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Quasicrystals (QCs), first discovered in 1984, generally do not exhibit long-range magnetic order. Here, we report on long-range magnetic order in the real icosahedral quasicrystals (i QCs) Au–Ga–Gd and Au–Ga–Tb. The Au65Ga20Gd15i QC exhibits a ferromagnetic transition at TC = 23 K, manifested as a sharp anomaly in both magnetic susceptibility and specific heat measurements, along with an appearance of magnetic Bragg peak below TC. This is the first observation of long-range magnetic order in a real quasicrystal, in contrast to the spin-glass-like behaviors observed for the other magnetic quasicrystals found to date. Moreover, when Gd is replaced by Tb, i.e., for the Au65Ga20Tb15i QC, a ferromagnetic behavior is still retained with TC = 16 K. Although the sharp anomaly in the specific heat observed for the Au65Ga20Gd15i QC becomes broadened upon Tb substitution, neutron diffraction experiments clearly show marked development of magnetic Bragg peaks just below TC, indicating long-range magnetic order for the Au65Ga20Tb15i QC also. Our findings can contribute to the further investigation of exotic magnetic orders formed on real quasiperiodic lattices with unprecedented highest global symmetry, i.e., icosahedral symmetry.

PyQCstrc.ico is a computer package for building a 6D structure model of icosahedral quasicrystals with the Python3 programming language., The atomic structure of quasicrystals (QCs) is described as a section of a higher-dimensional structure that consists of a periodic arrangement of occupation domains (ODs). Determination of the shape of ODs and their partitioning is crucial in the structural analysis of QCs. However, owing to the complicated shape of ODs, building the initial structure model requires a great deal of time and effort. Thus, a computer program for building structure models of QCs is needed. Presented here is a Python3 package for structure modelling of icosahedral QCs.

The atomic structures of 2/1 and 1/1 quasicrystalline approximants in the ternary R-Cd-Mg (R = Y, Er) system are revealed using X-ray structural analysis., The atomic structures of three cubic approximants (cAPs), Y12.7Cd61.8Mg25.5 [2/1 cAP with space group Pa 3, a = 25.0654 (1) Å] and Er12.5Cd72.0Mg15.5 [2/1 cAP with Pa 3, a = 24.9658 (1) Å], and Y14.5Cd66.1Mg19.4 [1/1 cAP with Im 3, a = 15.4577 (1) Å], were investigated using X-ray structure analysis. The two 2/1 cAPs were found to be isostructural to the binary 2/1 cAP, YbCd5.8, which is composed of two building units, namely Tsai-type rhombic triacontahedron (RTH) cluster and double-Friauf polyhedron (DFP). The 1/1 cAP, in contrast, was found to be isostructural to the binary 1/1 cAP, YbCd6, which is composed solely of the RTH cluster. The refined structure models of the three cAPs exhibit substitutional disorders due to the Mg content that enters into Cd sites of the parent binary cAPs. In addition, in the 2/1 cAPs, the Y3(Er3) site on the third icosahedron shell of the RTH cluster and two positions inside DFP, Y5(Er5) sites, are partially mixed with Mg. Moreover, characteristic positional disorders owing to orientational disorder in the first shell of the RTH cluster is observed in all the three cAPs. A close relationship between the occupational disorder of the Y3(Er3) and Y5(Er5) sites in 2/1 cAPs and the elemental distribution in their first coordination shells is revealed.

The superstructure and basic structure of ternary Yb-Cd-Mg 1/1 quasicrystal approximants with the compositions Yb 12.9 Cd 78.4 Mg 8.8 and Yb 13.3 Cd 64.2 Mg 22.5 were investigated using X-ray struc...

A four-dimensional (4D) model is presented of the first oxide dodecagonal quasicrystal found in a Ba–Ti–O ultra-thin film on a Pt(111) single-crystal substrate. The 4D model, with a 4D dodecagonal lattice constant a d = 8.39 Å, was derived by considering a tile decoration model of dodecagonal Niizeki–Gähler tiling composed of squares, triangles and 30° rhombuses. The model consists of four kinds of occupation domain, and 4D positional vectors defining the shape of each occupation domain are given. Moreover, the atomic arrangement of two Ba–Ti–O periodic approximants, the sigma-phase approximant and a 25.6 Å approximant were derived from the 4D model by the introduction of linear phason strains.

