ZnO-treated TiO2 inverse opal electrodes for dye-sensitized solar cells

We report that the photovoltaic properties of inverse opal TiO₂ (io-TiO₂) electrodes in dye-sensitized solar cells can be enhanced by ZnO treatment of the inverse opal structures. ZnO was coated on the surface of io-TiO₂ via the sol–gel reaction of ZnO precursors. Energy dispersive X-ray spectroscopy (EDX) measurements showed that the amount of ZnO on the io-TiO₂ surface was measured to be 0.12–0.50 wt% of zinc, depending on the number of coatings. Compared to bare inverse opal electrodes, the energy conversion efficiency of cells increased for the 0.35 wt% ZnO-coated electrodes, and then decreased for the 0.50 wt% ZnO-coated electrodes. The maximum efficiency of 5.3% was achieved, corresponding to a 23% increase in efficiency compared with bare io-TiO₂ electrodes. The enhanced efficiency was mainly attributed to the improvement of the open-circuit voltage (V_OC). EIS and dark current measurements confirmed that this enhancement in V_OC was due to the movement of the conduction band edge in a negative direction after ZnO treatment, rather than the formation of a barrier layer for electron recombination.     

Preferential neutralization in low energy helium ion scattering from the second layer of MoS2 basal plane surfaces

Low energy ³He⁺ and ⁴He⁺ scattering along the [100] direction of single crystal MoS₂ basal plane surfaces has been investigated. The layered atomic structure of this compound was used to demonstrate that preferential neutralization accompanies scattering from the second surface layer. Preferential neutralization that takes place upon scattering at molybdenum atomic sites leads to a marked increase in the Mo/S LEISS intensity ratio with increasing primary ion energy (0.38–2 keV).     

NH3-induced c(4 × 2) to (2 × 2) transition on the Ge(001) surface by a domino-like dimer flip

Under the conditions of thermodynamic adsorption-desorption equilibrium, the first strongly bound molecular adsorption state of ammonia on Ge(001) saturates at one molecule per Ge reconstruction dimer (1/2 ML). High-resolution electron diffraction studies show that this adsorption is accompanied by a structural transition from c(4 × 2) on the clean surface to a (2 × 2) structure which is already completed for a coverage of about 0.04 ML, far below saturation. We propose a model implying the formation of NH₃ islands locally covered with 1/2 ML and a (2 × 2) periodicity caused by a flip of the dimer tilt direction of every second dimer Beyond the edge of these islands, the dimer flip continues domino-like along the dimer rows over the clean parts of the surface. Elongated (2 × 2) domains about 280–330Å long and 30–65Å wide are formed, depending on coverage.     

Adsorption of Ag and Au atoms on wurtzite ZnO (0001) surface

We perform first-principles calculations to investigate various surface structures in the absorption of Ag and Au atoms on wurtzite ZnO (0001) surface. The results show that both Ag and Au atoms prefer to be absorbed on the H₃ sites (the center of Zn–O ring) of the surface, and the most favorable monolayer (ML) coverage is 1. The calculated electron structure shows that the Ag- and Au-adsorbed ZnO (0001) surfaces exhibit metallic characteristics even the ML coverage of the adatoms is very low. Finally, the work functions of Ag- and Au-adsorbed ZnO (0001) surfaces are calculated and discussed for the first time in the present work.     

Enhancement of Fluorescence of Nanosized ZnO: SiO<Subscript>2</Subscript> Films in the Presence of Human Serum Albumin

The optical properties of the films of new nanosized of ZnO: SiO₂ materials with intense ultraviolet luminescence (UVL) with a maximum at 362 nm were studied. When human serum albumin (HSA) is applied on the surface of films, an effective fluorescent energy transfer occurs, which is manifested in an increase in the intensity of ultraviolet luminescence of ZnO: SiO₂. The increase in integrated UVL intensity is inversely proportional to HSA concentration; it has 9.2–12.6 times (with a decrease in the HSA concentration from 10^–8 to 10^–12 M) the UVL intensity of purified ZnO: SiO₂ film. The dependence of the UVL intensity on the HSA concentration is close to linear. Compared to the intensity at a concentration of 10–8 M, the gain is 8, 19, 31, and 36% for protein concentrations in the solution applied to the surface of ZnO: SiO₂ of 10^–9, 10^–10, 10^–11, and 10^–12 M, respectively. These supramolecular systems can be used to create biosensors and to simulate the physicochemical processes of photosynthesis. In the former case, the linear dependence of fluorescence on concentration is a significant advantage.     

