Midgap Defect States Research Articles

Defect engineering in organic semiconductor based metal-dielectric photonic crystals

We investigate the band structure of metal-dielectric photonic crystals comprising stacked organic semiconductor microcavities with silver metal mirrors incorporating crystal defects: individual unit cells with aperiodic dimensionality. Both transfer matrix simulation and experimental verification are performed to investigate the impact on the photonic band structure as a single cavity is varied in size. The resulting mid-gap defect states are shown to hybridize with a photonic band at certain resonant dimensions. The resonance of the defect cavity affects the transmittance of light through the device, disrupting or enhancing the coupling between otherwise resonant cavities. We outline potential applications for defect engineering of these devices through controlled manipulation of the transmission spectrum.

Biexciton Emission in CsPbBr3 Nanocrystals: Polar Facet Matters.

The metal halide perovskite nanocrystals exhibit a remarkable tolerance to midgap defect states, resulting in high photoluminescence quantum yields. However, the potential of these nanocrystals for applications in display devices is hindered by the suppression of biexcitonic emission due to various Auger recombination processes. By adopting single-particle photoluminescence spectroscopy, herein, we establish that the biexcitonic quantum efficiency increases with the increase in the number of facets on cesium lead bromide perovskite nanocrystals, progressing from cube to rhombic dodecahedron to rhombicuboctahedron nanostructures. The observed enhancement is attributed mainly to an increase in their surface polarity as the number of facets increases, which reduces the Coulomb interaction of charge carriers, thereby suppressing Auger recombination. Moreover, Auger recombination rate constants obtained from the time-gated photon correlation studies exhibited a discernible decrease as the number of facets increased. These findings underscore the significance of facet engineering in fine-tuning biexciton emission in metal halide perovskite nanocrystals.

Tailoring p-Type Behavior in ZnO Quantum Dots through Enhanced Sol-Gel Synthesis: Mechanistic Insights into Zinc Vacancies.

The synthesis and control of properties of p-type ZnO is crucial for a variety of optoelectronic and spintronic applications; however, it remains challenging due to the control of intrinsic midgap (defect) states. In this study, we demonstrate a synthetic route to yield colloidal ZnO quantum dots (QD) via an enhanced sol-gel process that effectively eliminates the residual intermediate reaction molecules, which would otherwise weaken the excitonic emission. This process supports the creation of ZnO with p-type properties or compensation of inherited n-type defects, primarily due to zinc vacancies under oxygen-rich conditions. The in-depth analysis of carrier recombination in the midgap across several time scales reveals microsecond carrier lifetimes at room temperature which are expected to occur via zinc vacancy defects, supporting the promoted p-type character of the synthesized ZnO QDs.

Bandgap study of quantum dot-sized SiGe alloy nanocrystals prepared in a nonthermal capacitively-coupled plasma by ambient scanning tunneling spectroscopy

The manuscript aims to elucidate the evolution of the bandgap and the semiconducting nature of quantum dot-sized SiGe alloy nanocrystals prepared at different plasma conditions in VHF PECVD. The technique of scanning tunneling spectroscopy (STS) is used for this, considering its highly localized nature, and to study the individual NCs. The STS analysis gives the density of states (DOS) spectrum of the SiGe alloy NCs. The present STS study reveals a dependence of the bandgap of SiGe alloy NCs on plasma parameters. The SiGe alloy NCs also exhibited a shallow p-type character despite the fact that no dopants were used during the deposition. Besides this, the midgap defect states are also observed in some of the samples. Further, a comparative bandgap study of the SiGe alloy NCs with its bulk indicates quantum confinement. These new findings from the QD-sized SiGe alloy NCs are important for the conceptual design and practical development of quantum dot-based third-generation solar cells.

Effect of oxygen vacancy and Si doping on the electrical properties of Ta2O5 in memristor characteristics

The resistive switching behavior in Ta2O5 based memristors is largely controlled by the formation and annihilation of conductive filaments (CFs) that are generated by the migration of oxygen vacancies (OVs). To gain a fundamental insight on the switching characteristics, we have systematically investigated the electrical transport properties of two different Ta2O5 polymorphs (epsilon-Ta2O5 and λ-Ta2O5), using density functional theory calculations, and associated vacancy induced electrical conductivity using Boltzmann transport theory. The projected band structure and DOS in a few types of OVs, (two-fold (O2fV), three-fold (O3fV), interlayer (OILV), and distorted octahedral coordinated vacancies (OεV)) reveal that the presence of OILV would cause Ta2O5 to transition from a semiconductor to a metal, leading to improved electrical conductivity, whereas the other OV types only create localized mid-gap defect states within the bandgap. On studying the combined effect of OVs and Si-doping, a reduction of the formation energy and creation of defect states near the conduction band edge, is observed in Si-doped Ta2O5, and lower energy is found for the OVs near Si atoms, which would be advantageous to the uniformity of CFs produced by OVs. These findings can serve as guidance for further experimental work aimed at enhancing the uniformity and switching properties of resistance switching for Ta2O5-based memristors.

