Luminescence properties of Sn2P2Se6 crystals

A large family of Sn_2yPb_2(1−y)P₂S_6xSe_6(1−x) semiconductor-ferroelectric crystals were obtained by the Bridgman technique. The photoluminescence properties of the Sn_2yPb_2(1−y)P₂S_6xSe_6(1−x) family crystals strongly depend on their chemical composition, excitation energy and temperature. The influence of the Pb → Sn and S → Se isovalent substitutions on the luminescence properties of a crystal with the Sn₂P₂Se₆ basic composition was investigated. A broad emission band observed in the Sn₂P₂Se₆ crystal with a maximum roughly at 600 nm (at T = 8.6 K) was assigned to a band-to-band electron-hole recombination, whereas broad emission bands, peaked near 785 nm (at T = 8.6 K) and 1025 nm (at T = 44 K) were assigned to an electron-hole recombination from defect levels localised within the bandgap. Possible types of recombination defect centres and specific mechanisms of luminescence in the Sn₂P₂Se₆ semiconductor-ferroelectric crystals were considered and discussed on the basis of the obtained results and the referenced data.     

Structural, electronic and optical properties of Sn1−xSbxO2

The goal of this paper is to undertake a detailed first principle calculation of the structural, electronic and optical properties of Sn_1−xSb_xO₂. The results show that the stability of Sn_1−xSb_xO₂ in the full range of Sb content points to the probability of a continuous solid solution, where the increasing Sb content leads to volume expansion with different variation trends in the lattice constants. The increase of Sb concentration in the semiconductor–metal–semimetal transition occurs in consonance with the corresponding changes in its structural, electronic and optical properties. Two competing mechanisms play essential roles in this transition, namely; the many body effect and the atom disorder. Our calculations concur with previous X-ray diffraction, sheet resistance, resistivity and optical parameters detections. The studies present a practical way of tailoring the physical behaviors of Sn_1−xSb_xO₂ through the alloying technique.     

Salt-assistant combustion synthesis of nanocrystalline Nd2(Zr1 − xSnx)2O7 (0 ≤ x ≤ 1) solid solutions

Nanocrystalline Nd₂(Zr_{1 − x}Sn_x)₂O₇ series solid solutions were prepared by a convenient salt-assisted combustion process using glycine as fuel. The samples were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, Raman spectroscopy, transmission electron microscopy and high-resolution transmission electron microscopy. The results showed the Zr ion can be partially replaced by Sn ion. The partial substituted products were still single-phase solid solutions and the crystal form remained unchanged. TEM images reveal that the products are composed of well-dispersed square-shaped nanocrystals. The method provides a convenient and low-cost route for the synthesis of nanostructures of oxide materials.     

Ca4REO(BO3)3 crystals for green and blue microchip laser generation: from crystal growth to laser and nonlinear optical properties

We have taken advantage of congruent melting behavior of the nonlinear rare-earth oxoborate Ca₄REO(BO₃)₃ family to perfect a process of collective fabrication of self-frequency doubling microchip laser based on Nd:GdCOB (Ca₄Gd_1−xNd_xO(BO₃)₃) crystals. The process goes from Czochralski boule to 1 × 3 mm² chips perfectly oriented (better than 0.1°) to the phase matching direction (θ=90°, φ=46°) in the XY principal plane, with dielectric mirrors directly deposited on both faces of the chips. 20 mW of self-frequency doubling output power at 530 nm was performed under 800 mW of diode laser as incident pump power at 812 nm. In addition, new compositions from the solid solution Ca₄Gd_1−xY_xO(BO₃)₃ (Gd_1−xY_xCOB) (x=0.13, 0.16, 0.44) have been grown by the Czochralski pulling method, in order to achieve noncritical phase matching (NCPM) second harmonic generation of ⁴F_3/2 → ⁴I_9/2 Nd³⁺ doped laser hosts. Three types of laser wavelengths have been chosen: Nd:YAP (YAlO₃) at 930 nm, Nd:YAG (Y₃Al₅O₁₂) at 946 nm, and Nd:ASL (Nd_ySr_1−x La_x−yMg_x Al_12−xO₁₉) at 900 nm. Angular acceptance measurements of these three types of compositions present very large values, compared to pure GdCOB or YCOB oriented in critical phase matching configurations.     

