Nanotribological Characteristics of Cu<Subscript>6</Subscript>Sn<Subscript>5</Subscript>, Cu<Subscript>3</Subscript>Sn,and Ni<Subscript>3</Subscript>Sn<Subscript>4</Subscript> Intermetallic Compounds

Nanotribological characteristics, including the coefficient of friction, wear coefficient, and wear resistance, of Cu₆Sn₅, Cu₃Sn, and Ni₃Sn₄ intermetallic compounds developed by the annealing of Sn–Cu or Sn–Ni diffusion couples were investigated in this work. The scratch test conditions combined a constant normal load of 10 mN, 20 mN, or 30 mN and a scratch rate of 0.1 μm/s, 1 μm/s, or 10 μm/s. Experimental results indicated that, as the normal load increases, the pile-up grows taller and the scratch deepens, leading to a greater coefficient of friction and wear coefficient, and reduced wear resistance. Moreover, the scratch rate does not have a significant effect on the nanotribological characteristics except for those of Cu₆Sn₅ and Cu₃Sn under a normal load of 10 mN. Though the hardness of Cu₆Sn₅, Cu₃Sn, and Ni₃Sn₄ is similar, Ni₃Sn₄ appears to be more prone to wear damage.     

The nanoindentation characteristics of Cu<Subscript>6</Subscript>Sn<Subscript>5</Subscript>, Cu<Subscript>3</Subscript>Sn,and Ni<Subscript>3</Subscript>Sn<Subscript>4</Subscript> intermetallic compounds in the solder bump

In general, formation and growth of intermetallic compounds (IMCs) play a major role in the reliability of the solder joint in electronics packaging and assembly. The formation of Cu-Sn or Ni-Sn IMCs have been observed at the interface of Sn-rich solders reacted with Cu or Ni substrates. In this study, a nanoindentation technique was employed to investigate nanohardness and reduced elastic moduli of Cu₆Sn₅, Cu₃Sn, and Ni₃Sn₄ IMCs in the solder joints. The Sn-3.5Ag and Sn-37Pb solder pastes were placed on a Cu/Ti/Si substrate and Ni foil then annealed at 240°C to fabricate solder joints. In Sn-3.5Ag joints, the magnitude of the hardness of the IMCs was in the order Ni₃Sn₄>Cu₆Sn₅>Cu₃Sn, and the elastic moduli of Cu₆Sn₅, Cu₃Sn, and Ni₃Sn₄ were 125 GPa, 136 GPa, and 142 GPa, respectively. In addition, the elastic modulus of the Cu₆Sn₅ IMC in the Sn-37Pb joint was similar to that for the bulk Cu₆Sn₅ specimen but less than that in the Sn-3.5Ag joint. This might be attributed to the strengthening effect of the dissolved Ag atoms in the Cu₆Sn₅ IMC to enhance the elastic modulus in the Sn-3.5Ag/Cu joint.     

Fluxon pinning in the nodeless pairing state of superconducting YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>7</Subscript>

Positive-muon spin rotation (μ+SR) spectroscopy and magnetic moment measurements were used to probe fluxon (or vortex) formation in the superconducting mixed state of a high-purity YBa₂Cu₃O₇ crystal. Random potentials caused by crystal-lattice defects pin fluxons. A fluxon lattice forms in an external magnetic field, and changes of thermal activation lead to fluxon pinning and depinning. The root second moment of the local magnetic field distribution (σ) determined by μ+SR contains information on the magnetic penetration depth and the pinning. Fluxon pinning leads to temperature-dependent transverse displacements of the fluxons that decrease σ and also fluctuations in the separation between fluxons that tend to increase σ. By accounting for the field-dependent and temperature-activated fluxon disorder, it is found that the experimental results for the penetration depth are consistent with a supercon-ducting order parameter of a strong-coupling two-fluid model, confirming that the superconductivity is nodeless with s-wave superconducting pairing. Quantitative results for fluxon displacements are discussed within the context of the fluxon field-temperature phase diagram.     

Formation of the low-resistivity compound Cu<Subscript>3</Subscript>Ge by low-temperature treatment in an atomic hydrogen flux

The systematic features of the formation of the low-resistivity compound Cu₃Ge by low-temperature treatment of a Cu/Ge two-layer system in an atomic hydrogen flux are studied. The Cu/Ge two-layer system is deposited onto an i-GaAs substrate. Treatment of the Cu/Ge/i-GaAs system, in which the layer thicknesses are, correspondingly, 122 and 78 nm, in atomic hydrogen with a flux density of 10¹⁵ at cm² s^–1 for 2.5–10 min at room temperature induces the interdiffusion of Cu and Ge, with the formation of a polycrystalline film containing the stoichiometric Cu₃Ge phase. The film consists of vertically oriented grains 100–150 nm in size and exhibits a minimum resistivity of 4.5 µΩ cm. Variations in the time of treatment of the Cu/Ge/i-GaAs samples in atomic hydrogen affect the Cu and Ge depth distribution, the phase composition of the films, and their resistivity. Experimental observation of the synthesis of the Cu₃Ge compound at room temperature suggests that treatment in atomic hydrogen has a stimulating effect on both the diffusion of Cu and Ge and the chemical reaction of Cu₃Ge-compound formation. These processes can be activated by the energy released upon the recombination of hydrogen atoms adsorbed at the surface of the Cu/Ge/i-GaAs sample.     

