Fabrication and photosensitivity of heterojunctions based on CuIn<Subscript>3</Subscript>Se<Subscript>5</Subscript> crystals

Heterojunctions based on p-CuIn₃Se₅ crystals are fabricated by magnetron sputtering of an n-ZnO:Al target and by putting naturally cleaved n-GaSe thin wafers onto polished surfaces of p-CuIn₃Se₅ wafers. The current-voltage characteristics and mechanisms of current flow in the diodes under study are analyzed. The photovoltaic effect revealed in the fabricated structures is discussed. It is shown that the fabricated photosensitive heterojunctions are promising for the development of selective analyzers of linearly polarized radiation.     

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.     

Anisotropy of the thermal expansion of CuIn<Subscript>5</Subscript>Se<Subscript>8</Subscript> single crystals in two structural modifications

Thermal expansion in the temperature range 80–700 K is studied for two (trigonal and hexagonal) structural modifications of CuIn₅Se₈ single crystals grown by planar crystallization of the melt. From the data, the thermal-expansion coefficients are calculated for both modifications. It is established that, in the temperature range under study, the thermal expansion of both modifications is anisotropic. For the trigonal modification, the thermal-expansion coefficient in the direction of the c axis (α_c) is larger than that in the direction of the orthogonal a axis (α_a). For the hexagonal modification of the CuIn₅Se₈ crystal, the thermal-expansion coefficient in the direction of the c axis exhibits anomalous behavior: as the temperature is increased, the coefficient α_c increases, after which it decreases to negative values, reaches a minimum, and then increases further. Such behavior of the coefficient α_c is associated with the phase transformation of the hexagonal modification of the CuIn₅Se₈ compound into the trigonal modification.     

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.     

<Emphasis Type="Italic">p</Emphasis><Superscript>+</Superscript>-Si-<Emphasis Type="Italic">n</Emphasis>-CdF<Subscript>2</Subscript> heterojunctions

Boron diffusion and the vapor-phase deposition of silicon layers are used to prepare ultrashallow p⁺-n junctions and p⁺-Si-n-CdF₂ heterostructures on an n-CdF₂ crystal surface. Forward portions of the I–V characteristics of the p⁺-n junctions and p⁺-Si-n-CdF₂ heterojunctions reveal the CdF₂ band gap (7.8 eV), as well as allow the identification of the valence-band structure of cadmium fluoride crystals. Under conditions in which forward bias is applied to the p⁺-Si-n-CdF₂ heterojunctions, electroluminescence spectra are measured for the first time in the visible spectral region.     

Effect of thallium doping on the mobility of electrons in Bi<Subscript>2</Subscript>Se<Subscript>3</Subscript> and holes in Sb<Subscript>2</Subscript>Te<Subscript>3</Subscript>

The Shubnikov–de Haas effect and the Hall effect in n-Bi_2–xTl_xSe₃ (x = 0, 0.01, 0.02, 0.04) and p-Sb_2–xTl_xTe₃ (x = 0, 0.005, 0.015, 0.05) single crystals are studied. The carrier mobilities and their changes upon Tl doping are calculated by the Fourier spectra of oscillations. It is found shown that Tl doping decreases the electron concentration in n-Bi_2–xTl_xSe₃ and increases the electron mobility. In p-Sb_2–xTl_xTe₃, both the hole concentration and mobility decrease upon Tl doping. The change in the crystal defect concentration, which leads to these effects, is discussed.     

Photoelectric properties of In/In<Subscript>2</Subscript>Se<Subscript>3</Subscript> structures

The hexagonal modification of In₂Se₃ single crystal is grown by planar crystallization from nearly stoichiometric melt and by the vapor-phase method. For the first time, the Schottky barriers In/n-In₂Se₃, which are photosensitive in a wide incident-photon energy range of 1–3.8 eV at 300 K, are obtained. The nature of the interband photoactive absorption is studied. The energy-barrier height and interband optical-transition energy are estimated. It is concluded that the grown crystals can be used in broadband optical-radiation converters.     