We report on the formation of a new icosahedral quasicrystal (iQC) in the Au-Sn-Yb alloy system. This iQC has a primitive icosahedral lattice with a lattice constant aico of 0.5447(7) nm and a composition that was determined to be Au60.0Sn26.7Yb13.3. X-ray absorption spectroscopy measurement of the near Yb L3 edge demonstrates that the Yb valence in the iQC is an intermediate valence between divalent (4f14) and trivalent (4f13) at ambient pressure and was determined to be 2.18+. The results are compared to those for a corresponding 2/1 cubic approximant crystal. The formation of this new iQC is discussed in terms of the atomic size factor (δ) and the valence electron-to-atom ratio (e/a).

The Yb-Ga-Au 1/1 quasicrystal approximant (AP) composition ranges from Yb14.0Ga20.6Au65.4 to Yb14.8Ga46.3Au38.9, and single crystals of the 1/1 AP having the composition Yb13.8Ga26.1Au60.1 were obtained by the self-flux technique. X-ray structural analysis demonstrated that the atomic structure [space group Im3; a = 14.6889(9) A] can be described by the body-centered packing of Tsai-type rhombic triacontahedron (RTH) clusters. The positional disorder in these clusters, interpreted as the average of an orientationally disordered tetrahedron and triangle, results in positional disorder in the outer shells. The elemental distributions and positions of mixtures of Au and Ga atoms in the RTH clusters correspond to those in the isostructural Yb15Al36Au49 1/1 AP.

Quasicrystals (QCs), first discovered in 1984, generally do not exhibit long-range magnetic order. Here, we report on long-range magnetic order in the real icosahedral quasicrystals (i QCs) Au–Ga–Gd and Au–Ga–Tb. The Au65Ga20Gd15 i QC exhibits a ferromagnetic transition at TC = 23 K, manifested as a sharp anomaly in both magnetic-susceptibility and specific-heat measurements. Quick magnetic saturation to almost the full moment (7μB/Gd3+) is observed under 100 Oe at 2 K. This is the first observation of long-range magnetic order in a real quasicrystal, in contrast to the spin-glass-like behaviours observed for the other magnetic quasicrystals found to date. Moreover, when Gd is replaced by Tb, i.e. for the Au65Ga20Tb15 i QC, a ferromagnetic behaviour is still retained with TC = 16 K. Although the sharp anomaly in the specific heat observed for the Au65Ga20Gd15 i QC is significantly broadened upon Tb substitution, neutron-diffraction experiments clearly show the marked development of magnetic Bragg peaks below TC, indicating long-range magnetic order for the Au65Ga20Tb15 i QC also. Our findings can contribute to the further investigation of exotic magnetic orders formed on real quasiperiodic lattices with unprecedented highest global symmetry, i.e. icosahedral symmetry.

International audience; In order to obtain high-quality single grains of the Al-Cu-Ru icosahedral quasicrystal (iQC), suitable for a structure analysis, the crystal growth conditions with the self-flux method have been studied. The melts of the master alloys with the compositions of Al57.0+xCu39.5-xRu3.5 (x = 0, 2.5, 5, 7.5, 10) and Al62.0Cu34.0+y Ru4.0-y (y = 0, 0.5, 1.5) were held at 1150°C for 2 h, then cooled down to 800, 900, or 1000°C at a rate of −2 K/h, and subsequently retained for various durations, up to 750 h. Single grain iQCs having several millimetre-sizes, which were evaluated their quality by powder X-ray diffraction (XRD), were grown throughout this study. The peak of (664004) reflection in powder XRD of the iQCs grown at 1000°C has approximately 50% narrower width than that grown at 800°C. The inhomogeneity of the compositions intra- as well as inter-grains grown at 800°C was observed. High-quality single grains with homogeneous composition could be achieved with a long-time annealing at 900°C or regardless of the annealing time at 1000°C. By changing the Al/Cu ratio of the master alloys, the composition could also be controlled for the iQCs grown at 1000°C. Single-crystal XRD experiment with synchrotron radiation on Al66.6Cu16.4Ru17.0 iQC, grown at 1000°C, resulted in the collection of 2680 independent Bragg reflections that confirms the high-quality of the sample. The phase retrieval of the diffraction data resulted successfully in obtaining the structure solution, which reveals some characteristic features of this face-centred iQC structure.