Defect-mediated saturable absorption and carrier dynamics in tin (II) monosulfide quantum dots.

Tin (II) monosulfide (SnS) has attracted considerable attention in emerging photonics and optoelectronics because of high carrier mobility, large absorption coefficient, anisotropic linear and nonlinear optical properties, and long-time stability. In this Letter, we report third-order nonlinear absorption and refraction of SnS quantum dots (QDs). Under excitation with 800-nm femtosecond pulses, QDs exhibit saturable absorption (saturation intensity ∼ 47.69 GW/cm2) and positive refractive nonlinearity (nonlinear refraction coefficient ∼ 1.24 × 10-15 cm2/W). Nonetheless, we investigate charge carrier dynamics using femtosecond transient absorption spectroscopy and propose the presence of midgap defect states which not only dictate carrier dynamics but also give rise to nonlinear optical properties in SnS QDs.

Detection of defect levels in vicinity of Al2O3/p-type GaN interface using sub-bandgap-light-assisted capacitance–voltage method

Defect levels in the vicinity of the Al2O3/p-type GaN interface were characterized using a sub-bandgap-light-assisted capacitance–voltage (C–V) method. For metal–oxide–semiconductor (MOS) diodes prepared using p-type GaN (p-GaN) and Al2O3 formed by atomic layer deposition, the C–V curves measured in the dark showed capacitance saturation at a negative bias and a large negative voltage shift compared with ideal curves, which implied the effects of donor-like gap states in the vicinity of the Al2O3/p-GaN interface. Upon illumination with monochromated sub-bandgap light with photon energies higher than 2.0 eV under a large positive bias, the subsequently measured C–V curves showed three plateaus. The plateau under the positive bias voltage due to the surface inversion appeared despite the sub-bandgap illumination, which did not appear at 1.8 eV light illumination, indicating the existence of midgap defect levels. Moreover, the other plateaus were attributed to defect levels at 0.60 and 0.7–0.8 eV above the valence band maximum. For a sample whose surface was prepared by photo-electrochemical (PEC) etching to a depth of 16.5 nm, the C–V curve measured in the dark showed a reduced voltage shift compared with the unetched sample. Furthermore, sub-bandgap-light-assisted C–V curves of the sample with PEC etching showed no plateau at a positive bias, which indicated the reduction in the density of the midgap defect states. Possible origins of the detected defect levels are discussed. The obtained results showed that the interface control can improve the properties of p-GaN MOS structures.

Tuning the Band Gap in the Halide Perovskite CsPbBr3 through Sr Substitution.

The ability to continuously tune the band gap of a semiconductor allows its optical properties to be precisely tailored for specific applications. We demonstrate that the band gap of the halide perovskite CsPbBr3 can be continuously widened through homovalent substitution of Sr2+ for Pb2+ using solid-state synthesis, creating a material with the formula CsPb1-xSrxBr3 (0 ≤ x ≤ 1). Sr2+ and Pb2+ form a solid solution in CsPb1-xSrxBr3. Pure CsPbBr3 has a band gap of 2.29(2) eV, which increases to 2.64(3) eV for CsPb0.25Sr0.75Br3. The increase in band gap is clearly visible in the color change of the materials and is also confirmed by a shift in the photoluminescence. Density-functional theory calculations support the hypothesis that Sr incorporation widens the band gap without introducing mid-gap defect states. These results demonstrate that homovalent B-site alloying can be a viable method to tune the band gap of simple halide perovskites for absorptive and emissive applications such as color-tunable light-emitting diodes, tandem solar cells, and photodetectors.

