Thermal expansion and thermal conductivity of single-crystal Cu<Subscript>x</Subscript>Ag<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>InS<Subscript>2</Subscript> solid solutions grown by the moving solvent method

Single crystals of Cu_xAg_1−x InS₂ solid solutions are grown by the moving solvent method. The compositions and structures of the single crystals are determined. The thermal expansion coefficients of these crystals are determined with a dilatometer. The thermal expansion coefficients are found to vary linearly with concentration x. The thermal conductivity of the crystals is measured by the absolute method, and the concentration dependence of the thermal conductivity is constructed. This dependence is shown to have a minimum near the equimolar composition.     

The ionic Seebeck effect and heat of cation transfer in Cu2−δSe superionic conductors

The ionic Seebeck coefficients of Cu_2?δSe superionic conductors are measured in the temperature range 340–380°C. The data obtained are used to determine the heat of transfer Q _i of copper ions as a function of the degree of nonstoichiometry and the temperature. The heat of transfer of copper cations increases from 0.19 to 0.22 eV as the degree of nonstoichiometry δ increases from 0.015 to 0.050. It is noted that the heat of transfer Q _i tends to increase with an increase in the temperature. Assumptions regarding the specific features of the cation diffusion in the Cu_2?δSe superionic conductors are made from the observed closeness of the heat of transfer and the activation energy for ionic conduction.     

Fast ionic transport in Ag<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>TiS<Subscript>2</Subscript>

The enthalpy of the subsystem of silver ions in the intercalation compounds Ag _x TiS₂ has been calculated from the electrochemically measured thermodynamic functions of the silver subsystem. The ionic conductivity and the coupled chemical diffusion coefficients for silver in the intercalation compound have been measured. The activation energy for diffusion of silver ions is determined and the obtained value is interpreted from analyzing the concentration dependence of the enthalpy of the ionic subsystem. The conclusion has been drawn that the high diffusion mobility is associated with the competition between the covalent and elastic interactions, which decreases the activation energy for diffusion of ions.     

Transmission spectra of films of Mn<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Fe<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Se solid solutions

Films of Mn_1−x Fe _x Se (x = 0–0.45) solid solutions were flash-sputtered. We measured the transmission spectra of the films in the wavelength range 200–1000 nm at room temperature. From these spectra, we calculated the absorption coefficients and determined the fundamental absorption edge, the position of which is shifted from 2.65 eV in MnSe to 2.30 eV in solid solutions of compositions x = 0.20–0.45. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 1, pp. 136–138, January–February, 2007.     

Photodesorption of O<Subscript>2</Subscript> from Ag<Subscript>2</Subscript><Superscript>-</Superscript>: A time-resolved study of Ag<Subscript>2</Subscript>O<Subscript>2</Subscript><Superscript>-</Superscript>

We present time-resolved photoelectron spectra of mass-selected Ag₂O₂ anions. The anions are photoexcited by photons with an energy of 3.1 eV, and photoelectron spectra of the excited species Ag₂O₂ ^{- *} and the subsequently appearing fragments are recorded using a probe laser pulse with a photon energy of 1.5 eV. The excited state of Ag₂O₂ ^- has a short lifetime of 130 fs±70 fs only and decays by direct photodesorption of O₂. The data demonstrate the ability of time-resolved photoelectron spectroscopy (TR-PES) to observe the breaking of chemical bonds if the decay process of the excited state is direct (non-thermal desorption). The data are compared to recent results of a NeNePo experiment [1] on the same system. PACS 68.43.Tj; 78.47.+p; 33.80.Eh; 36.40.-c     

Photochromism in Cu-and Ag-doped Bi<Subscript>12</Subscript>SiO<Subscript>20</Subscript> crystals

The equilibrium and photoinduced absorption spectra of copper-and silver-doped Bi₁₂SiO₂₀ crystals are studied. It is demonstrated that the impurity absorption is due to Ag²⁺, Ag⁺, Cu³⁺, Cu²⁺, and Cu⁺ ions occupying almost octahedral Bi³ positions. A mechanism of photochromism is suggested, involving changes in the charge states of copper and silver impurity ions according to schemes Cu²⁺-e → Cu³⁺ and Ag⁺-e → Ag²⁺.     

O<Subscript>2</Subscript> photodesorption from a Ag<Subscript>8</Subscript>O<Stack><Subscript>2</Subscript><Superscript>-</Superscript></Stack> cluster

The decay path of an Ag₈(O₂)^- cluster photoexcited by a 3.1 eV photon is elucidated using time-resolved photoelectron spectroscopy. Photoabsorption results in the formation of an excited state giving rise to a peak in the photoelectron spectra with well-resolved vibrational finestructure. With a lifetime of about 100 fs this bound state decays into an anti-bonding state which dissociates into O₂ and Ag₈^- on a timescale of 10 ps. In the photoelectron spectra, this corresponds to a broad maximum shifting gradually towards higher binding energy while the O₂ and Ag₈^- separate. Finally, the spectrum of bare Ag₈^- appears. This process is unique to small clusters, because on metal surfaces excited state lifetimes are too short to allow for direct dissociation.     

