Behavior of zirconium in the ZrOW(100) system at high temperature, studied by ISS, AES and work-function measurements

The behavior of zirconium atoms at the W(100) surface associated with oxygen adsorption at different sample temperatures has been studied by Auger electron spectroscopy (AES), ion scattering spectroscopy (ISS), and the relative change of the work function (Δф) measured by the onset of the secondary electron energy distribution. The results have revealed: (i) adsorption of zirconium onto the W(100) surface followed by the elevation of the sample temperature up to 1710 K in an oxygen partial pressure of 2.7 × 10⁻⁴ induces complete diffusion of zirconium atoms into the W(100) substrate; (ii) further exposure of oxygen induces co-existence of oxygen and tungsten on the surface at 1710 K, resulting in a work function of 4.37 eV; (iii) keeping the sample temperature at 1710 K, simple evacuation of the system has resulted in surface segregation of zirconium atoms to the surface to form a zirconium atomic layer on the top-most surface, reducing the work function to 2.7 eV. The results have revealed that this specific behavior of zirconium atoms at high temperature assures, with very good reproducibility, the highly stable performance and long service life of Zr---O/W(100)-emitters in practical use, even in a low vacuum of 10⁻⁶ Pa.     

Studies on the ZrO/W(100) surface by means of low-energy electron diffraction and X-ray photoelectron spectroscopy

The low work-function ZrO/W(100) surface was examined with the aim of understanding the reducing mechanism of the work function. Low-energy electron diffraction (LEED) was employed to analyze the surface atomic arrangement, and X-ray photoelectron spectroscopy (XPS) was used to identify the surface chemical condition. The ZrO/W(100) surface was made as follows: (i) around three monolayers of Zr were deposited on a clean W(100) surface, (ii) the sample was heat treated in an oxygen ambience of 1.3x10⁻⁵ Pa for several tens of minutes at 1500 K, and (iii) the sample was flash heated at 2000 K in ultrahigh vacuum (UHV). During heat treatment in O₂, the deposited Zr was oxidized to ZrO₂, and the LEED pattern formed was p(2×1). The work function increased to 5.3 eV. Subsequent flash heating in UHV changed the p(2×1) LEED pattern into a c(4×2) pattern, and transformed ZrO₂ into the so-called Zr–O complex, the oxidized level of which is between ZrO₂ and metallic Zr. A drastic decrease in the work function to 2.7 eV ensued. The angular dependence of XPS showed that the Zr–O complex segregated within a few monolayers at the surface.     

Interaction of cesium and oxygen on W(110): I. Cesium adsorption on oxygenated and oxidized W(110)

Cesium adsorption on oxygenated and oxidized W(110) is studied by Auger electron spectroscopy, LEED, thermal desorption and work function measurements. For oxygen coverages up to 1.5 × 10¹⁵ cm^?2 (oxygenated surface), preadsorbed oxygen lowers the cesiated work function minimum, the lowest (～1 eV) being obtained on a two-dimensional oxide structure with 1.4 × 10¹⁵ oxygen atoms per cm². Thermal desorption spectra of neutral cesium show that the oxygen adlayer increases the cesium desorption energy in the limit of small cesium coverages, by the same amount as it increases the substrate work function. Cesium adsorption destroys the p(2 × 1) and p(2 × 2) oxygen structures, but the 2D-oxide structure is left nearly unchanged. Beyond 1.5 × 10¹⁵ cm^?2 (oxidized surface), the work function minimum rises very rapidly with the oxygen coverage, as tungsten oxides begin to form. On bulk tungsten oxide layers, cesium appears to diffuse into the oxide, possibly forming a cesium tungsten bronze, characterized by a new desorption state. The thermal stability of the 2D-oxide structure on W(110) and the facetting of less dense tungsten planes suggest a way to achieve stable low work functions of interest in thermionic energy conversion applications.     

