KDP晶体本征中性点缺陷的第一性研究

 用第一性原理研究了KH2PO4(KDP)晶体中性本征点缺陷的形成能并计算了常温下点缺陷的浓度。计算得到中性填隙氢原子的形成能为2.05 eV,进而得到298 K下的浓度约为1.21×10^-17 mol/L。由于填隙氢原子在带隙中形成缺陷能级,并使能隙降低了2.6 eV, 因此消除填隙氢原子有利于提高晶体在355 nm附近的激光损伤阈值。计算得到的氧间隙、氧空位、钾空位和氢空位的形成能分别为0.60、5.25、6.50 和6.58 eV,常温下它们在晶体中也以较高的浓度存在。钾空位使晶胞体积增大约3.2%,并可能提高晶体电导率,从而降低光损伤阈值。P取代K的反位结构缺陷形成能尽管较低(4.1 eV), 但由于晶体生长溶液中P是以PO4四面体的形式存在,故此点缺陷的存在几率很小。     

用第一性原理研究K空位对KDP晶体激光损伤的影响

 用基于密度泛函理论及超软赝势的第一性原理研究了KH­­­₂PO₄(KDP)晶体中K空位的电子结构、形成能及驰豫构型。讨论了K空位形成后电荷密度的重新分布、相应的电子态密度和能带结构等性质。计算得到中性K空位的形成能为6.5 eV, 远小于间隙K原子点缺陷形成能13.07 eV。K空位的存在使晶胞体积增大, 分别沿结晶学轴a方向增大近0.8%, b方向增大近0.87%, c方向增大近1.2%，同时使与之配位的8个氧原子发生较大位移，使这8个氧形成的空腔体积增大近3.2%。空腔体积的增大不仅促进了各种点缺陷的扩散迁移，而且有利于其它杂质原子的填隙。K原子迁移率的增大会引起离子电导率的增大，因而会降低KDP的激光损伤阈值，因此从这个方面讲，K空位的存在是不利的。但是如果能从实验上（如热退火）利用K空位所造成的扩散通道排出或改善缺陷结构，则可提高KDP晶体的光学质量。     

锐钛矿型TiO2(101)面本征点缺陷的理论研究

采用平面波超软赝势方法计算了锐钛矿型TiO₂(101)面存在本征空位和间隙点缺陷的几何结构以及缺陷形成能.首先分析了点缺陷对表面结构的影响,发现不同类型缺陷导致缺陷周围原子有不同的位移趋势：O空位的产生导致空位周围的Ti原子向空位外移动,Ti₁和Ti₂空位的产生均使O₁自发地与周围的O原子团聚,O_i原子易被周围的氧原子吸附而成键,而Ti_i2缺陷几乎 关键词： 第一性原理 2')" href="#">TiO₂ 点缺陷 表面结构     

不同荷电态替位缺陷Sp对磷酸二氢钾激光损伤的影响

采用第一性原理方法计算了KH₂PO₄(KDP)晶体中各种荷电态的硫取代磷替位缺陷(S_P)的几何驰豫构型及电子结构.讨论了该缺陷形成后电荷密度的重新分布、相应的电子态密度、能带结构等性质.主要结果为:虽然中性态、±1以及+2荷电态的S_p替位缺陷并没有在带隙中形成占据态,但它们削弱了SO₄基团与周围原子的结合力,从而形成相对孤立的SO₄基团,相对于无缺陷晶体而言,这种局域松散的结 关键词： 光学材料 晶体缺陷 激光损伤 第一性原理计算     

锐钛矿二氧化钛体相缺陷的准粒子能带结构

Quasiparticle band structures of the defective anatase TiO₂ bulk with O vacancy, Ti interstitial and H interstitial are investigated by the GW method within many-body Green''s function theory. The computed direct band gap of the perfect anatase bulk is 4.3 eV, far larger than the experimental optical absorption edge (3.2 eV). We found that this can be ascribed to the inherent defects in anatase which drag the conduction band (CB) edge down. The occupied band-gap states induced by these defects locate close to the CB edge, excluding the possible contribution of these bulk defects to the deep band-gap state below CB as observed in experiments.     

