Highly Luminescent Shell-Less Indium Phosphide Quantum Dots Enabled by Atomistically Tailored Surface States.

Contrary to the prevailing notion that shell structures arise from the intricate chemistry and surface defects of InP quantum dots (QDs), an innovative strategy that remarkably enhances the luminescence efficiency of core-only InP QDs to over 90% is introduced. This paradigm shift is achieved through the concurrent utilization of group 2 and 3 metal-derived ligands, providing an effective remedy for surface defects and facilitating charge recombination. Specifically, a combination of Zn carboxylate and Ga chloride is employed to address the undercoordination issues associated with In and P atoms, leading to the alleviation of in-gap trap states. The intricate interplay and proportional ratio between Ga- and Zn-containing ligands play pivotal roles in attaining record-high luminescence efficiency in core-only InP QDs, as successfully demonstrated across various sizes and color emissions. Moreover, the fabrication of electroluminescent devices relying solely on InP core emission opens a new direction in optoelectronics, demonstrating the potential of the approach not only in optoelectronic applications but also in catalysis or energy conversion by charge transfer.

Water-Soluble Alumina-Coated Indium Phosphide Core-Shell Quantum Dots with Efficient Deep-Red Emission Beyond 700 nm.

Solution-processed colloidal III-V semiconductor-based quantum dots (QDs) represent promising and environmentally-friendly alternatives to Cd-based QDs in the realms of optoelectronics and biological applications. While InP-based core-shell QDs have demonstrated efficient light-emitting diode (LED) performance in the visible region, achieving deep-red emission (above 700 nm) with a narrow linewidth has proven challenging. Herein, the study presents a novel strategy for synthesizing InP/ZnSe/ZnS core-shell-shell QDs tailored for emission in the first biological transparency window. The resulting QDs exhibit an emission wavelength up to 725 nm with a narrow peak full width at half maximum (FWHM) down to 107 meV (45 nm). To enhance the biocompatibility and chemical stability of the QDs, their surface is further capped with a layer of amorphous alumina resulting in an InP/ZnSe/ZnS/Al2O3 heterostructure. This surface passivation not only ensures environmental- and photostability but also enhances the photoluminescence quantum yield (PLQY). The alumina capping enables the aqueous phase transfer via surface ligand exchange using mercaptopropionic acid (MPA) while maintaining the initial quantum yield. The resulting QDs demonstrate a significant potential for advancing next-generation optoelectronic technologies and bio-applications.

Understanding Trap States in InP and GaP Quantum Dots through Density Functional Theory.

The widespread application of III-V colloidal quantum dots (QDs) as nontoxic, highly tunable emitters is stymied by their high density of trap states. Here, we utilize density functional theory (DFT) to investigate trap state formation in a diverse set of realistically passivated core-only InP and GaP QDs. Through orbital localization techniques, we deconvolute the dense manifold of trap states to allow for detailed assignment of surface defects. We find that the three-coordinate species dominate trapping in III-V QDs and identify features in the geometry and charge environment of trap centers capable of deepening, or sometimes passivating, traps. Furthermore, we observe stark differences in surface reconstruction between InP and GaP, where the more labile InP reconstructs to passivate three-coordinate indium at the cost of distortion elsewhere. These results offer explanations for experimentally observed trapping behavior and suggest new avenues for controlling trap states in III-V QDs.

Potassium Iodide Doping for Vacancy Substitution and Dangling Bond Repair in InP Core-Shell Quantum Dots.