The adsorption and nucleation of zirconium on tungsten field emitters

The adsorption of zirconium on clean tungsten, at residual gas pressures below 1 × 10⁻¹⁰ Torr, has been studied by field emission microscopy. It was necessary to outgas the Zr above 2400 °K to obtain reproducibility. The gases evolved during degassing of the zirconium were predominantly CO, CH₄ and H₂. Mass spectra of the evaporant flux showed no tungsten or oxide contamination after thorough outgassing. It was found that heating below the -β phase transition temperature of Zr (1135 °K) resulted in the formation of large cap-shaped nuclei on the high index planes, while above this temperature the deposit became smoothed on the {100} planes. A model is proposed involving a closepacked square array of Zr atoms on the W(100). We conclude that the above two temperature regions are eminently suitable for studying epitaxy following the initial growth processes of nucleation or of monolayer addition. The presence of contamination impeded both surface migration and nucleation and lowered the work function.     

Dependence of work function on coverage for aluminum/tungsten in the field electron microscope

Aluminum adsorption on tungsten has been investigated by field electron microscope techniques. Changes in average work function and work functions of the (001) plane and (111) region were determined as a function of aluminum deposition. The average work function exhibits a minimum of about (4.11 × 0.04)eV (relative to an assumed value of 4.50 eV for the tungsten substrate) and reaches a value of (4.21 ± 0.04) eV for thick deposits. The (001) plane and (111) region exhibit complicated work function dependences on aluminum coverage. Some qualitative observations of aluminum on tungsten surface diffusion are also reported.     

Field electron emission changes by face specific adsorption of aluminum oxide and corresponding decomposition products on tungsten {110} and {100} planes

After deposition of aluminum oxide on a tungsten field emission microscope (FEM) tip and stepwise heating, three stages of emission changes were observed on {100}. Stages I and II cause work function decreases of 0.28 and 0.07 eV, respectively. Stage III is characterized by a large increase (Δ??+3 eV). The changes are discussed in terms of interaction of decomposition products (oxygen and aluminum) and adsorption of aluminum oxide. On {110} only a single aluminum oxide layer growth, which results in a work function decrease to ?=4.69 eV, is observed. The field electron emission from this layer was measured between 1400°K and room temperature. The experimental values were compared with those determined from Christov's unified theory of field and thermionic emission. The {110} layer values coincide with those obtained earlier from an aluminum oxide covered tungsten {112}.     

Oxygen adsorption on Ge(111) surface: II. Alkali metal-covered surfaces

Oxygen adsorption on an alkali metal (a.m.)-covered Ge(111) surface has been studied by means of Auger electron spectroscopy (AES), electron energy loss spectroscopy (ELS), thermal desorption (TD), and work function measurements (WF). It was found that the presence of a.m. results in enhancement of the oxygen adsorption rate. The initial values of the sticking coefficient, S₀, are exponential functions of the work function changes caused by the a.m. adsorption. It was shown that no germanium oxide phases are formed on an alkali-covered Ge surface at 300 K. The oxidation rate at high temperatures is limited by the rearrangement processes taking place in the surface GeO layer. The results obtained show that the alkali metal perturbs the GeO bond to a certain extent but no alkali oxide formation was observed at a.m. covertages under investigation.     

Decomposition of carbon monoxide on a (110) nickel surface

New investigations of the (110) nickel/carbon monoxide system have been made using low energy electron diffraction (LEED), Auger electron spectroscopy (AES), mass spectroscopy and work function measurements. Room temperature adsorption of CO on the surface was reversible with the CO easily removable by heating in vacuum to 450°K. The CO formed a double-spaced structure on the surface which, however, was unstable at room temperature for CO pressures less than 1×10^?7 torr. Work function changes greater than + 1.3 eV accompany this reversible CO adsorption. Irreversible processes leading to the build-up of carbon, and under certain circumstances oxygen, on the surface were the primary concern of the measurements reported here. These processes could be stimulated by the electron beams used in LEED and AES, or by heating the clean surface in CO. The results of AES investigations of this carbon (and oxygen) build-up, together with CO desorption results could be explained on the basis of two surface reactions. The primary reaction was the dissociation of chemisorbed CO leaving carbon and oxygen atomically dispersed on the surface. The second reaction was the reduction of the surface oxygen by CO from the gas phase. The significance of the dissociation reaction to COdesorption studies is discussed.     

