Behavior of manganese impurities in Hg3In2Te6

The behavior of manganese impurities in Hg₃In₂Te₆ is investigated. The carrier concentration remains considerably smaller than the impurity concentration in the doped crystals. The introduction of manganese into Hg₃In₂Te₆ does not alter the position of the Fermi level, which is located near the middle of the band gap of the material. The electrical conductivity remains intrinsic down to 150 K. It is shown that manganese exists in the Mn²⁺ (3d ⁵) charge state in the Hg₃In₂Te₆ lattice and does not lead to the appearance of new chemical bonds in the host, but does influence the short-range structure. When N _Mn<9.2×10¹⁹ cm⁻³, Hg₃In₂Te₆ has higher values of the carrier mobility than does the undoped material. Fiz. Tekh. Poluprovodn. 33, 1416–1419 (December 1999)     

Superionic conductivity and switching effect with memory in TlInSe<Subscript>2</Subscript> and TlInTe<Subscript>2</Subscript> crystals

The temperature dependences of the conductivity σ(T) and the switching and memory effects in one-dimensional TlInSe₂ and TlInTe₂ single crystals have been studied. A specific feature is found in the dependence σ(T) above 333 K, which is related to the transition of crystals to the state with superionic conductivity. It is suggested that the ion conductivity is caused by the diffusion of Tl⁺ ions over vacancies in the thallium sublattice between (In³⁺Te₂²⁻)⁻ and (In³⁺Se₂²⁻)⁻ nanochains (nanorods). S-type switching and memory effects are revealed in TlInSe₂ and TlInTe₂ crystals, as well as voltage oscillations in the range of negative differential resistance. It is suggested that the switching effect and voltage oscillations are related to the transition of crystals to the superionic state, which is accompanied by “melting” of the Tl sublattice. The effect of electric-field-induced transition of TlInSe₂ and TlInTe₂ crystals to the superionic state is found.     

Improvement of Thermoelectric Power Factor of Hydrothermally Prepared Bi<Subscript>0.5</Subscript>Sb<Subscript>1.5</Subscript>Te<Subscript>3</Subscript> Compared with its Solvothermally Prepared Counterpart

We report on the successful hydrothermal synthesis of Bi_0.5Sb_1.5Te₃, using water as the solvent. The products of the hydrothermally prepared Bi_0.5 Sb_1.5Te₃ were hexagonal platelets with edges of 200–1500 nm and thicknesses of 30–50 nm. Both the Seebeck coefficient and electrical conductivity of the hydrothermally prepared Bi_0.5Sb_1.5Te₃ were larger than those of the solvothermally prepared counterpart. Hall measurements of Bi_0.5Sb_1.5Te₃ at room temperature indicated that the charge carrier was p-type, with a carrier concentration of 9.47 × 10¹⁸ cm⁻³ and 1.42 × 10¹⁹ cm⁻³ for the hydrothermally prepared Bi_0.5Sb_1.5Te₃ and solvothermally prepared sample, respectively. The thermoelectric power factor at 290 K was 10.4 μW/cm K² and 2.9 μW/cm K² for the hydrothermally prepared Bi_0.5Sb_1.5Te₃ and solvothermally prepared sample, respectively.     

Thermoelectric Performance of Zn and Nd Co-doped In<Subscript>2</Subscript>O<Subscript>3</Subscript> Ceramics

Polycrystalline In₂O₃ ceramics co-doped with Zn and Nd were prepared by the spark plasma sintering (SPS) process, and microstructure and thermoelectric (TE) transport properties of the ceramics were investigated. Our results indicate that co-doping with Zn²⁺ and Nd³⁺ shows a remarkable effect on the transport properties of In₂O₃-based ceramics. Large electrical conductivity (~130 S cm⁻¹) and thermopower (~220 μV K⁻¹) can be observed in these In₂O₃-based ceramic samples. The maximum power factor (PF) reaches 5.3 × 10⁻⁴ W m⁻¹ K⁻² at 973 K in the In_1.92Nd_0.04Zn_0.04O₃ sample, with a highest ZT of ~0.25.     

