闪锌矿GaN(110)表面原子和电子结构的理论计算

在密度泛函理论的基础上,采用平面波赝势方法计算了立方GaN(110)表面的原子和电子结构。结构优化表明最表层原子都向体内弛豫,且金属Ga原子弛豫幅度比非金属N原子大,同时各层层间距呈交错分布。表面弛豫后,最表层原子发生键长收缩的弛豫特性,表面Ga原子趋于形成sp2杂化得到的平面型构形,而表面N原子趋于形成p3型锥形结构。另外,理想立方GaN(110)表面在带隙中有两个明显的表面态,经过弛豫后,分别向价带和导带方向移动,并解释了导带底附近的表面态移动的幅度比价带顶附近的表面态大的原因主要由于表面Ga、N原子弛豫幅度不同引起的。此外,弛豫后,表面电荷重新分布,Ga原子周围的部分电子转移到N原子上。     

Analysis of PTCDA/ITO Surface and Interface Using X-ray Photoelectron Spectroscopy and Atomic Force Microscopy

利用X射线光电子能谱(XPS)对苝四甲酸二酐[3,4,9,10-perylenetetracarboxylic dianhydride(PTCDA)]/铟锡氧化物(ITO)表面和界面进行了研究.用原子力显微镜(AFM)对PTCDA/ITO样品的表面形貌进行了分析.XPS表明,在原始表面的C1s精细谱存在两个主谱峰和一个伴峰,主谱峰分别由结合能为284.6eV的苝环中的C原子和结合能为288.7eV的酸酐基团中的C原子激发;而结合能为290.4eV的伴峰的存在,说明发生了来源于ITO膜中的氧对C原子的氧化现象.O原子在C=O键和C-O-C键的结合能分别为531.5和533.4eV.在界面处,C1s谱中较高结合能峰消失,且峰值向低结合能方向发生0.2eV的化学位移;O1s谱向低结合能方向发生1.5eV的化学位移.由此可以推断,在界面处PTCDA与ITO的结合是PTCDA中的苝环与ITO中的In空位的结合.AFM的结果显示,PTCDA薄膜为岛状结构,岛的直径约为100～300nm,表面起伏约为14nm.相邻两层PTC-DA分子由于存在离域大π键而交叠和PTCDA分子中的苝环与ITO的In空位的紧密结合是最终导致PTCDA岛状结构形成的原因.     

PTCDA/ITO表面和界面的AFM和XPS分析

利用X射线光电子能谱(XPS)对苝四甲酸二酐[3,4,9,10-perylenetetracarboxylic dianhydride(PTCDA)]/铟锡氧化物(ITO)表面和界面进行了研究.用原子力显微镜(AFM)对PTCDA/ITO样品的表面形貌进行了分析.XPS表明,在原始表面的C1s精细谱存在两个主谱峰和一个伴峰,主谱峰分别由结合能为284.6eV的苝环中的C原子和结合能为288.7eV的酸酐基团中的C原子激发;而结合能为290.4eV的伴峰的存在,说明发生了来源于ITO膜中的氧对C原子的氧化现象.O原子在C=O键和C-O-C键的结合能分别为531.5和533.4eV.在界面处,C1s谱中较高结合能峰消失,且峰值向低结合能方向发生0.2eV的化学位移;O1s谱向低结合能方向发生1.5eV的化学位移.由此可以推断,在界面处PTCDA与ITO的结合是PTCDA中的苝环与ITO中的In空位的结合.AFM的结果显示,PTCDA薄膜为岛状结构,岛的直径约为100～300nm,表面起伏约为14nm.相邻两层PTC-DA分子由于存在离域大π键而交叠和PTCDA分子中的苝环与ITO的In空位的紧密结合是最终导致PTCDA岛状结构形成的原因.     

氮掺杂浓度对氮掺杂PbTiO3电子结构和光学性能的影响

用第一性原理计算研究了不同N掺杂浓度的P型N掺杂PbTiO3的电荷密度差分、能带结构、态密度和光学性质。用N原子取代PbTiO3中的O原子后,PbTiO3的价带向高能级发生移动,费米能级进入价带顶部。随着N掺杂浓度的增加,能带带隙值变窄,结构稳定性变差。掺杂浓度2.5 at%时,N掺杂PbTiO3显示最好的P型导电性和最强的可见光吸收。N掺杂PbTiO3在半导体光电器件和光催化领域具有重要的应用价值。     

Si(111)表面顶位吸附的双心键理论

采用双心键理论计算 Si(111)表面上顶位吸附 H、O、F和Cl原子的键长、电荷分配、力常数和局域振动频率,同时用自治键轨道方法计算价带的电子结构,其结果与ab initio和CNDO理论方法得出的基本一致,同O和Cl原子吸附的实验数据也大致相符,从而表明双心键理论可用于顶位原子吸附的研究.     

