Defect States Research Articles

Effects of oxygen vacancies on the structural, electronic, and optical properties of the photocatalytic InTaO4 compound

We conducted first-principles calculations based on density functional theory to investigate the impact of the oxygen vacancies on the structural, electronic, and optical properties of the InTaO4 compound. The latter is a famous photocatalytic semiconductor with its optical absorption in the visible range being an object of controversial interpretations. The presence of two types of isolated oxygen vacancies, O1 and O2, occupying 4g(1) and 4g(2) Wyckoff positions respectively, has been simulated within the frame of the supercell approach. Electronic structure and optical absorption (OA) have been calculated using the Becke-Johnson exchange-correlation potential. It is found that the presence of both types of vacancies generates defect states (DS) inside the band gap, primarily involving In-6s and O-2p states. The calculated valence-to-conduction-band band gap (4.25 eV) and DS-to-conduction-band band gap (2.5 eV) closely align with the experimentally determined OA edges for two onsets of InTaO4 absorption. The analysis of the calculated OA spectra leads to the conclusion that only O1 vacancy-induced absorption is consistent with the experimental OA, while O2 vacancy-induced absorption appears absent. This discrepancy probably arises from a higher concentration of O1 vacancies formed during crystal growth, attributed to the fact that the calculated defect formation energy of O1 vacancy is 0.258 eV lower compared to O2 vacancy. Consequently, the photocatalytic activity of InTaO4 is ascribed to intrinsic defects, primarily O1-type vacancies, though the influence of other defects cannot be entirely ruled out.

The key role of methylenediammonium and tetrahydrotriazinium in the phase stability of FAPbI3

Formamidinium lead triiodide (FAPbI3) is the prime candidate for single-junction perovskite solar cells, despite the metastability of the phase. To improve its ambient-phase stability and produce world-record photoelectric conversion efficiencies, methylenediammonium (MDA) has been used as an additive in FAPbI3. However, the exact function and role of MDA are still uncertain. The MDA doping may exist in the perovskite lattice in either the original structure or the THTZ-H (tetrahydrotriazinium) structure. In this research, the effects of the MDA and THTZ-H doping FAPbI3 perovskite on its stability are explored by first-principles calculations. Both MDA and THTZ-H doping can improve the stability of FAPbI3 perovskite from a structural perspective due to lattice strain and stronger H–I bonds. However, the doping mechanisms differ significantly in terms of electronic properties. The MDA doping acts by the traditional passivation mechanism. It can eliminate the iodine interstitial defect states that trap charge carriers and inhibit iodine interstitial defect migration. The THTZ-H cation can directly contribute to the band edge construction in the FAPbI3 bulk. Electron delocalization in the π-conjugated ring structure lowered the frontier orbital separation of the THTZ-H organic molecule and enabled orbital overlap with the inorganic moiety. The in-depth understanding of the mechanism of improving stability in this study would facilitate the application of FAPbI3 perovskite optoelectronic devices.

Shaping the Future of the Neurotransmitter Sensor: Tailored CdS Nanostructures for State-of-the-Art Self-Powered Photoelectrochemical Devices.

Semiconductor-based photoelectrochemical (PEC) test protocols offer a viable solution for developing efficient individual health monitoring by converting light and chemical energy into electrical signals. However, slow reaction kinetics and electron-hole complexation at the interface limit their practical application. Here, we reported a triple-engineered CdS nanohierarchical structures (CdS NHs) modification scheme including morphology, defective states, and heterogeneous structure to achieve precise monitoring of the neurotransmitter dopamine (DA) in plasma and noninvasive body fluids. By precisely manipulating the Cd-S precursor, we achieved precise control over ternary CdS NHs and obtained well-defined layered self-assembled CdS NHs through a surface carbon treatment. The integration of defect states and the thin carbon layer effectively established carrier directional transfer pathways, thereby enhancing interface reaction sites and improving the conversion efficiency. The CdS NHs microelectrode fabricated demonstrated a remarkable negative response toward DA, thereby enabling the development of a miniature self-powered PEC device for precise quantification in human saliva. Additionally, the utilization of density functional theory calculations elucidated the structural characteristics of DA and the defect state of CdS, thus establishing crucial theoretical groundwork for optimizing the polymerization process of DA. The present study offers a potential engineering approach for developing high energy conversion efficiency PEC semiconductors as well as proposing a novel concept for designing sensitive testing strategies.

