High Hole Concentration Research Articles

Unprecedented Hole Concentration of NiSe2 Electrodes Leading to Hole Degeneration of Entire WSe2 Channels.

Semimetal electrodes for 2D semiconductors have been extensively studied; however, research on p-type semimetals has been limited due to the scarcity of materials that satisfy both high work functions and low resistances. In response, we investigated the behavior of NiSe2 as an electrode. Utilizing a novel co-evaporation method that suppresses oxidation and contamination, we synthesized NiSe2 demonstrating a high work function of 5.53 eV, a low resistance of 5.81 × 10-5 Ω cm, and a record hole concentration exceeding 1023 cm-3. We confirmed that when WSe2 comes into contact with NiSe2, the Fermi level of WSe2 falls below the work function of NiSe2, leading to complete hole degeneration of the channel. This unusual Fermi level alignment correlates with the high hole concentration in NiSe2 and the maximum energy level of its hole pockets. Our research provides new insights into how an electrode's hole concentration affects channel behavior.

Theoretical Optimization of an Earth-Abundant and Environmentally Friendly Photovoltaic Absorber Cu3PSe4 from First-Principles Study to Device Simulation.

To seek an earth-abundant and environmentally friendly absorber for thin-film solar cells, Cu3PSe4 is investigated by first-principles calculations and device simulations. We demonstrate that the compound has a suitable band gap width of 1.3 eV as well as a high sunlight absorption coefficient. However, drawbacks like small electron affinity, high hole concentration, large lattice mismatch with CdS, etc., are revealed, which may degrade the photovoltaic performance. To address those shortcomings, we propose (1) to optimize the carrier concentration by preparing the samples at low temperature and under a Cu-rich environment, (2) to replace the CdS buffer layer by a more suitable wide-gap semiconductor with smaller lattice mismatch, and (3) that the selected buffer layer should have small electron affinity in order to reduce the open-circuit voltage losses. After implementation of these optimization approaches, the device simulations demonstrate that the power conversion efficiency reaches 17.7% for a solar cell with the configuration Mo/Cu3PSe4/WS2/n-ZnO. The combination of first-principles calculations at the atomistic level and device simulations at the macroscopic level provides an appropriate approach to design ideal solar cells.

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In this correspondence, we deduce the non-parabolic band dispersion within the framework of effective mass representation (EMR) using k→⋅π→ perturbation theory in the presence of s.o interaction, magnetic impurity and external magnetic field. We measure the electronic parameters like Fermi energy, density of states, effective g factor and effective mass etc. in p-type Sn1−xEuxTe by taking into account a 6-level band structure with normal and bumped band edges. In the study, we use the experimental and simulated band gap values as functions of Eu+2 impurity and temperature. Apart from the general trend, the electronic parameters exhibit extreme behaviour near the band inversion point x=0.020 at T=300 K (Nayak et. al.2023), but in the range of impurity concentration and temperature considered; from x=0.0005 to x=0.001 and T=1.5 K to T=300 K, the behaviour is normal. Again, we follow the expression for spin-electron paramagnetic resonance (EPR) shift (Ps) where the perturbation expansion of Green’s function is used in the presence of the above-mentioned interactions. To get around the problem of loss of translational symmetry in the presence of the magnetic field, Green’s function is redefined in terms of Peierl’s phase factor. Here we have made an extensive study of the shift of Eu+2 ion in p-type Sn1−xEuxTe for several impurity concentrations from x=0.0005 to x=0.001 in the temperature range T=1.4 K to T=300 K. Lastly, we analyze the EPR shift and other electronic parameters and their anisotropies in p-type Sn1−xEuxTe as functions of carrier concentration and Eu impurity from T=1.5K to T=300K. We report the EPR shift is 2.97×10−3 at T=300 K and 3.31×10−3 at T=1.5 K with anisotropy at p=5×1020cm−3 in contrast to the experimental observation of +(3.4±0.4)×10−3 in the same system. The discrepancy is attributed to the reduction in the density of available states at Fermi energy at the L-band caused by the simultaneous rise in that at the Σ− band noticeable particularly at/above high hole concentrations p≥5×1020cm−3.