This work highlights the novel approach of incorporating potassium iodide (KI) doping during the synthesis of In0.53P0.47 core quantum dots (QDs) to significantly reduce the concentration of vacancies (i.e., In vacancies; VIn-) within the bulk of the core QD and inhibit the formation of InPOx at the core QD-Zn0.6Se0.4 shell interfaces. The photoluminescence quantum yield (PLQY) of ~97% and full width at half maximum (FWHM) of ~40 nm were achieved for In0.53P0.47/Zn0.6Se0.4/Zn0.6Se0.1S0.3/Zn0.5S0.5 core/multi-shell QDs emitting red light, which is essential for a quantum-dot organic light-emitting diode (QD-OLED) without red, green, and blue crosstalk. KI doping eliminated VIn- in the core QD bulk by forming K+-VIn- substitutes and effectively inhibited the formation of InPO4(H2O)2 at the core QD-Zn0.6Se0.4 shell interface through the passivation of phosphorus (P)-dangling bonds by P-I bonds. The elimination of vacancies in the core QD bulk was evidenced by the decreased relative intensity of non-radiative unpaired electrons, measured by electron spin resonance (ESR). Additionally, the inhibition of InPO4(H2O)2 formation at the core QD and shell interface was confirmed by the absence of the {210} X-ray diffraction (XRD) peak intensity for the core/multi-shell QDs. By finely tuning the doping concentration, the optimal level was achieved, ensuring maximum K-VIn- substitution, minimal K+ and I- interstitials, and maximum P-dangling bond passivation. This resulted in the smallest core QD diameter distribution and maximized optical properties. Consequently, the maximum PLQY (~97%) and minimum FWHM (~40 nm) were observed at 3% KI doping. Furthermore, the color gamut of a QD-OLED display using R-, G-, and B-QD functional color filters (i.e., ~131.1%@NTSC and ~98.2@Rec.2020) provided a nearly perfect color representation, where red-light-emitting KI-doped QDs were applied.

3D molecular structural modeling and characterization of indium phosphide via irregularity topological indices.

Indium phosphide (InP) is a binary semiconductor composed of indium and phosphorus. It has a zinc blende crystal structure, which is a type of cubic lattice structure. This lattice is composed of indium and phosphorus atoms arranged in a lattice of cube-shaped cells, with each cell containing four indium atoms and four phosphorus atoms. This lattice structure is the same for all materials with a zinc blende crystal structure and is the most common type of lattice structure in semiconductors. Indium phosphide (InP) has several chemical applications. It is commonly used as a dopant in the production of semiconductors, where it helps control the electrical properties of the material. InP is also utilized in the synthesis various indium-containing compounds, which can have applications in catalysts and chemical reactions. Additionally, InP nanoparticles have been investigated for their potential use in biomedical imaging and drug delivery systems. The topological characterization of 3D molecular structures can be performed via graph theory. In graph theory, the connections between atoms are represented as edges and the atoms themselves are represented as nodes. Furthermore, graph theory can be used to calculate the topological descriptors of the molecule such as the degree-based and reverse degree-based irregularity toplogical indices. These descriptors can be used to compare the topology of different molecules. This paper deals with the modeling and topological characterization of indium phosphide ( InP ) via degree-based and reverse irregularity indices. The 3D crystal structure of the InP is topologically modeled via partition of the edges, and derived closed form expressions for its irregularity indices. Our obtained results will be surely be helpful in investigating the QSPR/QSAR analysis as well as understanding the deep irregular behavior of the indium phosphide ( InP ) .

Integrated optical phased array with on-chip amplification enabling programmable beam shaping.

We present an integrated optical phased array (OPA) which embeds in-line optical amplifiers and phase modulators to provide beam-forming capability with gain and beam steering in the 1465-1590 nm wavelength range. We demonstrate up to 21.5 dB net on-chip gain and up to 35.5 mW optical output power. The OPA circuit is based on an InP photonic integration platform and features the highest measured on-chip gain and output power level recorded in an active OPA (i.e., with amplification), to the best of our knowledge. Furthermore, the OPA enables the independent control of both amplitude and phase in its arms and through this we demonstrate programmable beam shaping for two cases. First, we carried out a Gaussian apodization of the power distribution profile in the OPA emitter waveguides, leading to 19.8 dB sidelobe suppression in the far-field beam, which is the highest value recorded for active OPAs, and then we demonstrated beam forming of 0th, 1st, and 2nd order 1D Hermite-Gaussian beams in free-space.

