X-ray absorption investigation of the site occupancies of the copper element in nominal Cu_3Zn(OH)_6FBr

With Zn substitution to the three-dimensional antiferromagnetically ordered barlowite Cu_4(OH)_6 FBr,Cu_3 Zn(OH)_6 FBr shows no magnetic phase transition down to 50 mK,and the system is suggested to be a two-dimensional kagome quantum spin liquid [Chin.Phys.Lett.34 077502(2017)].A key issue to identify such phase diagram is the exact chemical formula of the substituted compound.With Cu L-edge x-ray absorption spectrum(XAS) combined with the MultiX XAS calculations,we evaluate the Cu concentration in a nominal Cu_3 Zn(OH)_6 FBr sample.Our results show that although the Cu concentration is 2.80,close to the expected value,there is 34% residual Cu occupation in intersite layers between kagome layers.Thus the Zn substitution of the intersite layers is not complete,and likely it intrudes the kagome layers.     

Gapped Spin-1/2 Spinon Excitations in a New Kagome Quantum Spin Liquid Compound Cu_3Zn(OH)_6FBr

We report a new kagome quantum spin liquid candidate Cu_3 Zn(OH)_6 FBr, which does not experience any phase transition down to 50 mK, more than three orders lower than the antiferromagnetic Curie-Weiss temperature(~200 K). A clear gap opening at low temperature is observed in the uniform spin susceptibility obtained from~(19)F nuclear magnetic resonance measurements. We observe the characteristic magnetic field dependence of the gap as expected for fractionalized spin-1/2 spinon excitations. Our experimental results provide firm evidence for spin fractionalization in a topologically ordered spin system, resembling charge fractionalization in the fractional quantum Hall state.     

Kapellasite: a kagome quantum spin liquid with competing interactions

Magnetic susceptibility, NMR, muon spin relaxation, and inelastic neutron scattering measurements show that kapellasite, Cu_{3}Zn(OH)_{6}Cl_{2}, a geometrically frustrated spin-1/2 kagome antiferromagnet polymorphic with herbertsmithite, is a gapless spin liquid showing unusual dynamic short-range correlations of noncoplanar cuboc2 type which persist down to 20?mK. The Hamiltonian is determined from a fit of a high-temperature series expansion to bulk susceptibility data and possesses competing exchange interactions. The magnetic specific heat calculated from these exchange couplings is in good agreement with experiment. The temperature dependence of the magnetic structure factor and the muon relaxation rate are calculated in a Schwinger-boson approach and compared to experimental results.     

Nonlocal Effects of Low-Energy Excitations in Quantum-Spin-Liquid Candidate Cu_3Zn(OH)_6FBr

We systematically study the low-temperature specific heats for the two-dimensional kagome antiferromagnet,Cu_3Zn(OH)_6FBr.The specific heat exhibits a T~(1.7) dependence at low temperatures and a shoulder-like feature above it.We construct a microscopic lattice model of Z_2 quantum spin liquid and perform large-scale quantum Monte Carlo simulations to show that the above behaviors come from the contributions from gapped anyons and magnetic impurities.Surprisingly,we find the entropy associated with the shoulder decreases quickly with grain size d,although the system is paramagnetic to the lowest temperature.While this can be simply explained by a core-shell picture in that the contribution from the interior state disappears near the surface,the 5.9-nm shell width precludes any trivial explanations.Such a large length scale signifies the coherence length of the nonlocality of the quantum entangled excitations in quantum spin liquid candidate,similar to Pippard's coherence length in superconductors.Our approach therefore offers a new experimental probe of the intangible quantum state of matter with topological order.     

Modified kagome physics in the natural spin-1/2 kagome lattice systems: kapellasite Cu3Zn(OH)6Cl2 and haydeeite Cu3Mg(OH)6Cl2

The recently discovered natural minerals Cu3Zn(OH)6Cl2 and Cu3Mg(OH)6Cl2 are spin 1/2 systems with an ideal kagome geometry. Based on electronic structure calculations, we develop a realistic model which includes couplings across the kagome hexagons beyond the original kagome model that are intrinsic in real kagome materials. Exact diagonalization studies for the derived model reveal a strong impact of these couplings on the magnetic ground state. Our predictions could be compared to and supplied with neutron scattering, thermodynamic data, and NMR data.     

