Scattering of surface states at step edges in nanostripe arrays

Surface states of noble metal surfaces split into Ag-like and Cu-like subbands in stepped Ag/Cu nanostripe arrays. The latter self-assemble by depositing Ag on vicinal Cu(111). Ag-like states scatter at nude step edges in Ag stripes, leading to umklapp bands, quantum size effects, and peak broadening. By contrast, Ag stripe boundaries become transparent to Cu-like states, which display band dispersion as in flat Cu(111). We find a linear relationship between the quantum size shift and peak broadening that applies in a variety of stepped systems, revealing the complex nature of step barrier potentials.     

Breakup of quasiparticles in thin-film quantum wells

Quantum well states in thin films are commonly described in terms of a quasiparticle confined in a quantum box, but this single-particle picture can fail dramatically near a substrate band edge, as shown by this angle-resolved photoemission study. Atomically uniform Ag films are prepared on Ge(111) to facilitate accurate line shape and dispersion relation measurements. A quantum well peak is observed to split into two peaks near the Ge valence band edge. The unusual line shapes are shown to be due to many-body interactions and are quantitatively explained by a Green's function calculation.     

Spin polarization of quantum well states in Ag films induced by the Rashba effect at the surface

The electronic structure of Ag(111) quantum well films covered with a (sqrt[3]xsqrt[3]) R30 degrees Bi/Ag surface ordered alloy, which shows a Rashba spin-split surface state, is investigated with angle-resolved photoemission spectroscopy. The band dispersion of the spin-split surface state is significantly modified by the interaction with the quantum well states of Ag films. The interaction is well described by the band hybridization model, which concludes the spin polarization of the quantum well states.     

表面增强机制中反常光吸收效应的理论研究

本文改进了银胶的制备方法 ,采用机械方法使银胶体系发生凝聚效应 ,其吸收峰位于435nm附近。当加入其他分子时 ,该吸收带没有明显移动 ,而在 435nm吸收带之外又出现了通常熟知的新的吸收带 ,其峰位随着加入其他分子的量的增加而向长波方向移动 ,本文的量子理论表明 ,435nm附近的吸收带是由银胶体系凝聚效应引起的 ,它应归属于银胶的凝聚特征峰。而在 435nm以外长波方向出现的吸收带 ,分析表明 ,它与银颗粒表面的化学吸附有关。     

Electronic structure study of ultrathin Ag(111) films modified by a Si(111) substrate and √3 × √3-Ag2Bi surface

Angle-resolved photoemission spectroscopy experiments show that the electronic structure of a Ag(111) film grown on Si(111) is markedly perturbed by the formation of a √3 × √3-Ag(2)Bi Rashba-type surface alloy. Four spin-split surface states, with different band dispersions and energy contours, intercept and hybridize selectively with the sp-derived quantum well states of the Ag layer. Detailed two-dimensional band mapping of the system was carried out and constant energy contours at different energies result in hexagonal-, star- and flower-like distortions of the quantum well states as a result of various interactions. Further wavy-like modulations of the electronic structure of the film are found to originate from umklapp reflections of the Ag film states according to the surface periodicity.     

Modulated photoemission spectroscopy: Application to Au

We describe modulated photoemission spectroscopy, in which an internal (sample) parameter such as temperature, or an external (apparatus) parameter such as wavelength is varied. A general formalism is developed for modulated photoemission spectroscopy and then illustrated using temperature modulated photoemission spectra and yields for Au obtained in the ～ 6 to 11.6 eV photon energy range. Modulated s-p band photoemission data are described in terms of photoemission critical points in order to explain the nature of the modulated structures in the s-p band region and relate experiment to energy band thresholds obtained from a recent band calculation for Au. Application of the formalism to modulated d-band emission leads to a method for extracting d-band deformation potentials. For example, we find that the upper d band edge moves upward with respect to E_F at a rate of 2 to 6 × 10^?4 eV/K. Modulation of the quantum yield is described and our measurements are compared with modulated optical data.     

