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.     

Hydrogen chemisorption on silicon (100) 2 × 1

Changes in the valence band density of states (DOS) of a (100) silicon surface that accompany he chemisorption of atomic hydrogen onto that surface are deduced from a study of the changes in the L_2,3VV Auger lineshape. Complementary changes in the conduction band DOS are inferred from changes in L_2,3VV-core-level characteristic loss spectra (CLS). The chemisorbed hydrogen layer is identified as the dihydride phase from low energy electron diffraction measurements. Upon hydrogen adsorption the DOS at the top of the valence band decreases and new energy levels associated with the Si-H bonds appear lower in the band. Assuming that the Auger signal from the hydrogen covered sample consists of a superposition of a signal from silicon atoms bonded to hydrogen in the dihydride layer and an elemental-Si signal from the substrate, a N(E) difference spectrum with features due only to the dihydride is obtained by subtracting the background corrected, loss deconvoluted L_2,3VV signal for a clean (100)Si surface rom the corresponding signal for the hydrogen covered surface. Comparisons of the energy position of the major peak in this difference spectrum with that of the main peak in a gas phase silane Si-L_2,3VV spectrum, and of the corresponding Auger energy calculated empirically, indicate a hole—hole interaction energy of ~8 eV for the two-hole final state in the gaseous system and zero for the dihydride surface system. Hydrogen induced changes in the conduction band DOS are less apparent than those of the valence band DOS with only the possibility of a decrease in the DOS at the bottom of the conduction band being inferred from the CLS measurements. Electron stimulated desorption of hydrogen from the dihydride layer is adduced from changes in the Auger lineshape under electron beam irradiation of the surface. Hydrogen induced changes in the near-elastic electron energy loss spectra (ELS) are also reported and compared with previously published ELS results.     

SiO2 surface defect centers studied by AES

A theoretical model is proposed on how a Si dangling bond associated with an oxygen vacancy on a SiO₂ surface (E_s′ center) should be observed by Auger electron spectroscopy (AES). The Auger electron distribution N_A(E) for the L₂₃VV transition band is calculated for a stoichiometric SiO₂ surface, and for a SiO_x surface containing Si-(e^?O₃) coordinations. The latter is characterized by an additional L₂₃VD transition band, where D is the energy level of the unpaired electron e^?. The theoretical N_A(E) spectra are compared with experimental N(E) spectra for a pristine, and for an electron radiation damaged quartz surface. Agreement with the theoretical model is obtained if D is assumed to lie ≈2 eV below the conduction band edge. This result shows that AES is uniquely useful in revealing the absolute energy level of localized, occupied surface defect states. As the L₂₃VD transition band (main peak at 86 eV) cannot unambiguously be distinguished from a SiSi₄ coordination L₂₃VV spectrum (main peak at 88 eV), supporting evidence is presented as to why we exclude a SiSi₄ coordination for our particular experimental example. Application of the Si-(e^?O₃) model to the interpretation of SiO₂Si interface Auger spectra is also discussed.     

Evaluation of plasmon-loss spectra of molybdenum using elastic-peak electron spectroscopy

Plasmon-loss spectra of clean polycrystalline molybdenum surfaces have been determined in the primary energy range E_p = 50–3000 eV. Spectra a distributions (nonderivative mode). A simplified model is described for evaluating plasmon-loss spectra using elastic-peak electron spectroscopy, as de of elastically reflected electrons is determined by integrating the N(E) spectrum of secondary and backscattered electrons. The ratio of the ar (23–24 eV) to that of the elastic peak is Pλ, the product of the probability for creating a volume plasmon loss and the inelastic mean free pat second plasmon-loss peak is (Pλ)². Evaluation of our experimental plasmon-loss spectra gives Pλ = 0.4–0.5 for E_p > 500 eV. Th constitutes ～50% of all losses determining the IMFP, interband loss processes being important in the remainder. For the low energy range, E_p found. For E_p < 100 eV, no volume plasmon-loss peak could be detected in our N(E) spectra. The simplified model proves to be valid fo plasmon-loss peak (11–12 eV), i.e., such that N_pls/N_e ? 10^?2. Some results are presented concerning surface plasmon losses as molybdenum surface.     

