Two new phases YbCu4.4 and YbCu4.25 are found as a result of careful phase diagram investigations. Between the congruent and peritectic formation of YbCu4.5 and YbCu3.5, respectively, the phases YbCu4.4 and YbCu4.25 are formed peritectically at 934(2)degC and 931(3)degC. Crystal growth was realised using a Bridgman technique and single crystalline grains of about 50-100 10^{-6}m were analyzed by electron diffraction and single crystal X-ray diffraction. Due to the only slight differences in both compositions and formation temperatures the growth of larger single crystals of a defined superstructure is challenging. The compounds YbCu4.4 and YbCu4.25 fit in Cerny`s (J. Solid State Chem. 174 (2003) 125) building principle {(RECu5)n(RECu2)} where RE = Yb with n = 4 and 3. YbCu4.4 and YbCu4.25 base on AuBe5/MgCu2-type substructures and contain approximately 4570 and 2780 atoms per unit cell. The new phases close the gap in the series of known copper-rich rare earth compounds for n = 1, 2 (DyCu3.5, DyCu4.0) and n = 5 (YbCu4.5, DyCu4.5).
Materials with ultralow thermal conductivity are of great interest for efficient energy conversion and thermal barrier coating. Copper-based semiconductors such as copper chalcogenides and copper halides are known to possess extreme low thermal conductivity, whereas the fundamental origin of the low thermal conductivity observed in the copper-based materials remains elusive. Here, we reveal that s-d coupling induced giant phonon anharmonicity is the fundamental mechanism responsible for the ultralow thermal conductivity of copper compounds. The symmetry controlled strong coupling of high-lying…
The compounds A2Cu3O(SO4)3 (A=Na,K) are characterized by copper hexamers which are weakly coupled along the b-axis to realize one-dimensional antiferromagnetic chains below TN=3 K, whereas the interchain interactions along the a- and c-axes are negligible. We investigated the energy-level splittings of the copper hexamers by inelastic neutron scattering below and above TN. The eight lowest-lying hexamer states could be unambiguously assigned and parametrized in terms of a Heisenberg exchange Hamiltonian, providing direct experimental evidence for an S=1 triplet ground-state associated with the…
The unit cell parameters, infrared and UV-Vis spectral data reported in the paper by Vijayabhaskaran et al (Indian J Pure & App Phys 49 (2011) 340-343) cannot belong to the colourless crystalline compound formulated as copper mercury thiocyanate CuHg(SCN)4 as claimed by the authors.
The minerals A2Cu3O(SO4)3 (A2=Na2, NaK, K2) constitute quantum spin systems with copper hexamers as basic structural units. Strong intra-hexamer spin couplings give rise to an effective triplet ground-state. Weak inter-hexamer spin couplings are responsible for two-dimensional long-range magnetic order in the (b,c)-plane below 3.0<Tc<4.7 K. We investigated the magnetic excitations at T=1.5 K by inelastic neutron scattering (INS). The INS technique was based on the observation of wavevector-dependent slices in reciprocal space in order to selectively probe the magnetic signals in different Bril…
Lead halide perovskite solar cells have recently emerged as a very promising photovoltaic technology due to their excellent power conversion efficiencies; however, the toxicity of lead and the poor stability of perovskite materials remain two main challenges that need to be addressed. Here, for the first time, we report a lead-free, highly stable C6H4NH2CuBr2I compound. The C6H4NH2CuBr2I films exhibit extraordinary hydrophobic behavior with a contact angle of approximately 90 degree, and their X-ray diffraction patterns remain unchanged even after four hours of water immersion. UV-Vis absorpti…
First-principles high-throughput screening of ruthenium compounds for advanced interconnects
Department of Electronics Engineering, Incheon National University（仁川国立大学电子工程系）；Research Institute for Engineering and Technology, Incheon National University（仁川国立大学工程技术研究院）
Silver and copper monohalides can be viewed as a class of compounds in the neutral zone between predominantly covalent and ionic compounds, thereby exhibiting neither strong ionicity nor strong covalency. We show ab initio calculation evidence that silver and copper monohalides entail relatively low transition barriers between the non-polar rock-salt phase and the polar zinc-blende phase, due largely to their unique chemical nature of modest iconicity or covalency. Notably, the low transition barriers endow both monohalides with novel mechanical and electronic properties, i.e., coupled ferroel…
On the basis of the first-principles evolutionary crystal structure prediction of stable compounds in the Cu-F system, we predict two experimentally unknown stable phases -- Cu2F5 and CuF3. Cu2F5 comprises two interacting magnetic subsystems with the Cu atoms in the oxidation states +2 and +3. CuF3 contains magnetic Cu 3+ ions forming a lattice with the antiferromagnetic coupling. We showed that some or all of Cu 3+ ions can be reduced to Cu 2+ by electron doping, as in the well known KCuF3. Significant similarities between the electronic structures calculated in the framework of DFT+U suggest…
Boron forms compounds with nearly all metals, with notable exception of copper and other group IB and IIB elements. Here, we report an unexpected discovery of ordered copper boride grown epitaxially on Cu(111) under ultrahigh vacuum. Scanning tunneling microscopy experiments combined with ab initio evolutionary structure prediction reveal a remarkably complex structure of 2D-Cu8B14. Strong intra-layer p-d hybridization and a large amount of charge transfer between Cu and B atoms are the key factors for the emergence of copper boride. This makes the discovered material unique and opens up the p…
We report the understanding of the electronic band structure of $Cs_4CuSb_2Cl_{12}$ perovskite through first-principles density-functional theory calculations. We find that the most stable state has the antiferromagnetic configuration where each $[CuCl_6]$ octahedral chain along the [010] direction is antiferromagnetic. The reasonable band structure of the compound can be obtained only if both the correct magnetic order and the improved exchange interaction of the Cu $\it{d}$ electrons are taken into account.
