Electronic Density Of States Research Articles

Thermoelectric performance of Ag2GeX3 (X = S, Se, Te) with intrinsically low lattice thermal conductivity: A first principles study

Low lattice thermal conductivity is one of the key factor for excellent thermoelectric performance of materials. In this work, we have systematically studied the thermoelectric properties of Ag2GeX3 (X = S, Se, Te) by first-principles calculations in combination with Boltzmann transport theory. In terms of phonon transmission performance, due to the low frequency of acoustic phonons, strong coupling between low-frequency optical phonons and acoustic phonons, and relatively strong anharmonicity, Ag2GeX3 (X = S, Se, Te) exhibits extremely low lattice thermal conductivity of 0.30 Wm−1K−1, 0.28 Wm−1K−1 and 0.65 Wm−1K−1 at room temperature, respectively. At the same time, Ag2GeX3 (X = S, Se, Te) also exhibits good electrical transport performance. The appropriate band gap and high slope of electronic density of states (DOS) near the Fermi level result in a large Seebeck coefficient of the materials. As a result, the optimal ZT values of p(n)-type Ag2GeX3 (X = S, Se, Te) are 1.4(1.2), 2.2(0.7), and 0.9(0.7) at 800 K, respectively. These results demonstrate outstanding thermoelectric performance of Ag2GeSe3 for energy conversion applications.

On Chemical Bonding in ht-Ga3Rh and Its Effect on Structural Organization and Thermoelectric Behavior.

In the course of systematic studies of intermetallic compounds Ga3TM (TM─transition metal), the compound Ga3Rh is synthesized by direct reaction of the elements at 700 °C. The material obtained is characterized as a high-temperature modification of Ga3Rh. Powder and single-crystal X-ray diffraction analyses reveal tetragonal symmetry (space group P42/mnm, No. 146) with a = 6.4808(2) Å and c = 6.5267(2) Å. Large values and strong anisotropy of the atomic displacement parameters of Ga atoms indicate essential disorder in the crystal structure. A split-position technique is applied to describe the real crystal structure of ht-Ga3Rh. Bonding analysis in ht-Ga3Rh performed on ordered models with the space groups P1̅, P42nm, and P42212 shows, besides the omnipresent heteroatomic Ga-Rh bonds in the rhombic prisms ∞3[Ga8/2Rh2], the formation of homoatomic Ga-Ga bonds bridging the Rh-Rh contacts and the absence of significant Rh-Rh bonding. These features are essential reasons for the experimentally observed disorder in the lattice. In agreement with the calculated electronic density of states, ht-Ga3Rh shows temperature-dependent electrical resistivity of a "bad metal". The very low lattice thermal conductivity of less than 0.5 W m-1 K-1 at 300 K, being lower than those for most other Ga3TM compounds, correlates with the enhanced bonding complexity.

Theoretical analysis of magnetic, optoelectronic, and thermoelectric properties of Cs2CuCrX6 (X = Cl and Br) double perovskites for spintronic and data storage devices

Spintronics is an emerging field that has the potential to replace conventional electronics due to their comparatively high speed, low power consumption, and infinite endurance. The phenomena of ferromagnetism with high spin polarization in double perovskites make them the desired materials for spintronics. In the present work, the structure of Cs2CuCrX6 (X = Cl and Br) and their magnetic and optoelectronic properties were studied by utilizing density functional theory (DFT). For the calculations of exchange-correlation potential, PBE-sol approximation was utilized while for the accurate measurement of electronic band structure and density of states (DOS), we employed mBJ potential. Both materials exhibit cubic structure and are thermodynamically stable as confirmed by volume optimization and negative formation energy respectively. Spin-based energy-volume optimization and values of exchange constants reveal the ferromagnetic nature of materials. It has been observed that 3-d states of Cr are responsible for ferromagnetism and have the major contribution to the net magnetic moment caused by exchange splitting. Furthermore, investigations of band structure and electronic density of states showed that both Cs2CuCrCl6 and Cs2CuCrBr6 were indirect bandgap (Eg) semiconductors with the Eg values of 1.2 eV and 0.33 eV respectively. The optical spectra of materials showed strong absorption in the ultraviolet region. Lastly, the transport and thermoelectric properties (TE) of materials were investigated in the range of temperature 300 K–800 K by using the BoltzTrap code. The transport parameter which included the electrical conductivity (σ/τ) and thermal conductivity (κe/τ) of the materials showed a decreasing trend with temperature whereas the Seebeck coefficient (S) and Power factor (P.F) showed an increasing trend for Cs2CuCrCl6 while decreases in case of Cs2CuCrBr6. Furthermore, a high figure of merit (ZT) with values of 0.75 and 0.64 was obtained for Cs2CuCrCl6 and Cs2CuCrBr6 respectively. The results of this work are encouraging and show the capabilities of the discussed materials in the fields of spintronics, thermoelectric, and optoelectronics.

