Atomistic deformation modes in strong covalent solids

We report on a first-principles study of the structural deformation modes in diamond, cubic boron nitride (c-BN), and cubic BC2N. We show that (i) the diamond C-C bonds remain strong up to the breaking point, leading to the large and nearly identical shear and tensile strength, (ii) c-BN exhibits a shear failure mode different from that in diamond and a significant softening in the B-N bonds at large tensile strains long before the bond breaking, and (iii) cubic BC2N displays a large disparity between the shear and tensile strength, contrary to the expectation for the hybrid of diamond and c-BN. We examine the microscopic bond-breaking processes to elucidate the atomistic mechanisms for the deformation modes and the implications for material strength.     

Electron-density distribution in diamond,silicon and germanium under high pressure

The valence-electron densities of C, Si, and Ge under high pressure are studied with the full-potential linearized APW method. For all three materials, the forbidden x-ray structure factor F(222) is stable under pressure and varies less than 3% under volume changes as big as ± 10%. The 30% drop of F(222) recently measured in Si just before the transition to the β - Sn structure is interpreted as an effect of the coexistence of the diamond and β - Sn phases over a 10 Kbar pressure range centered at the transition pressure.     

Low-temperature phase transformation from nanotube to sp~3 superhard carbon phase

Numerous new carbon allotropes have been uncovered by compressing carbon nanotubes based on our computational investigation.The volume compression calculations suggest that these new phases have a very high anti-compressibility with a large bulk modulus(B0).The predicted B0 of new phases is larger than that of c-BN(373 GPa) and smaller than that of diamond(453 GPa).All of the predicted structures are superhard transparent materials with a larger band gap and possess the covalent characteristics with sp3-hybridized electronic states.The simulated results will help us better understand the structural phase transition of cold-compressed carbon nanotubes.     

Phonon dispersion of ice under pressure

We report measurements of the phonon dispersion of ice Ih under hydrostatic pressure up to 0.5 GPa, at 140 K, using inelastic neutron scattering. They reveal a pronounced softening of various low-energy modes, in particular, those of the transverse acoustic phonon branch in the [100] direction and polarization in the hexagonal plane. We demonstrate with the aid of a lattice dynamical model that these anomalous features in the phonon dispersion are at the origin of the negative thermal expansion (NTE) coefficient in ice below 60 K. Moreover, extrapolation to higher pressures shows that the mode frequencies responsible for the NTE approach zero at approximately 2.5 GPa, which explains the known pressure-induced amorphization (PIA) in ice. These results give the first clear experimental evidence that PIA in ice is due to a lattice instability, i.e., mechanical melting.     

Data-driven exploration for pressure-induced superconductors using diamond anvil cell with boron-doped diamond electrodes and undoped diamond insulating layer

ABSTRACT

Data-driven exploration for pressure-induced superconductors was performed based on the high-throughput first-principles screening of electronic band structures. In the screening conditions, we focused on the characteristics including a narrow band gap, flat band feature, and possibility of metallization under high pressure. The 27 promising compounds were screened out from the database of Atomwork for the candidates of new pressure-induced superconductors. Among the candidates, we actually synthesized three compounds in a single crystal, and all candidates exhibited the pressure-induced superconductivity. For the in-situ electrical transport measurements, we developed a novel configuration of diamond anvil cell with boron-doped diamond electrodes and an undoped diamond insulating layer. The discovered new pressure-induced superconductors via the data-driven approach and the developed diamond anvil cell were summarized in this paper.     

High-pressure phase transitions of Mg2Ge and Mg2Sn: First-principles calculations

Phase transitions of the anti-fluorite compounds Mg₂Ge and Mg₂Sn under high pressure were investigated using the first-principles plane-wave method within the pseudopotential and generalized gradient approximations. The calculated results show that Mg₂Ge and Mg₂Sn undergo two first-order phase transitions at high pressure and the sequence of the pressure-induced phase transitions is from the anti-fluorite to the anti-cotunnite, and then to the Ni₂In-type structure. The high pressure behaviors of Mg₂Ge and Mg₂Sn are similar to Mg₂Si and the isostructural alkali-metal oxide Li₂O. Moreover, the electronic and optical properties of both the anti-fluorite and the high-pressure phases are presented.     