磁性和非磁性元素掺杂的自旋梯状化合物Sr_(14)(Cu_(0.97)M_(0.03))_(24)O_(41)(M=Zn,Ni,Co)的结构和电输运性质

利用固相反应法制备了Sr14Cu24O41及其系列B位掺杂Sr14(Cu0.97M0.03)24O41(M=Zn,Ni,Co)的样品.X射线衍射分析显示,所有样品均为纯相,晶格常数a与c没有明显的变化;Zn掺杂样品晶格常数b没有明显变化,而Ni,Co掺杂样品晶格常数b分别稍有增加.选区电子衍射研究揭示:磁性元素Ni,Co及非磁性元素Zn掺杂,可能主要替代了Sr14Cu24O41结构中自旋链上的Cu原子,从而影响了自旋链上的dimer排列,破坏电荷有序超结构.电输运测量显示:Zn2+,Ni2+,Co3+离子掺杂样品的电阻率降低,但仍体现半导体行为,所有的掺杂样品都存在一个渡越温度Tρ,当TTρ时,其导电机理是以单空穴热激发导电占主要地位,在TTρ时,配对的局域化空穴的一维变程跳跃导电占主要优势;在相同的掺杂量下,非磁性元素Zn掺杂对电阻率值的影响大于磁性元素Ni,Co掺杂的影响,而磁性元素Ni,Co掺杂对渡越温度Tρ的影响大于非磁性元素Zn掺杂的影响.     

Regulation of Zn/Sn ratio in kesterite absorbers to boost 10% efficiency of Cu_2ZnSn(S,Se)_4 solar cells

The Zn/Sn ratio in Cu_2ZnSn(S,Se)_4(CZTSSe)films has been regulated to control the composition-related phase,defect,and photoelectric properties for high performance kesterite solar cells.It is found that the increase in the Zn/Sn ratio can slightly narrow the energy band gap to extend the light absorption range and improve the photocurrent.Optimal Zn/Sn ratio of 1.39 in CZTSSe film is obtained with the least secondary phase,the lowest defect density,and the longest charge recombination lifetime.Up to 10.1%photoelectric conversion efficiency has been achieved by this composition regulation.     

Heredity of clusters in the rapidly cooling processes of Al-doped Zr_(50)Cu_(50) melts and its correlation with the glass-forming ability

The heredity of clusters in rapidly cooled(Zr_(50)Cu_(50))_(100-x)Al_x melts and its correlation with glass-forming ability(GFA) are studied via molecular dynamics simulations. Pair distribution function and the largest standard cluster(LSC)are adopted to characterize the local atomic structures in the(Zr_(50)Cu_(50))_(100-x)Al_x systems. The [12/555] icosahedra and their medium-range order(IMRO) play an important role in forming(Zr_(50)Cu_(50))_(100-x)Al_x metallic glasses(MGs). The fraction of [12/555], the number of IMRO, and the maximum size of IMRO in MGs increase significantly with increasing x. A tracking study further reveals that the configuration heredity of icosahedral clusters starts from supercooled liquids.No direct correlation exists between the GFA and the onset temperature of continuous or stated heredity. Instead, a larger hereditary supercooled degree of icosahedra matches with better GFA of Al-doped Zr_(50)Cu_(50) alloys.     

Band offsets engineering at Cd_xZn_(1-x)S/Cu_2ZnSnS_4 heterointerface

Cd_xZn_(1-x)S/Cu_2ZnSnS_4 (CZTS)-based thin film solar cells usually use Cd S as a buffer layer, but due to its smaller band gap(2.4 e V), Cd S film has been replaced with higher band gap materials. The cadmium zinc sulfide(Cd Zn S) ternary compound has a higher band gap than other compounds, which leads to a decrease in window absorption loss. In this paper, the band offsets at Cd_xZn_(1-x)S/Cu_2ZnSnS_4 (CZTS) heterointerface are calculated by the first-principles, densityfunctional and pseudopotential method. The band offsets at Cd_(1-x)Zn_x S/CZTS heterointerface are tuned by controlling the composition of Zn in Cd_(1-x)Zn_x S alloy, the calculated valence band offsets are small, which is consistent with the commonanion rule. The favorable heterointerface of type-I with a moderate barrier height( 0.3 e V) can be obtained by controlling the composition of Zn in Cd_(1-x)Zn_x S alloy between 0.25 and 0.375.     

Luminescence investigations on sulfate apatite Na6(SO4)2FCl:RE (RE=Dy, Ce or Eu) phosphors