Microstructures and thermoelectric properties of p-type pseudo-binary AgxBi0.5Sb1.5−xTe3 (x = 0.05–0.4) alloys prepared by cold pressing

The p-type pseudo-binary Ag_xBi_0.5Sb_1.5−xTe₃ (x = 0.05–0.4) alloys were prepared by cold pressing. The thermal conductivities (κ) were calculated from the values of heat capacities, densities and thermal diffusivities measured, and range approximately from 0.66 to 0.56 (W K^− 1 m^− 1) for the Ag_xBi_0.5Sb_1.5−xTe₃ alloy with molar fraction x being 0.4. Combining with the electrical properties obtained in the previous study, the maximum dimensionless figure of merit ZT of 1.1 was obtained at the temperature of 558 K.     

Superconductivity at 103 K in CdBa2(Ca0.7Y0.3)Cu2Oy

A cadmium analogue of the mercury system with nominal composition CdBa₂(Ca_1–xY_x)Cu₂O_y has been synthesized. Thex=0 samples contain about 12 vol.% of the 1212 phase but are not superconducting. Thex=0.3 samples are superconducting atT _on = 103 K. The EDX analysis of 18 microcrystals shows a broad cationic distribution of the different components. The observed broad superconducting transition is attributed to the variousT _c of the different microcrystals.     

Partial substitution of Li for Cu in superconducting YBa2Cu3Oy

0.33–33% of the Cu in superconducting YBa₂Cu₃O _y has been replaced by Li (i.e.,x=0.01–1 in single-phase or nominal YBa₂Cu_3–x Li_xO_y). X-ray diffraction powder patterns remain the same as for YBn₂Cu₃O _y , with identical patterns up to about 17% substitution (i.e.,x=0.5). At higher percentages an additional phase appears. Electrical conductivity measurements indicate a small elevation ofT _c at low Li content. Starting at about 5% Li (x=0.15),T _c declines progressively and its width increases asx is raised.     

Doping-induced microstructural, textural and optical properties of In2Ti1−xVxO5+δ semiconductors and their role in the photocatalytic splitting of water

The physicochemical properties of V-doped indium titanates (In₂Ti_1−xV_xO_5+δ, 0.0 ≤ x ≤ 0.2) were investigated by using XPS, powder XRD, UV–vis, SEM and luminescence spectroscopy techniques. The Rietveld refinement of XRD data revealed that even though the V-containing samples were isostructural with In₂TiO₅ (orthorhombic space group Pnma), a systematic x-dependent variation was noticeable in the Ti–O bond lengths in [TiO₆] octahedral units, cell parameters and in the value of δ. XPS results confirmed the coexistence of V⁵⁺ and V⁴⁺ states, leading thereby to an enhancement in oxygen non-stoichiometry in the doped samples. A loading-dependent progressive shift from 400 to 750 nm was also observed in the onset of the absorption edge, indicating a significant narrowing of the band gap. Furthermore, the samples with higher V-content were comprised of the grain clusters having larger size and an irregular shape. The UV–vis, photoluminescence and thermoluminescence studies indicate that the doping-induced lattice defects may give rise to certain closely spaced acceptor/donor energy levels in between the band gap of host matrix. The indium titanates are found to serve as stable photocatalysts for water splitting under visible light, where oxygen was the major reaction product. The role of microstructural and morphological properties in the photocatalytic activity is discussed.     