Estimates of isothermal bulk moduli for group iva crystals with the zincblende structure

By equating the differential changes in macroscopic work of compression and potential energy for group IVA crystals of the zincblende structure we have obtained an expression for the isothermal bulk modulus as a function of pressure. The model used for the potential energy for these covalent crystals is that of distinct nearest-neighbor bonds with force constants taken directly from the molecular seriesX₂H₆ andXYH₆. We calculate this isothermal bulk modulus in the limit of zero external pressure to be 4070 (4420, 5450, 5600), 1060 (970·8, 988), 960 (712, 724·3, 771·7), 720±50 (?) and 2240 (?) kbar for diamond, Si, Ge, sn (α, gray), and SiC (β, cubic) respectively, with experimental data in parentheses. It would seem that the value for α-Sn lies in the range 400–800 kbar, while that for β-SiC may not differ much from the calculated one. The treatment of a zincblende structure covalent crystal as a giant molecule for purposes of estimating low pressure isothermal bulk moduli is thus fairly satisfactory. For extending the moduli to higher pressures it suffers a serious defect as the (dimensionless) pressure derivative of the isothermal bulk modulus in the limit of zero pressure turns out to be 1·0 for all covalent solids regardless of the number of bound neighboring atoms, compared to e.g. 4·16 and 4·35 for Si and Ge.     

高压下c-BN的力学、电子结构及光学性质研究

为了研究不同压力下c-BN的力学性质、电子结构以及光学性质的变化,基于密度泛函理论构建了不同压力下c-BN的晶体模型。发现c-BN在不同压力下均力学稳定,随着压力增加,c-BN的弹性常数逐渐增大,材料的可压缩性逐渐变差;c-BN在零压下的禁带宽度为4.367 eV,表明c-BN是间接宽带隙半导体,随着压力增加,c-BN的禁带宽度逐渐增大,态密度谱图变化不明显;对Milliken 布居分布在不同压力下进行分析,表明随着压力增加,B、N原子杂化后形成的B-N共价性增强。对c-BN的复介电函数、折射率、反射率等进行分析,发现随着压力增大,它们都产生一定蓝移,且在整个可见光谱范围以及红外与紫外（约从204nm开始）光谱的很大范围内都透明。研究结果对高压下c-BN的应用有一定参考价值。     

CaAl2X2(X=C,Si,Ge)的稳定性、电子结构和力学性质研究

由于AB2X2类型的材料在储能、催化、超导、发光等领域都有着潜在应用价值,因此得到了广泛关注。本文通过第一原理方法计算分析了CaAl2X2(X=C,Si,Ge)的材料声子谱、电子结构、力学性质和硬度,其主要结果为：材料晶格常数的计算结果和实验值都与理论结构符合的很好;CaAl2C2和CaAl2Si2材料的声子谱没有出现虚频,表明这两种材料在热力学及动力学上是稳定的;计算的材料的能带结构表明,CaAl2Si2和 CaAl2Ge2具有金属特性, CaAl2C2具有较小带隙的间接半导体材料。这类材料的金属特性,热稳定性及力学各项异性特征对于其作为二次电池活性电极有着重要影响,因此本文的研究结果可为相关领域的研究提供较好的理论依据及参考。     

高质量宽带隙立方氮化硼薄膜的研究进展

文章着重介绍了最近研制出的高质量宽带隙立方氮化硼薄膜的三种制备方法和结构特性 :(1)用射频溅射法在Si衬底上制备出立方相含量在 90 %以上 ,Eg>6 .0eV的c-BN薄膜 ;(2 )用离子束辅助的化学气相沉积法(CVD) ,在金刚石上外延生长出立方含量达 10 0 %的单晶c -BN薄膜 ;(3)用微波电子回旋共振CVD法 (MW -ECR-CVD)在金刚石上外延生长出高纯c-BN薄膜 .这些高纯c -BN薄膜 ,可应用于制作各种半导体 (主要是高温、高频大功率 )电子器件 .     