A new phosphor in the Cl-F system doped with Dy, Ce and Eu has been reported. Characterization of this phosphor using XRD, PL and TL techniques is described. Polycrystalline Na₆(SO₄)₂FCl:Dy; Na₆(SO₄)₂FCl:Ce and Na₆(SO₄)₂FCl:Eu phosphors prepared by a solid state diffusion method have been studied for their X-ray diffraction, photoluminescence (PL) and thermoluminescence (TL)characteristics. The PL excitation and emission spectra of phosphors were obtained. Dy³⁺ emission in the host at 475 and 570 nm is observed due to ⁴F_9/2→⁶H_15/2 and ⁴F_9/2→⁶H_13/2 transition, respectively, whereas the PL emission spectra of Na₆(SO₄)₂FCl:Ce phosphor shows the Ce³⁺ emission at 322 nm due to 5d→4f transition of Ce³⁺ ion. In Na₆(SO₄)₂FCl:Eu lattice, Eu²⁺ as well as Eu³⁺ emissions are observed. The emission of europium ion in this compound exhibits the blue as well as red emission. The TL glow curves of the same compounds have the simple structure with a prominent peak at 150, 175 and 200 °C. TL response, fading, reusability and trapping parameters of the phosphors are also studied. The TL glow curves of γ-irradiated Na₆(SO₄)₂FCl sample show one glow peak indicating that only one set of traps is being activated within the particular temperature range each with its own value of activation energy (E) and frequency factor (s). The trapping parameters associated with the prominent glow peak are calculated using Chen’s half width method. The release of hole/electron from defect centers at the characteristic trap site initiates the luminescence process in these materials. The intensity of the TL glow peaks increases with increase of the added γ-ray dose to the samples.     

Bar-shaped nanoparticles of iron(II) hydroxide

Formation of elongated nanoparticles was observed when was precipitated from solutions containing excess of Fe²⁺. The average diameter of the particles was 23 nm; the length to diameter ratio was up to 14. This shape was an unexpected phenomenon because bar- or needle-like nanoparticles have been earlier reported only for Fe(III)-based materials. Chemical analysis revealed Fe(OH)₂ nature of the obtained particles. In addition, this conclusion was verified with a new simple method for quantitative evaluation of the particle morphology. Application of this method to the mixed samples allowed to distinguish between the two different compounds and to attribute different morphologies to Fe(OH)₂ or Results indicate that bars are frequent shapes of nano-sized iron oxides/hydroxides.     

Multinary diamond-like chalcogenides for promising thermoelectric application

Thermoelectric(TE)materials have been considered as a strong candidate for recovering the waste heat from industry and vehicles due to the ability to convert heat directly into electricity.Recently,multinary diamond-like chalcogenides(MDLCs),such as Cu In Te_2,Cu_2Sn Se_3,Cu_3Sb Se_4,Cu_2ZnSnSe_4,etc.,are eco-friendly Pb-free TE materials with relatively large Seebeck coefficient and low thermal conductivity and have aroused intensive research as a popular theme in the TE field.In this review,we summarize the TE performance and device development of MDLCs.The features of crystalline and electronic structure are first analyzed,and then the strategies that have emerged to enhance the TE figure of merits of these materials are illustrated in detail.The final part of this review describes the advance in TE device research for MDLCs.In the outlook,the challenges and future directions are also discussed to promote the further development of MDLCs TE materials.     

Mott Transition and Superconductivity in Quantum Spin Liquid Candidate NaYbSe_2

The Mott transition is one of the fundamental issues in condensed matter physics,especially in the system with antiferromagnetic long-range order.However,such a transition is rare in quantum spin liquid(QSL) systems without long-range order.Here we report the experimental pressure-induced insulator to metal transition followed by the emergence of superconductivity in the QSL candidate NaYbSe_2 with a triangular lattice of 4 f Yb~(3+) ions.Detail analysis of transport properties in metallic state shows an evolution from non-Fermi liquid to Fermi liquid behavior when approaching the vicinity of superconductivity.An irreversible structure phase transition occurs around 11 GPa,which is revealed by the x-ray diffraction.These results shed light on the Mott transition in the QSL systems.     

原子吸收硫化锌法间接测定精氨酸络合反应的机理研究

通过编程计算精氨酸和锌离子在不同pH条件下的各种存在形式,通过分析拟合分布图,研究了在硫化锌法原子吸收间接测定精氨酸时的pH对原子吸收响应的影响及络合反应的机理.经对不同形态的精氨酸与金属锌离子的共存区域的各种组合探讨,指出在pH 9.0左右最佳测定条件下的pH响应峰是由于精氨酸和锌离子的两种不同存在形式的变化所引起的左右峰边缘,精氨酸是以正一价荷电形态的精氨酸基Arg -与Zn(OH)2形成了可溶性络合离子[HN=CH(NH 3)-NH-(CH2)3-CH(NH 3)-COO]2Zn(OH)2.结果表明,理论分析计算的结果与实验数据得到了基本吻合,确定了硫化锌法原子吸收间接测定精氨酸时的络合物反应机理及络合物的组成结构.     