Multifunctional buried interface modification of SnO2-based planar perovskite solar cells via phosphorus hetero-phenanthrene flame retardants

Tin dioxide (SnO2) is widely utilized for the cost-effective electron transport layer (ETL) in perovskite solar cells (PSCs) owing to its excellent optoelectronic properties. However, the surface defect states present in SnO2 ETL prepared by conventional solution methods seriously hinder the further improvement of device photovoltaic performance. It is urgently essential to develop a facile strategy to effectively minimize the adverse effects of SnO2 ETL on PSCs. Herein, a phosphorus hetero-phenanthrene flame retardant, DOPO, is introduced as a multifunctional surface modifier to improve the interfacial properties between SnO2 ETL and perovskite. Through systematic characterization analysis, the PO group in DOPO not only passivates the defective states on the surface of SnO2 ETL, but also provides chemical chelation sites for the uncoordinated Pb2+ ions in the upper perovskite structure to improve the film crystalline quality. Eventually, the photoelectric conversion efficiency (PCE) of the optimized device is improved from an initial 19.74 %–22.57 %, along with significantly improved device stability. This work provides an important reference for the development of new multifunctional interface modification materials required for SnO2-based planar PSCs with excellent properties.

Oxygen-related defects in 4H-SiC from first principles

We investigated the abundance, structures, energy levels, and spin states of oxygen-related defects in 4H-SiC on the basis of first-principles calculations. We applied a hybrid functional in the overall calculations, which gives reliable defect properties, and also considered relevant defect charge states. We identified the oxygen interstitial (O i,1), substitutional oxygen (OC), and oxygen-vacancy (OC V Si) complex as prominent defects in n-type conditions. Among them, OC V Si was predicted as a spin-1 defect with NIR emission in a previous study. On the basis of the obtained results, we discuss the possible spin decoherence sources when employing OC V Si as a spin-to-photon interface.

Tuning the Poisson’s ratio of two-dimensional model network materials with application to 2D-silica bilayer structures

A fundamental understanding of the elastic properties of 2D network structures is highly beneficial for research and applications of 2D materials. In this context, Poisson’s ratio has been studied elaborately for different crystallographic structures of crystalline phases of bilayer silica structures. This paper focuses on the elastic structure–property relationship of crystalline and vitreous polymorphs of plane network materials. We generate defective crystalline network states and seven sets of disordered states, each with a different level of network heterogeneity, using a dual Monte Carlo bond switching algorithm. Firstly, uniaxial tensile deformation is applied to a model material in a two-dimensional framework, concentrating only on the in-plane network topologies. Secondly, uniaxial tensile deformation is applied to bilayer silica structures, considering the out-of-plane morphology of the material. Mechanical testing is performed using the athermal quasistatic deformation protocol, which allows one to study the influence of the network topology exclusively without any thermal disturbances. We show that manipulating the network heterogeneity allows one to directly tune the Poisson’s ratio of the material, creating possibilities for novel mechanical applications.

Energetic disorder dominates optical properties and recombination dynamics in tin-lead perovskite nanocrystals

Tin-lead alloyed perovskite nanocrystals (PNCs) offer a promising pathway toward low-toxicity and air-stable light-emitting devices. However, substantial energetic disorder has thus far hindered their lighting applications compared to pure lead-based PNCs. A fundamental understanding of this disorder and its impact on optical properties is crucial for overcoming this limitation. Here, using temperature-dependent static and transient absorption spectroscopy, we meticulously distinguish the contributions of static disorder (including defects, impurities, etc.) and dynamic disorder (carrier–phonon interactions). We reveal how these disorders shape band-tail structure and ultimately influence inter-band carrier recombination behaviors. Surprisingly, we find that static and dynamic disorder primarily control band-tail defect states and bandgap renormalization, respectively, which together modulate fast carrier trapping and slow band-band recombination rates. Furthermore, we link these disorders to the tin-induced symmetry-lowering distortions in tin-lead alloyed PNCs. These findings illuminate critical design principles for highly luminescent, low-toxicity tin-lead PNCs, accelerating their adoption in optoelectronic applications.