Ball Mill Synthesis of Bulk Quaternary Cu<Subscript>2</Subscript>ZnSnSe<Subscript>4</Subscript> and Thermoelectric Studies

In this work, quaternary chalcogenide Cu₂ZnSnSe₄ (CZTSe) was synthesized using a mechanochemical ball milling process and its thermoelectric properties were studied by electrical resistivity, Seebeck coefficient, and thermal conductivity measurements. The synthesis process comprises three steps viz., wet ball milling of the elemental precursors, vacuum annealing, and densification by hot pressing. The purpose of this is to evaluate the feasibility of introducing wet milling in place of vacuum melting in solid state synthesis for the reaction of starting elements. We report the structural characterization and thermoelectric studies conducted on samples that were milled at 300 rpm and 500 rpm. X-ray diffraction (XRD) analysis showed the existence of multiple phases in the as-milled samples, indicating the requirement for heat treatment. Therefore, the ball milled powders were cold pressed and vacuum annealed to eliminate the secondary phases. Annealed samples were hot pressed and made into dense pellets for further investigations. In addition to XRD, energy dispersive spectroscopy (EDS) studies were performed on hot pressed samples to study the composition. XRD and EDS studies confirm CZTSe phase formation along with ZnSe secondary phase. Electrical resistivity and Seebeck coefficient measurements were done on the hot pressed samples in the temperature range 340–670 K to understand the thermoelectric behaviour. Thermal conductivity was calculated from the specific heat capacity and thermal diffusivity values. The thermoelectric figure of merit zT values for samples milled at 300 rpm and 500 rpm are ～0.15 and ～0.16, respectively, at 630 K, which is in good agreement with the values reported for solid state synthesized compounds.     

Thickening kinetics of interfacial Cu<Subscript>6</Subscript>Sn<Subscript>5</Subscript> and Cu<Subscript>3</Subscript>Sn layers during reaction of liquid tin with solid copper

Thickening behavior of interfacial η (Cu₆Sn₅) phase and ɛ (Cu₃Sn) phase intermetallic layers was investigated in liquid tin/solid copper reaction couples over reaction times from 30 sec to over 4,000 min and temperatures from 250°C to 325°C. A scanning electron microscope (SEM) was used to quantify the interfacial microstructure at each processing condition. The η developed with a scalloped morphology, while the ɛ always grew as a somewhat undulated planar layer in phase with the η. The thickness of each phase was quantitatively evaluated from SEM micrographs using imaging software. Thickening kinetics of the ɛ and η compounds were modeled using time- and temperature-dependent empirical power-law equations. From the model, values for the kinetic exponent, rate constant, and activation energy were established for each intermetallic layer. Measured values for the kinetic exponents and activation energies suggest that thickening of the η is controlled by a grain-boundary diffusion mechanism, and growth of the ɛ occurs by solid-state diffusion, probably grain-boundary diffusion.     

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.     

Optical and structural properties of Cu<Subscript>2</Subscript>ZnSnS<Subscript>4</Subscript> thin films obtained by pulsed laser deposition in a H<Subscript>2</Subscript>S atmosphere with subsequent annealing in a N<Subscript>2</Subscript> atmosphere

The structural and optical properties of Cu₂ZnSnS₄ thin-film layers formed by reactive pulsed laser deposition in a H₂S atmosphere at room temperature with the use of a Cu metal target and a Zn–Sn alloy target are studied in relation to the parameters of annealing in a N₂ atmosphere.     

Microstructure and optical properties of In<Subscript>2</Subscript>S<Subscript>3</Subscript> films produced by thermal evaporation

The data on the influence of the microstructure of In₂S₃ films produced by thermal evaporation upon their optical properties in relation to the film’s thickness are reported. The atomic force spectroscopy data for the layers that are produced in identical technological conditions, but exhibit different spectral positions of the optical absorption edge are presented and discussed. Variations in the optical band gap from 2.0 to 3.6 eV under variations in the thickness of the In₂S₃ films from 800–450 nm to 50–30 nm are observed. The variations are interpreted as a result of variations in the content of grains, specific in dimensions and microstructure.     