Superconductivity and Ferromagnetism of the Ru-1232 Compounds in the (Ru1?xNbx)Sr2(GdCe1.8Sr0.2)Cu2Oz System

The Ru-1232 compounds have been synthesized in the (Ru_1–xNb _x )Sr₂(GdCe_1.8Sr_0.2)Cu₂O _z system, and effects of Nb substitution for Ru on superconductivity and ferromagnetism of the Ru-1232 compounds have been investigated. First, X-ray powder diffraction study shows that nearly the single 1232 phase samples can be obtained in the x composition range from 0.0 to 0.3. Then, from the electrical resistivity study, it is found that each of the samples shows resistivity dropping phenomenon at two temperatures of T _c ^l and T _c ^h, which originates from superconductivity of the Ru-1232 phase and the Ru-1222 one, respectively. Both of the starting temperatures are lowering with increasing Nb content x. Lastly, from the magnetic susceptibility study, it is found that superconducting transition temperature T _c is 20 K for the Ru-1232 sample with x = 0.0 and the ferromagnetic transition temperature T _m is about 90 K. This study also shows that both of the values of T _c and T _m become low with increasing x from 0.0 to 0.3.     

Investigations of Bi substitution in NdBa2Cu3Oy

Attempts to substitute Bi for Nd in orthorhombic NdBa₂Cu₃O _y , prepared in air or oxygen at about 950°C led instead to formation of Ba₂NdBiO₆, a new cubic compound witha=0.8703 nm. The possibility was then explored of preparing superconducting (Nd_1–x Bi _x )Ba₂Cu₃O _y , by first forming the tetragonal phase at 880–950°C in nitrogen or argon followed by reheating in oxygen or air at 250–500°C in order to insert the additional oxygen required to yield the orthorhombic form while avoiding oxidation of Bi³⁺ to Bi⁵⁺. X-ray diffraction studies, electrical conductivity measurements, and thermogravimetric analysis of products indicate that Bi does not enter the NdBa₂Cu₃O _y , lattice in either the tetragonal or the orthorhombic phase. Ba₂NdBiO₆ clearly forms on reheating in oxygen or air even at low temperatures, and evidence is presented that a poorly crystallized oxygen-deficient form of this compound is already present prior to the reheating.     

Study on structural phase transitions and relaxation processes of Cs2Co(SO4)2·6H2O and Cs2Zn(SO4)2·6H2O crystals

The structural phase transitions and relaxation processes of Cs₂Co(SO₄)₂·6H₂O and Cs₂Zn(SO₄)₂·6H₂O single crystals were investigated, with the phase transitions of both crystals being determined from NMR data. The spin–lattice relaxation time, T₁, of the ¹³³Cs nucleus in two crystals undergoes a significant change near the phase transition temperature, T_C, and these changes coincide with the changes in the splitting of the ¹³³Cs resonance lines. The variations in the temperature dependence for the splitting of the ¹³³Cs resonance lines and T₁ near T_C are related to changes in the symmetry of surrounding Cs⁺. In addition, the ¹³³Cs T₁ of Cs₂Co(SO₄)₂·6H₂O, which contains paramagnetic ions, was found to be shorter than that of Cs₂Zn(SO₄)₂·6H₂O. This relaxation time is inversely proportional to the square of the magnetic moment of the paramagnetic ions. The differences between the ¹³³Cs T₁ of these compounds are probably due to the differences between the electronic structures of their metal ions.     

Zero resistance at 117 K in Bi1.6Pb0.4Sr2Ca2Cu2+xOy compounds

In the Pb-doped Bi-Sr-Ca-Cu-O system, optimization of the composition and heat treatment conditions at which a greater amount of the high-T _c phase forms has been reported in our early paper [1], where the temperature of zero resistance was 107K. Recently, we have achieved zero resistance at 117 K and observed an a.c. susceptibility step at around 150 K by changing the Cu composition in the Bi^1.6Pb^0.4Sr²Ca²Cu^2+x O ^y system (x=0, 0.4, 0.8, 1.2, and 1.6).     

d-Hole localization and the suppression of superconductivity in YBa2(Cu1-xZnx)3O7?y

