Band States Research Articles

87‐4: Control of LTPS Flat‐Band Voltage to Improve the Short‐Term Image Sticking of AMOLED Displays

In this paper, the certain relation between threshold voltage and flat‐band voltage to improve the image sticking for AMOLED display was investigated. Flat band state generally refers to a state in which the energy bands of each region in an ideal MOSFET system are flattened. However, it is requiring an additional voltage to flatten the energy band for actual MOS systems due to the difference in metal and semiconductor work function, which is called the flat‐band voltage. It is investigated that this flat‐band voltage is strongly linked to the short‐term image sticking.

Defect Engineering in Composition and Valence Band Center of Y2(YxRu1-x)2O7-δ Pyrochlore Electrocatalysts for Oxygen Evolution Reaction.

Oxygen evolution reaction (OER) takes place in various types of electrochemical devices that are pivotal for the conversion and storage of renewable energy. This paper describes a strategy in the design of solid-state structures of OER electrocatalysts through controlling the cation substitution on the active metal site and consequently valence band center position of site-mixed Y2(YxRu1-x)2O7-δ pyrochlore to achieve high catalytic activity. We found that partially replacing the B-site Ru4+ cation with A-site Y3+ in pyrochlore-structured Y2Ru2O7-δ modifies the oxidation state of B-site Ru from 4+ to 5+, as observed by electron paramagnetic resonance (EPR) spectroscopy but does not continuously increase the oxygen vacancy concentration in these oxygen substoichiometric compositions, as quantified by thermogravimetric analysis (TGA) decomposition studies. We found the increased Ru oxidation state leads to a downshift in valence band center. X-ray photoelectron spectroscopy (XPS) analysis was performed to quantitatively determine the optimal band center to be ∼1.27 eV below the Fermi energy level based on the analysis of the valence band edge of these Ru-based Y2(YxRu1-x)2O7-δ OER electrocatalysts. This work highlights that defect engineering can be a practical, effective approach to the optimization of oxidation state and electronic band center for high OER catalytic performance in a quantitative manner.

Exploring Rare-Earth compound ErMn2Si2 for thermoelectric and photoelectrochemical applications using Density functional theory

The physical and magnetic properties of the ErMn2Si2 compound are investigated with PDE and RPBE functions using the generalized gradient approximations (GGA) approach within the ferromagnetic phase. The obtained structural optimization results carried out using general gradient approximation (GGA) applying Perdew-Burke-Ernzerhof (PBE), which were consistent with the previously experimental findings. The result shows that the ferromagnetic phase of ErMn2Si2 exhibits the highest thermodynamic stability. Furthermore, the electronic band structure analysis within the ferromagnetic phase indicates the metallic behaviour of the compound in both spin channels. A hybridization between Er-f and Mn-d states is observed in the valence band along with the Si-p state in the conduction band. Total magnetic moments confirm the ferromagnetic characteristics of the ternary inter-metallic ErMn2Si2 compound. In this study, analysis of the Seebeck coefficient was discussed in detail. The electrical and thermal conductivities of the compound were investigated in a broad range of temperatures (0 to 600 K). Additionally, we present the quasi-harmonic model-calculated thermodynamic characteristics as a function of pressure (0–60 GPa) and temperature (0–1200 K). Evaluating the optical characteristics, ErMn2Si2 shows strong dielectricmaterial characteristics in the visible regions of the electromagnetic spectrum. Further, the figure of merit (ZT) was probed. The enhanced ZT values of ErMn2Si2 compounds at elevated temperatures make it a potential candidate for high-temperature applications especially for thermoelectric devices. These results may be useful for further investigations of the rear-earth substituted ErMn2Si2-based compounds for various applications.