Efficient performance of InP and InP/ZnS quantum dots for photocatalytic degradation of toxic aquatic pollutants.

In recent years, the growing concern over the presence of toxic aquatic pollutants has prompted intensive research into effective and environmentally friendly remediation methods. Photocatalysis using semiconductor quantum dots (QDs) has developed as a promising technology for pollutant degradation. Among various QD materials, indium phosphide (InP) and its hybrid with zinc sulfide (ZnS) have gained considerable attention due to their unique optical and photocatalytic properties. Herein, InP and InP/ZnS QDs were employed for the removal of dyes (crystal violet, and congo red), polyaromatic hydrocarbons (pyrene, naphthalene, and phenanthrene), and pesticides (deltamethrin) in the presence of visible light. The degradation efficiencies of crystal violet (CV) and congo red (CR) were 74.54% and 88.12% with InP, and 84.53% and 91.78% with InP/ZnS, respectively, within 50 min of reaction. The InP/ZnS showed efficient performance for the removal of polyaromatic hydrocarbons (PAHs). For example, the removal percentage for naphthalene, phenanthrene, and pyrene was 99.8%, 99.6%, and 88.97% after the photocatalytic reaction. However, the removal percentage of InP/ZnS for pesticide deltamethrin was 90.2% after 90 min light irradiation. Additionally, advanced characterization techniques including UV-visible spectrophotometer (UV-Vis), photoluminescence (PL), X-ray diffractometer (XRD), energy-dispersive spectrometer (EDS) elemental mapping, transmission electron microscopy (TEM), and thermogravimetric analysis (TGA) were used to analyze the crystal structure, morphology, and purity of the fabricated materials in detail. The particle size results obtained from TEM are in the range of 2.28-4.60 nm. Both materials (InP and InP/ZnS) exhibited a spherical morphology, displaying distinct lattice fringes. XRD results of InP depicted lattice planes (111), (220), and (311) in good agreement with cubic geometry. Furthermore, the addition of dopants was discovered to enhance the thermal stability of the fabricated material. In addition, QDs exhibited efficacy in the breakdown of PAHs. The analysis of their fragmentation suggests that the primary mechanism for PAHs degradation is the phthalic acid pathway.

Characteristics and Degradation Mechanisms under High Reverse Base-Collector Bias Stress in InGaAs/InP Double HBTs.

In this paper, the reliability of InP/InGaAs DHBTs under high reverse base-collector bias stress is analyzed by experiments and simulation. The DC characteristics and S parameters of the devices under different stress times were measured, and the key parameters with high field stress were also extracted to fully understand and analyze the high-field degradation mechanism of devices. The measurements indicate that the high-field stress leads to an increase in base current, an increase in base-collector (B-C) and base-emitter (B-E) junction leakage current, and a decrease in current gain, and different degrees of degradation of key parameters over stress time. The analysis reveals that the degradation caused by reverse high-field stress mainly occurs in the B-C junction, access resistance degradation, and passivation layer. The physical origins of these failure mechanisms have been studied based on TCAD simulation, and a physical model is proposed to explain the experimental results.

A short review of the electrochemical technologies for pit arrays fabricated on the surfaces of indium phosphide wafer.

Fabricating a pit array on the surface of indium phosphide wafer can change its photoelectric properties, improve its photoelectric conversion efficiency, and expand its application range. There are few reviews devoted to the fabrication of regular hole arrays on the surface of indium phosphide wafers by electrochemical methods. In this paper, twelve electrochemical approaches for assembling pit arrays on the surface of indium phosphide wafers were introduced, the structure and experimental process of the electrochemical device were highlighted, and the resulting top and section views were also shown by animation. It can provide a useful reference guide for the large-scale fabrication of regular hole arrays on the surface of indium phosphide wafers.

Efficient Semi-Artificial Photosynthesis of Ethylene by a Self-Assembled InP-Cyanobacterial Biohybrid System.

