High-resolution photoemission study of adatom bonding effects: Cl (√2 × √2) R 45° on Cu (100)

We have investigated photoemission from an ordered $\text{(}\text{2}\text{×}\text{2}\text{) R 45°}$ Cl-overlayer on Cu (100) at good angular (Δθ ? 1°) and energy (ΔE = 100 meV) resolution. We observe two prominent adsorbate- induced features at 1.95 eV (FWHM ≈ 100 meV) and 5.4 eV (0.65 eV) below E_F. By determination of their angular momentum character, their spatial orientation and their energy dispersion, they are identified as “antibonding” and “bonding” resonances, respectively. Significant modification of the Cu d-band emission is observed and interpreted in terms of substrate orbitals which are involved in bonding.     

Copper,the dominant acceptor in refined,undoped zinc telluride

Comparative measurements have been made of optical absorption and photoluminescence of refined undoped and Cu in-diffused ZnTe single crystals. Strong increases in a bound exciton BE line near 2.375 eV previously identified with the electrically dominant point defect acceptor ‘a’, with binding energy E_A ? 149 meV, suggests that this acceptor is substitutional Cu_Zn. Similarly strong increases in a relatively broad band at slightly higher energy suggests the simultaneous incorporation of shallow donors, possibly interstital Cu_I. These findings indicate that intrinsic defects such as V_Zn neither control the Fermi level in refined ZnTe nor produce shallow acceptors with E_A ? 250 meV, contrary to much previous speculation.     

Study of acceptor states in CdTe by donor-acceptor pair excitation luminescence

Excitation of donor-acceptor pair luminescence has been studied in CdTe doped with lithium or chlorine. The excitation spectrum of the lithium acceptor is determined and fitted with the effective mass theory of Baldereschi and Lipari. Revised values of the valence band parameters are deduced: μ = 0.8, δ = 0.054, Ry = 24 meV. The analysis of the 1.45 eV luminescence band in compensated Cl-doped crystals shows the existence of donor-acceptor pair transitions. Three acceptor centers are identified: E_A = 89, 111 and 119 meV, and the contribution of a deep donor (E_D > 40 meV) is demonstrated. Besides intracentre type excitation transitions of the 1.45 eV band have been observed in non-compensated chlorine-doped crystals. Thus several recombination channels and distinct acceptor states contribute to the composite 1.45 eV luminescence band.     

Band-edge emission in CuI single crystals

The photoluminescence spectra of CuI single crystals have been studied at T = 4.2 K and at various excitation levels. The emission band of donor-acceptor pairs (DAP) with a maximum at about 4200 Å has been shown to possess a complex structure. Theoretical analyses and exciton spectroscopy data make it possible to calculate the ionization energies for the donors and acceptors participating in the formation of DAP, which are equal to E_D = = 0.045?0.065 eV and E_A = 0.155?0.170 eV, respectively. The fine structure of emission due to the annihilation of excitons bound on acceptor pairs (band maximum 4075 Å) has been detected and calculated. The energy of the longitudinal optical phonon participating in the exciton-phonon interaction (LO ? 18.7 meV) has been determined.     

Evidence for a donor-acceptor pair band in CuInSe2

The broad-band emission, observed in p-type crystals, was studied as a function of excitation intensity and temperature. The band peak is usually in the energy range of 0.93–0.95 eV at 4.2°K. The band shifts to higher energy as the excitation intensity of temperature increases. This behavior is consistent with a donor-acceptor pair-band mechanism. The acceptor energy E_A is 85 ± 2 meV. The acceptors and donors involved in the pair band appear to be Cu and Se vacancies.     

