N空位、Ga空位对GaN∶Mn体系电磁性质和光学性质影响的第一性原理研究

基于密度泛函理论的第一性原理平面波超软赝势法分别计算了VGa和VN距掺入Mn原子为近邻、次近邻、远近邻各3种情况下GaN体系的电子结构和光学性质,分析比较了空位的不同位置对Mn掺杂GaN体系磁性的影响。计算结果表明,Mn掺杂会导致GaN体系带隙增大且体系表现为半金属铁磁性;VN的存在会增强缺陷复合物体系的铁磁性,且随着VN相对杂质Mn距离越近,体系总磁矩增加;而VGa的存在会降低缺陷复合物体系的铁磁性,且随Ga空位相对杂质Mn距离越近,体系总磁矩减少。不同位置的VGa和VN均会导致缺陷复合物体系主吸收峰和光吸收边相对于单Mn掺杂而言向低能方向移动,出现红移现象。     

Cu掺杂β-Ga2O3电子结构和磁学性质的第一性原理研究

采用基于密度泛函理论框架下的第一性原理方法,结合广义梯度近似研究了Cu掺杂β-Ga2O3系统的磁学特性。计算结果表明,单Cu的掺杂,稳定体系倾向于自旋极化态,且Cu替代八面体的Ga(B)时系统更稳定,容易在实验上形成;Cu掺杂β-Ga2O3呈现出半金属特性,Cu的掺杂引入了2.0μB磁矩,其中局域在Cu原子上的磁矩为0.45μB,其余主要来自于Cu杂质周围的氧原子。由于电荷补偿效应,在Cu掺杂β-Ga2O3系统中引入氧空位时,体系磁矩减小到零。在2个Cu取代Ga的10种构型中,A1-B3构型的能量最低,且显示出铁磁性,磁矩为3.8μB。考虑氧空位后,A1-B3构型的反铁磁性和铁磁性能量差增大,磁矩减小到1.0μB。     

Zn0．9O1-xCo0．1体系磁性和电子结构研究

在第一性原理框架理论下应用KKR-CPA-LDA方法计算了Zn0.9O1-xCo0.1体系(x=0～10%)下的电子结构、磁矩分布和3种不同的状态下的能量.结果表明:(1)在不同的氧空位缺陷的条件下,材料都显示半金属特性;(2)随着氧空位缺陷的增加,掺杂体系的能量逐渐升高,稳定性逐渐变弱,说明了基态条件下,Zn0.9O1-xCo0.1掺杂体系中的氧空位缺陷是不容易形成的,这个和文献报道的是一致的;(3)根据计算结果可以推断,在Zn0.9O1-xCo0.1体系中,磁性原子的磁矩随着氧空位缺陷的增加,体系的饱和磁化强度降低,符合双交换理论.     

受主掺杂 BaPbO3中的非化学计量比

采用高温平衡电导法测定了高温平衡电导率随氧分压（10^-12～10^5 Pa）的变化曲线,由此确定了未掺杂和Al受主掺杂BaPbO3陶瓷多晶体中的主导缺陷及其电荷补偿缺陷.同时讨论了受主掺杂浓度对材料的高温平衡电导率、高氧分压和低氧分压下主导缺陷转变点的影响,确定了受主掺杂BaPbO3缺陷行为随掺杂量的变化机理.在高氧分压下,材料表现出本征缺陷行为,Pb离子空位占主导,电荷补偿缺陷为空穴;随着氧分压的下降,材料由本征缺陷控制区域进入非本征缺陷控制区域,受主杂质取代Pb离子空位占主导;在低氧分压区域,随着氧离子空位浓度的上升,氧离子空位取代空穴,成为受主杂质的电荷补偿缺陷.     

缺陷对RRAM材料阻变机理的影响

基于密度泛函理论(DFT)的第一性原理和VASP仿真软件,分析了阻变随机存储器(RRAM)阻变效应的物理机制。对比计算了单斜晶相HfO2中Ag掺杂体系、氧空位缺陷体系和Ag及氧空位缺陷共掺杂复合缺陷体系的能带、态密度、分波电荷态密度面和形成能,结果表明在相同浓度下Ag掺杂体系能形成导电通道,而氧空位缺陷体系不能形成导电通道;共掺杂体系中其阻变机制以Ag传导为主,氧空位缺陷为辅,且其形成能变小,体系更加稳定。计算共掺杂体系的布居数和迁移势垒,得出在氧空位缺陷存在的前提下,Ag—O键长明显增加,Ag离子的迁移势垒变小,电化学性能增强。进一步计算了缺陷间的相互作用能,其值为负,表明缺陷间具有相互缔合作用,体系更加稳定。     

