First-principles study of electronic structures and optical properties of Cu, Ag, and Au-doped anatase TiO2

We perform first-principles calculations to investigate the band structure, density of states, optical absorption, and the imaginary part of dielectric function of Cu, Ag, and Au-doped anatase TiO₂ in 72 atoms systems. The electronic structure results show that the Cu incorporation can lead to the enhancement of d states near the uppermost of valence band, while the Ag and Au doping cause some new electronic states in band gap of TiO₂. Meanwhile, it is found that the visible optical absorptions of Cu, Ag, and Au-doped TiO₂, are observed by analyzing the results of optical properties, which locate in the region of 400-1000 nm. The absorption band edges of Cu, Ag, and Au-doped TiO₂ shift to the long wavelength region compared with the pure TiO₂. Furthermore, according to the calculated results, we propose the optical transition mechanisms of Cu, Ag, and Au-doped TiO₂. Our results show that the visible light response of TiO₂ can be modulated by substitutional doping of Cu, Ag, and Au.     

过渡金属Fe或Ag掺杂K2Ti6O13的电子结构和光学性质

本文利用基于密度泛函理论（DFT）的第一性原理计算研究了它们的电子结构和光学性质.光学性质的计算结果和实验相一致.结果表明,Fe或Ag掺杂后,K₂Ti₆O₁₃的带隙中出现了杂质带且其带隙值变小,因而使掺杂后的K₂Ti₆O₁₃的吸收边发生红移并实现了其对可见光吸收.其中杂质带主要由Fe 3d态或Ag 4d态与Ti 3d态和O 2p态杂化而成.对于Fe掺杂的K₂Ti₆O₁₃,杂质带位于带隙中间,因此可以作为电子从价带跃迁到导带的桥梁.对于Ag掺杂的K₂Ti₆O₁₃,杂质带位于价带顶附近为受主能级,可以降低光生载流子的复合概率.实验和计算研究表明,通过Fe或Ag的掺杂可以实现了K₂Ti₆O₁₃对可见光的吸收,这对进一步研究K₂Ti₆O₁₃的光学性质具有重要意义.     

Impurity-state-like nature of Fermi-liquid states in Bi2Sr2CaCu2O8 observed by photoemission and x-ray absorption

Photoemission and X-ray absorption spectroscopy have been performed on Bi₂Sr₂Ca_1−xY_xCu₂O₈ in which the hole concentration is controlled by the ratio between Ca and Y atoms. It was found that the density of electronic states at the Fermi level gradually increases as the hole concentration with almost no rigid shift of the electronic structure with respect to the Fermi level. This suggests that the electronic states at the Fermi level (Fermi-liquid states) would not be simple one-electron states but be a kind of impurity states produced through the strong hybridization between doped O2p hole orbitals and empty Cu3d orbitals.     

Optical absorption spectrum of X-irradiated CaF2:Cr and SrF2:Cr

The optical absorption spectra of X-irradiated CaF₂:Cr and SrF₂:Cr are studied. X-irradiation induces the formation of a prominent band in the u.v. region (centered at 277 nm in CaF₂ and 285 nm in SrF₂) as well as a weak absorption in the visible region. Combined EPR and optical absorption measurements together with some optical bleaching experiments suggest that the u.v. absorption bands are related with either Cr⁺ or Cr³⁺ ions. Several arguments are presented in order to tentatively associate these bands with an interconfigurational transition of Cr⁺ in a cubal environment.     

Cu、Ag和Au掺杂AlN的电磁性质的第一性原理研究

采用基于密度泛函理论（DFT）的平面波超软赝势法,研究了Cu、Ag、Au掺杂AlN的晶格常数、磁矩、能带结构和态密度。电子结构表明,Cu、Ag、Au的掺杂使在带隙中引入了由杂质原子的d态与近邻N原子的2p态杂化而成的杂质带,都为p型掺杂,增强了体系的导电性。Cu掺杂AlN具有半金属铁磁性,半金属能隙为0.442eV,理论上可实现100%的自旋载流子注入;Ag掺杂AlN具有很弱的半金属铁磁性;而Au掺杂AlN不具有半金属铁磁性。因此,与Ag、Au相比,Cu更适合用来制作AlN基稀磁半导体。     

Absorption and photoluminescence of Eu2+-doped 1-D CsCdBr3 single crystal

Eu²⁺-doped CsCdBr₃ single crystals are studied by polarized variable-temperature optical absorption and luminescence spectroscopy for different excitation wavelengths. Whereas the low-energy absorption band is assigned to f→d transitions within Eu²⁺ electronic configuration, the high-energy absorption bands are assigned to Eu-trapped exciton due to the proximity of the high-energy d levels to the conduction band.     