一个彻底的调查的介电性能的Cu 2 Ta 4 O 12，材料结晶在一个伪立方，钙钛矿衍生的结构。我们测量了单晶的介电常数和电导率在一个非常宽的频率范围高达GHz的频率和温度从25 - 500 K。检测到的介电常数异常高（达到值高达105），几乎恒定在一个广泛的频率和温度范围。Cu 2 Ta 4 O 12具有类似于CaCu 3 Ti4 O 12的晶体结构，CaCu 3 Ti4 O 12是首次观察到如此高介电常数的化合物。使用一个简单的等效电路和不同类型的接触测量结果的分析表明，外在的界面极化效应，来自表面势垒电容器的起源所观察到的巨介电常数。Cu 2 Ta 4 O 12的本征性质的特征在于在100的量级的（仍然相对较高的）介电常数和通过安德森局域化的载流子的跳跃传导的电荷传输。
Thermoelectric Properties of Copper-based Chalcopyrite Semiconductors Cu$MX_2$ ($M$ = Al, Ga, and In; $X$ = S, Se, and Te) from First-Principles Calculations
The copper silver selenide has two phases: the low-temperature semimetal phase (α-CuAgSe) and high-temperature phonon-glass superionic phase (\b{eta}-CuAgSe). In this work, the electric transport and thermoelectric properties of the two phases are investigated. It is revealed that the \b{eta}-CuAgSe is a p-type semiconductor and exhibits low thermal conductivity while the α-CuAgSe shows metallic conduction with dominant n-type carriers and low electrical resistivity. The thermoelectric figure of merit zT of the polycrystalline \b{eta}-CuAgSe at 623 K is ~0.95, suggesting that superionic CuAgSe…
On the magnetism of Ln{2/3}Cu{3}Ti{4}O{12} (Ln = lanthanide)
研究了Ln $_{2/3}$ Cu $_3$ Ti $_4$ O $_{12}$系列化合物的磁性和热力学性质。这里$Ln$代表镧系元素La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm和Yb。%大多数化合物被制备为单相多晶粉末%，没有任何痕量的杂质。通过$Ln=$ Gd、Er和Tm检测到杂质$(< 2%)$ %的边缘量。对于$Ln=$ Ce和Yb，发现了显著量的杂质相。研究的所有样品都在空间群$Im\bar{3}$中结晶，晶格常数遵循镧系收缩。Ce化合物的晶格常数揭示了Ce $^{4+}$的存在，导致组成Ce $_{1/2}$ Cu $_3$ Ti $_4$ O $_{12}$。从磁化率和电子自旋共振实验可以得出结论，铜离子总是携带一个自旋$S=1/2$和反铁磁秩序接近25\，K。Curie-Weiss温度可以近似地计算，假设两个亚晶格模型分别对应于铜和镧系离子。似乎重稀土的磁矩弱耦合到铜自旋，而对于轻镧系元素没有这样的耦合被发现。$4f$矩保持顺磁性下降到最低温度，与Tm化合物，这表明增强的Van-Vleck磁性由于非磁性单重基态的晶体场分裂$4f$歧管的例外。从比热测量，我们准确地确定了反铁磁有序温度，并获得有关稀土离子的晶体场状态的信息。热容量的结果还揭示了存在一小部分的Ce $^{3+}$的磁性$4f^1$状态。
Copper borate Cu$_3$(BO$_3$)$_2$ is a complex compound with a layered crystallographic structure in which the Jahn-Teller active and magnetic copper Cu$^{2+}$ ions occupy sixteen nonequivalent positions in the unit cell displaying controversial magnetic behavior. In this paper, we report on the infrared and Raman spectroscopic studies of the lattice dynamics and the electronic structure of 3$d^9$ copper states below the fundamental absorption band. The lattice dynamics is characterized by a large number of phonons due to a low $P\overline{1}$ space group symmetry and a large unit cell with Z=1…
A search for new topological quantum systems is challenging due to the requirement of non{trivial band connectivity that leads to protected surface states of electrons. A progress in this field was primarily due to a realization of band inversion mechanism between even and odd parity states that was proven to be very useful in both predicting many of such systems and our understanding their topological properties. Despite many proposed materials assume the band inversion between s and p (or p/d, d/f) electrons, here, we explore a different mechanism where the occupied d states subjected to a t…
Transition metal impurities such as nickel, copper, and iron, in solid-state materials like silicon have a significant impact on the electrical performance of integrated circuits and solar cells. To study the impact of copper impurities inside bulk silicon on the electrical properties of the material, one needs to understand the configurational space of copper atoms incorporated inside the silicon lattice. In this work, we performed ReaxFF reactive force field based molecular dynamics simulations, studying different configurations of individual and crystalline copper atoms inside bulk silicon …
Some of the three-dimensional (3D) crystal structures are constructed by stacking two-dimensional (2D) layers. It remains unclear whether this geometric concept is related to the stability of ordered compounds and whether this can be used to computational materials design. Here, using first principles calculations, we investigate the dynamical stability of copper-based compounds Cu$X$ (a metallic element $X$) in the B$_h$ and L1$_1$ structures constructed from the buckled honeycomb (BHC) structure and in the B2 and L1$_0$ structures constructed from the buckled square (BSQ) structure. We demon…
