Study of electronic and magnetic properties of the CuFeS<Subscript>2</Subscript> semiconductor compound in the temperature range 77–300 K

The conductivity of polycrystalline chalcopyrite (CuFeS₂) samples is studied in the temperature range 77–300 K. Some differences in the low-temperature behavior of the conductivity in different samples are observed. The nuclear magnetic resonance spectrum of Cu in the local field in CuFeS₂ is studied in detail.     

Plasmon–phonon coupling in the infrared reflectance spectra of Bi<Subscript>2</Subscript>Se<Subscript>3</Subscript> films

The results of studies of optical reflection in the far- and mid-infrared spectral regions are reported. The reflectance of five Bi₂Se₃ topological insulator films grown by molecular-beam epitaxy on Si(111) substrates is measured. The characteristic parameters of phonons and plasmons are determined by means of dispersion analysis for multilayer structures. It is found that the plasma frequency in a layer close to the Si–film interface is noticeably higher than that in the film bulk. Calculations of the loss function show that plasmon–phonon coupling plays an important role in Bi₂Se₃ films. The attenuated total internal reflection method is used to determine the frequency of the surface plasmon–phonon mode.     

Structure and Properties of Nanostructured YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>7–δ</Subscript>, BiFeO<Subscript>3</Subscript>, and Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>

The development of new nanostructured materials based on YBa₂Cu₃O_7–δ, BiFeO₃, and Fe₃O₄ compounds is considered. The structure, morphology, and properties of these materials are studied. The possibilities of fabricating YBa₂Cu₃O_7–δ ceramics with given densities from nanopowders in a single stage by an energy efficient method and growing superconducting films of the same composition on a silicon substrate (on a SiO₂ layer) are demonstrated. The technique for fabricating BiFeO₃ nanopowder, making it possible to obtain nanostructured ceramics without additional accompanied phases commonly forming during BiFeO₃ synthesis is developed. Two methods of the single-stage synthesis of Fe₃O₄ nanopowder are presented: burning of nitrate-organic precursors and the electrochemical three-electrode method in which one of the electrodes, i.e., an anode containing scrap iron and slurry, is used as an expendable material.     

Deposition of heteroepitaxial layers of topological insulator Bi<Subscript>2</Subscript>Se<Subscript>3</Subscript> in the trimethylbismuth–isopropylselenide–hydrogen system on the (0001) Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and (100) GaAs substrates

Thin solid layers that are formed upon heating of the gaseous trimethylbismuth–isopropylselenide–hydrogen system on the (0001) Al₂O₃ and singular and vicinal (100) GaAs surfaces are studied. The conditions for deposition of metal Bi and phases of Bi₄Se₃, BiSe, and topological insulator Bi₂Se₃ using the MOCVD method are determined. Pure metastable phase BiSe is obtained for the first time. Bi₂Se₃ films with a thickness of no less than 200 nm, a relatively low volume concentration of 3 ×10¹⁸ cm^–3, and a high mobility of carriers at 300 K (1000 cm² V^–1 s^–1) are fabricated.     

Synthesis and Transport Properties of In<Subscript>4</Subscript>(Se<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Te<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>)<Subscript>3</Subscript>

Polycrystalline samples of In₄(Se_1−x Te _x )₃ were synthesized by using a melting–quenching–annealing process. The thermoelectric performance of the samples was evaluated by measuring the transport properties from 290 K to 650 K after sintering using the spark plasma sintering (SPS) technique. The results indicate that Te substitution can effectively reduce the thermal conductivity while maintaining good electrical transport properties. In₄Te₃ shows the lowest thermal conductivity of all compositions tested.     

On the band gap of Cu<Subscript>2</Subscript>ZnSn(S<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Se<Subscript>1–<Emphasis Type="Italic">x</Emphasis></Subscript>)<Subscript>4</Subscript> alloys

The transmittance spectra of single-crystal Cu₂ZnSnS₄ and Cu₂ZnSnSe₄ compounds and Cu₂ZnSn(S _x Se_1–x )₄ alloys grown by chemical vapor-transport reactions are studied in the region of the fundamental absorption edge. From the experimental spectra, the band gap of the compounds and their alloys is determined. The dependences of the band gap on the composition parameter x of the alloy are constructed. It is established that the band gap nonlinearly varies with x and can be described as a quadratic dependence.     