Electronic transitions of Ar,Xe, N2, CO physisorbed on Ag(111) and Al(111)

High Resolution Electron Energy Loss Spectroscopy has been extended to study also the excitonic (low lying electronic) transitions of physisorbed rare gas atoms (Ar, Xe) and diatomic molecules (N₂, CO) on Ag(111) and Al(111) surfaces at ～20K. Electron Loss Spectra were performed using a pair of hemispherical analyzers mounted at a fixed scattering angle (90°). This spectrometer allowed high transmission in the range of 0–15eV loss energies and incident beam energies up to 2OeV. AES, LEED and UV Photoemission (HeI) were also used in situ to characterize these surfaces and to identify the adsorbed gases and delineate their absolute coverage regimes.In contrast to optical absorption experiments, we observe both, optical (dipole) forbidden and allowed electronic transitions which show vibrational line structure for condensed multilayers. By comparison to gas phase data we find only weak perturbations in the condensed state. The observed electronic excitations show changes in intensity and FWHM depending on the coverage of the adsorbed gases.The FWHM of the electronic excitations of CO and N₂ adsorbed in the monolayer regime is larger than in multilayers. Nitrogen, on both surfaces exhibits an increase from 60meV to 120meV (FWHM) whereas for CO the vibronic features are broadened out leaving peaks with FWHM of ～1eV.The intensities of the electronic losses for all gases are smaller in the first monolayer than in the second or in multilayers. At submonolayer coverage the loss intensifies due to electronic excitations are strongly reduced and no longer observable although vibrational bands and photoelectron spectra show the presence of physisorbed adsorbates.Our results will be compared to optical absorption experiments (ref.1) on similar systems and to atom-on-jellium calculations (ref.2).     

Sensitized luminescence of SrS:Dy,Cu,Cl phosphor

SrS:Dy,Cu,Cl phosphors for a fixed Dy concentration and different Cu concentrations were prepared by solid-state reaction. Studies on the structural and optical properties of the samples were carried out. From analysis of photoluminescence measurements, it was observed that the excitation in the absorption bands of Cu⁺ ion leads to transfer of energy to Dy³⁺ ion, thereby enhancing the intensity of its luminescence.     

Temperature dependence of photo-hole decay in 4d derived Quantum Well States in monolayer Ag(111) films on Pd(111), Ni(111), Mo(110) and Cu(100)

We present experimental data on the temperature dependence of photo-hole decay obtained by Angle Resolved Photoemission (ARPES) measurements from 4d derived Quantum Well States (QWS) on Ag(111) monolayer films deposited on Pd(111), Ni(111), Mo(110) and Cu(100). We have found a significant increase of the Ag 4d electron–phonon (e-ph) coupling strength with respect to the bulk values. The increase is attributed to different mechanisms that are associated with the interaction of the Ag film with under laying substrate. It is proposed that the main channels that contribute to the increased e-ph coupling originate from the inter-band transitions that involve bulk states of the substrates.     

Evidence for localizing properties of XPS applied to valence bands

X-ray photoelectron spectroscopy (XPS)-measurements of the valence bands of Cu, Ag and Au have been performed and their integrated intensities have been compared. A model calculation which considers the influence of the x-ray absorption length as well as the electronic escape depth on the obtained intensities was established and applied to the measurements. An additional electron microscopic study on the surface structure of the evaporated samples has been performed. Its influence on the obtained photoelectron yield is discussed. The results support a marked dependence of the integrated valence band intensity on the atomic number. The implications for the interpretation of XPS valence band spectra of alloys are discussed and compared with corresponding x-ray isochromat spectroscopy (XIS)-measurements. Furthermore we deal with the important question whether XPS-as well as XIS-spectra can be described mainly in terms of the electronic band structure or whether atomic features are also present, though both methods are free from participation of core levels. The results are discussed in terms of localizing properties of XPS.     

Third-order nonlinear optical response of Cu/Ag nanoclusters by ion implantation under 1064 nm laser excitation

The evolution of nanoclusters in sequentially ion-implanted Cu/Ag into silica glasses has been studied. The doses for implantation (×10¹⁶ ions/cm²) were 5Cu/5Ag, 5Cu/10Ag and 5Cu/15Ag, respectively. The microstructural properties of the nanoclusters are characterized by optical absorption spectra and transmission electron microscopy (TEM). Fast nonlinear optical refraction and nonlinear optical absorption coefficients were measured at 1064 nm of wavelength using Z-scan technique. Results in this project indicate that different optical nonlinearities could be selectively obtained at the near-infrared region of 1064 nm of wavelength by changing the metal ingredient percentage in silica.     

