Electrical conductivity of (Bi,Pb)2MO4 (M = Pd,Pt) linear chain compounds

Partial oxidation of Pd in Bi₂PdO₄ is achieved by substitution of Pb²⁺ for Bi³⁺ up to Bi₁₉₁Pb₀₀₉PdO₄, partial oxidation is necessary to stabilize the isostructural Pt compound, Bi_1?xPb_xPtO₄ within the range 0.33 ? x ? 0.52. In both cases, the tetragonal cell c parameter, therefore metal-metal distance $\text{(d}{}_{\mathrm{<mtext>M?M</mtext>}}\text{=}\text{c}\text{2}\text{)}$, decreases linearly with increasing mean oxidation degree (MOD) of transition metal atom For the insulator B1₂CuO₄, no substitution occurs Powder electrical conductivity measurements of the partially oxidized compounds show that these materials are semiconductors Platinum compounds exhibit relatively high conductivities $\text{(σ?10 (Ω}\text{cm}\text{)}{}^{\mathrm{?1}}\text{)}$ and low activation energies (?0 02 eV) with small variations with x Palladium compounds exhibit lower conductivities which linearly increases with MOD These electronic properties are comparable with those of the most one-dimensional Pt or Pd chain conductors.     

Interactions of CO molecules adsorbed on oxidised Cu(111) and Cu(110)

Reflection absorption infrared spectroscopy has been used in conjunction with LEED and surface potential measurements to study low temperature CO adsorption on the oxidised Cu surfaces Cu(111)O|$\text{3}\text{2}\text{?}\text{2}$|, Cu(110)O(2 × 1) and Cu(110)Oc(6 × 2). On all three surfaces adsorption at 80 K yields surface potential changes in excess of 0.6 V and does not lead to the formation of an ordered overlayer. At high coverages the adsorption enthalpy is lower than on the clean surfaces. Infrared spectra show the growth of a doublet band with components initially at 2100 and 2117 cm^?1 on the oxidised Cu(111) surface. Similar features seen on the oxidised Cu(110) surfaces are accompanied by a band at 2140 cm^?1: a very weak band at the same frequency on oxidised Cu(111) is attributed to defect sites. Studies of the temperature dependence of the spectrum from oxidised Cu(111) lead to the conclusion that two different binding sites are occupied. Spectra of ${}^{12}\text{CO}{}^{13}\text{CO}$ mixtures show that the molecules occupying these sites are in close proximity to each other, and that the spectrum is subject to large but opposing coverage-dependent frequency shifts.     

Adsorption of potassium on iron

Adsorption of K on Fe(110), (100) and (111) surfaces was studied by means of LEED, AES, thermal desorption and work function measurements. The monolayer capacity is about 5.5 × 10¹⁴ K-atoms/cm² in all three cases. With Fe(111) an ordered 3 × 3 overlayer was found at fairly low coverages. The work function decreases to a minimum and the initial dipole moments were determined to μ₀ = 7.0 Debye for Fe(110), μ₀ = 4.4 Debye for K/Fe(100) and μ₀ = 3.9 Debye for K/Fe(111). The heat of adsorption decreases from its initial value (Fe(110): 57; Fe(100): 54; Fe(111): 52 kcal/mole) continuously with increasing coverage which parallels the continuous decrease of the dipole moment of the adsorbate complex.     

On the interaction of cesium with cleaved GaAs(110) and Ge(111) surfaces: Work function measurements and adsorption site model

The work function of UHV cleaved p-Ge(111) and n-GaAs(110) surfaces has been measured in dependence of the Cs coverage. At very low coverages θ < 0.001 the decrease of the contact potential difference is extremely steep. For GaAs the initial slope of the CPD versus coverage curve amounts to ?740 eV for Ge to ?130 eV per monolayer. Up to the saturation coverage the curves exhibit straight line segments with breaks at distinct coverages. Breaks are found for GaAs at approximately $\text{1}\text{12}$, $\text{1}\text{6}$, and $\text{1}\text{3}$ of a monolayer, for Ge at about $\text{1}\text{12}$, $\text{1}\text{4}$, $\text{1}\text{2}$, and $\text{3}\text{4}$. A new model is developed to explain this behaviour. It is based on the assumption of specific adsorption sites for the Cs atoms at the surfaces. With this model the experimental results, including the breaks, may be described in the whole coverage range from θ = 0.03 up to the saturation. Furthermore the dipole moments derived from the straight line segments are in excellent agreement with those values calculated for different surface molecules between the adsorbed cesium and substrate atoms at the specific adsorption sites.     