Changes of structure and composition of a zinc ion-implanted silicon surface during nanoparticle formation upon thermal treatment

Data from investigating the formation of nanoparticles (NPs) on a surface of silicon wafers after zinc ion implantation and thermal annealing are presented. The investigation is conducted by means of trans-mission electron microscopy, electron diffraction analysis, energy dispersive microanalysis, scanning tunneling microscopy, scanning electron microscopy, and X-ray photoelectron spectroscopy. It is found that on their surfaces, the implanted samples have only films of amorphous silicon containing implanted zinc, oxygen, and carbon contamination. Thermal treatment in the range of 400–800°C leads to the formation NP with 20–50 nm wide and 10 nm tall on a wafer’s surface, plus a silicon oxide layer about 20 nm thick. NPs are composed of zinc compounds of the ZnO, ZnSiO₃, or Zn₂SiO₄ types. These NPs disappear after annealing at 1000°C.     

Atomistic simulations of the adsorption and migration barriers of Cu adatoms on ZnO surfaces using COMB potentials

Cu/ZnO heterogeneous systems are used to catalyze the CO₂ hydrogenation to methanol, but questions remain about the nature of the active site and the role of Cu–ZnO interactions in the catalyst performance. The way in which ZnO surfaces support Cu clusters and stabilize their active sites is a key factor for maintaining catalyst activity. Processes such as sintering, alloying and encapsulation may play an important role in the activity of the catalyst but are difficult to model directly with density functional theory (DFT). In this work, we report the development of charge-optimized many-body (COMB) potentials to model the Cu/ZnO system. This potential is then used in conjugation with the dimer method, which uses the first derivative of the potential energy and the initial state of the transition to find saddle points, to examine the migration barriers of Cu adatoms on Cu and ZnO surfaces. These findings are validated against the results of density functional theory (DFT) calculations and published experimental data.     

Properties of ZnO thin films deposited on (glass,ITO and ZnO:Al) substrates

ZnO thin films were deposited on glass, ITO (In₂O₃; Sn) and on ZnO:Al coated glass by spray pyrolysis. The substrates were heated at 350 °C. Structural characterization by X-ray diffraction (XRD) measurements shows that films crystallize in hexagonal structure with a preferential orientation along (0 0 2) direction. XRD peak-shift analysis revealed that films deposited on glass substrate (−0.173) were compressive, however, films deposited onto ITO (0.691) and on ZnO:Al (0.345) were tensile. Scanning electron microscopies (SEM) show that the morphologies of surface are porous in the form of nanopillars. The transmittance spectra indicated that the films of ZnO/ITO/glass and ZnO/ZnO:Al/glass exhibit a transmittance around 80% in the visible region. An empirical relationship modeled by theoretical numerical models has been presented for estimating refractive indices (n) relative to energy gap. All models indicate that the refractive index deceases with increasing energy band gap (E_g).     

Grazing incidence scattering of vibrationally excited H2 molecules from metal surfaces

We have studied the scattering of vibrationally excited H₂ molecules from metal surfaces under fast grazing incidence conditions, by means of quasi-classical calculations based on six-dimensional potential energy surfaces. We show that, in spite of the fast parallel motion, the reorientation of the molecule along the trajectory plays a fundamental role on the scattering, being responsible for the nonmonotonic behavior observed as a function of the normal incidence energy, similar to that observed under slow normal incidence conditions. The present study has allowed us to further prove that the interaction between a H₂ molecule and an ordered metal surface under fast grazing incidence conditions is, in general, governed by the normal momentum of the molecule.     

