Why do gallium clusters have a higher melting point than the bulk?

Density functional molecular dynamical simulations have been performed on Ga17 and Ga13 clusters to understand the recently observed higher-than-bulk melting temperatures in small gallium clusters [Phys. Rev. Lett. 91, 215508 (2003)]]. The specific-heat curve, calculated with the multiple-histogram technique, shows the melting temperature to be well above the bulk melting point of 303 K, viz., around 650 and 1400 K for Ga17 and Ga13, respectively. The higher-than-bulk melting temperatures are attributed mainly to the covalent bonding in these clusters, in contrast with the covalent-metallic bonding in the bulk.     

Elastic properties of crystalline and liquid gallium at high pressures

The elastic properties of gallium, such as the bulk modulus B, the shear modulus G, and the Poisson’s ratio σ, are investigated and the relative change in the volume is determined in the stability regions of the Ga I, Ga II, and liquid phases at pressures of up to 1.7 GPa. The observed lines of the Ga I-Ga II phase transition and the melting curves of the Ga I and Ga II phases are in good agreement with the known phase diagram of gallium; in this case, the coordinates of the Ga I-Ga II-melt triple point are determined to be 1.24 ± 0.40 GPa and 277 ± 2 K. It is shown that the Ga I-Ga II phase transition is accompanied by a considerable decrease in the moduli B (by 30%) and G (by 55%) and an increase in the density by 5.7%. The Poisson’s ratio exhibits a jump from typically covalent values of approximately 0.22–0.25 to values of approximately 0.32–0.33, which are characteristic of metals. The observed behavior of the elastic characteristics is described in the framework of the model of the phase transition from a “quasi-molecular” (partially covalent) metal state to a “normal” metal state. An increase in the Poisson’s ratio in the Ga I phase from 0.22 to 0.25 with an increase in the pressure can be interpreted as a decrease in the degree of covalence, i.e., the degree of spatial anisotropy of the electron density along the bonds, whereas the large value of the pressure derivative of the bulk modulus (equal to approximately 8) observed up to the transition to the Ga II phase or the melt is associated not only with the quasicovalent nature of the Ga I phase but also with the structural features. In view of the presence of seven neighbors for each gallium atom in the Ga I phase, the gallium lattice can be treated as a structure intermediate between typical open-packed and close-packed structures. Premelting effects, such as a flattening of the isothermal dependence of the shear modulus G(p) with increasing pressure and an increase in the slope of the isobaric dependences G(T) with increasing temperature, are revealed in the vicinity of the melting curve. The bulk modulus of liquid gallium near the melting curve proves to be rather close to the corresponding values for the normal metal Ga II.     

Optical behaviour of melting for a thin metal film

Reflectance measurements have been performed for gallium films at normal incidence (from 0.3 to 0.9 μm) in terms of temperature (from -20°C to + 40°C). The basic results are: (i) a drastic change in reflectance when melting occurs (about 20% at 0.6 μm), and (ii) a shift in the temperature of the solid-liquid transition with the thickness of the film which only takes place on and after the second melting (about 7°C for a film 250A?thick).     

Measurement of the specific resistance of CuGa alloys at high temperatures

The specific resistance of CuGa alloys is determined by a four-point dc-method. Samples from zero to one hundred atomic percent concentration of gallium in copper were measured from their melting temperature up to 1450 K.     

镓原子集团结构的第一性原理分子动力学研究

用第一性原理分子动力学方法和模拟退火技术研究了镓原子集团(n≤8)的平衡结构,并与可得到的实验数据进行了比较。随着原子数的增加,发现在n=5时结构发生了从二维到三维的变化。所有集团可看作为由镓分子和原子链两种结构单元所构成,这两种结构单元分别出现在固相α-Ga和亚稳相β-Ga中。 关键词：     

Zur Supraleitung einiger Mischsysteme von Verbindungen mit A15-Struktur auf Vanadiumbasis

Ternary intermetallic compounds on the base of V₃Ga and V₃Si have been prepared by arc melting, substituting gallium and silicon partly by aluminium, gallium, indium, silicon, and germanium. In similar way part of the niobium in the compounds Nb₃Al and Nb₃Ga has been replaced by vanadium. All these ternary compounds have been investigated for superconductivity. Only by substituting gallium in V₃Ga partly by aluminium or silicon, the transition temperature could be raised.     