Features of reflection spectra of single crystals of Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript>-Sb<Subscript>2</Subscript>Te<Subscript>3</Subscript> solid solutions in the region of plasma effects

Reflectance spectra of single crystals of Bi₂Te₃-Sb₂Te₃ solid solutions containing 0, 10, 25, 40, 50, 60, 65, 70, 80, 90, 99.5, and 100 mol % of Sb₂Te₃ have been studied in the range of 400–4000 cm⁻¹ at the temperature T = 291 K and with orientation of the vector of the electric-field strength E perpendicular to the trigonal axis of the crystal C ₃ (E ⊥ C ₃). The shape of the spectra is characteristic of plasma reflection; the spectra include the features in the range 1250–3000 cm⁻¹ corresponding to the optical band gap E _{g opt}. The features become more pronounced as the content of Bi₂Te₃ is increased to 80 mol % in the composition of the Bi₂Te₃-Sb₂Te₃ solid solution. A further increase in the content of Sb₂Te₃ is accompanied by discontinuities in the functional dependences of the parameters characterizing the plasma oscillations of free charge carriers on the solid-solution composition and also by a sharp increase in E _{g opt}.     

Effect of a high-energy proton-irradiation dose on the electron mobility in <Emphasis Type="Italic">n</Emphasis>-Si crystals

n-Si single crystals produced by the floating zone method are studied. The concentration of electrons in the crystals is 6 × 10¹³ cm⁻³. The samples are irradiated with 25-MeV protons at 300 K. The irradiation dose is varied in the range (1.8–8.1) × 10¹² cm⁻². The measurements are carried out by means of the Hall technique in the range of temperatures T = 77−300 K. In samples irradiated with different proton doses, a sharp increase in the experimental effective Hall mobility μ_eff or a deep minimum in the dependence μ_eff(T) in the region of phonon scattering of electrons is observed immediately after irradiation or after aging of the samples, respectively. The observed effect is attributed to the formation of high-conductivity (metal-like) inclusions in the irradiated samples and to changes in the degree of screening of the inclusions by impurity-defect shells in relation to the irradiation dose, the time of natural aging, and the temperature of measurements. The impurity-defect shells are formed around metal-like inclusions during isochronal annealing or natural aging of the irradiated samples. It is suggested that metal-like inclusions formed in the n-Si crystals on irradiation with protons with the energy 25 MeV are atomic nanoclusters with an 80-nm radius.     

Conductivity of layers of a chalcogenide glassy semiconductor Ge<Subscript>2</Subscript>Sb<Subscript>2</Subscript>Te<Subscript>5</Subscript> in high electric fields

Effect of high electric fields on the conductivity of 0.5-1-μm-thick layers of a chalcogenide glassy semiconductor with a composition Ge₂Sb₂Te₅, used in phase memory cells, has been studied. It was found that two dependences are observed in high fields: dependence of the current I on the voltage U, of the type I ∝ U ⁿ , with the exponent (n ≈ 2) related to space-charge-limited currents, and a dependence of the conductivity σ on the field strength F of the type σ = σ₀exp(F/F ₀) (where F ₀ = 6 × 10⁴ V cm⁻¹), caused by ionization of localized states. A mobility of 10⁻³–10⁻² cm² V⁻¹ s⁻¹ was determined from the space-charge-limited currents.     