CaWO4晶体中F型色心电子结构的研究

运用相对论的密度泛函离散变分法(DV-Xα)研究了CaWO₄晶体中F型色心的电子结构. 计算结果表明，F和F⁺心在禁带中引入了新的施主能级；分析了晶体内可能存在的光学跃迁模式，并通过过渡态的方法计算了F，F⁺心跃迁到导带底的能量分别为1.92eV和2.42eV. 因此，从理论上推断了F和F⁺心在CaWO₄晶体中可能引起650nm和515nm的吸收，由此说明CaWO₄晶体中650nm和515nm吸收带起源于晶体中的F和F⁺心. 关键词： 4晶体')" href="#">CaWO₄晶体 +心')" href="#">F和F⁺心 DV-Xα     

First-principles study on electronic and optical properties of Cu-doped LiF with Li vacancy

Taken into account the presences of Li vacancy (V_Li), we calculate the formation energy, electronic structure and optical properties of Cu doped LiF (LiF:Cu) by using the density functional theory. The presence of V_Li leads to a decrease of the formation energies of Cu, in favor of Cu doping into LiF. Due to Cu doping, an impurity band of Cu-3d states is formed at the Fermi level, which is then split by the introduction of V_Li. A wide absorption band and some new absorption peaks are obtained in LiF:Cu with an adjacent V_Li to Cu. There appears an absorption peak at 9.3 eV, which is consistent with the experiment observation (133 nm). The results are useful for understanding of the optical properties of the doped systems.     

Ag掺杂AlN半导体光电性质的第一性原理研究

采用基于密度泛函理论的第一性原理平面波超软赝势法,对Ag掺杂AlN 32原子超晶胞体系进行几何结构优化,计算并分析体系的电子结构、磁性和光学性质.结果表明:Ag掺杂后,Ag4d态电子与其近邻的N2p态电子发生杂化,引入杂质带形成受主能级,实现p型掺杂,使体系的导电能力增强,同时表现出金属性和弱磁性,其净磁矩为1.38μ_в.掺杂形成的N-Ag键电荷集居数较小,表现出强的离子键性质.掺杂后体系的介电函数虚部和光吸收谱在低能区出现新的峰值,同时复折射率函数在低能区发生变化,吸收边向低能方向延展,体系对长波吸收加强,能量损失明显减小.     

UV-photoemission measurements on erbium and samarium

Photoemission measurements have been made on samarium and erbium in the photon energy range 4 to 21 eV. The photoelectron energy distributions are dominated by electron emission from valence band states whereas emission from 4f-states is unimportant. The width and energy of the occupied and unoccupied 5d-bands has been determined as well as the energy relative to the Fermi level of the bottom of the valence band. A model for the unscattered yield is presented allowing a determination of the hot electron scattering length for some rare-earths using available optical and photoemission data.     

Electronic structure of HgTe nanocrystals: An observation of p-d weakening

Photoemission studies to identify the electronic structure of the HgTe nanocrystals revealed a new phenomenon of p-d weakening, as a consequence of size quantization effect associated with the mean crystalline size, 5.35 ± 0.83 nm. The weakening of the p-d hybridization by a factor of 0.33, to that of the bulk HgTe suggests the valence band maxima and core level shifts toward higher binding energy. The widening of the band gap due to size quantization is confirmed from optical absorption and photoluminescence measurements. The upward and downward shift of the conduction band minima and the valence band maxima with respect to the bulk value of HgTe are found to be 1.6 eV and 0.54 eV respectively.     

Effect of the material of metal nanoparticles on local field intensification in copper phthalocyanine

For spherical Cu, Ag, and Au nanoparticles with a radius of 1–3 nm in copper phthalocyanine (CuPc), with allowance for internal size effects, we calculate the scattering efficiency factor in the near zone, the extinction efficiency factor due to scattering and absorption of incident radiation, and the efficiency of the increase in absorption by the matrix material. This occurs in the CuPc absorption bands, as well as in the weak absorption region of CuPc, where, owing to surface plasmon resonance, an additional absorption band arises for nanoparticles of all three materials. For Ag nanoparticles, the increase in absorption is twice as high as for Cu and Au nanoparticles; for these it differs inconsiderably.     

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.     

AES and PYS studies of the polar GaAs(111) as surface after thermal cleaning in ultrahigh vacuum

Auger Electron Spectroscopy (AES) and Photoemission Yield Spectroscopy (PYS) have been used in the investigations of elemental composition and electronic properties of the polar GaAs-(111) As surface after thermal cleaning by electron bombardment heating at 770 K in an ultrahigh vacuum of 10⁻⁷ Pa. The surface concentration of As was 0.01 ML which corresponds to the (1 × 1) and weak (3 × 3) atomic structure, whereas the work function and absolute band bending were 4.05 ± 0.02 eV and −0.21 ± 0.04 eV, respectively. Moreover, two filled electronic surface state bands localized in the band gap below the Fermi level EF and in the upper part of the valence band were observed which have been described as the dangling-bond surface state and back-bond surface state bands, respectively.     

Growth, alloy formation and reaction with oxygen of Ag and Au submonolayers on W(1 1 0) studied by valence band and core level photoemission

We have studied epitaxial submonolayers of Ag and Au deposited one after another onto W(1 1 0) at room temperature and subsequently annealed at 600 K. Photoemission spectroscopy of valence bands and the Ag3d_5/2 core level has been used to monitor two-dimensional alloy formation. The extent of alloying depends on the order of deposition, composition and annealing. We have also studied the reaction of alloy surfaces to exposure of molecular oxygen at 300 and 600 K.