MgS晶体结构性质的密度泛函研究

采用基于密度泛函理论(DFT)基础上的第一性原理赝势平面波方法对MgS晶体四种构型(B1，B2，B3，B4)的体相性质进行了系统研究.计算结果表明，B1构型的晶体是间接带隙型半导体，而B2，B3和B4构型的晶体则是直接带隙型材料，其中B2构型的带隙宽度最窄，其值为0.42eV.在压力不超过200.3GPa时，B1构型的MgS 晶胞是最稳定的，当压力大于该值时，会发生B1构型到B2构型的转化. 关键词： MgS 第一性原理赝势平面波方法 电子结构 转化压力     

m-BiVO_4与t-BiVO_4的电子结构和光学性质的第一性原理研究

采用第一性原理的密度泛函理论赝势平面波方法,计算了单斜m-BiVO_4与四方t-BiVO_4的电子结构和光学性质.计算结果表明:m-BiVO_4为间接带隙半导体,禁带宽度为2.171 e V,t-BiVO_4为直接带隙半导体,禁带宽度为2.644 e V;m-BiVO_4与t-BiVO_4均可吸收紫外光及可见光,m-BiVO_4还可以吸收部分红外光.     

第一性原理研究B掺杂Mn_4Si_7的电子结构和光学性质

采用基于密度泛函理论的第一性原理计算方法,对未掺杂及B掺杂Mn_4Si_7的电子结构和光学性质进行理论计算.研究结果表明,未掺杂Mn_4Si_7是间接带隙半导体,其禁带宽度为0.786 eV,B掺杂后其禁带宽度下降为0.723 eV. B掺杂Mn_4Si_7是p型半导体材料.未掺杂Mn_4Si_7在近红外区的吸收系数达到10~5 cm~(-1),B掺杂引起Mn_4Si_7的折射率、吸收系数、反射系数及光电导率增加.     

稀土掺杂金红石相TiO2的第一性原理的定性计算

稀土掺杂金红石相TiO2的禁带宽度(带隙)是影响其吸收波长的主要因素,其决定TiO2的光催化活性.利用第一性原理密度泛函理论(Ab initio DFT)得出17种稀土掺杂金红石相TiO2的能态密度(DOS),结果表明:除Lu、Y、Yb和Sc四种稀土增大金红石相TiO2带隙外,其余13种稀土均很大程度地降低金红石相TiO2的带隙.因此,稀土掺杂金红石相TiO2具有广阔的研究前景.     

β-Si3N4电子结构和光学性质的第一性原理研究

采用基于密度泛函的平面波赝势方法(PWP)和广义梯度近似(GGA),计算了β相氮化硅(β-Si3N4)的电子结构和光学性质,得到的晶格常数、能带结构等均与实验结果较好符合.进一步还研究了β-Si3N4的光吸收系数以及禁带宽度随外压力的变化规律,为β-Si3N4材料在高压条件下的应用提供了理论参考.     

AlN_(1-x)P_x合金电子结构及光学性质的第一性原理研究

基于密度泛函理论第一性原理的平面波超软赝势,采用广义梯度近似及Heyd-Scuseria-Ernzerhof 03(HSE03)方法对能带及态密度进行修正,研究了AlN_(1-x)P_x(x=0,0.25,0.50,0.75,1)合金的晶体结构、电子结构和光学性质。结果表明,随P含量的增加,AlN_(1-x)P_x晶格常数呈线性递增趋势,AlN_(1-x)P_x(x=0,0.25,0.75,1)属于立方晶系,而AlN0.50P0.50属于四方晶系。AlN_(1-x)P_x带隙随P含量的增加呈先减后增趋势,AlN和AlP是间接带隙半导体,而AlN_(1-x)P_x(x=0.25,0.50,0.75)属于直接带隙半导体。P的存在破坏了AlN原本的本征值和简并态,改变了电子能带结构。随P含量的增加,AlN_(1-x)P_x的光学性质曲线向低能区移动,介电函数虚部的次强峰逐渐消失。AlN_(1-x)P_x合金对紫外光具有较强吸收,P的存在拓宽了可见光吸收范围。     