Electron energy loss spectroscopy of A {111} oriented aluminum single crystal

Recently, the electron energy loss spectroscopy (ELS) and secondary electron spectroscopy (SES) of the interaction of oxygen with polycrystalline aluminum were reported for primary energies in the range 30 ? E_p ? 250 eV. Two new transitions were resolved in the ELS spectra (one at 4 eV for clean aluminum and the other at 12 eV for oxide-covered aluminum) for low primary energies (E_p ~ 30 eV). In this paper we report on experiments utilizing a {111} oriented single crystal of aluminum that confirm the existence of these loss peaks for low primary energies and show that the 4 eV peak position for pure aluminum depends on the primary beam energy. This suggests that this low energy loss peak is due to direct nonvertical inter- and intraband transitions which differs from the previous assignment.     

Treatment of pairing in small systems by Green functions

A finite system of fermions with pairing interaction is treated by the Green function method. It is shown that a finite number of “bound pairs” must be assumed to get the correct properties of the system in that region of the interaction strength where the BCS-solution is incorrect. Also the difference betweenE ₀(N+2)?E ₀(N) andE ₀(N)?E ₀(N?2),E ₀(N) being the ground state energy of theN-particle system, has to be considered. The formulae derived give an interpolation between the region where perturbation theory applies and the region of validity of the BCS-equations.     

Collective electron excitations in 3D graphite clusters

Group-theoretical analysis and subsequent quantum-chemical calculations based on the molecular orbital method applied to a cyclic model of 3D semimetallic graphite lead to a multiplet of spectroscopic combinations of Slater determinants. The transition energies ΔE between terms of the multiplet are interpreted as the energies of collective electron mesoscopic excitations ?ω in the entire set of electron states characterizing the metal-type conductivity of a cluster. The estimate ?ω～0.2ΔE(N ₀/1000)^2/3 is obtained for a cluster consisting of N ₀ primitive cells. Depending on the thermal processing, N ₀=(0.3–20)×10⁶ in pyrolytic graphite, and accordingly ?ω～(10–150) eV. In the case when the energy cannot be determined accurately, methods permitting the variation of an excitation over a wide range (such as the spectroscopy of synchrotron radiation absorption and the characteristic energy losses of charged particles) appear to be the most promising.     

Ion molecule collisions investigated via nuclear resonance fluorescence

The method of nuclear resonance fluorescence has been applied to analyse the profileN(E) of the 285 keV gamma line of⁷⁵As after electron capture decay of⁷⁵Se in gaseous⁷⁵SeH₂ sources. The profileN(E) depends on the velocity distribution of the radioactive As ions at the moment of γ-decay and, hence, is strongly dependent on the slowing down mechanism. Investigating sources with pressures of 1.5, 15, and 177 Torr different states of the slowing down process could be studied. A simple model is developed that describes the basic properties of the experimental line profiles.     

Electronic structure of new multiple band Pt-pnictide superconductors APt3P

We report LDA calculated band structure, densities of states and Fermi surfaces for recently discovered Pt-pnictide superconductors APt₃P (A = Ca, Sr, La), confirming their multiple band nature. Electronic structure is essentially three dimensional, in contrast to Fe pnictides and chalcogenides. LDA calculated Sommerfeld coefficient agrees rather well with experimental data, leaving little space for very strong coupling super-conductivity, suggested by experimental data on specific heat of SrPt₃P. Elementary estimates show, that the values of critical temperature can be explained by rather weak or moderately strong coupling, while the decrease in superconducting transition temperature T _c from Sr to La compound can be explained by corresponding decrease in total density of states at the Fermi level N(E _F). The shape of the density of states near the Fermi level suggests that in SrPt₃P electron doping (such as replacement Sr by La) decreases N(E _F) and T _c , while hole doping (e.g., partial replacement of Sr with K, Rb or Cs, if possible) would increase N(E _F) and possibly T _c .     