Structural, optical and electrochemical properties of Sr-doped ZnO nanoparticles

The Sr-doped ZnO nanoparticles have been synthesized by the chemical precipitation method at room temperature. The prepared nanoparticles are annealed at 500 °C for 4 h. The nanoparticles have been characterized using X-ray diffraction (XRD) technique, scanning electron microscope and UV–Vis spectroscopy. The XRD studies reveal the formation of a wurtzite geometry. The crystallite size, dislocation density and strain are examined as a function of Sr-doping concentration. The band gap of the prepared nanoparticles ranges from 3.46 eV to 3.56 eV. The nanoparticles have a higher hole concentration than electron concentration. Supercapacitor cells have been prepared by using synthesized nanoparticle electrodes and it is characterized using cyclic voltammetry (CV) by using KOH as an electrolyte solution. The calculated specific capacitance is high at a high doping concentration of ‘Sr’.

The growth evolution of SnSe-doped SnTe alloy by in-situ selenization substitution method

In the era of increasing environmental pollution and energy crisis, the development of thermoelectric materials to achieve the reuse of waste heat energy is of great significance. SnTe, as an environmentally friendly thermoelectric material, its high electronic-thermal conductivity and coupled high electrical conductivity originated from intrinsic high carrier hole concentration leads to the unsatisfactory thermoelectric properties. With a lot of research going on to optimize thermoelectric performance by decoupling the thermo-electrical contradiction, the entropy engineering strategy, which can independently modulate lattice thermal conductivity is proved to be feasible by increasing the internal configurational entropy through doping. However, due to the uncontrollable growth microscopic process and the perturbation of film quality, the desired precise phase doping remains a challenge. In this work, we report an instantiation of the entropy increase of SnSe-doped SnTe alloy thin films prepared by two-step magnetron sputtering and selenization method. The microstructure and physical properties of thin films were investigated for replaying and controlling the growth evolution of in-situ selenization substitution. When the reaction temperature and duration were adjusted to 300℃ and 30 mins respectively, the desired pure phase doping was obtained. This work provides a new method of doping modification of SnTe materials, and the product as a new functional material expands the thermoelectric material library. In particular, it has positive reference significance for the development of synthesis controllability and structure establishment of complex polycrystalline materials.

Realizing high average zT in GeTe through band modulation and suppressing Ge vacancies

GeTe is regarded as an excellent thermoelectric material, while its intrinsically high hole concentration impedes its further enhancement in thermoelectric performance. In this work, we introduce a two-step strategy by Bi and Y co-doping and Pb alloying to optimize the thermoelectric properties of the GeTe compound. Aliovalent Bi doping on the Ge site is found to effectively reduce the hole concentration, and a small substitution of Bi by Y atoms can further increase the effective mass, resulting in a high thermoelectric figure of merit (zT) of ∼ 1.92 at 723 K. Alloying Pb with high concentration elaborately decreases the carrier concentration to around 1.09 × 1020 cm−3, leading to an enhancement of Seebeck coefficient. In addition, Pb alloying maintains stable carrier mobility, contributing to a high power factor. PbTe alloying induces a strong point defect scattering and strain field fluctuation, leading to a low lattice thermal conductivity. Benefiting from the synergistically optimized effects of Bi and Y co-doping and Pb alloying, a peak zT of ∼ 2.26 at 723 K and an average zT of 1.64 over 300–773 K are realized in Ge0.8Pb0.15Bi0.04Y0.01Te.