Optoelectronic and transport properties of Lead-Free halide based Na2AgTlZ6 (Z = Cl, Br, I) double perovskites for energy harvesting applications

The bandgap engineering and deliberate band edge manipulation of perovskites make them potential candidates for the photovoltaic industry. Here we theoretically investigate the structure, density of states, and photovoltaic and thermoelectric characteristics of Na2AgTlZ6 (Z = Cl, Br, I) using WIEN2k code. The incorporation of Br and I at the Cl site caused the increase in lattice constant which leads to the decrease in bulk modulus and Debye temperature. The computed values of Poisson (<0.26) and Pugh (<1.75) ratio verified their brittle nature. The bandgap analysis reveals direct bandgap nature and bandgap value lie in the visible region for parent composition and infrared and far infrared when Cl is replaced with Br and I. The density of state plots uncovers the shifting of energy states in valence and conduction bands towards the Fermi level with the increasing number of electrons in the halogens. The increase in the value of dielectric constant, refractive index, and shifting of peaks towards lower energy value is witnessed with atomic number of halogen atoms. The viability of these compositions for thermoelectric devices is further confirmed when electrical conductivity and Seebeck coefficient dependent Figure of merit and power factor are evaluated in the temperature range of 200–800 K. In addition, the anisotropic nature of studied compositions is explored through the computation of the modulus of elasticity including Young’s modulus, Shear modulus in addition to compressibility, and Poisson’s ratio.

Ultrafast Exciton Dynamics of CH3NH3PbBr3 Perovskite Nanoclusters.

Exciton dynamics of perovskite nanoclusters has been investigated for the first time using femtosecond transient absorption (TA) and time-resolved photoluminescence (TRPL) spectroscopy. The TA results show two photoinduced absorption signals at 420 and 461 nm and a photoinduced bleach (PB) signal at 448 nm. The analysis of the PB recovery kinetic decay and kinetic model uncovered multiple processes contributing to electron-hole recombination. The fast component (∼8 ps) is attributed to vibrational relaxation within the initial excited state, and the medium component (∼60 ps) is attributed to shallow carrier trapping. The slow component is attributed to deep carrier trapping from the initial conduction band edge (∼666 ps) and the shallow trap state (∼40 ps). The TRPL reveals longer time dynamics, with modeled lifetimes of 6.6 and 93 ns attributed to recombination through the deep trap state and direct band edge recombination, respectively. The significant role of exciton trapping processes in the dynamics indicates that these highly confined nanoclusters have defect-rich surfaces.

Thin Film Resistance Gating by Redox Charge Exchange: Evidence for a Quantum Transition State.

Field effect transistors (FETs) and related devices have enabled tremendous advances in electronics, as well as studies of fundamental phenomena. FETs are classically actuated as fields charge/discharge materials, thereby modifying their resistance. Here, we develop charge exchange transistors (CETs) that comprise thin films whose resistance is modified by quantum charge exchange processes, e.g., redox and bonding. We first use CETs to probe the metallocene-thin film interaction during cyclic voltammetry. Remarkably, CETs reveal transient resistance peaks associated with charge transfer during both oxidation and reduction. Our data combined with kinetics and density functional theory modeling are consistent with a multistep redox pathway, including the formation/destruction of a quantum transition state that overlaps molecule + thin film band states. As a further proof-of-principle demonstration, we also use CETs to monitor n-alkanethiol self-assembly on thin Au films in real-time. CETs exhibit monotonic resistance increase consistent with previously reported fast-then-slow kinetics attributed to thiol-thin film bond formation (charge localization) and etching and/or molecule reorganization.

Highly active ZnO/Fe3+-TiO2 photocatalysts for visible-light photodegradation application and its colour change behaviour by d-d transition

Highly active novel ZnO/Fe-TiO2 composite catalysts with p-n junction heterostructure have been fabricated by adding commercial ZnO and sol–gel derived Fe-TiO2 nano-powders controlled by grinding and drying. This work reported that doped Fe (III) with TiO2 form a p-type semiconductor and whereas ZnO is an n-type semiconductor. The slight variation of electronegativity between ZnO and TiO2 causes a strong rectifying action for the formation of an interface between ZnO and Fe-TiO2. The occurrence of red shift phenomenon in absorption spectrum of the samples suggest the outcome of d-d transition of Fe3+ (2T2g → 2A2g, 2T1g) and the charge transfer transition between interacting Fe3+ ions (Fe3+ + Fe3+ → Fe4+ + Fe2+). These Fe3+ 3d states in addition to oxygen vacancies and Ti3+ centers create band states, thereby favouring the electronic transition to these levels and resulting in narrowing of TiO2 band gap. A direct confirmation is the increase of Urbach energy with the lowering in the band gap of ZnO/Fe-TiO2.The crystal field splitting of d orbitals (5 degenerate orbitals) of Fe3+ and the approach of free ligand ions which split into two sets and Fe3+ ligand field transition is discussed schematically. The photocatalytic activities of these heterostructure photocatalysts were evaluated by degrading toxic cationic organic dyes such as Methylene Blue (MB) and Malachite Green Oxalate (MG) under visible light. The mechanism of photocatalysis has been recommended which is based on the relative band structure of the semiconductor and integrated heterostructure. The formation of a spike barrier in the CB at the interface gives rise to trap sites that capture the migration of charge carriers and occurs recombination of electron-hole pair at higher Fe(III) doping concentration. The dark adsorption property of the catalysts sample has been also studied.