Synthesis and characterization of novel Cu3Bi3S7 nanoparticle by combustion using green fuel for photocatalytic degradation and electrochemical sensing applications

In this study, we used an environmentally friendly green fuel combustion synthesis method to create Cu3Bi3S7 (CBS) nanoparticles (NPs). A thorough characterization was carried out, including XRD, UV spectroscopy, SEM, TEM, PL spectroscopy, zeta potential analysis, BET Spectra and XPS Spectra. The formation of single-phase CBS NPs with average diameters of 50 nm was unequivocally confirmed by XRD analysis. UV spectroscopy revealed that the NPs absorbed significant visible light, highlighting their potential for use in photocatalytic degradation processes. The images from SEM and TEM clearly showed NPs with uniform size distribution and spherical morphology. The CBSNPs' defect state presence may be determined from the PL spectra. CBS NPs were particularly effective in photo-catalyzing the degradation of the indigo carmine (IC) dye when exposed to Uv light. Additionally, during an electrochemical sensing examination, the NPs demonstrated extraordinary sensitivity to glucose. Overall, our results highlight the tremendous potential for CBS NPs produced using ecologically friendly green fuel combustion synthesis to advance photocatalytic degradation and electrochemical sensing applications.

Near-infrared laser induced direct ignition of 4,4′,5,5′-tetranitro-1H,1′H-[2,2′-biimidazole]-1,1′-diamine by constructing diverse crystal structures

Although laser ignition is considered to be one of the most promising ways to detonate energetic materials due to its high safety and reliability, it is still a challenge to achieve direct ignition of energetic materials by a laser with low-power and near-infrared (NIR) band. In this paper, a molecular self-assembly strategy based on recrystallization was utilized to prepare 4,4′,5,5′-tetranitro-1H,1′H-[2,2′-biimidazole]-1,1′-diamine (DATNBI) crystals with various micro-nano structures. The characterization results suggest that DATNBI crystals with different degrees of roughness and defects by the induction of solvents and surfactants. The crystal defects can not only bring about the enhancement of light absorption of DATNBI in NIR band, but also advance its thermal decomposition, providing reliable support for direct laser ignition of DATNBI profit from the hot spot ignition theory. Combined with density functional theory, it is speculated that electrons of defect states achieve electron-hole recombination by laser radiation, thereby enhancing photothermal conversion. Compared with raw DATNBI, DATNBI crystals with rough surface and abundant defects can be directly ignited by a NIR laser and exhibits self-sustainable combustion. In summary, a direct NIR laser-ignitable energetic material has been prepared via appropriate crystal structure design.

Impact of Cobalt-Doping on the Optical, Magnetic, and Electronic Features of Hexagonal Cadmium Sulfide

CdS and Cd0.9Co0.1S samples were prepared under an N2 atmosphere. The structural analysis was conducted using X-ray diffraction. The structural and microstructure parameters were determined using Rietveld refinement method. The incorporation of cobalt ions into CdS matrix was confirmed by energy-dispersive spectroscopy and Fourier-transform infrared analysis. CdS sample has a non-magnetic feature while the Co-doped sample exhibited a magnetic behavior. The origin of magnetic property transformation has been investigated, revealing the emergence of ferromagnetic ordering and the conversion to a diluted magnetic semiconductor (DMS) with a calculated magnetic moment of 2.56 μ B upon Co doping. We also investigated how this Cobalt-doping-driven transformation affected optical, photoluminescence, and electronic properties. These effects correlated with the emergence of hyper-deep defect states. Electronic properties were calculated using density functional theory (DFT) with the HSE06 hybrid functional approximation. The calculated energy bandgaps for both Co-doped and pure CdS were 2.13 and 2.12 eV, respectively, while experimental measurements from our UV analysis yielded values of 2.26 and 2.15 eV. DFT calculations were employed to explore the magnetic properties, absorption coefficients, refractive indices, real and imaginary dielectric components, and energy loss spectra in both samples.