压力下CaN_2结构稳定性和电子结构的第一性原理研究

通过运用基于密度泛函理论的第一性原理计算方法结合广义梯度近似对压力下CaN_2的结构稳定性和电子结构进行了理论研究.对结构稳定性的研究表明,ZnCl_2型结构是CaN_2在环境压力下最稳定的结构,而实验上观察到的CaC_2-I型结构是CaN_2高压下(8.7 GPa)的稳定性结构.在50 GPa的压力范围内,CaN_2将发生从ZnCl_2型结构到ThC_2型结构再到CaC_2-I型结构的两次压致结构相变,其相变压力分别为0.81 GPa和8.77 GPa.而对电子结构的研究表明ZnCl_2型、ThC_2型和CaC_2-I型三种结构的CaN_2都表现出了金属特征,三种结构CaN_2当中Ca-N键的离子-共价性特征和N原子间的N=N双键特征得到了确认.     

Microscopic theory of the static structural properties and phase transformation of Ge

Using the atomic number as the only input, the static structural properties and the pressure-induced phase transformation of Ge are calculated within an ab initio density-functional pseudopotential scheme. Among a set of likely crystal structures, the diamond structure is found to be the most stable. The calculated lattice constant, cohesive energy, and bulk modulus are in excellent agreement with experiment, and the properties of the phase transformation to the β-tin structure under pressure accurately reproduced.     

锗酸盐晶体压致非晶化的研究

高压拉曼散射研究表明．ＣｕＧｅＯ３，Ｌｉ２ＧｅＯ３和Ｌｉ６Ｇｅ２Ｏ７三种晶体分别在７，１２和１１ＧＰａ压力下转变为非晶。在高于起始转变压力以上一定范围压致非晶是可逆的，ＣｕＧｅＯ３，Ｌｉ２ＧｅＯ３和Ｌｉ６Ｇｅ２Ｏ７压致非晶的不可逆转变压力分别为１４．１，２０和２０ＧＰａ。压致非晶ＣｕＧｅＯ３的重新晶化温度在６００℃附近。锗酸及系列晶体的压致非晶化与它们的成份和结构有关，随着在这一系列晶体中Ｌｉ２Ｏ含量的增加，压致非晶化的压力趋于减小。     

高压下Zn2GeO4带隙变化的第一性原理研究

采用基于密度泛函理论的第一性原理计算研究了Zn₂GeO₄晶体在高压下的电子结构和带隙变化行为. 研究结果发现, 随着压强的增加, Zn₂GeO₄ 能带间隙先变大, 在压强为9.7 GPa时达到最大值, 然后减小. 通过电子态密度、电荷布居数和电子差分密度分布图的研究分析可知:在低压区域(0< P< 9.7 GPa), 带隙的变大主要是由于原子间距离的减小造成的共价性增强和Ge原子随压强的变大局域性增强引起的; 在高压区域(P>9.7 GPa), 则是出现了离域现象, 诱发了离域电子的产生, 从而使带隙减小.     

Electronic, magnetic and transport properties of Co2TiZ (Z=Si, Ge and Sn): A first-principle study

We have studied the electronic structure, magnetic and transport properties of some Co based full Heusler alloys, namely Co₂TiZ (Z=Si, Ge and Sn), in the frame work of first-principle calculations. The calculations show that Co₂TiZ (X=Si, Ge and Sn) are to be half-metallic compounds with a magnetic moment of 2 μ_B, well consistent with the Slater-Pauling rule. The electronic structure results reveal that Co₂TiZ has the high density of states at the Fermi energy in the majority-spin state and show 100% spin polarization. Our results also suggest that both the electronic and magnetic properties in these compounds are intrinsically related to the appearance of the minority-spin gap. The origin of energy gap in the minority-spin states is discussed in terms of the electron splitting of Z (Z=Si, Ge and Sn) and 3d Co atoms and also the d-d hybridization between the Co and Ti atoms. The transport properties of these materials are discussed on the basis of Seebeck coefficients, electrical conductivity coefficients and thermal conductivity coefficients.     