Surface state density distribution at vacuum-annealed InP(1 0 0) surface as derived from the rigorous analysis of photoluminescence efficiency

The surface state density distribution N_SS(E) and surface Fermi level E_Fs position on a sequentially ultra-high vacuum-annealed n-InP(1 0 0) sample are investigated using rigorous computer analysis of dependences of the room temperature band-edge photoluminescence efficiency (Y_PL) on the photon flux density (Φ). We have found that the minimum density of a U-shaped N_SS(E) distribution as well as the donor-like surface state density are reduced by one order of magnitude after the annealing at 250 and 300 °C. This can be assigned to the decrease in the disorder in the unintentionally formed InP native oxides. On the other hand, we demonstrate that the annealing simultaneously generates discrete surface states probably due to missing group V element (P) in the interface region which may account for electrical interface instabilities observed in InP-based devices. The results are discussed quantitatively and compared to other reports.     

Magnetic susceptibility of titanium diselenide intercalated with copper

The temperature dependence of the magnetic susceptibility of Cu _x TiSe₂ polycrystalline samples has been measured. The electron density of states near the Fermi level N(E _F) in the Pauli model of paramagnetism has been calculated and discussed. The concentration dependences of the density of states N(E _F) and the unit cell parameter in the direction perpendicular to the layers in Cu _x TiSe₂ correlate with the concentration of centers V-Ti-Cu and Cu-Ti-V (V is the vacancy).     

Ionic implantation of N2+ in Ni(110) at 300 K

The present work gives results of a preliminary investigation, carried out by SES, AES, LEED and ELS, on the implantation of nitrogen ions in Ni(110) as a function of ion dose and subsequent surface heat treatment at different temperatures. The fine structure in the SES spectrum is the most sensitive to implantation: peaks at 9, 17.5 and 31.5 eV are shifted towards lower energies by E = 1 eV for the first two peaks and 2.8 eV for the last. At high nitrogen doses a disordered layer is observed by LEED. The p(2 × 3) structure is obtained when the crystal is heated to 750 K. The two electron loss peaks of 4.8 and 10 eV arise from an induced electron N_2p level situated 4.8 eV below the Fermi level.     

Analyses of the thermal shifts of spectral lines in Nd3+-doped LiYF4 laser crystal

The red-shift of spectral line E ₁(R ₁????Y ₂) and blue-shift of line E ₂(R ₁????X ₅) with temperature in Nd³⁺-doped LiYF₄ laser crystal are studied by considering both the static contribution due to lattice thermal expansion and vibrational contribution due to electron?Cphonon interaction. The study is based on the analyses of pressure and temperature dependences of these spectral lines. It is found that for both lines, the static and vibrational contributions result in the blue- and red-shift, respectively. So, the observed red-shift of line E ₁ and blue-shift of line E ₂ are due respectively to the static contribution being smaller and larger than the vibrational one. Also, we infer that the thermal shifts of lines E ₃(R ₁????Y ₅) and E ₄(R ₂????Y ₅) are very small because both contributions may be approximately canceled. When both the contributions are contained, whether the red-shift or blue-shift of a spectral line can be fitted with the almost same theoretical expression as that by including only the vibrational contribution used in red-shift in the previous papers if we change the expression concerning electron?Cphonon interaction coefficient.     

Some nuclear and atomic properties of201Hg determined by conversion electron spectroscopy

Conversion electron measurements with an electrostatic spectrometer proved the existence of the 1,565±6 eV transition in²⁰¹Hg. The conversion intensity ratios,N ₁/N ₂ =1.2±0.2,N ₁/N ₃=1.1±0.2,N ₂/N ₃=0.92±0.15,N ₄/N ₃=0.03± 0.02 andN ₅/N ₃=0.04 ±0.02 were determined. These values agree with our calculations for the M1±E2 multipolarity with theE2/M1 mixing ratioδ ²=(l.l±0.3)xl0^?4 and exclude all pure multipolarities withL≦4. The total conversion coefficient for the aboveM1 +E2 mixture was evaluated to be (4.7±0.7)× 10⁴. The reducedB(M1, 1/2→3/2) probability was derived to be (3.9 ±1.2) × 10^?3 (e?/2Mc)². The natural widths of theN-subshell conversion lines in mercury were found to beΓ(N ₁)=8.3± 1.5,Γ(N ₂) =5.8±1.5 and Γ(N ₃) =6.5±1.0 eV. Monte Carlo calculations of electron scattering in matter yielded the conversion line shapes in qualitative agreement with the experiment.     

