超二代像增强器多碱阴极光电发射特性研究

通过测量超二代像增强器多碱阴极的光谱反射率和透射率,根据能量守恒定律计算得到了多碱阴极的光谱吸收率.结果表明,只有当光子的能量大于1.333 eV以后,多碱阴极的吸收率才开始快速增大.这说明多碱阴极的光谱吸收存在一个1.333 eV的长波吸收限,入射光的光子能量如果小于该吸收限,多碱阴极将不吸收.在多碱阴极的表面电子亲合势进一步降低的情况下,多碱阴极光电发射的长波理论阈值由长波吸收限所决定.多碱阴极在吸收光子之后的电子跃迁过程中,跃迁电子的能量增加小于所吸收入射光子的能量,即存在一个"能量损失".光子的能量越高,所激发的跃迁电子所处的能级越高,能量损失越大.同时光子的能量越高,跃迁电子所处的能级越高,电子跃迁的几率越低.多碱阴极的量子效率由吸收率、跃迁几率和跃迁能级、扩散过程中的能量损失等因素共同决定,因此多碱阴极的量子效率存在长波阈的同时也存在短波阈.多碱阴极的量子效率在2.11 eV达到最大值之后,随着光子能量的增加而单调减小,在3.6 eV时,量子效率减小到零.多碱阴极在3.6 eV时的吸收系数仍然很高,但由于电子跃迁的几率低,同时电子扩散过程中的能量损失大,导致尽管多碱阴极对短波具有较高的吸收系数,但量子效率仍然较低.因此对多碱阴极所吸收的光子能量中,转换成为光电导、晶格热振动等其他非光电发射形式能量的比例而言,短波较长波高,对光电发射的贡献率而言,短波较长波低.     

Comparison of cross sections in high resolution electron energy loss spectroscopy and infrared reflection spectroscopy

Electron energy losses and absorption of infrared radiation are both caused by the dipole moment of the surface vibration. A comparison of absolute intensities between both techniques should therefore be possible. In this paper the appropriate formulas are derived. For the adsorption system CO on Pt(111) which has been investigated by both techniques a perfect agreement is found. For a number of adsorbate systems the effective ionic charge is calculated from previously published electron energy loss data.     

Influence of Solvent on Dye-Sensitized Solar Cell Efficiency: What is so Special About Acetonitrile? (Part. Part. Syst. Charact. 5/2021)

The selection of solvent for preparing a working electrode (and to act as the electrolyte) is known to influence the efficiency of dye-sensitized solar cells. In this topical review, results taken from a systematic study are presented from the authors’ own lab examining how protic and aprotic solvents, as well as solvent polarity, affect adsorption of carboxylic dyes on the titanium dioxide nanoparticle surface and electron injection from the dye to the semiconductor. Adsorption of dye molecules on nanoparticle surfaces is measured through second harmonic light scattering and electron injection through ultrafast transient mid-infrared absorption. It is revealed that protic solvents do not allow direct adsorption of the dye onto the semiconductor surface, due to hydrogen bonding with the dye and competitive binding to the semiconductor surface. Aprotic solvents, on the other hand, support solvation of the dye molecules but also facilitate dye adsorption on the semiconductor nanoparticle. Among aprotic solvents, it is found that solvents with higher polarity result in larger adsorption free energy for the dye and faster electron injection. Overall, these studies reveal that aprotic solvents with high solvent polarity (such as acetonitrile) yield more efficient solar cell devices.     

含Nb或Ge的锆合金表面氧吸附行为的第一性原理研究

采用基于密度泛函理论的第一性原理方法, 研究了纯锆表面和含Nb或Ge锆合金表面上氧的吸附性质. 结果表明, Nb和Ge对Zr(0001), (1120)和(1010)表面吸附性质的影响各不相同. 根据计算得到的偏聚能结果, Nb和Ge迁移到Zr(0001)表面比迁移到其他两个表面更容易, 而Nb和Ge 都可以降低Zr(0001)表面对氧原子的吸附能力, 因此这两种元素都能抑制锆合金的初始氧化. 进一步的电子结构分析发现, Nb和Ge改变表面对氧原子的吸附能力是通过改变表面d能带的分布来实现的.     

Theory of the resonant properties of electrons localized on the surface of liquid helium

The problem of the shape of the line of optical transition of an electron between bound states on the surface of liquid helium is solved within the independent boson model. Such bound states are realized, for example, in the potential of a positively charged impurity located on a substrate or in the field of a He⁺ ion located beneath the surface. Reference is made to the importance of the relaxation processes of the dimple on the helium surface under the electron. The adiabatic approximation, in the case of which the dimple does not change during the time of electron transition, is not always valid. At low temperatures, two maxima may appear on the absorption line. It is demonstrated that the far tails of the optical absorption line feature a universal (Urbach rule) exponential dependence on the electron transition energy.     