Tracking deep-level defects in degrading perovskite solar cells with a multifactorial approach

In this work, we provide a mechanistic understanding of the degradation of perovskite solar cells in operation by focusing on methylammonium lead triiodide (CH3NH3PbI3 or MAPbI3) and tracking the evolution of electronic defects via photo-induced current transient spectroscopy (PICTS). Moreover, we also record the degradation of its photovaltaic characteristics over time under various electric load and temperature conditions. Using PICTS, we found that bands of trap states, initially highly localized deep within the band gap of the perovskite, widened over the exposure period. This effect was exacerbated with increasing temperature. Further, using the design of experiment methodology for this multifactorial study, we found that two interaction factors (temperature× load & temperature× time) were significant in the degradation of the perovskite cells, validating the importance of our holistic approach. Through these observations, we establish a mechanistic link between deep-level traps and photovoltaic characteristics.

Long-Range Effects in Topologically Defective Arm-Chair Graphene Nanoribbons.

The electronic structure of 7/9-AGNR superlattices with up to eight unit cells has been studied by means of state-of-the-art Density Functional Theory (DFT) and also by two model Hamiltonians, the first one including only local interactions (Hubbard model, Hu) while the second one is extended to allow long-range Coulomb interactions (Pariser, Parr and Pople model, PPP). Both are solved within mean field approximation. At this approximation level, our calculations show that 7/9 interfaces are better described by spin non-polarized solutions than by spin-polarized wavefunctions. Consequently, both Hu and PPP Hamiltonians lead to electronic structures characterized by a gap at the Fermi level that diminishes as the size of the system increases. DFT results show similar trends although a detailed analysis of the density of states around the Fermi level shows quantitative differences with both Hu and PPP models. Before improving model Hamiltonians, we interpret the electronic structure obtained by DFT in terms of bands of topological states: topological states localized at the system edges and extended bulk topological states that interact between them due to the long-range Coulomb terms of Hamiltonian. After careful analysis of the interaction among topological states, we find that the discrepancy between ab initio and model Hamiltonians can be resolved considering a screened long-range interaction that is implemented by adding an exponential cutoff to the interaction term of the PPP model. In this way, an adjusted cutoff distance λ=2 allows a good recovery of DFT results. In view of this, we conclude that the correct description of the density of states around the Fermi level (Dirac point) needs the inclusion of long-range interactions well beyond the Hubbard model but not completely unscreened as is the case for the PPP model.

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.

Resonance photoemission in pure and Tb doped CePO4 luminescent nanowires

The resonance photoemission spectroscopy (RPES) studies on pure and Terbium doped CePO4 nanowires (NWs) are reported here with the supporting characterizations using structural, optical and morphological properties. The NWs with varying Terbium (Tb) doping concentrations were synthesized using chemical synthesis route. Photoluminescence (PL) showed high PL emission intensity in the visible wavelength range indicating strong green luminescence due to efficient Ce3+ to Tb3+ energy transfer. The PL intensity increased up to a doping concentration of 15 wt% Tb3+, beyond which it decreased due to concentration quenching or cross-relaxation effect. Based on PL studies, pure, 5 wt% (the lowest doping amount) and 15 wt% (that shows the highest PL) doped samples were chosen for RPES studies. To understand the comparative contribution of Ce3+ and Ce4+ in the valence band, RPES measurements performed around the Ce 4d →4 f resonance threshold indicated strong presence of Ce 4 f states in pure CePO4 NWs, which reduced upon 5 wt% Tb doping in CePO4 NWs. At 15 wt% Tb3+ doping, the sample did not show resonance of Ce 4 f feature, which may be because Tb3+ ions have replaced Ce3+ ions in the CePO4 lattice. The results are crucial to understand the relative participation of Ce3+ and Ce4+ oxidation states in the valence band, which is an important factor in defining the optical properties of the material that determine the PL intensity.

