Growth of piezoelectric water-free GeO2 and SiO2-substituted GeO2 single-crystals

Using the slow-cooling method in selected fluxes, we have grown spontaneously nucleated single-crystals of pure GeO(2) and SiO(2)-substituted GeO(2) materials with the α-quartz structure. These piezoelectric materials were obtained in millimeter size as well-faceted, visually colorless, and transparent crystals. Cubic-like or hexagonal prism-like morphology was identified depending on the chemical composition of the single-crystals and on the nature of the flux. Both the silicon substitution rate and the homogeneity of its distribution were estimated by Energy Dispersive X-ray spectroscopy. The cell parameters of the flux-grown GeO(2) and Ge(1-x)Si(x)O(2) (0.038 ≤ x ≤ 0.089) solid-solution were deduced from their X-ray powder diffraction pattern. As expected, the cell volumes decrease as the silicon content substitution increases. A room temperature Infrared spectroscopy study confirms the absence of hydroxyl groups in the as-grown crystals. Unlike what was observed for hydrothermally grown GeO(2) crystals, these flux-grown oxide materials did not present any phase transition before melting as pointed out by a Differential Scanning Calorimetry study. Neither a α-quartz/β-quartz transition as encountered in SiO(2) near 573 °C nor a α-quartz to rutile transformation were detected for these GeO(2) and Ge(1-x)Si(x)O(2) single-crystals.     

In situ X-ray absorption spectroscopy study of Si(1-x)Ge(x)O2 dissolution and germanium aqueous speciation under hydrothermal conditions

The dissolution of Si(1-x)Ge(x)O(2) solid solutions under hydrothermal conditions was studied by in situ X-ray absorption spectroscopy. Experiments were performed at the Ge K-edge using a high-pressure cell mounted on the FAME beamline of the European Synchrotron Radiation Facility. Spectra in both transmission and fluorescence mode were collected in isobaric conditions (100 and 150 MPa) up to 475 °C. The local atomic structure around the Ge atom was investigated as a function of the temperature and in pure water and sodium hydroxide solutions. In pure water, the solubility of the cristobalite-type Si(0.8)Ge(0.2)O(2) increases with the temperature and the Ge atom is in 4-fold coordination. In a sodium hydroxide aqueous solution, a complex between Ge and Na atoms forms and gives rise to precipitation of sodium germanates. Under these conditions, the Ge content in the solution decreases with increasing temperature. These results show that a sodium hydroxide aqueous solution, usually used for quartz crystal growth, is not suitable for Ge-containing crystals. The dissolution kinetics and phase transformation of the solid solution were studied as a function of the atomic fraction of Ge. Ge-rich solid solutions dissolve and transform to stable phases faster than Ge-poorer composition, giving rise to important variations of the Ge content in solution.     

Small gas-phase dianions of Zn3O(4)(2-), Zn4O(5)(2-), CuZn2O(4)(2-), Si2GeO(6)(2-), Ti2O(5)(2-) and Ti3O(7)(2-)

We have searched for new species of small oxygen-containing gas-phase dianions produced in a secondary ion mass spectrometer by Cs+ ion bombardment of solid samples with simultaneous exposure of their surfaces to O2 gas. The targets were a pure zinc metal foil, a copper-contaminated zinc-based coin, two silicon-germanium samples (Si(1-x)Ge(x)(with x= 6.5% or 27%)) and a piece of titanium metal. The novel dianions Zn3O(4)(2-), Zn4O(5)(2-), CuZn2O(4)(2-), Si2GeO(6)(2-), Ti2O(5)(2-) and Ti3O(7)(2-) have been observed at half-integer m/z values in the negative ion mass spectra. The heptamer dianions Zn3O(4)(2-) and Ti2O(5)(2-) have been unambiguously identified by their isotopic abundances. Their flight times through the mass spectrometer are approximately 20 micros and approximately 17 micros, respectively. The geometrical structures of the two heptamer dianions Ti2O(5)(2-), and Zn3O(4)(2-) are investigated using ab initio methods, and the identified isomers are compared to those of the novel Ge2O(5)(2-) and the known Si2O(5)(2-) and Be3O(4)(2-) dianions.     