The magnetic susceptibility of the 1/1 approximants to icosahedral quasicrystals in a series of Cd85-xMgxTb15 (x = 5, 10, 15, 20) alloys was investigated in detail. The occurrence of antiferromagnetic to spin-glass-like transition was noticed by increasing Mg. Transmission electron microscopy analysis evidenced a correlation between the magnetic transition and suppression of the monoclinic superlattice ordering with respect to the orientation of the Cd4 tetrahedron at T > 100 K. The possible origins of this phenomenon were discussed in detail. The occurrence of the antiferromagnetic to spin-glass -like magnetic transition is associated with the combination of chemical disorder due to a randomized substitution of Cd with Mg and the orientational disorder of the Cd4 tetrahedra., 9 pages, 9 figures

A systematic investigation has been performed to elucidate effects of Rare-Earth (RE) type and local atomic configuration on magnetic properties of icosahedral quasicrystal (iQC) and their cubic approximants (2/1 and 1/1 ACs) in the ternary Cd-Mg-RE (RE = Gd, Tb, Dy, Ho, Er, and Tm) systems. At low temperatures, iQC and 2/1 ACs exhibit spin-glass-like freezing for RE = Gd, Tb, Dy, and Ho, while Er and Tm systems do not show freezing behaviour down to the base temperature ~ 2 K. The 1/1 ACs exhibit either spin-glass-like freezing or antiferromagnetic (AFM) ordering depending on their constituent Mg content. The Tf values show increasing trend from iQC to 2/1 and 1/1 ACs. In contrast, the absolute values of Weiss temperature for iQCs are larger than those in 2/1 and 1/1 ACs, indicating that the total AFM interactions between the neighboring spins are larger in aperiodic, rather than periodic systems. Competing spin interactions originating from the long-range Ruderman-Kittel-Kasuya-Yoshida mechanism along with chemical disorder of Cd/Mg ions presumably account for the observed spin-glass-like behavior in Cd-Mg-RE iQCs and ACs., 12 pages, 8 Figures, 2 Tables

We report the observation of antiferromagnetic (AFM) transitions in 1/1 and 2/1 quasicrystal approximants having slightly different electron-per-atom $(e/a)$ ratios, in the same Au-Ga-Eu system, at N\'eel temperatures of 7.0 and 8.5 K, respectively. This clearly demonstrates that an antiferromagnetic order survives when the degree of approximation to the quasicrystals is raised provided that the $e/a$ ratio is kept nearly the same. Since, unlike the 1/1 approximant, the 2/1 approximant has all the building blocks necessary for the construction of the quasicrystal, this finding can be a significant leap toward the long-sought realization of an AFM quasicrystal.

The atomic structure of a 0.2 atom % Pt-doped complex metallic alloy, monoclinic Al13Fe4, was investigated using a single crystal prepared by the Czochralski method. High-angle annular dark-field scanning transmission electron microscopy showed that the Pt atoms were dispersed as single atoms and substituted at Fe sites in Al13Fe4. Single-crystal X-ray structural analysis revealed that the Pt atoms preferentially substitute at Fe(1). Unlike those that have been reported, Pt single atoms in the surface layers showed lower activity and selectivity than those of Al2Pt and bulk Pt for propyne hydrogenation, indicating that the active state of a given single-atom Pt site is strongly dominated by the bonding to surrounding Al atoms.

Atomic structures of ternary icosahedral (i) Yb–Cd–Mg quasicrystals (QCs) with five different Mg contents up to 46.4 at.% and a corresponding 1/1 approximant (AP), which has a composition of Yb13.3Cd70.3Mg16.5, have been analysed by single-crystal X-ray diffraction. The structures of the iQCs were found to be isostructural to the parent i-YbCd5.7, which consists of a so-called Tsai-type rhombic triacontahedron (RTH) cluster and double Friauf polyhedron, and that of the 1/1 AP was found to be isostructural to YbCd6, which is described by a body-centred packing of the same type of RTH cluster. In the iQCs, it was found that there are three types of Cd/Mg occupation, namely, Cd preferential site, Mg preferential site and Cd/Mg mixed site, and the occupation probabilities of Mg atoms at the Mg preferential site show a saturation behaviour around the Mg content of 20 at.%. This selective Mg occupation is identified as a cause of the non-linear increase in the icosahedral lattice constant with increasing Mg content. The 1/1 AP has a similar selective Mg occupation to that of the iQCs in terms of the shell structures of the Tsai-type RTH cluster. In both iQCs and the 1/1 AP, the Mg preferential sites have a smaller number of Yb atoms among their coordination numbers. Moreover, short-range order (s.r.o.) diffuse scattering was observed on the diffraction patterns of the iQCs at the positions corresponding to a face-centred-type (F-type) icosahedral superlattice. The F-type s.r.o. was found to result from the Mg substitution.

