N掺杂Cu2O薄膜的光学性质及第一性原理分析

采用射频磁控溅射技术, 在不同温度下制备了N掺杂Cu₂O薄膜．透射光谱分析发现, N掺杂导致Cu₂O成为允许的带隙直接跃迁半导体, 并使Cu₂O的光学禁带宽度增加．不同温度下沉积的薄膜光学禁带宽度E_g=2.52± 0.03 eV．第一性原理计算表明, N掺杂导致Cu₂O的禁带宽度增加了约25%, 主要与价带顶下移和导带底上移有关, 与实验报道基本符合．N的2p电子态分布不同于O原子, 在价带顶附近具有较大的态密度是N掺杂Cu₂O变成允许的带隙直接跃迁半导体的根本原因．     

第一原理研究Sn(O1-xNx)2材料的光电磁性质

基于第一原理的密度泛函理论, 以量子化学从头计算软件 为平台研究了Sn(O_1-xN_x)₂材料的光电磁性能, 分析了体系的态密度、 能带结构、 磁性、 介电虚部及折射率. 计算结果表明, N替代O后, 随着掺杂浓度的增加, 体系的带隙先减小后增大, 掺杂量为12.50%时带隙最窄. 由于N 2p轨道电子的贡献, 在0.55-1.05 eV范围内产生了浅受主能级, 价带和导带处的能级均出现了劈裂及轨道的重叠现象, Sn-O键的键强大于N-O键的键强. 从磁性来看, N原子决定了磁矩的大小. 从介电虚部可知, 掺杂后体系的光学吸收边增宽, 主跃迁峰发生红移, 反射率和介电谱相对应, 各峰值与电子的跃迁吸收有关.     

使用金属掺杂SnO2(110)作为表面催化剂的电催化CO2还原反应：通过调控Sn:O原子比例来控制产物

电催化CO₂还原反应可以产生HCOOH和CO,目前该反应是将可再生电力转化为化学能存储在燃料中的最有前景的方法之一. SnO₂作为将CO₂转换为HCOOH和CO的良好催化剂,其反应发生的晶面可以是不同的. 其中(110)面的SnO₂非常稳定,易于合成. 通过改变SnO₂(110)的Sn:O原子比例,得到了两种典型的SnO₂薄膜：完全氧化型(符合化学计量)和部分还原型. 本文研究了不同金属(Fe、Co、Ni、Cu、Ru、Rh、Pd、Ag、Os、Ir、Pt和Au)掺杂的SnO₂(110),发现在CO₂还原反应中这些材料的催化活性和选择性是不同的. 所有这些变化都可以通过调控(110)表面中Sn:O原子的比例来控制. 结果表明,化学计量型和部分还原型Cu/Ag掺杂的SnO₂(110)对CO₂还原反应具有不同的选择性. 具体而言,化学计量型的Cu/Ag掺杂的SnO₂(110)倾向于产生CO(g),而部分还原型的表面倾向于产生HCOOH(g). 此外,本文还考虑了CO₂还原的竞争析氢反应. 其中Ru、Rh、Pd、Os、Ir和Pt掺杂的SnO₂(110)催化剂对析氢反应具有较高的活性,其他催化剂对CO₂还原反应具有良好的催化作用.     

Li掺杂8-羟基喹啉铝的密度泛函理论研究

采用密度泛函理论研究了Li原子掺杂8-羟基喹啉铝(Alq₃)分子的几何构型、 前线分子轨道及电子转移特性. 研究结果表明, Li原子掺杂Alq₃后, Li原子与Alq₃的O, N原子键合, 形成电子转移复合物. Li原子将部分电子转移到Alq₃的吡啶环上, 在Alq₃的带隙内形成施主能级, 这种n型掺杂结构有效地提高了电子的传输效率; 但过多的Li原子的掺杂会使Alq₃分解, 从而减弱其电子传输能力. 为使Alq₃的电子传输能力达到最高, Li原子的掺杂应保持在2:1左右的比例.     