Molecular dynamics simulation of defects production in the vicinity of voids

We report on the results of computer simulation of point defect production near voids in crystalline Cu at primary knock-on atom (PKA) kinetic energies ranging from 5 to 1000?eV. The PKA energy dependence of numbers of created defects are revealed. The threshold energy for a stable vacancy formation is found to be much smaller than that for an interstitial atom, which results in a biased formation of vacancies in the void proximity in the whole investigated range of PKA energies. Dissolution of small voids by subthreshold irradiation is simulated. The impact of considered radiation effects on kinetics of radiation damage is discussed.     

Intrinsic polyatomic defects in Sc2(WO4)3

The intrinsic formation of polyatomic defects in Sc₂(WO₄)₃-type structures is studied by Mott Littleton calculations and Molecular Dynamics simulations. Defects involving the WO₄²⁻ tetrahedron are found to be energetically favorable when compared to isolated W and O defects. WO₄²⁻ Frenkel and (2Sc³⁺, 3WO₄²⁻) Schottky defects exhibit formation energies of 1.23 eV and 1.97 eV, respectively and therefore may occur as intrinsic defects in Sc₂(WO₄)₃ at elevated temperatures. WO₄²⁻ vacancy and interstitial migration processes have been simulated by classical Molecular Dynamics simulations. The interstitial defect exhibits a nearly 10 times higher mobility (with a migration energy of 0.68 eV), than the vacancy mechanism (with a slightly higher migration energy of 0.74 eV) and thus should dominate the overall ionic conduction. Still both models reproduce the experimental activation energy (0.67 eV) nearly within experimental uncertainty.     

Point defects related to 260 K thermostimulated luminescence in α-Al2O3

Abstract

Thermo- and photostimulated processes are studied in reduced hydrogen containing α-Al₂O₃ excited by UV light. It is found that UV excitation in F absorption band at 90 K results in a ionization of the F-centers and capture of released electrons at defects thus producing an anisotropy absorption band at 4.2 eV and the dominant thermoluminescence (TL) peak at 260 K. The 260 K TSL peak is accompanied by complete bleaching of the 4.2 eV absorption band and vice versa—by light stimulation in the region of the 4.2 eV band the 260 K TSL peak disappear and released electrons recombine with F⁺-centers. Both the effect of the preliminary high-temperature thermal treatment of samples on formation of 4.2 eV-centers and the observed dichroism characteristics allows to conclude that corresponding complex defect contains hydrogen and can involve vacancy pair.     

四方相BaTiO3缺陷性质的第一性原理计算

采用基于密度泛函理论的第一性原理方法,研究了BaTiO₃在四方相下的各种缺陷性质.计算结果表明,在富氧环境下,钛的中性氧空位、分肖特基缺陷2V^3-_Ti+3V²⁺_O形成能分别为最低;而当体系处在还原环境下时,氧空位逐渐成为主要缺陷,其形成能最低.由于四方相下存在较强的Ti—O键共价杂化,四方相下全肖特基缺陷V^2-_Ba关键词： 缺陷 第一性原理 3')" href="#">BaTiO₃     

Zn$lt;sub$gt;1-$lt;i$gt;x$lt;/i$gt;$lt;/sub$gt;Mg$lt;sub$gt;$lt;i$gt;x$lt;/i$gt;$lt;/sub$gt;O薄膜的光致发光特性研究

采用脉冲激光沉积方法在单晶Si（100）衬底上制备出c轴取向的Zn_1-xMg_xO单晶薄膜,通过荧光光谱仪研究了薄膜的光致发光特性.实验结果表明,Mg含量增加,Zn_1-xMg_xO单晶薄膜的紫外发光峰蓝移,发光峰强度减弱,缺陷发光强度增强.同时发现,由于Mg的掺杂,引入了一些束缚能较大的局域束缚态.对于氧气氛下制备的样品,实验发现紫外峰和绿光带发光峰同时增强,但是R值减小,紫外峰红移.对绿光发光机理研究发现,绿光发光带主要与锌空位、氧间隙（O_i）或锌位氧（O_Zn）等缺陷有关,它是由多个缺陷发光峰组成,各缺陷发光峰强度相对变化导致了绿光发光带的整体移动. 关键词： 1-xMg_xO薄膜')" href="#">Zn_1-xMg_xO薄膜 光致发光 脉冲激光沉积     

