Charge transport in thin layers of ferroelectric Hf<Subscript>0.5</Subscript>Zr<Subscript>0.5</Subscript>O<Subscript>2</Subscript>

The mechanism responsible for the charge transport in thin ferroelectric Hf_0.5Zr_0.5O₂ films has been studied. It is shown that in these films the transport mechanism is phonon-assisted tunneling between the traps. The optimal thickness of dielectric film for TiN/Hf_0.5Zr_0.5O₂/Pt structures is determined. As a result of comparing the experimental current–voltage (I–V) characteristics of TiN/Hf_0.5Zr_0.5O₂/Pt structures with the calculated ones, the thermal and optical energies of the traps are determined and the concentration of the traps is estimated. A comparison between the transport properties of ferroelectric and amorphous Hf_0.5Zr_0.5O₂ films is carried out. It is shown that the charge transport mechanism in this dielectric does not depend on its crystalline phase. A method for decreasing leakage currents in Hf_0.5Zr_0.5O₂ is proposed. A study of the resource of repolarization cycles for TiN/Hf_0.5Zr_0.5O₂/TiN metal-dielectric-metal (MDM) structures fully grown by atomic layer deposition (ALD) has been carried out.     

Fabrication and properties of ZnFe<Subscript>2</Subscript>S<Subscript>4</Subscript> single crystals and structures based on them

A new class of ternary semiconductor compounds has been proposed and synthesized. ZnFe₂S₄ single crystals, which belong to this class, have been grown for the first time; and their structural, electrical, and optical properties have been investigated. The first photosensitive structures have been fabricated, and their photoelectric characteristics have been studied. A conclusion was made that heterostructures and surface-barrier structures based on ZnFe₂S₄ single crystals are promising for practical applications.     

First-Principles Study of Semiconducting Clathrate Ba<Subscript>8</Subscript>Al<Subscript>16</Subscript>Ge<Subscript>30</Subscript>

We calculated electronic structures of Ba₈Al₁₆Ge₃₀ in some Al-Ge framework configurations without nearest-neighbor Al-Al bonds by using a first-principles method. The calculated band structures are similar in outline but different in detail. We also calculated thermoelectric properties by using the electronic structures to analyze the experimental results on a sintered Ba₈Al₁₆Ge₃₀ sample. The calculated properties nearly agree with the experimental results; however, the calculated temperature dependences of electrical conductivity are slightly different from one another, because of differences in electronic structure. In this paper, we discuss the temperature dependence from the viewpoints of nonparabolic band effects.     

Electrical properties of In<Subscript>2</Subscript>Se<Subscript>3</Subscript> single crystals and photosensitivity of Al/In<Subscript>2</Subscript>Se<Subscript>3</Subscript> Schottky barriers

In₂Se₃ single crystals ∼40 mm long and 14 mm in diameter were grown by the Bridgman method. The composition of grown single crystals and their crystal structure were determined. The conductivity (σ) and Hall constant (R) of grown single crystals were measured and the first Schottky barriers Al/n-In₂Se₃ were fabricated. Rectification and photovoltaic effect were detected in the new structures. Based on the study of the photosensitivity spectra of Al/n-In₂Se₃ structures, the nature of the interband transitions and band gap of In₂Se₃ crystals were determined. It was concluded that the new structures can be applied to develop broadband photoconverters of optical radiation.     

Development and photoelectric properties of In/<Emphasis Type="Italic">p</Emphasis>-Ag<Subscript>3</Subscript>AsS<Subscript>3</Subscript> surface-barrier structures

Homogeneous p-Ag₃AsS₃ bulk single crystals with rhombic structure have been grown by planar crystallization from melts with atomic composition corresponding to this ternary compound. Photosensitive surface-barrier structures based on the interface between the surface of these crystals and thin films of pure indium are fabricated for the first time. The photosensitivity of fabricated structures is studied in natural and linearly polarized light. Photosensitivity spectra of In/p-Ag₃AsS₃ structures are measured for the first time and used to determine the nature and energy of interband transitions in p-Ag₃AsS₃ crystals. The phenomenon of natural photopleochroism is studied for surface-barrier structures grown on oriented p-Ag₃AsS₃ single crystals. It is concluded that Ag₃AsS₃ single crystals can be used in photoconverters of natural and linearly polarized light.     