Determination of Thermodynamic Parameters in the Cu<Subscript>1.95</Subscript>Ni<Subscript>0.05</Subscript>S Phase-Transition Regions

X-ray diffraction and differential thermal analysis data obtained in the Cu_1.95Ni_0.05S phase-transition region are analyzed. It is established that the low-temperature rhombic α phase in Cu_1.95Ni_0.05S transforms to the hexagonal β phase at temperatures of 370–390 K and to the cubic γ phase at temperatures of 740–765 K according to the scheme \(\alpha \to \mathop {\alpha + \beta }\limits_{370 - 390K} \to \mathop {\alpha + \gamma }\limits_{740 - 765K} \to \gamma \). It is determined (using the temperature dependence of differential thermal analysis) that the transition α → β is accompanied by heat absorption while the transition β → γ is accompanied by heat release. It is found that both transitions are allowed and belong to the reconstructive type. Both transitions are found to occur in a fluctuation volume of ~10^–20 cm³ at temperature rates of 0.11 and 0.08 K^–1. It is demonstrated that the transition α → γ is accompanied by alternation of the structures passing through the intermediate β phase, which is incommensurate with respect to the α and γ phases.     

CeB<Subscript>6</Subscript> thin films produced on different substrates by electron-beam deposition

Films of cerium hexaboride, a material promising for use in thermoelectric devices at liquidhelium temperatures, are produced by electron-beam deposition. Deposition is carried out from ceramic targets onto insulator, semiconductor, and metal substrates at different temperatures. The microstructure, the elemental and phase compositions, the temperature dependences of the resistivity and the Seebeck coefficient are thoroughly studied. CaB₆-structured films, for which the structure is characteristic of cerium hexaboride and the elemental composition is close to the stoichiometric composition, are obtained. At low temperatures, the resistivity of the films is somewhat higher than that of single-crystal samples, and the Seebeck coefficient is close to the corresponding coefficient for single-crystal samples. The main cause of the difference between the resistance values is a high concentration of oxygen impurity detected in the films.     

Microstructure and Raman Scattering of Cu<Subscript>2</Subscript>ZnSnSe<Subscript>4</Subscript> Thin Films Deposited onto Flexible Metal Substrates

Cu₂ZnSnSe₄ thin films are produced by selenizing electrochemically layer-by-layer deposited and preliminarily annealed Cu–Zn–Sn precursors. For flexible metal substrates, Mo and Ta foils are used. The morphology, elemental and phase compositions, and crystal structure of Cu₂ZnSnSe₄ films are studied by scanning electron microscopy, X-ray spectral microanalysis, X-ray phase analysis, and Raman spectroscopy.     

Thermoelectric figure of merit of Ag<Subscript>2</Subscript>Se with Ag and Se excess

In the temperature range of 100–300 K, the electric (σ) and thermoelectric (α₀) properties of Ag₂Se with an excess of Ag as high as ～0.1 at. % and Se as high as ～1.0 at. %, respectively, are investigated. From the data on σ, α₀, and χ_tot (thermal conductivities), the thermoelectric power α ₀ ² σ and the figure of merit Z are calculated. It is found that α ₀ ² σ and Z attain the peak values at room temperature and the electron concentration n ≈ 6.5 × 10¹⁸ cm^?3.     

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.     

Crystal Growth,Structure, and Stoichiometry of the Superconducting Pyrochlore Cd<Subscript>2</Subscript>Re<Subscript>2</Subscript>O<Subscript>7</Subscript>

We report single-crystal growth of the superconducting pyrochlore Cd₂Re₂O₇ using a vapor transport technique. Several parameters of the growth conditions, including hot-zone temperature and starting stoichiometry, were varied in order to control the formation of ReO₂ inclusions, as confirmed by the electron microscopy, resistivity, and magnetic susceptibility measurements. The Rietveld refinement of x-ray (neutron) powder diffraction was found to be consistent with a cubic structure Fd3m with lattice constant a = 10.2250 (10.2358) Å and reduced coordinate of O1 = 0.3184 (0.3177) at 293 K (250 K). We also studied the oxygen stoichiometry by means of redox reactions, electron microprobe analysis (EMPA), and x-ray/neutron diffractions. Particularly, the neutron powder diffraction on the ¹¹⁴Cd-enriched specimens yielded an oxygen deficiency δ = 0.14 ± 0.03 solely at the O2 site, which was consistent with the EMPA results. The EMPA indicated that the oxygen deficiency is homogeneous in the bulk and in a range of 0.01 ± 0.18–0.23 ± 0.19.     