Oxygen vacancies in KTiOPO4 : Optical absorption from hybrid DFT

Density functional theory is used to calculate the optical absorption of oxygen vacancies in potassium titanyl phosphate ($\mathrm{K}\mathrm{Ti}\mathrm{O}\mathrm{P}{\mathrm{O}}_{4}$, KTP) crystals. A modified hybrid functional is used for the description of the midgap defect states and the optical excitation energies. Oxygen vacancies in the $+2$ charge state lead to rather minor modification of the bulk KTP optical response, while the $+1$ and neutral charge states give rise to characteristic midgap optical absorption covering the whole near-infrared and visible spectrum. Its intensity is strongly polarization dependent and strongest for light polarized parallel to the $z$ axis. The modification of the KTP optical absorption by oxygen vacancies predicted here corroborates the picture that the gray-track formation in KTP, i.e., its photochromic damage, is related to a successive charging of oxygen vacancies.

Pathways for Electron Transfer at MgO-Water Interfaces from Ab Initio Molecular Dynamics.

The nature of electron transfer across metal oxide-water interfaces depends significantly on the band gap of the oxide and its band edge energies relative to the potentials of relevant aqueous redox couples. Here we focus on the water interface with MgO, a prototypical wide band gap oxide whose conduction band edge is close in energy to that of water. We investigate the behavior of an excess electron at and out of equilibrium near the interface using ab initio molecular dynamics based on hybrid density functional theory. Our simulations show that under equilibrium conditions the excess electron (donated by an Al impurity in MgO) localizes to a midgap defect state comparable in energy and shape to a hydrated electron in bulk water. To characterize the electron transfer from the conduction band of MgO to interfacial product states, we dope near-equilibrium configurations of the pristine MgO-water system with Al and run short trajectories of these instantaneously out-of-equilibrium systems. We observe two distinct products associated with the excess electron: a surface-localized electron (esurf-) and an aqueous hydrogen radical (H•). The H• pathway exhibits a much higher activation barrier despite being more exoergic, making esurf- the kinetic product. Our characterization of the pathways on the basis of Marcus theory is consistent with the poor observed utility of MgO for water radiolysis. Moreover, we anticipate that the computational framework employed here will be broadly applicable to assessing electron transfer mechanisms at aqueous, photocatalytic interfaces.

Optical Transitions and Magnetism in Mn-Implanted Gallium Nitride for Three-Level Magnetooptic Devices

A method of preparing passive materials suitable for magnetooptic interactions is shown using manganese implantation into gallium nitride (GaN) epitaxial layers, which establishes both dilute ferromagnetism and a three-level optical system with persistence to over 300 K. A sweep of thermal anneal parameters for a high implant dose into Mg-doped p-type GaN films is presented, and the materials are tested for both their magnetization and photoluminescence (PL). The optimal anneal process at 825 °C for 5 min maintains ferromagnetism with $T_{C}$ > 305 K, confirming magnetic alignment at room temperature with a coercivity of ~100 Oe. PL and spectrophotometry of the optimally prepared materials show the effects of the mid-gap defect state on the material's optical characteristics. The anneal process returns the real part index to its baseline dispersion while retaining an onset of absorption starting at the defect level $E_{A}$ = 1.8 eV, signifying a stable mid-gap energy transition with a measured state lifetime of $τ _{PL}$ = 2.7 ns. The scalability of this process for producing three-level transition magnetic materials suggests passive optical or magnetooptic devices can be constructed that interconnect photonic and spintronic effects for emerging system designs and potential applications in quantum information.

Oxygen-Driven Growth Regulation and Defect Passivation in Chemical Vapor Deposited MoS2 Monolayers

Due to the lowest formation energies, sulfur vacancies are inevitable in the vapor-phase chemical vapor deposition (CVD) of MoS2, which act as deep donors and induce midgap defect states, making the material intrinsically n-type. The postgrowth oxygen passivation of such defects has been the subject of a large number of recent studies because passivation of defects augments the photoluminescence quantum yield by several orders. In this study, by introducing an SiO2/Si wafer in close proximity to the growth substrate, we were able to supply trace oxygen in situ during the growth while simultaneously enabling chemisorption of oxygen at defect sites on the basal plane of large-area MoS2 monolayers. Low-temperature photoluminescence spectroscopy allowed us to distinguish clearly the nature of oxygen bonding in defective MoS2 grown with and without the trace oxygen. Chemisorption of oxygen enabled elimination of defect-related bound exciton emission at the near band edge transition of MoS2, leading to about 300% enhancement in the photoluminescence. We observed unusual splitting of the first-order A1g Raman mode in monolayer MoS2 films when the sulfur vacancies are not compensated by oxygen. The present study provides new experimental evidence to better distinguish between chemisorption and physisorption of oxygen and may serve as an effective way to tune the optical properties of van der Waals crystals during the large-area CVD process.