Surface-enhanced p-type transparent conducting CuI−Ga2O3 films with high hole transport performance and stability

CuI is a wide bandgap p-type transparent conductor with promising optoelectronic properties. However, conventional CuI films prepared through the iodination of Cu films exhibit rough surface, poor stability and excessively high hole concentration, hindering its application. Herein, we introduce CuI−Ga2O3 composite films as a substitution to overcome the shortcomings of pure CuI. During the iodination process, Ga2O3 hindered the mobility of CuI grain boundaries, resulting in small grain size and low surface roughness. After the charge re-equilibrium and low-energy carrier filtering at the interface between Ga2O3 and CuI, the hole concentration in the films decreased by an order of magnitude. Due to the interface effect of Ga2O3 at the grain boundaries of CuI, the hole mobility increased by 5 times, and the conductivity improved by 53%. The ultra-wide band gap of Ga2O3 enhanced the transmittance of CuI films in short wavelength region. Ga2O3 served to passivate the grain boundaries of CuI, preventing the oxidation of CuI and the loss of iodine, consequently improving the stability of the films. This work will deepen the understanding of the failure and hole transport mechanisms of CuI films.

Hole Conduction Mechanism in In–Mg‐Codoped GaN Prepared via Pulsed Sputtering Deposition

This study reports the pulsed sputtering deposition (PSD) epitaxial growth of In–Mg‐codoped GaN with a high hole concentration of 6.2 × 1018 cm−3 and its hole conduction mechanism. X‐ray diffraction analysis shows that In–Mg‐codoped GaN coherently grows on a GaN substrate without structural degradation and In concentration is 1.3%. Temperature‐dependent conductivity is explained by the combination of the band and nearest‐neighbor hopping conduction models. Curve fitting in the band conduction region is used to estimate the Mg activation energy, which is as low as 89 meV. This is responsible for the high hole concentration of 6.2 × 1018 cm−3. These results indicate that In–Mg codoping using low‐temperature PSD is a promising technique for the preparation of GaN with a high hole concentration without structural degradation.

Preparation, characterization, and antibacterial activity of Ni, Sn co-doped ZnO nanoparticles: Effect of Sn doping concentration

Ni, Sn co-doped ZnO nanoparticles have been prepared by chemical method at room temperature. The effects of Sn on the structural, morphological, optical, electrical, and anti-microbial properties of the prepared nanoparticles have been evaluated and discussed. The crystallite size and the unit cell properties have been influenced by the doping concentration of Sn. The addition of Sn enhances the texture coefficient of the nanoparticles. The optical band gap of the material is blue-shifted as the doping concentration of Sn increases. The prepared nanoparticles have high hole concentration than electron concentration. The nanoparticles became more transparent at high doping concentrations. The effect of Sn concentration against E. coli, S. aureus, and P. aeruginosa has been evaluated.

The Remarkable Role of Indium in Synergistically Optimizing Carrier Concentration and Phase Distribution of AgCuTe-Based Materials.

Carrier regulation has proven to be an effective approach for optimizing the thermoelectric performance of materials. One common method to adjust the carrier concentration is through element doping. In the case of AgCuTe-based materials, it tends to form with cation vacancies, resulting in a high hole concentration and complex phase composition at low temperatures, which also hinders material stability. However, this also offers additional opportunities to manipulate the carrier concentration. In this study, the improved performance of AgCuTe through indium doping is reported, which leads to a reduction in hole concentration. In combination with a significant increase in the effective mass of the carriers, the enhanced Seebeck coefficient is also realized. Particularly, a notable improvement in power factor is observed in the hexagonal phase near room temperature. Furthermore, a lower electron thermal conductivity is achieved, contributing to an average figure of merit value of ≈1.21 (between 523 and 723K). Additionally, the presence of indium inhibits the formation of the second phase and ensures a homogeneous phase distribution, which reduces the instability arising from phase transition. This work significantly enhances the potential of AgCuTe-based materials for low to medium-temperature applications.