Effect of Proton Irradiation on Interface State Density in Sc<Subscript>2</Subscript>O<Subscript>3</Subscript>/GaN and Sc<Subscript>2</Subscript>O<Subscript>3</Subscript>/MgO/GaN Diodes

Proton irradiation of Sc₂O₃/GaN and Sc₂O₃/MgO/GaN metal-oxide semiconductor diodes was performed at two energies, 10 MeV and 40 MeV, and total fluences of 5 × 10⁹ cm⁻², corresponding to 10 years in low-earth orbit. The proton damage causes a decrease in forward breakdown voltage and a flat-band voltage shift in the capacitance-voltage characteristics, indicating a change in fixed oxide charge and damage to the dielectric. The interface state densities after irradiation increased from 5.9 × 10¹¹ cm⁻² to 1.03 × 10¹² cm⁻² in Sc₂O₃/GaN diodes and from 2.33 × 10¹¹ to 5.3 × 10¹¹ cm⁻² in Sc₂O₃/MgO/GaN diodes. Postannealing at 400°C in forming gas recovered most of the original characteristics but did increase the interfacial roughness.     

Effect of copper doping on kinetic coefficients and their anisotropy in PbSb<Subscript>2</Subscript>Te<Subscript>4</Subscript>

In anisotropic PbSb₂Te₄ and PbSb₂Te₄:Cu single crystals, nine main independent components of the Hall, electrical-conductivity, thermopower, and Nernst-Ettingshausen effects and their anisotropy in the range 77–450 K have been studied. PbSb₂Te₄ single crystals exhibit a high hole concentration (p ≈ 3 × 10²⁰ cm⁻³). Copper exhibits a donor effect and significantly (approximately by a factor of 2) reduces the hole concentration in PbSb₂Te₄. The temperature dependences of the kinetic coefficients, except for the Hall effect, have a form typical of the one-band model. The significant anisotropy of the Hall coefficient R ₁₂₃/R ₃₂₁ ≈ 2 at low temperatures corresponds to the multi-ellipsoid model of the energy spectrum of holes in PbSb₂Te₄. An important feature of the data on transport phenomena is the high thermopower anisotropy (ΔS ≈ 60–75 μV/K) in the mixed conductivity region caused by the mixed scattering mechanism. Data on the anisotropy of the transverse Nernst-Ettingshausen effect confirm the mixed mechanism of hole scattering; in the cleavage plane, scattering at acoustic phonons dominates, while in the trigonal axis direction, impurity scattering appears significant. Doping with copper enhances the role of impurity scattering in the direction of the trigonal axis c ₃; as a result, two components of the Nernst-Ettingshausen tensor Q ₃₂₁ and Q ₁₃₂ in the PbSb₂Te₄:Cu single crystal are positive at low temperatures, whereas, in the undoped crystal, only the Q ₃₂₁ component is positive.     

Electronic properties and deep traps in electron-irradiated <Emphasis Type="Italic">n</Emphasis>-GaN

The study is concerned with the effect of electron irradiation (with the energies E = 7 and 10 MeV and doses D = 10¹⁶−10¹⁸ cm⁻²) and subsequent heat treatments in the temperature range 100–1000°C on the electrical properties and the spectrum of deep traps of undoped (concentration of electrons n = 1 × 10¹⁴−1 × 10¹⁶ cm⁻³), moderately Si-doped (n = (1.2−2) × 10¹⁷ cm⁻³), and heavily Si-doped (n = (2−3.5) × 10¹⁸ cm⁻³) epitaxial n-GaN layers grown on Al₂O₃ substrates by metal-organic chemical vapor deposition. It is found that, on electron irradiation, the resistivity of n-GaN increases, this is due to a shift of the Fermi level to the limiting position close to E _c −0.91 eV. The spectrum of deep traps is studied for the initial and electron-irradiated n-GaN. It is shown that the initial properties of the irradiated material are restored in the temperature range 100–1000°C, with the main stage of the annealing of radiation defects at about 400°C.     