Thin noble metal films on Si (111) investigated by optical second-harmonic generation and photoemission

Thin noble metal films (Ag, Au and Cu) on Si (111) have been investigated by optical second-harmonic generation (SHG) in combination with synchrotron radiation photoemission spectroscopy. The valence band spectra of Ag films show a quantization of the sp-band in the 4-eV energy range from the Fermi level down to the onset of the d-bands. For Cu and Au the corresponding energy range is much narrower and quantization effects are less visible. Quantization effects in SHG are observed as oscillations in the signal as a function of film thickness. The oscillations are strongest for Ag and less pronounced for Cu, in agreement with valence band photoemission spectra. In the case of Au, a reacted layer floating on top of the Au film masks the observation of quantum well levels by photoemission. However, SHG shows a well-developed quantization of levels in the Au film below the reacted layer. For Ag films, the relation between film thickness and photon energy of the SHG resonances indicates different types of resonances, some of which involve both quantum well and substrate states. Received: 16 October 2001 / Revised version: 14 March 2002 / Published online: 29 May 2002     

Interface effects on the quantum well states of Pb thin films

Using scanning tunneling spectroscopy, we have studied the interface effect on quantum well states of Pb thin films grown on various metal-terminated (Pb, Ag, and Au) n-type Si(111) surfaces and on two different p-type Si(111) surfaces. The dispersion relation E(k) of the electrons of the Pb film and the phase shift at the substrate interface were determined by applying the quantization rule to the measured energy positions of the quantum well states. Characteristic features in the phase shift versus energy curves were identified and were correlated to the directional conduction band of the silicon substrate and to the Schottky barrier formed between the metal film and the semiconductor. A model involving the band structure of the substrate, the Schottky barrier, and the effective thickness of the interface was introduced to qualitatively but comprehensively explain all the observed features of the phase shift at the substrate interface. Our physical understanding of the phase shift is critically important for using interface modification to control the quantum well states.     

五边形截面的Ag纳米线局域表面等离子体共振模式

五边形截面的单晶Ag纳米线对ZnO量子点荧光具有增强的现象. 为解释这一现象, 利用时域有限差分法对五边形截面的Ag纳米线的局域表面等离子体共振模式进行了理论模拟. 结果表明, 五边形截面的Ag纳米线在紫外区域存在两个消光峰, 分别由Ag纳米线的横向偶极共振(340 nm)和四极共振(375 nm)引起; 这两个消光峰与ZnO量子点荧光增强峰相一致, 而且随着Ag纳米线的半径增大而红移; 消光峰对应的共振模式取决于Ag纳米线的截面形状; 根据Ag纳米线电场增强倍数与激发光波长变化关系曲线可知, 最大增强电场位于五边形截面的顶点处, 而边线处电场增强较小. 理论模拟的结果较好地解释了Ag纳米线/ZnO量子点体系的荧光增强现象, 也为Ag纳米线在提高半导体材料发光效率、生物探测等方面的应用提供有益的参考.     

GaAs/AlGaAs超晶格的光致发光

在室温下测量了GaAs/A l0.3Ga0.7As超晶格的光致发光,发现在波长λ=761 nm处存在一较强的发光光峰,此发光峰目前尚未见报道。经理论分析表明,此峰是量子阱中的第一激发态电子与受主空穴复合发光。实验还观测到在λ=786 nm处,λ=798 nm处和λ=824 nm处分别存在一发光峰,分析表明λ=786 nm处的发光峰为量子阱阱中费米能级附近的电子与轻空穴复合发光;λ=798 nm处的发光峰为量子阱内的基态电子到轻空穴的复合发光;λ=824 nm处的发光峰为阱中激子复合复合发光。理论计算与实验结果符合的很好。     

A density functional theory study of H2S decomposition on the (1 1 1) surfaces of model Pd-alloys

