Interpretation of AES data of impregnated cathodes

Many surface studies of impregnated cathodes involve a measurement of the Ba₅₉₀, O₅₁₀ and W₁₇₀ Auger peak heights. This paper shows how these measurements plotted in terms of O/Ba versus W/Ba concentration ratios can be used to interpret experimental results on impregnated B-type cathodes. Data are presented from actual cathodes and simulated cathode surfaces using well defined BaO films on W. These results as well topographic data will be compared to various calculated models. It will be shown that an active B-type cathode consists of nearly a monolayer of BaO on W with a slight excess of O compared to Ba. This excess O, however, is associated with W rather than the BaO. Ageing increases the O/Ba ratio and this takes place principally by the removal of Ba from the BaO surface, again with the excess O being associated with the W rather than the BaO. The work function increase during ageing corresponds only to the area-decrease of BaO. If the surface accumulates so much O that it exceeds the available empty Ba sites (i.e., all W is covered by Ba or O), then any additional O appears to sit on top of the remaining Ba and the surface will be poisoned. These conclusions are not only the result of work function observations but are also consistent with interatomic Auger analysis of Ba---O interactions as well as surface plasmon and ISS results. Toporgaphic data obtained from pore/impregnant regions are also in good agreement with calculated values of partial coverage of typical tungstate and impregnant residues.     

Zündspannung und normaler Katodenfall der Glimmentladung für Edelgase und reine Molybdänkatoden

Breakdown voltage near PASCHEN -minimum and normal cathode fall of the glow discharge were calculated for inert gases and molybdenum cathodes on the basis of a simple theory. The method used was similar to TAKEISHI 's one. The calculated breakdown voltages are in good agreement with measured values, if back scattering of the y_i -electrons and the distance which electrons travel from the cathode without ionization is taken into account. In the case of the normal cathode fall the values calculated with the same assumptions for inert gases and molybdenum cathodes are much higher (up to 50%) than the well known experimental values. It was concluded, that the y_i-process in the glow discharge ist not the only important one. Comparing the calculated and experimental values of the normal cathode fall we obtain the result, that photons and/or ions from the glow release about 40–60% of all electrons at the cathode.     

Ion scattering spectroscopy studies of barium and oxygen on tungsten and tungsten-based dispenser cathodes

In order to use Ion Scattering Spectroscopy (ISS) for studies of tungsten dispenser cathodes, the relevant ISS sensitivities must be measured. Calibrations have been made using a polycrystalline tungsten ribbon with controlled coverages of oxygen, barium and combinations thereof. Auger Electron Spectroscopy (AES) was used to monitor these controlled surfaces and the escape depths of the tungsten Auger electrons in barium and oxygen have been measured. The absolute ISS sensitivities of all three elements were found to be strongly dependent on the barium coverage of the tungsten surface. This effect has been attributed to the lowering of the work function of the tungsten surface caused by the barium adsorption. However, the relative ISS sensitivities of the three elements are not affected in this way when both barium and oxygen (or oxygen alone) are present on the tungsten surface. ISS spectra of such surfaces have been analyzed quantitatively and found to be in reasonable agreement with AES measurements. The analysis has also been applied to ISS spectra of uncoated tungsten matrix dispenser cathodes in an active state and following exposure to oxygen. Compared to AES, these spectra indicate less oxygen on the active cathode surfaces as a result of the oxygen (associated with barium) not contributing to the oxygen ISS signal. Comparisons of the spectra from the active and oxygen poisoned cathodes suggest that oxygen adsorbed during the oxygen exposure sits on the topmost barium layer whereas the oxygen on the active cathode surface does not.     

Changes in surface chemistry of an Ir---W mixed metal coated cathode during activation

A comparative study has been made between a mixed metal (60% Ir-40%W) coated cathode and a “B” cathode during activation and also in their respective steady states. The rate limiting factor in the activation of the coated cathode is the oxidation of the initial Ba type surface to a BaO type surface. Since on the “B” cathode Ba and O emerge together, its activation is faster than the coated cathode. In the steady state of operation, both cathodes exhibit a surface near BaO stoichiometry which is the optimum composition for the minimum work function. This work function is about 0.2 eV lower on the coated cathode than on the “B” cathode. An accelerated life test at 1575 K indicated a gradual decrease of the Ir concentration in the coating.     

