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).     

Enhancing Thermoelectric Properties of Polycrystalline Bi<Subscript>2</Subscript>S<Subscript>3</Subscript> by Optimizing a Ball-Milling Process

Bismuth sulfide (Bi₂S₃) polycrystalline samples were fabricated by mechanical alloying (MA) combined with spark plasma sintering (SPS). The microstructure and electrical transport properties were investigated with special emphasis on the influence of the ball-milling process. Bi₂S₃ compound powders could be readily synthesized directly from elemental powders under all the investigated conditions, and highly dense n-type bulk Bi₂S₃ samples with high density (>95%) were fabricated by the subsequent SPS process. Changing the MA conditions had no apparent influence on the microstructure or phase structure of the MA-derived Bi₂S₃ powders, but the electrical properties and thermopower of the SPS-sintered Bi₂S₃ bulk samples were greatly dependent on the MA speed and time. The power factor of Bi₂S₃ was increased to 233 μW K⁻² m⁻¹ at 573 K by optimizing the ball-milling process. This power factor is higher than values reported to date for Bi-S binary samples without texture.     

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.     

Thermoelectric Properties of Chevrel-Phase Sulfides M<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Mo<Subscript>6</Subscript>S<Subscript>8</Subscript> (M: Cr,Mn, Fe,Ni)

Chevrel-phase sulfides M _x Mo₆S₈ (M, Cr, Mn, Fe, Ni; x: 1.3, 2.0) were prepared by reacting appropriate amounts of M, Mo, and MoS₂ powders. The samples were then consolidated by pressure-assisted sintering to fabricate dense compacts. While Cr_1.3Mo₆S₈ crystallized in a triclinic structure, Mn_1.3Mo₆S₈, Fe_1.3Mo₆S₈, and Ni_2.0Mo₆S₈ crystallized in a hexagonal structure. The Seebeck coefficient, electrical resistivity, and thermal conductivity of the sintered samples were measured over the temperature range of 300 K to 973 K. All the samples exhibited a positive Seebeck coefficient. The Seebeck coefficient, electrical resistivity, and thermal conductivity of M_1.3Mo₆S₈ (M: Cr, Mn, Fe) were almost identical and increased with temperature. However, the corresponding values and temperature dependent behavior of Ni_2.0Mo₆S₈ were different from those of M_1.3Mo₆S₈ (M: Cr, Mn, Fe). For Ni_2.0Mo₆S₈, as temperature increased, the Seebeck coefficient and thermal conductivity increased while the electrical resistivity decreased. The highest value of the thermoelectric figure of merit (0.17) was observed in Cr_1.3Mo₆S₈ at 973 K.     

Thermoelectric Properties of NdGd<Subscript>1+<Emphasis Type="Italic">x</Emphasis></Subscript>S<Subscript>3</Subscript> Prepared by CS<Subscript>2</Subscript> Sulfurization

Ternary rare-earth sulfides NdGd_1+x S₃, where 0 ≤ x ≤ 0.08, were prepared by sulfurizing Ln₂O₃ (Ln = Nd, Gd) with CS₂ gas, followed by reaction sintering. The sintered samples have full density and homogeneous compositions. The Seebeck coefficient, electrical resistivity, and thermal conductivity were measured over the temperature range of 300 K to 950 K. All the sintered samples exhibit a negative Seebeck coefficient. The magnitude of the Seebeck coefficient and the electrical resistivity decrease systematically with increasing Gd content. The thermal conductivity of all the sintered samples is less than 1.9 W K⁻¹ m⁻¹. The highest figure of merit ZT of 0.51 was found in NdGd_1.02S₃ at 950 K.     

Thermoelectric Properties of Mo<Subscript>3</Subscript>Sb<Subscript>5.4</Subscript>Te<Subscript>1.6</Subscript> and Ni<Subscript>0.06</Subscript>Mo<Subscript>3</Subscript>Sb<Subscript>5.4</Subscript>Te<Subscript>1.6</Subscript>

Mo₃Sb₇, crystallizing in the Ir₃Ge₇ type structure, has poor thermoelectric (TE) properties due to its metallic behavior. However, by a partial Sb-Te exchange, it becomes semiconducting without noticeable structure changes and so achieves a significant enhancement in the thermopower with the composition of Mo₃Sb₅Te₂. Meanwhile, large cubic voids in the Mo₃Sb₅Te₂ crystal structure provide the possibility of filling the voids with small cations to decrease the thermal conductivity by the so-called rattling effect. As part of the effort to verify this idea, we report herein the growth as well as measurements of the thermal and electrical transport properties of Mo₃Sb_5.4Te_1.6 and Ni_0.06Mo₃Sb_5.4Te_1.6.     