表面氢化双层硅烯的结构和电子性质

采用密度泛函理论(DFT)广义梯度近似GGA和HSB06方法研究了氢化双层硅烯(silicene)的结构和电子性质, 结果表明: 氢化后的双层硅烯可能存在三种稳定的构型, AA椅型、AB椅型和AA船型, 其中AA椅型和AB椅型结构最为稳定, 氢化后这三种稳定构型材料的性质由零带隙的半金属(semimetal)转变为禁带宽度分别为1.208, 1.437和1.111 eV 的间接带隙的半导体, 采用混合泛函HSB06计算修正得到的带隙分别为1.595, 1.785 和1.592 eV. 进一步分析了在双轴应变下氢化双层硅烯的带隙随应变的关系, 得到应变可以连续的调节材料的带隙宽度, 这些性质有可能应用于未来的纳米电子器件.     

Cu-X(X=B, Al, Ga, In)共掺杂对ZnS可见光吸收的影响

ZnS能够用于光解水制氢,但是由于ZnS带隙较宽在一定程度上制约了可见光的吸收。为了减小闪锌矿ZnS的带隙宽度,增加对可见光的吸收,采用密度泛函理论研究了Cu-X(X=B, Al, Ga, In)共掺杂对ZnS电子结构和可见光吸收的影响。计算结果表明Cu-X(X=B, Al, Ga, In)共掺杂ZnS的结合能都是负值,都属于稳定结构;掺杂使得闪锌矿ZnS的带隙宽度由2.9eV分别减小到2.68eV、2.41 eV、2.18 eV、1.82 eV,导致了吸收谱和光导产生红移,有利于可见光的吸收;掺杂后导带底向低能级方向移动,同时在禁带中产生p-d杂化能级,导致了带隙宽度减小,有利于可见光的吸收和阻止光生载流子的复合;最后掺杂ZnS的带边位置满足水解制氢的条件,可用于制造光催化剂。综上所述Cu-X(X=B, Al, Ga, In)共掺杂ZnS有利于可见光的吸收。     

金属插层对C60/AlN一维光子晶体带隙的影响

利用传输矩阵方法,研究了金属Ag插层对C60/AlN一维光子晶体带隙宽度以及反射率的影响.结果表明：在C60与AlN之间插入Ag组成的［C60/Ag/AlN］n一维光子晶体,与未插入Ag层相比可使带隙增宽73.91%,最大反射率提高到91.01% .该结构可望用于制作紫外线波段的宽带反射镜.     

锰掺杂二硅化铬电子结构和光学性质的第一性原理计算

采用基于第一性原理的密度泛函理论(DFT)赝势平面波方法计算了锰掺杂二硅化铬(CrSi2)体系的能带结构、态密度和光学性件质.计算结果表明末掺杂CrSi2属于间接带隙半导体间接带隙宽度△ER=0.35 eV;Mn掺杂后费米能级进入导带,带隙变窄,且间接带隙宽度△Eg=0.24 eV,CrSi2转变为n型半导体.光学参数发生改变,静态介电常数由掺杂前的ε1(O)=32变为掺杂后的ε1(O)=58;进一步分析了掺杂对CrSi2的能带结构、态密度和光学性质的影响,为CrSi2材料掺杂改件的研究提供r理论依据.     

Pressure-induced phase transition and electronic properties of AlN nanowires: an ab initio study

The structural stability of AlN nanowires have been analyzed in wurtzite (B4), zincblende (B3), rocksalt (B1) and CsCl (B2) type phases using density functional theory based ab initio approach. The total energy calculations have been performed in a self-consistent manner using local density approximation as exchange correlation functional. The analysis finds the B4 type phase as most stable amongst the other phases taken into consideration and observes the structural phase transition from B4?→?B3, B4?→?B1, B4?→?B2, B3?→?B1 and B3?→?B2 at 42.7, 76.54, 142, 30.4 and 108.9?GPa respectively. Lattice parameter, bulk modulus and pressure derivatives of AlN nanowires have also been calculated for all the stable phases. The electronic band structure analysis of AlN nanowires shows a semiconducting nature in its B4, B3 and B1 type phases, whereas the B2 type phase is found to be metallic.     