Ce3Bi4Ni3 – A large hybridization-gap variant of Ce3Bi4Pt3

The family of cubic noncentrosymmetric 3-4-3 compounds has become a fertile ground for the discovery of novel correlated metallic and insulating phases. Here, we report the synthesis of a new heavy fermion compound, Ce3Bi4Ni3. It is an isoelectronic analog of the prototypical Kondo insulator Ce3Bi4Pt3 and of the recently discovered Weyl-Kondo semimetal Ce3Bi4Pd3. In contrast to the volume-preserving Pt-Pd substitution, structural and chemical analyses reveal a positive chemical pressure effect in Ce3Bi4Ni3 relative to its heavier counterparts. Based on the results of electrical resistivity, Hall effect, magnetic susceptibility, and specific heat measurements, we identify an energy gap of 65–70 meV, about eight times larger than that in Ce3Bi4Pt3 and about 45 times larger than that of the Kondo-insulating background hosting the Weyl nodes in Ce3Bi4Pd3. We show that this gap as well as other physical properties do not evolve monotonically with increasing atomic number, i.e., in the sequence Ce3Bi4Ni3−Ce3Bi4Pd3−Ce3Bi4Pt3, but instead with increasing partial electronic density of states of the d orbitals at the Fermi energy. This work opens the possibility to investigate the conditions under which topological states develop in this series of strongly correlated 3-4-3 materials. Published by the American Physical Society 2024

Prediction of electronic density of states in guanine-TiO2 adsorption model based on machine learning

The electronic density of states is a property of the material that is extensively used in quantum systems in condensed matter physics. It refers to the energy level of the electrons in a solid crystal. One of the most current ways to compute it is by Density Functional Tight Binding (DFTB), given the geometry of the material. Nevertheless, this computation could be very computationally demanding, although applied to some materials with a very reduced number of atoms. This paper presents a method to deduce the electronic density of states, which is based on a neural network, thus, almost linear with respect to the number of atoms in the material. Specifically, we have applied our method to a metal oxide structure interacting with a nucleic base guanine. We have focused on stoichiometric and O-defective anatase TiO2 (101) surfaces. The data set of the electronic density of states needed to train the neural network has been obtained by a DFTB+ numerical solver given an initial molecular geometry model, which computed a track of time-dependent geometry and their associated electronic density of states. We validated that the predicted electronic density of states deduced by our method and by DFTB tends to be very similar, thus, opening the door to other computations such that introducing our method in the process of generating the time-dependent geometry analysis.

Luminescence enhancement effects of CaxSr2‒xNb2O7:Er3+,Tm3+ phosphors for temperature sensing and anti-counterfeiting applications

Er3+- and Tm3+-doped CaxSr2‒xNb2O7 (CxS2‒xN, x = 0.6, 0.8, 1.0, 1.2, 1.4) phosphors with layered perovskite structure were designed. These phosphors exhibit a dominant emission peak at 549 nm under 980 nm laser excitation, attributed to the 4S3/2→4I15/2 transition. By increasing the content of Ca2+, the crystal field regulation of rare earth ions is realized and the luminescence enhancement is induced, which is manifested by the increase of 2H11/2,4S3/2→4I15/2 emission. Furthermore, the temperature sensing sensitivities of C0.6S1.4N:Er,Tm and C0.6S1.4N:Er,Tm based on non-thermally coupled energy levels were studied. Finally, an anti-counterfeiting imprint was prepared using phosphors, which have high brightness and excellent photothermal stability. This work not only confirms that closer ionic radii substitution enables to increase the electronic density of states, improve the crystal field symmetry and enhance the luminescence, but also provides a promising phosphor system for temperature sensing and anti-counterfeiting applications, opening up new prospects in the optimization of the optical properties of phosphors.