Promising variants of single crystal tungsten electrodes for high-performance thermionic converters

New variants of tubular single crystal tungsten electrodes with an electron work function of 5.3–5.7 eV are considered. An appreciable increase in the work function is achieved due to special technologies ensuring the “monofaceting” of a cylindrical electrode surface and doping of the vapor-phase-grown epitaxial tungsten with oxygen.     

Adsorption and surface diffusion of titanium on tungsten in a field emission microscope

The adsorption, thermal desorption and surface diffusion of titanium on tungsten in ultra-high vacuum have been studied by field emission microscopy. The work function versus coverage curve has a minimum of 3.95 eV. The theory of metallic adsorbate-induced work function changes given by Gyftopoulos and Levine gives results which are in good agreement with our experimental values. In some experiments the work function minimum occurs at 3.65 eV. This value corresponds to the value of the work function of β-titanium. It is believed that α-titanium to β-titanium phase transformation occurs when the emitter tip is annelaed at 1100 °K to sperad the titanium uniformly over its surface. Surface diffusion of titanium on tungsten occurs with a sharp boundary at 800 °K and the activation energies for the (211)→(411) directions are 43.0 and $\text{42.3}\text{kcal}\text{mole}$ respectively. The activation energy of thermal desorption was dependent on the coverage and ranges from 115.3 to $\text{160.4}\text{kcal}\text{mole}$. A satisfactory qualitative correlation between the theory and experiment is established.     

Silicon diffusion through thin tungsten films on silicon,studied with Auger spectroscopy

Silicon out-diffusion through ? 3000 Å tungsten films deposited on silicon by r.f. sputtering was studied using Auger spectroscopy. Silicon first diffuses to the tungsten film surface by grain boundary diffusion and surface migration. The out-diffusion kinetics were most strongly dependent on the thickness of the silicon dioxide layer between tungsten and silicon, and this (native) oxide thickness varied with substrate doping. The out-diffusion rate was independent of tungsten film thickness at 540 Å and 2400 Å. For substrates from which the native oxide was removed by backsputtering just prior to tungsten deposition, no Si out-diffusion to the W film surface was observed until almost the entire film had converted to WSi².     

Electron beam effects on oxygen exposed aluminum surfaces

The damaging effects of electron beams during the acquisition of electron spectra have long been an obstacle in surface analysis. In order to understand the physico-chemical processes which take place under electron irradiation in an AlO system, we have carried out an experiment in which artifices, such as heating, charging, and gas contamination, were absent. We have observed with Auger Electron Spectra increases of the oxidation extent and the oxygen concentration on an oxygen exposed (111) textured polycrystalline surface under electron irradiation (5 keV, 9 × 10^?5 A/cm²). These increases were not observed on a clean surface, and were very feeble on a (100) single crystal surface. The increase of oxygen concentration was independent of residual gas pressure (3 × 10^?9 to 6 × 10^?10 Torr) and its composition; and therefore cannot be explained by gas contamination during the experimental period (about 70 min). We attribute the increase of oxidation degree to the transition of chemisorbed oxygen atoms into oxide through direct momentum transfer from the incident electrons. We suggest that the increase of oxygen within the irradiated area is due to the surface diffusion of chemisorbed oxygen atoms from outside the irradiated area. These oxygen atoms are excited by the electrons scattered from the vacuum chamber walls and gain energy through Franck-Condon type mechanism. The absence of chemisorbed oxygen atoms on (100) surface explains the near absence of these increases on this surface.     