Adsorption and diffusion of an Au atom and dimer on a θ-Al2O3 (001) surface

With density-functional calculations we have investigated adsorption and diffusion of an Au atom and an Au₂ dimer on a θ-Al₂O₃(001) surface. The surface structure of θ-Al₂O₃(001) has an armchair-like configuration containing flat and trench areas and the Au_n (n = 1 or 2) cluster prefers to adsorb on the flat area. A single Au atom adsorbs on an O–Al bridge site with adsorption energy 0.35 eV, whereas an Au₂ dimer bonds to the oxide with adsorption energy 0.78 eV, with one Au coordinated singly to a surface O. Formation of Au₂ from Au₁ is favored, with a negligible energy barrier. The calculated energy barriers for diffusion indicate that an Au atom diffuses more rapidly than an Au₂ dimer but both prefer to diffuse anisotropically, along the flat area of the θ-Al₂O₃(001) surface.     

X-ray photoelectron spectroscopy study on the CrN surface grown on sapphire substrate to control the polarity of ZnO by plasma-assisted molecular beam epitaxy

We have studied on the polarity selection procedure of ZnO grown on CrN buffer by using X-ray photoelectron spectroscopy (XPS). XPS studies have been performed on the O- and Zn-treated CrN/Al₂O₃surfaces and revealed that Cr₂O₃ and Zn-chromate-like structures are formed on O- and Zn-treated CrN surfaces, respectively. The polarity selection procedure is explained in terms of the variation of bonding coordination by the formation of ZnO on the topmost O- and Zn-atoms of each surface.     

Electronic energy alignment at the PbSe quantum dots/ZnO(101̅0) interface

A number of solar energy conversion strategies depend on exciton dissociation across interfaces between semiconductor quantum dots (QDs) and other electron or hole conducting materials. A critical factor governing exciton dissociation and charge transfer in these systems is the alignment of electronic energy levels across the interface. We probe interfacial electronic energy alignment in a model system, sub-monolayer films of PbSe QDs adsorbed on single crystal ZnO(101?0) surfaces using ultraviolet photoemission spectroscopy. We establish electronic energy alignment as a function of quantum dot size and surface chemistry. We find that replacing insulating oleic-acid capping molecules on the QDs by the short hydrazine or ethanedithiol molecules results in pinning of the valence band maximum (VBM) of QDs to ZnO substrate states, independent of QD size. This is in contrast to similar measurements on TiO₂(110) where the alignment of the PbSe QD VBM to that of the TiO₂ substrate depends on QD size. We interpret these findings as indicative of strong electronic coupling of QDs with the ZnO surface but less with the TiO₂ surface. Based on the measured energy alignment, we predict that electron injection from the 1s_e level in photo-excited PbSe QDs to ZnO can occur with small QDs (diameter ? = 3.4 nm), but energetically unfavorably for larger dots (? = 6.7 nm). In the latter, hot electrons above the 1s_e level are necessary for interfacial electron injection.     