Copper monolayer formation on platinum single crystal surfaces: Optical and electrochemical studies

The formation of a Cu monolayer on Pt(100), (110) and (111) was investigated by optical and electrochemical techniques. The adsorption isotherms as obtained by cyclic current-potential curves clearly show that the monolayer is deposited in various steps at underpotentials. Differential reflectance spectroscopy at normal incidence was used to detect structural changes of the adsorbate as the coverage increases. For Cu on Pt(110) a pronounced anisotropy in $\text{ΔR}\text{R}$was observed as the electric field vector of the linearly polarized light was rotated. From these measurements it was deduced that Cu in the submonolayer range is deposited onto Pt(110) in rows along the [11&#x0304;0] direction of the substrate. No such anisotropy was found for Cu on Pt(100) and Pt(111) and for surface oxide formation on all three low index faces of Pt. The spectral dependence of the normalized reflectance change,$\text{ΔR}\text{R}$, for the Cu monolayer on Pt(hkl) is shown and discussed.     

Static sims studies of adsorbate structure: II. CO adsorption on Pd(111); adsorbate-adsorbate interactions on Ru(001), Ni(111) and Pd(111)

In a study of CO adsorption on Pd(111) it is shown that the secondary ion mass spectrum contains information on both adsorbate site geometry and adsorbate coverage. The fractional yields of PdCO⁺, Pd₂CO⁺ and Pd₃CO⁺, as a function of CO coverage are correlated with the changing site geometries suggested by reflection IR data. A relationship between secondary ion emission and the adsorbate-adsorbate interactions revealed by IR and EELS is also demonstrated for CO adsorption on Ru(001), Ni(111) and Pd(111).     

Electrodeposition of Pb onto Pt(111) in aqueous chloride solutions: Studies by LEED and Auger spectroscopy

Studies by LEED and Auger spectroscopy of Pb electrodeposited from aqueous HCl solutions onto well-defined Pt(111) surfaces are reported. Adsorption of HCl from pure aqueous HCl solutions (pH = 0 to 4) onto Pt(111) at electrode potentials from 0.4 to 0.8 volt (versus AgCl reference electrode) resulted in a stable (3×3) adlattice; however, below 0.4 volt adsorption was weak and desorption occurred readily under the influence of the electron beams employed for LEED or Auger spectroscopy. When Pb²⁺ ions were present in the chloride solution, spontaneous (open circuit) electrodeposition of Pb occurred (θ_Pb = 0.05), altering the sizes, shapes, and intensities of beams in the (3×3) pattern. Electrodeposition of Pb under conditions of negative linear potential scan resulted in a series of ten peaks at potentials more positive than the peak for deposition of bulk Pb. LEED patterns obtained after emersion of the surface at various stages during the scan revealed that the electrodeposited layer was ordered and underwent a series of structural transitions with increasing Pb coverage. Comparison of the Auger signal for Pb with the coulometric charge for Pb deposition demonstrated that the Pb deposit was not stable at open circuit (as in emersion) when the packing density exceeded about θ_Pb = 1. The Auger signal for Cl was not generally attenuated by deposition of Pb. indicating that Cl was present in the topmost layer of the surface at all Pb coverages.     

Absolute coverages of CO and O on Pt(111); Comparison of saturation CO coverages on Pt(100), (110) and (111) surfaces

Nuclear microanalysis (NMA) has been used to determine the absolute coverages of oxygen and CO adsorbed on Pt(111). The saturation oxygen coverage at 300 K is 3.9 ± 0.4 × 10¹⁴ O atoms cm^?2 (θ = 0.26 ± 0.03), confirming the assignment of the LEED pattern as p(2 × 2). The saturation CO coverage at 300 K is 7.4 ± 0.3 × 10¹⁴ CO cm^?2 (θ = 0.49 ± 0.02). The low temperature saturation CO coverages on Pt(100), (110) and (111) surfaces are compared.     