质子对BaTiO3薄膜辐照损伤的计算机模拟

本文先应用分子动力学模拟BaTiO₃体系在初级击出原子(primary knock-on atom, PKA)轰击下缺陷产生和复合的动力学过程, 模拟结果表明：PKA的方向和能量对缺陷数目有重要影响, 并计算了Ba, O和Ti原子的平均位移阈能分别为69 eV, 51 eV和123 eV, 远大于SRIM程序默认的位移阈能25 eV. 然后应用蒙特卡罗软件包SRIM, 模拟质子在BaTiO₃薄膜中的能量损失过程, 比较位移阈能对模拟结果的影响, 分析质子能量和入射角度对空位数量以及分布的影响. 结果表明空位数量随着质子能量增加而增加, 增加的速率随能量的增加是降低的;当入射角度大于60°, 空位数量随入射角增大而明显减少.     

制备工艺对Zn1-xMgxO薄膜结构及光学性能的影响

采用脉冲激光沉积（PLD）方法在单晶Si（100）衬底上沿c轴方向生长单晶Zn_1-xMg_xO薄膜,通过X射线衍射（XRD）、原子力显微镜（AFM）、扫描电镜（SEM）和荧光光谱（PL）研究了膜厚、Mg含量、退火温度及氧气氛等制备工艺对Zn_1-xMg_xO薄膜的结构、形貌和光学性质的影响.实验结果表明,Mg含量x≤0.15时, Zn_{关键词： 1-x}Mg_xO薄膜')" href="#">Zn_1-xMg_xO薄膜 制备工艺 结构 光学性质     

Positron studies of hydrogen-defect interactions in proton irradiated molybdenum

Molybdenum single crystals are irradiated at 20 K with 6 MeV protons. The radiation damage and lattice defect annealing is studied by positron lifetime spectroscopy in the temperature range from 15 to 720 K. Loss of vacancies due to recombination with mobile interstitials is observed at 40 K (Stage I) in agreement with resistivity measurements. This is the first time Stage I is observed by positrons below 77 K. The implanted hydrogen decorates the vacancies around 100 K, which is consistent with a hydrogen migration energy in molybdenum:E _M ^H = 0.3–0.4 eV. Clustering of spatially correlated vacancies takes place in a wide temperature region below the usual vacancy clustering stage (Stage III). Stage III is observed at rather low temperatures (400–480 K) due to the very high vacancy concentration. Hydrogen bound to vacancies and vacancy clusters is released above 540 K, which puts an upper limit to the hydrogen binding energy:E _B ^H 1.4 eV. The present work emphasizes the advantage of employing a vacancy sensitive technique to study hydrogen in metals, where its intrinsic solubility is low. In such metals (as molybdenum) both the effective solubility and the effective mobility of hydrogen are strongly influenced by the presence of vacancies.     

Photoluminescence characterization of polycrystalline n-type Cu2O films

Electrodeposition was used to deposit Cu₂O thin films on ITO substrates. Photoresponse of the film clearly indicated n-type behavior of Cu₂O in photoelectrochemical cells. The temperature dependence of photoluminescence (PL) revealed that the spectra consist of donor-acceptor pair emissions and the recombination between electrons bound to donors and free holes. We observed that the dominant intrinsic defect, oxygen vacancies, creates a donor energy level at 0.38 eV below the bottom of the conduction band. As a result, this donor level acts as a center for both PL emissions and to produce n-type conductivity in the electrodeposited Cu₂O films. In addition, an acceptor energy level at 0.16 eV from the top of the valence band was observed.     

Electronic structures and optical properties of rutile TiO2 with different point defects from DFT + U calculations

The electronic states and formation energies of four types of lattice point defects in rutile TiO₂ are studied using the first-principles calculations. The existence of oxygen vacancy leads to a deep donor defect level in the forbidden band, while the Ti interstitial forms two local states. It is predicted that oxygen vacancy prefers to combine with Ti-interstitial to form V_O–Ti_i dimer by a partial 3d electron transfer from the Ti_i to its neighboring V_O. The charge distribution between a Ti interstitial and its neighboring Ti ions partially shields the Coulomb interactions. Lastly, optical properties of these defective lattices are discussed.     