过渡金属Fe或Ag掺杂K2Ti6O13的电子结构和光学性质

本文利用基于密度泛函理论（DFT）的第一性原理计算研究了它们的电子结构和光学性质.光学性质的计算结果和实验相一致.结果表明,Fe或Ag掺杂后,K₂Ti₆O₁₃的带隙中出现了杂质带且其带隙值变小,因而使掺杂后的K₂Ti₆O₁₃的吸收边发生红移并实现了其对可见光吸收.其中杂质带主要由Fe 3d态或Ag 4d态与Ti 3d态和O 2p态杂化而成.对于Fe掺杂的K₂Ti₆O₁₃,杂质带位于带隙中间,因此可以作为电子从价带跃迁到导带的桥梁.对于Ag掺杂的K₂Ti₆O₁₃,杂质带位于价带顶附近为受主能级,可以降低光生载流子的复合概率.实验和计算研究表明,通过Fe或Ag的掺杂可以实现了K₂Ti₆O₁₃对可见光的吸收,这对进一步研究K₂Ti₆O₁₃的光学性质具有重要意义.     

In掺杂ZnO电子结构的第一性原理研究

采用第一性原理平面波超软赝势,计算了纤锌矿ZnO和不同掺杂量下In掺杂ZnO晶体的能带结构、态密度和分波态密度.计算表明,In的掺杂导致ZnO禁带宽度变窄.随着掺杂量的增大,In_xZn_1－xO的导带底和价带顶同时下降,但是导带底比价带顶下降得多,这导致了带隙的变窄.此外,In掺杂使晶胞晶格常数增大,这对带隙的变窄也有一定作用.     

Cd掺杂纤锌矿ZnO电子结构的第一性原理研究

采用密度泛函理论结合投影缀加波方法，对掺杂Cd导致ZnO禁带宽度下降的机理进行了研究. 通过对掺杂前后电子能带结构，态密度以及分态密度的计算和比较，发现Cd_xZn_1-xO价带顶端(VBM)始终由O-2p占据；而导带顶端(CBM)则由Cd-5s与Zn-4s杂化轨道控制. 随着掺杂浓度的增加，决定带隙宽度的CBM的位置下降，同时VBM的位置上升，从而导致了带隙的变窄，出现了红移现象. 此外，Cd掺杂会使晶胞发生膨胀，这种张应变也是导致Cd     

共轭低聚物中光生分子间电荷转移态的第一性原理研究

本文基于第一性原理中的Heyd-Scuseria-Ernzerh方法研究了单层In_1-xGa_xN的电子结构和光学性质.计算得到单层In_1-xGa_xN的能带结构和态密度（DOS）,发现随着掺杂比例的变化,体系带隙的变化范围是1.8~3.8 eV,表明通过Ga的掺杂可以实现体系带隙值的调节.并且还研究了单层In_1-xGa_xN的介电函数,折射率和吸收系数等光学性质,结果表明随着Ga掺杂浓度的增加,介电函数谱的主峰和吸收谱发生了显著的蓝移.此外,基于能带结构和态密度图谱,对单层In_1-xGa_xN的光学性质进行分析,预测这种材料独特的光学性质在纳米电子学和光学器件中会有广泛的应用.     

Fe, S共掺杂SnO2材料第一性原理分析

本文采用基于第一性原理的全电势线性缀加平面波(FP-LAPW)法, 计算了Fe, S两种元素共掺杂SnO₂材料的电子结构和光学性质. 结果表明: 材料仍为直接禁带半导体, 体系呈现半金属性; Fe, S共掺可以窄化带隙, 且随S浓度增加, 态密度向低能方向移动, 带隙减小; 共掺体系电荷密度重新分布, 随S浓度增加, Fe原子极化程度增强, 原子间键合能力增强. 共掺后介电函数虚部谱与光学吸收谱各峰随S浓度增加而发生红移, 光学吸收边减小.     

非晶SnO2：(Cu，In)薄膜的荧光特性及带尾态

用反应蒸发法在玻璃等衬底上制备出铜和铟掺杂的氧化锡SnO₂：(Cu,In)薄膜.对制备薄膜的发光性质做了研究,制备样品为非晶态,具无定形结构.测量了薄膜在220—1100nm范围的透过率,得到的带隙宽度E^opt_g=4.645eV.室温条件下对样品进行光致发光测量,得到了显著的紫外(276—550nm)蓝绿光连续谱,通过发光谱的研究给出了这种材料的隙态分布.     

First principle study on the electronic structure of fluorine-doped SnO2

The electronic properties of fluorine-doped SnO₂ films were calculated using the plane-wave-based pseudopotential method based on the density functional theory within the local density approximation. The calculated band structure and density of states show that the band gap of SnO₂ narrows due to the presence of the F impurity energy levels in the bottom of the conduction band. The energy of the valence electrons is reduced as the optical absorption edge shifts towards a higher frequency. The charge density and effective masses of carriers of fluorine-doped SnO₂ were also calculated.     