In this work, we report density functional theory calculations exploring H₂S dissociation on the (1 1 1) surfaces of Pd, Cu, Ag, Au, and various bimetallic surfaces consisting of those metals. To understand the contributions of lattice strain and electronic ligand effects, the thermodynamics of each elementary dissociation step were explored on model bimetallic surfaces, including PdMPd sandwiches and Pd pseudomorphic overlayers, as well as strained Pd(1 1 1) surfaces and homogeneous Pd₃M alloys. Sulfuric (H₂S, SH, and S) adsorption energies were found to correlate very well with lattice constant, which can be explained by the strong correlation of the lattice constant with d-band center, Fermi energy, and density of states at the Fermi level for strained Pd(1 1 1) surfaces. Compressing the Pd lattice shifts the d-band center away from the Fermi level, lowers the Fermi energy, and reduces the density of d-states at the Fermi level. All three effects likely contribute to the destabilization of sulfuric adsorption on Pd alloys. Introducing ligand effects was found to alter the distribution of the d-states and shift the Fermi level, which eliminates the correlation of the d-band center with the density of states at the Fermi level and the Fermi energy. As a result, the d-band center by itself is a poor metric of the H₂S reaction energetics for bimetallic surfaces. Furthermore, combining strain with ligand effects was found to lead to unpredictable alterations of the d-band. Therefore, adsorption of H₂S, SH, and S on PdMPd surfaces do not accurately predict adsorption on Pd₃M surfaces.     

Optical properties of Ag nanoparticle embedded silicate glass prepared by field-assisted diffusion

Ag nanoparticle embedded silicate glass was prepared by field-assisted diffusion, combined with post-annealing process. Surface plasmon resonance (SPR) bands were observed in the optical absorption measurement. The properties of optical absorption were strongly affected by the process parameters. With increasing electric field intensity and diffusion time, the SPR peak position and the full width at half maximum (FWHM) of the plasmon band were almost invariable. With increasing post-annealing time, the SPR peak was blue-shifted and the FWHM of SPR band decreased. The experimental results could be well simulated using modified Mie scattering theory considering the spill-out effects and the limitation of the mean free path.     

Optical dynamics of energy-transfer from a CdZnO quantum well to a proximal Ag nanostructure

We studied photoluminescence (PL) and energy-transfer dynamics in a hybrid structure comprising a Cd(0.08)Zn(0.92)O quantum well (QW) and an Ag nanostructure. The observed PL quenching was dependent on the electronic states in the QW. Quenching occurred at low temperature where excited carriers recombined radiatively because of excitonic localization, which disappeared with increasing temperature due to delocalization of excitons. Furthermore, nanostructured Ag surfaces produced local surface plasmon (LSP) absorption that was resonant with the PL peak energy of the QW emission. These results indicate that the recombination energy of excitons transfers nonradiatively to induce LSP excitation, which was revealed using time-resolved PL measurements.     

Nonlinear energy absorption of femtosecond laser pulses in noble metals

We use calorimetry to determine the energy absorption of femtosecond (fs) laser pulses as a function of incident fluence for Ag, Ag alloys (Ag–Cu and Ag–Pt), and Pt. At low fluences, the measured absorption agrees well with reflectivity data derived from ellipsometry measurements. For Ag and Ag–Cu, the absorbed energy increases nonlinearly with the incident fluence for fluences larger than approximately half of the melting threshold. Near this threshold, the absorption increases by a factor of 3–4. Similar nonlinear absorption is not observed in Pt or Ag–Pt. We propose that the nonlinear absorption is caused by the excitation of d-band electrons below the Fermi surface. For pulse widths longer than 850 fs, the observed nonlinear absorption in Ag diminishes, indicating that diffusive transport and not ballistic transport is the major mechanism of cooling at this excitation level.     

Electronic-structure dependence of the electron-phonon interaction in Ag

The linewidths of sp- and d-band derived electronic quantum-well states in thin films of Ag on Fe(100) are measured as a function of temperature to yield the electron-phonon coupling parameters. The results vary by a factor of up to 35 among the different states. The origin of these huge differences is traced to the decay path selection for the various initial states of the holes created by the photoemission process. The electron-phonon coupling parameter for the top d-band quantum-well state, 0.015+/-0.006, is the smallest ever reported.     

Probing quasiparticle states bound by disparate periodic potentials

Thin films of Ag(111) with two-dimensional crystallinity of large lateral coherence grow on Ge(111), free of in-plane registry with the underlying substrate. Ag s-p electrons forming two-dimensional quantum well states scatter coherently at the buried interface potential, resulting in an unexpected set of new quasiparticle states, as observed by angle-resolved photoemission. These new features originate from interactions among Ag quantum well bands, gaining a momentum equivalent to a reciprocal vector of the substrate lattice.     