Thermal Properties of K（Y1-xYbx）（WO4）2（x=0.098,0.196,0.294） Crystal

Thermal properties of pure KY(WO4)2 and K(Y1-xYbx)(WO4)2(x=0.098,0.196,0.294) crystals were investigated.The specific heat and thermal diffusivity of crystals were calculated at a range of 50～300 ℃.The calculated result shows that the specific heat and thermal diffusivity of K(Y1-xYbx)(WO4)2(x=0.098,0.196,0.294) crystals were slightly affected by the Yb3+ concentration.The thermal expansion coefficient of K(Y0.804Yb0.196)(WO4)2 crystals along x,y and z axes were determined to be 13.51,4.474 and 16.60×10-6 K-1,respectively.These results suggest the K(Y1-xYbx)(WO4)2(x=0.098,0.196,0.294) crystal as a laser crystal of low-middle power.     

Structural and thermochemical chemisorption of CO2 on Li(4+x)(Si(1-x)Al(x))O4 and Li(4-x)(Si(1-x)V(x))O4 solid solutions

Different Li(4)SiO(4) solid solutions containing aluminum (Li(4+x)(Si(1-x)Al(x))O(4)) or vanadium (Li(4-x)(Si(1-x)V(x))O(4)) were prepared by solid state reactions. Samples were characterized by X-ray diffraction and solid state nuclear magnetic resonance. Then, samples were tested as CO(2) captors. Characterization results show that both, aluminum and vanadium ions, occupy silicon sites into the Li(4)SiO(4) lattice. Thus, the dissolution of aluminum is compensated by Li(1+) interstitials, while the dissolution of vanadium leads to lithium vacancies formation. Finally, the CO(2) capture evaluation shows that the aluminum presence into the Li(4)SiO(4) structure highly improves the CO(2) chemisorption, and on the contrary, vanadium addition inhibits it. The differences observed between the CO(2) chemisorption processes are mainly correlated to the different lithium secondary phases produced in each case and their corresponding diffusion properties.     

Comprehensive interpretation of a substitution effect on an order-disorder phase transition in A(1-x)MxW2O(8-y) (A = Zr, Hf; M = trivalent cations) and other ZrW2O8-based solid solutions

Hf(1-x)Lu(x)W(2)O(8-y) solid solutions up to x = 0.04, based on a negative thermal expansion material HfW(2)O(8), were synthesized by a solid state reaction method. X-ray diffraction experiments of these solid solutions from 90 to 560 K indicated thermal contraction with increasing temperature. Temperatures of order-disorder phase transition (T(trs)) associated with the orientation of WO(4) tetrahedra were determined from disappearance of a characteristic diffraction peak (310). The T(trs) of the solid solutions drastically decreased with increasing Lu content. Saturated order parameters (eta(s)) associated with the orientational order of the WO(4) pairs were estimated from the characteristic diffraction peak at sufficient low temperature. These behaviors of Hf(1-x)Lu(x)W(2)O(8-y) are consistent with those of Zr(1-x)M(x)W(2)O(8-y) (M = Sc, Y, In, Lu). The drastic suppression of T(trs) in Hf(1-x)Lu(x)W(2)O(8-y) can be interpreted in the framework of a model proposed for Zr(1-x)M(x)W(2)O(8-y), which states the existence of a local nanoregion including the WO(4) pairs having the frozen-in orientational disorder. To understand the substitution effect on the order-disorder phase transition comprehensively, classification based on the saturated order parameter eta(s) of the phase transition of AW(2)O(8) (A = Hf, Zr)-based solid solutions was carried out and discussed.     

Overall water splitting on (Ga(1-x)Zn(x))(N(1-x)O(x)) solid solution photocatalyst: relationship between physical properties and photocatalytic activity

The physical and photocatalytic properties of a novel solid solution between GaN and ZnO, (Ga(1-x)Zn(x))(N(1-x)O(x)), are investigated. Nitridation of a mixture of Ga(2)O(3) and ZnO at 1123 K for 5-30 h under NH(3) flow results in the formation of a (Ga(1-x)Zn(x))(N(1-x)O(x)) solid solution with x = 0.05-0.22. With increasing nitridation time, the zinc and oxygen concentrations decrease due to reduction of ZnO and volatilization of zinc, and the crystallinity and band gap energy of the product increase. The highest activity for overall water splitting is obtained for (Ga(1-x)Zn(x))(N(1-x)O(x)) with x = 0.12 after nitridation for 15 h. The crystallinity of the catalyst is also found to increase with increasing the ratio of ZnO to Ga(2)O(3) in the starting material, resulting in an increase in activity.     

