稀土元素(Nd/Sm/Gd/Dy)掺杂SnO2的第一性原理计算

基于密度泛函理论的第一性原理,计算分析了Nd、Sm、Gd和Dy四种稀土元素掺杂SnO2的电子结构和光学性质.计算结果表明:掺杂稀土元素Nd、Sm、Gd、Dy后,Sn7 XO16体系的晶胞体积及晶格常数都有不同程度的增大,禁带宽度减小,在费米能级附近出现了杂质能级.光学性质方面,掺杂稀土元素Nd、Sm、Gd、Dy后,体系的吸收边都向低能方向移动,发生了红移,拓宽了光谱响应范围,与未掺杂之前相比,掺杂稀土元素Nd后的静态介电常数减小,其余三种体系增大.     

Zn1-x HfxO的电子结构和光学性质的第一性原理计算

基于第一性原理密度泛函理论,计算分析了Zn1-xHfxO(x=0,0.0312,0.0417,0.0625和0.1250)体系的晶格结构、电子结构,Mulliken电荷布居和光学性质.计算结果表明,随着Hf掺杂摩尔百分比的增大,晶体体积膨胀,费米能级进入导带,其附近的导带部分主要由杂质原子Hf的5d态贡献,Hf-O离子键成分作用凸显,故Hf的掺杂引入施主能级进而形成n型ZnO材料的可能性较大.且通过比较吸收谱、反射谱和折射谱,发现适量掺入Hf原子可使ZnO体系在高能区的透过率增加,能量损失谱出现红移.这些性质均与实验中Hf掺杂有类似结果,由此可知适量掺杂Hf的ZnO体系有望在制备光电子器件等领域发挥作用.     

稀土元素(Ce/Nd/Eu/Gd)与N共掺金红石相TiO2的第一性原理研究

基于密度泛函理论的第一性原理平面波超软赝势计算方法,计算分析了纯金红石相TiO2,Ce、Nd、Eu和Gd四种稀土元素单掺杂金红石相TiO2,以及与N共掺金红石相TiO2的晶体结构、电子结构和光学性质.由掺杂前后的结果分析发现,掺杂后晶胞膨胀,晶格发生畸变;费米能级上移进入导带,导带底部引入杂质能级,提高了掺杂体系的电导率和对可见光的响应;光学性质、介电函数和吸收谱掺杂体系峰值比纯TiO2小,反射谱和能量损耗谱出现红移现象.     

Nd、N掺杂和Nd/N共掺杂锐钛矿相TiO2电子结构和光学性质的第一性原理研究

采用基于密度泛函理论的第一性原理研究了 N掺杂, Nd掺杂,和Nd/N共掺杂对锐钛矿相TiO2晶格参数、能带结构、电荷布居、电子态密度和光吸收性质的影响.结果表明,杂质的引入不同程度的改变了TiO2的晶格参数,Nd的掺杂使TiO6八面体畸变最大;N掺杂TiO2使带隙宽度减小,且在价带顶出现杂质能级;Nd掺杂和Nd/N共掺杂不仅使TiO2带隙宽度减小并在其价带和导带之间出现了空带,空带主要由Nd原子的4f轨道能级所贡献;由于禁带宽度的减小和杂质能级的出现使得掺杂后TiO2的吸收光谱的吸收边向可见光方向移动,增加了物质对光吸收的响应范围.     

Ni、Co掺杂对ZnTe电子结构影响的研究

研究了Ni、Co单掺杂ZnTe以及Ni-Co共掺杂ZnTe晶体材料的稳定性、磁性性质、能带结构、 态密度.结果发现:由杂质替换能分析得到Co掺杂体系的稳定性最强;掺杂都使ZnTe晶体体系产生磁性,磁性的主要起源主要是Co、Ni与Te原子d轨之间的相互耦合;Co、Ni、Co-Ni共掺杂ZnTe晶体体系的禁带中都出现杂质能级,使ZnTe晶体体系的导电能力增强;Co、Ni掺杂以及Co-Ni共掺杂ZnTe结构的态密度总体向低能区移动.     