Velocity Map Imaging Photoelectron Spectroscopy of Silver Iodide Aerosol Particles.

The valence band electronic structure of isolated silver iodide nanoparticles (AgI NP) was investigated by vacuum-ultraviolet aerosol photoelectron spectroscopy using the velocity map imaging technique (VUV VMI-PES). The VUV VMI-PES results were obtained for polydisperse aerosol produced by aggregation of hydrocolloid of silver iodide particles 8-15 nm in size. The ionization energy of the AgI particles was found to be 6.0±0.1 eV with respect to the vacuum level. The DFT calculations showed that the main contribution to the density of AgI electronic states in the valence region originates from I 5p orbitals. The dependence of the asymmetry parameter on the electron energy showed that the value of the characteristic energy loss of excited photoelectrons was 2.7 eV, which coincided with the band gap of the nanomaterial.

Amorphous MoS2 from a machine learning inter-atomic potential.

Amorphous molybdenum disulfide has shown potential as a hydrogen evolution catalyst, but the origin of its high activity is unclear, as is its atomic structure. Here, we have developed a classical inter-atomic potential using the charge equilibration neural network method, and we have employed it to generate atomic models of amorphous MoS2 by melting and quenching processes. The amorphous phase contains an abundance of molybdenum and sulfur atoms in low coordination. Besides the 6-coordinated molybdenum typical of the crystalline phases, a substantial fraction displays coordinations 4 and 5. The amorphous phase is also characterized by the appearance of direct S-S bonds. Density functional theory shows that the amorphous phase is metallic, with a considerable contribution of the 4-coordinated molybdenum to the density of states at the Fermi level. S-S bonds are related to the reduction of sulfur, with the excess electrons spread over several molybdenum atoms. Moreover, S-S bond formation is associated with a distinctive broadening of the 3s states, which could be exploited for experimental characterization of the amorphous phases. The large variety of local environments and the high density of electronic states at the Fermi level may play a positive role in increasing the electrocatalytic activity of this compound.

Electronic and optical properties of S vacancy and Br and I doped monolayer MoS2: A first-principle study

This study investigated the energy band structure (BS), electronic state density, and optical properties of monolayer molybdenum disulfide (ML-MoS2) with undoped, sulfur vacancy (VS), bromine (Br), and iodine (I) doped MoS2 systems using the first-principle approach based on density functional theory (DFT). Our results show that compared to undoped MoS2 system, Br, and I doped MoS2 systems induced lattice distortions. In addition, and the bandgap widths was reduced in VS, Br, and I doped systems, thereby effectively suppressing the compounding of electron–hole pairs. Moreover, the recombination rate of electron–hole pairs was reduced, which in turn increased the mobility of electrons transferred from the valence band (VB) to the conduction band (CB). Moreover, the VS and Br doped systems exhibited superior optical properties compared to undoped MoS2 system. Notably, the VS system exhibited the best optical properties, thereby demonstrating the strongest polarization capability. Our findings pave the way for realizing electronic devices and photocatalytic materials on MoS2 nanostructures.