Biomanufacturing of ethylene is particularly important for modern society. Cyanobacterial cells are able to photosynthesize various valuable chemicals. A promising platform for next-generation biomanufacturing, the semiconductor-cyanobacterial hybrid systems are capable of enhancing the solar-to-chemical conversion efficiency. Herein, the native ethylene-producing capability of a filamentous cyanobacterium Nostoc sphaeroides is confirmed experimentally. The self-assembly characteristic of N. sphaeroides is exploited to facilitate its interaction with InP nanomaterial, and the resulting biohybrid system gave rise to further elevated photosynthetic ethylene production. Based on chlorophyll fluorescence measurement and metabolic analysis, the InP nanomaterial-augmented photosystem I activity and enhanced ethylene production metabolism of biohybrid cells are confirmed, the mechanism underlying the material-cell energy transduction as well as nanomaterial-modulated photosynthetic light and dark reactions are established. This work not only demonstrates the potential application of semiconductor-N. sphaeroides biohybrid system as a good platform for sustainable ethylene production but also provides an important reference for future studies to construct and optimize nano-cell biohybrid systems for efficient solar-driven valuable chemical production.

Revealing the Band-Edge Exciton Fine Structure of Single InP Nanocrystals.

We investigate the fundamental optical properties of single zinc-blende InP/ZnSe/ZnS nanocrystals (NCs) using frequency- and time-resolved magneto-photoluminescence spectroscopy. At liquid helium temperature, highly resolved spectral fingerprints are obtained and identified as the recombination lines of the three lowest states of the band-edge exciton fine structure. The evolutions of the photoluminescence spectra and decays under magnetic fields show evidence for a ground dark exciton level 0L with zero angular momentum projection along the NC main elongation axis. It lies 300 to 600 µeV below the ±1L bright exciton doublet, which is finely split by the NC shape anisotropy. These spectroscopic findings are well reproduced with a model of exciton fine structure accounting for shape anisotropy of the InP core. Our spectral fingerprints are extremely sensitive to the NC morphologies and unveil highly uniform shapes with prolate deviations of less than 3% from perfect sphericity.

Charge Injection and Energy Transfer of Surface-Engineered InP/ZnSe/ZnS Quantum Dots.

Surface passivation is a critical aspect of preventing surface oxidation and improving the emission properties of nanocrystal quantum dots (QDs). Recent studies have demonstrated the critical role of surface ligands in determining the performance of QD-based light-emitting diodes (QD-LEDs). Herein, the underlying mechanism by which the capping ligands of InP/ZnSe/ZnS QDs influence the brightness and lifetime of the QD-LEDs is investigated. The electrochemical results demonstrate that highly luminescent InP/ZnSe/ZnS QDs exhibit modulated charge injection depending on the length of the surface ligand chains: short alkyl chains on the ligands are favorable for charge transport to the QDs. In addition, the correlation between the spectroscopic and XRD analyses suggests that the length of the ligand chain tunes the ligand-ligand coupling strength, thereby controlling the inter-QD energy transfer dynamics. The present findings shed new light on the crucial role of surface ligands for InP/ZnSe/ZnS QD-LED applications.

Narrow Intrinsic Line Widths and Electron-Phonon Coupling of InP Colloidal Quantum Dots.

InP quantum dots (QDs) are the material of choice for QD display applications and have been used as active layers in QD light-emitting diodes (QDLEDs) with high efficiency and color purity. Optimizing the color purity of QDs requires understanding mechanisms of spectral broadening. While ensemble-level broadening can be minimized by synthetic tuning to yield monodisperse QD sizes, single QD line widths are broadened by exciton-phonon scattering and fine-structure splitting. Here, using photon-correlation Fourier spectroscopy, we extract average single QD line widths of 50 meV at 293 K for red-emitting InP/ZnSe/ZnS QDs, among the narrowest for colloidal QDs. We measure InP/ZnSe/ZnS single QD emission line shapes at temperatures between 4 and 293 K and model the spectra using a modified independent boson model. We find that inelastic acoustic phonon scattering and fine-structure splitting are the most prominent broadening mechanisms at low temperatures, whereas pure dephasing from elastic acoustic phonon scattering is the primary broadening mechanism at elevated temperatures, and optical phonon scattering contributes minimally across all temperatures. Conversely for CdSe/CdS/ZnS QDs, we find that optical phonon scattering is a larger contributor to the line shape at elevated temperatures, leading to intrinsically broader single-dot line widths than for InP/ZnSe/ZnS. We are able to reconcile narrow low-temperature line widths and broad room-temperature line widths within a self-consistent model that enables parametrization of line width broadening, for different material classes. This can be used for the rational design of more spectrally narrow materials. Our findings reveal that red-emitting InP/ZnSe/ZnS QDs have intrinsically narrower line widths than typically synthesized CdSe QDs, suggesting that these materials could be used to realize QDLEDs with high color purity.

