Adsorption of nitrogen on single crystal faces of iridium,studied by field emission microscopy

The adsorption of nitrogen on iridium was studied with a field emission microscope equipped with a probe-hole assembly to enable emission experiments on individual emitter regions. The adsorption of nitrogen is markedly face-specific. Temperature programmed desorption reveals three binding states: γ₁ on the (100) face with a maximum heat of adsorption of 7–8 kcal/mole, γ₂ on the regions around (110) with a maximum heat of adsorption of 10–11 kcal/mole and γ₃ on the roughest tip regions (210), (320), (531) and (731) with a maximum heat of adsorption of 13–14 kcal/mole. Nitrogen adsorbed in the γ₁ and γ₃ states causes a decrease, but in the γ₂ state a small increase, in the work function. These results are discussed in relation with data on nickel, palladium, platinum and rhodium. While nitrogen is only weakly adsorbed on all these metals there is a marked difference in the nature of the pertinent adsorption complex.     

A field emission study of silver on rhenium

Field emission measurements of the change in average work function ?f of rhenium with adsorbed silver indicate that a rhenium-silver dipole forms with silver positive, of moment μ₀=5.2±1.5 ×10^?30 C m and polarizability $\text{α=29±12}\text{A}\text{?}{}^3$. Measurement of the rate of thermal desorption yields a mean binding energy of 2.31 ± 0.04 eV for sub-monolayer silver and 2.69±0.04 eV for a 2.5 monolayer deposit. Changes in work function induced by adsorption of silver on low-index rhenium plane surfaces are characterised by the formation of well-defined states and in this, silver resembles gold. These states are thought to result from a relatively large difference between the binding energy of adatoms on the low-index planes and on the surrounding surfaces, and this differnce is maintained when the surfaces are covered with silver. At the lowest coverage, silver is believed to be absent from all four observed planes and the measured rise in work function is thought to be apparent and to result from a decrease in field strength on the plane due to extension of the plane area by surrounding adsorbed silver. The structures adopted by silver overlayers are not known, but it is argued that on (101?0) and (101?1?) the final state at high coverage has the Ag(111) surface structure. On (112?0) and (112?2?) the silver layer at high coverage is thought to have either Ag(110) or Ag(100) surface structure. The structures of intermediate states found on all four low-index planes remain unkown. Field emission spectroscopy shows that emission from clean (101?0) is free-electron like and confirms earlier observations that emission from (202?1) is not. Spectroscopy also reveals a feature in the spectrum from silver on (101?0) which may be identified with a known surface state on Ag(111), thus providing some support for the assignment of Ag(111) to the surface structure of thick silver layers (> 3 monolayers) on (101?0).     

Study of adsorption of titanium on tungsten and rhenium by field electron emission

The deposition and layer growth of titanium, evaporated on to tungsten and rhenium field emitter tips has been studied, and field emission average work-functions measured at varying titanium layer thicknesses from less than a monolayer to several monolayers. Titanium evaporated on to a clean tungsten tip at 293 K in the submonolayer region tended to collect preferentially on atomically rough planes. With further deposition, a “pseudo-clean” emission pattern was obtained at about a monolayer coverage when the titanium atoms were concluded to be in epitaxial registry with the BCC substrate; at about this coverage the work-function for the system passed through a minimum. Further titanium deposition in excess of three monolayers resulted in a progressive roughening of the surface due to microcrystallinity: brief heating (~ 1 min, 1300 K) of such a surface resulted in a well ordered layer identified as ß-titanium (BCC) presumably epitaxed to the tungsten. This epitaxed layer remained indefinitely stable at 293 K.     

Electron field emission from a patterned array of diamond-like carbon on anodic aluminum oxide template

A patterned array of diamond-like carbon (DLC) was grown on anodic aluminum oxide (AAO) template by filtered cathodic arc plasma (FCAP) technique at room temperature. The diameters of patterned array of DLC were ∼150 nm, and the patterned array density was estimated to ∼10⁹ cm⁻². A broad asymmetric band ranging from 1000 cm⁻¹ to 2000 cm⁻¹ was detected by Raman spectrum attributed to characteristic band of DLC. The fraction of sp³ bonded carbon atoms of the patterned array of DLC was measured by X-ray photoelectron spectrum (XPS) and the ratio was about 62.4%. Field emission properties of the patterned array of DLC were investigated. A low turn-on field of 3.4 V/μm at 10 μA/cm² with an emission area of 3.14 mm² was achieved. The results indicated that the electrons were emitted under both the effect of enhanced field because of the geometry and the work function of the DLC sample. Based on Fowler-Nordheim plot, the values of work function for the patterned array of DLC were estimated in range of 0.38 to 1.75 from a linearity plot.     