Non-reciprocity in photonic crystal due to parity time symmetric defect state

In this article, defect state of photonic crystal regarding parity time known as PT-symmetric is explored thoroughly. For this purpose, transfer matrix technique in setting Bloch theorem is employed to characterize the dispersion relation regarding PT-symmetric defect state. The study uncovers the norteworthy wave phenomenon entitle “non-reciprocity” is exhibited. Moreover, an increasing the in-plane component of wavevector contributes two or more branches in the short wavelength boundary of the stop-band which is not observed in conventional structures. The reflectance of structure is conducted across the optical regime leads to minimum point that aligns with the wavelength of the eigen mode for wavevector value (kx = 0). These findings of research may have significant applications in various areas of photonics and optics likes filters, modern optical photonic cavity resonators and thermo-photovoltaic devices etc.

Quantum Defect Sensitization via Phase-Changing Supercharged Antibody Fragments.

Quantum defects in single-walled carbon nanotubes promote exciton localization, which enables potential applications in biodevices and quantum light sources. However, the effects of local electric fields on the emissive energy states of quantum defects and how they can be controlled are unexplored. Here, we investigate quantum defect sensitization by engineering an intrinsically disordered protein to undergo a phase change at a quantum defect site. We designed a supercharged single-chain antibody fragment (scFv) to enable a full ligand-induced folding transition from an intrinsically disordered state to a compact folded state in the presence of a cytokine. The supercharged scFv was conjugated to a quantum defect to induce a substantial local electric change upon ligand binding. Employing the detection of a proinflammatory biomarker, interleukin-6, as a representative model system, supercharged scFv-coupled quantum defects exhibited robust fluorescence wavelength shifts concomitant with the protein folding transition. Quantum chemical simulations suggest that the quantum defects amplify the optical response to the localization of charges produced upon the antigen-induced folding of the proteins, which is difficult to achieve in unmodified nanotubes. These findings portend new approaches to modulate quantum defect emission for biomarker sensing and protein biophysics and to engineer proteins to modulate binding signal transduction.

Investigating the electrical and optical characteristics of lead-free all-inorganic Cs3Sb2Br9 single crystals

In recent years, halide perovskites have emerged as promising materials for electronic devices. While lead-based perovskites have been extensively studied, exploration of lead-free variants has been limited. Here, we highlight the innovation of observing negative photoconductivity (NPC) induced by light, followed by self-recovery, in lead-free Cs3Sb2Br9 perovskite single crystals. Our study reveals the self-trapping of holes at the Vk center, corresponding to the Br2− dimer, within the midband states of this vacancy-ordered perovskite. This leads to the entrapment of photogenerated charge carriers by charged defect states denoted as Vk, creating an internal electrical field that counteracts the externally imposed field, resulting in NPC. We demonstrate the innovation through the construction of a prototype photodetector with notable sensitivity, featuring high responsivity (6.77 mA/W), detectivity (2.83 × 1012 Jones), and a dark-to-light current ratio of approximately 10. This recognition of retroactive photocurrent in optically active perovskite materials holds promise for advancing highly sensitive detectors.