Structural characterization and oxidative dehydrogenation activity of V2O5/Ce(x)Zr(1-x)O2/SiO2 catalysts

The thermal stability of a nanosized Ce(x)Zr(1-x)O2 solid solution on a silica surface and the dispersion behavior of V2O5 over Ce(x)Zr(1-x)O2/SiO2 have been investigated using XRD, Raman spectroscopy, XPS, HREM, and BET surface area techniques. Oxidative dehydrogenation of ethylbenzene to styrene was performed as a test reaction to assess the usefulness of the VOx/Ce(x)Zr(1-x)O2/SiO2 catalyst. Ce(x)Zr(1-x)O2/SiO2 (1:1:2 mol ratio based on oxides) was synthesized through a soft-chemical route from ultrahigh dilute solutions by adopting a deposition coprecipitation technique. A theoretical monolayer equivalent to 10 wt % V2O5 was impregnated over the calcined Ce(x)Zr(1-x)O2/SiO2 sample (773 K) by an aqueous wet impregnation technique. The prepared V2O5/Ce(x)Zr(1-x)O2/SiO2 sample was subjected to thermal treatments from 773 to 1073 K. The XRD measurements indicate the presence of cubic Ce0.75Zr0.25O2 in the case of Ce(x)Zr(1-x)O2/SiO2, while cubic Ce0.5Zr0.5O2 and tetragonal Ce0.16Zr0.84O2 in the case of V2O5/Ce(x)Zr(1-x)O2/SiO2 when calcined at various temperatures. Dispersed vanadium oxide induces more incorporation of zirconium into the ceria lattice, thereby decreasing its lattice size and also accelerating the crystallization of Ce-Zr-O solid solutions at higher calcination temperatures. Further, it interacts selectively with the ceria portion of the composite oxide to form CeVO4. The RS measurements provide good evidence about the dispersed form of vanadium oxide and the CeVO4 compound. The HREM studies show the presence of small Ce-Zr-oxide particles of approximately 5 nm size over the surface of amorphous silica and corroborate with the results obtained from other techniques. The catalytic activity studies reveal the ability of vanadium oxide supported on Ce(x)Zr(1-x)O2/SiO2 to efficiently catalyze the ODH of ethylbenzene at normal atmospheric pressure. The remarkable ability of Ce(x)Zr(1-x)O2 to prevent the deactivation of supported vanadium oxide leading to stable activity in the time-on-stream experiments and high selectivity to styrene are other important observations.     

Cubic aluminum silicides RE8Ru12Al49Si9(Al(x)Si12-x) (RE = Pr, Sm) from liquid aluminum. Empty (Si,Al)12 cuboctahedral clusters and assignment of the Al/Si distribution with neutron diffraction.

Two new quaternary aluminum silicides, RE8Ru12Al49Si9(Al(x)Si12-x) (x approximately 4; RE = Pr, Sm), have been synthesized from Sm (or Sm2O3), Pr, Ru, and Si in molten aluminum between 800 and 1000 degrees C in sealed fused silica tubes. Both compounds form black shiny crystals that are stable in air and NaOH. The Nd analog is also stable. The compounds crystallize in a new structural type. The structure, determined by single-crystal X-ray diffraction, is cubic, space group Pm3m with Z = 1, and has lattice parameters of a = 11.510(1) A for Sm8Ru12Al49Si9(Al(x)Si12-x) and a = 11.553(2) A for Pr8Ru12Al49Si9(Al(x)Si12-x) (x approximately 4). The structure consists of octahedral units of AlSi6, at the cell center, Si2Ru4Al8 clusters, at each face center, SiAl8 cubes, at the middle of the cell edges, and unique (Al,Si)12 cuboctohedral clusters, at the cell corners. These different structural units are connected to each other either by shared atoms, Al-Al bonds, or Al-Ru bonds. The rare earth metal atoms fill the space between various structural units. The Al/Si distribution was verified by single-crystal neutron diffraction studies conducted on Pr8Ru12Al49Si9(Al(x)Si12-x). Sm8Ru12Al49Si9(Al(x)Si12-x) and Pr8Ru12Al49Si9(Al(x)Si12-x) show ferromagnetic ordering at Tc approximately 10 and approximately 20 K, respectively. A charge of 3+ can be assigned to the rare earth atoms while the Ru atoms are diamagnetic.     