氧在GaP(-1-1-1)表面上的吸附特性

利用单色的HeII(40.8eV)光电子谱研究了氧在GaP(111)表面上的化学吸附特征.实验表明,在室温下被吸附的氧存在两种形态:α氧和β氧。α氧在价带中的两个光电子峰分别低于价带顶6.0和10.0eV; β氧在价带顶下5.2eV处有一个主峰和在8—9eV处有一个肩峰,它对应于离解态的氧与表面原子的键合.β氧引起Ga3d能级的化学位移为0.8±0.1eV,而α氧不引起位移.在～250℃下退火,大部分的α氧脱附,并有小部分转变为β氧,后者在～550℃时脱附.所有这些结果都与氧在GaAs表面上的吸附特性类似.     

氧在GaP(■■■)表面上的吸附特性

利用单色的HeII(40.8eV)光电子谱研究了氧在GaP(111)表面上的化学吸附特征.实验表明,在室温下被吸附的氧存在两种形态:α氧和β氧。α氧在价带中的两个光电子峰分别低于价带顶6.0和10.0eV; β氧在价带顶下5.2eV处有一个主峰和在8—9eV处有一个肩峰,它对应于离解态的氧与表面原子的键合.β氧引起Ga3d能级的化学位移为0.8±0.1eV,而α氧不引起位移.在～250℃下退火,大部分的α氧脱附,并有小部分转变为β氧,后者在～550℃时脱附.所有这些结果都与氧在GaAs表面上的吸附特性类似.     

Si/GaP(111)和(■)界面的研究

本文报道用EHT方法计算Si/GaP(111)、(111)和(110)界面的电子结构,得到它们的价带不连续值△E_v分别为:0.88eV、0.97eV和0.87eV,这和Si/GaP的实验结果:△E_v=0.80eV和0.95eV相符合.不同晶向△E_v相差达0.1eV.分析Si和GaP价带顶位置的变化情况,发现对Si/GaP(111),界面态对价带顶的影响不大.但对于Si/GaP(111)异质结,由于界面态的影响,使Si价带顶明显上移.此时,界面态对△E_v的非线性影响不可忽略。     

铅锌矿ZnO(0001)和(000-1)表面结构的第一性原理研究

采用基于密度泛函理论（DFT）的第一性原理平面波超软赝势法计算了铅锌矿ZnO{0001}表面的电子结构.分析表面能发现,ZnO-Zn表面的表面能比ZnO-O略大,两者相比,ZnO-Zn表面活性强、不稳定.表面弛豫后,ZnO-Zn和ZnO-O发生表面收缩,ZnO-Zn表面收缩较小.研究发现,由于表层Zn和O原子的强轨道杂化作用导致ZnO-Zn表面显示n型特性;而ZnO-O表面的O-2p悬挂键能级占据价带顶导致ZnO-O表面显示p型特性.计算结果和实验事实基本一致.     

Si/GaP(111)和(-1-1-1)界面的研究

本文报道用EHT方法计算Si/GaP(111)、(111)和(110)界面的电子结构,得到它们的价带不连续值△E_v分别为:0.88eV、0.97eV和0.87eV,这和Si/GaP的实验结果:△E_v=0.80eV和0.95eV相符合.不同晶向△E_v相差达0.1eV.分析Si和GaP价带顶位置的变化情况,发现对Si/GaP(111),界面态对价带顶的影响不大.但对于Si/GaP(111)异质结,由于界面态的影响,使Si价带顶明显上移.此时,界面态对△E_v的非线性影响不可忽略。     

锐钛矿TiO2(101)面电子性质和光学性质的第一性原理研究

The TiO₂（101） surface was studied using the plane-wave ultrasoft pseudopotential method based on the density functional theory,with emphasis on the structure,surface energy,band structure,density of states, and charge population.The anatase TiO₂（101） crystal surface structure,whose outermost and second layers were terminated by twofold coordinated oxygen atoms and fivefold coordinated titanium atoms,was found to be much more stable.The surface energy of the 18-layer atoms model was 0.580 J/m2.The surface electronic structure was similar to that of the bulk and no surface state.Compared with the bulk structure,the band gap increased 0.36 eV, the Ti5c-02c bond lengths reduced 0.171（?） after relaxation,and the charges of the surface were transferred to the body.Analysis of the optical properties of the TiO₂（101） surface showed that it did not absorb in the low-energy region.An absorption edge in the ultraviolet region corresponding to the energy of 3.06 eV was found.     