The temperature and Zn concentration dependence of the electrical resistivity, specific heat, magnetic susceptibility, and electron paramagnetic resonance (EPR) spectra of YBa₂(Cu_1–x Zn _x )₃O_7–y withy0.1 has been measured forx0.16. In addition, the temperature and field dependence of the magnetization has been measured for 2<T<300K and 0<H<9.0T, along with the temperature and quasihydrostatic pressure dependence of the electrical resistivity for selected samples for 0<P<13 GPa. The substitution of Zn for Cu in YBa₂Cu₃O_7–y causes a rapid and nearly linear depression of the superconducting transition temperature,T _c , withT _c going to 0 K forx 0.10. YBa₂(Cu_1–x Zn _x )₃O_7–y retains the YBa₂Cu₃O_7-y orthorhombic structure forx0.16 for both the superconducting and nonsuperconducting samples. Initially, the unit cell volume increases nearly linearly with Zn content; however, an abrupt change occurs in the vicinityx=0.8–0.10. Forx<0.10, the temperature dependence of the electrical resistivity,(T), is metallic-like (d/dT>0) and increases gradually with increasing Zn content. However, forx 0.10,(T) becomes semiconductor-like, with a very rapid increase of the resistivity with increasingx. The electrical resistivity, magnetic susceptibility, EPR spectra, and specific heat all indicate that thed-holes associated with the Cu ions become localized in the nonsuperconducting phase,x>-0.10.     

Chemical solution deposition of YBa2Cu3O7−x coated conductors

At present, the development of superconducting YBa₂Cu₃O_7−x coated conductors attracts much attention due to their enormous application potential in electric power systems. Worldwide research is focused on the investigation and improvement of buffer materials and YBa₂Cu₃O_7−x superconducting properties as well as low-cost manufacturing processes in cooperation with industrial companies. Accordingly, chemical solution deposition has emerged as a highly competitive, versatile, and cost-effective technique for fabricating coated conductors of high performance. New chemical solution approaches are under development for buffer layer deposition. In order to achieve high critical current carrying YBa₂Cu₃O_7−x layers, the established trifluoroacetate route is favored. This paper reviews the most recent work on chemical solution deposition within the IFW Dresden while also considering achievements on this specific research topic worldwide.     

Superconducting transition temperatures in the Ru-1232 system, RuSr2(Gd1? x Ln x Ce1.8Sr0.2)Cu2O z (Ln = Sm, Dy, and Ho)

We have investigated effects of the lanthanide element Ln and the composition changes on the superconducting transition temperatureT _c in the Ru-1232 system, RuSr₂(Gd_1−x Ln _x Ce_1.8Sr_0.2)Cu₂O _z (Ln = Sm, Dy, and Ho). At first, in the case of the samples with Ln = Sm among almost the single 1232 phase samples, the values of the superconducting onset temperatureT _co are almost the same forx=0.00−0.15, and each of the lattice parametersa andc is almost constant. While, in each of the cases of the samples with Ln = Dy and Ho, the sample withx=0.05 shows the maximum values for both the superconducting onset temperatureT _co and the zero resistivity temperatureT _cz. Especially for the sample with Ln = Dy, the values ofT _co andT _cz are 18.5 and 6.5 K, respectively. These are higher than those of the mother sample of RuSr₂(GdCe_1.8Sr_0.2)Cu₂O _z . Moreover, from variations ofT _co, lattice parameters ofa andc in the RuSr₂(Gd_1−x Dy _x Ce_1.8Sr_0.2)Cu₂O _z system as a function of Dy contentx, the relationship between the superconducting transition temperature and the lattice parameters in the present system are investigated.     

Correlation of magnetic properties to oxygen and potassium stoichiometry in single-crystal Ba1?xKxBiO3?y

Recent theoretical calculations have suggested the coupling of electrons to high-energy oxygen phonons as an explanation of superconductivity in the Ba_1–x K _x BiO_3–y system. We have synthesized high-quality single crystals of the material and have examined the behaviors of critical field and critical current parameters as a function of changes in the oxygen content and in the Ba/K ratio. We have determined, via positron lifetime spectroscopy and singlecrystal X-ray measurements, that the oxygen stoichiometry in this system can be varied without significant impact on the metal atom sublattice. These results facilitate an investigation of the dependence of critical parameters on dopant and defect levels in this system.     