Mn双掺间距对ZnO磁光性能的影响

采用自旋密度泛函理论(DFT)下的广义梯度近似(GGA)平面波超软赝势法构建了含氧空位以及不含氧空位的Mn双掺ZnO超胞模型,分析了电子自旋极化处理下两个磁性Mn离子之间的距离变化(分为沿c轴和沿垂直c轴方向变化)对ZnO的结构稳定性、磁性以及吸收光谱的影响。随着磁性离子距离逐渐增大,无氧空位掺杂体系ZnO超胞的形成能沿着c轴和垂直c轴都逐渐减小,而含氧空位掺杂体系ZnO超胞的形成能沿垂直c轴方向逐渐减小,沿c轴方向逐渐增大;含氧空位和不含氧空位ZnO体系的反铁磁性随着Mn-Mn间距增大而减弱,沿着c轴方向减弱更加明显,而且氧空位促进体系的反铁磁性减弱;不含氧空位组态沿c轴方向吸收光谱发生了红移现象,而沿垂直c轴方向吸收光谱发生了蓝移现象;但是含氧空位组态沿c轴和沿垂直c轴方向吸收光谱都发生了红移。     

Ga掺杂前后LaCoO_3的电子结构研究

采用基于密度泛函理论(DFT)的第一性原理平面波超软赝势方法,结合局域自旋密度近似和Hubbard U修正,对不同Co离子自旋态下及Ga掺杂LaCoO_3的超晶胞体系进行了几何结构优化,计算并分析了它们的电子结构。结果表明,当Co离子处于低自旋态时,LaCoO_3为非磁绝缘性的绝缘体;当Co离子被激发到中间自旋态时,由于强烈的p-d轨道杂化作用,LaCoO_3转变成一个有磁性的半金属体;当Co离子处于高自旋态时,体系呈现金属铁磁性,磁矩由中间自旋态的0.91μB增大到高自旋态的2.2μB。Ga掺杂后,体系的Co3d态电子和Ga4p态电子以及O2p态电子在费米能级附近发生p-d轨道杂化,引入杂质带,形成受主能级,使体系的导电能力增强,体系呈现半金属铁磁性,其净磁矩为4.01μB。     

衬底温度对脉冲激光沉积在Si衬底上Zn0.95Co0.05O薄膜的影响

在不同的衬底温度下在n型Si(111)衬底上采用脉冲激光沉积的方法生长了(002)择优取向的具有室温铁磁性的Zn0.95Co0.05O薄膜。X射线衍射显示所生长的薄膜呈六方纤锌矿结构。X射线光电子能谱测试表明薄膜中出现的室温铁磁性不是由于Co团簇产生的。发现薄膜生长过程中产生的间隙锌、氧空位以及晶格缺陷对铁磁性有显著的影响。通过改变衬底温度可以控制薄膜中间隙锌、氧空位及晶格缺陷的数量,薄膜的铁磁性同时也可以被明显地改变,这是缺陷与薄膜的室温铁磁性相关的直接证据。     

Co掺杂CuAlO2粉体磁性的讨论

利用固态反应法合成了纯相的CuAlO2和过渡金属元素Co掺杂的CuAlO2样品。通过X射线衍射仪分析可知:未掺杂样品和1%(摩尔分数)Co掺杂的样品都是单相,其中没有CuO等杂相存在,而掺杂浓度分别为5%、10%和20%的样品中都出现了CuAlO2以外的杂相,这表明Co在CuAlO2粉体样品中的杂质固溶度一般低于5%。综合物性测试系统测得的与磁性有关数据表明:未掺杂及Co掺杂(1%)的纯相CuAlO2样品只具有顺磁性,而多相的Co掺杂样品从5～300K都没有表现出如第一性原理理论所预言的铁磁性,这说明样品中所掺入的Co离子只是具有局域磁矩的顺磁杂质中心,并不能形成长程的铁磁序,进一步表明基于第一性原理的理论计算可能高估了过渡金属磁性杂质在氧化物半导体这种关联体系中的铁磁耦合作用。     

Co掺杂CeO2稀磁氧化物陶瓷和纳米颗粒的铁磁性能

分别采用固相烧结法及激光液相烧蚀(LAL)技术,成功制备出Co掺杂CeO_2稀磁氧化物陶瓷块体和纳米颗粒。XRD和SEM研究发现所制备的材料具有良好的结晶性和形貌。Co掺杂CeO_2稀磁氧化物陶瓷块体和纳米颗粒均为多晶立方结构,与纯立方相的CeO_2结构相同,说明Co掺杂未形成其他结构和杂相。磁性测量表明固相烧结法和激光烧蚀液相法制备的Co掺杂CeO_2样品均具有较高的室温铁磁性,且远高于文献中报道的结果。将陶瓷块材经激光烧蚀成纳米颗粒后,纳米颗粒的铁磁性与陶瓷块材保持一致。这说明激光烧蚀法制备的纳米材料可以很好地保持母材的特性,是一种很好的纳米颗粒制备方法。根据XRD和SEM研究结果,笔者认为Co掺杂CeO_2陶瓷块材及纳米颗粒的室温铁磁性是内禀性质;磁性产生的机理源于氧空位诱导的铁磁性耦合。     