Adsorption of hydrogen on palladium single crystal surfaces

The adsorption of hydrogen on clean Pd(110) and Pd(111) surfaces as well as on a Pd(111) surface with regular step arrays was studied by means of LEED, thermal desorption spectroscopy and contact potential measurements. Absorption in the bulk plays an important role but could be separated from the surface processes. With Pd(110) an ordered 1 × 2 structure and with Pd(111) a 1 × 1 structure was formed. Maximum work function increases of 0.36, 0.18 and 0.23 eV were determined with Pd(110), Pd(111) and the stepped surface, respectively, this quantity being influenced only by adsorbed hydrogen under the chosen conditions. The adsorption isotherms derived from contact potential data revealed that at low coverages θ ∞ √p_H2, indicating atomic adsorption. Initial heats of H₂ adsorption of 24.4 kcal/mole for Pd(110) and of 20.8 kcal/mole for Pd(111) were derived, in both cases E_ad being constant up to at least half the saturation coverage. With the stepped surface the adsorption energies coincide with those for Pd(111) at medium coverages, but increase with decreasing coverage by about 3 kcal/mole. D₂ is adsorbed on Pd(110) with an initial adsorption energy of 22.8 kcal/mole.     

Adsorption and surface structural chemistry of Na and Na + O2 on Ag(110)

The adsorption of Na and the coadsorption of Na and O₂ on Ag(110) have been studied by LEED, thermal desorption, and Auger spectroscopy. For Na coverages in the regime 0 < θ_Na < 2 the Na desorption spectra show a single peak (β) corresponding to a desorption energy of ～195 kJ mol^?1, and at θ_Na ～ 2 a (1 × 2) LEED pattern appears. At still higher coverages (2 < θ_Na < 5), a (1 × 3) surface phase is formed, and a new peak (α) appears in the desorption spectra; this is identified with Na desorption from an essentially Na surface. The desorption energy of αNa (～174 kJ mol^?1) indicates that Na adatoms beyond the first chemisorbed layer are significantly influenced by the presence of the Ag substrate. The initial sticking probability of O₂ on Na-dosed Ag(110) is enormously enhanced over the clean surface value, being of the order of unity, and O₂ chemisorption ultimately leads to a (4 × 1) surface structure. The presence either subsurface Na alone, or of both Na and O below the surface, causes substantial changes in surface behaviour. In the former case, submonolayer doses of Na lead to the appearance of a (1 × 2) structure; and in the latter case, Na + O₂ coadsorption results in a c(4 × 2) structure. Auger spectroscopy indicates that the Ag(110)-c(4 × 2)$\text{Na}\text{O}$ phase forms with a constant stoichiometry which is independent of the initial Na dose. The Na:O ratio in this adlayer is believed to be of the order of unity. The structures of the various ordered phases, the nature of the AgNa bonding, and the interatomic spacing between the alkali adatoms on Ag(110) are discussed.     

Adsorption isotherms of oxygen on tungsten (100), (110) and (111) surfaces in the pressure range 10−9 to 10−4 torr and temperature range 1500 to 2600 k,as measured by AES

This paper is a continuation of a previous investigation of oxygen adsorption on tungsten at high temperature using Auger electron spectroscopy. In this paper the adsorption isotherms of oxygen on (100), (110) and (111) faces of tungsten are reported. It is shown that these isotherms can be described by an equation of the form pO₂ = AF(θ) exp [?q(θ)/ kT]. The coverage depended functions F(θ) and q(θ) evaluated from the isotherms are different for all three investigated faces. The isosteric adsorption energy q has following initial values at very low oxygen coverage: q₁₀₀ = 6.1 eV, q₁₁₀ = 6.8 eV and q₁₁₁ = 6.5 eV. Increasing the oxygen coverage has only small influence on q₁₁₁; it changes from the initial value to q₁₁₁ ≈ 6.0 eV at θ ≈ 0.3 and remains constant at this value up to θ ≈ 1. q₁₁₀ shows the strongest dependence on oxygen coverage. It decreases rapidly at low coverages, slowly at moderate coverages and reaches the value q₁₁₀ = 5.0 atθ ≈ 1. The variation of q₁₁₀ with increasing oxygen coverage is monotonie from the initial value to q₁₁₁ = 4.9 eV at θ ≈ 1. Assuming that the atomic oxygen is the dominant species leaving the tungsten surface at high temperatures the functions F(θ) are used to calculate the oxygen equilibration probability ζO₂ (high temperature sticking probability) as a function of oxygen coverage θ. The main characteristic of ζO₂(θ) for all three faces is that it shows a maximum for (100) and (111) faces at θ = 0.3 and for (110) face at θ = 0.55.     