The ZnO non-polar (10 0) surface: an X-ray structural investigation

We performed a structural analysis of the non-polar ZnO (10 0) surface by means of grazing incidence X-ray diffraction. The analysis was conducted on ten rods, smooth surface domains, though of small coherent width, having been obtained after several Ar⁺ sputtering–annealing cycles. The surface derived from the bulk structure exposes one ZnO dimer per unit cell, parallel to the [001] axis. All the existing models, derived from ab initio calculations or low-energy electron diffraction (LEED) analyses, consist in a surface dimer whose O and Zn atoms are shifted inwards, with the O pointing outwards with respect to Zn. Whereas the LEED studies conclude on a dimer distance greater than in the bulk, the theoretical studies agree on a dimer contracted by amounts ranging from 5.5 to 7.5%. This contraction is interpreted as a result of the strong ionicity of ZnO, and is associated with a moderate dimer rotation. The latter, however, is found between 2.3 and 11.4°. Despite the discrepancies between the models, the Zn atom is always found shifted downwards by more than 0.25 Å. This is unambiguously rejected by our data, which show that the Zn atom keeps very close to its bulk position. It is displaced downwards by ΔZ_Zn=−0.06±0.02 Å, and it moves along [001] towards O by ΔX_Zn=0.05±0.02 Å. We denote a trend for the O atom to be displaced downwards too, with a concomitant displacement towards Zn. The faint X-ray scattering of O prevents us from assessing its position with accuracy. Depending on the choice of position for Zn in the error bar range, the buckling is evaluated as between −6.5 and 3°, or between −4 and 0.5°. The dimer distance is evaluated equal to 1.90 Å, with a deviation equal either to 0.06 or 0.11 Å.     

氢在担载金属表面的吸附研究

应用格林函数方法在紧束缚近似下研究了氢在担载金属表面的吸附性质。采用自洽的Anderson-Newns吸附模型,对氢在Pt/ZnO,Cu/ZnO和Ni/ZnO三种担载式复合体系表面的吸附能△E、吸附态能级E_ad作了计算,并讨论了金属簿层在ZnO衬底上的沉积厚度及金属-衬底相互作用对氢在该类复合体系表面的吸附性质的影响。计算表明,金属-衬底相互作用越强,氢在Pt(Cu,Ni)/ZnO体系表面的吸附能及电荷转移量越小。金属-衬底相互作用抑制了氢在金属表面的吸附。衬底对金属表面吸附性质的影 关键词：     

Surface morphology and surface chemical states of epitaxial Pb(Zr0.95Ti0.05)O3 thin films grown on SrTiO3(100) by sputter deposition

0.95 Ti_0.05)O₃ thin films of an orthorhombic perovskite structure were obtained on SrTiO₃(100) substrates by radio frequency sputter deposition. The surface morphology of the films was investigated with atomic force microscopy, scanning electron microscopy, and reflection electron microscopy. It is shown that the film surfaces are rather bumpy. There are undulations of about 400 nm in length in an in-plane direction. The mean roughness perpendicular to the surface is 39.6 nm, for the film thickness of 0.45 μm. The surface roughening was probably caused by island-shaped nucleation and growth during the film growth. It has also been found that some gorges and a number of small pits remain at the film surfaces. The surface chemical states of the films were characterized by using X-ray photoelectron spectroscopy. A Pb enrichment layer and a large amount of adsorbed oxygen have been found at the surfaces of the films. Near the film surface Pb and Zr exist mainly in the forms of, besides Pb(Zr,Ti)0₃, metal Pb, metal Zr, oxygen-chemisorbed Pb, and various lead oxides. In addition, a small amount of lead, whose binding energy of Pb 4f_7/2 is much lower than that of metal Pb, was observed at the film surfaces, but its chemical state is unknown up to now. Received: 2 June 1997/Accepted: 22 September 1997     

Chemisorption,photodesorption and conductivity measurements on ZnO surfaces

Experimental results of a mass-spectro metric analysis of photodesorption from ZnO single crystals at different temperatures are reported. They provide direct evidence that CO₂ is the only photodesorbed species from both the single crystal and powder samples studied. The CO₂ photodesorption occurs only when the incident photon energy exceeds the ZnO band gap energy. Excellent agreement between the illumination time dependence of the CO₂ photodesorption and surface conductivity data in both single crystals and powder samples strongly suggests a substrate dependent mechanism in which photodesorption occurs by the neutralization of chemisorbed CO₂^? “ion-molecules” by photogenerated holes. In addition, measurements of the chemisorption kinetics of oxygen on ZnO single crystal and powder surfaces are reported. The results are compared with CO₂ and CO chemisorptiun experiments to show that, of these gases, only oxygen chemisorbs from the gas phase. Auger analysis of oxygen saturated and photodesorbed surfaces of ZnO show a significant relation between the carbon content and the photo-desorptive and conductive activities of those surfaces. These observations indicate that impurity carbon atoms on ZnO surfaces can be oxidized by electron capture to produce chemisorbed CO₂^? “ion-molecules’ which will then readily photodesorb by bandgap radiation. This proposed process is discussed together with further supporting evidence.     