Frustrated Lewis Pair Adduct of Atomic P(-1) as a Source of Phosphinidenes (PR), Diphosphorus (P2 ), and Indium Phosphide.

We report phosphinidenes (PR) stabilized by an intramolecular frustrated Lewis pair (FLP) chelate. These adducts include the parent phosphinidene, PH, which is accessed via thermolysis of coordinated HPCO. The reported FLP-PH species acts as a springboard to other phosphorus-containing compounds, such as FLP-adducts of diphosphorus (P2 ) and InP3 . Our new adducts participate in thermal- or light-induced phosphinidene elimination (of both PH and PR, R=organic group), transfer P2 units to an organic substrate, and yield the useful semiconductor InP at only 110 °C from solution.

Study of the Interfacial Oxidation of InP Quantum Dots Synthesized from Tris(dimethylamino)phosphine.

InP quantum dots (QDs) are the most competitive in terms of environmentally friendly QDs. However, the synthesis of InP QDs requires breakthroughs in low-cost and safe phosphorus precursors such as tri(dimethylamino)phosphine [(DMA)3P]. It is found that even if the oxygen is completely avoided, there are still oxidation state defects at the core/shell interface of InP QDs. Herein, the record-breaking (DMA)3P-based red InP QDs were synthesized with the assist of HF processing to eliminate the InPOx defect and improve the fluorescence efficiency. The maximum photoluminescence quantum yield was 97.7%, which is the highest of the red InP QDs synthesized by the aminophosphine. The external quantum efficiency and brightness of the QD light-emitting diode device are also improved accordingly from 0.6% and 1276 cd·m-2 to 3.5% and 2355 cd·m-2, respectively.

Zinc Carboxylate Surface Passivation for Enhanced Optical Properties of In(Zn)P Colloidal Quantum Dots.

Indium phosphide (InP) colloidal quantum dots (CQDs) have generated great interest as next-generation light-emitting materials owing to their narrow emission spectra and environment-friendly components. The minimized surface defects is essential to achieve narrow full-width at half-maximum (FWHM) and high photoluminescence quantum yield (PLQY). However, InP CQDs are readily oxidized in ambient condition, which results in formation of oxidation defect states on the surface of InP CQDs. Herein, we introduce a strategy to successfully passivate the surface defects of InP core by zinc complexes. The zinc carboxylates passivation reduces FWHM of InP CQDs from 130 nm to 70 nm and increases PLQY from 1% to 14% without shelling. Furthermore, the photoluminescence (PL) peak has shifted from 670 nm to 510 nm with an increase of zinc carboxylates passivation, which suggests that excessive zinc carboxylates functions as a size-regulating reagent in the synthesis.

Ligand Effect in 1-Octanethiol Passivation of InP/ZnSe/ZnS Quantum Dots-Evidence of Incomplete Surface Passivation during Synthesis.