Interaction of an electron and a uniformly charged spherical donor impurity

In this study, we propose an interaction potential between an electron and a uniformly charged spherical donor impurity in a quantum dot and numerically solve the Schrödinger equation using the finite difference method. We investigate the effects of the potential depth, donor radius, temperature, and hydrostatic pressure on the electronic and optical properties of an electron-donor impurity in a quantum dot, including absorption coefficients and the total change in the relative refractive index during the transition of an electron from the ground (1s) to excited (2p) states in the conduction band. Our findings indicate that an increase in donor radius or temperature leads to a red shift in the optical response, holding the parameters constant. Conversely, an increase in potential depth or hydrostatic pressure induces a blue shift in the optical response under the constant parameters.

A Crystalline 2D Fullerene‐Based Metal Halide Semiconductor for Efficient and Stable Ideal‐bandgap Perovskite Solar Cells

AbstractDespite advances in mixed tin‐lead (Sn‐Pb) perovskite‐based solar cells, achieving both high‐efficiency and long‐term device stability remains a major challenge. Current device deficiencies stem partly from inefficient carrier transport, originating from defects and improper band energy alignment among the device's interfaces. Developing multifunctional interlayer materials simultaneously addressing the above concerns poses an excellent strategy. Herein, through molecular and crystal engineering, an amine‐functionalized C60 mono‐adduct derivative (C60‐2NH3 = bis(2‐aminoethyl) malonate‐C60) is utilized for the synthesis of the first crystalline fullerene‐based 2D metal halide semiconductor, namely (C60‐2NH3)Pb2I6. Single crystal XRD studies elucidated the structure of the new material, while DFT calculations highlighted the strong contribution of C60‐2NH3 to the electronic density of states of the conduction band of (C60‐2NH3)Pb2I6. Utilization of C60‐2NH3 as an interlayer between a FA0.6MA0.4Pb0.7Sn0.3I3 perovskite and a C60 layer offered superior band energy alignment, reduced nonradiative recombination, and enhanced carrier mobility. The corresponding perovskite solar cell (PSC) device achieved a power conversion efficiency (PCE) value of 21.64%, maintaining 90% of its initial efficiency, after being stored under a N2 atmosphere for 2400 h. This work sets the foundation for developing a new family of functional materials, namely Fullerene Metal Halide Semiconductors, targeting applications from photovoltaics to catalysis, transistors, and supercapacitors.

Conduction Band Replicas in a 2D Moiré Semiconductor Heterobilayer.

Stacking monolayer semiconductors creates moiré patterns, leading to correlated and topological electronic phenomena, but measurements of the electronic structure underpinning these phenomena are scarce. Here, we investigate the properties of the conduction band in moiré heterobilayers of WS2/WSe2 using submicrometer angle-resolved photoemission spectroscopy with electrostatic gating. We find that at all twist angles the conduction band edge is the K-point valley of the WS2, with a band gap of 1.58 ± 0.03 eV. From the resolved conduction band dispersion, we deduce an effective mass of 0.15 ± 0.02 me. Additionally, we observe replicas of the conduction band displaced by reciprocal lattice vectors of the moiré superlattice. We argue that the replicas result from the moiré potential modifying the conduction band states rather than final-state diffraction. Interestingly, the replicas display an intensity pattern with reduced 3-fold symmetry, which we show implicates the pseudo vector potential associated with in-plane strain in moiré band formation.

Photogalvanic spectroscopy on MnBi2Te4 topological insulator thin films

We demonstrate zero-bias mid-infrared photocurrent generation in topological insulator MnBi2Te4 thin films. The symmetry breakings at the surface and interfaces lead to the coexistence of Dirac and Rashba band states, which enable two kinds of photogalvanic responses. One is the magneto-photogalvanic effect in the presence of an external in-plane magnetic field perpendicular to photocurrent direction, and the other is the light-polarization-dependent linear photogalvanic effect arising from in-plane symmetry breakings, both observed up to room temperature. We disentangle these contributions by light-polarization and temperature dependent spectroscopy under the varying magnetic field.