The optical properties of Be,Mg and Zn-diffused gallium phosphide

Interest in the Ga-site acceptors Be and Mg was stimulated by the possibility that they might produce efficient luminescence on association with O, analogous to the well-known red Zn-O luminescence in GaP but at higher transition energy. Attention was directed to diffusion doping by Be and Mg of GaP O-doped during growth because the reactivity of Be and Mg with O renders double doping during crystal growth very difficult. Structured green donor-acceptor pair spectra were observed at 1.6°K from many Be-diffused crystals, yielding an accurate measure of (E_A)_BE, 50 ± 1 meV. Moderately efficient orange-red luminescence was also observed below ∼ 100 °K from these crystals, but the intensity of this luminescence decreased rapidly to negligible levels by ∼ 200°K. This luminescence also contains sharp structure at 1.6°K, of a form characteristic of the decay of excitons bound to complex centres. Many sharp phonon replicas occur, involving local modes as well as characteristic GaP modes. One set of no-phonon lines, at least, near 2.19 eV, shows zero-field splitting, luminescence decay times and behaviour in magnetic and external strain fields characteristic of exciton decay at a centre with <100>; or <111>-type symmetry axes, containing no extra electronic particles. The exciton state is split by 2.4 meV by J-J coupling, and the axial field of the centre splits the hole states by ∼ 1.0 meV. These bound excitons are specifically characteristics of diffused GaP and appear analogous to bound excitons observed below 2.12 eV in Zn-diffused GaP. It is probable that the relevant centres contain diffusion components such as Be or Zn interstitials and improbable that O_P is involved. By contrast, weak orange bound exciton luminescence observed in Mg-diffused GaP does involve O, presumably as O_P. No analysis of the magneto-optical behaviour of this Mg-related bound exciton was possible in our crystals, so its symmetry axis was not established. It is possible that this is the Mg_Ga-O_P bound exciton. If so, the two-fold reductions in the exciton localisation energy from ∼ 0.32 eV to ∼ 0.15 eV and in the mass of the Ga-site substituent has produced dramatic changes in the form of the phonon cooperation between the Zn-O and “Mg-O” excitons. The “Mg-O” exciton luminescence is not dominant in our crystals, even at low temperature. The exciton state is again split by a local crystal field as well as by J-J coupling, but here the former splitting is predominant; 2_∈0 = 3.9 meV, Δ = 0.60 meV.     

Electroabsorption in TlInS2

Electroabsorption spectra of single crystals have been studied near the fundamental absorption edge at 77 and 300 K. At 300 K two positive peaks (2.34 and 2.42 eV) and a negative peak (2.38 eV) are observed in the electroabsorption spectrum. At liquid-nitrogen temperature a fine structure corresponding to the formation of a parabolic exciton (2.503 eV) is observed.Values of the width of the forbidden gap E_g, the n = 1 exciton positions, the exciton activation energy ΔE_b, the effective Bohr radius a_exc, the reduced effective mass of an electron-hole pair μ, and the exciton ionization field F(E_g = 2.535 eV, E_exc = 2.503 eV, E_b = 32 meV, $\text{a}{}_{\mathrm{<mtext>exc</mtext>}}\text{=}\text{28}\text{A}\text{A;}\text{;}$;, μ = 0.15 m₀, and F = 1.2 × 10⁵ V cm^-1) have been determined from the electroabsorption spectrum.     

Tellurium-related trap levels in silicon

Tellurium-related defects inn-type silicon have been analysed by deep level transient spectroscopy (DLTS). The tellurium doping of the samples was performed by ion implantation or during epitaxy. In all the samples, a level having a thermal activation energy around 0.37 eV is observed. This activation energy is found to be dependent on the electric field. Taking into account the Poole-Frenkel (FP) effect and a temperature dependence proportional toT ^?2 in the capture cross-section, a value ofE _A=0.41eV is obtained. A second Te-related level having an activation energy ofE _A=0.14eV without correction of the FP effect could only be measured in the implanted samples. The same concentration is observed for the two levels in the implanted samples thus indicating that both peaks in the DLTS spectra are caused by the identical Te-related defect.     

Combined effects of donor and acceptor impurities on the thermoelectric properties of cadmium antimonide

A study was made of the effect of the simultaneous doping with donor (Te) and acceptor (Cu, Ag, Au) elements on the thermoelectric properties of CdSb. Doping with tellurium changes the p-type conductivity of the CdSb crystals to an n-type conductivity with an impurity (Te) activation energy of E_d = (0. 11 ± 0. 01) eV. Doping with an acceptor impurity changes the energy of the donor level, by E_d = 0. 14 eV for doping with silver, by E_d = 0. 10 eV for doping with gold and by E_d = 0. 095 eV for doping with copper. It is shown that the type of conductivity and the thermoelectric properties of CdSb can be adjusted in the desired direction through simultaneous doping with two impurities.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii Fizika, No. 6, pp. 90–94, June, 1970.     

Chlorine adsorption on copper: III. Angle-resolved electron energy loss spectroscopy

Electronic excitations on Cu(001) and Cu(001)c(2 × 2)-Cl have been investigated by angle-resolved electron energy loss spectroscopy at an angular resolution of Δθ = ±1° and an energy resolution of ΔE = 60 meV. Primary energies in the 50–100 eV range were chosen and the specular reflection was studied for angles 35° ? θ ? 71° with respect to the surface normal. The results are summarized as follows: The specular Cu(001) spectra are compared to optical data and good agreement is found for the energetic position of direct transitions. The electronic losses observed for the ordered overlayer system may be interpreted by one-electron excitations from occupied surface bands (known from angle-resolved photoemission results) into an empty band with a minimum energy at 0.4 eV above the Fermi level.     