Progress and Outlook of 10% Efficient AlGaN‐Based (290–310 nm) Band UVB LEDs

Eco‐friendly and low‐cost aluminum gallium nitride (AlGaN) for the epitaxial growth of ultraviolet‐B (UVB) light‐emitting diodes (LEDs) on c‐Sapphire has the possibility of high external‐quantum efficiency (EQE). In this review paper a special growth techniques for 50% relaxed and 4 μm thick AlGaN buffer layer underneath the multi‐quantum wells (MQWs) are challenged to achieve a maximum internal‐quantum efficiency of 50–57% in 310–290 nm band UVB LEDs. The influence of a thin “Valley” layer in p‐type multi‐quantum barrier electron‐blocking layer on 2D hole generation and injection via intraband tunneling was attempted. Finally, the influence of soft polarized Mg‐doped p‐type Al‐graded AlGaN hole injection layer assisted by excimer laser annealing for better hole injection toward the MQWs was investigated and quite high hole concentration of 2 × 1016 cm−3 and resistivity of 24 Ω‐cm at room temperature was achieved. Consequently, the EQE of transparent 310 and 304 nm UVB LEDs, respectively, reached to a confirmed world record values of ≈5% and ≈10% with light powers of 29 and 40 mW on wafer. This EQE value can surpass 21% if flip‐chip, nanoPSS, photonic crystal, and lens with highly reflective p‐electrodes are incorporated in LED.

The impact of thickness-related grain boundary migration on hole concentration and mobility of p-type transparent conducting CuI films.

CuI films present promising optoelectronic properties for transparent conductors. However, the high hole concentration in CuI films hinders the controllable modulation of hole mobility, limiting their application in low-dimensional thin-film transistors. In this study, CuI films were prepared through a Cu film iodination method at room temperature, and a systematic investigation was conducted on the modulation of hole concentration and mobility with varying film thickness. The films exhibited a zinc blende structure (γ-phase) with increasing grain size as the thickness increased. The transmittance and optical bandgap of the films decreased with increasing thickness. The correlation of vacancy concentration with changing film thickness was analyzed through photoluminescence spectroscopy, revealing the influence of grain boundary migration on vacancy formation. The reduction in film thickness diminishes the migration of CuI grain boundaries, consequently reducing the probability of Cu vacancy and I vacancy formation, resulting in diminished hole concentration and enhanced hole mobility and film conductivity. The film with a thickness of 20 nm demonstrated optimal performance, with a transmittance of 90%, hole concentration of 4.09 × 1017 cm-3, hole mobility of 506.50 cm2 V-1 s-1, and conductivity of 33.19 S cm-1. This work deepens the understanding of hole transport such as hole concentration and mobility modulation in CuI films, highlighting the importance of controlling grain boundary migration during the film growth process.

On the grain boundary charge transport in p-type polycrystalline nanoribbon transistors.

Grain boundaries (GB) profoundly influence charge transport, and their localized potential barrier with a high density of defect states plays a crucial role in polycrystalline materials. There are a couple of models to estimate the density of states (DoS) of nanostructured materials in field-effect transistors (FETs) that probe interface traps between the semiconductor and dielectric but not at the grain boundaries. Here, we report on utilizing Levinson's and Seto's models of grain boundary transport and correlate them with the temperature-dependent hopping transport in copper iodide (CuI) polycrystalline nanoribbon (PNR) FETs. Experimentally, PNRs are obtained by e-beam lithography and thermal evaporation of CuI. To investigate the impact of GB, the devices are fabricated with different channel aspect ratios by varying widths (80, 260, and 570 nm) and lengths (20 to 90 μm). Owing to the high hole concentration, PNR FETs operate in depletion mode at 300 K. At various low temperatures (80-300 K), the figures-of-merits of FETs are estimated to understand device performance. We determine GB barrier heights, activation energy, and density of GB trap states and find equivalence between the two models. Furthermore, we calculate temperature-dependent hopping and trap-limited transport parameters to obtain DoS at the Fermi energy, trapped and free charge carrier density, localization length, hopping distance, hopping energy, etc. at various channel lengths. Based on this quantitative analysis, we propose a channel length-dependent GB barrier height variation due to the in-plane electric field and elucidate CuI energy band levels.

Band and microstructure engineering toward high thermoelectric performance in SnTe

AgBiS2 alloying combining with Ge doping facilitates the band convergence and suppresses the phonon transport, leading to a competitive zT of 1.6 in SnTe.