The lack of anionic carboxylate ligands on the surface of InP/ZnSe/ZnS quantum dots (QDs), where zinc carboxylate ligands can be converted to carboxylic acid or carboxylate ligands via proton transfer by 1-octanethiol, is demonstrated. The as-synthesized QDs initially have an under-coordinated vacancy surface, which is passivated by solvent ligands such as ethanol and acetone. Upon exposure of 1-octanethiol to the QD surface, 1-octanethiol effectively induces the surface binding of anionic carboxylate ligands (derived from zinc carboxylate ligands) by proton transfer, which consequently exchanges ethanol and acetone ligands that bind on the incomplete QD surface. These systematic chemical analyses, such as thermogravimetric analysis-mass spectrometry and proton nuclear magnetic resonance spectroscopy, directly show the interplay of surface ligands, and it associates with QD light-emitting diodes (QD-LEDs). It is believed that this better understanding can lead to industrially feasible QD-LEDs.

Interatomic Potential for InP.

Classical modeling of structural phenomena occurring in InP crystal, for example plastic deformation caused by contact force, requires an interatomic interaction potential that correctly describes not only the elastic properties of indium phosphide but also the pressure-induced reversible phase transition B3↔B1. In this article, a new parametrization of the analytical bond-order potential has been developed for InP. The potential reproduces fundamental physical properties (lattice parameters, cohesive energy, stiffness coefficients) of the B3 and B1 phases in good agreement with first-principles calculations. The proposed interaction model describes the reversibility of the pressure-induced B3↔B1 phase transition as well as the formation of native point defects in the B3 phase.

Enhanced Luminous Efficacy and Stability of InP/ZnSeS/ZnS Quantum Dot-Embedded SBA-15 Mesoporous Particles for White Light-Emitting Diodes.

Environmentally friendly quantum dots (QDs) of InP-based materials are widely investigated, but their reliability remains inadequate to realize their full potential and wide application. In this study, InP/ZnSeS/ZnS QDs (pristine QDs) were dispersed and embedded into Santa Barbara Amorphous-15 mesoporous particles (SBA-15 MPs) for the first time. A solvent-free method for preparing QD white light-emitting diodes (WLEDs) that is compatible with the WLED packaging process was developed. The photoluminescence (PL) spectrum of pristine QD powder exhibited cluster states and had huge redshift of approximately 23 nm. By comparison, the PL spectrum of the SBA-15 MP/QD hybrid powder had a slight redshift of approximately 8 nm, only because the pristine QDs were dispersed and embedded well in the SBA-15 MPs. The PL intensity of the SBA-15 MP/QD hybrid powder slightly decreased after heating and cooling compared with that of the pristine QDs. Moreover, the luminous efficacy of the SBA-15 MP/QD hybrid WLEDs was enhanced by approximately 14% compared with that of the pristine QD-WLEDs. Furthermore, reliability analysis revealed that the SBA-15 MPs could improve the stability of the pristine QDs on chips. Thus, these MPs promise good potential for applications in mini-LEDs in the future.

Quasi-Shell-Growth Strategy Achieves Stable and Efficient Green InP Quantum Dot Light-Emitting Diodes.

Indium phosphide (InP) based quantum dots (QDs) have been known as an ideal alternative to heavy metals including QDs light emitters, such as cadmium selenium (CdSe) QDs, and show great promise in the next-generation solid-state lighting and displays. However, the electroluminescence performance of green InP QDs is still inferior to their red counterparts, due to the higher density of surface defects and the wider particle size distribution. Here, a quasi-shell-growth strategy for the growth of highly luminescent green InP/ZnSe/ZnS QDs is reported, in which the zinc and selenium monomers are added at the initial nucleation of InP stage to adsorb on the surface of InP cores that create a quasi-ZnSe shell rather than a bulk ZnSe shell. The quasi-ZnSe shell reduces the surface defects of InP core by passivating In-terminated vacancies, and suppresses the Ostwald ripening of InP core at high temperatures, leading to a photoluminescence quantum yield of 91% with a narrow emission linewidth of 36 nm for the synthesized InP/ZnSe/ZnS QDs. Consequently, the light-emitting diodes based on the green QDs realize a maximum luminance of 15606 cd m-2 , a peak external quantum efficiency of 10.6%, and a long half lifetime of > 5000 h.