Precisely tuning Ge substitution for efficient solution-processed Cu_2ZnSn(S,Se)_4 solar cells

The kesterite Cu_2ZnSn(S,Se)_4(CZTSSe) solar cells have yielded a prospective conversion efficiency among all thinfilm photovoltaic technology. However, its further development is still hindered by the lower open-circuit voltage(Voc), and the non-ideal bandgap of the absorber is an important factor affecting this issue. The substitution of Sn with Ge provides a unique ability to engineer the bandgap of the absorber film. Herein, a simple precursor solution approach was successfully developed to fabricate Cu_2Zn(SnyGe_(1-y))(SxSe_(1-x))_4(CZTGSSe) solar cells. By precisely adjusting the Ge content in a small range, the V_(oc) and J_(sc) are enhanced simultaneously. Benefitting from the optimized bandgap and the maintained spike structure and light absorption, the 10% Ge/(Ge+Sn) content device with a bandgap of approximately 1.1 eV yields the highest efficiency of 9.36%. This further indicates that a precisely controlled Ge content could further improve the cell performance for efficient CZTGSSe solar cells.     

Synthesis of dimension-tunable ZnO nanostructures via the design of zinc hydroxide precursors

A facile synthesis route is presented to achieve dimension-tunable ZnO nanostructures by the design of zinc hydroxide precursors under the surfactant-free condition. From three types of zinc hydroxide precursors, namely, crystalline Zn(OH)(NO₃)(H₂O) nanobelts, amorphous zinc hydroxides microparticles and soluble Zn(OH)^2-₄\mathrm{Zn}(\mathrm{OH})^{2-}_{4} species, the porous ZnO nanosheets, ZnO nanoparticles and ZnO nanowires can be achieved, respectively. The porous ZnO nanosheets exhibit large polar surface area. Thermal analysis indicates that the crystalline Zn(OH)(NO₃)(H₂O) nanobelts were converted to the porous ZnO nanosheets by in situ lattice reconstruction, which was attributed to the unique fibrous structure of Zn(OH)(NO₃)(H₂O) nanobelts. The as-prepared dimension-tunable ZnO nanostructures have potential applications in solar cells, photocatalysis, novel chemical and biological sensors, etc.     

LnCu_3(OH)_6Cl_3(Ln = Gd,Tb, Dy): Heavy lanthanides on spin-1/2 kagome magnets

The spin-1/2 kagome antiferromagnets are key prototype materials for studying frustrated magnetism. Three isostructural kagome antiferromagnets LnCu_3(OH)_6Cl_3(Ln = Gd, Tb, Dy) have been successfully synthesized by the hydrothermal method. LnCu_3(OH)_6Cl_3 adopts space group P■m1 and features the layered Cu-kagome lattice with lanthanide Ln~(3+) cations sitting at the center of the hexagons. Although heavy lanthanides(Ln = Gd, Tb, Dy) in LnCu_3(OH)_6Cl_3 provide a large effective magnetic moment and ferromagnetic-like spin correlations compared to light-lanthanides(Nd, Sm, Eu)analogues, Cu-kagome holds an antiferromagnetically ordered state at around 17K like YCu_3(OH)_6Cl_3.     

Y0.5Gd0.5Ba2Cu3O7-δ体系中通氧时间对超导转变温度的影响

研究了高温氧化物超导体Y0.5Gd0.5Ba2Cu3O7-δ体系中通氧时间对超导转变温度及超导转变温区的影响。Y0.5Gd0.5Ba2Cu3O7-δ样品是按相等摩尔数的Gd与Y元素配比,采用传统的固相反应法烧结而成的多晶块材。实验结果显示:Y0.5Gd0.5Ba2Cu3O7-δ烧结样品与YBa2Cu3O7-δ烧结样品均具有很好的单相性,在一定的通氧条件下其超导临界转变温度TC与超导初始转变温度TCO值相对YBa2Cu3O7-δ烧结样品有提高。文中对此结果进行了讨论。     

磁流化床强化烟气脱硫反应机理研究

磁流化床对脱硫反应的强化作用分铁磁颗粒强化和磁场强化两方面.铁磁颗粒强化体现在铁磁颗粒对SO2脱除具有催化氧化作用;磁场强化,体现在磁场能增强Ca(OH)2的溶解度,从而增强Ca(OH)2浆滴的脱硫能力.磁流化床烟气脱硫的试验研究结果证实了上述分析的正确性.     

Elastic properties of magnetic materials

This review discusses the theoretical aspects of magnetoelastic coupling with emphasis on the magnetic perturbation of elastic properties. The basic theory of magnetostriction is set out with application to ferromagnets, ferrimagnets and antiferromagnets, and is followed by a discussion of the physical origin of the magnetoelastic coupling coefficients in both localized and itinerant magnetic systems. Magnetic contributions to elastic compliance are then discussed and sound velocity anomalies near magnetic phase transitions investigated, including the cooperative Jahn-Teller limit for which the acoustic mode itself drives a structural transition even when magnetic ordering does not occur. The review concludes with discussion of magnetoelastic (or mixed magnon-phonon) waves in low temperature magnetically ordered phases and with a study of local striction phenomena in magnetically dilute materials. The latter leads to a recognition of internal rearrangement modes which may also be present in concentrated magnetic systems, and which may or may not couple significantly to bulk homogenous strain.