Model and theory for the determination of diffusion coefficients by Auger electron spectroscopy measurements and an application to oxygen diffusion along the [0001] and [101¯0] axes in single crystal zirconium

A simple hopping model of the diffusion of adsorbed species from a surface into the bulk of a material has been formulated and solved mathematically. The difference in the energy barriers for an atom moving between the atomic layers at the surface and in the bulk are explicitly considered. This model is also capable of describing the initial stages of diffusion, something that conventional solutions of the continuum diffusion equation cannot handle. Auger electron spectroscopy has been used to measure the dissolution rate of oxygen from Zr(0001) and Zr(101¯0) surface into the bulk. Satisfactory results were obtained by applying our model to the diffusion data for these two zirconium surfaces for two different heating schedules: (i) rapid temperature ramp-and-hold and (ii) continuous linear heating with respect to time. The resulting Arrhenius expressions for diffusion are: D = (0.115 ± 0.031)exp[(−44.45 ± 4.82)kcal/RT]cm²/s along Zr[0001] and D = (1.07 ± 0.26)exp[(−46.18 ± 4.22)kcal/RT]cm²/s along Zr[101¯0].     

Stoichiometric and oxygen deficient MoO3(010) surfaces

The (010) surface of single crystal MoO₃ has been prepared and examined using LEED, XPS, UPS, and ELS. Three methods yield the stoichiometric surface: scraping in UHV and annealing, ion etching followed by reoxidation (770 K, 10² Pa O₂), or oxygen treatment to remove carbon contamination. LEED shows the surface periodicity is the same as that of the bulk (010). The MoO₃ valence band is 7 eV wide with density of states maxima at 1.5, 3.6, and 5.6 eV below the top of the valence band. Heating MoO₃ in vacuum reduces the surface region. XPS indicates the O/Mo atomic ratio decreases to 2.85 ± 0.12 on heating to 600 K. Ar ion bombardment disorders the surface and reduces the surface O/Mo atomic ratio to 1.6. Annealing of reduced surfaces at > 770 K incompletely reoxidizes them by diffusion of oxygen from the bulk. UPS of reduced and annealed MoO₃ exhibits two new emission features in the bandgap at 0.9 and 2.0 eV above the top of the valence band. These features originate from Mo derived states of a defect involving two or more Mo atoms, such as crystallographic shear planes. Because of the insulating nature of MoO₃, surface charging and electron beam induced damage were substantial hindrances to electron spectroscopic examination.     

The surface ionization of gadolinium,terbium and dysprosium on the tungsten (110) surface

A study of the surface ionization of gadolinium, terbium, and dysprosium (Gd, Tb, and Dy) is described and the results compared with the predictions of the Saha-Langmuir equation. A tentative measurement of holmium is also included. The experimental index parameter, E, which should be equal to the difference between the first ionization potential of the element and the apparent work function of the surface, was found to exceed the predicted value by the following amounts: Gd, 0.66 ± 0.14 eV; Tb, 0.27 ± 0.13 eV; and Dy, 0.24 ± 0.12 eV. The absolute ionization efficiencies were estimated by comparison of our gadolinium results with those reported by Dresser and Hudson. The preexponential coefficients are found to exceed the theoretically predicted values by an order of magnitude. Surface ionization efficiency of these rare earths is larger than predicted by the Saha-Langmuir equation by factors ranging from 5 to 25 at 2500 K. The (110) face of a tungsten single crystal was used as the ionizing surface, and its work function was determined to be 5.46 ± 0.11 eV in an auxiliary study of the emission of tungsten ions.     