Eight years since the discovery of the binary antiferromagnetic (AFM) quasicrystal approximants $\mathrm{C}{\mathrm{d}}_{6}R$ [R. Tamura et al., Phys. Rev. B 82, 220201 (2010)], we report the observation of an AFM transition in quasicrystal approximants Au-Al-R ($R=\mathrm{Gd}$ and Tb), which represent examples of AFM in ternary quasicrystal approximants. Magnetic susceptibility, magnetization, and specific heat coherently show that the Au-Al-R ($R=\mathrm{Gd}$ and Tb) approximants undergo an AFM transition at ${T}_{\mathrm{N}}=9.4$ and 11.8 K, respectively. The AFM transitions are found near the phase boundary of the wide single-phase region where the chemical disorder is substantially low. This finding of ternary AFM approximants has far deeper implications compared with that of the binary AFM approximants: It now indicates the possibility to synthesize new AFM approximants in many other systems by the appropriate replacement of Cd with two other elements, and thus enables exploration of various magnetic orders over AFM spin icosahedra in solids, in particular, their evolution as a function of the electron-per-atom (e/a) ratio. Moreover, the finding provides us a missing route to synthesize an AFM quasicrystal by similar composition tuning.

The atomic structure of a 0.2 atom % Pt-doped complex metallic alloy, monoclinic Al

We study the electronic structure of Tsai-type cluster-based quasicrystalline approximants, ${\mathrm{Au}}_{64}{\mathrm{Ge}}_{22}{\mathrm{Yb}}_{14}$ (AGY-I), ${\mathrm{Au}}_{63.5}{\mathrm{Ge}}_{20.5}{\mathrm{Yb}}_{16}$ (AGY-II), and ${\mathrm{Zn}}_{85.4}{\mathrm{Yb}}_{14.6}$ (Zn-Yb), by means of photoemission spectroscopy. In the valence band hard x-ray photoemission spectra of AGY-II and Zn-Yb, we separately observe a fully occupied $\mathrm{Yb} 4f$ state and a valence fluctuation derived Kondo resonance peak, reflecting two inequivalent Yb sites, a single Yb atom in the cluster center and its surrounding Yb icosahedron, respectively. The fully occupied $4f$ signal is absent in AGY-I containing no Yb atom in the cluster center. The results provide direct evidence for a heterogeneous valence state in AGY-II and Zn-Yb.

We present the refinement results of atomic structures of binary icosahedral (i) ScZn7.3, GdCd7.9, DyCd7.5 and TmCd7.3 quasicrystals (QCs) [1, 2] and the study of phason modes. Bragg peak intensities data collection has been carried out on the CRISTAL beamline at the synchrotron SOLEIL, using an incoming X-ray energies equal to 25.5 keV (Sc-Zn) and 24.2 keV (R-Cd), and a CCD camera located at 8 cm from the samples. For all iQC samples a high redundancy (average 50) has been obtained resulting in 4057 (Sc-Zn) and 4871 ~ 5130 (R-Cd) unique reflections having intensity larger than 3 sigma and internal R factors around 8 %. The atomic structures of the iQCs were solved using the measured Bragg intensity data based on a six-dimensional model that is isostructural to the i-YbCd5.7 one [3] and the refinement program named qcdiff by A. Yamamoto, resulting in R factors equal to 10.9 % (Sc-Zn) and 8.9 ~ 10.9 % (R-Cd). The resulting structures are described with a quasiperiodic packing of large Tsai-type rhombic triacontahedron clusters (RTH) and double Friauf polyhedra (DFP), both resulting from a close-packing of large (Sc, R) and small (Zn, Cd) atoms. The significant difference in alloy composition between i-ScZn7.3, i-RCd~7.9 and the ideal model of i-YbCd5.7 was found to lay mainly on the DFP where one of the two large atom site (Sc, R) is replaced by a small atom (Zn, Cd) resulting in a significant distortion of the DFP. Residual disorder with relative occupancies of Sc(R)/Zn(Cd)=80/20 was also found on the icosahedral site. This illustrates that a detailed understanding of the atomic structure can now be achieved in QCs. The stabilization mechanism for these binary iQCs and the microscopic origins to explain the phason fluctuations will be discussed in this presentation. (1) Canfield, P. C., Caudle, M. L., Ho, C. S., Kreyssig, A., Nandi, S., Kim, M. G., Lin, X., Kracher, A., Dennis, K. W., McCallum, R. W. & Goldman, A. I. (2010) Phys. Rev. B, Solution growth of a binary icosahedral quasicrystal of Sc12Zn88, 81, 020201. (2) Goldman, A. I., Kong, T., Kreyssig, A., Jesche, A., Ramazanoglu, M., Dennis, K. W., et al. (2013). Nature Materials, A family of binary magnetic icosahedral quasicrystals based on rare earths and cadmium, 12(8), 714–718. (3) Takakura, H., Gómez, C. P., Yamamoto, A., de Boissieu, M., & Tsai, A. P. (2006). Nature Materials, Atomic structure of the binary icosahedral Yb–Cd quasicrystal, 6(1), 58–63.