Development of Molecular Beam Epitaxially Grown Hg<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Cd<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Te for High-Density Vertically-Integrated Photodiode-Based Focal Plane Arrays

Hg_1−x Cd _x Te samples of x ~ 0.3 (in the midwave infrared, or MWIR, spectral band) were prepared by molecular beam epitaxy (MBE) for fabrication into 30-μm-pitch, 256 × 256, front-side-illuminated, high-density vertically-integrated photodiode (HDVIP) focal plane arrays (FPAs). These MBE Hg_1−x Cd _x Te samples were grown on CdZnTe(211) substrates prepared in this laboratory; they were ~10-μm thick and were doped with indium to ~5 × 10¹⁴ cm⁻³. Standard HDVIP process flow was employed for array fabrication. Excellent array performance data were obtained from these MWIR arrays with MBE HgCdTe material. The noise-equivalent differential flux (NEΔΦ) operability of the best array is 99.76%, comparable to the best array obtained from liquid-phase epitaxy (LPE) material prepared in this laboratory.     

Effect of gadolinium impurity on transmittance and reflectance of Hg<Subscript>3</Subscript>In<Subscript>2</Subscript>Te<Subscript>6</Subscript> crystals

The results of measuring the optical transmission and reflection spectra in the transparency region of Hg₃In₂Te₆:Gd semiconducting crystals are reported. It is shown that, in the entire wavelength range under investigation (2–25 µm), doping with Gd results in an increase in the continuous structureless absorption by impurities and defects, which introduce a quasi-continuous spectrum of localized states within the band gap. A decrease in transmittivity is accompanied by a decrease in the wavelength-independent reflectivity. Variation in the refractive index is attributed to changes in the bonding and electronic polarization of Hg₃In₂Te₆:Gd crystals. It is ascertained that polarization constants depend linearly on the strength of internal electric fields which exist in the vicinity of impurity defects.     

Electrodeposition of <Emphasis Type="Italic">p</Emphasis>-Type Sb<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Te<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript> Thermoelectric Films

Thermoelectric Sb _x Te _y films were potentiostatically electrodeposited in aqueous nitric acid electrolyte solutions containing different concentrations of TeO₂. Stoichiometric Sb _x Te _y films were obtained by applying a voltage of −0.15 V versus saturated calomel electrode (SCE) using a solution consisting of 2.4 mM TeO₂, 0.8 mM Sb₂O₃, 33 mM tartaric acid, and 1 M HNO₃. The nearly stoichiometric Sb₂Te₃ films had a rhombohedral structure, R[`3]m R\bar{3}m , with a preferred orientation along the (015) direction. The films had hole concentration of 5.8 × 10¹⁸/cm³ and exhibited mobility of 54.8 cm²/Vs. A more negative potential resulted in higher Sb content in the deposited Sb _x Te _y films. Furthermore, it was observed that the hole concentration and mobility decreased with increasingly negative deposition potential, and eventually showed insulating properties, possibly due to increased defect formation. The absolute value of the Seebeck coefficient of the as-deposited Sb₂Te₃ thin film at room temperature was 118 μV/K.     

Superionic conductivity in TlGaTe<Subscript>2</Subscript> crystals

Temperature dependences of electrical conductivity σ(T) and permittivity ɛ(T) of one-dimensional (1D) TlGaTe₂ single crystals are investigated. At temperatures higher than 305 K, superionic conductivity of the TlGaTe₂ is observed and is related to diffusion of Tl⁺ ions via vacancies in the thallium sublattice between (Ga³⁺Te₂^{2− −} nanochains. A relaxation character of dielectric anomalies is established, which suggests the existence of electric charges weakly bound to the crystal lattice. Upon the transition to the superionic state, relaxors in the TlGaTe₂ crystals are Tl⁺ dipoles ((Ga³⁺Te₂²⁻)⁻ chains) that arise due to melting of the thallium sublattice and hops of Tl⁺ ions from one localized state to another. The effect of a field-induced transition of the TlGaTe₂ crystal to the superionic state is detected.     