Multi‐Wavelength Optoelectronic Synaptic Transistors Based on Transition Metal Telluride‐Sulfide Heterostructures

AbstractNeuromorphic visual systems based on optogenetic techniques have colossal potential for in‐memory computing with prospects of developing artificial intelligence vision systems. However, conventional transistor architectures face formidable challenges in efficient signal processing owing to limitations in the intrinsic properties of active channel materials. In this work, a novel transition metal telluride‐sulfide hybrid heterojunction‐based optoelectronic synaptic phototransistor is proposed, in which UV–vis responsive zinc oxide encapsulated few‐layer tungsten disulfide channel is decorated with near‐infrared sensitive 0D cobalt ditelluride (CoTe2) nanocrystals (NCs), eliciting the ability to sense, store, and process optical signals across a broad range of the electromagnetic spectrum. This meticulously designed three‐layered heterostructure, based on their interfacial band alignments, enables high photoresponsivity up to ≈2.6 × 103 A W−1 at a back‐gate bias of 20 V, leading to the brain‐inspired synaptic applications with an average power consumption as low as 75 pJ for each training process. The device exhibits excitatory postsynaptic current, paired‐pulse facilitation with an index above 150%, as well as light‐modulated synaptic plasticity by mimicking biological synapses, which mainly originate from trapped holes in Co‐vacancy mediated surface defect states of CoTe2 NCs. Hence, this 2D material‐based hybrid phototransistor appears to be a promising candidate for energy‐efficient next‐generation brain‐inspired neuromorphic vision systems.

Construction of Ag/Au bimetallic alloying nanoparticles on GaN films for high-performance SERS substrate, and modification of defect states

Construction of Ag/Au bimetallic alloying nanoparticles on GaN films for high-performance SERS substrate, and modification of defect states

Experimental realization of three types of acoustic localized states at topological interface

Wave localization has been the subject of extensive investigation due to its crucial importance in both applied and fundamental research. In particular, the focus has shifted to topologically protected states and flatband states. Here, we develop an acoustic topological heterostructure with one dispersive band and one flatband. In the bandgap, there is one topological state and two defect states. Drawing on this topological heterostructure, we combine three different types of wave localization and realize the flatband bound states, topological interface state, and defect states in both theory and experiment. Then, we examine how the localization of these three types of localized states varies with respect to the local coupling coefficient κBI. Our findings indicate that the topological interface state is robust in relationship to local parameter κBI, while two defect states are strongly influenced by this parameter. As for the flatband states, their eigenfrequencies are unaffected by parameter κBI, but the flatband bound state around the topological interface is dependent on this parameter. Additionally, by modifying the excitation conditions, three types of localized states can be transformed into each other. Leveraging the advantages of the localization of different types of localized states, our proposal represents a significant advancement in the potential applications of acoustic sensors and filters.

Orbital hybridization and defective states of vacancy defects in AlN

Intrinsic atomic defects pose a great effect in wide-bandgap semiconductors owing to the high tendency of forming in-gap defective states. Utilizing density-functional theory, the atomic vacancy defects of Al and N vacancies in hexagonal wurtzite aluminum nitride (AlN) are investigated. We find that the most energetically favorable form of vacancies is predicted to be negatively trivalent charged Al vacancy (VAl−3) in n-type AlN and positively monovalent charged N vacancy (VN+1) in p-type AlN, respectively. N vacancy generally has a low formation energy and could be either an acceptor or a donor: Under p-type conduction, it is a deep donor with a positively monovalent charge of +1, acting as a compensating center for holes; Under n-type conduction, it is a deep acceptor carrying charge of −3, acting as a compensating center for electrons. For the Al vacancy, it tends to be a shallow acceptor in p-type AlN but a high formation energy or a deep acceptor in n-type AlN with low formation energy, most possibly at a negatively trivalent charged state. Our orbital hybridization analysis shows that these vacancies can be facilely generated which are rooted in the antibonding coupling Al3 s-N2p states in valence band. The above finding is independent of the chemical potential of nitrogen and aluminum and holds true under both nitrogen rich and poor conditions. Our work provides a guide to experimental works by providing the energetics and atomic-scale mechanism of doping nature of atomic vacancies in AlN.