Impact of Various Dopants on Thermoelectric Transport Properties of Polycrystalline GeSb2Te4

GeSb2Te4 (GST124), one of the well‐known phase‐change materials for nonvolatile memory and rewritable optical storage, has been recently found to be promising thermoelectric materials with low lattice thermal conductivity and high electrical conductivity. However, its thermoelectric performance is greatly restricted by the excessively high hole concentration. Herein, the impact of a series of group IIIA (Al, Ga, In) and group VIA (S, Se) dopants on the electrical transport properties of polycrystalline GST124 has been studied. It is found that element sulfur (S) has the best doping efficiency because the GeS bonds are very strong and ionic that are beneficial for suppressing Ge vacancies to reduce the carrier concentration. Meanwhile, element indium (In) also shows decent doping efficiency because its ionic radius is close to the Ge ion and the InTe bonds have moderate bonding strength. Moreover, In doping introduces a resonant level in the valence band, leading to enhanced Seebeck coefficient and power factor. A high figure of merit (zT)of 0.73 at 700 K and an average zT of 0.48 over 300–750 K are obtained in Ge0.92In0.08Sb2Te4, which are 26% and 66% higher than pristine GST124. This study will advance the understanding and development of high‐performance GeSbTe‐based thermoelectric materials.

Surface states modulation via vacancy engineering for creating band bending on semiconductor BiOBr photocatalysts

In microelectronic devices, surface modification could be used to introduce acceptor or donor surface states by defect engineering method to modify the alignment of energy band for desired properties, which was not used in the catalytic performance enhancement of powder photocatalysts. In this work, surface oxygen vacancies are induced to adjust the surface electrical structures and characteristics of the semiconductor bismuth oxybromide (BiOBr). In addition to being defect states to trap photoexcited electrons, surface oxygen vacancies also bring acceptor surface states, which result in an enhanced upward band bending and attract more photoexcited holes to the surface. Significantly, with a high concentration of electrons and holes accumulated on the surface, the BiOBr with surface oxygen vacancies shows good activity in the activation of O2 and oxidation of water compared to the one with bulk oxygen vacancies. Especially, it can decompose Rhodamine B (RhB) under natural sunlight in one minute, exceeding the majority of previously reported photocatalytic materials under comparable conditions. This work demonstrates that the surface oxygen vacancies could induce strengthened band bending at the BiOBr surface and remarkably improve catalytic performance, which provides a scalable strategy to practically manipulate the surface built-in electric field of powder photocatalysts.

Effect of local chemical disordering on magnetic properties in high entropy manganite of variable hole concentration

A series of high entropy manganite perovskites (La0.2Pr0.2Nd0.2Bi0·2Ba0.2)MnO3, (La1/6Pr1/6Gd1/6Bi1/6Sr1/6Ba1/6)MnO3, (La0.2Nd0.2Gd0.2Sr0·2Ba0.2)MnO3 and (La1/6Pr1/6Nd1/6Ca1/6Sr1/6Ba1/6)MnO3 with variable hole concentration at fixed A-site ionic radius (<rA> = 1.253 Å) have prepared by sol-gel technique. Single phase samples were characterized by the powder X-ray diffraction (PXRD), Field Emission Scanning Electron Microscopy (FE-SEM), Energy Dispersive X-ray (EDX) analysis and elemental mapping which confirm the phase purity of the samples, surface morphology, elemental ratio and chemical homogeneity. X-ray photoelectron spectroscopic (XPS) studies reveal the increase of Mn4+ ions systematically with the substitution of hole concentration at A-site. Magnetization study in this high entropy sample with variable hole concentration at fixed <rA> = 1.253 Å exhibits several contrasting behaviour compare to the conventional hole doped samples. In these high entropy manganites the variation in critical temperature (TC) does not follow expected trend neither with the hole concentration nor to the cationic size disorder parameter, σ2. Though the <rA> is fixed, there is a slight increase in tolerance factor (f) due to hole variation in B-site. Interestingly, TC variation with f shows similar trend to the hole concentration, which is expected to be increased linearly. The effect of f on TC is rather weaker in comparison to σ2. The large drop in TC for high entropy system with respect to the conventional manganite is related to the local structural distortion which severely hampers the Mn3+—O—Mn4+ double exchange interaction. The competing magnetic interactions lead to magnetic phase separation as well as Griffith like phase. Spin pinning is noticed for the samples containing six elements in A-site which is independent on hole concentration. Possible spin clustering is also realized above ferromagnetic TC. Careful analysis of the magnetization data suggests that observed anomaly in magnetic behaviour can be ascribed to the local chemical disordering apart from the size disorder parameter. The possible role on magnetic properties of the number of elements occupying in a crystallographic site is emphasized.

