金红石相TiO_2(110)面吸附H_2S分子光学气敏效应的微观机制与特性

光学气敏材料吸附气体分子后导致光学性质发生变化,运用这一原理来检测环境中的气体成分,称为光学气敏效应。采用基于密度泛函理论(DFT)体系下的第一性原理平面波超软赝势方法,研究了光学气敏材料金红石相TiO2(110)表面吸附H2S分子的微观特性,计算了TiO2(110)表面吸附能、电荷密度、态密度和光学性质的变化。结果表明,TiO2最稳定的表面是终止于二配位O原子的(110)面,只有含有氧空位的表面才能稳定吸附H2S,且氧空位比例越高,越有助于H2S吸附于表面;表面吸附H2S以水平吸附方式为主,在氧空位比例达到33%时,吸附能为0.7985eV;吸附的实质是表面氧空位具有氧化性,氧化了H2S分子。在可见光400~760nm范围内,存在氧空位的TiO2(110)表面吸附H2S后都可改善表面的光学性质。氧空位缺陷浓度越高,改善材料对可见光的吸收和反射能力越强,光学气敏响应能力越佳。     

N/Rh共掺杂金红石TiO_2表面对CO气体光学气敏传感特性的影响

采用基于密度泛函理论的第一性原理平面波超软赝势方法计算了金红石TiO_2(110)纯净表面以及掺杂N、掺杂Rh和N/Rh共掺表面吸附CO分子后的光学气敏传感特性。研究发现:纯净和掺杂表面吸附CO分子后均表现出光学气敏传感特性,其原因是表面氧空位的氧化作用;而N/Rh共掺杂对表面氧化性改善得最多,吸附CO分子后吸附距离最小,吸附能最大,稳定性最好,且易于实现。因此,相比于纯净及单掺杂体系,N/Rh共掺杂表面对气体有更好的光学气敏传感效应,是一种改进TiO_2光学气敏传感材料的良好方式。     

O2分压和退火对TiO2/SiO2纳米多层膜结构和光学性能的影响

利用Mass软件设计了TiO2/SiO2纳米多层光学增透膜膜系,并采用高真空电子束蒸发系统在不同O2分压条件下制备了TiO2/SiO2纳米多层膜,TiO2/SiO2薄膜多层膜体系在沉积条件下获得了很好的宽光谱光学透射性能,在可见光谱范围内透射率接近设计值,平均透射率达到90%以上。通过一系列测试方法对多层膜退火前后的透射率、组分结构和退火以后的残余应力以及表面形貌进行了研究。实验结果表明:在较高O2分压条件下,由于多层膜结构中O空位的减少,使得多层膜透射率逐渐增加。在退火条件下,随着退火温度的增加,导致了表面均方根粗糙度(RMS)的增加以及晶粒的聚集长大,500℃时多层膜组分结晶化明显加强,使得缺陷增多;同时受退火温度的影响,残余应力逐渐增加,组分相互扩散加剧使得多层膜界面受到破坏。这些因素最终导致TiO2/SiO2多层膜的透射率逐渐降低。     

双电子CO2模型及其高次谐波模拟

根据三原子CO2分子的电子结构,建立了双电子一维模型,采用对称分裂算符法求解含时薛定谔方程,计算了CO2分子模型体系在800nm波长脉冲激光激发下的高次谐波(HHG)谱。结果发现,该模型计算量适中,可很好地描述CO2分子的HHG谱性质,用于激发HHG的激光脉冲宽度对HHG谱性质影响很大,多正电中心导致HHG谱呈现干涉相消现象。     

掺杂纳米SnO2气敏传感器的研究进展

介绍了半导体气敏传感器的发展历史和掺杂纳米SnO2气敏传感器的特性与应用;详细分析了掺杂金属单质、金属氧化物和稀土元素对SnO2气敏性的影响,通过掺杂可以显著改善其对特定气体的灵敏度、稳定性和选择性等参数;利用元件表面的氧吸附理论分析掺杂纳米SnO2的气敏机理;展望了SnO2气敏传感器的发展前景.     