Optical Study of Filled Tetrahedral Compounds Li<Subscript>3</Subscript>AlN<Subscript>2</Subscript> and Li<Subscript>3</Subscript>GaN<Subscript>2</Subscript>

A detailed analysis of the optical properties of filled tetrahedral semiconductors Li₃AlN₂ and Li₃GaN₂ has been performed, using the full potential linearized augmented plane wave method within the density functional theory. The real and imaginary parts of the dielectric function ε(ω), the optical absorption coefficient I(ω), the reflectivity R(ω), and the electron energy loss function are calculated within the random phase approximation. The interband transitions responsible for the structures in the spectra are specified. Looking at optical matrix element, we note that the major peaks are dominated by transition from metal s, N 2p states to N 2p, Ga 3d states. The theoretical calculated optical properties and electron energy loss spectrum yield a static dielectric constant of 5.34 and a plasmon energy of 19.47 eV for Li₃GaN₂. In the Li₃AlN₂ compound, the static dielectric constant decreases to 4.75 and yields a plasmon energy of 18.5 eV. The effect of spin–orbit coupling on the optical properties is also investigated and found to be quite small, especially in the low-energy region. In order to check the reliability of our calculations, analogous results obtained for Be₃N₂ in the same structure [space group Ia3(206)] are included in this work.     

Effect of Vacancy Distribution on the Thermal Conductivity of Ga<Subscript>2</Subscript>Te<Subscript>3</Subscript> and Ga<Subscript>2</Subscript>Se<Subscript>3</Subscript>

Our group has focused attention on Ga₂Te₃ as a natural nanostructured thermoelectric material. Ga₂Te₃ has basically a zincblende structure, but one-third of the Ga sites are structural vacancies due to the valence mismatch between Ga and Te. It has been confirmed that (1) vacancies in Ga₂Te₃ exist as two-dimensional (2D) vacancy planes, and (2) Ga₂Te₃ exhibits an unexpectedly low thermal conductivity (κ), most likely due to highly effective phonon scattering by the 2D vacancy planes. However, the effect of the size and periodicity of the 2D vacancy planes on κ has been unclear. In addition, it has also been unclear whether only the 2D vacancy planes reduce κ or if point-type vacancies can also reduce κ. In the present study, we tried to prepare Ga₂Te₃ and Ga₂Se₃ with various vacancy distributions by controlling annealing conditions. The atomic structures of the samples were characterized by means of transmission electron microscopy, and κ was evaluated from the thermal diffusivity measured by the laser flash method. The effects of vacancy distributions on κ of Ga₂Te₃ and Ga₂Se₃ are discussed.     

Properties of CuIn<Subscript>3</Subscript>Se<Subscript>5</Subscript> crystals and In/CuIn<Subscript>3</Subscript>Se<Subscript>5</Subscript> structures

Using the method of planar crystallization from the melt with deviations from the stoichiometric composition, p-CuIn₃Se₅ single crystals are grown. The electrical properties of the homogeneous crystals are studied. It is found that the resistivity of the p-CuIn₃Se₅ crystals depends on the excess Se content in the melt. It is established that the voltaic photosensitivity of the In/CuIn₃Se₅ structures is enhanced with an increasing excess of Se content in the melt. The energy spectrum and the character of interband transitions in the CuIn₃Se₅ crystals are discussed. It is concluded that the CuIn₃Se₅ ternary compound can be used in high efficiency photoelectric converters of solar radiation.     

Fabrication and photoelectric properties of oxide/CuIn<Subscript>5</Subscript>Se<Subscript>8</Subscript> heterojunctions

Single crystals of the n-CuIn₅Se₈ compound of hexagonal modification have been grown by direct crystallization from melt. On the basis of the experimental study of its thermal interaction with air oxygen, a method for fabricating new oxide/n-CuIn₅Se₈ heterojunctions is proposed. Electrical and photoelectric properties of the structures obtained have been investigated. It is shown that the interaction of n-CuIn₅Se₈ of hexagonal modification with air oxygen makes it possible to obtain heterojunctions with high photosensitivity. The new technology can be used in the design of broadband optical radiation converters based on n-CuIn₅Se₈ crystals.     

Photosensitive structure on CdGa<Subscript>2</Subscript>S<Subscript>4</Subscript> single crystals

Single crystals of the CdGa₂S₄ ternary compound were grown either from melt or by chemical-vapor deposition. The crystal-lattice parameters and some physical properties of homogeneous crystals having defect chalcopyrite structure with the point symmetry group \(I\bar 4(S_4^2 )\) are determined. A number of photosensitive structures—Schottky barriers, heterostructures, photoelectrochemical cells, and natural-protein-CdGa₂S₄ barriers—were formed for the first time on the basis of the single crystals under investigation. The photoelectric properties of the structures obtained were studied using natural and linearly polarized light at T=300 K. The main parameters of these structures are determined, and it is concluded that they can be used in photodetectors.     