UV light modulated synaptic behavior of MoTe2/BN heterostructure

Electrical synaptic devices are the basic components for the hardware based neuromorphic computational systems, which are expected to break the bottleneck of current von Neumann architecture. So far, synaptic devices based on three-terminal transistors are considered to provide the most stable performance, which usually use gate pulses to modulate the channel conductance through a floating gate and/or charge trapping layer. Herein, we report a three-terminal synaptic device based on a two-dimensional molybdenum ditelluride (MoTe2)/hexagonal boron nitride (hBN) heterostructure. This structure enables stable and prominent conductance modulation of the MoTe2 channel by the photo-induced doping method through electron migration between the MoTe2 channel and ultraviolet (UV) light excited mid-gap defect states in hBN. Therefore, it is free of the floating gate and charge trapping layer to reduce the thickness and simplify the fabrication/design of the device. Moreover, since UV illumination is indispensable for stable doping in MoTe2 channel, the device can realize both short- (without UV illumination) and long- (with UV illumination) term plasticity. Meanwhile, the introduction of UV light allows additional tunability on the MoTe2 channel conductance through the wavelength and power intensity of incident UV, which may be important to mimic advanced synaptic functions. In addition, the photo-induced doping method can bidirectionally dope MoTe2 channel, which not only leads to large high/low resistance ratio for potential multi-level storage, but also implement both potentiation (n-doping) and depression (p-doping) of synaptic weight. This work explores alternative three-terminal synaptic configuration without floating gate and charge trapping layer, which may inspire researches on novel electrical synapse mechanisms.

Neutralizing Defect States in MoS2 Monolayers.

We report a method to neutralize the mid-gap defect states in MoS2 monolayers using laser soaking of an organic/transition metal oxide (TMO) blend thin film. The treated MoS2 monolayer shows negligible emission from defect states as compared to the as-exfoliated MoS2, accompanied by a photoluminescence quantum yield improvement from 0.018 to 4.5% at excitation power densities of 10 W/cm2. The effectiveness of the method toward defect neutralization is governed by the polaron pair generated at the organic/TMO interface, the diffusion of free electrons, and the subsequent formation of TMO radicals at the MoS2 monolayer. The treated monolayers are stable in air, vacuum, and acetone environments, potentially enabling the fabrication of defect-free optoelectronic devices based on 2D materials and 2D/organic heterojunctions.

Suppression of non-radiative recombination to improve performance of colloidal quantum-dot LEDs with a Cs2CO3 solution treatment

We report a five-fold luminance increase of green-light-emitting CdSe@ZnS quantum-dot LEDs (QLEDs) in response to treatment with a 2-ethoxyethanol solution of cesium carbonate (Cs2CO3). The maximum luminous yield of Cs2CO3-treated QLED is as high as 3.41 cd A−1 at 6.4 V. To elucidate device-performance improvement, we model measured currents as the sum of radiative and non-radiative recombination components, which are respectively represented by modified Shockley equations. Variations in model parameters show that a shift in Fermi level, reduction of barrier heights, and passivation of mid-gap defect states are the main results of Cs2CO3 treatment. In spite of a large luminance difference, light-extraction efficiency remains the same at 9% regardless of Cs2CO3 treatment because of the similarity in optical structures.

A Faster Path to Solar Water Splitting

Finding new wide-bandgap light absorbers that are stable in aqueous solutions is a long-standing challenge in photoelectrochemical water splitting research. Two papers in this issue describe recent advances in high throughput experimentation that may accelerate the discovery of suitable materials.

Unveiling defect-mediated carrier dynamics in few-layer MoS2 prepared by ion exchange method via ultrafast Vis-NIR-MIR spectroscopy

Defect-mediated processes in two-dimensional transition metal dichalcogenides have a significant influence on their carrier dynamics and transport properties, however, the detailed mechanisms remain poorly understood. Here, we present a comprehensive ultrafast study on defect-mediated carrier dynamics in ion exchange prepared few-layer MoS2 by femtosecond time-resolved Vis-NIR-MIR spectroscopy. The broadband photobleaching feature observed in the near-infrared transient spectrum discloses that the mid-gap defect states are widely distributed in few-layer MoS2 nanosheets. The processes of fast trapping of carriers by defect states and the following nonradiative recombination of trapped carriers are clearly revealed, demonstrating the mid-gap defect states play a significant role in the photoinduced carrier dynamics. The positive to negative crossover of the signal observed in the mid-infrared transient spectrum further uncovers some occupied shallow defect states distributed at less than 0.24 eV below the conduction band minimum. These defect states can act as effective carrier trap centers to assist the nonradiative recombination of photo-induced carriers in few-layer MoS2 on the picosecond time scale.