The adsorption of CO on Cu surfaces studied by electron energy loss spectroscopy

Electron energy loss spectroscopy (ELS) in the energy range of electronic transitions (primary energy 30 < E₀ < 50 eV, resolution ΔE ≈ 0.3 eV) has been used to study the adsorption of CO on polycrystalline surfaces and on the low index faces (100), (110), (111) of Cu at 80 K. Also LEED patterns were investigated and thermal desorption was analyzed by means of the temperature dependence of three losses near 9, 12 and 14 eV characteristic for adsorbed CO. The 12 and 14 eV losses occur on all Cu surfaces in the whole coverage range; they are interpreted in terms of intramolecular transitions of the CO. The 9 eV loss is sensitive to the crystallographic type of Cu surface and to the coverage with CO. The interpretation in terms of d(Cu) → 2π¹(CO) charge transfer transitions allows conclusions concerning the adsorption site geometry. The ELS results are consistent with information obtained from LEED. On the (100) surface CO adsorption enhances the intensity of a bulk electronic transition near 4 eV at E₀ < 50 eV. This effect is interpreted within the framework of dielectric theory for surface scattering on the basis of the Cu electron energy band scheme.     

等离子体氧轰击硅生成缺陷的研究

本文对等离子体氧轰击硅产生的缺陷进行了研究。发现等离子体氧轰击在硅中引入两个缺陷E₁(E_c—0.46eV)及E₂(E_c—0.04eV)。测量了缺陷的光电离截面谱,分析表明,缺陷E₂的电子声子相互作用很强,其Frank-Condon移动达0.76eV,缺陷E₁的电子声子相互作用较小,其Frank-Condon移动为0.04eV。由实验结果得到与缺陷E₁、E₂相耦合的声子模分别为hω_p⁽¹⁾=28meV,hω_p⁽²⁾=20meV。 关键词：     

Study on the structure and optical property of Zn1−xCuxO sol–gel thin films on quartz substrate

Zn_1−xCu_xO thin films (x=0, 1.0, 3.0, 5.0%) are prepared on quartz substrate by sol–gel method. The structure and morphology of the samples are investigated by X-ray diffraction (XRD) and atomic force microscopy (AFM). The results show that Cu ions were effectively penetrated into the ZnO crystal lattices with substitutional and interstitial impurities to form stable solid solutions without changing the polycrystalline wurtzite structure. Two peaks at 420 nm (2.95 eV, violet), 485 nm (2.56 eV, blue) have been observed from the photoluminescence (PL) spectra of the samples. It is concluded that the violet peak may correspond to the exciton emission; the blue emission corresponds to the electron transition from the bottom of the conduction band to the acceptor level of zinc vacancy. The optical test shows that the optical band gap E_g is decreased with the increase amount of Cu doping in ZnO. The band gap decrease from 3.40 eV to 3.25 eV gradually. It is also found that the transmission rate is increased rapidly with the increase of Cu ions concentration.     

Quantum size effect in electron transmission through Cu and Ag films on W(110)

The transmission coefficient of very low energy electrons ( ? 10 eV) normally incident on (111) epitaxial films of Cu and Ag on W(110) is modulated by interference between scattering from the vacuum/metal and metal/metal interfaces. Comparison with calculations of free-electron scattering from a one-dimensional potential model, in which grading of the metal/metal interface is represented by a smoothing of the potential step, indicates that this interface is abrupt within approximately one layer spacing. We obtain a value of 11.0 (8.0) ± 1.0 eV for the inner potential of Cu (Ag) and mean free path lengths of $\text{39 ± 8}\text{A}\text{?}$ at an energy of 7.0 eV relative to the Fermi energy and $\text{29 ± 11}\text{A}\text{?}$ at 9.0 eV for Cu, and $\text{25 ± 10}\text{A}\text{?}$ at 7.5 eV for Ag. Work function values are obtained by the field emission retarding potential technique. We investigate the effects of the surface potential barrier, inelastic scattering and surface roughness, and evaluate the validity of the one-dimensional model presented.     

High resolution angle-resolved photoelectron spectrum of CO2, excited with polarized resonance radiation

The He(I) excited and angle-resolved photoelectron spectrum of CO₂ is investigated using a focussing VUV-polarizer. High resolution combined with the additional information given by comparing spectra taken at different angles permits detailed analysis of the vibrational structure. β-values are given for all vibrational components hitherto observed in the photoelectron spectrum of the ≈X, ≈A,≈B and ≈C electronic bands. Single excitations of the v₃ mode with vibrational energies 181 meV in the estate and 279 meV in the ≈B-state are reported. The peak at 360 meV vibrational energy in the (≈C-state is reinterpreted as a single v₃ excitation. The β-values of the most intense peaks are also measured using Ne(I) (16.67 and 16.85 eV), Ne(II) (26.86 and 26.95 eV) and He(II) (40.81) resonance radiations.     