The Effect of Zn-Substitution on the Anomalous Resistance Behavior of La1−x Ca x Mn1−y Zn y O3 Compounds

We have studied the effect of Zn substitution on the temperature dependence of the resistivity and the Curie temperature T _p of La_1–x Ca _x Mn_1–y Zn _y O₃ system (with x=0, y=0, and x=0.33, 0.00y0.15) during their pass to the paramagnetic conducting phase. All the specimens show a clear metal-insulator transition passing through the Curie temperature T _p . With increasing Zn concentration, T _p decreases for La/Ca substitution and also for Zn/Mn substitution with fixed 33 at.% of Ca. T _p is found to be slightly decreases for low concentrations of Zn (up to y=0.075) followed by a sharp decrease up to y=0.15. A possible explanation is given. Moreover, the activation energy E _a is calculated in the three different temperature regions characterized in the (-T) curve. Decreasing the temperature below T _p can increase the parallel alignment of the Mn spins and, thus decreases the resistivity of the samples. E _a increases with Zn content (up to y=0.075) followed by a sharp decrease. A strong correlation in the behavior of the normal state and residual resistivity as well as T _p and E _a with Zn content is reported.     

High-pressure studies on Tc and crystal structure of iron chalcogenide superconductors

The superconducting transition temperature, T_c, in iron-based solids can be enhanced by applied pressure: T_c increases from 8 to 37 K for the 11-type FeSe when the pressure is raised from 0 to 4 GPa. High-pressure studies can elucidate the mechanism of superconductivity in such novel materials. In this paper, we present a high-pressure study of Fe(Se_1−xTe_x) and Fe(Se_1−xS_x). In the case of Fe(Se_1−xTe_x), the maximum T_c under high pressure did not exceed the T_c of FeSe, which can be attributed to the structural transition to the monoclinic phase. For Fe(Se_1−xS_x) (0 < x < 0.3), T_c exhibited a significant increase with pressure; however, the maximum T_c under high pressure did not exceed the T_c of FeSe. This may be due to the disorder induced by substituting S for Se, which is similar to the pressure effect on T_c for the 1111-type superconductor Ca(Fe_1−xCo_x)AsF. The T_c of Fe(Se_1−xS_x) showed a complex behavior below 1 GPa, first decreasing and then increasing with increasing pressure. From high-pressure x-ray diffraction measurements, the T_c (P) curve was correlated with the local structural parameter.     

Comparison of Superconductivity and Structure for YBa2Cu3Oy with Potassium and Sodium Doping

The nominal composition of YBa_2–x M _x Cu₃O _y (M = K, Na) cuprates with x 0.30 were synthesized by the standard solid-state reaction technique. X-ray diffraction (XRD) and the resistivity measurements were used to characterize the structure and the superconductivity of the doped cuprates. There was no impurity phase detected within the whole doping range. The structure of the main phase (123) has the orthorhombic with P _mmm symmetry. With increasing the content of dopants, the lattice constants and some other structural parameters are almost unchanged for M = K, whereas they changed for M = Na. The refined contents of dopants are consistent with that of the nominal ones. The zero resistance temperature T _c0 decreases sharply with the increase of the content of potassium in potassium-doped samples as x 0.20. For sodium-doped YBa_2–z Na _x Cu₃O _y cuprates, T _c0 varies very little. The difference in superconductivity depression may result from the shift oxygen, which transfers conducting carriers from Cu-O chains to Cu-O₂ sheets or the structural stress effect.     

New Pb-Based 1222 Cuprates, (Pb0.5B0.5)Sr2(RE2−x−y Ce x Sr y )Cu2O z (RE = Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, and Y)

New Pb-based layered cuprates with the 1222 structure have been synthesized in the (Pb_0.5B_0.5)Sr₂ (RE_2−x−y Ce _x Sr _y )Cu₂O _z (RE = Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, and Y) systems. The almost-single-phase samples in the systems can be obtained for a nominal composition of x=0.7 and y=0.1. The crystal structure of the samples has a tetragonal symmetry, the lattice parameters of a and c are increasing with increasing the ionic radius of RE element. Despite treatment under high O₂ pressure of 100 atm, the samples are semiconductors with the transport process characteristic of three-dimensional variable range hopping conduction.