Structure of Bi<Subscript>2</Subscript>Se<Subscript>0.3</Subscript>Te<Subscript>2.7</Subscript> alloy plates obtained by crystallization in a flat cavity by the Bridgman method

The property anisotropy in Bi₂Se_0.3Te_2.7 alloy is analyzed by constructing index surfaces for the thermoelectric figure of merit and thermal expansion coefficient. Texture is an important factor forming the property anisotropy and technological applicability of an ingot for fabricating modules. The property anisotropy is analyzed based on studying the texture in ingots produced by the modified Bridgman method (thermoelectric plate growth in a flat cavity). Analysis of the texture shows that not only the crystallization rate, but also the crystallization cavity design is an important factor for the proposed crystallization method, affecting the formation of the thermoelectric-material structure. As the plate thickness is decreased by changing the heat removal conditions in a thin gap, a more perfect structure can be obtained.     

Development of (Bi,Sb)<Subscript>2</Subscript>(Te,Se)<Subscript>3</Subscript>-Based Thermoelectric Modules by a Screen-Printing Process

In major applications, optimal power will be achieved when thermoelectric films are at least 100 μm thick. In this paper we demonstrate that screen-printing is an ideal method to deposit around 100 μm of (Bi,Sb)₂(Te,Se)₃-based films on a rigid or flexible substrate with high Seebeck coefficient value (90 μV K⁻¹ to 160 μV K⁻¹) using a low-temperature process. Conductive films have been obtained after laser annealing and led to acceptable thermoelectric performance with a power factor of 0.06 μW K⁻² cm⁻¹. While these initial material properties are not at the level of bulk materials, the complete manufacturing process is cost-effective, compatible with large surfaces, and affords a mass-production technique.     

Cu<Subscript>3</Subscript>Mo<Subscript>2</Subscript>O<Subscript>9</Subscript>: An Ultralow-Firing Microwave Dielectric Ceramic with Good Temperature Stability and Chemical Compatibility with Aluminum

An ultralow-firing microwave dielectric ceramic Cu₃Mo₂O₉ with orthorhombic structure has been fabricated via a solid-state reaction method. X-ray diffraction analysis, Rietveld refinement, Raman spectroscopy, energy-dispersive spectrometry, and scanning electron microscopy were employed to explore the phase purity, crystal structure, and microstructure. Pure and dense Cu₃Mo₂O₉ ceramics could be obtained in the sintering temperature range from 580°C to 680°C. The sample sintered at 660°C for 4 h exhibited the highest relative density (～ 97.2%) and best microwave dielectric properties with ε _r = 7.2, Q × f = 19,300 GHz, and τ _f = ? 7.8 ppm/°C. Chemical compatibility with aluminum electrodes was also confirmed. All the results suggest that Cu₃Mo₂O₉ ceramic is a promising candidate for use in ultralow-temperature cofired ceramic applications.     

Effect of Annealing Temperature on Flowerlike Cu<Subscript>3</Subscript>BiS<Subscript>3</Subscript> Thin Films Grown by Chemical Bath Deposition

For widespread application of thin-film photovoltaic solar cells, synthesis of inexpensive absorber material is essential. In this work, deposition of ternary Cu₃BiS₃ absorber material, which contains abundant and environmentally benign elements, was carried out on glass substrate. Flowerlike Cu₃BiS₃ thin films with nanoflakes as building block were formed on glass substrate by chemical bath deposition. These films were annealed at 573 K and 673 K in sulfur ambient for structural improvement. Their structure was characterized using Raman spectroscopy, as well as their surface morphological and optical properties. The x-ray diffraction profile of as-deposited Cu₃BiS₃ thin film revealed amorphous structure, which transformed to orthorhombic phase after annealing. The Raman spectrum exhibited a characteristic peak at 290 cm^?1. Scanning electron microscopy of as-deposited Cu₃BiS₃ film confirmed formation of nanoflowers with diameter of around 1052 nm. Wettability testing of as-deposited Cu₃BiS₃ thin film demonstrated hydrophobic nature, which became hydrophilic after annealing. The measured ultraviolet–visible (UV–Vis) absorption spectra of the Cu₃BiS₃ thin films gave an absorption coefficient of 10⁵ cm^?1 and direct optical bandgap of about 1.42 eV after annealing treatment. Based on all these results, such Cu₃BiS₃ material may have potential applications in the photovoltaic field as an absorber layer.     

Specific features of the transport properties of the Lu<Subscript>0.1</Subscript>Bi<Subscript>1.9</Subscript>Te<Subscript>3</Subscript> compound

The temperature and electric- and magnetic-field dependences of the resistivity of the R_0.1Bi_1.9Te₃ compound are investigated. It is shown that, in the low-temperature region, variable-range hopping conductivity is realized in this compound. In the temperature range of hopping conductivity, the electrical resistivity decreases with increasing electric-field strength in the sample, which is typical of charge-carrier tunneling from one localized state in the impurity band to another. Investigation of the transverse magnetoresistance revealed the crossover from the parabolic dependence of the magnetoresistance in low fields to the linear dependence in high fields. The established features of the transport properties of the R_0.1Bi_1.9Te₃ compound are characteristic of inhomogeneous and disordered semiconductors.