Analysis of adsorbate-substrate configuration by admolecule-probe field emission microscopy

By means of field electron emission microscopy with Faraday collector and magnetic deflection the emission current fluctuations between two or more levels caused by single Cu-phthalocyanine admolecules have been recorded. Relative abundance distribution functions of the times of sojourn in distinct adsorption states are given. From measurements at various temperatures in case of stationary fluctuations Arrhenius plots of the mean time of sojourn were obtained. They yield the energy differences E_i between trough and saddle positions of single admolecules as well as the preexponential factors A_i and the entropy differences ΔS_i, respectively, according to the Frenkel equation

$\text{τ}{}_{\mathrm{i}}\text{= A}{}_{\mathrm{i}}\text{exp(}\text{E}{}_{\mathrm{i}}\text{/kT}\text{) = (}\text{h}\text{kT}\text{) exp(?}\text{ΔS}{}_{\mathrm{i}}\text{k}\text{) exp (}\text{E}{}_{\mathrm{i}}\text{kT}\text{)}$

. The average values and standard deviations of all measurements are E_i = 0.22 eV, σ_Ei = = 0.11 eV, and log A_i = ?6.0, σ_logA_i = 1.6.The use of Cu-phthalocyanine as a molecular probe to investigate and characterize the adsorbate-substrate configuration, is discussed.     

Some studies of lead and iron adsorption on the W(100) surface by field emission microscopy

The behaviour of lead and iron adsorbed on the W(100) surface has been studied by probe hole field emission microscopy, field desorption, and by measurement of the total energy distribution (TED) of field-emitted electrons. Lead adsorbed at 300 K which reduces the work function of W(100) can be completely removed at 78 K by field desorption below 3.2 V Å^?1 and the resulting surface has both the work function and TED, which are characteristic of the clean plane. Condensation at 800 K followed by field desorption, results in a plane surface of work function 4.17 eV and an altered TED. This effect is attributed to the microfacetting, which is observed by LEED. The Swanson peak in the W(100) TED which is removed by submonolayer amounts of lead re-emerges at monolayer coverage when lead adopts the (1 × 1) structure. Such behaviour is consistent with the model proposed by Kar and Soven. A spectral peak observed when lead is adsorbed on the reconstructed W(100) surface is thought to derive from the atomic ¹D state. Adsorption of iron on a W(100) surface reduces φ considerably due to dipole formation and efficiently quenches the Swanson peak. Higher coverages introduce other peaks in the TED enhancement curve, and by adopting an energy scale based on the work of Hagstrum, an attempt is made to interpret the observed peaks in terms of the known energy structure of the free iron atom. One of the three spectral peaks is assigned to the 4s² ground state of the iron atom, and the remaining two peaks are tentatively attributed to atomic p-states. It is concluded that while the excited state structure of the iron atom is too complex to permit complete interpretation of the spectra, this approach offers the hope that, for simpler atoms, such features may be interpreted in this way.     

Field emission patterns with atomic resolution of single-walled carbon nanotubes by field emission microscopy

Electron emission properties of single-walled carbon nanotubes (SWCNTs) assembled on a tungsten tip were investigated using field emission microscopy (FEM). The transmission electron microscopy (TEM) micrograph confirmed the existence of an SWCNT bundle on the W tip. Under appropriate experimental conditions,a series of FEM patterns with atomic resolution were obtained. These patterns arose possibly from the field emission of the open end of an individual (16,0) SWCNT protruding from the SWCNT bundle. The magnification factor and the resolution under our experimental conditions were calculated theoretically. If the value of the compression factor β was set at β= 1.76, the calculated value of the magnification factor was in agreement with the measured value. The resolving powerof FEM was determined by the resolution equation given by Gomer. The resolutionof 0.277 nm could be achieved under the typical electric field of 5.0×107 V/cm, which was close to the interatomic separation 0.246 nm between carbon atoms along the zigzag edge at the open end for the (16, 0) SWCNT. Consequently, our experimental results were further supported by our theoretical calculation.     