Dielectric relaxation and ac conductivity of sodium tungsten phosphate glasses

Studies of dielectric relaxation and ac conductivity have been made on three samples of sodium tungsten phosphate glasses over a temperature range of 77–420 K. Complex relative permitivity data have been analyzed using dielectric modulus approach. Conductivity relaxation frequency increases with the increase of temperature. Activation energy for conductivity relaxation has also been evaluated. Measured ac conductivity (σ_m(ω)) has been found to be higher than σ_dc at low temperatures whereas at high temperature σ_m(ω) becomes equal to σ_dc at all frequencies. The ac conductivity obeys the relation σ_ac(ω)=Aω ^S over a considerable range of low temperatures. Values of exponent S are nearly equal to unity at about 78 K and the values decrease non-linearly with the increase of temperature. Values of the number density of states at Fermi level (N(E _F)) have been evaluated at 80 K assuming values of electron wave function decay constant α to be 0.5 (Å)^?1. Values of N(E _F) have the order 10²⁰ which are well within the range suggested for localized states. Present values of N(E _F) are smaller than those for tungsten phosphate glasses.     

Systematic study of the product((E(2_2~+)/E(2_1~+)) * B(E2)↑) through the asymmetric rotor model

A systematic study of the product((E(2_2~+)/E(2_1~+))*B(E2)↑) is carried out in the major shell space Z=50-82,N=82-126 within the framework of the asymmetric rotor model where the asymmetry parameter γ0reflects change in the nuclear structure.A systematic study of the product((E(2+)/E(2+))*B(E2)↑) with neutron number N is also discussed.The product((E(2_2~+)/E(2_1~+))*B(E2)↑) provides a direct correlation with the asymmetry parameter γ0.The effect of subshells is visible in Ba-Gd nuclei with N 82,but not in Hf-Pt nuclei with N 104.We study,for the first time,the dependency of the product((E(2_2~+)/E(2_1~+))*B(E2)↑) on the asymmetry parameterγ0.     

Investigation of quasicrystalline Al<Subscript>62.5</Subscript>Cu<Subscript>25</Subscript>Fe<Subscript>12.5</Subscript> and crystalline β-Al<Subscript>50</Subscript>Cu<Subscript>33</Subscript>Fe<Subscript>17</Subscript> alloys by X-ray photoelectron spectroscopy

The electronic spectra of the valence band and core levels of the surface of polygrain alloys with the icosahedral structure and the β-(CsCl)-type solid solution of Al₅₀Cu₃₃Fe₁₇ were investigated by X-ray photoelectron spectroscopy (XPS). The obtained XPS spectra of the Al_62.5Cu₂₅Fe_12.5 alloy, in comparison with those of the crystalline Al₅₀Cu₃₃Fe₁₇ alloy demonstrate narrowing and a decrease in asymmetry of the Fe2p core level and a decrease in the electron state density N(E _F ) near the Fermi level, features expected for the poorly conducting icosahedral phase. The XPS data are compared with the estimates of N(E _F ) based on the low-temperature specific heat measurements.     