Computer controlled techniques for high emission density mapping of thermionic cathodes

Some of the techniques commonly used (e.g. SLEEP and thermionic emission microscope) for measuring emission or work function uniformity of thermionic cathode surfaces require the use of very low or near zero current densities, thus the cathode is characterized at current densities and temperatures much lower than that of a normally operating cathode. The system reported on here uses a high voltage pulse technique and is capable of measuring emission densities in the range 1 to 80 A/cm² at normal cathode operating temperatures. The cathode surface is scanned with an anode having a 0.025 mm aperture whose position is controlled by computer operated stepping motors. The current through the aperture to a collector electrode is measured using a sample-and-hold amplifier. Pulsing and sampling are computer synchronized with the scanning, and data for each pulse are accumulated and can be processed and displayed in several ways using the computer, including a detailed “three-dimensional” map of either the electron emission density or work function variations. The entire surface of the cathode or any portion of it can be mapped in steps as small as 0.001 mm (1μm), but typically steps of 5–100 μm were used. Measurements are presented illustrating the uniformity or nonuniformity of the electron emission densities and work functions for type-B and type-M cathodes.     

Fast turn-on characteristics of tungsten-based dispenser cathodes. II

In the Proceedings of the 1982 Tri-Service Cathode Workshop, the authors described studies of the reactivations of tungsten-based dispenser cathodes following poisonings of the kind expected during shelf storage of a microwave tube [Appl. Surface Sci. 16 (1983) 73]. Further work on the problems of reactivation following such poisoning is described here. In addition to coated (“M”) and uncoated tungsten matrix cathodes, the tungsten-iridium mixed metal matrix (“MM”) cathode has been studied. In general reproducible results have been obtained from different examples of the same type of “M” and uncoated cathodes. However, although some “MM” cathodes have exhibited good reactivation characteristics, a large variation has been observed between different examples of “MM” cathodes. The composition of the impregnant in the dispenser cathodes has been found to be an important factor in determining the reactivation rate of a cathode. As the barium oxide concentration in the impregnant increases, the cathode will recover faster from a poisoning exposure. Studies of the poisoning caused by combinations of different gases suggest that poisoning will occur if there is a sufficient exposure of a poisoning agent, regardless of the total exposure. The exposures necessary to poison a cathode are so small, that poisoning of the cathode appears probable during shelf storage of a microwave tube. The reactivation results have been summarised in terms of the times and temperatures required to achieve both a given current density and a given degree of reactivation from a poisoned cathode. The studies also indicate that the limiting step during the reactivation process involves the dispensing of fresh material to the cathode surface rather than the desorption or conversion of a poisoned surface layer.     

表面形貌对热阴极电子发射特性的影响

为了研究热阴极表面形貌对电子发射能力的影响,使用飞秒激光微纳加工技术在光滑的热阴极表面制备不同尺寸和形状的周期性条纹结构,并使用相同的制备工艺对阴极进行除气和激活.测试结果显示:阴极表面周期性条纹结构可有效增强阴极的电子发射能力,正交双向条纹结构表面阴极的发射电流密度高于单向条纹结构表面阴极的发射电流密度,而且随条纹结构尺寸的降低,阴极的电子发射能力逐渐增强.对阴极表面形貌进行仿真,发现微尖顶端位置在强电场的作用下具有较强的电子发射能力.当阴极表面微尖底部直径与高度比值(r/h)较小时,微尖的侧面仍是阴极电子发射的主要区域,但是随着r/h减小,阴极的电子发射区域逐渐由微尖侧面发射向微尖顶端转移,场助电子发射效应成为阴极电子发射的主要组成部分.     