Ordered ultra thin ZnO films on metal substrate

Ultra thin ZnO films were prepared on metal Mo(1 1 0) substrate under ultrahigh vacuum conditions either by depositing Zn in 10⁻⁵ Pa oxygen or by oxidizing pre-deposited Zn films. The films were characterized in situ by various surface analytical techniques, including Auger electron spectroscopy, X-ray and ultraviolet photoelectron spectroscopies, low energy electron diffraction and high resolution electron energy loss spectroscopy. The results indicate that a long-range ordered and stoichiometric ZnO films are formed along its [0 0 0 1] direction. The annealing experiments show that as-prepared ZnO films are thermal stable until 800 K. This study provides constructive information to further understand the growth mechanism of ZnO films on different substrates.     

Water adsorption on the Be(0001) surface: from monomer to trimer adsorption

In this paper, the density functional theory has been used to perform a comparative theoretical study of water monomer, dimer, trimer, and bilayer adsorptions on the Be(0001) surface. In our calculations, the adsorbed water molecules are energetically favoured adsorbed on the atop sites, and the dimer adsorption is found to be the most stable with a peak adsorption energy of ～437 meV. Further analyses have revealed that the essential bonding interaction between the water monomer and the metal substrate is the hybridization of the water 3a₁-like molecular orbital with the (s, p_z) orbitals of the surface beryllium atoms. While in the case of the water dimer adsorption, the 1b₁-like orbital of the H₂O molecule plays a dominant role.     

Desorption kinetics and directional dependence of the surface diffusion of potassium on stepped W(100) surfaces

Using a surface ionisation ion microscope the desorption parameters and the diffusion constant of potassium were measured on stepped W(100) surfaces. The activation energy of ionic desorption as well as the corresponding prefactor do not depend on the step density; the mean adsorption lifetime τ can be expressed as τ=1.6×10^?14s exp(2.44 eV/kT).Whereas the surface diffusion of potassium on “flat” W(100) and on W(S)-[9(100)×(110)] was found to be isotropic, on W(S)- [5(100)×(110)] and W(S)-[3(100)×(110)] it occurs preferentially parallel to the step direction. The diffusion constant D_∥ for this direction has roughly the same value for all investigated surfaces: D_∥=7.8×10^?2 cm²s^?1 exp(?0.42 eV/kT). For the direction perpendicular to the steps D⊥ depends on the step density, whereby the activation energy as well as the prefactor increase with increasing step density.     

An influence of deposition temperature on structural,optical and electrical properties of sprayed ZnO thin films of identical thickness

Nanocrystalline ZnO thin films were deposited at different temperatures (T_s = 325 °C–500 °C) by intermittent spray pyrolysis technique. The thickness (300 ± 10 nm) independent effect of T_s on physical properties was explored. X-Ray diffraction analysis revealed the growth of wurtzite type polycrystalline ZnO films with dominant c-axis orientation along [002] direction. The crystallite size increased (31 nm–60 nm) and optical band-gap energy decreased (3.272 eV–3.242 eV) due to rise in T_s. Scanning electron microscopic analysis of films deposited at 450 °C confirmed uniform growth of vertically aligned ZnO nanorods. The films deposited at higher T_s demonstrated increased hydrophobic behavior. These films exhibited high transmittance (>91%), low dark resistivity (～10^?2 Ω-cm), superior figure of merit (～10^?3 Ω^?1) and low sheet resistance (～10² Ω/□). The charge carrier concentration (η -/cm³) and mobility (μ – cm²V^?1s^?1) are primarily governed by crystallinity, grain boundary passivation and oxygen desorption effects.