Effect of the behavior on direct–indirect electronic transitions of SrZrO3 nanowires grown in the crystallographic directions [100] and [110]: Ab-initio study

In the present work, we studied a set of strontium zirconate nanowires of different diameters oriented in the directions [100] and [110]. The density functional theory calculations were performed using the quantum espresso code, which confidently employs a combination of plane waves. In this study, we utilized a pseudopotential proposed by Perdew, Burke, and Ernzerhof to model the exchange–correlation energy using a generalized gradient approximation. In the study’s first phase, we performed a structural optimization of the nanowires by adjusting the atomic positions and lattice parameters. After calculating the electronic band structure and density of states, we found that the strontium zirconate nanowires in this study are semiconductors. The nanowires in the [100] direction have an indirect transition, while those in the [110] direction have a direct transition. Besides, the bandgap varies with diameter. We also calculated the density of states projected. Based on the results, it can be observed that the p orbital of oxygen is the primary contributor to the density of states in the valence region. On the other hand, in the conduction region, the density of states is mainly affected by the d and s orbitals of zirconium. Due to their exceptional electronic properties, strontium zirconate nanowires are up-and-coming candidates for photocatalysis and solar cell applications.

First-principles study of Ni clusters growth on graphene with a vacancy

In this work, we performed first-principles calculations to study the interactions of Nin clusters (n = 2-5) with graphene. Nin clusters were adsorbed on pristine graphene and graphene with a vacancy. We observed that the adsorption energy is significantly lowered when graphene has a single vacancy. The single vacancy gives place to a charge redistribution that favors chemisorption. The dangling bonds of the carbon atoms produced by the vacancy increase the magnetic moment of the C atoms around the hole induced by the Ni clusters. We found that the situation is very different when the Ni cluster is adsorbed with atoms on both sides of the vacancy. We consider the cases in which one of the Ni atoms is located on one side of the graphene sheet and the rest on the other, Nin,1. The adsorption energy for Ni3,1 and Ni4,1 clusters are slightly larger than when the whole cluster is chemisorbed on one side only, but the charge redistribution, occurring on both sides of the graphene, increases the possibility to adsorb other molecules. For all cases, we analyzed the electronic density of states to account for the electronic changes on the graphene sheet as a function of the size of the Nin cluster. Finally, the Bader effective charges were computed to follow the charge transfer between Nin clusters and the graphene atoms.

Superconductivity in Twisted Bismuth Bilayers

AbstractTwo twisted bismuth bilayers, TBB, each with 120 atoms, are studied using their electron density of states and their vibrational density of states using first‐principles calculations. Metallic character at the Fermi level is found for the non‐rotated sample as well as for each sample rotated 0.5°, 1.0°, 1.5°, 2.0°, 2.5°, 3.0°, 4.0°, 5.0°, 6.0°, 7.0°, 8.0°, and 10° with respect to each other. Assuming that the superconductivity is BCS‐type and the invariance of the Cooper pairing potential, a maximum superconducting temperature TC ≈1.8 K is predicted for a magic angle of 0.5° between the two bilayers, increasing the superconducting transition temperature from the experimentally measured value of 0.53 mK for the Wyckoff structure of crystalline bismuth.

Analysis of the Optical Properties and Electronic Structure of Semiconductors of the Cu2NiXS4 (X = Si, Ge, Sn) Family as New Promising Materials for Optoelectronic Devices

In this work, the optoelectronic characteristics of kesterites of the Cu2NiXS4 system (X = Si, Ge, Sn) were studied. The electronic properties of the Cu2NiXS4 (X = Si, Ge, Sn) system were studied using first-principles calculations within the framework of density functional theory. For calculations, ab initio codes VASP and Wien2k were used. The high-precision modified Beke-Jones (mBJ) functional and the hybrid HSE06 functional were used to estimate the bandgap, electronic, and optical properties. Calculations have shown that when replacing Si with Ge and Sn, the band gap decreases from 2.58 eV to 1.33 eV. Replacing Si with Ge and Sn reduces the overall density of electronic states. In addition, new deep (shallow) states are formed in the band gap of these crystals, which is confirmed by the behavior of their optical properties. The obtained band gap values are compared with existing experimental measurements, demonstrating good agreement between HSE06 calculations and experimental data. The nature of changes in the dielectric constant, absorption capacity, and optical conductivity of these systems depending on the photon energy has also been studied. The statistical dielectric constant and refractive index of these materials were found. The results will help increase the amount of information about the properties of the materials under study and will allow the use of these compounds in a wider range of optoelectronic devices, in particular, in solar cells and other devices that use solar radiation to generate electric current.