F掺杂SnO2电子结构的模拟计算

采用基于密度泛函理论的平面波赝势方法对SnO₂:F体系的电子结构进行了第一性原理模拟计算.用广义梯度近似方法优化SnO₂:F体系的晶胞结构，计算了体系基态总能.通过确定F掺杂对O的优先替代位置，计算了SnO₂:F的能带结构、态密度、分波态密度.分析了F掺杂对SnO₂晶体的电子结构和晶体性质及光学吸收边的影响，从理论上得出光学吸收边发生蓝移.对不同掺杂量的体系电子结构进行了分析. 关键词： F掺杂 2')" href="#">SnO₂ 电子结构 态密度     

The study of optical properties of amorphous thin films of mixed oxides In<Subscript>2</Subscript>O<Subscript>3</Subscript>—SnO<Subscript>2</Subscript> system,deposited by co-evaporation

A discussion of optical properties of mixed oxides In₂O₃—SnO₂ system is presented. Film thickness, substrate temperature, composition (in molar %) and annealing have a profound effect on the structure and optical properties of these films. Initially the increase in band gap with the increase of SnO₂ content in In₂O₃ is due to the increase in carrier density as a result of donor electrons from tin. The decrease in band gap above the critical Sn content is caused by the defects formed by Sn atoms, which act as carrier traps rather than electron donors. The increase in band gap with film thickness is caused by the increase in free carrier density which is generated by (i) Sn atom substitution of In atom, giving out one extra electron and (ii) oxygen vacancy acting as two electrons donor. The decrease in band gap with substrate temperature and annealing is due either to the severe deficiency of oxygen, which deteriorate the film properties and reduce the mobility of the carriers, or to the formation of indium species of lower oxidation state (In²⁺).     

SnO$lt;sub$gt;2$lt;/sub$gt;纳米晶体的制备、结构与发光性质

使用软化学方法在碱性溶液中制备出了颗粒尺寸分布均匀的SnO₂纳米颗粒,使用透射电子显微镜（TEM）、X射线衍射（XRD）、光致发光谱（PL）和光吸收谱等方法分析与表征了SnO₂纳米颗粒的结构和光学性能.实验中通过表面活性剂的加入来控制纳米颗粒的结晶与凝聚.XRD,TEM的结果表明,原始制备出的SnO₂纳米颗粒的平均粒径小于4 nm,为完好的晶体状态.纳米颗粒经过400—1000 ℃退火后晶粒尺寸进一步增大.光吸收谱表明,相对于体材料,纳米颗粒的禁带宽度展宽并随颗粒尺寸增大而红移.光致发光谱测试表明,不同温度下退火的SnO₂纳米颗粒在350—750 nm有较强的发光,研究表明这是来源于颗粒表面的氧空位缺陷发光. 关键词： 氧化锡 表面活性剂 纳米颗粒 光致发光     

The role of Co impurities and oxygen vacancies in the ferromagnetism of Co-doped SnO2: GGA and GGA+U studies

The electronic structure and ferromagnetic stability of Co-doped SnO₂ are studied using the first-principle density functional method within the generalized gradient approximation (GGA) and GGA+U schemes. The addition of effective U_Co transforms the ground state of Co-doped SnO₂ to insulating from half-metallic and the coupling between the nearest neighbor Co spins to weak antimagnetic from strong ferromagnetic. GGA+U_Co calculations show that the pure substitutional Co defects in SnO₂ cannot induce the ferromagnetism. Oxygen vacancies tend to locate near Co atoms. Their presence increases the magnetic moment of Co and induces the ferromagnetic coupling between two Co spins with large Co-Co distance. The calculated density of state and spin density distribution calculated by GGA+U_Co show that the long-range ferromagnetic coupling between two Co spins is mediated by spin-split impurity band induced by oxygen vacancies. More charge transfer from impurity to Co-3d states and larger spin split of Co-3d and impurity states induced by the addition of U_Co enhance the ferromagnetic stability of the system with oxygen vacancies. By applying a Coulomb U_O on O 2 s orbital, the band gap is corrected for all calculations and the conclusions derived from GGA+U_Co calculations are not changed by the correction of band gap.     

