First-principles study of structural stability and elastic property of pre-perovskite PbTiO3

The structural stability and the elastic properties of a novel structure of lead titanate,which is named preperovskite PbTiO₃ （PP-PTO） and is constructed with TiO₆ octahedral columns arranged in a one-dimensional manner,are investigated by using first-principles calculations.PP-PTO is energetically unstable compared with conventional perovskite phases,however it is mechanically stable.The equilibrium transition pressures for changing from preperovskite to cubic and tetragonal phases are 0.5 GPa and 1.4 GPa,respectively,with first-order characteristics.Further,the differences in elastic properties between pre-perovskite and conventional perovskite phases are discussed for the covalent bonding network,which shows a highly anisotropic character in PP-PTO.This study provides a crucial insight into the structural stabilities of PP-PTO and conventional perovskite.     

Strain-induced ferroelectric phase transitions in incipient ferroelectric rutile TiO2

Uniaxial strain induced ferroelectric phase transitions in rutile TiO₂ are investigated by first-principles calculations. The calculated results show that the in-plane tensile strain induces rutile TiO₂, paraelectric phase with P_4-2/mnm (D_4h) space group, to a ferroelectric phase with P_m (C_s) space group,driven by the softening behaviour of the E_u1 mode. In addition, the out-of-plane tensile strain, vertical to the ab plane, leads to a ferroelectric phase with P_42nm (C_4v) space group, driven by the softening behaviour of the A_2u mode. The critical tensile strains are 3.7% in-plane and 4.0% out-of-plane, respectively. In addition, the in-plane compression strain, which has the same structure variation as out-of-plane tensile strain due to Poisson effect, leads the paraelectric rutile TiO₂ to a paraelectric phase with P_nnm (D_2h) space group driven by the softening behaviour of the B_1g mode. These results indicate that the sequence ferroelectric (or paraelectric) phase depends on the strain applied. The origin of ferroelectric stabilization in rutile TiO₂ is also discussed briefly in terms of strain induced Born effective charge transfer.     

一种获得半导体薄膜光学参数的方法

实现薄膜光学参数的简便测量对于薄膜的制备和应用具有重要意义。引入适用于半导体材料的Forouhi_Bloomer模型,用其表征薄膜折射率与色散的关系。考虑到粗糙度的影响,假设薄膜厚度服从正态分布,给出了模拟退火法与迭代法相结合、由可见光光谱测定薄膜光学参数的方法。作为尝试,以硅系薄膜为例进行了计算。结果表明,获得的厚度与用椭偏仪测量的结果较为吻合。该方法适用于研究和测量半导体薄膜的光学性能和膜厚,具有很高的实用价值。     

First-principles study of structural stability and elastic property of pre-perovskite PbTiO3

The structural stability and the elastic properties of a novel structure of lead titanate, which is named pre-perovskite PbTiO₃ (PP-PTO) and is constructed with TiO₆ octahedral columns arranged in a one-dimensional manner, are investigated by using first-principles calculations. PP-PTO is energetically unstable compared with conventional perovskite phases, however it is mechanically stable. The equilibrium transition pressures for changing from pre-perovskite to cubic and tetragonal phases are -0.5 GPa and -1.4 GPa, respectively, with first-order characteristics. Further, the differences in elastic properties between pre-perovskite and conventional perovskite phases are discussed for the covalent bonding network, which shows a highly anisotropic character in PP-PTO. This study provides a crucial insight into the structural stabilities of PP-PTO and conventional perovskite.     

薄膜生长初期多原子移动影响的模拟

模拟了在低温底上沉积单层薄膜初期的表面形貌．提出了新的算法，实现了多个原子同时在沉积基底上移动的过程，克服了以往只能模拟基底上仅有一个运动原于的缺点，同时引入了沉积流量，并在此基础上讨论了移动步数、沉积流量等因素对生长的影响作用．模拟结果与实验相近，获得的花样具有分形特征．     

锐钛矿相和金红石相Nb:TiO_2电学性质的GGA(+U)法研究

采用基于密度泛函理论第一性原理GGA和GGA+U相结合的方法研究了不同掺杂浓度下锐钛矿相和金红石相Nb:TiO2的晶体结构、电子结构以及稳定性.结果表明:锐钛矿相Nb:TiO2能带结构与简并半导体类似,呈类金属导电机理.金红石相Nb:TiO2呈半导体导电机理.Nb原子比Ti原子电离产生出更多的电子.锐钛矿相Nb:TiO2中Nb原子的电离率比金红石相Nb:TiO2的大.以上结果说明锐钛矿相Nb:TiO2比金红石相Nb:TiO2更适宜用作TCO材料;掺杂浓度对其杂质能级,费米能级和有效质量都有影响.Nb原子掺杂浓度越高,材料电离率呈降低趋势;形成能计算结果显示:在富钛条件下不利于Nb原子的掺杂,而在富氧条件下有利于Nb原子的掺杂.对于金红石相和锐钛矿相Nb:TiO2,不论是在贫氧或富氧条件下,随着Nb原子掺杂浓度的提高,形成能均增大.     