Special features of charge transport in PbGa<Subscript>2</Subscript>Se<Subscript>4</Subscript> crystals

The current-voltage (I-V) characteristics of PbGa₂Se₄ single crystals grown by the Bridgman-Stockbarger method with a resistivity of 10¹⁰–10¹² Ω cm were measured. The value of the majority carrier mobility μ=14 cm² V^?1 s^?1, calculated by the differential method of analysis of I-V characteristics, makes it possible to evaluate a number of parameters: the carrier concentration at the cathode (n_c0=2.48 cm^?3), the width of the contact barrier d_c=5.4×10^?8 cm, the cathode transparency D _c ^* =10^?5–10^?4 eV, and the quasi-Fermi level E_F=0.38 eV. It is found that a high electric field provides the charge transport through PbGa₂Se₄ crystals in accordance with the Pool-Frenkel effect. The value of the dielectric constant calculated from the Frenkel factor is found to be equal to 8.4.     

Fabrication and photoelectric properties of the ZnO-Cu(In,Ga)Se<Subscript>2</Subscript> heterojunctions

Thin-film n-ZnO:Al/p-Cu(In,Ga)Se₂ heterojunctions are fabricated by magnetron sputtering of an ZnO target, leading to a deposition of Cu(In,Ga)Se₂ films on the surface. The photoelectric properties of the fabricated heterojunctions are studied under exposure to natural and linearly polarized light. It is concluded that the resulting cadmium-free environmentally safe heterostructures can be used as high-efficiency broad-band photoconverters of natural and linearly polarized light.     

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.     

Specific thermoelectric properties of lightly doped Bi<Subscript>2</Subscript>(TeSe)<Subscript>3</Subscript> solid solutions

Electrical and thermoelectric properties of a lightly doped n-Bi₂Te_2.7Se_0.3 solid solution have been studied in the temperature range 77–300 K. The results are compared with data for the compound PbTe_0.9Se_0.1 with a similar magnitude of the Seebeck coefficient S at 84 K. Along with lower thermal conductivity, Bi₂Te_2.7Se_0.3 has a higher electrical conductivity σ and a much weaker temperature dependence. As a result, the power coefficient S ²σ in optimal samples begins to decrease only when the density of minority carriers becomes significant. In this case, |S| considerably exceeds the standard value of 200 μV/K. The reduction of the electron density reduces the thermoelectric figure of merit Z at its maximum and slightly lowers the temperature of the maximum; therefore, the expected effect on the average value of Z in the range 77–300 K is absent. Similar behavior is observed in Bi₂Te_2.88Se_0.12, although the effect is less pronounced. The experimental results are discussed taking into account possible changes in the dominant scattering mechanisms, carrier density, and electron energy spectrum. __________ Translated from Fizika i Tekhnika Poluprovodnikov, Vol. 38, No. 7, 2004, pp. 811–815. Original Russian Text Copyright ? 2004 by Konstantinov, Prokof’eva, Ravich, Fedorov, Kompaniets.     

Photoluminescence and composition of amorphous As<Subscript>2</Subscript>Se<Subscript>3</Subscript> films modified with Er(<Emphasis Type="Italic">thd</Emphasis>)<Subscript>3</Subscript> complex compound

The photoluminescence and composition of amorphous As₂Se₃ films modified with an Er(thd)₃ complex compound have been studied. A band centered at 1.54 μm, characteristic of photoluminescence from Er embedded in amorphous matrices, has been revealed at room temperature. The composition of thin amorphous As₂Se₃ films modified with an Er(thd)₃ complex compound has been examined by methods of nuclear microanalysis: Rutherford backscattering and nuclear resonant reactions. Dependences of the concentrations of Er ions, oxygen, and carbon on the growth conditions of the films are obtained. It is shown that the Er concentration in a thin film varies nonlinearly as the relative concentration of the starting complex compound increases. In addition, the increase in the Er content of a film is accompanied by a simultaneous rise in the content of such light elements as oxygen and carbon. Comparative analysis of the nuclear microanalysis data and IR spectra demonstrates that, in modification of As₂Se₃ with the Er(thd)₃ complex compound by the given method, the nearest environment of Er in the complex compound is partly preserved.     

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.     