ZnO/TiO2多层薄膜氨气敏光学特性研究

介绍用SG法制备了ZnO/TiO2多层薄膜的方法,研究了在几种还原性气体中的气敏透射光谱,发现其对氨气具有优良的选择性,且其光学透过率在一定浓度范围内随氨蒸气浓度增加而显著地单调上升,敏感波段扩展到整个可见光区域。这是一种有实用价值的气敏光纤传感材料。讨论了该多层薄膜的气敏光学机理和高选择性的机理。     

空位缺陷金红石型TiO2电子结构和光学性质的理论研究

基于密度泛函理论(DFT)的第一性原理模守恒赝势 方法,对纯金红石型TiO₂和Ti、O两种空位缺 陷相的几何结构、能带结构、态密度(DOS)以及光学性质进行了 系统地对比研究。结果发现,含有空 位缺陷的TiO₂键长增大,原子布局值减小并出现微弱的磁性;空位缺陷导致导带变窄,导 带和价带 都向低能级方向移动,由空位原子贡献的载流子增强了体系的电导率,费米能级上移进入导 带;与 纯金红石型TiO₂的直接带隙宽度(3.0eV)相比较,Ti空位缺陷相转 变为P型半导体且直接带隙为1.816 eV,而O空位缺陷相转变为n型半导体且间接带隙为1.961eV。同时, 两种空位缺陷结构的介电峰显 著红移,折射率有明显变化,对可见光区的吸收系数均比纯TiO₂高。与O空位结构相比,Ti 空位结构的 介电常数、折射率、消光因子和对可见光的吸收强度更大,更能增强电子在低能端的光学跃 迁,具有更佳的可见光催化性能。     

基于第一性原理的单层SnSe2二维薄膜的气敏效应

为探索SnSe2二维薄膜材料的气敏特性,采用分子力场方法系统地研究了SnSe2二维单层材料对H2,CO,NH3及NO2等4种典型气体分子的最优吸附位置和吸附能力,并基于密度泛函理论(DFT)的第一性原理方法计算了吸附前后的键长键角变化率、能带结构、态密度及电荷差分密度等参数,分析了吸附前后的电子结构变化与气敏效应之间的内在关联。计算结果发现,吸附H2和CO未能对SnSe2单层的能带结构和电子结构产生改变,而NO2和NH3却在导带底(CBM)和价带顶(VBM)之间分别产生了新的杂质能级,并使费米能级发生位移,从而改变SnSe2单层电子结构。电荷差分密度分析进一步表明SnSe2二维单层未能对H2和CO产生响应,而对NH3和NO2却有明显的气敏效应,其中对NO2有良好的敏感性能和选择性。     

TiO2/SiO2多层膜系一维光子晶体缺陷态特性研究

建立了一种基于TiO2/SiO2多层膜系并含缺陷层的一维光子晶体模型。基于时域有限差分(FDTD)算法,对其基本层周期数,缺陷层位置、光学厚度以及不同材料等情况下的带隙特性在理论上进行了系统的模拟与分析,发现这种一维光子晶体的缺陷态的透过率和带隙宽度受基本层周期数、缺陷层所在位置和材料的影响较大,而缺陷态中心波长位置仅由缺陷层的光学厚度决定。     

SiC/SiO2核壳结构纳米线制备及光学性质研究

采用简单的气固反应,在Si衬底上成功制备了SiC一维纳米材料。用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线电子能谱(EDX)、X射线衍射谱(XRD)和光致发光谱(PL)等手段研究了材料的表面形貌、结构组成和光学性质。研究结果表明,制备的纳米材料为SiC/SiO2核壳结构纳米线,在室温时发射中心波长分别为380nm和505nm的紫外峰和绿光带。经分析认为,波长380nm的紫外峰来源于SiO2中的O空位缺陷;而中心波长505nm的绿光带则来源于受量子尺寸效应影响并包覆了SiO2外壳的SiC内核。     