Optoelectronic properties of mechanically stable cubic Niobate compounds under hydrostatic pressure: A systematic DFT investigation

Perovskite oxides, particularly cubic Niobate compounds, have been studied for their potential application in the development of optoelectronic devices. The mechanical stability of these compounds has been verified by determining their elastic constants. Based on an analysis of their electronic band structures and densities of states, it has been found that both compounds exhibit non-magnetic behavior and possess properties typical of indirect bandgap semiconductors. The bandgap energies of the compounds are 1.524 eV and 1.392 eV, respectively. The optical properties of the compounds are analyzed under varying hydrostatic pressure conditions. Bandgap modulation results in a shift in absorption spectra from ultraviolet to visible wavelengths, rendering the materials appropriate for use in optoelectronic devices. Perovskites with (K,Rb)NbO3 exhibit potential as non-magnetic indirect bandgap semiconductors for the advancement of optoelectronic devices.

Structural stability, electronic, magnetic, thermoelectric, optical and thermodynamic properties of CoTiFeGe and Co2Fe0.25Mn0.75-xTixGe alloys

Density Functional Theory (DFT) calculations are performed using full potential linearized augmented plane wave (FP-LAPW) method to study CoTiFeGe and Co2Fe0.25Mn0.75-xTixGe (x = 0, 0.25, 0.50, 0.75) systems through GGA and mBJ-GGA formalisms. The lattice equilibrium optimization was conducted to determine the stable magnetic phase state of these systems. It was found that the systems exhibit stability in a ferromagnetic nature, with the exception of the Co2Fe0.25Mn0.75Ge compound, which displays ferrimagnetic behavior. Electronic band structures and density of states for our systems show a half-metallic character using mBJ-GGA, except the Co2Fe0.25Mn0.75Ge system, which exhibits metallic behavior. Furthermore, the studied systems adhere to the Slater-Pauling rule condition for half-metallicity of alloys Mtot = ZV-24. Optoelectronic properties have been analyzed using optical parameters, confirming semiconducting behavior. Optical reflections with minimal loss and the existence absorption are observed in the infrared and visible areas suggest that the studied systems are suitable for optoelectronic devices. Additionally, a comprehensive assessment of the thermodynamic properties of the systems was carried out to investigate their thermodynamical stability against temperature and pressure change. The transport properties of these systems were systematically investigated, revealing that our alloys present the poor thermoelectric matter.

Hafnium dinitride/poly(9-vinylcarbazole) heterojunction: Structural, electronic, optical and vibrational properties. A DFT and DFPT study

Photosensitivity of semiconducting polymers can be enhanced by blending donor and acceptor polymers to optimize photoinduced charge separation. With a motivation to understand microscopic aspects of HfN2 and PVK relevant to optoelectronic properties of transition metal-dinitride/semiconductor interfaces, we examined their structural, electronic, optical and vibrational properties using first-principles calculations based on density functional theory (DFT) and density functional perturbation theory (DFPT) levels of theory. We computed a large direct energy gap of 3.751 eV for PVK and an indirect narrow band gap of 1.396 eV in HfN2. The gap value computed for the composite structure, HfN2/PVK, was 0.958 eV. The heterojunction displayed an indirect energy gap. The charge transfer between HfN2 and PVK results in a polarized field within the interface region, which will benefit the separation of photogenerated carriers. The calculated density of electronic states, Lowdin charge transfer and charge density difference certify that this proposed layered nanoheterojunction is an excellent light-harvesting semiconductor. These findings indicate that the conjugated polymer PVK is a promising candidate as a non-noble metal co-catalyst for HfN2 photocatalysis. It also provides useful information for understanding the observed enhanced photocatalytic mechanisms in experiments.