Photoelectric characteristics of nanostructured hydrochemically deposited films of the Pb<Subscript>0.975</Subscript>Sn<Subscript>0.025</Subscript>Se substitutional solid solution

The photoelectric characteristics of Pb_0.975Sn_0.025Se solid solution films prepared by the hydrochemical codeposition of PbSe and SnSe with the subsequent heat treatment in air at 573–700 K have been investigated. The thermal and optical band gaps, the temperature coefficient of the optical band gap, the dark resistance, the volt-watt sensitivity, and the range of spectral sensitivity have been determined in the temperature range of 220–300 K. It has been found that, after heat treatment below 573 K, the films of the Pb_0.975Sn_0.025Se solid solutions possess metallic conductivity, while being heat treated at elevated temperatures, they become semiconductors with p-type conductivity. The composition of the solid solution is independent of the heat treatment temperature; it is formed during deposition.     

Synthesis of highly non-stoichiometric Cu<Subscript>2</Subscript>ZnSnS<Subscript>4</Subscript> nanoparticles with tunable bandgaps

Non-stoichiometric Cu₂ZnSnS₄ nanoparticles with average diameters of 4–15 nm and quasi-polyhedral shape were successfully synthesized by a colloidal method. We found that a non-stoichiometric composition of Zn to Cu in Cu₂ZnSnS₄ nanoparticles yielded a correlation where Zn content increased with a decrease in Cu content, suggesting formation of lattice defects relating to Cu and Zn, such as a Cu vacancy (V_Cu), antisite with Zn replacing Cu (Zn_Cu), and/or defect cluster of V_Cu and Zn_Cu. The bandgap energy of Cu₂ZnSnS₄ nanoparticles systematically varies between 1.56 and 1.83 eV depending on the composition ratios of Cu and Zn, resulting in a wider bandgap for Cu-deficient Cu₂ZnSnS₄ nanoparticles. These characteristics can be ascribed to the modification in electronic band structures due to formation of V_Cu and Zn_Cu on the analogy of ternary copper chalcogenide, chalcopyrite CuInSe₂, in which the top of the valence band shifts downward with decreasing Cu contents, because much like the structure of CuInSe₂, the top of the valence band is composed of a Cu 3d orbital in Cu₂ZnSnS₄.     

Optical properties of thin Cu<Subscript>2</Subscript>ZnSnS<Subscript>4</Subscript>, films produced by RF magnetron sputtering

Optical properties of thin Cu₂ZnSnS₄ films produced by RF magnetron sputtering of preliminarily synthesized material are studied. Transmission and reflection coefficients are studied in a range from 0.4 to 26 μm. The optical band-gap width depending on substrate temperature is estimated; in optimal modes, it is equal to 1.47 eV. The study of electrical properties shows that Cu₂ZnSnS₄ possesses low charge-carrier mobility, μ = 1.9 cm²/(V s), at room temperature and hole concentration р = 5 × 10¹⁸ cm^–3. Electron microscopy shows that the film possesses a polycrystalline structure with a crystallite size on the order of 100 nm.     

Structural and optical properties of CdS/Cu(In,Ga)Se<Subscript>2</Subscript> heterostructures irradiated by high-energy electrons*

Thin films of Cu(In, Ga)Se₂ (CIGS) with a Ga/(Ga + In) ratio of ~0.27 corresponding to the standard elemental composition for solar-energy transducers were grown on Mo-coated glass substrates by the Cu, In, Ga, and Se co-evaporation technique from different sources. Transmission (T), photoluminescence (PL), and photoluminescence excitation (PLE) spectra at 4.2 K were used to analyze electronic properties in the asgrown and electron-irradiated CIGS films. The band-gap energy (E_g) of the CIGS films measured using both transmission and PLE methods was found to be about 1.28 eV at 4.2 K. Two deep bands in the PL spectra of the irradiated CIGS films, P₁ at ~0.91 eV and P₂ at ~0.77 eV, have been detected. These bands are tentatively associated with copper atoms substituting indium (Cu_In) and indium vacancies V_In, respectively, as the simplest radiation-induced defects.     