Unusual physical and chemical properties of Cu in Ce(1-x)Cu(x)O(2) oxides

The structural and electronic properties of Ce(1-x)Cu(x)O(2) nano systems prepared by a reverse microemulsion method were characterized with synchrotron-based X-ray diffraction, X-ray absorption spectroscopy, Raman spectroscopy, and density functional calculations. The Cu atoms embedded in ceria had an oxidation state higher than those of the cations in Cu(2)O or CuO. The lattice of the Ce(1)(-x)Cu(x)O(2) systems still adopted a fluorite-type structure, but it was highly distorted with multiple cation-oxygen distances with respect to the single cation-oxygen bond distance seen in pure ceria. The doping of CeO(2) with copper introduced a large strain into the oxide lattice and favored the formation of O vacancies, leading to a Ce(1-x)Cu(x)O(2-y) stoichiometry for our materials. Cu approached the planar geometry characteristic of Cu(II) oxides, but with a strongly perturbed local order. The chemical activities of the Ce(1-x)Cu(x)O(2) nanoparticles were tested using the reactions with H(2) and O(2) as probes. During the reduction in hydrogen, an induction time was observed and became shorter after raising the reaction temperature. The fraction of copper that could be reduced in the Ce(1-x)Cu(x)O(2) oxides also depended strongly on the reaction temperature. A comparison with data for the reduction of pure copper oxides indicated that the copper embedded in ceria was much more difficult to reduce. The reduction of the Ce(1-x)Cu(x)O(2) nanoparticles was rather reversible, without the generation of a significant amount of CuO or Cu(2)O phases during reoxidation. This reversible process demonstrates the unusual structural and chemical properties of the Cu-doped ceria materials.     

Electrodeposition of Ge, Si and Si x Ge 1-x from an air- and water-stable ionic liquid

The electrodeposition of Ge, Si and, for the first time, of Si(x)Ge(1-x) from the air- and water-stable ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide ([Py(1,4)]Tf(2)N) containing GeCl(4) and/or SiCl(4) as precursors is investigated by cyclic voltammetry and high-resolution scanning electron microscopy. GeCl(2) in [Py(1,4)]Tf(2)N is electrochemically prepared in a two-compartment cell to be used as Ge precursor instead of GeCl(4) in order to avoid the chemical attack of Ge(iv) on deposited Ge. Silicon, germanium and Si(x)Ge(1-x) can be deposited reproducibly and easily in this ionic liquid. Interestingly, the Si(x)Ge(1-x) deposit showed a strong colour change (from red to blue) at room temperature during electrodeposition, which is likely to be due to a quantum size effect. The observed colours are indicative of band gaps between at least 1.5 and 3.2 eV. The potential of ionic liquids in Si(x)Ge(1-x) electrodeposition is demonstrated.     

A full interionic potential for Na(1+x)Zr(2)Si(x)P(3-x)O(12) superionic conductors

Most inorganic solids are made up of octahedral and tetrahedral units interconnected to give an infinite framework. Use of computer simulation to study these materials has not been as prevalent as in the organic or biomolecules. Na(1+x)Zr(2)Si(x)P(3-x)O(12) is a typical inorganic solid with ZrO(6) octahedra and (Si/P)O(4) tetrahedra which are shown along with a few Na(+) sites marked M1, M2, and M3. We report here a full interionic potential which reproduces the structure and conductivity of these solids. This augurs well for the study of other inorganic solids.     

Structure and white luminescence of Eu-activated (Ba,Sr)(13-x)Al(22-2x)Si(10+2x)O66 materials

The optical properties of Eu-activated (Ba,Sr)(13-x)Al(22-2x)Si(10+2x)O66 materials have been determined after the structural reinvestigation of the hypothetical Ba 13Al 22Si 10O 66 material on the basis of the Gebert's model. The white fluorescence and phosphorescence of the (Ba,Sr)(13-x)Al(22-2x)Si(10+2x)O66:Eu series result from the existence of two broad emission bands associated with (8)H-4f(6)5d(1)-->(8)S-4f(7) transitions peaking at 534 and 438 nm, the intensities of which may be tuned at room temperature via the control of the europium concentration and the substitution of Sr for Ba. This suggests the possibility to adjust the emission of the material to white LED requisites.     