不同退火温度下Zn0.96Co0.04O薄膜的磁性研究

通过对磁控溅射方法制备的Zn_0.96Co_0.04O薄膜退火前后结构和磁性的研究发现,Co进入ZnO的晶格中并取代了Zn的位置,形成稀磁半导体结构,显示了室温铁磁性。后期真空退火可以产生更多的氧空位,提高BMP之间发生交叠的几率,从而使磁矩增大。因此可以认为氧空位是产生磁性的必要条件,其磁性来源机制符合J.M.D.Coey的BMP模型。     

Effect of oxygen vacancies on Li-storage of anatase $$\hbox {TiO}_{2}$$ (001) facets: a first principles study

Effect of oxygen vacancies on Li-storage of anatase \(\hbox {TiO}_{2}\) (001) facets was stimulated by density functional theory (DFT). The lattice parameters, adsorbed energy and energy barriers of \(\hbox {TiO}_{2}\) with oxygen vacancies were calculated. High adsorption energy of 5.91 eV for Li atoms indicates that oxygen vacancies have a positive effect on the Li storage of nanostructured anatase \(\hbox {TiO}_{2}\). The theoretical capacity was enhanced by an extra Li atom storaged at the oxygen vacancies.     

Controlled surface modification of boron nitride nanotubes

Controlled surface modification of boron nitride nanotubes has been achieved by gentle plasma treatment. Firstly, it was shown that an amorphous surface layer found on the outside of the nanotubes can be removed without damaging the nanotube structure. Secondly, it was shown that an oxygen plasma creates nitrogen vacancies that then allow oxygen atoms to be successfully substituted onto the surface of BNNTs. The percentage of oxygen atoms can be controlled by changing the input plasma energy and by the Ar plasma pre-treatment time. Finally, it has been demonstrated that nitrogen functional groups can be introduced onto the surface of BNNTs using an N(2) + H(2) plasma. The N(2) + H(2) plasma also created nitrogen vacancies, some of which led to surface functionalization while some underwent oxygen healing.     

High-temperature electrical conductivity of aluminium nitride

The electrical conductivity of hot-pressed polycrystalline aluminium nitride doped with oxygen and beryllium was measured as a function of temperature from 800 to 1200° C and over a range of nitrogen partial pressure from 10² to 10⁵ Pa. The effect of beryllium dopant, the independence of conductivity from nitrogen partial pressure, and the observed activation energy suggested extrinsic electronic species or aluminium vacancies as charge carriers. Polarization measurements made with one electrode blocking to ionic species indicated that the aluminium nitride with oxygen impurity was an extrinsic electronic conductor.     

Annealing temperature and oxygen-vacancy-dependent variation of lattice strain,band gap and luminescence properties of CeO2 nanoparticles

CeO₂ nanoparticles are annealed in vacuum at 200°C and in air at 200°C, 600°C and 1000°C, respectively. Vacuum-annealed CeO₂ contains high concentration of oxygen vacancies and exhibits very high lattice strain, whereas the corresponding values decrease on air annealing. Oxygen-deficient CeO₂ has redshift in band gap with high Urbach energy. The magnitude of this energy decreases as CeO₂ is annealed in air at 600°C. At 1000°C, thermal disorder increases the Urbach energy. Photoluminescence property of the samples depends on the presence of radiative and non-radiative oxygen vacancy centres. Vacuum-annealed ceria have large numbers of non-radiative oxygen vacancies that act as emission quencher. CeO₂ annealed at 600°C contains requisite amount of oxygen vacancies to show better luminescence property.     

Homojunction of Oxygen and Titanium Vacancies and its Interfacial n–p Effect

The homojunction of oxygen/metal vacancies and its interfacial n–p effect on the physiochemical properties are rarely reported. Interfacial n–p homojunctions of TiO₂ are fabricated by directly decorating interfacial p‐type titanium‐defected TiO₂ around n‐type oxygen‐defected TiO₂ nanocrystals in amorphous–anatase homogeneous nanostructures. Experimental measurements and theoretical calculations on the cell lattice parameters show that the homojunction of oxygen and titanium vacancies changes the charge density of TiO₂; a strong EPR signal caused by oxygen vacancies and an unreported strong titanium vacancies signal of 2D ¹H TQ‐SQ MAS NMR are present. Amorphous–anatase TiO₂ shows significant performance regarding the photogeneration current, photocatalysis, and energy storage, owing to interfacial n‐type to p‐type conductivity with high charge mobility and less structural confinement of amorphous clusters. A new “homojunction of oxygen and titanium vacancies” concept, characteristics, and mechanism are proposed at an atomic‐/nanoscale to clarify the generation of oxygen vacancies and titanium vacancies as well as the interface electron transfer.     