Electrical properties of InAs-SiO<Subscript>2</Subscript>-In<Subscript>2</Subscript>O<Subscript>3</Subscript> MIS structures with a modified interface

The effect of composition of the electrolyte used in producing a thin anodic oxide layer at the surface of a semiconductor substrate on the electrical properties of the InAs-SiO₂-In₂O₃ metal-insulator-semiconductor structures is studied. It is shown that introduction of ammonium fluoride into the electrolyte results in the formation of an interface with the density of surface states below 5 × 10¹⁰ cm^?2 eV^?1, the built-in charge (4–5 × 10¹¹ cm^?2, and the maximum relaxation time of the surface potential.     

AC Electrical Conductivity of FeIn<Subscript>2</Subscript>Se<Subscript>4</Subscript> Single Crystals

The results obtained in a study of the frequency and temperature dependences of the ac electrical conductivity of FeIn₂Se₄ single crystals are presented. It is found that the law σ ~ f ^S (0.1 ≤ S ≤ 1.0) is obeyed for electrical conductivity in the 295–375 K temperature range at frequencies of 2 × 10⁴–10⁶ Hz. It shown that the frequency dependence of the conductivity in an FeIn₂Se₄ single crystal can be accounted for in terms of the multiplet model, and, consequently, the conductivity in these single crystals is characterized by the band-hopping mechanism.     

Temperature dependence of the band gap of the single-crystal compounds In<Subscript>2</Subscript>S<Subscript>3</Subscript> and AgIn<Subscript>5</Subscript>S<Subscript>8</Subscript>

For the single-crystal compounds In₂S₃ and AgIn₅S₈ produced by chemical gas-transport reactions and the Bridgman method (vertical version), the transmission spectra in the region of the fundamental absorption edge are studied in the temperature range from 20 to 300 K. From the recorded spectra, the band gaps of the In₂S₃ and AgIn₅S₈ single crystals are determined and the temperature dependences of the band gaps are constructed. It is established that, as the temperature is lowered, the band gap increases for both of the compounds. Calculation of the temperature dependences is performed. It is shown that the calculated and experimental values are in agreement with each other.     

Photovoltaic effects in CdV<Subscript>2</Subscript>S<Subscript>4</Subscript> single crystals and structures based on them

Single crystals of the CdV₂S₄ ternary compound are grown, and their crystal structure, electrical properties, and optical absorption are studied. The substitution of vanadium for Group III element in A^IIB ₂ ^III C ₄ ^VI compounds results in the formation of crystals of n-type conduction with an electron density of ～10¹⁸ cm^?3 and a Hall mobility U_n≈150 cm²/(V s) at T=300 K, which is limited by scattering on lattice vibrations. Rectifying photosensitive structures based on CdV₂S₄ single crystals are fabricated for the first time, their photoelectric properties are studied, and a conclusion is made on their applicability in the design of wide-spectral-range photodetectors of unpolarized light.     

Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript>-Sb<Subscript>2</Subscript>Te<Subscript>3</Subscript> Superlattices Grown by Nanoalloying

In this work, Bi₂Te₃-Sb₂Te₃ superlattices were prepared by the nanoalloying approach. Very thin layers of Bi, Sb, and Te were deposited on cold substrates, rebuilding the crystal structure of V₂VI₃ compounds. Nanoalloyed super- lattices consisting of alternating Bi₂Te₃ and Sb₂Te₃ layers were grown with a thickness of 9 nm for the individual layers. The as-grown layers were annealed under different conditions to optimize the thermoelectric parameters. The obtained layers were investigated in their as-grown and annealed states using x-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive x-ray (EDX) spectroscopy, transmission electron microscopy (TEM), and electrical measurements. A lower limit of the elemental layer thickness was found to have c-orientation. Pure nanoalloyed Sb₂Te₃ layers were p-type as expected; however, it was impossible to synthesize p-type Bi₂Te₃ layers. Hence the Bi₂Te₃-Sb₂Te₃ superlattices consisting of alternating n- and p-type layers showed poor thermoelectric properties.     