Interaction of Keggin anions of 12-tungstophosphoric acid with Ce(x)Zr(1-x)O2 solid solutions

The interaction of 20 wt% 12-tungstophosphoric acid with Ce(x)Zr(1-x)O(2) solid solutions has been studied by PXRD, FTIR, FT-Raman, H(2)-TPR, NH(3)-TPD, diffuse reflectance UV-vis-NIR, and (31)P MAS NMR techniques. The study indicates that the Keggin anions are attached to Lewis metal ion centres and anion vacancies on Ce(x)Zr(1-x)O(2) supports through WO terminal bonds. The Keggin units at the interface are chemically perturbed as indicated by non-intrinsic IR bands observed at 958 cm(-1) (WO(ter) bond), and 1052, 1102 cm(-1) (PO bond). NH(3)-TPD shows that the Keggin anions fixed to Lewis sites and/or oxygen ion vacancies decrease the ammonia uptake on Ce(x)Zr(1-x)O(2) solid solutions. H(2)-TPR shows modified redox behaviour of Ce(x)Zr(1-x)O(2) solid solutions due to the simultaneous reduction of ceria, decomposition of Keggin anions and the reduction of WO(3). The broadening of (31)P MAS NMR and DR-UV-vis-NIR spectra demonstrate the existence of chemical interactions between the Keggin anions and Ce(x)Zr(1-x)O(2) supports.     

Solid state NMR characterization of individual compounds and solid solutions formed in Sc(2)O(3)--V(2)O(5)--Nb(2)O(5)--Ta(2)O(5) system

In this study, (51)V, (45)Sc and (93)Nb MAS NMR combined with satellite transition spectroscopy analysis were used to characterize the complex solid mixtures: VNb(9(1-x))Ta(9x)O(25), ScNb((1-x))Ta(x)O(4) and ScNb(2(1-x))Ta(2x)VO(9) (x = 0, 0.3, 0.5, 0.7, 1.0). This led us to describe the structures of Sc and V sites. The conclusions were based on accurate values for (51)V quadrupole coupling and chemical shift tensors obtained with (51)V MAS NMR/SATRAS for VNb(9)O(25), VTa(9)O(25) and ScVO(4). The (45)Sc NMR parameters have been obtained for Sc(2)O(3), ScVO(4), ScNbO(4) and ScTaO(4). On the basis of (45)Sc NMR and data available from literature, the ranges of the (45)Sc chemical shift have been established for ScO(6) and ScO(8). The gradual change of the (45)Sc and (51)V NMR parameters with x confirms the formation of solid solutions in the process of synthesis of VNb(9(1-x))Ta(9x)O(25) and ScNb((1-x))Ta(x)O(4), in contrast to ScNb(2(1-x))Ta(2x)VO(9). The cation sublattice of ScNb((1-x))Ta(x)O(4) is found to be in octahedral coordination. The V sites in VNb(9(1-x))Ta(9x)O(25) are present in the form of slightly distorted tetrahedra. The (93)Nb NMR parameters have been obtained for VNb(9)O(25).     

Mullite-derivative Bi2Mn(x)Al(7-x)O14 (x~1): structure determination by powder X-ray diffraction from a multi-phase sample

As a supplementary method to single crystal X-ray diffraction (XRD), nowadays crystal structure determination by powder XRD has become popular, especially for those areas with difficulties getting high quality single crystals. Here we observed an intermediate phase Bi(2)Mn(x)Al(7-x)O(14) (x~1) during the decomposition of mullite-Bi(2)Mn(x)Al(4-x)O(9+δ) (solid solution of Bi(2)Mn(4)O(10)-Bi(2)Al(4)O(9)). As a metastable phase, it started to decompose while forming, thus no single-phase sample can be obtained. We successfully determined its structure by powder XRD from a multi-phase sample. A modified Le Bail fitting using the atomic structure information of known impurities showed a more reliable intensity extraction from a multi-phase powder XRD than that without using atomic structures for the known impurities. The charge-flipping algorithm and Monte-Carlo based simulated annealing technique were then applied to obtain the full structural model. In principle, this strategy is applicable to more complex problems, and not limited to the oxide materials. Bi(2)Mn(x)Al(7-x)O(14) possesses a mullite-related structure. There are one tetrahedral and two octahedral sites for Mn and Al, where disordering with substantial site preferences is observed. Specifically, M1O(6) and M3O(6) octahedra share edges along the c-direction with the periodicity of 1 : 2. These octahedral chains are further connected into a 3D structure through M2O(4) dimmers and Bi.     

"Nanoscale zippers" in Gd5(SixGe(1-x))4: symmetry and chemical influences on the nanoscale zipping action

One critical parameter influencing the structural nature of the phase transitions in magnetocaloric materials Gd5(SixGe(1-x))4 is the Si/Ge ratio (x/1-x), because transition temperatures and structures depend crucially on this value. In this study, single-crystal X-ray diffraction indicates that Si and Ge atoms are neither completely ordered nor randomly mixed among the three crystallographic sites for these elements in these structures. Ge atoms enrich the T sites linking the characteristic slabs in these structures, while Si atoms enrich the T sites within them. Decomposition of the total energy into site and bond energy terms provides a rationale for the observed distribution, which can be explained by symmetry and electronegativity arguments. For any composition in Gd5(SixGe(1-x))4, a structure map is presented that will allow for a rapid assessment of the specific structure type.     