We report on the six-dimensional (6D) structural refinement of three members of the i-$R$-Cd quasicrystals ($R$ = Gd, Dy, Tm) via synchrotron x-ray diffraction from single-grain samples, and show that this series is isostructural to the i-${\mathrm{YbCd}}_{5.7}$ quasicrystal. However, our refinements suggest that the $R$ occupancy on the Yb icosahedron sites within the Tsai-type atomic cluster is approximately 80%, with the balance taken up by Cd. Similarities between the i-$R$-Cd series and i-${\mathrm{ScZn}}_{7.33}$, and their differences with i-${\mathrm{YbCd}}_{5.7}$ and i-${\mathrm{Ca}}_{15}{\mathrm{Cd}}_{85}$, indicate that there are at least two subclasses of Tsai-type icosahedral quasicrystals. We further show from x-ray resonant magnetic scattering (XRMS) measurements on a set of closely related ${\mathrm{Tb}}_{1\ensuremath{-}x}{\mathrm{Y}}_{x}{\mathrm{Cd}}_{6}$ 1/1 approximants that the dilution of the magnetic $R$ ions on the icosahedron within the Tsai-type cluster by nonmagnetic Y disrupts the commensurate magnetic ordering in the approximant phase.

Effect of atom substitution on the low-temperature phase transitions in binary Cd6Ca and Zn6Sc 1/1 cubic approximants were investigated by means of electrical resistivity and X-ray diffraction. By adding thirdelements such as Yb, Cu and Fe to the binary approximants, it is concluded that Yb is substituted to the icosahedron site in both Cd6Ca and Zn6Sc, and Cu and Fe are substituted to the Zn sites in Zn6Sc. Upon the substitutions of the third elements, the temperature of the resistivity anomaly decreases without an exception and the anomaly disappears above a certain level of substitutions. Moreover, it is found that the chemical disorder introduced in the 2nd shell of the icosahedral cluster plays a crucial role in the suppression of the ordering of the Zn tetrahedron. On the other hand, the chemical disorder introduced in the 3rd icosahedron shell affects the transition temperature (T c ) rather weakly. Finally, the variation of T c has been found to depend on the difference of the atomic radius between the host and the guest elements and the distortion of the outer shells is considered to be mainly responsible for the suppression of the ordering of the tetrahedra.

International audience; The Zn6Sc 1/1 cubic approximant to a quasicrystal has been studied in-situ at high pressures by single-crystal X-ray diffraction. This phase can be described as a bcc packing of Tsai-type icosahedral clusters whose center is occupied by a disordered Zn-4 tetrahedron. At ambient pressure the Zn6Sc undergoes a structural phase transition at 159 K to a monoclinic superstructure in which the Zn-4 tetrahedra are orientationally ordered along the [101] direction of the high-temperature bcc phase. In the pressure range up to 35 GPa, two new superstructures have been observed. The second phase corresponds to a four-fold pseudo cubic superstructure, i.e. a very large unit cell with a lattice parameter of about 5.5 nm. The resulting pressure-temperature phase diagram is different from that of Cd6Yb, which was reported by Watanuki et al. (2006).