Morphological, and Optical Properties of BaTiO3 Nano Particles

Barium titanate (BaTiO3) nano particles have garnered significant attention due to their unique structural, morphological and optical properties, which hold promise for various technological applications. This study presents a comprehensive investigation in to the synthesis potential of BaTiO3 nano particle. The synthesis of BaTiO3 nano particles was achived through various methods, including sol-gel, hydrothermal, and solvothermal routes, with meticulous control over parameters such as temperature, pH, and precursor concentration to tailor the nano particle size and morphology. The structural characterization using techniques such as x-ray diffraction (XRD) revealed the formation of pure –phase BaTiO3nanoparticles with crystallite sizes in the nanometer range, exhibiting a perovskite strucure. Morphological analysis using scanning electron microscopy (SEM) and transmission electron microscopy (TEM) elucidated the morphology, size distribution, and surface chacteristics of the nano particles. The results showcased well –defined, uniform nano particles with controllable sizes and shapes, ranging from spherical to cubic, depending onthe synthesis conditions. futher more, the optical properties ofBaTiO3 nanoparticles were investigated using UV-visible spectroscopy and photoluminescence spectroscopy. The UV- visible spectra exhibited characteristic absorption peaks corresponding to the electronic transitions within the band structure of BaTio3,while photoluminescence spectra revealed emission peaks indicative of defect states with in the nanoparticle. These optical properties were found to be tunable by varying the nano particle size, morphology, and surface characteristics, offering opportunities for optoelectronic and photonic device applications. The key findings of this study underscore the importance of understanding the interplay between synthesis parameters and resulting structural, morphological, and optical properties of BaTiO3 nanoparticles.

Perovskite Crystallization and Hot Carrier Dynamics Manipulation Enables Efficient and Stable Perovskite Solar Cells with 25.32% Efficiency

AbstractModulating perovskite crystallization and understanding hot carriers (HCs) dynamics in perovskite films are very critical to achieving high‐performance perovskite solar cells (PSCs). Herein, a small organic molecule (6BAS) with multisite anchors (C═O) as an efficient additive is introduced into PbI2 precursors to modulate perovskite crystallization during two‐step sequential deposition. The chemical interaction between 6BAS and PbI2 enables more preferential PbI2 crystal with enlarged interplanar spacing of PbI2 lattice, which is beneficial to the penetration of organic ammonium salts into PbI2 layer and the complete conversion to perovskite, consequently promoting the preferential crystallization of perovskite to realize high‐quality perovskite films with larger grain size and reduced defect state. By ultrafast spectroscopy, it is found that the incorporation of 6BAS can efficiently prolong HCs cooling, which helps to enhance HCs transfer and retard the charge carrier recombination in device. As a result, 6BAS doped‐PSCs efficiency significantly enhances to 25.32% from 22.91%. The target device achieves the enhanced long‐term stability. Only a 6% efficiency degradation is realized for un‐encapsulated device with 6BAS after 70 days under N2. Meanwhile, the 6BAS‐treated device retains 95% of its initial PCE after 1160 h of operation at the maximum power point under continuous AM 1.5 G illumination.

Anomalous X-ray pulse responses in MAPbBr3 single crystal-based detectors

Organic-inorganic perovskite single crystals (SCs) are considered promising semiconductors for high-sensitivity X-ray detectors because of their strong X-ray interaction, low-temperature processability, and excellent properties such as long diffusion length, low defect density, and long carrier lifetime. However, the specific pulse response of MAPbBr3 SC-based X-ray detectors frequently exhibits a tail and over/undershoots at several conditions, which degrades the X-ray image quality; however, no detailed analysis of these characteristics has been reported thus far. For high-resolution X-ray imaging, it is necessary to obtain an ideal pulse response that is free of tails and over/undershoots. In this study, we investigated the specific X-ray responses of solution-grown MAPbBr3 SC-based X-ray detectors under various externally applied voltages. Based on the study on charge carrier dynamics, we analyzed the origin of the tail and over/undershoots in X-ray pulse response shapes. We theoretically verified that the unideal pulse response in perovskite SC-based X-ray detectors is attributed to the defect states inherent in perovskite SCs.