丁酰胆碱和硫代胆碱与CdTe量子点的络合特征以及光谱性质的理论研究

本文利用密度泛函理论,研究了丁酰胆碱和硫代胆碱在CdTe量子点上的络合特征.优化了稳定的络合构型,计算了吸附能、电荷密度、前沿分子轨道以及紫外可见吸收光谱.研究发现：丁酰胆碱在CdTe量子点上的吸附能较小、与量子点之间的电子相互作用较弱,属于物理吸附,紫外可见光吸收强度较弱.而硫代胆碱与量子点之间存在化学吸附,存在强的电子相互作用,紫外可见光吸收强度增强.我们的研究结果为实验中使用CdTe量子点检测丁酰胆碱酯酶提供了理论支持.     

A first-principles study on the interaction of CO molecules with VIII transition metals-embedded graphitic carbon nitride as an excellent candidate for CO sensor

We studied the adsorption behavior of CO molecules over graphitic carbon nitride (gCN) and VIII transition metals (TM)-embedded gCN systems (TM=Ni, Pd, and Pt atoms) using density functional theory. The results indicated that the Pt-embedded gCN is excellent candidate for adsorption of CO molecules with adsorption energy of −2.77 eV, which is much better than those of the other adsorbents. Furthermore, it was observed that the band gap energies of TM-embedded systems were less than that of pristine gCN and decoration of transition metal atoms leads to the formation of mid gap impurity states, resulting in increase of electrical conductivity. Additionally, the Lowdin charges displayed that upon adsorption of CO molecules, this molecule acts as an electron acceptor and gCN systems behave as an electron donor with electron transfer from d-orbitals of transition metal atoms to the states of CO molecule. The results of spin polarized band structure indicated that the pristine gCN, Ni and Pd-embedded systems are non-magnetic, whereas Pt-embedded gCN induces non-zero magnetic moment equal to 1.35 μB. Therefore, our results revealed that among the TM-embedded systems, Pt-embedded gCN is more effective than those of the other adsorbents in sensing and removing of this gas from the atmosphere.     

VO2薄膜表面氧缺陷的修复:F4TCNQ分子吸附反应

VO₂表面氧缺陷的存在对VO₂材料具有显著的电子掺杂效应, 极大地影响材料的本征电子结构和相变性质. 通过2, 3, 5, 6-四氟-7, 7', 8, 8'-四氰二甲基对苯醌(F₄TCNQ)分子表面吸附反应, 可以有效消除表面氧缺陷及其电子掺杂效应. 利用同步辐射光电子能谱和X射线吸收谱原位研究了修复过程中电子结构的变化以及界面的化学反应, 发现这种方式使得VO₂薄膜样品氩刻后得到的V³⁺失去电子成功地被氧化成原先的V⁴⁺, 同时F₄TCNQ分子吸附引起电子由衬底向分子层转移, 界面形成带负电荷的分子离子物种. 受电化学性质的制约, F₄TCNQ分子吸附反应修复氧缺陷较氧气氛退火更安全有效, 不会引起表面过度氧化形成V₂O₅.     

A Surface Study of Ultrathin Ceria Nanoparticles Decorated with Transition‐Metal Ions

A wide range of nanoparticle properties can be tuned by changing their surface characteristics, especially when dealing with ultrathin nanomaterials. Surface modification with transition‐metal ions may affect a variety of the nanoparticles' properties including the surface charge, the electronic structure, and the electrical and optical characteristics. In this work, a surface study of ceria nanoparticles modified by attachment of various transition‐metal ions to their surface is conducted. Characterization of the decorated particles as well as of the modifying transition‐metal ion is carried out using zeta potential in organic solution, UV–Vis absorption, and electron paramagnetic resonance measurements, together with isothermal titration calorimetry, X‐ray photoelectron spectroscopy, and energy dispersive X‐ray spectroscopy. All measurements confirm the attachment of the cation to the surface of ceria, both in solid state and in colloidal suspension. It is suggested that the modifying ion‐complex attaches to ceria both via chemical or strong physical interactions and weak physical interactions, demonstrated by a case‐study modification of ceria using a copper‐oleylamine complex. The metalization has a significant effect on the surface charge of the nanoparticles by shifting the zeta potential to more positive values and on the optical properties of the modifying transition‐metal ions by red‐shifting their absorption peak.     