The Zn–Sc–Fe icosahedral quasicrystal and its 1/1 crystal approximant have been studied with 57Fe Mossbauer spectroscopy at room temperature. The spectra for the two phases exhibit substantially different features, indicating largely different local atomic environments in the two phases. This is in contrast to the results previously reported for the Al–Cu–Fe(–Si) system, in which the icosahedral phase and its crystal approximants show similar features in Mossbauer spectra, indicating similar local atomic environments. Possible Fe sites in the Zn–Sc–Fe approximant phase are discussed on the basis of the crystal structure determined previously.

International audience; A comparison of periodic approximants and their quasicrystalline counterparts offers the opportunity to better understand the structure, physical properties and stabilizing mechanisms of these complex phases. We present a combined experimental and molecular dynamics study of the lattice dynamics of the icosahedral quasicrystals i-ZnMgSc and i-ZnAgSc and compare it to recently published results obtained for the cubic 1/1-approximant Zn6Sc [1]. Both phases, quasicrystal and approximant, are built up from large atomic clusters which contain a tetrahedral shell at the cluster centre and are packed either quasiperiodically or on a bcc lattice. Using quasielastic neutron scattering and atomic scale simulations, we show that in the quasicrystal the tetrahedra display a dynamics similar to that observed in the 1/1-approximant: the tetrahedra behave as a 'single molecule' and reorient dynamically on a timescale of the order of a few ps. The tetrahedra reorientation is accompanied by a large distortion of the surrounding cluster shells which provide a unique dynamical flexibility to the quasicrystal. However, whereas in the 1/1-approximant the tetrahedron reorientation is observed down to T-c = 160 K, where a phase transition takes place, in the quasicrystal the tetrahedron dynamics is gradually freezing from 550 to 300 K, similarly to a glassy system.

Using quasielastic neutron scattering (QENS) and molecular dynamics (MD) simulations, dynamical disorder was shown to be present in the Zn6Sc cubic 1/1-approximant to Tsai type quasicrystals. This dynamical disorder originates from reorientations of the innermost tetrahedron shell inside the Tsai type clusters’ building blocks. To enable such a rotational motion inside a close-packed alloy, a unique dynamical flexibility is necessary. We present a study of the tetrahedron dynamics with respect to this structural flexibility.

Complex Metallic Alloys (CMAs) are metallic solids of high structural complexity, consisting of large numbers of atoms in their unit cells. Consequences of this structural complexity are manifold and give rise to a variety of exciting physical properties. The impact that such structural complexity may have on the lattice dynamics will be discussed. The surprising dynamical flexibility of Tsai-type clusters with the symmetry breaking central tetrahedron will be addressed for Zn6Sc, while in the Ba-Ge-Ni clathrate system the dynamics of encaged Ba guest atoms in the surrounding Ge-Ni host framework is analysed with respect to the experimentally evidenced strong reduction of lattice thermal conductivity. For both systems experimental results from neutron scattering are analyzed and interpreted on atomistic scale by means of ab initio and molecular dynamics simulations, resulting in a picture with the respective structural building blocks as the origin of the peculiarities in the dynamics.

International audience; Periodic approximants to quasicrystals offer a unique opportunity to better understand the structure, physical properties and stabilizing mechanisms of their quasicrystal counterparts. We present a detailed study of the order-disorder phase transition occurring at about 160 K in the Zn6Sc cubic approximant to the icosahedral quasicrystal i-MgZnSc. This transition goes along with an anti-parallel ordering of the tetrahedra located at the centres of large atomic clusters, which are packed on a bcc lattice. Single crystal x-ray diffuse scattering shows that the tetrahedra display pre-transitional short range ordering above T-c (Yamada et al 2012 in preparation). Using quasielastic neutron scattering (QENS) we clearly evidence this short range order to be dynamical in nature above T-c. The QENS data are consistent with a model of tetrahedra 'jumping' between almost equivalent positions, which is supported by molecular dynamics simulations. This demonstrates a unique dynamical flexibility of the Zn6Sc structure even at room temperature.

Electrical resistivity, heat capacity, and x-ray diffraction studies on a ${\text{Zn}}_{6}\text{Sc}$ 1/1 cubic approximant [$Im\overline{3}$, $\text{a}=1.38311(5)\text{ }\text{nm}$] of high structural order unambiguously demonstrates that it undergoes a phase transition at a low temperature. Anomalies in the resistivity and the specific heat as well as a lattice distortion are clearly observed at the transition temperature $({T}_{c})$ and x-ray diffraction experiment manifests the existence of a short-range order above ${T}_{c}$ as well as the formation of a long-range order below ${T}_{c}$. In contrast, no anomalies are observed in magnetic susceptibility, suggesting that the resistivity anomaly is not due to a change in the electron density of states but related with scattering of conduction electrons induced by orientational disordering of ${\text{Zn}}_{4}$ tetrahedron at the center of the icosahedral cluster.