S-La共掺杂ZnO性能的第一性原理研究

采用基于广义梯度近似的第一性原理方法,研究了纯ZnO、S单掺、La单掺和S-La共掺ZnO的能带结构、态密度和光学性质。S单掺ZnO后,价带和导带同时向低能量转移,导致带隙减小。La单掺ZnO后在导带底产生杂质能级使得带隙减小。S-La共掺ZnO导致La的局部化减弱,表明La形成的施主能级由于S的3p态的影响变得更浅,从而减小了带隙。和纯ZnO相比,掺杂后的ZnO吸收系数和反射系数都减小,导致透射能力增强,为ZnO作为透明导电氧化物应用于太阳能电池提供了潜在的理论依据。     

Ru、Rh、Pd掺杂GaSb的电子结构和光学性质

运用第一性原理计算方法研究了过渡族金属TM(TM=Ru、Rh、Pd)掺杂GaSb的电子结构和光学性质,结果表明:TM掺杂GaSb主要以TM替代Ga(TM @Ga)缺陷存在,并可增强GaSb半导体材料对红外光区光子的响应,使体系光学吸收谱的吸收边红移;TM@Ga所引入的杂质能级分布于零点费米能级附近,这极大地增强了体系的介电性能,促进了电子-空穴对的产生和迁移,因而提升了掺杂体系的光电转换效率;Ru 掺杂对GaSb光学性质的改善最为明显,当掺杂浓度为6.25%(原子数分数)且均匀掺杂时,Ru掺杂GaSb体系对红外光区光子的吸收幅度最大,有效提升了GaSb光电转换效率和光催化活性。     

Pt掺杂CdS光学性质的第一性原理研究

采用基于密度泛函理论的平面波超软赝势方法分析了CdS和Pt掺杂CdS的几何、电子结构和光学性质,计算结果表明Pt掺杂的CdS结构引入了由Pt贡献的导电载流子,增强了CdS的电导率,另外,费米能级下移进入价带.研究表明,Pt掺杂的CdS结构在费米能级附近出现了杂质能级,这是由Pt的5d态电子所形成;在光学性质上,Pt掺杂的CdS在可见光区的吸收系数比理想CdS高,能量损失峰出现红移现象,可见,Pt掺杂的CdS晶体具有更高的光催化活性.     

Hf/Ta/W单掺锐钛矿相TiO2的电子结构和光学性质的第一性原理研究

运用第一性原理赝势方法计算过渡金属X(Hf、Ta、W)单掺锐钛矿相TiO2后的电子能带结构、态密度和光学性质.计算结果表明,X掺锐钛矿相TiO2,使得掺杂后体系的体积增大,并随着X掺杂浓度的增加而增大;掺杂体系的禁带宽度都比纯TiO2的要小;由能带图可知,Ta、W单掺后,费米能级进入导带,说明这两种单掺体系属于N型半导体;随着不同浓度Hf、Ta、W的掺入,发现吸收光谱都发生了不同程度的红移,其中Ta、W掺杂体系的光响应范围覆盖了整个可见光区域,对比所有掺杂体系发现Ti0.9375 W0.0833 O2在可见光区域的光响应能力最强,这些现象说明X的掺入大大提升了TiO2光催化能力.     

第一性原理研究Cd掺杂对ZnO电子结构与光学性质的影响

采用第一性原理平面波超软赝势方法超软赝势方法,研究了Cd掺杂前后ZnO的电子结构以及光学性质.计算结果发现:Cd的掺入使得ZnO的电子结构发生了改变,晶胞变大,禁带宽度变窄.Cd掺杂使ZnO的光学性质也发生了变化,4.3 eV处的介电峰增强并发生红移,12.9 eV处的介电峰减弱,对紫外光吸收作用增强.     