Quantitative Auger electron spectroscopy analysis with co-evaporated AuCu films

A method for the quantitative Auger electron spectroscopy (AES) analysis by using a co-evaporation technique is extended to the AuCu system following the previous work. The calibration curves for lower Auger energy have peaks at 60 eV for Cu and at 69 eV for Au, and for higher Auger energy peaks at 239 eV for Au and at 920 eV for Cu. It is found that a simple linear relation does not exist in the results for AES measurements and the bulk analysis by atomic absorption spectroscopy (AAS) because of the back-scattering effect and the overlap of the spectra at lower energies in the Au-Cu system. It is also found that the adsorption of oxygen caused by electron beam bombardment has a significant influence on the AES results. The calibration curves obtained after a correction for oxygen adsorption are successfully applied to the determination of the composition at the surface of a sputtered AuCu alloy.     

石墨烯吸附钛原子的第一性原理研究

基于密度泛函理论研究了单个钛原子分别位于本征石墨烯GR、点缺陷石墨烯（包括空位石墨烯DGR和氮掺杂石墨烯N-GR）薄片表面的吸附机理。通过计算钛原子在本征石墨烯表面不同位置时的吸附结构和吸附能,发现最稳定吸附位置是碳六元环的中心;计算了各个吸附体系的吸附能、态密度和差分电荷密度,研究表明三个吸附体系碳钛间均产生了电子轨道杂化,掺氮后的石墨烯对钛原子的吸附性能略微增强,而空位石墨烯对钛的吸附能是本征石墨烯的4倍,费米能级附近电子态局域化程度最大,吸附效果最好。     

Optical properties of transition metal atom adsorbed graphene: A density functional theoretical calculation

Electronic and optical properties of 3d-transition metal adsorbed graphene system, theoretically studied in the framework of density functional theory, reveals significant modification compared to the pristine system. Due to adsorption of transition metal, the emergence of closely separated electronic bands leads to substantial amount of low energy optical absorption below 2.0 eV photon energy. Very significant enhancement of static dielectric constant and large value of reflectivity in the low optical energy regime has been identified for different adsorbed systems. In the different 3d-transition metal adsorbed systems, particularly up to the half filled d-shell transition metal atom, pronounced emergence of optical absorption line in the deep ultraviolet regime beyond 30.0 eV photon energy is observed.     

Observation of hopping transitions for delocalized electrons by temperature-dependent conductance in silicon junctionless nanowire transistors

We demonstrate transitions of hopping behaviors for delocalized electrons through the discrete dopant-induced quantum dots in n-doped silicon junctionless nanowire transistors by the temperature-dependent conductance characteristics.There are two obvious transition platforms within the critical temperature regimes for the experimental conductance data,which are extracted from the unified transfer characteristics for different temperatures at the gate voltage positions of the initial transconductance gm peak in V_(g1) and valley in V_(g2). The crossover temperatures of the electron hopping behaviors are analytically determined by the temperature-dependent conductance at the gate voltages V_(g1) and V_(g2). This finding provides essential evidence for the hopping electron behaviors under the influence of thermal activation and long-range Coulomb interaction.     

Sb induced (7×7) to (1×1) surface phase transformation of the Si(111) surface

Adsorption of Sb at a very low flux rate results in an epitaxial layer-by-layer growth on Si(111) surface held at room-temperature. Band-bending is not observed for submonolayer Sb coverages while sharp changes in the photoemission features are observed for 1.0 monolayer (ML) Sb adsorption. Changes in the core level binding energy and width in X-ray photoelectron spectroscopy, surface related feature in Electron energy loss spectroscopy and spot intensity ratios in Low energy electron diffraction studies suggest a surface phase transition upon adsorption of 1.0 monolayer of Sb. A plausible model is proposed to explain the abrupt metal-semiconductor transformation at this critical coverage of 1.0 ML.     

第一性原理研究H_2O分子在CaCO_3(104)表面吸附

基于密度泛函理论的第一性原理方法模拟研究H_2O在CaCO_3(104)表面的吸附特征.首先,研究H_2O分子在CaCO_3(104)表面的顶位、桥位(短桥位、长桥位)和穴位上垂直和平行表面两种类型下的8种高对称吸附结构模型,结合吸附能和稳定吸附构象确定最优吸附位.而后,基于H_2O/CaCO_3(104)最优吸附结构模型,研究吸附前后H_2O和CaCO_3(104)表面的物理结构、电子结构(Mulliken电荷布居数、态密度、电子局域函数)的特征,分析H_2O/CaCO_3(104)表面之间的相互作用以及成键机理.研究结果:吸附能和体系稳定构象显示H_2O分子/CaCO_3(104)表面的最稳定吸附结构为穴位-平行.在穴位-平行位吸附后,H_2O分子的O-H键长和H-O-H键角均发生改变; CaCO_3晶体平行和垂直(104)表面方向上原子位置均发生改变,表面层变化最大;即吸附作用对H_2O分子和CaCO_3晶体的物理结构均产生较大影响; H_2O/CaCO3(104)最优吸附体系的Mulliken电荷布居数、电子态密度、电子局域函数的研究均说明H_2O分子与CaCO3(104)之间存在电子的转移形成化学键.其中,Ca-O(H_2O)形成离子键,H(H_2O)-O(CaCO_3)之间存在氢键作用.本文研究揭示了方解石表面水湿性的原因,同时为方解石润湿性的深入研究奠定基础.     