Magnetic susceptibility of Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript>-Sb<Subscript>2</Subscript>Te<Subscript>3</Subscript> alloys

The magnetic susceptibility of Czochralski-grown single crystals of Bi₂Te₃-Sb₂Te₃ alloys containing 0, 10, 25, 40, 50, 60, 65, 70, 80, 90, 99.5, or 100 mol % Sb₂Te₃ has been investigated. The magnetic susceptibility of these crystals was determined at the temperature T = 291 K and the magnetic field H oriented parallel (χ_‖) and perpendicularly (χ_⊥) to the trigonal crystallographic axis C ₃. A complicated concentration dependence of the anisotropy of magnetic susceptibility χ_‖/χ_⊥ has been revealed. The crystals with the free carrier concentration p ≈ 5 × 10¹⁹ cm^?3 do not exhibit anisotropy of magnetic susceptibility. The transition to the isotropic magnetic state occurs for the compositions characterized by a significantly increased (from 200 to 300 meV) optical bandgap.     

LaAlO<Subscript>3</Subscript>/SrTiO<Subscript>3</Subscript> Epitaxial Heterostructures by Atomic Layer Deposition

Thin films of LaAlO₃ were deposited on TiO₂-terminated (100) SrTiO₃ crystals by atomic layer deposition (ALD), using tris(iso-propylcyclopentadienyl)lanthanum and trimethyl aluminum precursors. Water was used as the oxidizer. The film composition was shown to be controlled by the ratio of La/Al precursor pulses during ALD, with near-stoichiometric LaAlO₃ resulting at precursor pulse ratios of 4/1 to 5/1. Films near the stoichiometric LaAlO₃ composition were shown to crystallize on subsequent annealing to form epitaxial LaAlO₃/SrTiO₃ heterostructures. Electrical characterization of these structures was done by two-terminal direct-current (DC) current–voltage scans at room temperature and under high-vacuum conditions. The results show electrical conductivity for the ALD-deposited epitaxial LaAlO₃/SrTiO₃ heterostructures, which turns on for thickness above four unit cells for the LaAlO₃ film.     

Preparation and Thermoelectric Properties of Nanoporous Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript>-Based Alloys

n-Type nanoporous Bi₂Te₃-based thermoelectric materials with different porosity ratios have been prepared by spark plasma sintering (SPS). The microstructure and phase morphology have been analyzed by x-ray diffraction (XRD) and field-emission scanning electron microscopy (FESEM), and the thermoelectric properties of the SPS samples have been measured. Experimental results show that the nanoporous structures lying in the sheet layers and among the plate grains of the Bi₂Te₃ bulk material can lead to an increase in the Seebeck coefficient and a decrease in the thermal conductivity, thus leading to an enhanced figure of merit.     

Fabrication and properties of photosensitive structures based on ZnIn<Subscript>2</Subscript>S<Subscript>4</Subscript> single crystals

Photosensitive structures based on single crystals of the ZnIn₂S₄ ternary compound were fabricated and studied for the first time. The optoelectronic properties of this compound and corresponding structures were analyzed using the results of measurements of the optical-absorption spectra of ZnIn₂S₄ crystals, steady-state current-voltage characteristics, and photosensitivity of the structures at T=300 K. It is concluded that surface-barrier structures and heterojunctions based on ZnIn₂S₄ can be used as wide-band photodetectors of natural optical radiation.     

Photosensitive structures based on In<Subscript>2</Subscript>S<Subscript>3</Subscript> crystals

Crystals of the compound In₂S₃ were grown by planar crystallization of the melt. The composition, structure, and electrical characteristics of the crystals obtained were determined. Photosensitive structures based on the grown In₂S₃ crystals were fabricated for the first time; spectral dependences of photoconversion quantum efficiency for H₂O/In₂S₃ cells were measured. The features of the band-to-band absorption are discussed; energies of the direct and indirect optical transitions for In₂S₃ crystals are estimated. It is stated that In₂S₃ crystals can be used in wide-range (1.5–3.5 eV) photoconverters of nonpolarized radiation (in particular, in solar cells).     

First-Principles Study of Electronic Structure,Mechanical, and Thermoelectric Properties of Ternary Palladates CdPd<Subscript>3</Subscript>O<Subscript>4</Subscript> and TlPd<Subscript>3</Subscript>O<Subscript>4</Subscript>

Ternary palladates CdPd₃O₄ and TlPd₃O₄ have been studied theoretically using the generalized gradient approximation (GGA), modified Becke–Johnson, and spin–orbit coupling (GGA–SOC) exchange–correlation functionals in the density functional theory (DFT) framework. From the calculated ground-state properties, it is found that SOC effects are dominant in these palladates. Mechanical properties reveal that both compounds are ductile in nature. The electronic band structures show that CdPd₃O₄ is metallic, whereas TlPd₃O₄ is an indirect-bandgap semiconductor with energy gap of 1.1 eV. The optical properties show that TlPd₃O₄ is a good dielectric material. The dense electronic states, narrow-gap semiconductor nature, and Seebeck coefficient of TlPd₃O₄ suggest that it could be used as a good thermoelectric material. The magnetic susceptibility calculated by post-DFT treatment confirmed the paramagnetic behavior of these compounds.     