Electronic structure and physical properties of ScN in pressure: density-functional theory calculations

Local density functional is investigated by using the full-potential linearized augmented plane wave （FP-LAPW） method for ScN in the hexagonal structure and the rocksalt structure and for hexagonal structures linking a layered hexagonal phase with wurtzite structure along a homogeneous strain transition path. It is found that the wurtzite ScN is unstable and the layered hexagonal phase, labelled as ho, in which atoms are approximately fivefold coordinated, is metastable, and the rocksalt ScN is stable. The electronic structure, the physical properties of the intermediate structures and the energy band structure along the transition are presented. It is found that the band gaps change from 4.0 to 1.0 eV continuously when c/a value varies from 1.68 to 1.26. It is noticeable that the study of ScN provides an opportunity to apply this kind of material （in wurtzite[h]-derived phase）.     

GaN结构相变、电子结构和光学性质

运用第一性原理平面波赝势和广义梯度近似方法,对纤锌矿结构和氯化钠结构GaN的状态方程及其在高压下的相变进行计算研究,分析相变点附近的电子态密度、能带结构和光学性质的变化机制.通过状态方程和焓相等原理得到GaN从纤锌矿到氯化钠结构的相变压强分别为43.9 Gpa和46.0 Gpa;在相变的过程中,GaN由典型的直接带隙半导体转变为间接带隙半导体材料;氯化钠结构GaN相比于纤锌矿结构,介电函数主峰值增强,本征吸收边明显往高能方向移动,氯化钠结构GaN在低能区域的光学性质差于纤锌矿结构.     

氮化铝纳米线的高压同步辐射研究

利用金刚石对顶砧和同步辐射光源,对用电弧法制备的、具有纤锌矿结构的氮化铝(AlN)纳米线进行了最高压力达51.1 GPa的原位角散X射线衍射研究。结果表明:当压力上升至24.9 GPa时,纤锌矿结构的AlN纳米线开始向岩盐矿结构转变;当完全卸压后,最终的岩盐矿结构被保留下来;纤锌矿AlN纳米线的轴向比例c/a随压力增加而线性减小。AlN纳米线独特的线状结构决定了其区别于AlN微晶和AlN纳米晶的高压行为。     

BeO高压相变和声子谱的第一性原理计算

采用第一性原理方法计算了BeO在零温时的高压相变和三种结构在零温零压时的声子谱.相变的计算表明,在122GPa左右的压力下BeO会发生从纤锌矿(B4)结构到氯化钠(B1)结构的相变,而闪锌矿(B3)结构在零温零压下是一种可能的亚稳态结构.采用冷声子方法计算了这三种结构的BeO在零温零压下的声子谱.计算结果表明:B1结构在零温零压下是一种不稳定的结构;尽管B4结构和B3结构具有明显的相似性,仍然可以通过声子谱来很好的区分.最后根据准简谐近似理论计算得到了BeO的高温高压相图.     

Amorphous boron nitride at high pressure

The pressure-induced phase transformation in hexagonal boron nitrite and amorphous boron nitrite is studied using ab initio molecular dynamics simulations. The hexagonal-to-wurtzite phase transformation is successfully reproduced in the simulation with a transformation mechanism similar to one suggested in experiment. Amorphous boron nitrite, on the other hand, gradually transforms to a high-density amorphous phase with the application of pressure. This phase transformation is irreversible because a densified amorphous state having both sp³ and sp² bonds is recovered upon pressure release. The high-density amorphous state mainly consists of sp³ bonds and its local structure is quite similar to recently proposed intermediate boron nitrite phases, in particular tetragonal structure (P4₂/mnm), rather than the known the wurtzite or cubic boron nitrite due to the existence of four membered rings and edge sharing connectivity. On the basis of this finding we propose that amorphous boron nitrite might be best candidate as a starting structure to synthesize the intermediate phase(s) at high pressure and temperature (probably below 800 °C) conditions.     