Synergetic effect of Bi and Al co-doping in GeTe-based thermoelectric materials leading to optimized carrier concentration tuning and high ZT

Improving the performance of thermoelectric (TE) materials that can convert waste heat into electricity is becoming increasingly important. Accordingly, the dimensionless figure of merit, ZT needs to be increased. Al, a group-III element, has not been widely used as a dopant in GeTe-based thermoelectric materials because it acts as a p-type dopant and thus further increases the hole carrier concentration of GeTe, which has already a high intrinsic hole concentration due to inherent Ge vacancies. Therefore, Al as a dopant in GeTe has been considered to have detrimental effects on the resulting thermoelectric performance. In this study, we aim to enhance the suitability of Al doping in GeTe-based materials through synergistically co-doping it with Bi. In this case, co-doping Al and Bi optimizes the carrier concentration and induces a high Seebeck coefficient from an additional increased effective mass and low total thermal conductivity arising from the numerous phonons scattering centers and decreased electronic contribution to heat transport. Consequently, a maximum ZT of ∼1.95 at 673 K with an increased average ZT is achieved. These results indicate that the p-type dopant Al, co-doped with Bi in GeTe-based thermoelectric materials is one of the very effective dopants which can eventually improve the overall TE performance of these materials for useful waste heat recovery application and cooling.

High Detectivity of PbS Films Deposited on Quartz Substrates: The Role of Enhanced Photogenerated Carrier Separation.

PbS films grown on quartz substrates by the chemical bath deposition method were annealed in an O2 atmosphere to investigate the role of oxygen in the sensitization process at different annealing temperatures. The average grain size of the PbS films gradually increased as the annealing temperature increased from 400 °C to 700 °C. At an annealing temperature of 650 °C, the photoresponsivity and detectivity reached 1.67 A W-1 and 1.22 × 1010 cm Hz1/2 W-1, respectively. The role of oxides in the sensitization process was analyzed in combination with X-ray diffraction and scanning electron microscopy results, and a three-dimensional network model of the sensitization mechanism of PbS films was proposed. During the annealing process, O functioned as a p-type impurity, forming p+-type PbS layers with high hole concentrations on the surface and between the PbS grains. As annealing proceeds, the p+-type PbS layers at the grain boundaries interconnect to form a three-dimensional network structure of hole transport channels, while the unoxidized p-type PbS layers act as electron transport channels. Under bias, photogenerated electron-hole pairs were efficiently separated by the formed p+-p charge separation junction, thereby reducing electron-hole recombination and facilitating a higher infrared response.

Influence of Bi doping on the electronic structure of (Ga,Mn)As epitaxial layers

The influence of the addition of Bi to the dilute ferromagnetic semiconductor (Ga,Mn)As on its electronic structure as well as on its magnetic and structural properties has been studied. Epitaxial (Ga,Mn)(Bi,As) layers of high structural perfection have been grown using low-temperature molecular-beam epitaxy. Post-growth annealing of the samples improves their structural and magnetic properties and increases the hole concentration in the layers. Hard X-ray angle-resolved photoemission spectroscopy reveals a strongly dispersing band in the Mn-doped layers, which crosses the Fermi energy and is caused by the high concentration of Mn-induced itinerant holes located in the valence band. An increased density of states near the Fermi level is attributed to additional localized Mn states. In addition to a decrease in the chemical potential with increasing Mn doping, we find significant changes in the valence band caused by the incorporation of a small atomic fraction of Bi atoms. The spin–orbit split-off band is shifted to higher binding energies, which is inconsistent with the impurity band model of the band structure in (Ga,Mn)As. Spectroscopic ellipsometry and modulation photoreflectance spectroscopy results confirm the valence band modifications in the investigated layers.