9.51% was achieved under AM 1.5 G illumination, which significantly surpassed the reported conventional p-type dye-sensitized solar cells. The replacement of the organic hole transport materials by a p-type metal oxide has the advantages to provide robust device architecture for further development of all-inorganic perovskite-based thin-film solar cells and tandem photovoltaics.

Use of two-dimensional nanorod arrays with slanted ITO film to enhance optical absorption for photovoltaic applications.

Two-dimensional (2D) Si-nanorod arrays offer a promising architecture that has been widely recognized as attractive devices for photovoltaic applications. To further reduce the Fresnel reflection that occurs at the interface between the air and the 2D Si-nanorod array because of the large difference in their effective refractive indices, we propose and adopt a slanted ITO film as an intermediate layer by using oblique-angle sputtering deposition. The nearly continuous surface of the slanted ITO film is lossless and has high electrical conductivity; therefore, it could serve as an electrode layer for solar cells. As a result, the combination of the above-mentioned nanostructures exhibits high optical absorption over a broad range of wavelengths and incident angles, along with a calculated short-circuit current density of JSC = 32.81 mA/cm2 and a power generation efficiency of η = 22.70%, which corresponds to an improvement of approximately 42% over that of its bare single-crystalline Si counterpart.