Influence of oxygen, hydrogen, helium, argon and vacuum on the surface behavior of molten InSb, other semiconductors, and metals on silica

Sessile drop experiments were performed on molten indium antimonide on clean quartz (fused silica) surfaces. A cell was constructed through which argon, helium, oxygen, hydrogen or a mixture of these was flowed at 600 °C. Some of the InSb was doped with 0.1% Ga. The surface tension σ of oxide-free molten InSb was smaller in Ar than in He, may have increased with increasing O₂ in the gas, and was not influenced by Ga or H₂. The contact angle θ on silica was higher in the presence of Ar, was lowered by O₂, and was not influenced by H₂ or Ga. The work of adhesion W and the surface energy σ_sv of the silica were higher in He than in Ar. The surface remained free of solid oxide only in flowing gas containing 0.8 ppm O₂. This behavior is attributed to reaction of O₂ at the surface of the melt to form In₂O gas. When solid oxide formed on Ga-doped material, it was strongly enriched in Ga, with the Ga/In ratio increasing with the concentration of O₂ in the gas.

Examination of published sessile-drop results for liquid metals and semiconductors on silica revealed that W and σ_sv were highest for reactive melts, in which SiO₂ dissolves. For non-reactive melts, W and σ_sv were lower and θ higher in a gas than in a vacuum, regardless of whether the experiments had been carried out in sealed ampoules, a flowing gas, or dynamic vacuum. The implication is that the surface of silica was different in a vacuum than in a gas at 1 bar.     

La,Pr,Nd掺杂对纳米TiO2光催化性能的影响

采用水解共沉淀法制备了稀土元素(La, Pr, Nd)掺杂量为0.5wt;～1.5wt;的TiO2光催化剂样本,并对其进行了XRD、TG-DTA、TEM、BET和UV-Vis表征.结果表明,所制备的TiO2光催化剂是以锐钛矿晶型为主的纳米颗粒,掺杂抑制了TiO2晶型由锐钛矿向金红石的转变,同时减小了晶粒尺寸、增大了比表面积、提高了吸光度,且使TiO2半导体的吸光范围发生了红移.将制得的TiO2光催化剂应用于溶液中草酸的降解反应,用K2MnO4滴定法分析降解效率,发现经掺杂改性后的TiO2样本光催化效率均有提高.其中,以掺杂量为1.0wt;的La掺杂样本具有最高的降解效率,与纯TiO2样本相比对草酸的降解率提高了近45;.     

Topology-symmetry analysis of the mixed frameworks in the structures of phosphates, germanates, gallates, and silicates based on fundamental building blocks

A topology-symmetry analysis is performed for a number of phosphate, silicate, and germanate (gallate) structures. The fundamental structural unit of these structures is an {M(TO₄)₆} block consisting of the central octahedron sharing vertices with six tetrahedra. It is shown that, in the germanate, silicate, and gallate structures, the blocks are joined either through common vertices of the terminal tetrahedra or through additional Ge, Si, or Ga tetrahedra attached to the terminal tetrahedra with the formation of three-membered and six-membered rings or chains depending on the symmetry operations relating the blocks, i.e., with the formation of Ge, Si, or Ga tetrahedral radical anions. In the phosphate structures, the blocks are joined together only by sharing terminal tetrahedra in the neighboring blocks. This is caused by the higher charge of the P⁵⁺ central cation in the tetrahedron and by electrostatic interactions.     

π桥(π=Py、Tz、THF)对聚吡咯并吡咯二酮-联噻吩光电性能影响的第一性原理研究

本文在聚吡咯并吡咯二酮-联噻吩(PDPP-2T,P1)的基础上,分别选取了吡啶(Py)、噻唑(Tz)、呋喃(THF)三种基团构造D-π-A共聚物P2、P3、P4,并通过密度泛函(DFT)第一性原理计算了四种聚合物的光电性质.计算结果表明,引入π桥后,能带曲率变大,有利于提升共聚物导电性,但带隙均增大;光吸收峰的短波吸收峰均发生红移,P2与P4的长波峰发生蓝移,而P3的长波峰变化不大,且长波吸收峰的强度均减弱.并用Bader电荷分析研究了三种π桥对D、A单元之间的电荷转移量的影响,发现引入π桥后,P2、P3电荷转移量减少,P4略微增加;且π桥在共聚物中既可以是得电子单元,又可以是失电子单元,表明引入π桥对D/A共聚物的电荷传输有一定影响.总之,用引入π桥的方法来提升共聚物的光电性质是一个需综合考虑的问题.     