Magnetic properties of the FeIn<Subscript>2</Subscript>S<Subscript>4</Subscript> ternary-compound crystals

Crystals of the ternary compound FeIn₂S₄ are grown by directional crystallization of a melt (the horizontal Bridgman method). Composition of the crystals and their crystal structure are determined. Magnetic properties of the FeIn₂S₄ crystals are studied in the temperature range 4–310 K in magnetic fields of 0–140 kOe. It is shown that the crystals under study are paramagnets up to ∼12 K and their specific magnetic moment monotonically increases with decreasing temperature. The antiferromagnetic character of indirect interactions between Fe²⁺ cations is established. The most probable causes and the mechanism of the formation of the magnetic state in the FeIn₂S₄ crystals are discussed.     

An impurity band in Hg<Subscript>3</Subscript>In<Subscript>2</Subscript>Te<Subscript>6</Subscript> crystals doped with silicon

The influence of silicon impurity on the energy-band spectrum in the Hg₃In₂Te₆ semiconductor compound, which incorporated a high concentration of stoichiometric vacancies, was studied on the basis of the results of electrical and optical measurements. It is shown that silicon impurity forms an impurity band of donor states whose density can be approximated by a Gaussian distribution with a peak at E_c-0.29 eV. The emergence of the impurity band is accompanied with the formation of a quasi-continuous spectrum of localized states in the band gap (E_g=0.74 eV); the density of these states is shown to increase as the doping level increases. All states merge into a continuous band if the impurity concentration N_Si>4.5×10¹⁷ cm^?3. Experimental data are explained on the basis of the effect of impurity self-compensation, in which case donor impurity states arise simultaneously with acceptor states of defects.     

Synthesis and Electronic Properties of the Misfit Layer Compound [(PbSe)<Subscript>1.00</Subscript>]<Subscript>1</Subscript>[MoSe<Subscript>2</Subscript>]<Subscript>1</Subscript>

An ultralow-thermal-conductivity compound with the ideal formula [(PbSe)_1.00]₁[MoSe₂]₁ has been successfully crystallized across a range of compositions. The lattice parameters varied from 1.246 nm to 1.275 nm, and the quality of the observed 00ℓ diffraction patterns varied through the composition region where the structure crystallized. Measured resistivity values ranged over an order of magnitude, from 0.03 Ω m to 0.65 Ω m, and Seebeck coefficients ranged from −181 μV K⁻¹ to 91 μV K⁻¹ in the samples after the initial annealing to form the basic structure. Annealing of samples under a controlled atmosphere of selenium resulted in low conductivities and large negative Seebeck coefficients, suggesting an n-doped semiconductor. Scanning transmission electron microscopy cross-sections confirmed the interleaving of bilayers of PbSe with Se-Mo-Se trilayers. High-angle annular dark-field images revealed an interesting volume defect, where PbSe grew through a region where a layer of MoSe₂ would be expected in the perfect structure. Further studies are required to correlate the density of these defects with the observed electrical properties.     

The effect of irradiation with electrons on the electrical parameters of Hg<Subscript>3</Subscript>In<Subscript>2</Subscript>Te<Subscript>6</Subscript>

The results of studying the electrical properties of Hg₃In₂Te₆ crystals irradiated with electrons with the energy E _e = 18 MeV and the dose D = 4 × 10¹⁶ cm⁻² are reported. It is shown that, irrespective of the charge-carrier concentration in the initial material, the Hg₃In₂Te₆ samples acquire the charge-carrier concentration (1.6–1.8) × 10¹³ cm⁻³ after irradiation. The phenomenon of Fermi level pinning in an irradiated material is discussed. The initial charge-carrier concentration, which remains virtually unchanged after irradiation and which ensures the high radiation resistance of Hg₃In₂Te₆ crystals, corresponds to a compensated material, similar to an intrinsic semiconductor at T > 260 K.     