Energy loss mechanisms in low energy electron scattering from W(100) and their use as a surface sensitive spectroscopy

The energy loss spectrum of low energy (0 < E_p < 200 eV) electrons scattered from W(100) has been experimentally investigated, and mechanisms giving rise to the fine structure analyzed using a dielectric response formalism. The dielectric medium is characterized by available optical data and energy band calculations for tungsten. All of the structure for loss energies, w, less than 18 eV is attributed to intra- and interband transitions involving the bulk valence and conduction bands. The surface and bulk plasmon excitations are observed at w = 21 eV and w = 25.5 eV respectively which is in reasonable agreement with the optical data. A very narrow peak in the density of conduction d-band states apparently functions strongly in well defined excitations involving the $\text{5p}\text{3}\text{2}$ and 4f tungsten orbitais and the 2s and 2p orbitais of adsorbed oxygen. These conduction band states form a “window” with which to measure the electronic orbital structure of both the substrate and adsorbate during adsorption and reaction. We demonstrate this for the room temperature adsorption of oxygen on W(100) in which we observe the sequential filling of two electronically inequivalent binding states. The stability of the “d-band window” during thermally activated reaction, and the likelihood of its existence in other transition metals makes this an attractive surface sensitive spectroscopy.     

Surface characteristics of Ag‐doped Au nanoparticles probed by Raman scattering spectroscopy

We have examined the surface characteristics of Ag‐doped Au nanoparticles (below 5 mol% of Ag) by means of the surface‐enhanced Raman scattering (SERS) of 2,6‐dimethylphenylisocyanide (2,6‐DMPI) and 4‐nitrobenzenethiol (4‐NBT). When Ag was added to Au to form ∼35‐nm‐sized alloy nanoparticles, the surface plasmon resonance band was blue‐shifted linearly from 523 to 517 nm in proportion to the content of Ag up to 5%. In the SERS spectra of 2,6‐DMPI, the N‐C stretching peak also shifted almost linearly from 2184 to 2174 cm⁻¹ when the Ag content was 5 mol% or less; the peak then remained the same as that of the pure Ag film. The potential variation of the SERS spectrum of 2,6‐DMPI in an electrochemical environment, as well as the effect of organic vapor, also showed a similar tendency. From the SERS of 4‐NBT, we confirmed the occurrence of a surface‐induced photoreaction converting 4‐NBT to 4‐aminobenzenethiol, when Ag was added to Au to form alloy nanoparticles. The photoreaction induction ability also increased linearly with the Ag content, reaching a plateau level at 5 mol% of Ag. All these observations suggest that the surface content of Ag should increase almost linearly as a function of the overall mole fraction of Ag and, once the Au/Ag nanoparticles reach 5 mol% of Ag, their surfaces are fully covered with Ag, showing the same surface characteristics of pure Ag nanoparticles. Copyright © 2011 John Wiley & Sons, Ltd.     

Spectral densities and the surface electronic structure of tungsten

The recursion method is used to calculate spectral densities at surfaces for the particular purpose of further analysing the nature of the central peak in the d-band density of states at the tungsten (100) surface.     

On the polarization self-screening effect in multiple quantum wells for nitride-based near ultraviolet light-emitting diodes

The tilted energy band in the multiple quantum wells(MQWs) arising from the polarization effect causes the quantum confined Stark effect(QCSE) for [0001] oriented III-nitride-based near ultraviolet light-emitting diodes(NUV LEDs). Here, we prove that the polarization effect in the MQWs for NUV LEDs can be self-screened once the polarization-induced bulk charges are employed by using the alloy-gradient In_xGa_(1-x)N quantum barriers. The numerical calculations demonstrate that the electric field in the quantum wells becomes weak and thereby flattens the energy band in the quantum wells, which accordingly increases the spatial overlap for the electron-hole wave functions. The polarization self-screening effect is further proven by observing the blueshift for the peak emission wavelength in the calculated and the measured emission spectra. Our results also indicate that for NUV LEDs with a small conduction band offset between the quantum well and the quantum barrier,the electron injection efficiency for the proposed structure becomes low. Therefore, we suggest doping the proposed quantum barrier structures with Mg dopants.