X-ray photoelectron spectroscopic study of the physical adsorption of xenon and the chemisorption of oxygen on tungsten (111)

X-ray photoelectron spectroscopy (ESCA) has been used to study the physical adsorption of Xe and the chemisorption of oxygen by W (111). An ultrahigh vacuum ESCA spectrometer has been modified such that thermal desorption behavior from the W (111) crystal can be directly compared with ESCA spectra of the adsorbed species. In addition, since the work function of a W (111) crystal covered with one monolayer of Xe is accurately known from previous work, the binding energy of the $\text{Xe}\text{(3}\text{d}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}\text{)}$ adsorbate level can be accurately compared to the gaseous $\text{Xe}\text{(3}\text{d}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}\text{)}$ level.When Xe is physisorbed to 1 monolayer the $\text{Xe}\text{(3}\text{d}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}\text{)}$ level exhibits a binding energy (relative to the vacuum level) which is 2.1 eV below that found for Xe (g). At lower Xe coverages the shift becomes monotonically greater, approaching 2.6 eV at a Xe coverage of 0.05. This 0.5 eV shift downward is accompanied by an increase of only 0.05 eV in adsorption energy as coverage decreases, and may be partially caused by the presence of ~ 10–20 % of extraneous adsorption sites other than W (111) which adsorb Xe with higher adsorption energy. The adsorption energy of Xe may also be increased by coadsorption of oxygen and the $\text{Xe}\text{(3}\text{d}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}\text{)}$ binding energy exhibits a corresponding shift downward as adsorbed oxygen coverage is increased to θ_o = 0.5. Electronic relaxation processes affecting the final state are dominant factors in determining the magnitude of the chemical shift upon adsorption, in agreement with the predictions of Shirley. The magnitude of the relaxation effect seems to be very sensitive to small changes in Xe adsorption energy. Similar effects have been seen for chemisorption of CO.The adsorption of O₂ at 120 K by W (111) yields a single broad O(1s) peak whose line-width decreases with increasing coverage. The final spectra at θ_o = 1 monolayer are very similar to those obtained at temperatures of 300 K or above on polycrystalline tungsten.     

Adsorption,coadsorption, and reactivity of sodium and nitric oxide on Ag(111)

The adsorption, desorption, and surface structural properties of Na and NO on Ag(111), together with their coadsorption and surface reactivity, have been studied by LEED, Auger spectroscopy, and thermal desorption. On the clean surface, non-dissociative adsorption of NO into the a-state occurs at 300 K with an initial sticking probability of ~0.1, saturation occurring at a coverage of $\text{~}\text{1}\text{20}$. Desorption occurs reversibly without decomposition and is characterised by a desorption energy of E_d ~ 103 kJ mol^?1. In the coverage regime 0 < θ_Na < 1, sodium adsorbs in registry with the Ag surface mesh and the desorption spectra show a single peak corresponding to E_d ~ 228 kJ mol^?1. For multilayer coverages (1 < θ _Na < 5) a new low temperature peak appears in the desorption spectra with E_d ~ 187 kJ mol^?1. This is identified with Na desorption from an essentially Na surface, and the desorption energy indicates that Na atoms beyond the first chemisorbed layer are significantly influenced by the presence of the Ag substrate. The LEED results show that Na multilayers grow as a (√7 × √7) R19.2° overlayer, and are interpreted in a way which is consistent with the above conclusion. Coadsorption of Na and NO leads to the appearance of a more strongly bound and reactive chemisorbed state of NO (β-NO) with E_d ~ 121 kJ mol^?1. β-NO appears to undego surface dissociation to yield adsorbed O and N atoms whose subsequent reactions lead to the formation of N₂, N₂O, and O₂ as gaseous products. The reactive behaviour of the system is complicated by the effects of Na and O diffusion into the bulk of the specimen, but certain invariant features permit us to postulate an overall reaction mechanism, and the results obtained here are compared with other relevant work.     