Self-consistent electronic structure of Si,Ge and diamond by the LMTO-ASA method

We have investigated the accuracy of the self-consistent LMTO-ASA method with interstitial spheres for open structure materials by studying the electronic structure of Si, Ge and diamond. Our band structures agree in detail with the results of the best state of the art self-consistent calculations. In addition we obtain quantitative agreement with the observed cohesive properties for all three systems. The success of these calculations suggests that the method should be useful for other open structure materials.     

衬底材料对制备立方氮化硼薄膜的影响

较系统地研究了不同衬底材料对制备氮化硼薄膜的影响。用热丝增强射频等离子体CVD法,以NH3,B2H6和H2为反应气体,在Si,Ni,Co和不锈钢等衬底材料上,成功生长出高质量的立方氮化硼薄膜,还用13.56MHz的射频溅射系统将c-BN薄膜沉积在Si衬底上,靶材为h-BN(纯度为99.99％）,溅射气体为氩气和氮气的混合气体,所得到的氮化硼薄膜中立方相含量高于90%,用X射线衍射谱和傅里叶变换红谱对样品进行了分析表明,衬底材料与c-BN的晶格匹配情况,对于CVD生长立方氮化硼薄膜影响很大,而对溅射生长立方氮化硼薄膜影响不大。     

Dangling bond modulating the electronic and magnetic properties of zigzag SiGe nanoribbon

First-principles nonmagnetic calculations reveal a metallic character in zigzag SiGe nanoribbons (ZSiGeNRs) regardless of their width. The partial DOS projected onto the Si and Ge atoms of ZSiGeNR shows that a sharp peak at the Fermi level is derived from the edge Si and Ge atoms. The charge density contours show the Si–Ge bond is covalent bond, while for the Si–H bond and Ge–H bond, the valence charges are strongly accumulated around H atoms due to their stronger 1 s potential and the higher electronegativity of 2.20 than that of 1.90 for Si atom and 2.01 for Ge atom, so that a significant charge transformation from Si or Ge atoms to H atoms and thus an ionic binding feature. Spin–polarization calculations show that the band structures of ZSiGeNR are modified by the dangling bonds. Compared with perfect ZSiGeNR which is a ferrimagnetic semiconductor, the bands of the ZSiGeNRs with bare Si edge, bare Ge edge, and bare Si and Ge edges shift up and nearly flat extra bands appear at the Fermi level. The ZSiGeNR with bare Si edge or bare Ge edge is a ferrimagnetic metal, while ZSiGeNR with bare Si and Ge edges is a nonmagnetic metal.     

Adiabatic electron-phonon interaction and high-temperature thermodynamics of A15 compounds

Inelastic neutron scattering was used to measure the phonon densities of states of the A15 compounds V3Si, V3Ge, and V3Co at temperatures from 10 to 1,273 K. It was found that phonons in V3Si and V3Ge, which are superconducting at low temperatures, exhibit an anomalous stiffening with increasing temperature, whereas phonons in V3Co have a normal softening behavior. First-principles calculations show that this anomalous increase in phonon frequencies at high temperatures originates with an adiabatic electron-phonon coupling mechanism. The anomaly is caused by the thermally induced broadening of sharp peaks in the electronic density of states of V3Si and V3Ge, which tends to decrease the electronic density at the Fermi level. These results show that the adiabatic electron-phonon coupling can influence the phonon thermodynamics at temperatures exceeding 1,000 K.     

Pressure enhancement of the giant magnetocaloric effect in Tb5Si2Ge2

Effects of temperature and pressure on magnetic, elastic, structural, and thermal properties of Tb5Si2Ge2 have been studied by means of macroscopic (thermal expansion and magnetization) and microscopic (neutron powder diffraction) techniques. We present evidence that the high-temperature second-order ferromagnetic transition can be coupled with the low-temperature first-order structural phase change into a single first-order magnetic-crystallographic transformation at and above a tricritical point in the vicinity of 8.6 kbar. This pressure-induced coupling has a remarkable effect on the magnetocaloric effect, transforming Tb5Si2Ge2 from an ordinary into a giant magnetocaloric effect material.