Intrinsically Optimizing Charge Transfer via Tuning Charge/Discharge Mode for Lithium–Oxygen Batteries

Lithium–oxygen batteries have an ultrahigh theoretical energy density, almost ten times higher than lithium‐ion batteries. The poor conductivity of the discharge product Li₂O₂, however, severely raises the charge overpotential and pulls down the cyclability. Here, a simple and effective strategy is presented for regular formation of lithium vacancies in the discharge product via tuning charge/discharge mode, and their effects on the charge transfer behavior. The effects of the discharge current density on the lithium vacancies, ionic conductivity, and electronic conductivity of the discharge product Li₂O₂ are systematically investigated via electron spin resonance, spin‐alignment echo nuclear magnetic resonance, and tungsten nanomanipulators, respectively. The study by density functional theory indicates that the lithium vacancies in Li₂O₂ generated during the discharge process are highly dependent on the current density. High current can induce a high vacancy density, which enhances the electronic conductivity and reduces the overpotential. Meanwhile, with increasing discharge current, the morphology of the Li₂O₂ changes from microtoroids to thin nanoplatelets, effectively shortening the charge transfer distance and improving the cycling performance. The Li₂O₂ grown in fast discharge mode is more easily decomposed in the following charging process. The lithium–oxygen battery cycling in fast‐discharge/slow‐charge mode exhibits low overpotential and long cycle life.     

Perovskites with Enriched Oxygen Vacancies as a Family of Electrocatalysts for Efficient Nitrate Reduction to Ammonia

Electrochemical nitrate reduction to ammonia (NRA) provides an efficient, sustainable approach to convert the nitrate pollutants into value-added products, which is regarded as a promising alternative to the industrial Haber–Bosch process. Recent studies have shown that oxygen vacancies of oxide catalysts can adjust the adsorption energies of intermediates and affect their catalytic performance. Compared with other metal oxides, perovskite oxides can allow their metal cations to exist in abnormal or mixed valence states, thereby resulting in enriched oxygen vacancies in their crystal structures. Here, the catalytic activities of perovskite oxides toward NRA catalysis with respect to the amount of oxygen vacancies are explored, where four perovskite oxides with different crystal structures (including cubic LaCrO₃, orthorhombic LaMnO₃ and LaFeO₃, hexagonal LaCoO₃) are chosen and investigated. By combining X-ray photoelectron spectroscopy, electron paramagnetic resonance spectroscopy and electrochemical measurements, it is found that the amount of oxygen vacancies in these perovskite oxides surprisingly follow the same order as their activities toward NRA catalysis (LaCrO₃ < LaMnO₃ < LaFeO₃ < LaCoO₃). Further theoretical studies reveal that the existence of oxygen vacancies in LaCoO₃ perovskite can decrease the energy barriers for reduction of *HNO₃ to *NO₂, leading to its superior NRA performance.     

Optical and Magnetic Properties of Half-metallic (Zn, Mn)O Behaviors with LDA and LDA-SIC Approximations

Based on first-principles spin-density functional calculations, the optical and magnetic properties of Mn-doped ZnO diluted magnetic semiconductors with acceptor defects by Zn vacancies (V_Zn) are studied, using the Korringa–Kohn–Rostoker method (KKR) combined with the coherent potential approximation (CPA). Ferromagnetic and half-metallic behaviors were observed and confirmed with the local-moment-disordered (LMD) state energy for local density approximation (LDA) and local density approximation-self-interaction correction (LDA-SIC). The mechanism of hybridization and the interaction between magnetic ions in P-type (Zn,?Mn)O are also investigated. Moreover, the optical absorption spectra obtained by ab-initio calculations confirm the ferromagnetic stability based on the charge state of magnetic impurities.     

First-principles study of A-site substitution in ferroelectric bismuth titanate

We employ density functional theory to investigate the effect of A-site rare earth substitution on the point defect formation in bismuth titanate (BIT) in the dilute substitution limit. Despite previous claims that the formation energy of neutral oxygen vacancies in La-substituted BIT (BLT) is higher than in pure BIT, our calculations show that this is only true for four out of the six distinct oxygen sites. Of these four sites, in two the difference is <0.1 eV while in the other two the difference is ~0.25 eV. In the case of +2 charged oxygen vacancies, in only two of the six distinct oxygen sites is the formation energy of the oxygen vacancy higher in BLT than in BIT, where they differ by ~0.14 eV. These results do not support the traditional explanation for the fatigue-free characteristic of BLT, which states that La substitution might avoid the ferroelectric fatigue of BIT by simply suppressing the formation of oxygen vacancies.