Influence of oxygen adsorption on the surface potential of a metal oxide semiconductor

Analytical expressions describing dependences of the surface density of adsorbed oxygen ions and energy band bending in the subsurface region of a metal oxide semiconductor on the oxygen concentration that consider not only the process of neutral gas particle adsorption, but also their charge transfer at the expense of electron capture from the conduction band are presented. It is demonstrated that the heat of oxygen ion absorption is equal to the sum of the heat of neutral particle adsorption and the energy gap between the Fermi level and the level of the oxygen ion on the semiconductor surface. When the adsorption equilibrium is established, an analytical expression describing the time dependence of the energy band bending can be obtained only for small change of the oxygen concentration in the gas mixture.     

Decrease in the bond energy of arsenic atoms on the GaAs(100)-(2×4)/c(2×8) surface due to the effect of adsorbed cesium

It has been found experimentally that the bond energy of arsenic atoms on the GaAs(100) surface decreases under the influence of adsorbed cesium. This is manifested in the disordering of the As-stabilized surface and in a decrease of ～(100 K in the temperature of the transition to the Ga-stabilized (100)GaAs(4×2)/c(8×2) surface. This effect is caused by the redistribution of the valence electron density between the arsenic atoms in the upper layer and the gallium atoms in the lower-lying layer as a result of charge transfer from the electropositive adsorbate to the semiconductor. In combination with the analogous effect of a decrease in the bonding energy of gallium atoms on the Ga-stabilized GaAs surface upon the adsorption of electronegative adsorbates (halogens), the effect observed allows the atomic layer etching of the polar GaAs(100) face.     

Generalized model of metal adsorption with inclusion of the effects of substrate lattice relaxation: Adsorption of gold atoms onto aluminum

The geometric and energy characteristics of Au atom adsorption onto an Al(100) surface have been calculated self-consistently in the framework of the electron density functional method. These calculations take into account the lattice relaxation of two near-surface substrate layers and the first Au adlayer. It is shown that the interstitial regions on the Al(100) surface are the most advantageous adsorption regions.     

Desorption of carbon dioxide from small potassium niobate particles induced by the particles’ ferroelectric transition

The aim of this work is to understand surface properties of ferroelectric crystals related to gas adsorption. Various ferroelectric crystals involved in these studies readily adsorb carbon dioxide, thus our studies were centered on adsorption studies of this molecule. It has been claimed that a dipole moment is induced on carbon dioxide molecules that are near an oxide surface. Our experiments explored the possibility of a dipole-dipole interaction between the gas molecule and the ferroelectric oxide surface in order to explain its adsorption. We characterized the samples with scanning electron microscopy, X-ray diffraction and Raman spectroscopy. We determined the ferroelectric nature of the particles and studied the temperature-dependent phase transitions in small particles of KNbO₃ using Raman spectroscopy. We were able to correlate desorption of CO₂ from one surface state of KNbO₃ with the occurrence of the orthorhombic to tetragonal transition in KNbO₃ in particles of 1 μm size. This CO₂ surface site was not observed in KTaO₃, which does not show ferroelectricity at room temperature.     

GGA+U方法研究不同浓度镧(La)与氮(N)掺杂纤锌矿ZnO的光学性质

本文运用基于密度泛函理论的GGA+U方法,计算了纯ZnO体系,La、N单掺ZnO体系及Zn_(1-x)La_xO_(0.875)N_(0.125)(x=0.125,0.25,0.375)三个共掺体系的电子结构和光学性质.计算结果表明,共掺体系中随着La浓度的增加,掺杂后体系的禁带宽度变小,电子跃迁所需能量减小,晶格畸变程度增大,有利于阻碍光生空穴和电子对的复合,吸收光谱吸收带边红移程度越来明显,覆盖了整个可见光区域.这些特征非常有利地说明共掺体系随La浓度的增加,其光催化功能和电学性能也在提升.