Chemically tuned intermediate band states in atomically thin CuxGeSe/SnS quantum material for photovoltaic applications.

A new generation of quantum material derived from intercalating zerovalent atoms such as Cu into the intrinsic van der Waals gap at the interface of atomically thin two-dimensional GeSe/SnS heterostructure is designed, and their optoelectronic features are explored for next-generation photovoltaic applications. Advanced ab initio modeling reveals that many-body effects induce intermediate band (IB) states, with subband gaps (~0.78 and 1.26 electron volts) ideal for next-generation solar devices, which promise efficiency greater than the Shockley-Queisser limit of ~32%. The charge carriers across the heterojunction are both energetically and spontaneously spatially confined, reducing nonradiative recombination and boosting quantum efficiency. Using this IB material in a solar cell prototype enhances absorption and carrier generation in the near-infrared to visible light range. Tuning the active layer's thickness increases optical activity at wavelengths greater than 600 nm, achieving ~190% external quantum efficiency over a broad solar wavelength range, underscoring its potential in advanced photovoltaic technology.

Bifunctional activity and theoretical study of transition metal molybdates for hydrogen and oxygen evolution reaction

Effective, sturdy and cheap electrocatalysts are extremely desirable for water electrolysis. In this work, transition metal molybdates (MMoO4, M = Fe, Co, Ni) with extraordinary oxygen evolution reaction (OER), and hydrogen evolution reaction (HER) in basic electrolyte solution was reported. β-Fe2(MoO4)3 catalyst exhibits better electrocatalytic performance and robustness for both HER and OER compared to NiMoO4 and CoMoO4. Theoretical study (DFT calculation) disclose that the Fe atoms increase the energy states near the Fermi level in β-Fe2(MoO4)3 which makes it more conductive leading to superior OER and HER activity. Compared to CoMoO4 and NiMoO4, β-Fe2(MoO4)3 have well defined multiple Mo 4d orbitals at the conduction band. These are empty states in conduction band, ready to receive the electrons. Further, the computed overpotential values for NiMoO4, CoMoO4, and β-Fe2(MoO4)3 surfaces follow the trend, β-Fe2(MoO4)3 < NiMoO4 < CoMoO4, corroborating with the experimental results.

Enhanced thermoelectric performance of Cu2SnSe3 by synergic effects via cobalt-doping

Diamond-like Cu2SnSe3 has drawn intensive attention as an excellent environmentally-friendly p-type thermoelectric material. In this study, the effects of Co-doping at Sn site on its thermoelectric properties were investigated. Results revealed an effective increase in carrier concentration and enhancement of density-of-states (DOS) effective mass m* due to the role of Co as acceptor and probably the contribution of its d states in the valence bands. Consequently, a remarkable power factor of up to 9.55 μW cm−1 K−2 has been achieved at 823 K. In addition, lattice thermal conductivity was strongly suppressed due to the intensified phonon scattering and softening of bonding as revealed by the sound velocity analysis. Ultimately, a maximal ZT of 0.97 at 823 K and an average ZT of ∼ 0.7 have been achieved in Cu2Sn0.88Co0.12Se3, almost double that of the pristine one.

Tailoring Ultrafast Near-Band Gap Photoconductive Response in GeS by Zero-Valent Cu Intercalation.

Zero-valent intercalation of atomic metals into the van der Waals gap of layered materials can be used to tune their electronic, optical, thermal, and mechanical properties. Here, we report the impact of intercalating ∼3 atm percent of zero-valent copper into germanium sulfide (GeS). Advanced many-body calculations predict that copper introduces quasi-localized intermediate band states, and time-resolved THz spectroscopy studies demonstrate that those states have prominent effects on the photoconductivity of GeS. Cu-intercalated GeS exhibits a faster rise of transient photoconductivity and a shorter lifetime of optically injected carriers following near-gap excitation with 800 nm pulses. At the same time, Cu intercalation improves free carrier mobility from 1100 to 1300 cm2 V-1 s-1, which we attribute to the damping of acoustic phonons observed in Brillouin scattering and consequent reduction of phonon scattering.

Complete zero-energy flat bands of surface states in fully gapped chiral noncentrosymmetric superconductors

Complete zero-energy flat bands of surface states in fully gapped chiral noncentrosymmetric superconductors