氮气在M-g-C3N4(M=Fe,Co,Ni)表面吸附的第一性原理研究

利用第一性原理密度泛函理论方法计算研究了N2分子在M-g-C3 N4(M=Fe,Co,Ni)上的吸附,研究计算了M-g-C3 N4-N2(M=Fe,Co、Ni)构型的吸附能、结构参数以及电子性质.结果表明,N2分子可以吸附在M-g-C3 N4(M=Fe,Co,Ni)的金属上,并且延长了N≡N叁键键长.根据吸附后电子态密度的分析表明,过渡金属Fe、Co、Ni能很好的活化N2分子.同时,从差分电荷密度图上可以看出过渡金属Fe、Co、Ni与N2分子之间发生了电子的转移,电子由过渡金属Fe、Co、Ni转移到N2分子上.     

Ti,Fe离子掺杂对水热法合成蓝宝石晶体的影响

本文研究了掺杂Fe、Ti离子对水热条件下合成α-Al2O3晶体的颜色和晶体形态的影响.在较低温度(430℃)和较低压力(40MPa)下合成出了蓝色刚玉晶体.在未掺入其他的离子时,水热反应生成透明α-Al2O3六棱柱形晶体.当在反应介质中加入FeSO4*7H2O时,水热反应生成黑色α-Al2O3晶体,晶体呈六棱柱体.加入FeSO4*7H2O和TiCl3时,生成的蓝色宝石晶体显露高指数晶面,晶体长度300μm,另外还生成大量的薄水铝石晶片.加入FeSO4*7H2O和TiCl4时,蓝宝石晶体显露底面{0001},柱面{1120},和菱面{1123},最大的孪晶长度为200μm,最小的晶粒只有2μm;同样有大量的薄水铝石晶片生成,还伴生有少量针状TiO2金红石晶体.     

Effect of polymerization on the boson peak, from liquid to glass

Reactive epoxy-amine mixtures during isothermal polymerization have been characterized by Raman scattering measurements in order to follow the modification of the vibrational density of states. In the initially liquid solutions an increasing number of Van der Waals bonds are replaced by stiffer covalent bonds. During the chemical reaction, the molecular diffusion slows down and ultimately the systems are frozen in a glassy structure. The transformation from reactive liquids to chemical glasses is accompanied by microscopic structural changes driven by the bonding process. During the reaction the samples density and the sound velocity increase, both of them contribute to significantly change the Debye level. By combining Raman with Brillouin inelastic X-ray scattering measurements, we compare the relative variations of the boson peak with that of the Debye level. We find that the shift and intensity variation of the boson peak are fully explained by the modification of the elastic properties of the medium and a boson peak master curve is obtained.     

DAST晶体的表面形貌、缺陷及显微硬度研究

利用自行合成的4-(4-二甲基氨基苯乙烯基)甲基吡啶对甲基苯磺酸盐(DAST)原料,用斜板法生长出了一定尺寸的DAST晶体.用X射线衍射仪(XRD)对所得样品进行了表征,用光学显微镜观察了不同晶体(001)面的形貌特征并对其进行了分析,对不同腐蚀剂作用下的腐蚀坑的特点和成因进行了研究,测定了不同载荷下DAST晶体(001)面的显微硬度值.     

非线性光学晶体BaBPO5的生长、结构研究

本文采用顶部籽晶高温溶液法,以Li4P2O7为助熔剂,生长了大尺寸BaBPO5单晶.进行了BaBPO5晶体的结构测定,结果表明该晶体属三方晶系,空间群:P3221,晶胞参数为a=b=0.71329(10)nm,c=0.70368(14)nm,α=β=90°,γ=120°, Z=3.该晶体结构中沿[001]方向存在BO4四面体链,每一个硼氧四面体用它的两个顶点分别与两个PO4四面体相连组成螺旋状的链.硼氧四面体、磷氧四面体和钡氧多面体结合在一起形成一个三维网络结构.同时,对BaBPO5的粉末倍频效应进行了研究.