First-principles study of the influences of oxygen defects upon the electronic properties of Nb-doped TiO_2 by GGA + U methods

The influence of oxygen defects upon the electronic properties of Nb-doped TiO2has been studied by using the general gradient approximation(GGA)+U method. Four independent models(i.e., an undoped anatase cell, an anatase cell with a Nb dopant at Ti site(NbTi), an anatase cell with a Nb-dopant and an oxygen vacancy(NbTi+VO), and an anatase cell with a Nb-dopant and an interstitial oxygen(NbTi+Oi)) were considered. The density of states, effective mass, Bader charge, charge density, and electron localization function were calculated. The results show that in the NbTi+VOcell both eg and t2glevels of Ti 3d orbits make contributions to the electronic conductivity, and the oxygen vacancies(VO) collaborate with Nb-dopants to favor the high electrical conductivity by inducing the Nb-dopants to release more excess charges. In NbTi+Oi, an unoccupied impurity level appears in the band gap, which served as an acceptor level and suppressed the electronic conductivity. The results qualitatively coincide with experimental results and possibly provide insights into the preparation of TCOs with desirable conductivity.     

KED-ICP-MS法测定电子级丙二醇甲醚中的银、镉和铅

建立了电感耦合等离子体质谱法(ICP-MS)测定电子级丙二醇甲醚中银(Ag)、镉(Cd)和铅(Pb)含量的方法。样品经超纯水稀释后直接进样,采用标准加入法作为定量方法,选择待测同位素为¹⁰⁷Ag,¹¹¹Cd, ²⁰⁸Pb,并通过选择检测模式和碰撞/反应池气体流量有效消除质谱干扰。结果表明,在碰撞模式下利用动能歧视技术(KED), He流量为4 mL/min时,质谱干扰消除效果最佳。该方法的线性范围为0.2～5μg/L,线性相关系数大于0.9995,各元素检出限(LODs)为0.002～0.009μg/L,加标回收率为93.8%～104.2%,相对标准偏差(RSDs)小于9.5%。使用KED-ICP-MS法可以准确测定电子级丙二醇甲醚中Ag,Cd和Pb的含量。     

锐钛矿相和金红石相TiO2:Nb的光电性能研究

采用基于密度泛函理论的第一性原理计算了锐钛矿相和金红石相TiO₂:Nb的晶体结构、电子结构和光学性质. 结果表明, 在相等的摩尔掺杂浓度下(6.25%), 锐钛矿相TiO₂:Nb的导带底电子有效质量小于金红石相TiO₂:Nb, 且前者室温载流子浓度是后者的两倍左右, 即具有更大的施主杂质电离率, 从而解释了锐钛矿相TiO₂:Nb比金红石相TiO₂:Nb具有更优异电学性能的实验现象. 光学计算也表明锐钛矿相在可见光区有更大的透过率, 从而在理论上解释了锐钛矿相TiO₂:Nb比金红石相TiO₂:Nb更适于做透明导电材料的原因. 计算结果与实验数据能较好符合. 关键词： 2:Nb')" href="#">TiO₂:Nb 第一性原理 电子结构 光学性能     

ICP-MS测定电子级丙二醇甲醚中的钠、镁、钙、铁和铅含量EI北大核心CSCD

本方法结合冷等离子体技术和碰撞反应池技术,消除质谱干扰。采用标准加入法定量检测电子级丙二醇甲醚中5种金属元素。优化实验条件为射频功率冷等离子体750 W,热等离子体1550 W;钠、镁、钙、铁、铅载气流速分别为0.6, 0.6, 0.65, 0.7, 0.42 L/min;积分时间0.3 s;H2和He流速分别为2和3 mL/min。结果表明,钠、镁、钙、铁、铅在1~5μg/L范围内线性相关系数(R2)均不小于0.9996,检出限(LOD)为6~87 ng/L,加标回收率分别为95.4%~103.2%, 98.1%~101.6%, 88.3%~117.2%, 94.0%~99.7%和86.0%~91.4%,相对标准偏差(RSD)≤9.2%。