The structural, mechanical, electronic, lattice dynamics and thermodynamic properties of TaTSi (T = Rh, Os, Ir) compounds by first-principles calculations

We have performed a theoretical calculation, based on density functional theory, to investigate the structural, mechanical, electronic, lattice dynamics, and thermodynamic properties of TaTSi (T = Rh, Os, Ir) within the full potential linearized augmented plane wave method. The calculated values of the lattice constant and unit cell volume are in excellent agreement with the available experimental data. The mechanical stability is substantiated by our calculated elastic constants, while the mechanical properties are subsequently derived. The results indicate that the compounds are ductile materials, except for TaRhSi which exhibits quasi-ductile behavior; however, all of them exhibit elastic anisotropy. In addition, the electronic density of states of the TaTSi (T = Rh, Os, Ir) compounds reveal that all these materials have a metallic character. Moreover, the dynamical stability is confirmed by our calculated phonon spectra. Finally, we present temperature-dependent thermodynamic properties including free energy, internal energy, entropy, and heat capacity.

Superhydrophobic Co/Fe sulfide nanoparticles and single-atoms doped carbon nanosheets composite air cathode for high-performance zinc-air batteries

Development of a high-performance bifunctional catalyst is essential for the actual implementation of zinc-air batteries in practical applications. Herein, a bifunctional cathode of Co3S4/FeS heterogeneous nanoparticles embedded in Co/Fe single-atom-loaded nitrogen-doped carbon nanosheets is designed. Cobalt-iron sulfides and single atomic sites with Co-N4/Fe-N4 configurations are confirmed to coexist on the carbon matrix by EXAFS spectroscopy. 3D self-supported super-hydrophobic multiphase composite cathode provides abundant active sites and facilitates gas–liquid-solid three-phase interface reactions, resulting in excellent electrocatalytic activity and batteries performance, i.e., an OER overpotential (η10) of 260 mV, a half-wave potential (E1/2) of 0.872 V for ORR, a ΔE of 0.618 V, and a discharge power density of 170 mW cm−2, a specific capacity of 816.3 mAh g−1. DFT analysis shows multiphase coupling of sulfide heterojunction through single-atomic metal doped carbon nanosheets reduces offset on center of electronic density of states before and after oxygen adsorption, and spin density of adsorbed oxygen with same spin orientation, leading to weakened charge/spin interactions between adsorbed oxygen and substrate, and a lowered oxygen adsorption energy to accelerate OER/ORR.

First-Principles Calculations of P-B Co-Doped Cluster N-Type Diamond

To achieve n-type doping in diamond, extensive investigations employing first principles have been conducted on various models of phosphorus doping and boron–phosphorus co-doping. The primary focus of this study is to comprehensively analyze the formation energy, band structure, density of states, and ionization energy of these structures. It is observed that within a diamond structure solely composed of phosphorus atoms, the formation energy of an individual carbon atom is excessively high. However, the P-V complex substitutes 2 of the 216 carbon atoms, leading to the transformation of diamond from an insulator to a p-type semiconductor. Upon examining the P-B co-doped structure, it is revealed that the doped impurities exhibit a tendency to form more stable cluster configurations. As the separation between the individually doped atoms and the cluster impurity structure increases, the overall stability of the structure diminishes, consequently resulting in an elevation of the ionization energy. Examination of the electronic density of states indicates that the contribution of B atoms to the impurity level is negligible in the case of P-B doping.

The origin of exceptionally large ductility in molybdenum alloys dispersed with irregular-shaped La2O3 nano-particles

Molybdenum and its alloys are known for their superior strength among body-centered cubic materials. However, their widespread application is hindered by a significant decrease in ductility at lower temperatures. In this study, we demonstrate the achievement of exceptional ductility in a Mo alloy containing rare-earth La2O3 nanoparticles through rotary-swaging, a rarity in Mo-based materials. Our analysis reveals that the large ductility originates from substantial variations in the electronic density of states, a characteristic intrinsic to rare-earth elements. This characteristic can accelerate the generation of oxygen vacancies, facilitating the amorphization of the oxide-matrix interface. This process promotes vacancy absorption and modification of dislocation configurations. Furthermore, by inducing irregular shapes in the La2O3 nanoparticles through rotary-swaging, incoming dislocations interact with them, creating multiple dislocation sources near the interface. These dislocation sources act as potent initiators at even reduced temperatures, fostering diverse dislocation types and intricate networks, ultimately enhancing dislocation plasticity.