Oxygen chemisorption and initial oxidation of Cr(110)

The initial stages of the interaction of oxygen with a Cr(110) surface have been investigated at 300 K by LEED, AES, electron energy loss spectroscopy (ELS), secondary electron emission spectroscopy (SES) and work-function change measurement (Δφ). In the exposure region up to 2 L, the clean-surface ELS peaks due to interband transition weakened and then disappeared, while the ～5.8 and 10 eV loss peaks attributed to the O 2p → Cr 3d transitions appeared, accompanied with a work-function increase (Δφ = +0.19 eV at2L). In the region 2–6 L the work function decreased to below the original clean-surface value (Δφ_min = ?0.24 eV at6L), and five additional ELS peaks were observed at ～2, 4, 11, 20 and 32 eV: the 2 and 4 eV peaks are ascribed to the ligand-field d → d transitions of a Cr³⁺ ion, the 11 eV peak to the O 2p → Cr 4s transition, the 20 eV peak to the Cr 3d → 4p transition of a Cr³⁺ ion and the 32 eV peak probably to the Cr 3d → 4f transition. A new SES peak at 6.1 eV, being attributed to the final state for t he 11 eV ELS peak, was observed at above 3 L and identified as due to the unfilled Cr 4s state caused by charge transfer from Cr to oxygen sites in this region. In the region 6–15 L the work function increased again (Δφ_max = +0.32 eV at15 L), the 33 and 46 eV Auger peaks due to respectively the M_2,3(Cr)L_2,3(O)L_2,3(O) cross transition and the M_2,3VV transition of the oxide appeared and the 26 eV ELS peak due to the O 2s → Cr 4s transition was also observed. Above 10 L, the ELS spectra were found to be practically the same as that of Cr₂O₃. Finally, above 15 L, the work function decreased slowly (Δφ = +0.13 eV at40L). From these results, the oxygen interaction with a Cr(110) surface can be classified into four different stages: (1) dissociative chemisorption stage up to 2 L, (2) incorporation of O adatoms into the Cr selvedge between 2–6 L, (3) rapid oxidation between 6–15 L leading to the formation of thin Cr₂O₃ film, and (4) slow thickening of Cr₂O₃ above 15 L. The change in the Cr 3p excitation spectrum during oxidation was also investigated. The oxide growth can be interpreted on the basis of a modified coupled current approach of low-temperature oxidation of metals.     

Spectra and mean energies of prompt neutrons from <Superscript>238</Superscript>U fission induced by primary neutrons of energy in the region <Emphasis Type="Italic">E</Emphasis><Subscript><Emphasis Type="Italic">n</Emphasis></Subscript><20 MeV

The time-of-flight technique is used to measure the ratios R(E, E _n )=N(E, E _n )/N_Cf(E) of the normalized (to unity) spectra N(E, E _n ) of neutrons accompanying the neutron-induced fission of ²³⁸U at primary-neutron energies of E _n =6.0 and 7.0 MeV to the spectrum N_Cf(E) neutrons from the spontaneous fission of ²⁵²Cf. These experimental data and the results of their analysis are discussed together with data that were previously obtained for the neutron-induced fission of ²³⁸U at the primary energies of E _n =2.9, 5.0, 13.2, 14.7, 16.0, and 17.7 MeV.     

Identification of Cu(I) and Cu(II) oxides by electron spectroscopic methods: AES,ELS and UPS investigations

The externally prepared black-coloured copper oxide (T? 700 K, P_O2 ? 100 torr) on a Cu(100) surface is identified by electron spectroscopy as CuO. Compared to the red-coloured Cu(I) oxide (in situ oxidation at T ? 400 K, P_O2 ? 0.5 torr, ～ 10⁹ L), the He(I)- excited photoemisson from CuO reveals characteristic shake-up satellites 10–12 eV below E_F and a broadened emission from overlapping oxygen-induced 2p and Cu 3d states. From the AES and ELS results, in correlation with the data from core electron spectroscopy, chemical shifts of Cu 2p, Cu 3s and Cu 3p in CuO to higher binding energy and decreases in binding energy of the oxygen-induced states were deduced. The unoccupied electron states of Cu at 5 and 7.5 eV above E_F — postulated from the ELS results — are preserved in Cu₂O and CuO compounds. Annealing of the Cu(II) oxide at 670 K is accompanied by decomposition into Cu₂O due to the solid-state reaction following the scheme: 2CuO → 1/2 O₂ + Cu₂O.