The microscopic understanding of high-temperature superconductivity in cuprates has been hindered by the apparent complexity of crystal structures in these materials. We used scanning tunneling microscopy and spectroscopy to study an electron-doped copper oxide compound Sr$_{1-x}$Nd$_x$CuO$_2$ that has only bare cations separating the CuO$_2$ planes and thus the simplest infinite-layer structure among all cuprate superconductors. Tunneling conductance spectra of the major CuO$_2$ planes in the superconducting state revealed direct evidence for a nodeless pairing gap, regardless of variation of…
Ba3Yb2Zn5O11 is unique among breathing pyrochlore compounds for being in the nearly decoupled limit where inter-tetrahedron interactions are weak, hosting isolated clusters or "molecular magnet" like tetrahedra of magnetic ytterbium (Yb3+) ions. In this work, we present the first study carried out on single-crystal samples of the breathing pyrochlore Ba3Yb2Zn5O11, using a variety of magnetometry and neutron scattering techniques along with theoretical modeling. We employ inelastic neutron scattering to investigate the magnetic dynamics as a function of applied field (with respect to both magni…
The lack of a mechanistic framework for chemical reactions forming inorganic extended solids presents a challenge to accelerated materials discovery. We demonstrate here a combined computational and experimental methodology to tackle this problem, in which in situ X-ray diffraction measurements monitor solid state reactions and deduce reaction pathways, while theoretical computations rationalize reaction energetics. The method has been applied to the La-Cu-S-O quaternary system, following an earlier prediction that enhanced superconductivity could be found in these of new lanthanum copper(II) …
Only several compounds bearing Ag(II) cation and other transition metal cation have been known. Herein, we predict stability and crystal structures of hypothetical ternary silver(II) fluorides with copper, nickel and cobalt in 1:1 stoichiometry at pressure range from 0 GPa up to 20 GPa within the frame of Density Functional Theory. Calculations show that AgCoF4 could be synthesized already at ambient conditions but this compound would host diamagnetic Ag(I) and high-spin Co(III). However, at increased pressure ternary fluorides of Ag(II) featuring Cu and Ni could be synthesized, in the pressur…
Research towards the production of renewable chemicals for fuel and energy industries has found lignin valorization as key. With a high carbon content and aromaticity, a fine-tuning of the depolymerization process is required to convert lignin into valuable chemicals. In context, model compounds have been used to understand the electrocatalyzed depolymerization for mimicking the typical linkages of lignin. In this investigation, 2-phenoxyacetophenone, a model compound for lignin \b{eta}-O-4 linkage, was electro-catalytically hydrogenated (ECH) in distinct three-electrode setups: an open and a …
The magnetic structure of the antiferromagnetic square cupola compound Ba(TiO)Cu$_4$(PO$_4$)$_4$ with the tetragonal structure is studied with 31P nuclear magnetic resonance techniques. The magnetic hyperfine shift K shows a clear splitting at the Néel temperature T$_N$ = 9.5 K, where the resonance splits into two lines when an external magnetic field is oriented along the c axis and into four lines when the field is along the a axis. In the paramagnetic region K(T) follows temperature dependence of the magnetic susceptibility $χ(T)$. From K vs $χ$ plot we determined nearly isotropic hyperfine…