We present an in-situ temperature study of the atomic structure of the 1/1 Cd6Tb approximant to an icosahedral quasicrystal. It belongs to the `Tsai' type family of quasicrystal and approximants whose archetype is the well-studied Cd-Yb system[1]. Its high temperature structure can be described as a bcc packing of a large Tsai atomic cluster, whose inner shell is a disordered tetrahedron at room temperature. As for most of the Cd6RE (RE=rare earth) approximant, the Cd6Tb phase undergoes a phase transition at 190 K to a phase of lower symmetry, resulting from an ordering of the inner tetrahedron[2]. Moreover, it has been shown that this phase undergoes a magnetic phase transition below 20 K, with an antiferromagnetic ordering of the Tb moment bearing atoms. It is thus particularly important to have a detailed structural study of this phase. We have carried out a systematic in situ measurement on a single grain from room temperature down to 40K on the crystal beam line located at the Soleil synchrotron. The structural phase transition is observed at about 190K. Using different attenuation, we have collected integrated intensity in a large dynamical range, leading to more than 60000 unique reflections in the C2/c monoclinic low temperature phase. The final wR2 values for room temperature and 40K are equal to 0.0726 and 0.0905 respectively. The resulting atomic structure will be compared to the well-studied approximant Zn6Sc, which is isostructural to Cd6Tb[3]. The ordering of the innermost tetrahedron leads to the distortion of the successive shells. The evolution of the high temperature phase, in particular just above Tc where pretransitional diffuse scattering is observed will be presented.

We are searching for intermediate-valence (IV) quasicrystals where IV ions are quasi-periodically arranged. Our previous study revealed that an icosahedral Au-Al-Yb quasicrystal forms an IV system [1]. X-ray absorption spectroscopy near the Yb L_3 edge indicated that the Yb ions in the quasicrystal assume a mean valence of 2.61, between a divalent state (4f^14, J = 0) and a trivalent one (4f^13, J = 7/2). Additionally we found that non-Fermi-liquid behaviour appears at low temperatures without doping, pressure, or field tuning. In this study we examined Au-M-Yb system, where M = Sn, Ge, and Ga. X-ray absorption spectroscopy measurements at SPring-8 (BL22XU) showed that each compounds forms IV system. The Yb valence values are respectively 2.27 for a Au-Sn-Yb 2/1 crystalline approximant, 2.24 for a Au-Ge-Yb 1/1 approximant, and 2.36 for a Au-Ga-Yb 1/1 approximant. By following the trend of Yb-based IV compounds, these valence values close to divalent suggest that the Yb 4f character in these compounds would be itinerant rather than localized one.

International audience; Using in situ x-ray scattering and synchrotron radiation, we have experimentally elucidated the mechanism of the cubic to monoclinic phase transition in the Zn6Sc 1/1 approximant to an icosahedral quasicrystal. The high-temperature cubic phase is described as a bcc packing of a large Tsai-type icosahedral cluster whose center is occupied by an orientationally disordered Zn-4 tetrahedron. A clear monoclinic distortion has been found to take place within 2 K around T-c = 157 K, in excellent agreement with the observed anomalies in the electrical resistivity and heat capacity. Also, a rapid variation of the super-structure reflection intensity is observed. The low-temperature monoclinic phase, as determined by single-crystal x-ray diffraction at 40 K, has been confirmed to consist of ordered Zn-4 tetrahedra, oriented in an anti-parallel way along the [(1) over bar 01] direction. Above T-c, a diffuse scattering signal is observed at the position of the super-structure reflections, which evidences that a short-range ordering of the Zn-4 tetrahedra takes place. In a way similar to a second-order phase transition, the correlation length describing this short-range ordering increases rapidly when the temperature diminishes and almost diverges when the temperature is close to T-c, going from 200 angstrom at 220 K to reach the very large value of 1200 angstrom at 161 K. Finally, using single-crystal x-ray diffraction, the atomic structure of the low-temperature monoclinic super-structure (space group C2/c) could be solved. The ordering of the Zn-4 tetrahedra is accompanied by a strong distortion of the surrounding shells