Atomic Cobalt Vacancy-Cluster Enabling Optimized Electronic Structure for Efficient Water Splitting

Vacancies created on a surface can alter the local electronic structure, thus enabling a higher intrinsic activity for the evolution of hydrogen and oxygen. Conventional strategies for vacancy engineering, however, have a strong focus on non-metal sulfur/oxygen defects, which have often overlooked metallic vacancies. Herein, evidence is provided that cobalt vacancies can be atomically tuned to have different sizes to achieve cobalt vacancy clusters through controlling the migration of iridium single atoms. The coalescence of Co vacancy clusters at the surface of an IrCo alloy results in an increased d-band level and eventually compromises H adsorption, leading to enhanced electrocatalytic activity toward the hydrogen evolution reaction. In addition, the Co vacancy clusters can improve the electronic conductivity with respect to the oxidized Co surface, which substantially aids in strengthening the adsorption of oxygen intermediates toward an effective oxygen evolution reaction at a low overpotential. These collective effects originate from the Co vacancy cluster and specifically enable highly efficient and stable water splitting with a low total overpotential of 384 mV in alkaline media and 365 mV in an acidic environment, achieving a current density of 10 mA cm^–2.     

The Gas‐Detection Properties of Light‐Emitting Diatoms

In recent years, the porous silica structures (frustules) created by living diatoms have been studied for several nanoengineering applications based on biomimetic approaches. We focus on the gas‐sensing properties of diatoms: investigation of different species shows that the photoluminescence emission of frustules is affected by even small modifications of the surrounding gas environment, exhibiting a detection limit of few tenths of ppm in the case of nitrogen dioxide. A new understanding of this phenomenon is discussed here in terms of “static‐type” luminescence quenching through suppression of radiative states (most probably surface oxygen vacancies) induced by adsorption of gas molecules. The modeling allows the free energy of desorption to be measured by all‐optical means: the value obtained suggests that a chemisorption process is involved, in agreement with the observed absorption/desorption kinetics. The findings encourage investigation of diatoms as low‐cost biological transducers for detection of gas species.     

Quantum-chemical study of adsorption of 2-propanol molecule on a GaAs (100) surface

Quantum-chemical cluster calculations employing density functional theory are used to study the adsorption mechanism of 2-propanol molecules on a Ga-rich GaAs (100) surface. It is shown that 2-propanol molecules can be adsorbed either molecularly or dissociatively. Dissociation of 2-propanol molecules at the GaAs(100) surface can proceed with the rupture of an O-H or C-OH bond. The state with the rupture of the C-OH bond has the lowest energy among all possible adsorption states. However, for transition into this state, a very high barrier should be overcome, which is possible only at the semiconductor/liquid interface. The calculated adsorption path agrees well with the available experimental data on the interaction of 2-propanol with the GaAs (100) surface.     

Surface Band Tuning of Bi2Te3 Topological Insulator Thin Films by Gas Adsorption

The surface band tuning of the topological insulator Bi₂Te₃ by gas adsorption is investigated on the basis of ab?initio calculations. It is shown that, with the increase of Te vacancies, the topologically non-trivial surface state which originates from the second quintuple layer coexists with the topologically trivial surface. Molecular dynamics simulation reveals that O₂ and NO₂ easily occupy the Te vacancy sites and further bind to the Bi atoms from the second atomic layer. Moreover, the surface band with the Dirac cone is observed. Our results suggest that the topological surface state can be effectively regulated by NO₂ and O₂ adsorption.     

光伏法研究硅单晶表面态真空敏感机理

根据光伏方法研究的半导体表面气体分子吸附机理,提出了硅单晶表面态真空敏感效应的机理模型,解释了表面态敏感型的真空传感器的各有关观测结果.因此可以确认,硅单晶表面态对真空敏感的实质原因就是由于构成大气主要成份的氮气和氧气两种元素的电子亲和势相对于硅元素,具有明显不同的且符号相反的差值,导致吸附于硅表面的N2、O2分子与硅表面态之间不同转移方向的电荷转移差值可以随真空度变化所引起的.     