Crack-free micromachining on glass substrates by visible LIBWE using liquid metallic absorbers

Laser induced backside wet etching (LIBWE) is a promising laser direct-write technique for etching transparent materials and for producing high precision and near-optical quality surfaces. In this study, visible LIBWE using gallium and eutectic indium/gallium as absorbers was used for crack-free microfabrication of sodalime and quartz. Eutectic indium/gallium (In/Ga) has a melting temperature lower than metallic gallium does and the etching rate by using In/Ga was found to be similar to that by gallium for visible LIBWE. When using the gallium absorber, the etching threshold of quartz by visible LIBWE was about one-third of that by UV LIBWE. The heat-affected zone of the quartz etching was negligible at the trench rim in the visible LIBWE process. The wettability of the metallic absorbers on the substrates affects aspect ratio and is a new important factor for LIBWE. In addition, etching rate decreased when repetition rate was increased.     

EFFECT OF THE SUBSTITUTION OF Ga ON THE STRUCTURE AND MAGNETIC PROPERTIES OF Dy2Fe17 COMPOUND

Dy₂Fe_17-xGa_x (x = 0,1,2,3,4, 5 and 6) compounds were prepared by arc melting. These compounds are of single phase, having a hexagonal Th₂Ni₁₇-type structure fox x=0 and rhombohedral Th₂Zn₁₇-type structure for x≥1. The substitution of Ga for Fe in the Dy₂Fe₁₇ leads to a linear increase of unit-cell volumes. The saturation magnetization M_s at 1.5K is found to decrease linearly with increasing Ga concentration, from 65emu/g for x= 0 to 5emu/g for x = 6; and the Fe magnetic moment μ_Fe is almost independent of Ga concentration. The Curie temperature T_C is found first to increase with increasing Ga content x, and goes through a maximum value of 559 K at about x = 3, then decreases. The sharp increase of T_C at lower Ga content may result from the increase of unit cell volumes. Dy₂Fe_17-xGa_x compounds with x≤5 exhibit easy plane anisotropy at room temperature, and those with x = 6 possess easy-axis.     

Ga含量对Mn2-xNiGa1+x结构和磁性的影响

系统研究了铁磁性形状记忆合金Mn_{2 -x}NiGa_1+x的结构、磁性和有序化转变. 研究表明: 随着Ga含量的增加, Mn_{2 -x}NiGa_1+x的母相结构由Hg₂CuTi 型逐渐转变到Cu₂MnAl型Heusler结构. 母相的晶格常数先增加后降低, 当x=0.3时达到最大值. 0.3 ≤x ≤0.8时, 材料除呈现Heusler结构的主相之外, 还出现了Ni₂In型六角相. 过渡金属中3d电子之间交换相互作用的减弱, 导致Mn_2-xNiGa_1+x主相的居里温度由Mn₂NiGa的590 K逐渐降低至Ga₂MnNi的220 K左右; 当x=0.6–0.8时, Ni₂In型六角相的居里温度与主相的居里温度出现分离. Ga对Mn的替代引起合金中原子间耦合作用的变化, 导致低温下Mn_{2 -x}NiGa_1+x的饱和磁化强度先增加后降低, 即x≤0.4时呈上升趋势, x>0.4时急剧下降. 差热分析结果显示, 随着x从0增加到1, 样品熔化温度逐渐降低, B2相到Heusler相的转变温度先降低后增加.     

Probing magnetoelastic coupling and structural changes in magnetoelectric gallium ferrite

Temperature dependent x-ray diffraction and Raman spectroscopic studies were carried out on flux-grown single crystals of gallium ferrite with a Ga:Fe ratio of 0.9:1.1. Site occupancy calculations from the Rietveld refinement of the x-ray data led to an estimated magnetic moment of ~0.60 μ(B)/f.u. which was in good agreement with the experimental data. A combination of these two measurements indicates that there is no structural phase transition in the material between 18 and 700 K. A detailed line shape analysis of the Raman mode at ~374 cm(-1) revealed a discontinuity in the peak position data indicating the presence of spin-phonon coupling in gallium ferrite. A correlation of the peak frequency with the magnetization data led to two distinct regions across a temperature ~180 K with appreciable change in the spin-phonon coupling strength from ~0.9 (T < 180 K) to 0.12 cm(-1) (180 K < T < T(c)). This abrupt change in the coupling strength at ~180 K strongly suggests an altered spin dynamics across this temperature.     