Energy spectrum of holes in Sb<Subscript>2</Subscript>Te<Subscript>2.9</Subscript>Se<Subscript>0.1</Subscript> solid solution according to the data on the transfer phenomena

The temperature dependence of the Hall coefficient of a single crystal of the p-Sb₂Te_2.9Se_0.1 solid solution grown by the Czochralski technique is studied in the temperature range 77–450 K. The data on the Hall coefficient of the p-Sb₂Te_2.9Se_0.1 are analyzed in combination with the data on the Seebeck and Nernst–Ettingshausen effects and the electrical conductivity with allowance for interband scattering. From an analysis of the temperature dependences of the four kinetic coefficients, it follows that, at T < 200 K, the experimental data are qualitatively and quantitatively described in terms of the one-band model. At higher temperatures, a complex structure of the valence band and the participation of the second-kind additional carriers (heavy holes) in the kinetic phenomena should be taken into account. It is shown that the calculations of the temperature dependences of the Seebeck and Hall coefficients performed in the two-band model agree with the experimental data with inclusion of the interband scattering when using the following parameters: effective masses of the density of states of light holes m_d1^*≈ 0.5m₀ (m₀ is the free electron mass) and heavy holes m_d2^*≈ 1.4m₀, the energy gap between the main and the additional extremes of the valence band ΔE_v ≈ 0.14 eV that is weakly dependent on temperature.     

Correlation between the dynamics of oxygen atoms and oxidation kinetics of solid solutions based on Bi<Subscript>2</Subscript>Sr<Subscript>2</Subscript>CaCu<Subscript>2</Subscript>O<Subscript>8</Subscript>

The oxidation kinetics of Bi_1.3Pb_0.8Sr₂Ca_0.8Y_0.2Cu₂O_8+δ solid solutions at different temperatures and \(p_{O_2 } = 0.21\) atm is investigated by thermogravimetry. The results obtained are compared with the previously studied oxidation kinetics of Bi_1.3Pb_0.8Sr₂Ca_0.8Y_0.2Cu₂O_8+δ solid solutions. It is found that the substitution of yttrium for calcium leads to an appreciable retardation of the initial oxidation stage associated with the oxygen diffusion. The phonon spectra of the solid solutions are examined using inelastic neutron scattering on a DIN-2PI direct-geometry spectrometer. The high-frequency (>50 meV) phonon densities of states for yttrium-containing and yttrium-free solid solutions are analyzed. The possible model is proposed for a correlation between the differences observed in the high-frequency phonon densities of states attributed to the vibrations of oxygen atoms and the differences in the oxidation kinetics of the solid solutions under consideration.     

A new green synthesis method of CuInS<Subscript>2</Subscript> and CuInSe<Subscript>2</Subscript> nanoparticles and their integration into thin films

A new preparation method for CuInS₂ and CuInSe₂ nanoparticles synthesis is described without using any organic solvent. Heating Cu, In, and S/Se precursors dissolved in water for 30 min in a microwave oven in the presence of mercapto-acetic acid leads to monodispersed chalcopyrite nanoparticles. No precipitation of these nanoparticles is observed after several months at room temperature. These new materials have been thoroughly characterized to confirm their compositions, sizes, and structure without any filtration. Transmission electron microscopy (TEM) confirmed particle sizes below 5 nm. Energy dispersive X-ray analysis (EDXA) confirmed the chemical composition of these samples. X-ray diffraction (XRD) showed a chalcopyrite-type structure with crystallite size of about 2 nm. No difference has been observed between batch and continuous synthesis processes. Cu _x InS₂ and Cu _x InSe₂ nanoparticles, with x < 1, have been also synthesized and identified. Simulation using a commercial software confirmed the difference between copper poor (Cu _x InS₂) and copper rich (CuInS₂) chalcopyrite structures. Conventional spray deposition techniques have been used to form relatively thin films on solid substrates.     

Investigation of ion transport in Li<Subscript>8</Subscript>ZrO<Subscript>6</Subscript> and Li<Subscript>6</Subscript>Zr<Subscript>2</Subscript>O<Subscript>7</Subscript> solid electrolytes

Lithium ionic conductivity and spin-lattice relaxation rates were measured in Li₈ZrO₆ and Li₆Zr₂O₇ solid electrolytes. It was found that the Li₈ZrO₆ solid electrolyte undergoes a transition to the superionic state in the temperature range 673–703 K. It was shown that Li⁺ ions are mobile in particular lattice positions of the Li₆Zr₂O₇ phase, and that ionic conductivity is monotonic at an activation energy of 79.4 kJ/mol.     