Effect of copper doping on kinetic phenomena in <Emphasis Type="Italic">n</Emphasis>-Bi<Subscript>2</Subscript>Te<Subscript>2.85</Subscript>Se<Subscript>0.15</Subscript>

In single crystals of copper-doped and undoped Bi₂Te_2.85Se_0.15 solid solutions with an electron concentration close to 1 × 10¹⁹ cm^?3, the temperature dependences are investigated for the Hall (R ₁₂₃, R ₃₂₁) and Seebeck (S ₁₁) kinetic coefficients, the electrical-conductivity (σ ₁₁), Nernst-Ettingshausen (Q ₁₂₃), and thermalconductivity (k ₁₁) coefficients in the temperature range of 77–400 K. The absence of noticeable anomalies in the temperature dependences of the kinetic coefficients makes it possible to use the one-band model when analyzing the experimental results. Within the framework of the one-band model, the effective mass of density of states (m _d ≈ 0.8m ₀), the energy gap (ε_g ≈ 0.2 eV), and the effective scattering parameter (r _eff ≈ 0.2) are estimated. The obtained value of the parameter r _eff is indicative of the mixed electron-scattering mechanism with the dominant scattering by acoustic phonons. Data on the thermal conductivity and the lattice resistivity obtained by subtracting the electron contribution according to the Wiedemann-Franz law are presented.     

The charge-transport mechanisms and photosensitivity of <Emphasis Type="Italic">n</Emphasis>-ZnO:Al/Cu<Emphasis Type="Italic">Pc/p</Emphasis>-Cu(In,Ga)Se<Subscript>2</Subscript> structures

The first photosensitive n-ZnO:Al/CuPc/p-Cu(In,Ga)Se₂ structures are produced by a vacuum sublimation of copper phthalocyanine onto the surface of thin p-Cu(In,Ga)Se₂ films and a subsequent magnetron deposition of n-ZnO:Al films. The steady-state current-voltage characteristics of the resulting structures are studied. The charge-transport and photosensitivity mechanisms of the thin-film structures are discussed. The structures appear promising for the fabrication of wide-range (1.2–3.3 eV) thin-film photoelectric converters.     

Effect of the magnetic phase transition on the charge transport in layered semiconductor ferromagnets TlCrS<Subscript>2</Subscript> and TlCrSe<Subscript>2</Subscript>

TlCrS₂ and TlCrSe₂ crystals were synthesized by solid-state reaction. X-ray diffraction analysis showed that TlCrS₂ and TlCrSe₂ compounds crystallize in the hexagonal crystal system with lattice parameters a = 3.538 Å, c = 21.962 Å, c/a ≈ 6.207, z = 3; a = 3.6999 Å, c = 22.6901 Å, c/a ≈ 6.133, z = 3; and X-ray densities ρ _x = 6.705 and 6.209 g/cm³, respectively. Magnetic and electric studies in a temperature range of 77–400 K showed that TlCrS₂ and TlCrSe₂ are semiconductor ferromagnets. Rather large deviations of the experimental effective magnetic moment of TlCrS₂ (3.26 μ_B) and TlCrSe₂ (3.05 μ_B) from the theoretical one (3.85 μ_B) are attributed to two-dimensional magnetic ordering in the paramagnetic region of strongly layered ferromagnets TlCrS₂ and TlCrSe₂. The effect of the magnetic phase’s transition on the charge transport in TlCrS₂ and TlCrSe₂ is detected.     

Dielectric Properties of (Bi<Subscript>0.5</Subscript>K<Subscript>0.5</Subscript>)ZrO<Subscript>3</Subscript> Modified (K<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>)NbO<Subscript>3</Subscript> Ceramics as High-Temperature Ceramic Capacitors

(1???x)K_0.5Na_0.5NbO₃-x(Bi_0.5K_0.5)ZrO₃ [abbreviated as (1???x)KNN-xBKZ, 0?≤?x?≤?0.08] lead-free ceramics have been fabricated by a solid-state processing route. Based on the x-ray diffraction data and temperature-dependent dielectric characteristics, an orthorhombic phase for x?≤?0.03 and single rhombohedral one for x?≥?0.05 at room temperature were determined. The cell volume firstly increases, then decreases and finally increases with increasing BKZ, depending on ionic size and crystallographic structure. For the sample of x?=?0.05, a temperature-stable high permittivity (~?1736?±?15%) along with low dielectric loss tangent (≤?5%) is recorded from 158°C to 407°C. In addition, the activation energies of dielectric relaxation and dc conductivity at high temperatures were characterized by impedance spectroscopy. A combined effect of lattice distortion and oxygen vacancies on the magnitude of activation energies was discussed.     