WSe2 Homojunction p-n Diode Formed by Photoinduced Activation of Mid-Gap Defect States in Boron Nitride.

A single nanoflake lateral p-n diode (in-plane) based on a two-dimensional material can facilitate electronic architecture miniaturization. Here, a novel lateral homojunction p-n diode of a single WSe2 nanoflake is fabricated by photoinduced doping via optical excitation of defect states in an h-BN nanoflake upon illumination. This lateral diode is fabricated using a mechanical exfoliation technique by stacking the WSe2 nanoflake partially on the h-BN and Si substrates. The carrier type in the part of the WSe2 film on the h-BN substrate is inverted and a built-in potential difference is formed, ranging from 5.0 to 4.50 eV, which is measured by Kelvin probe force microscopy. The contact potential difference across the junction of p-WSe2 and n-WSe2 is found to be ∼492 mV. The lateral diode shows an excellent rectification ratio, up to ∼3.9 × 104, with an ideality factor of ∼1.1. A typical self-biased photovoltaic behavior is observed at the p-n junction upon the illumination of incident light, that is, a positive open-circuit voltage (Voc) is generated, that is, voltage obtained (at Ids = 0 V), and also a negative short-circuit current (Isc) is generated, that is, current obtained (at Vds = 0 V). The presence of built-in potential in the proposed homojunction diode establishes Isc and Voc upon illumination, which can be implemented for a self-powered photovoltaic system in future electronics. The proposed doping technique can be effectively applied to form planar homojunction devices without a photoresist for future electronic and optoelectronic applications.

Bandgap engineering in CuO nanostructures: Dual-band, broadband, and UV-C photodetectors

In this work, the bandgap of CuO (p-type semiconductor) has been engineered from an indirect bandgap of ∼1 eV to a direct bandgap of 4 eV just by tuning the nanostructure morphology and midgap defect states. The absorption in near-infrared (NIR) and visible regions is ordinarily suppressed by controlling the growth parameters. Considering the increasing scope and demand of varying spectral range (UV-C to NIR) photodetectors, the systematic variation of the available density of states (DOS) at a particular energy level in CuO nanostructures has been utilized to fabricate dual-band (250 nm and 900 nm), broadband (250 nm–900 nm), and UV-C (250 nm) photodetectors. The sensitivity and detectivity of the photodetector for broadband detectors were ∼103 and 2.24 × 1011 Jones for the wavelengths of 900 nm and 122 and 2.74 × 1010 Jones for 250 nm wavelength light, respectively. The UV-C detector showed a sensitivity of 1.8 and a detectivity of 4 × 109 Jones for 250 nm wavelength light. A plausible mechanism for the photoconduction has been proposed for explaining the device operation and the effect of variation in available DOS. The obtained photodetectors are the potential candidates for future optoelectronic applications.

Energy band and optical modeling of charge transport mechanism and photo-distribution of MoO3/Al-doped MoO3 in organic tandem cells

The promising potential of achieving high efficiency organic tandem cells due to the widened absorption spectrum range has resulted in significant research in novel device concepts such as the modification of the recombination layer. In this study, a typically used charge transport interlayer in the recombination layer, MoO3, is modified by tuning the energy band and work function, with the help of an energy band model, to achieve energetic alignment without additional metallic layers. The energy level tuning is demonstrated by the co-evaporation of aluminum, which results in a doping effect. This shifts the work function of pristine MoO3 from 5.8[Formula: see text]eV to 4.3[Formula: see text]eV. The shift is proposed to be due to the formation of oxidized Al3+ and reduced MoO6+ that generates further mid-gap defect states and this shift increases with respect to Al concentration. The energy band shift changes the transport mechanism from hole-transporting to electron-transporting and the modification is modeled in this work. This suggests that recombination layer of MoO3/Al-MoO3 may have better energetic alignment and integrating this modified recombination layer results in improvement in the stacked device efficiency from 1.38% to 3.38% with enhancement in [Formula: see text], [Formula: see text] and fill factor. This enhancement is contributed from better aligned energy level and higher transparency of the recombination layer. The effective transparent recombination allows greater photon distribution to the top cell and increasing maximum matched photocurrent to the limiting subcell, thus improving photocurrent by 25% and overall efficiency up to 4.6%.