Reconstruction at a metallic interface studied by field ion and field emission microscopy

Reconstruction of a tungsten surface by adsorbed layers of gold, silver and copper has been studied by field emission and field ion microscopy. Gold reconstructs the surface in three ways, termed the α, β and γ rearrangements. The α rearrangement, which results in a smoothing of the tungsten surface, takes place at around 400° K with gold coverages of 5 monolayers (5θ), and is thought to be an increase in structural perfection of the tungsten surface by gold-assisted surface diffusion of tungsten atoms, β-reconstruction takes place in the temperature range 480–950°K at coverages ? 1.7θ, producing a faceted surface which comprises {211} and {110} facets, and is thought to result from the need to minimise the free energy at the gold/tungsten interface. The γ structure, which appears above 1400°K, is believed to represent a change in the shape of the tip by transport of tungsten to the (110) locality. Adsorbed silver produces neither β nor γ structures, and the degree of α rearrangement is very small, being confined to the {230} regions of the substrate. Copper lies between silver and gold in its ability to rearrange the tungsten surface, some degree of α rearrangement is detectable, and the β structure is very poorly developed unlike the γ structure which is clearly formed. The binding strength of copper to tungsten is greater than that of silver, but less than that of gold; the capacity of an adsorbate, to reconstruct the tungsten substrate is therefore thought to be related to the strength of the adsorbate-substrate bond.     

Work function of single-walled carbon nanotubes determined by field emission microscopy

The field emission characteristics of a single micro-bundle of single-walled carbon nanotubes (SWCNTs) were investigated using field emission microscopy (FEM). Fowler–Nordheim plots revealed that the work function of the SWCNTs was reduced with increasing heating temperature, and reached a minimum value around 1000 °C, assuming that the β factor was constant during the heating process. Field emission patterns also demonstrated fine structures that were believed to be images of the cap of a SWCNT, which was in a clean state. The radius of the SWCNT micro-bundle was measured by transmission electron microscopy (TEM), and the β factor was calculated using two empirical formulae. Then, the work function of the SWCNT was determined from the slope, K, of its Fowler–Nordheim plot. The work function values were Φ₁=4.76 eV and Φ₂=4.88 eV, respectively. Received: 26 October 2001 / Revised version: 19 February 2002 / Published online: 6 June 2002     

Adsorption of single alkali atoms on tungsten using field emission and field desorption

Single adatom events have been detected and the binding energies and dipole moments of single sodium, potassium and cesium adatoms have been measured on the (110), (112) and (111) planes of tungsten in a probe hole field emission microscope. The Fowler-Nordheim formulation has been modified to include averaging effects implicit in probe hole measurements on single adsorbed atoms. The work function changes and consequent dipole moments associated with single alkali adatoms on a tungsten surface have been estimated. A model has been proposed to obtain binding energies from measurements of the field required to desorb a single alkali adatom. The results are in good agreement with current theoretical predictions for the adsorption of single alkali atoms on metals.     

57Co emission studies of cupric oxide

Results on the incorporation, valence and spin states of Fe(Co) in CuO (with reference to similar studies on high temperature superconductors) and coupling of the Fe(Co) moment to the Cu magnetism in CuO are presented. Freshly prepared⁵⁷Co: CuO shows two quadrupole doublets D₁ and D₂ withQ.S. of 2.49 and 1.52,I.S. of 0.35 and 0.70 mm/s and relative abundance of 74% and 26%, respectively at room temperature, the abundance being dependent on time in a sample exposed to ambient conditions and reaching 38 to 62% fifteen months after preparation. Below,T _N=225¹K, a typical combined magnetic-quadrupole interaction pattern is observed with a single saturation magnetic hfs of 25.6 T, central shift of 0.82 mm/s and a single |E _Q|=1.62 mm/s at 4.2 K. External magnetic field spectra reveal an antiferromagnetic behaviour of the Fe(Co) ion. Temperature dependence of the magnetic hfs is fitted in the framework of the molecular field approximation allowing different spins and coupling constants for Cu and Fe(Co).     

A spectrum of rhenium oxide

The arc emission spectrum of the ReO molecule has been photographed in the region 590–860 nm and three bands of a single electronic transition have been rotationally analyzed. The separation of lines of the isotopic molecules ¹⁸⁵ReO and ¹⁸⁷ReO leads to the conclusion that the vibrational assignments for these bands are 1-0, 0-0, and 0–1. It is conceivable that an electronic isotope shift of ～0.08 cm^?1 exists. The following vibrational and rotational data (cm^?1) have been determined: ν₀(0-0) = 14 038.42, $\text{Δ}\text{G′(}\text{1}\text{2}\text{) = 867.85}$, $\text{Δ}\text{G″(}\text{1}\text{2}\text{) = 979.14}$; B′_e = 0.3889, α′_e = 0.0019, B″_e = 0.4257, α″_e = 0.0043. It is concluded that Λ′ ? Λ″ = +1 with Λ″ ≥ 2.     