Synthesis and photocatalytic performance of Ag3PO4/AgCl hybrids

Ag3POa/AgC1 hybrids have been synthesized via a facile ion-exchange method. The hybrids exhibit an enhanced photocatalytie activity for degradation of rhodamine B （RhB） than the single Ag-3PO_4 or AgCl under a visible light irradiation. Such a behavior might be attributed to the increased number of high active sites and suitable energy band structure. The possible mechanism is also discussed.     

The structural and electrical properties of the SrTa2O6/In0.53Ga0.47As/InP system

The structural and electrical properties of SrTa₂O₆(SrTaO)/n-In_0.53GaAs_0.47(InGaAs)/InP structures where the SrTaO was grown by atomic vapor deposition, were investigated. Transmission electron microscopy revealed a uniform, amorphous SrTaO film having an atomically flat interface with the InGaAs substrate with a SrTaO film thickness of 11.2 nm. The amorphous SrTaO films (11.2 nm) exhibit a dielectric constant of ∼20, and a breakdown field of >8 MV/cm. A capacitance equivalent thickness of ∼1 nm is obtained for a SrTaO thickness of 3.4 nm, demonstrating the scaling potential of the SrTaO/InGaAs MOS system. Thinner SrTaO films (3.4 nm) exhibited increased non-uniformity in thickness. From the capacitance-voltage response of the SrTaO (3.4 nm)/n-InGaAs/InP structure, prior to any post deposition annealing, a peak interface state density of ∼2.3 × 10¹³ cm⁻² eV⁻¹ is obtained located at ∼0.28 eV (±0.05 eV) above the valence band energy (E_v) and the integrated interface state density in range E_v + 0.2 to E_v + 0.7 eV is 6.8 × 10¹² cm⁻². The peak energy position (0.28 ± 0.05 eV) and the energy distribution of the interface states are similar to other high-k layers on InGaAs, such as Al₂O₃ and LaAlO₃, providing further evidence that the interface defects in the high-k/InGaAs system are intrinsic defects related to the InGaAs surface.     

Highly efficient photocatalytic treatment of mixed dyes wastewater via visible-light-driven AgI–Ag3PO4/MWCNTs

A high-performance photocatalyst of AgI–Ag₃PO₄/multi-walled carbon nanotubes (MWCNTs) was fabricated by chemical precipitation method using KI, K₂HPO₄ and AgNO₃ in the presence of MWCNTs. Its structure and physical properties were characterized by means of scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), transmission electron microscope (TEM), X-ray diffraction (XRD), UV–vis absorption spectra, X-ray photo-electron spectroscopy (XPS), photoluminescence spectra (PL) and photocurrent techniques. SEM, TEM and EDS analyses verified that AgI–Ag₃PO₄ is successfully loaded on MWCNTs. AgI–Ag₃PO₄/MWCNTs possess the absorption edge of red shift and small band gap energy, and could absorb more photons in the visible region. PL and photocurrent analyses illustrated that AgI–Ag₃PO₄/MWCNTs have the lowest emission peak intensity and the highest photoelectric current, compared with Ag₃PO₄, AgI and AgI–Ag₃PO₄. By using the photocatalytic degradation of mixed dyes wastewater of Orange II and ponceau 4R as a model reaction, the photocatalytic efficiencies of Ag₃PO₄, AgI, AgI–Ag₃PO₄ and AgI–Ag₃PO₄/MWCNTs were evaluated. The reaction results showed that AgI–Ag₃PO₄/MWCNTs have strong photocatalytic activity and excellent chemical stability in repeated and long-term applications. Therefore, the prepared AgI–Ag₃PO₄/MWCNTs could act as a high-performance catalyst for the photocatalytic degradation of mixed dyes wastewater and also suggested the promising applications.     