Electrical and Thermal Conductivity and Conduction Mechanism of Ge<Subscript>2</Subscript>Sb<Subscript>2</Subscript>Te<Subscript>5</Subscript> Alloy

Ge₂Sb₂Te₅ alloy has drawn much attention due to its application in phase-change random-access memory and potential as a thermoelectric material. Electrical and thermal conductivity are important material properties in both applications. The aim of this work is to investigate the temperature dependence of the electrical and thermal conductivity of Ge₂Sb₂Te₅ alloy and discuss the thermal conduction mechanism. The electrical resistivity and thermal conductivity of Ge₂Sb₂Te₅ alloy were measured from room temperature to 823 K by four-terminal and hot-strip method, respectively. With increasing temperature, the electrical resistivity increased while the thermal conductivity first decreased up to about 600 K then increased. The electronic component of the thermal conductivity was calculated from the Wiedemann–Franz law using the resistivity results. At room temperature, Ge₂Sb₂Te₅ alloy has large electronic thermal conductivity and low lattice thermal conductivity. Bipolar diffusion contributes more to the thermal conductivity with increasing temperature. The special crystallographic structure of Ge₂Sb₂Te₅ alloy accounts for the thermal conduction mechanism.     

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.     

Fabrication and Characterization of Pb(Zr<Subscript>0.53</Subscript>,Ti<Subscript>0.47</Subscript>)O<Subscript>3</Subscript>-Pb(Nb<Subscript>1/3</Subscript>,Zn<Subscript>2/3</Subscript>)O<Subscript>3</Subscript> Thin Films on Cantilever Stacks

0.9Pb(Zr_0.53,Ti_0.47)O₃-0.1Pb(Zn_1/3,Nb_2/3)O₃ (PZT–PZN) thin films and integrated cantilevers have been fabricated. The PZT–PZN films were deposited on SiO₂/Si or SiO₂/Si₃N₄/SiO₂/poly-Si/Si membranes capped with a sol–gel-derived ZrO₂ buffer layer. It is found that the membrane layer stack, lead content, existence of a template layer of PbTiO₃ (PT), and ramp rate during film crystallization are critical for obtaining large-grained, single-phase PZT–PZN films on the ZrO₂ surface. By controlling these parameters, the electrical properties of the PZT–PZN films, their microstructure, and phase purity were significantly improved. PZT–PZN films with a dielectric constant of 700 to 920 were obtained, depending on the underlying stack structure.     

Structural disordering and viedemann-franz relation in melts of some II-IV-V<Subscript>2</Subscript> semiconductors

The thermal and electrical conductivities, as well as the thermoelectric power of the CdSnAs₂, CdGeAs₂, ZnSnAs₂, and ZnGeAs₂ ternary semiconductor compounds, were studied in both solid and liquid states. It was shown that the thermal and electrical conductivities of these compounds increase, while the thermoelectric power decreases in the course of melting to the values characteristic of liquid metals. In contrast to metal melts, the electrical conductivity and the Lorentz numbers calculated from the Viedemann-Franz relation increase with temperature in II-IV-V₂ semiconductor melts. According to the Mott classification, the melts of these compounds are related to group B. Melting of II-IV-V₂ semiconductors causes their metallization.     

Electronic Processes in CdIn<Subscript>2</Subscript>Te<Subscript>4</Subscript> Crystals

The results of investigations of electrical, optical, and photoelectric properties of CdIn₂Te⁴ crystals, which were grown by the Bridgman method are presented. It is shown that electrical conductivity is determined mainly by electrons with the effective mass m_n = 0.44m₀ and the mobility 120–140 cm²/(V s), which weakly depends on temperature. CdIn₂Te₄ behaves as a partially compensated semiconductor with the donor-center ionization energy E_d = 0.38 eV and the compensation level K = N_a/N_d = 0.36. The absorption-coefficient spectra at the energy hν < E_g = 1.27 eV are subject to the Urbach rule with a typical energy of 18–25 meV. The photoconductivity depends on the sample thickness. The diffusion length, the charge-carrier lifetime, and the surface-recombination rate are determined from the photoconductivity spectra.