Photoluminescence and excitation features of Nd<Superscript>3+</Superscript> ions in (La<Subscript>0.97</Subscript>Nd<Subscript>0.03</Subscript>)<Subscript>2</Subscript>S<Subscript>3</Subscript> · 2Ga<Subscript>2</Subscript>O<Subscript>3</Subscript> glasses

A combined study of the spectral photoluminescence distribution and excitation spectra of photoluminescence in La₂S₃ · 2Ga₂O₃ and (La_0.97Nd_0.03)₂S₃ · 2Ga₂O₃ glasses, along with the study of the transmission spectra of these glasses, was carried out. The radiative channel was ascertained to be the main channel for the energy transfer from the host matrix to the Nd³⁺ ions upon excitation of the glasses with light at a wavelength of the fundamental absorption band. Oxygen centers with the level E _c -2.0 eV act as sensitizing agents. The structural disordering of the glass host increases the variance in the magnitude of splitting of the multiplet levels from the 4f electronic states of the Nd³⁺ ion. This promotes nonradiative relaxation of the electrons from excited states to the laser ⁴F_3/2 level. The (La_0.97Nd_0.03)₂S₃ · 2Ga₂O₃ glasses can be considered as promising laser materials for obtaining the stimulated emission of radiation of Nd³⁺ ions under an optical pump in the range of the fundamental absorption band of the glass.     

Study of dielectric processes in (As<Subscript>2</Subscript>Se<Subscript>3</Subscript>)<Subscript>1 − <Emphasis Type=Italic>x</Emphasis></Subscript>Bi<Subscript><Emphasis Type=Italic>x</Emphasis></Subscript> amorphous films

A comparative analysis of dielectric polarization processes in undoped and Bi-doped layers of modified As₂Se₃ has been performed. It is established that both the similarity and difference in polarization phenomena are due to specific features of the internal structure of studied materials. The mechanism of the observed effects is discussed.     

Enhanced Photocatalytic Activity of Two-Pot-Synthesized BiFeO<Subscript>3</Subscript>–ZnFe<Subscript>2</Subscript>O<Subscript>4</Subscript> Heterojunction Nanocomposite

BiFeO₃–ZnFe₂O₄ heterojunction nanocomposites have been produced by a chemical synthesis method using one- and two-pot approaches. X-ray diffraction patterns of as-calcined samples indicated formation of pure zinc ferrite (ZnFe₂O₄) and bismuth ferrite (BiFeO₃) phases, each retaining its crystal structure. Diffuse reflectance spectrometry was applied to calculate the optical bandgap of the photocatalysts, revealing values in the range from 2.03 eV to 2.17 eV, respectively. The maximum photodegradation of methylene blue of about 97% was achieved using two-pot-synthesized photocatalyst after 120 min of visible-light irradiation due to the higher probability of charge separation of photogenerated electron–hole pairs in the heterojunction structure. Photoluminescence spectra showed lower emission intensity of two-pot-synthesized photocatalyst, due to its lower recombination rate originating from greater charge separation.     

Thermoelectric Properties of the Clathrate I Ba<Subscript>8</Subscript>Ge<Subscript>43</Subscript>□<Subscript>3</Subscript>

The clathrate I Ba₈Ge₄₃□₃ [space group Ia[`3]d Iabar{3}d , no. 230, a = 21.307(1) ?] has been synthesized as a single phase and characterized by x-ray powder diffraction and metallographic analysis. Electrical and thermal transport measurements have been performed in the temperature range of 5 K to 673 K. Ba₈Ge₄₃□₃ displays the electrical resistivity of a poor metal at low temperatures, with semiconducting-like behavior appearing above 300 K.     