Study on titanium carbide field emitters by field-ion microscopy,field-electron emission microscopy,Auger electron spectroscopy,and atom-probe field-ion microscopy

Surface structure, composition, and some field-electron emission properties are examined for thermally annealed titanium carbide emitters. As a result of high temperature heating, low-index planes of {100} and {111} become facetted and are observed as dark areas in field-electron emission patterns. Electrons are emitted predominantly from the {110} planes. The surface composition becomes enriched with carbon when the carbon deficient titanium carbide, TiC_0.71, is heated at high temperatures in vacuum better than 10^?7 Pa. The topmost (110) layer consists of both Ti and C atoms. The instability in the electron emission current of titanium carbide is considered to be due to the local work function change caused by an interaction between vacuum residual gases and chemically active titanium atoms on the emitter surface.     

Visualization of field induced ferroelectric electron emission from TGS using emission electron microscopy

Field induced electron emission from triglycinesulfate (TGS) has been investigated using parallel imaging electron emission microscopy (EEM). The emission phenomenon has been induced by applying an ac electrical field up to 2 kV/mm to a single crystal of approximately 0.1 mm thickness. Emission patterns have been observed as a function of the applied field amplitude and of the crystal temperature. At voltages below the coercive field, no emission is visible. When approaching the Curie temperature, emission gradually disappears. This indicates an electron emission mechanism relying on the existence of a switchable ferroelectric phase. The information content of the images is discussed, an interpretation is given on the basis of existing theories. PACS 68.37.-d; 77; 77.80.Fm; 77.80.-e     

Luminescence studies on swift heavy ion irradiated nanocrystalline aluminum oxide

Pellets of nanocrystalline aluminum oxide synthesized by a combustion technique are irradiated with 120 MeV Au⁹⁺ ions for fluence in the range 5×10¹¹-1×10¹³ ions cm⁻². Two photoluminescence (PL) emissions, a prominent one with peak at ∼525 nm and a shoulder at ∼465 nm are observed in heat treated and Au⁹⁺ ion irradiated aluminum oxide. The 525 nm emission is attributed to F₂²⁺-centers. The PL intensity at 525 nm is found to increase with increase in ion fluence up to 1×10¹² ions cm⁻² and decreases beyond this fluence. Thermoluminescence (TL) of heat-treated and swift heavy ion (SHI) irradiated aluminum oxide gives a strong and broad TL glow with peak at ∼610 K along with a weak shoulder at 500 K. The TL intensity is found to increase with Au⁹⁺ ion fluence up to 1×10¹³ ions cm⁻² and decreases beyond this fluence.     

Adsorption of gold on low index planes of rhenium

On atomically rough areas of a thermally cleaned rhenium field emitter, adsorbed gold behaves like it does on tungsten. The average work function $\text{}\text{?}$gf increases at low average gold coverage $\text{}\text{?}$gq due to formation of gold-rhenium dipoles, and at high coverage a structural transformation in the gold layer leads to a $\text{}\text{?}$gq-independent work function. Broadly similar behaviour is found for gold on the low-index planes of tungsten, but on low-index rhenium planes gold behaves rather differently. When thermally cleaned at > 2200 K and annealed below 800 K, the work function, φ(clean), of (101&#x0304;1&#x0304;) takes one of two values 5.25 ± 0.04 eV, and 5.36 ± 0.04 eV, which are tentatively attributed to the two possible structures of this plane. Similar behaviour is expected and observed for (101&#x0304;0),but the values taken by φ(clean) are not well defined. Both forms of (101&#x0304;1&#x0304;) are thought to undergo reconstruction above 800 K forming a single structure with φ(clean) = 5.55 ± 0.03 eV. (112&#x0304;0) and (112&#x0304;2&#x0304;) each have only one possible structure, and in keeping with this, φ(clean) has a single well-defined value for each plane. The flatness of (101&#x0304;1&#x0304;) and (101&#x0304;0) leads to field reduction at their centres which produces an increase in their measured work functions by up to 10%. The initial increase in φ produced by gold condensed at 78 K and spread at low equilibration temperatures T_s on (112&#x0304;2&#x0304;), (101&#x0304;1&#x0304;) and (112&#x0304;0) is attributed to gold-rhenium dipoles, which, on the latter two planes approximate to the Topping model, giving dipoles characterised by μ₀(1011) = 0.1 × 10^?30 C-m with α = 10 ų and μ₀(112&#x0304;0) = 0.32 × 10^?30 C-m with α = 22 ų, where μ₀ is the zero-coverage dipole moment and α its polarizability. Failure of the Topping model on (112&#x0304;2&#x0304;) is attributed to its atomically rough structure. No dipole effect is seen on (101&#x0304;0). Energy spectroscopy of electrons field emitted at (202&#x0304;1&#x0304;) and (101&#x0304;1&#x0304;) demonstrates the non-free character of electrons in rhenium, while the small effect of adsorbed gold strengthens the belief that gold is bound through a greatly broadened 6s level centred 5.6 eV below the Fermi level and the dipolar nature of the bond supports this model. At higher values of T_s and $\text{}\text{?}$gq gold appears to form states which are well-characterised by a coverage-independent work function. (101&#x0304;0), (101&#x0304;1&#x0304;) and (112&#x0304;0) each form two such states, one in the range 2 < $\text{}\text{?}$gq < 4 (state 1), and the second at $\text{}\text{?}$gq > 4 (state 2). The atomic radii of gold and rhenium are thought to be sufficiently similar to allow the possibility that state 1 is a replication of the Re plane structure by gold. The high work function and thermal stability of state 2, taken together with the observed temperature dependence of the transformation of state 1 to state 2, encourages the belief that state 2 results from atomic rearrangement of state 1 into a close-packed Au(111) structure. State 2 also forms on (112&#x0304;2&#x0304;) and the absence of state 1 on this plane suggests some surface alloying at coverages below 4 $\text{}\text{?}$gq.     