非晶纳米过氧聚钨酸的Raman谱、热稳定性及UV-Vis光吸收特性

过氧聚钨酸是通过化学途径合成各种纳米结构氧化钨的重要前驱物之一。本文以双氧水(H₂O₂)、钨粉(W)和无水乙醇为原料合成了过氧聚钨酸溶胶,随后在常温下长时间放置,直至自然凝固,并在120 ℃干燥3 h后得到最终的深黄色胶状固体。利用XRD、SEM、Raman谱、TG/DSC分析和UV-Vis谱等分别考察了样品的成分结构、热稳定性和UV-Vis光吸收特性。宽的XRD峰表明样品是非晶结构,明显峰位的高斯型拟合表明样品是氧化钨与水合氧化钨的复合物。SEM表明样品呈纳米颗粒状(50～100 nm)和片层状形貌(厚约50 nm)。宽而明显的Raman峰的高斯型拟合进一步表明样品是非晶氧化钨和水合氧化钨的复合物,不仅拥有非常明显的O—W—O对称伸缩、非对称伸缩和WO振动,而且伴有O—W—O对称弯曲、非对称弯曲及吸附水的振动模式。TG/DSC分析表明过氧聚钨酸凝胶固体在120～500 ℃范围内存在四个不同的热力学过程：(Ⅰ)过氧聚钨酸凝胶固体的缓慢晶化(120～165 ℃);(Ⅱ)H₂O₂的分解和H₂O的去吸附(165～236 ℃);(Ⅲ)水合氧化钨的快速分解(236～287 ℃);(Ⅳ)最终产物WO₃的晶化和相变(287～500 ℃)。UV-Vis谱表明样品在350～600 nm范围存在一个明显的带边吸收,其光学带隙约2.25 eV,明显低于当前已报道的WO₃和H₂WO₄的带隙值(2.45～3.50 eV)。存留在复合物中的水分子、氧缺陷以及结构性畸变应该是导致其拥有较窄带隙的关键因素。     

The effect of surface sulfur on the oxidation of zirconium

In order to examine the effect of surface sulfur on the oxidation of zirconium, we have tried to make a quantitative analysis of sulfur segregation on Zr and made a study of the oxidation of sulfur segregated Zr. Depth profiles of the S-segregated Zr surface determined after high temperature annealing in vacuum show that the saturated surface concentration of sulfur has an S/Zr atomic ratio of about 1 and the total amount of segregated S is about 1 monolayer. These values do not depend on the annealing time. The S-segregated surface is exposed to an oxygen atmosphere in a pressure range of 10⁻⁶−10⁻⁵ Pa up to a total exposure of 9000 L at RT. Changes of the surface concentration of S, O and Zr are monitored by in situ AES analysis. Depth profiling of O, S and Zr for the oxidized specimen is also carried out. Surface oxidation is clearly delayed by segregated sulfur. This effect, however, is not so significant as for the S---Fe system, and three oxidation stages are clearly distinguished in the same manner as in the oxidation of clean Zr surfaces. This is because S is simultaneously oxidized and removed in the form of a volatile oxide such as SO or SO₂.     

蓝色氧化钨吸附丙烯和氧的热脱附谱

在超高真空条件下,用对样品进行闪烁加热的方法测定了蓝色氧化钨WO_2.90吸附丙烯和氧的热脱附谱。发现在室温下,丙烯在蓝色氧化钨表面只有一个吸附态,对应于热脱附谱中在100℃附近出现一个脱附峰。实验测定的热脱附参数为n=1(一级脱附),脱附活化能E_D=10.1kcal/mol。温度升高,丙烯在蓝色氧化钨表面形成稳定吸附态的几率减小。在125℃以上,不能形成稳定的吸附态,蓝色氧化钨在室温下对氧的吸附并不明显,温度升高到300℃以上,WO_2.90 关键词：     

Adsorption studies of aluminum oxide on rhenium by means of field emission microscopy

Aluminum oxide deposited on a clean rhenium field emission microscope tip at room temperature starts to migrate on the metal surface at about 600° C. Various face specific layer formations occur above this temperature. They either increase or decrease the local electron emission. Complete desorption of the aluminum oxide is obtained at about 1350°C. The remaining oxygen can be removed by heating at 1900°C. Average work function changes are discussed together with the corresponding FEM patterns of the various adsorption stages. Comparisons are made with the adsorption system aluminum oxide on tungsten.     

Trapping of oxygen by zirconium in dilute niobium-zirconium alloys

We have shown by X-ray absorption spectroscopy that oxygen is trapped by Zr in dilute NbZr alloys. Oxygen occupies the nearest octahedral sites next to a Zr ztom. There is one O atom trapped by each Zr atom. The angular information needed for the exact location of the O is obtained from a “lens” effect in the EXAFS which is observed when the O shadows a Nb back-scatterer. At 1075°C and below there is no precipitation of zirconium oxides in Nb.