Effect of ZnO Nanoparticles on the Sintering Behavior and Physical Properties of Bi<Subscript>0.5</Subscript>(Na<Subscript>0.8</Subscript>K<Subscript>0.2</Subscript>)<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript> Lead-Free Ceramics

Sintered Bi_0.5(Na_0.8K_0.2)_0.5TiO₃ + x wt.% ZnO nanoparticle (BNKT–xZnO_n) ceramics have been fabricated by conventional annealing with the aid of ultrasound waves for preliminary milling. Because of the presence of the liquid Bi₂O₃–ZnO phase at the eutectic point of 738°C, the sintering temperature decreased from 1150°C to 1000°C, and the morphology phase boundary of BNKT–xZnO_n ceramics can be clarified by two separated peaks at (002)_T and (200)_T of 2θ in the x-ray diffraction (XRD) patterns. The improvement of ferroelectric properties has been obtained for BNZT–0.2 wt.% ZnO_n ceramics by the increase of remanent polarization up to 20.4 μC/cm² and a decrease of electric coercive field down to 14.2 kV/cm. The piezoelectric parameters of the ceramic included a piezoelectric charge constant of d ₃₁ = 78 pC/N; electromechanical coupling factors k _p = 0.31 and k _t = 0.34, larger than the values of 42 pC/N, 0.12 and 0.13, respectively, were obtained for the BNKT ceramics.     

Cadmium-free thin-film Cu(In,Ga)Se<Subscript>2</Subscript>/(In<Subscript>2</Subscript>S<Subscript>3</Subscript>) heterophotoelements: Fabrication and properties

The method of heat treatment of metallic Cu-In-Ga layers in the N₂ inert atmosphere in the presence of selenium and sulfur vapors was used to grow homogeneous films of Cu(In,Ga)(S,Se)₂ alloys onto which the CdS or In₂S₃ films were deposited and, on the basis of these structures, the thin-film glass/Mo/p-Cu(In,Ga) (S,Se)₂/n-(In₂S₃,CdS)/n-ZnO/Ni-Al photoelements were fabricated. The mechanisms of charge transport and the processes of photosensitivity in the obtained structures subjected to irradiation with natural and linearly polarized light are discussed. The broadband photosensitivity of thin-film heterophotoelements and the induced photopleochroism were detected; these findings indicate that there is an interference-related blooming of the structures obtained. It is concluded that it is possible to use ecologically safe cadmium-free thin-film heterostructures as high-efficiency photoconverters of solar radiation.     

Optical Properties of K<Subscript>2</Subscript>O-Li<Subscript>2</Subscript>O-WO<Subscript>3</Subscript>-B<Subscript>2</Subscript>O<Subscript>3</Subscript> Glasses: Evidence of Mixed Alkali Effect

Glass with compositions xK₂O-(30 ? x)Li₂O-10WO₃-60B₂O₃ for 0 ≤ x ≤ 30 mol.% have been prepared using the normal melt quenching technique. The optical reflection and absorption spectra were recorded at room temperature in the wavelength range 300–800 nm. From the absorption edge studies, the values of the optical band gap (E _opt) and Urbach energy (ΔE) have been evaluated. The values of E _opt and ΔE vary non-linearly with composition parameter, showing the mixed alkali effect. The dispersion of the refractive index is discussed in terms of the single oscillator Wemple Di-Domenico model.     

Photoconversion in <Emphasis Type="Italic">n</Emphasis>-ZnO:Al/Pd<Emphasis Type="Italic">Pc/p</Emphasis>-CuIn<Subscript>3</Subscript>Se<Subscript>5</Subscript> structures

n-ZnO:Al/PdPc/p-CuIn₃Se₅ photosensitive structures have been proposed and fabricated for the first time by vacuum sublimation of palladium phthalocyanine on the surface of wafers of the ternary semiconductor compound CuIn₃Se₅ and by magnetron sputtering of n-ZnO:Al films on the surface of palladium phthalocyanine films. The current-voltage characteristics and spectra of the photoconversion quantum efficiency of the obtained structures are investigated. It is shown that these structures can be used as multiband white-light converters.