Effect of thermal treatment on the thermoelectric properties of Sb<Subscript>0.9</Subscript>Bi<Subscript>1.1</Subscript>Te<Subscript>2.9</Subscript>Se<Subscript>0.1</Subscript> solid solution thin films

The effect thermal treatment in a vacuum has on the thermoelectric properties of Sb_0.9Bi_1.1Te_2.9Se_0.1 solid solution thin films obtained via ion-beam sputtering in an argon atmosphere is considered. It is established that the specific resistance and thermopower are determined by the type and concentration of intrinsic point defects of the Sb_0.9Bi_1.1Te_2.9Se_0.1 solid solution. The power factor values are found to be comparable to those of nanostructured materials based on (Bi,Sb)₂(Te,Se)₃ solid solutions.     

Mobility and diffusion of oxygen isotopes in YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>6+<Emphasis Type="Italic">x</Emphasis></Subscript>: Monte carlo simulation

The self-diffusion (D₀) and isotope diffusion (D*) coefficients of oxygen in YBa₂Cu₃O_6+x are calculated as functions of the temperature (600–1200 K) and the oxygen content (0<x<1). The Monte Carlo simulation is performed with due regard for both the interaction of oxygen ions at lattice sites in the basal planes of YBa₂Cu₃O_6+x and the interaction between a jumping ion at a saddle point and the environment. Equilibrium thermodynamic characteristics (including the phase diagram and the heat capacity) are calculated in terms of the Hamiltonian of interaction between oxygen ions at the lattice sites. It is found that an increase in the oxygen content leads to a decrease in the diffusion coefficients D₀ and D*, an increase in the effective activation energies for diffusion by 0.3–0.5 eV, and a decrease in the Haven ratio from 1 to ～0.5.     

Dissociation channels of silver bromide cluster Ag<Subscript>2</Subscript>Br,silver cluster Ag<Subscript>3</Subscript> and their ions studied by using alkali metal target

Various dissociation channels of silver bromide cluster ion Ag₂Br⁺ and silver cluster ion Ag₃ ⁺ were observed in high-energy collisionally-activated dissociation (CAD) using a Cs target. The fragment patterns of the high-energy CAD were compared with those of the metastable dissociation and low-energy CAD. The difference in the fragment patterns between the high-energy CAD and the other dissociation methods was explained in terms of the internal energy distributions. The dissociation mechanisms of neutral silver bromide cluster Ag₂Br and silver cluster Ag₃ were also investigated by charge inversion mass spectrometry using the Cs target. While the fragment ions AgBr^- and Ag₂ ^- were dominantly observed in the charge inversion spectrum of Ag₂Br⁺, the undissociated ion Ag₃ ^- was observed as a predominant peak in the case of Ag₃ ⁺. The dissociation behavior of Ag₂Br^* can be explained on the basis of the calculated thermochemical data. Contrary to this, the predominant existence of the undissociated Ag₃ ^- cannot be explained by the reported thermochemical data. The existence of undissociated Ag₃ ^- suggests that the dissociation barrier is higher than the internal energy of Ag₃ ^* (theoretical: 1.03 eV, experimental: 2.31 eV) estimated from the ionization potentials of Ag₃ and Cs.     

Synthesis and electrical conductivity of a new Ag<Subscript>6</Subscript>SnS<Subscript>4</Subscript>Br<Subscript>2</Subscript> superionic compound

The conditions of synthesizing a new Ag₆SnS₄Br₂ compound were studied. The crystallographic parameters of the unit cell were determined as follows: space group Pnma, a=6.67050(10) Å, b=7.82095(9) Å, c=23.1404(3) Å, and Z=4. The total electrical conductivity and its ionic component were measured by a dc probe method in the temperature range 210–380 K. Kinks in the conductivity curve and the differential thermogram of heating the alloy were revealed at 235 K. It was concluded that the mass and charge transfers in the compacted Ag₆SnS₄Br₂ alloy powder have an intragrain character.     

Ab initio study of thermoelectric properties of Cu<Subscript>3</Subscript>PSe<Subscript>4</Subscript> and Cu<Subscript>3</Subscript>PS<Subscript>4</Subscript>: alternative materials for thermoelectric applications

This letter discusses the thermoelectric properties of Cu₃PSe₄ and Cu₃PS₄ compounds, using the Ab initio calculations. These compounds are predicted to be good thermoelectric materials thanks to the nature of their band edge states. Seebeck coefficient of Cu₃PSe₄ exhibits a maximum value of 1256 µV/K at roopm temperature, whereas it is 2389 µV/K for Cu₃PS₄. Furthermore, the electrical conductivity is significantly enhanced with doping level while the electronic thermal conductivity is weakly increased. Besides, the factor of merit of these compounds shows a value around the unity only at low doping levels. Hence, this predicts that these compounds may present excellent thermoelectric properties, therefore they could be considered as alternatives for thermoelectric applications.