Cooperative interactions in the lattice of LaF3-Type superionic crystals

The mechanism and energy parameters of cooperative interactions between point defects, vacancies, and interstitial ions, in the lattice of LaF3-type superionic trifluorides are studied. The mean energy of interaction between two pairs of the defects is determined (λ = 0.032 eV) in the dipole approximation. It is shown that cooperative interactions in the “quasi-liquid” lattice of LaF₃ decrease the defect formation energy down to values on the order of ≈kT.     

Si1-xGex合金半导体中CiCs和CiOi缺陷随Ge含量的变化

采用从头计算(ab initio)的方法对Si和Si_1-xGe_x合金半导体材料中C_iC_s缺陷的性质进行探讨,同时也对比调查了C_iO_i缺陷在Si和Si_1-xGe_x合金中的性质. 在不同Ge含量的Si_1-xGe_{x关键词： 1-x}Ge_x合金')" href="#">Si_1-xGe_x合金 从头计算法 iC_s缺陷')" href="#">C_iC_s缺陷 iO_i缺陷')" href="#">C_iO_i缺陷     

Thermoelectric power measurements in polycrystalline AgI: Cd system

Thermoelectric power of polycrystalline AgI: Cd system was measured as a function of temperature from 50 to 180°C. The heat of transport $\text{Q}{}^1$, intrinsic vacancy concentration c_o and ratio of interstitial to vacancy mobilities in the β phase were deduced under the assumption of no association. The heat of transport $\text{Q}{}^1$ was also temperature dependent in β-AgI: 0.27 eV at 80°C, 0.21 eV at 100°C and 0.17 eV at 120°C. It was estimated that the formation energy of the defect pair h_F was 0.66 ± 0.06 eV and the activation energies for motion of vacancies and interstitials were 0.55 ± 0.03 and 0.38 ± 0.03 eV, respectively. These approximately agree with data reported up to date in single and poly- crystal β-AgI. The heat of transport of vacancies was approximately equal to the activation energy of vacancy migration.     

Energy dependence of electron-induced radiation damage in tungsten

Abstract

The energy dependence of low dose damage production in commercial and high purity polycrystalline tungsten wires was studied near 350 K with 1.6 to 2.4 MeV electrons. From resistivity measurements at 291 K the threshold energy for the onset of observable damage was determined as 50 × 2 eV. An ‘effective’ threshold of 52 ±2 eV was also determined by directly fitting the energy dependence of the damage rates to theoretical displacement cross sections calculated from step-function displacement probabilities. A decrease of two orders of magnitude in impurity content reduced damage rates by about a factor of two but did not affect threshold. These results combined with current defect recovery models for tungsten, low temperature threshold data, and computer-calculated bcc damage theory suggest: (1) Observed damage consisted of equal concentrations of vacancies and impurity-trapped Stage I free interstitials. (2) Across Stage II (100 K to 600 K) onset threshold should be within 50 ±2 eV. (3) Minimum recoil energy required for free interstitial production near 0 K is 53 ± 5 eV. (4) Threshold has little dependence on crystal direction. An empirical method is presented for predicting threshold energies in the bcc transition metals by assuming the directional dependence of threshold is directly proportional to that of Young's modulus. By the use of one universal proportionality constant (1.2 × 10^?11 eV.cm²/dyne), thresholds for a number of metals and directions are calculated and shown to have significantly better agreement with experiment than the best available theoretical estimates.     

Elucidating hydrogen assisting vacancy formation in metals: Mo and Nb as examples

Impurity H is inclined to be trapped by some defects with more space such as vacancy and grain boundary when it dissolves in a metal. Inversely, H can also enhance formation of large amount of vacancies even if there are few vacancies in intrinsic metals initially. Using first-principles simulation combined with statistical model, Mo and Nb as examples, we quantitatively calculate the concentration of vacancies including pure vacancy and H _n -vacancy (H _n V) complexes. The concentrations of vacancies in the form of H _n V notably increase due to the decrease of effective formation energy of vacancy from H stimulation. Our finding solves a long-standing puzzle on the atomistic mechanism underlying H assisting vacancy formation in some metals.