The gallium-site donors germanium and silicon in gallium phosphide

The node in the Bloch part of the electron wave function expected for a Ga-site donor in GaP removes the usual valley-orbit splitting and associated chemical shift. However, the T₂ ground state can still show a small spin-valley splitting into Γ₈ and Γ₇ states, as previously verified for the Sn donor. We find that the optical properties of the Ge and Si donors deviate appreciably from this “normal” behaviour. The Ge donor is anomalously deep, E_D ～ 202 meV, yet binds an exciton by ～63 meV consistent with the Haynes rule for neutral donors in GaP. We find that this exciton possesses the large oscillator strength, f～3.5 × 10^-3, Zeeman and piezo-optical splittings characteristic of a Γ₆, 1s(A₁) ground state, like a P rather than Ga-site donor. However, f and the exciton localization energy are consistent with expectation for E_D ～ 200 meV, as measured from the lowest set of X conduction band minima, if we assume a symmetric A₁-like wave function. A possible explanation for this unexpected result is advanced. The much shallower Si donor, E_D～82 meV, binds an exciton by only ～ 14 meV, also consistent with the Haynes rule. By contrast, we find this Ga-site donor to be normal except that our Zeeman and piezo-optical results indicate an inverted spin-valley splitting, about 25% of that for the still shallower Sn donor. We also discuss the numerous low-lying excited states, some anomalous phonon replicas in the Ge and Si donor bound exciton spectra and the magneto-optical properties of a sharp line near 2.24 eV, attributed to the decay of excitons bound to (S)_p-(Ge)_p donor-acceptor associates.     

Thermal activation measurement of positron binding energies at surfaces

The formation of positronium by low-energy positrons incident on “clean” metal surfaces is thermally activated by increasing temperature. The activation energy E_a has been measured for a number of surfaces. E_a is understood as the energy required to form positronium (binding energy 1/2Ry) from positrons bound at the surface by an energy E_b, E_a = E_b+φ_-? 1/2Ry, where φ_- is the electron work function. Representative values of E_b derived are Al(100):3.03(5) eV; Al(110):2.92(4) eV; Cu(111):2.80(5) eV.     

Evidence for a double charge transfer contribution to SERS in the Ag/Ag (CN)2− system

Using a square wave potential perturbation and monitoring the Raman intensity in parallel, the potential dependence of Ag(CN)₂⁻ spectra was studied with different exciting wavelengths. A double peak structure was found for the C-N stretch frequency both peaks having different excitation characteristics. In addition, the quenching rate of ad-complexes was measured at negative potentials together with the activation energy. From E_A = 75 kJ mol⁻, the energy of an acceptor level can be estimated located about 3 eV above E_F. This level presumably corresponds to the Ag 5s orbital which is shifted upwards due to the interaction with the ligands of the ad-complex. Since the CN⁻ 5σ or 1π orbitals form a donor level, the possibility of a double charge transfer contribution to the SERS enhancement exists.     

Temperature dependance of the fundamental absorption edge in CdTe

Optical measurements made on CdTe put in light an extrinsic transition previously used to determine the interband edge of this compound. The donor level involved has a depth of 30 meV inside the bandgap at 77°K and of 60meV at 300°K. The value obtained for its temperature coefficient, suggests an association of this level with the L minimum of the conduction band.Also, determined is the true optical bandgap of CdTe between many conflicting results. One obtains: E_g = 1.529 meV with a temperature coefficient of ?3.10^?4eV/°K.     

Adsorption and reaction of bromine with Ag(110): A photoemission study

The adsorption of bromine on the (110) surface of silver has been studied by ultraviolet (hυ = 21.2 and 40.8 eV) photoelectron spectroscopy in the temperature range of 100–300 K. Four different adsorption and reaction states could be detected. For fractional monolayer coverages Br₂ adsorbs dissociatively on the Ag(110) surface. The chemisorption of bromide leads to new emission features at about 3 and 5.2 eV below E_F, which are assigned as occupied antibonding structures (3 eV) and as bonding Br4p_{x, y} orbitals (5.2 eV). At 100 K, further bromide adsorption leads to the formation of an AgBr layer with molecular adsorbed bromine on top of this corrosion layer. The He I spectrum is dominated by structures at 3.5, 5.8 and 7.5 eV which are due to emission from the π_g, π_u and σ_g molecular orbitals of Br₂. The buildup of the AgBr layer is clearly demonstrated by desorbing the molecular bromine at about 150 K. The resulting spectrum of the AgBr layer shows peaks at 2.5 and 3.4 eV with p- and mixed-in d-character and peaks at 4.1, 5.2 and 6.1 eV which are primarily d-like. Heating of the AgBr layer up to 300 K results in a transformation from a 2D layer into a 3D agglomeration of larger AgBr clusters on top of a Br/Ag(110) chemisorption layer.