The Power Factor of Bi<Subscript>2−<Emphasis Type="Italic">x</Emphasis></Subscript>Tl<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Se<Subscript>3</Subscript> Single Crystals

Single crystals of the ternary system Bi_2−x Tl _x Se₃ (nominally x = 0.0 to 0.1) were prepared using the Bridgman technique. Samples with varying content of Tl were characterized by measurement of lattice parameters, electrical conductivity σ _⊥c, Hall coefficient R _H(B║c), and Seebeck coefficient S(ΔT⊥c). The measurements indicate that incorporation of Tl into Bi₂Se₃ lowers the concentration of free electrons and enhances their mobility. This effect is explained within the framework of the point defects in the crystal lattice, with formation of substitutional defects of thallium in place of bismuth (Tl_Bi) and a decrease in the concentration of selenium vacancies (V_Se ^{+ 2} V_{\rm{Se}}^{ + 2} ). The temperature dependence of the power factor σS ² of the samples is also discussed. As a consequence of the thallium doping we observe a significant increase of the power factor compared with the parent Bi₂Se₃.     

Optical properties of AgGa<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>In<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Se<Subscript>2</Subscript> alloys

Coarse-grained crystals of AgGaSe₂ and AgInSe₂ ternary compounds and their alloys are grown by planar crystallization of the melts. For the crystals produced in this way, the transmittance spectra near the fundamental absorption edge are studied. From the experimental spectra, the band gap (E _g) and its variation with composition are determined. It is established that E _g is a nonlinear function of the composition parameter x. The dependence E _g (x) is calculated theoretically in the context of the Van Vechten-Bergstresser model and Hill-Richardson pseudopotential model.     

Preparation and Thermoelectric Properties of Ag<Subscript>0.5</Subscript>In<Subscript>0.5−<Emphasis Type="Italic">x</Emphasis></Subscript>Pb<Subscript>5</Subscript>Sn<Subscript>4</Subscript>Te<Subscript>10</Subscript>

A series of compounds with composition Ag_0.5In_0.5−x Pb₅Sn₄Te₁₀ (x = 0.05 to 0.20) were prepared by slowly cooling the melts of the corresponding elements, and the effect of In content on the thermoelectric transport properties of these compounds has been investigated. Results indicate that the compounds’ electronic structure is sensitive to In content, and that the carrier concentration of these compounds at room temperature increases from 4.86 × 10¹⁸ cm⁻³ to 3.85 × 10²¹ cm⁻³ as x increases from 0.05 to 0.20. For these compounds, electrical conductivity decreases and Seebeck coefficient increases with increasing In content. Ag_0.05In_0.03Pb_0.5Sn_0.4Te₁₀ shows very low lattice thermal conductivity, and has a maximum dimensionless figure of merit ZT of 1.2 at 800 K.     

Photoelectric properties of surface-barrier structures based on Zn<Subscript>2−2<Emphasis Type="Italic">x</Emphasis></Subscript>Cu<Subscript>x</Subscript>In<Subscript>x</Subscript>Se<Subscript>2</Subscript> films obtained by selenization

p-Zn_2?2xCu_xIn_xSe₂ (ZCIS) polycrystalline films 1–2 ¼m thick have been obtained by selenization. Photosensitive surface-barrier In/p-ZCIS structures are fabricated based on the films. The spectra of relative quantum efficiency of the structures obtained by selenization of the initial ZnSe/(Cu-In) and (Zn-Cu-In) films are examined. The optical band gap of the Zn_2?2xCu_xIn_xSe₂ films is determined. Conclusions are reached on the prospects for the use of the obtained films as broadband photoconverters of natural optical radiation.     

Conductivity of Ga<Subscript>2</Subscript>O<Subscript>3</Subscript>–GaAs Heterojunctions

The effect of annealing in argon at temperatures of T_an = 700–900°C on the I–V characteristics of metal–Ga₂O₃–GaAs structures is investigated. Samples are prepared by the thermal deposition of Ga₂O₃ powder onto GaAs wafers with a donor concentration of N _d = 2 × 10¹⁶ cm^–3. To measure theI–V characteristics, V/Ni metal electrodes are deposited: the upper electrode (gate) is formed on the Ga₂O₃ film through masks with an area of S _k = 1.04 × 10^–2 cm² and the lower electrode in the form of a continuous metallic film is deposited onto GaAs. After annealing in argon at T_an ≥ 700°C, the Ga₂O₃-n-GaAs structures acquire the properties of isotype n-heterojunctions. It is demonstrated that the conductivity of the structures at positive gate potentials is determined by the thermionic emission from GaAs to Ga₂O₃. Under negative biases, current growth with an increase in the voltage and temperature is caused by field-assisted thermal emission in gallium arsenide. In the range of high electric fields, electron phonon-assisted tunneling through the top of the potential barrier is dominant. High-temperature annealing does not change the electron density in the oxide film, but affects the energy density of surface states at the GaAs–Ga₂O₃ interface.     