(η(2)-(Si/Ge)(4))Zn(η(2)-(Si/Ge)(4))](6-)- novel Zintl clusters with mixed Si/Ge tetrahedra bridged by a Zn atom

The solubility of the ternary Zintl phase K(12)Si(17-x)Ge(x) (x = 5), containing mixed group 14 element clusters, was investigated. Novel dimeric tetrahedral Zintl clusters [(η(2)-E(4))Zn(η(2)-E(4))](6-) with mixed site occupation (E = Si/Ge) were obtained through reaction with (C(6)H(6))(2)Zn in ammonia solutions and investigated by means of X-ray single crystal diffraction.     

Ca(2+)/vacancies and O2-/F- ordering in new oxyfluoride pyrochlores Li(2x)Ca1.5-x square 0.5-xM2O6F (M = Nb,Ta) for 0 < or = x < or = 0.5

New oxyfluorides Li(2x)Ca(1.5-x) square (0.5-x)M2O6F (M = Nb, Ta), belonging to the cubic pyrochlore structural type (Z = 8, a approximately 10.5 angstroms), were synthesized by solid state reaction for 0 < or = x < or = 0.5. XRD data allowed us to determine their structures from single crystals for the two alpha and beta-Ca(1.5) square (0.5)Nb2O6F forms and from powder samples for the others. This characterisation was completed by TEM and solid state 19F NMR experiments. For the Ca(1.5) square (0.5)M2O6F (x = 0) pyrochlore phases, the presence of a double ordering phenomenon is demonstrated, involving on one hand the Ca(2+) ions and the vacancies and on the other hand the oxide and the fluoride anions which are strictly located in the 8b sites of the Fd3m aristotype space group. The Ca(2+) ions/vacancies ordering leads to a reversible phase transition, a (P4(3)32) <--> beta (Fd3m). The 19F NMR study strongly suggests that, in the beta-phases, the fluoride ions are only on average at the centre of the Ca3 square tetrahedron. It shows that slightly different Ca-F distances occuring in alpha-Ca(1.5) square (0.5)Nb2O6F may be related to a more difficult thermal ionic and vacancies diffusion process than in the tantalate compound. This may explain the hysteresis phenomenon presented by the phase transition. A solid solution Li(2x)Ca(1.5-x) square (0.5-x) Ta2O6F (0 < or = x < or = 0.5) was prepared and the order-disorder phase transition observed for Ca(1.5) square (0.5)M2MO6F compounds disappears for all the other compositions where less or no more vacancies exist in the 16d sites. In the LiCaM2O6F compounds, the 19F NMR study allows us to determine the Ca(2+) and Li+ ions distributions around the fluoride ions and shows that the [FLi2Ca2] environment is clearly favoured.     

Crystal structure of YbCu6In6 and mixed valence behavior of Yb in YbCu(6-x)In(6+x) (x = 0, 1, and 2) solid solution

High quality single crystals of YbCu(6)In(6) have been grown using the flux method and characterized by means of single crystal X-ray diffraction data. YbCu(6)In(6) crystallizes in the CeMn(4)Al(8) structure type, tetragonal space group I4/mmm, and the lattice constants are a = b = 9.2200(13) ? and c = 5.3976(11) ?. The crystal structure of YbCu(6)In(6) is composed of pseudo-Frank-Kasper cages filled with one ytterbium atom in each ring. The neighboring cages share corners along [100] and [010] to build the three-dimensional network. YbCu(6-x)In(6+x) (x = 0, 1, and 2) solid solution compounds were obtained from high frequency induction heating and characterized using powder X-ray diffraction. The magnetic susceptibilities of YbCu(6-x)In(6+x) (x = 0, 1, and 2) were investigated in the temperature range 2-300 K and showed Curie-Weiss law behavior above 50 K, and the experimentally measured magnetic moment indicates mixed valent ytterbium. A deviation in inverse susceptibility data at 200 K suggests a valence transition from Yb(2+) to Yb(3+) as the temperature decreases. An increase in doping of Cu at the Al2 position enhances the disorder in the system and enhancement in the trivalent nature of Yb. Electrical conductivity measurements show that all compounds are of a metallic nature.