Zn掺杂和Sn空位对p型SnO2电子结构和光学性能的影响

用第一性原理计算了本征SnO2、Zn掺杂SnO2、带Sn 空位(VSn)的SnO2和Zn-VSn共掺杂 SnO2的电子结构和光学性能。结果表明,Zn 原子替位SnO2中的Sn原子后费米能级进入价带,价带顶的空能态由Zn 3d和O 2p态组成,Zn掺杂SnO2显示p型半导体性能。 带Sn空位的Zn掺杂SnO2的相对空穴数量较Zn掺杂SnO2的相对空穴数量有明显增加,Sn空位有助于增加Zn掺杂SnO2的p型导电性。Zn掺杂SnO2在可见光区域有明显的光吸收,带Sn空位的Zn掺杂SnO2的光吸收较Zn掺杂SnO2明显增强,吸收光谱发生蓝移。     

Unveiling the Synergy of Interfacial Contact and Defects in α-Fe2O3 for Enhanced Photo-Electrochemical Water Splitting

Photo-electrochemical (PEC) water splitting is a promising method for converting solar energy into clean energy, but the mechanism of improving PEC efficiency through the interfacial contact and defect strategy remains highly controversial. Herein, reduced graphene oxide (rGO) and oxygen vacancies are introduced into α-Fe₂O₃ nanorod (NR) arrays using a simple spin-coating method and acid treatment. The resultant oxygen vacancy–α-Fe₂O₃/rGO-integrated system exhibits a higher photocurrent, four times than the pristine α-Fe₂O₃. It is well evidenced that the electronic interface interaction between α-Fe₂O₃ and rGO is boosted with the oxygen vacancies, facilitating electron transfer from α-Fe₂O₃ to rGO. Moreover, the oxygen vacancies not only create interband states in α-Fe₂O₃ that can trap photogenerated holes and thus facilitate charge separation but significantly also strengthen the adsorption of oxidative intermediates and reduce the energy barrier of rate-determining step during oxygen evolution reaction (OER). This study demonstrates an rGO–oxygen vacancy synergistic interfacial contact and defect modification approach to design semiconducting photocatalysts for high-efficiency solar energy capture and conversion. The generated principle is expected to be extendable to another material system.     

Ce:YIG薄膜中氧空位对光吸收性能的影响

讨论了Ce替代石榴石薄膜制备条件对其光吸收性能的影响.通过引入氧空位概念,提出了溅射气氛中的氧含量对薄膜中Ce元素价态影响的理论模型.基于该模型,讨论了Ce：YIG晶体中氧空位的产生机理.研究表明,当晶格中存在过量氧空位时,会导致部分Fe^3＋被还原成Fe^2＋,使得薄膜的光吸收显著增大.实验结果证实,在Ce：YIG薄膜的晶化过程中,采用富氧气氛可以使得薄膜中Ce元素的价态以Ce^3＋离子为主而Ce^4＋离子含量较少,从而有效降低薄膜的光吸收.溅射气氛中的氧含量及后续热处理过程中氧含量的大小均会直接影响Ce：YIG薄膜的光吸收特性.     

Role of surface oxygen vacancies in photoluminescence of tin dioxide nanobelts

The role of surface oxygen vacancies in the optical properties of tin dioxide nanobelts is investigated in this paper. Using a first-principles approach, based on the density functional theory combined to a very accurate exchange correlation functional, we characterize SnO₂ (1 0 1), that is the nanobelt largest surface. We show that the presence of surface oxygen vacancies leads to the appearance of (i) occupied states located at about 1 eV above the valence band and (ii) unoccupied states lying in resonance with the conduction band. Photoluminescence characterization performed on samples of SnO₂ nanobelts at low temperature shows that the basic spectral features of luminescence are in excellent agreement with theoretical predictions.