Effect of Al Substitution on the Thermoelectric Properties of the Type VIII Clathrate Ba<Subscript>8</Subscript>Ga<Subscript>16</Subscript>Sn<Subscript>30</Subscript>

Single-crystal samples of the type VIII clathrate Ba₈Ga_16−x Al _x Sn₃₀ (0 ≤ x ≤ 12) were prepared by the Sn-flux method, and the structural and electrical properties were studied from 300 K to 600 K. The lattice parameter increases linearly as x is increased from 0 to 10.5, which is the solubility limit of Al. For all samples, the electrical conductivity σ decreases monotonically as the temperature is increased. σ(T = 300 K) increases from 1.88 × 10⁴ S/m for x = 0 to 3.03 × 10⁴ S/m for x = 2, and then gradually decreases to 2.4 × 10⁴ S/m with further increase of x to 8. The increase of σ for Al-substituted samples is attributed to enhancement of carrier mobility. The Seebeck coefficients of samples with 0 ≤ x ≤ 8 are negative with large values, and the absolute values increase from 240 μV/K to 320 μV/K as the temperature increases from 300 K to 600 K. At 300 K, the effective mass m*/m ₀ is in the range from 0.53 to 0.67, and the samples with x = 6 and x = 8 have a rather low thermal conductivity of 0.72 W/mK and 0.78 W/mK, respectively. ZT reaches 1.2 at 500 K for x = 6.     

Thermoelectric Properties of (Na<Subscript>1−<Emphasis Type="Italic">y</Emphasis></Subscript>M<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript>)<Subscript>1.4</Subscript>Co<Subscript>2</Subscript>O<Subscript>4</Subscript> (M = Sr,Li)

Oxide thermoelectric materials (Na_1−y M _y )_1.4Co₂O₄ (M = Sr, Li; y = 0 to 0.4) were prepared by a sol–gel method. The influence of doping on the thermoelectric properties was investigated, and the phase composition was characterized by x-ray diffraction. Experimental results showed that the main crystalline phase of the undoped and Sr/Li-doped samples was γ-Na_1.4Co₂O₄. The thermoelectric properties of Na_1.4Co₂O₄ can be improved slightly by doping with Sr. Doping with Li improves the thermoelectric properties of Na_1.4Co₂O₄. For a doping fraction of y = 0.1, the electrical conductivity of (Na_1−y Li _y )_1.4Co₂O₄ at 288 K achieves its maximum value of 301.19 (Ω mm)⁻¹. The Seebeck coefficient and power factor of (Na_1−y Li _y )_1.4Co₂O₄ at 288 K achieve their maximum values of 172.28 μV K⁻¹ and 7.44 mW m⁻¹ K⁻² at a doping fraction of y = 0.4.     

Analysis of the magnetic properties of (La<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Sr<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>)<Subscript>0.93</Subscript>MnO<Subscript>3</Subscript> manganites at high temperatures

For the first time, the Faraday method is used to measure the temperature dependence of paramagnetic susceptibility χ(T) of (La_{1 ? x} Sr _x )_0.93MnO₃ (x = 0.2, 0.25, or 0.3) manganites in the temperature interval 60–850°C. It is demonstrated that the dependences have two kinks and three linear sections. The kink of curve χ^?1(T) is related to polymorphic transformations (Q′ → Q* and Q* → R) that take place in the crystal lattices of the samples. The main magnetic characteristics of the samples are determined with the least-squares processing of curve χ^?1. Is is demonstrated that dependence χ^?1(T) obeys the Curie-Weiss law. The energy state of the magnetoactive manganese atom in the Q′-and Q*-phase samples is close to the energy state of a free Mn²⁺ ion. In the R phase, this state is close to the state of a free Mn³⁺ ion.