Transport coefficients of <Emphasis Type="Italic">n</Emphasis>-Bi<Subscript>2</Subscript>Te<Subscript>2.7</Subscript>Se<Subscript>0.3</Subscript> in a two-band model of the electron spectrum

The Hall factor and thermoelectric properties of an n-Bi₂Te_2.7Se_0.3 solid solution with the roomtemperature Seebeck coefficient |S| = 212 μV/K have been studied in the temperature range 77–350 K. The observed temperature dependences demonstrate a number of specific features, which were earlier found in samples with a lower electron density N. The effect of these specific features on the thermoelectric figure of merit Z appears to be more favorable for the sample under study: this sample is most efficient in the temperature range 120–340 K, and the average value of ZT is 0.71. It is found that a rise in the density N enhances the factor responsible for the effective mass decreasing as the temperature increases. This effect appears when the analysis is carried out in terms of a single-band parabolic model with N = const(T). This finding suggests that the most probable reason for the unusual behavior of these properties is the complex structure of the electron spectrum. Temperature dependences obtained from calculations of the transport coefficients show good agreement with the experimental data for two samples of the mentioned composition with different electron densities. The calculations have been performed in terms of a two-band model and an acoustic scattering mechanism and take into account the anisotropy and nonparabolicity of the light-electron spectrum.     

Electrical and photoelectric properties of <Emphasis Type="Italic">n</Emphasis>-TiN/<Emphasis Type="Italic">p</Emphasis>-Hg<Subscript>3</Subscript>In<Subscript>2</Subscript>Te<Subscript>6</Subscript> heterostructures

n-TiN/p-Hg₃In₂Te₆ heterostructures are fabricated by depositing a thin n-type titanium nitride (TiN) film onto prepared p-type Hg₃In₂Te₆ plates using reactive magnetron sputtering. Their electrical and photoelectric properties are studied. Dominant charge-transport mechanisms under forward bias are analyzed within tunneling-recombination and tunneling models. The fabricated n-TiN/p-Hg₃In₂Te₆ structures have the following photoelectric parameters at an illumination intensity of 80 mW/cm²: the open-circuit voltage is V_OC = 0.52 V, the short-circuit current is I_SC = 0.265 mA/cm², and the fill factor is FF = 0.39.     

Effect of modifying a Bi nanolayer on the charge transport in Sb-<Emphasis Type="Italic">n</Emphasis>-Si-Bi-Ge<Subscript>33</Subscript>As<Subscript>12</Subscript>Se<Subscript>55</Subscript>-Sb heterostructures

The current-voltage characteristics of the Sb-n-Si-Ge₃₃As₁₂Se₅₅-Sb and Sb-n-Si-Bi-Ge₃₃As₁₂Se₅₅-Sb heterostructures are studied. It is found that the presence of bismuth atoms in the transition region causes the current through the structure to increase. The width of the space-charge region and, correspondingly, the extent of penetration of the contact field into the p-type region are in the range from 0.2 to 0.5 μm. The introduction of a modifying bismuth layer also leads to radical changes in the current-voltage characteristic, which indicates that the mechanism of the charge-carrier transport in the structure is changed. The introduction of the Bi nanolayer leads to the transformation of an abrupt heterojunction into a gradient heterojunction. A soft breakdown is not observed in the structures with the modified transition layer. The soft breakdown is observed at a reverse bias; the cutoff voltage of ∼0.62 V corresponds to the barrier height of 0.65 eV for electrons. __________ Translated from Fizika i Tekhnika Poluprovodnikov, Vol. 38, No. 11, 2004, pp. 1339–1342. Original Russian Text Copyright ? 2004 by Kondrat, Popovich, Dovgoshej.