Planar channeling of helium ions along (100), (110) and (111) MgO

Planar channelling of 1, 1.5 and 2 MeV ⁴He⁺ ions along (100), (110) and (111) MgO have been studied experimentally using Rutherford backscattering. Values of the half angle $\text{ψ}{}^{\mathrm{P}}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$, shoulder half angle $\text{ψ}{}^{\mathrm{s}}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ and surface minimum yield x^P_min have been determined for channelling with respect to the two sublattices. Agreements and discrepancies with existing theories are discussed.     

The interaction of oxygen with the Rh(111) surface a

The adsorption of oxygen on Rh(111) at 100 K has been studied by TDS, AES, and LEED. Oxygen adsorbs in a disordered state at 100 K and orders irreversibly into an apparent (2 × 2) surface structure upon heating to T? 150 K. The kinetics of this ordering process have been measured by monitoring the intensity of the oxygen $\text{(1,}\text{1}\text{2}\text{) LEED}$ beam as a function of time with a Faraday cup collector. The kinetic data fit a model in which the rate of ordering of oxygen atoms is proportional to the square of the concentration of disordered species due to the nature of adparticle interactions in building up an island structure. The activation energy for ordering is $\text{13.5 ± 0.5}\text{kcal}\text{mole}$. At higher temperatures, the oxygen undergoes a two-step irreversible disordering (T? 280 K) and dissolution (T?400K) process. Formation of the high temperature disordered state is impeded at high oxygen coverages. Analysis of the oxygen thermal desorption data, assuming second order desorption kinetics, yields values of 56 ± 2 kcal/ mole and 2.5 ± 10^?3 cm² s^?1 for the activation energy of desorption and the pre-exponential factor of the desorption rate coefficient, respectively, in the limit of zero coverage. At non-zero coverages the desorption data are complicated by contributions from multiple states. A value for the initial sticking probability of 0.2 was determined from Auger data at 100 K applying a mobile precursor model of adsorption.     

Adsorption of sodium and its effect upon some electric properties of clean germanium (111) surfaces

The effect of adsorbed Na on the surface conductivity, Δσ, and surface recombination velocity, S, of a clean (114)Ge surface is studied. The surface conductivity is a complicated function of the surface Na concentration, N_Na; at N_Na ≈ 1.5 × 10¹³ atoms/cm², it has a minimum; at ca. (3–5) × 10¹⁴atoms/cm², it has a maximum. For a monolayer coverage (ca. 7.2 × 10¹⁴atoms/cm²) the values of Δσ are not much different from those of a clean Ge surface. The surface recombination velocity is a three-valued function of the surface potential, U_S (calculated from the Δσ values), depending on the Na overlayer coverage and heat treatment of the sample. Three different surface structures (LEED data) were found to correspond to the three S versus U_S curves reported here. Thermal desorption studies show that Na is desorbed in a wide temperature interval. Two peaks have been isolated, studied and discussed. At low coverages a single peak is found to exist, which obeys the first-order desorption kinetics, with a desorption energy of (52 ± 3)kcal/mol. This peak is attributed to the surface defects. For coverages close to$\text{1}\text{4}$ monolayer a new peak was observed in the spectrum. The desorption energy of this binding state exceeds that of all the other states. When the overlayer coverage is increased, this peak is shifted to higher temperatures, as predicted for a half-order desorption kinetics. By comparing also with LEED data, it may be concluded that this most tightly bound sodium has formed on the Ge(111) surface patches of an ordered structure in which one Na atom is bonded to three Ge atoms.     