Interaction of aluminum with the rhenium surface: Adsorption, desorption, and growth of surface compounds

The interaction of aluminum with the ( $10\bar 10$ ) rhenium surface was studied experimentally within a broad temperature range, 300–2000 K. Surface aluminide (SA) ReAl with a concentration of adsorbed Al atoms N _Al=1.6×10¹⁵ cm^?2 was found to form. It was shown that aluminum escapes from the surface by thermal desorption at temperatures from 1300 to 1600 K, with the desorption activation energy changing abruptly from ～3.6 to ～4.2 eV when passing through the concentration corresponding to the SA.     

Color tuning of up-conversion emission in ytterbium,erbium, aluminum tri-doped zinc oxide crystal by adjusting aluminum concentration

Ytterbium, erbium, aluminum tri-doped zinc oxide crystal was synthesized, which can turn color from red to green up-conversion luminescence through adjusting aluminum content. When the aluminum concentration reached 4?mol%, the color of up-conversion emission first turn from red to green. Meanwhile, the ratio of red to green emission reduced from 25.32 to 0.26, and the coordinates of chromaticity coordinate calculation changes from (0.5749, 0.3378) to (0.2190, 0.7169) with aluminum concentration range from 0 to 4?mol%. The up-conversion emission peaks at 521, 542, and 660?nm of sample originate from the transitions of ²H_11/2 → ⁴I_15/2, ⁴S_3/2 → ⁴I_15/2, and ⁴F_9/2 → ⁴I_15/2 of erbium ions, respectively. X-ray diffraction patterns perform the better crystallization degree with increasing aluminum concentration. The scanning electron microscopy images show the porous and lamellar structures with different aluminum concentrations. A convenient but effective design to obtain ytterbium, erbium, aluminum tri-doped zinc oxide up-conversion luminescence is reported, which can turn color from red to green.     

Study of mercury surface diffusion on tantalum with and without an electric field by means of a field emission microscope

The surface diffusion of mercury atoms on tantalum substrate with and without high electric field was studied by means of a field emission microscope (Müller's). The activation energy during surface migration Q_m of mercury atoms with and without an electric field F on tantalum substrate depending on the thickness of the adsorbate was measured. It is shown that the electron density distribution at coverage θ < 0.65 with adsorbate is due to a dipole momentum P. At θ > 0.65 the slope of the curves of Q^F_m = ?(θ) is explained with the appearance of the effect of polarization. The energy of desorption Q_d as a function of the thickness of the adsorbed layer in the temperature range 100–300 K was measured also.     

High-temperature field evaporation of rhenium

High-temperature field emission of Re, Pt, Ta, and W is studied by field-emission methods. Metal ions are found to evaporate mainly from the tops of thermal-field microprotrusions produced by high electric fields and temperatures on the emitter surface. For fi eld intensities of up to F=1–2 V/Å and temperatures of 1500–2000 K, the ion currents i are recorded from the entire emitter surface. They range from several tenths of nanoamperes to several nanoamperes. The activation energies of field evaporation determined from the Arrhenius plots logi=f(1/T) are found to be appreciably lower than those calculated within the charge exchange model for known parameters of the process and the metals evaporated. Reasons for such a difference in the activation energies and mechanisms of ion evaporation at high F and T are discussed.