Phase Relations and EOS of ZrO 2 and HfO 2 Under High-temperature and High-pressure

The phase relations and equations of state of ZrO 2 and HfO 2 high-pressure polymorphs have been investigated by means of in situ observation using multi-anvil type high-pressure devices and synchrotron radiation. Baddeleyite (monoclinic ZrO 2 ) transforms to two distorted fluorite (CaF 2 )-type phases at 3-4 GPa depending on temperature: an orthorhombic phase, orthoI, below 600 °C and a tetragonal phase, which is one of the high-temperature forms of ZrO 2 , above 600 °C. Both orthoI and tetragonal phases then transform into another orthorhombic phase, orthoII, with a cotunnite (PbCl 2 )-type structure above 12.5 GPa and the phase boundary is almost independent of temperature. OrthoII is stable up to 1800 °C and 24 GPa. In case of HfO 2 , orthoI is stable from 4 to 14.5 GPa below 1250-1400 °C and transforms to the tetragonal phase above these temperatures. OrthoII of HfO 2 appears above 14.5 GPa and is stable up to 1800 °C at 21 GPa. The unit cell parameters and the volumes of these high-pressure phases have been determined as functions of pressure and temperature. The orthoI/tetragonal-to-orthoII transition of both ZrO 2 and HfO 2 is accompanied by about 9% volume decrease. The bulk moduli of orthoII calculated using Birch-Murnaghan's equations of state are 296 GPa and 312 GPa for ZrO 2 and HfO 2 , respectively. Since orthoII of both ZrO 2 and HfO 2 are quenchable to ambient conditions, these are candidates for super-hard materials.     

First principle study of nitrogen vacancy in aluminium nitride

In the framework of density functional theory, using the plane-wave pseudopotential method, the nitrogen vacancy ($V_{\rm N})$ in both wurtzite and zinc-blende AlN is studied by the supercell approach. The atom configuration, density of states, and formation energies of various charge states are calculated. Two defect states are introduced by the defect, which are a doubly occupied single state above the valance band maximum (VBM) and a singly occupied triple state below the conduction band minimum (CBM) for wurtzite AlN and above the CBM for zinc-blende AlN. So $V_{\rm N}$ acts as a deep donor in wurtzite AlN and a shallow donor in zinc-blende AlN. A thermodynamic transition level $E({3 + } \mathord{\left/ {\vphantom {{3 + } + }} \right. \kern-\nulldelimiterspace} + )$ with very low formation energy appears at 0.7 and 0.6eV above the VBM in wurtzite and zinc-blende structure respectively, which may have a wide shift to the low energy side if atoms surrounding the defect are not fully relaxed. Several other transition levels appear in the upper part of the bandgap. The number of these levels decreases with the structure relaxation. However, these levels are unimportant to AlN properties because of their high formation energy.     

Specific features of Raman spectra of III–V nanowhiskers

Raman spectra of GaAs nanowhiskers that are grown on different substrates and differ from one another by the content of the sphalerite and wurtzite phases have been investigated. Special attention has been focused on the manifestation of structural features in the scattering spectra of nanowhiskers. It has been established that the nanowhiskers are characterized both by random inclusions of wurtzite layers in the sphalerite structure and by the continuous growth in the wurtzite phase. The interpretation of the scattering spectrum agrees with the concept of summation of the dispersion curves of the sphalerite structure upon transition to the wurtzite structure, which leads to a transformation of zone-boundary modes at the L point of the Brillouin zone into zone-center modes of the wurtzite structure and, as a consequence, to the appearance of a number of new fundamental modes of different symmetries. An analysis of the Raman spectra has revealed the formation of the hexagonal 4H polytype in narrow layers of nanowhiskers due to a random packing of hexagonal layers. The coexistence of the sphalerite and wurtzite phases in GaAs nanowhiskers completely correlates with the photoluminescence spectra measured for the same samples.     

Structural stabilities, electronic, elastic and optical properties of SrTe under pressure: A first-principles study

The structural, electronic, elastic and optical properties as well as phase transition under pressure of SrTe have been systematically investigated by first-principles pesudopotential calculations. Five possible phases of SrTe have been considered. Our results show that SrTe undergoes a phase transition from NaCl-type (B1) to CsCl-type (B2) structure at 10.9 GPa with a volume collapse of 9.43%, and no further transition is found. We find that SrTe prefer h-MgO instead of wurtzite (B4) structure for its metastable phase because that the ionic compound prefers a high coordination. The elastic moduli, energy band structures, real and imaginary parts of the dielectric functions have been calculated for all considered phases, and we find that a smaller energy gap yields a larger high-frequency dielectric constant. Our calculated results are discussed and compared with the available experimental and theoretical data.