A study of the (00) LEED beam intensity at normal incidence from CdS(0001), Cu(001), Cu(111), and Ni(111)

A Faraday cage apparatus is used for the measurement of the (00) LEED beam intensity, I₍₀₀₎, and the total secondary emission coefficient, δ(E_k), for angles of incidence from 0° ± 2° to 8° ± 2°, with an energy resolution of ± 0.037 of the incident beam energy, in the energy range 1 to 200 eV. The data are normalized and expressed as a fraction of the incident beam intensity. The basic principle of operation is the separation of the incident and specularly diffracted beams in a uniform magnetic field. Monolayer, or in-plane, resonances associated with the emergence of nonspecular beams, as well as beam threshold minima, are observed in I₍₀₀₎ at normal incidence from clean CdS(0001), Cu(111), and Ni(111). Some major differences are observed in the I₍₀₀₎ profiles for the clean (111) surfaces of nickel and copper. All secondary Bragg peaks, except the 2$\text{2}\text{3}$ order, have greater intensities for Ni(111) in the energy range 50–150 eV, thus indicating that the atomic scattering cross-section for electrons in this energy range is larger for nickel than for copper. For the (111) surface of nickel, the (11) resonance is missing, but the (10) resonance and all $\text{1}\text{3}$ order secondary Bragg peaks between the second and fifth orders are observed. For Cu(111) both the (10) and (11) resonances are observed, but the $\text{1}\text{3}$, $\text{2}\text{3}$, 1$\text{2}\text{3}$, and 3$\text{1}\text{3}$ order secondary Bragg peaks are missing in this energy range. These data indicate that multiple scattering with evanescent intermediate waves, or “shadowing”, is predominate on the (111) surfaces on nickel and copper for energies above 30 eV, and that below 30 eV multiple scattering with propagating intermediate waves is predominate on Cu(111). Correlation of the (00) beam intensity profiles from clean Ni(111) at 0°, 2°, and 6° with the intensity profiles of the (10). (1&#x0304;0), and (11) non-specular beams is nearly one-to-one from 30 eV to 100 eV, thus supporting the dynamical theories of LEED in which peaks in the (00) beam are expected to occur at nearly the same energies as peaks in the non-specular beams.     

Adsorption and reaction of nitric oxide and oxygen on Rh(111)

Adsorption of NO and O₂ on Rh(111) has been studied by TPD and XPS. Both gases adsorb molecularly at 120 K. At low coverages (θ_NO < 0.3) NO dissociates completely upon heating to form N₂ and O₂ which have peak desorption temperatures at 710 and 1310 K., respectively. At higher NO coverages NO desorbs at 455 K and a new N₂ state obeying first order kinetics appears at 470 K. At saturation, 55% of the adsorbed NO decomposes. Preadsorbed oxygen inhibits NO decomposition and produces new N₂ and NO desorption states, both at 400 K. The saturation coverage of NO on Rh(111) is approximately 0.67 of the surface atom density. Oxygen on Rh(111) has two strongly bound states with peak temperatures of 840 and 1125 K with a saturation coverage ratio of 1:2. Desorption parameters for the 1125 peak vary strongly with coverage and, assuming second-order kinetics, yield an activation energy of $\text{85 ± 5}\text{kcal}\text{mol}$ and a pre-exponential factor of 2.0 cm² s^?1 in the limit of zero coverage. A molecular state desorbing at 150 K and the 840 K state fill concurrently. The saturation coverage of atomic oxygen on Rh(111) is approximately 0.83 times the surface atom density. The behavior of NO on Rh and Pt low index planes is compared.     

Chemisorption of indium on (111) silicon substrates: I. Adsorption and nucleation by mass-spectrometric technique

The adsorption and nucleation of indium on clean (111) silicon surfaces are studied by a UHV molecular beam mass-spectrometric technique. The thermal accommodation of the adatoms on the surface is complete. At very low surface coverages θ, an adsorption energy of $\text{57}\text{kcal}\text{mole}$ and a preexponential term τ₀ of the Frenkel relation equal to 8 × 10^?13 s are found from transient response measurements. The isosteric heat of adsorption E_a varies very slowly with θ, E_a is equal to $\text{59}\text{kcal}\text{mole}$ for θ ～ 10^?3 and $\text{57}\text{kcal}\text{mole}$ for θ = 0.9. The nucleation occurs without supersaturation in an adsorbed layer near a monolayer.