生长条件对Ga掺杂ZnO薄膜微观结构及光致发光性能的影响

利用热氧化法在不同参数条件下生长了Ga掺杂范围较宽的ZnO薄膜, 研究了ZnO薄膜的表面微观结构和光致发光性能. 研究表明: Ga以Ga³⁺存在并掺入ZnO晶格取代Zn²⁺, Ga的掺入改变了ZnO薄膜中的缺陷类型及浓度、化学计量比、薄膜表面结晶质量, 进而影响了薄膜的光致发光性能. 随着热氧化温度升高, Ga掺杂量增大, ZnO薄膜的晶粒尺寸增大, 尺寸更均一, 紫外光与可见光强度比增大. 随着热氧化时间延长, Ga掺杂量降低, ZnO薄膜的晶粒尺寸均一性变差, 紫外光与可见光强度比减小.     

MAGNETIC PROPERTIES OF Pr2Co17-x Mx ( M＝Ga,Si) COMPOUNDS

The influence of Ga or Si substitution for Co on the structural and magnetic properties of Pr₂Co₁₇ compounds is investigated. All samples studied here are single phase and have the rhombohedral Th₂Zn₁₇-type structure. The unit-cell volume is found to increase linearly by the substitution of Ga for Co,but reduce by the substitution of Si for Co in Pr₂Co₁₇ compounds. In Pr₂Co_17-x M_x, the Curie temperature decreases monoto nically with increasing at an approximate rate of 153K per Ga atom and 175K per Si atom. The saturation magnetic moment of Pr₂Co_17-x M_x ( M=Ga,Si) decreases with increasing x. The rates of the decrease are larger than that expected as a simple dilution. For Pr₂Co_17-xSi_x ,the spin reorientation transition is observed above room temperature. The spin-reorientation temperature Tsrfirst decreases with increasing Si content and then increases at higher x values (x>2). The spin reorientat ion behavior is interpreted by the competition between the Pr and Co sublattice anisotropies. The easy magnetization direction in Pr₂Co_17-xGa_x compounds is perpendicular to the c-axis, and no spin reorientation transition is observed.     

Na(n)(5<=n<=10)小团簇相变

采用紧密结合的分子动力学模型,对Na(n)(5<=n<=10)小团簇的键长涨落、势能、热容量等熔化性质在50K到1500K温区进行了模拟研究,结果表明：它们发生两次相变,一种在230K到300K的温度范围内,依次有块体玻璃态转变;一种在550K到870K温度段,依次经历了熔化相变.同时也得到随着团簇体系的减小,势能由下向上排列的曲线,即体系的势能由低变高.     

Size effects on melting and wetting in the Ga–Pb nano-alloy

Ga–Pb alloys with 15 at% Pb mean concentration have been prepared at the nanoscale by means of evaporation-condensation technique in ultra high vacuum conditions. Transmission electron microscope images indicate that at room temperature, the system is a two-components breath figure composed of liquid Ga nanodrops containing Pb nanocrystals. Some thermodynamic properties of this nano-alloy are investigated for different temperatures and particle sizes. The results obtained put in evidence a large modification of the Ga–Pb bulk phase diagram: a decrease of the melting temperatures of the two components as well as the ones of the miscibility gap. Changes in the microscopic structure of the system as a function of temperature have been investigated and a full wetting transition from a dry to a completely wet state has been put in evidence.     

Phase transitions in uranium dioxide at high pressures and temperatures

The melting curve is plotted for uranium dioxide with fluorite structure in a pressure range from ?2.5 to +100 GPa. This curve has a peak at the point 3348 K, 6 GPa, and has a negative derivative at high pressures. The pressure corresponding to a polymorphic transition of uranium dioxide (37 GPa) at a temperature of 1015 K is determined. The slope of the equilibrium curve of the polymorphic transition in UO₂ in the temperature range 300–1000 K is ? 56 K/GPa.     