Current-voltage characteristics of ZnGa<Subscript>2</Subscript>Se<Subscript>4</Subscript> compound polycrystals

Current-voltage characteristics of the In-ZnGa₂Se₄-In structure have been studied in the temperature range of 90–335 K. Based on the data calculated for the concentration of three trap types in ZnGa₂Se₄, the values N _t = 1.4 × 10¹³, 8.2 × 10¹², and 2.6 × 10¹² cm⁻³ are obtained. The contact region transparency D _k ^*= 10⁻⁵, surface recombination velocity S _k = 0.65 m/s, and carrier lifetime τ = 1.5 × 10⁻⁴ s were determined. It was found that the current transmission mechanism in electric fields weaker than 10³ V/cm is caused by monopolar carrier injection.     

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.     

Anomalous scattering of electrons in <Emphasis Type="Italic">n</Emphasis>-Si crystals irradiated with protons

The aim of this study was to gain insight into the effect of irradiation with 25-MeV protons on the Hall mobility of electrons in n-Si crystals. Irradiated crystals with an initial electron concentration 6 × 10¹³ cm^-3 were studied using the Hall method in the range of temperatures 77–300 K. The studies showed that, in crystals irradiated with the proton dose Φ = 8.1 × 10¹² cm^-2, the effective mobility of conduction electrons μ_eff increases drastically. This effect is direct evidence that inclusions with relatively high conductivity and with nonrectifying junction at interfaces with semiconductor matrix are predominantly formed in n-Si crystals under these conditions. Agglomerations of interstitial atoms or their associations can represent such inclusions.     

Metal-Organic Chemical Vapor Deposition of Hg<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Cd<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Te Fully Doped Heterostructures Without Postgrowth Anneal for Uncooled MWIR and LWIR Detectors

Uncertainty in precursor pulse delays and shapes has been found to be an important factor in Hg_1−x Cd _x Te metal-organic chemical vapor deposition (MOCVD) growth using the interdiffused multilayer process (IMP). Herein, metal-organic concentration changes in the growth zone are examined using an in␣situ infrared (IR) absorption gas monitoring system, and modifications to the interdiffused multilayer process are applied for in␣situ control of stoichiometry, improved morphology, minimized process length, and consumption of precursors. Dimethylcadmium (DMCd) introduction during IMP flush stages in HgTe was used for stoichiometry control. The final stage of heterostructure formation was optimized to prevent Hg outdiffusion. As a result, vacancy concentration was reduced far below the equilibrium level at the growth conditions so the background of n-type doping was revealed. Acceptor doping with arsine (AsH₃) and trisdimethylaminoarsenic (TDMAAs) was examined over a wide range of compositions, and doping levels of 5 × 10¹⁵ cm⁻³ to 5 × 10¹⁷ cm⁻³ were obtained. The presence of both arsenic dopants significantly increased the CdTe growth rate. This caused an increase of Cd mole fraction in the grown material. Doped heterostructures can be grown without any postgrowth anneal and used for mid- and long-wavelength infrared (MWIR and LWIR) devices operating at near-ambient temperatures. Student paper; supervisors are A. Rogalski, J. Piotrowski and J. Szmidt     

Thermoelectric Properties of In<Subscript>0.3</Subscript>Ga<Subscript>0.7</Subscript>N Alloys

We report on the experimental investigation of the potential of InGaN alloys as thermoelectric (TE) materials. We have grown undoped and Si-doped In_0.3Ga_0.7N alloys by metalorganic chemical vapor deposition and measured the Seebeck coefficient and electrical conductivity of the grown films with the aim of maximizing the power factor (P). It was found that P decreases as electron concentration (n) increases. The maximum value for P was found to be 7.3 × 10⁻⁴ W/m K² at 750 K in an undoped sample with corresponding values of Seebeck coefficient and electrical conductivity of 280 μV/K and 93␣(Ω cm)⁻¹, respectively. Further enhancement in P is expected by improving the InGaN material quality and conductivity control by reducing background electron concentration.     

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.