Electronic structure and enhanced visible‐light absorption of N,B‐codoped TiO2

We present GGA+U calculations to investigate the electronic structure and visible‐light absorption of N,B‐codoped anatase TiO₂. The N_sB_i (substitutional N, interstitial B) codoped TiO₂ produces significant Ti 3d and N 2p mid‐gap states when the distance of N and B atoms is far, whereas the N_iB_i (interstitial N and B) and N_sB_s (substitutional N and B) codoped TiO₂ prefer to form localized p states at 0.3–1.2 eV above the valence band maximum. Further, the optical band edges of the three codoped systems shift slightly to the visible region, but only the far‐distance N_sB_i codoped TiO₂ clearly shows an optical transition. These results indicate that N_sB_i codoped TiO₂ has a dominant contribution to the optical absorption of N,B‐codoped TiO₂. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

First-principles study of electronic structures and optical properties of Cu, Ag, and Au-doped anatase TiO2

We perform first-principles calculations to investigate the band structure, density of states, optical absorption, and the imaginary part of dielectric function of Cu, Ag, and Au-doped anatase TiO₂ in 72 atoms systems. The electronic structure results show that the Cu incorporation can lead to the enhancement of d states near the uppermost of valence band, while the Ag and Au doping cause some new electronic states in band gap of TiO₂. Meanwhile, it is found that the visible optical absorptions of Cu, Ag, and Au-doped TiO₂, are observed by analyzing the results of optical properties, which locate in the region of 400-1000 nm. The absorption band edges of Cu, Ag, and Au-doped TiO₂ shift to the long wavelength region compared with the pure TiO₂. Furthermore, according to the calculated results, we propose the optical transition mechanisms of Cu, Ag, and Au-doped TiO₂. Our results show that the visible light response of TiO₂ can be modulated by substitutional doping of Cu, Ag, and Au.     

Preparation and photovoltaic property of a new hybrid nanocrystalline SnO2/Polypyrrole p–n heterojunction

Hybrid photovoltaic structures based on transparent conductive SnO₂ and electrically conductive polypyrrole (PPy) were prepared. Nanocrystalline SnO₂ is considered an n-type barrier and window layer on p-type PPy layer in cell structures. The surface morphology and thickness of the layers were studied using scanning electron microscopy. The optical absorbance data showed an increase of absorbance in contrast with PPy and SnO₂. There was a red shift in absorbance wavelengths and a decrease in band gaps for the prepared PV structures. To investigate the electrical properties of the obtained structures, current-voltage characteristic was measured. The best structure showed an open-circuit voltage of 0.170?V, a short-circuit current density of 0.017?mA/cm², a fill factor of 0.36 and power conversion efficiency of 0.076.     

Optical band-edge absorption of oxide compound SnO2

Tin oxide (SnO₂) is an important oxide for efficient dielectrics, catalysis, sensor devices, electrodes and transparent conducting coating oxide technologies. SnO₂ thin film is widely used in glass applications due to its low infra-red heat emissivity. In this work, the SnO₂ electronic band-edge structure and optical properties are studied employing a first-principle and fully relativistic full-potential linearized augmented plane wave (FPLAPW) method within the local density approximation (LDA). The optical band-edge absorption α(ω) of intrinsic SnO₂ is investigated experimentally by transmission spectroscopy measurements and their roughness in the light of the atomic force microscopy (AFM) measurements. The sample films were prepared by spray pyrolysis deposition method onto glass substrate considering different thickness layers. We found for SnO₂ qualitatively good agreement of the calculated optical band-gap energy as well as the optical absorption with the experimental results.     

Nitrogen doping-mediated room-temperature ferromagnetism in insulating Co-doped SnO2 films

Co-doped SnO₂ films codoped with nitrogen (N) have been prepared by magnetron sputtering to investigate the effect of p-type defects on magnetic properties. The incorporation of N modifies the preferential growth orientation of the films. Multiple characterization techniques reveal that the incorporated Co²⁺ and N³⁻ ions substitute for Sn⁴⁺ and O²⁻ sites in SnO₂ lattice, respectively. As N concentration increases, the band gap of the films decreases because of the formation of Sn-N bond. Room-temperature ferromagnetism is observed in (Co, N)-codoped SnO₂ films, and the saturated magnetic moment is sensitive to the incorporated N concentration. The variations in the magnetic properties as a function of N concentration are discussed on the basis of bound magnetic polaron model.