Influence of passivating interlayer on Ge/HfO2 and Ge/Al2O3 interface band diagrams

The energy band alignment between Ge, HfO₂ and Al₂O₃ was analyzed as influenced by passivating interlayers (ILs) of different composition (GeO₂, Ge₃N₄, Si/SiO_x). From internal photoemission and photoconductivity experiments we found no IL-sensitive dipoles at the Ge/HfO₂ interfaces, the latter being universally characterized by conduction and valence band offsets of 2.1 and 3.0 eV, respectively. However, in the case of HfO₂ growth using H₂O-based atomic layer deposition, the Ge oxide IL appears to have a narrower bandgap, 4.3 eV, than the 5.4–5.9 eV gap of bulk germania. Accordingly, formation of this IL yields significantly reduced barriers for hole and, particularly, electron injection from Ge into the insulator. Changing to a H-free process for HfO₂ and Al₂O₃ deposition suppresses the formation of the narrow-gap Ge oxide.     

Atomic and electronic structure of the CdTe(111)<Emphasis Type="Italic">B</Emphasis>–(2√3 × 4) orthogonal surface

The atomic and electronic structure of four variants of Te-terminated CdTe(111)B–(2√3 × 4) orthogonal polar surface (ideal, relaxed, reconstructed, and reconstructed with subsequent relaxation) are calculated ab initio for the first time. The surface is modeled by a film composed of 12 atomic layers with a vacuum gap of ~16 Å in the layered superlattice approximation. To close Cd dangling bonds on the opposite side of the film, 24 fictitious hydrogen atoms with a charge of 1.5 electrons each are added. Ab initio calculations are performed using the Quantum Espresso program based on density functional theory. It is demonstrated that relaxation leads to splitting of the four upper layers. The band energy structures and total and layer-by-layer densities of electronic states for the four surface variants are calculated and analyzed.     

Electronic structure of SnO2 (110) surface

The electronic structure of the stoichiometric and reduced SnO₂ (110) surfaces is studied with first-principles calculations. Calculations are carried out with two complementary self-consistent ab initio–DFT–GGA methods. Surface relaxation is considered, where the most prominent feature turns out to be the surface layer in-plane oxygen displacement of the reduced surface outwards, about 0.4 Å with respect to the surface layer tin atoms. The electronic structure of the relaxed surfaces is considered in terms of atomic orbitals and rehybridization, and the surface band structure. The bands are flat at the stoichiometric surface, but strong dispersion occurs at the reduced surface. The dispersion results in electronic levels into the band gap, which have also been experimentally observed.     

Band offsets at the (1 0 0)GaSb/Al2O3 interface from internal electron photoemission study

From electron internal photoemission and photoconductivity measurements at the (1 0 0)GaSb/Al₂O₃ interface, the top of the GaSb valence band is found to be 3.05 ± 0.10 eV below the bottom of the Al₂O₃ conduction band. This interface band alignment corresponds to conduction and valence band offsets of 2.3 ± 0.10 eV and 3.05 ± 0.15 eV, respectively, indicating that the valence band in GaSb lies energetically well above the valence band of In_xGa_1−xAs (0 ? x ? 0.53) or InP.     

Highly efficient visible-light driven AgBr/Ag3PO4 hybrid photocatalysts with enhanced photocatalytic activity

Highly efficient visible-light-driven AgBr/Ag₃PO₄ hybrid photocatalysts with different mole ratios of AgBr were prepared via an in-situ anion-exchange method and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), UV–vis diffuse reflectance spectroscopy (DRS) and photoluminescence (PL) technique. Under visible light irradiation (>420 nm), the AgBr/Ag₃PO₄ photocatalysts displayed the higher photocatalytic activity than pure Ag₃PO₄ and AgBr for the decolorization of acid orange 7 (AO 7). Among the hybrid photocatalysts, AgBr/Ag₃PO₄ with 60% of AgBr exhibited the highest photocatalytic activity for the decolorization of AO 7. X-ray photoelectron spectroscopy (XPS) results revealed that AgBr/Ag₃PO₄ readily transformed to be Ag@AgBr/Ag₃PO₄ system while the photocatalytic activity of AgBr/Ag₃PO₄ remained after 5 recycling runs. In addition, the quenching effects of different scavengers displayed that the reactive h⁺ and O₂^∙− play the major role in the AO 7 decolorization. The photocatalytic activity enhancement of AgBr/Ag₃PO₄ hybrids can be ascribed to the efficient separation of electron–hole pairs through a Z-scheme system composed of Ag₃PO₄, Ag and AgBr, in which Ag nanoparticles act as the charge separation center.