Melting, premelting, and structural transitions in size-selected aluminum clusters with around 55 atoms

Heat capacities have been determined for unsupported aluminum clusters, Al49(+) - Al63(+), from 150 to 1050 K. Peaks in the heat capacities due to melting occur between 450 and 650 K (well below the bulk melting point of 933 K). The peaks for Al+51 and Al+52 are bimodal, suggesting the presence of a premelting transition where the surface of the clusters melts around 100 K before the core. For clusters with n > 55 the melting temperatures suddenly drop, and there is a dip in the heat capacities due to a transition between two solid forms before the clusters melt.     

Reaction of oxygen with gallium surfaces

The adsorption of oxygen molecules on evaporated gallium films has been studied by UV photoelectron spectroscopy between 10 and 300 K. In addition to the oxygen levels, the chemical shift of the Ga 3d core level has been investigated using monochromatized light from a He discharge lamp at ?ω = 40.8 eV. Four different states of oxygen have been found depending on temperature. At 10 K the molecules of the first layer are physisorbed onto which several additional layers can be condensed. The rigid relaxation shifts to smaller binding energies are 2.7 eV for physisorbed and 1.3 eV for condensed oxygen. During warming-up the oxygen reacts with the gallium surface. Between 70 and 130 K an oxygen species develops which is interpreted as chemisorbed molecular oxygen. This is concluded from the valence band UP spectra, the chemical shift of the Ga 3d level, and the work function change. At 300 K oxygen is dissociatively bound and the bulk oxide grows.     

Effect of high pressure on the thermopower in gallium

The absolute thermopower and relative electrical resistance of gallium have been measured at room temperature and at a pressure increased up to 7 GPa. As the initial phase, all of the Ga phases retain the positive value of the thermopower. At 4 GPa, a phase transition has been revealed.     

Unusual freezing and melting of gallium encapsulated in carbon nanotubes

The freezing and melting behavior of gallium (Ga) encapsulated in carbon nanotubes was investigated through in situ observation in a transmission electron microscope. It is shown that Ga remains liquid up to -80 degrees C when encapsulated in carbon nanotubes. Results of detailed electron diffraction analysis show that the encapsulated Ga can crystallize in either beta phase or gamma phase rather than the common alpha phase upon freezing. Both beta-Ga and gamma-Ga melt at around -20 degrees C. While this is very close to the melting point of bulk beta-Ga (-16 degrees C), it is considerably higher than that of bulk gamma-Ga (-35.6 degrees C). It was observed that upon solidification, Ga has its unique crystallographic orientation relative to the host carbon nanotube.     

Influence of Ga/(Ga + In) grading on deep‐defect states of Cu(In,Ga)Se2 solar cells

The benefits of gallium (Ga) grading on Cu(In,Ga)Se₂ (CIGS) solar cell performance are demonstrated by comparing with ungraded CIGS cells. Using drive‐level capacitance profiling (DLCP) and admittance spectroscopy (AS) analyses, we show the influence of Ga grading on the spatial variation of deep defects, free‐carrier densities in the CIGS absorber, and their impact on the cell's open‐circuit voltage V_oc. The parameter most constraining the cell's V_oc is found to be the deep‐defect density close to the space charge region (SCR). In ungraded devices, high deep‐defect concentrations (4.2 × 10¹⁶cm^–3) were observed near the SCR, offering a source for Shockley–Read–Hall recombination, reducing the cell's V_oc. In graded devices, the deep‐defect densities near the SCR decreased by one order of magnitude (2.5 × 10¹⁵ cm^–3) for back surface graded devices, and almost two orders of magnitude (8.6 × 10¹⁴ cm^–3) for double surface graded devices, enhancing the cell's V_oc. In compositionally graded devices, the free‐carrier density in the absorber's bulk decreased in tandem with the ratio of gallium to gallium plus indium ratio GGI = Ga/(Ga + In), increasing the activation energy, hindering the ionization of the defect states at room temperature and enhancing their role as recombination centers within the energy band. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)