新型的覆纳米粒子薄膜阴极的研究

采用直流磁控溅射的方法制备出Ir金属纳米粒子薄膜.利用扫描电子显微镜分析了纳米粒子的形态和分布以及不同工艺条件对粒子粒径及形貌的影响,表明纳米粒子的大小可通过调节溅射气体压强来控制.在25%孔度的W海绵基体内浸入6∶1∶2铝酸盐发射物质,然后在其表面沉积上厚度为200—500 nm的纳米粒子薄膜层,最后在H₂气中1200℃烧结,即制成了新型纳米粒子薄膜阴极.利用阴极发射微观均匀性测试仪对纳米粒子薄膜阴极和传统覆膜阴极的热电子发射的均匀性进行了对比研究.采用飞行时间质谱仪测试了真空本底、纳米粒子薄膜阴极、传统覆膜阴极等各种阴极蒸发物的成分,研究了阴极蒸发速率与阴极温度的关系,比较了不同阴极蒸发速率的大小.研究了Ba-W阴极覆上纳米粒子薄膜后的发射特性. 关键词： 纳米粒子薄膜 热阴极 发射均匀性 蒸发     

Diffusion and desorption of barium and oxygen on tungsten dispenser cathode surfaces

Auger measurements have been made on the concentration of barium and oxygen diffusing out of a pore and slot onto the surface of a simulated tungsten dispenser cathode. Profiles of concentration vs distance from the source were obtained at different temperatures. It is found that at cathode operating temperatures very little gradient of oxygen concentration exists on the surface, and under steady state conditions Ba is the main diffusing species. Ba diffusion distances derived are consistent with previous measurements. However it is found that this distance increases with concentration in spite of the fact that the Ba surface lifetime decreases with concentration. Time dependent measurements made on a clean surface show that the rate of Ba and O build up is limited by the supply rate of oxygen to the surface. This supply rate is not diffusion limited but seems to be limited by the mechanism generating free oxygen. A comparison of emission microscope measurements on a tungsten matrix dispenser cathode with the simulated cathode data indicates that similar oxygen generation processes may be controlling the activation of these cathodes.     

Auger studies comparing the surface concentration of barium on tungsten impregnated and M-cathodes

A study comparing the surface concentration of barium on both an impregnated tungsten cathode surface and M-type cathode surface was made to determine whether the higher electron emission capability of the latter can be attributed to a higher average surface barium concentration. Relative quantitative data was obtained by the use of a computerized Auger microprobe spectrometer on the surface of the cathode, half of whose area was M-type, the other half being the tungsten impregnated type. The results indicate that both cathode surfaces have equivalent barium concentrations and that they are approximately equal to a barium monolayer after 3000 h of cathode life.     

Oxygen exchange kinetics of La0.58Sr0.4Co0.2Fe0.8O3 at 600 °C in dry and humid atmospheres

The time-dependent degradation of the oxygen exchange kinetics of the solid oxide fuel cell cathode material La_0.58Sr_0.4Co_0.2Fe_0.8O_3 − δ (LSCF) is investigated at 600 °C. Special emphasis is placed on systematic long-term dc-conductivity relaxation measurements (t > 1000 h) in dry as well as in humidified atmospheres in order to obtain representative trends for the application of LSCF in intermediate-temperature SOFCs. The determination of the chemical surface exchange coefficient k_chem of oxygen is combined with investigations of the elemental surface compositions and depth profiles of fresh and degraded samples by X-ray photoelectron spectroscopy (XPS), providing further insight into the mechanisms of degradation. The slow decrease of k_chem by a factor of 2 during exposure of the sample to a dry O₂-Ar reference atmosphere for 1000 h at 600 °C can be ascribed to an enrichment of La and Sr in correlation with an elevated oxygen concentration within about 30-35 nm depth. The interpretation of the XPS core level spectra indicates the formation of SrO and La₂O₃ secondary phases in this zone. The subsequent treatment in a humidified atmosphere for 1000 h results in a pronounced initial decrease of k_chem by an additional factor of 10, followed by a time dependent decay of about 15% kh^− 1. A Sr-rich silicate layer of about 10 nm thickness is identified by XPS as the major cause of the degradation in humidified atmosphere. The evidence of Si-poisoning over the whole sample surface could also be confirmed by post-test SEM analysis. In addition, indications of a re-structuring of the sample surface during the degradation are shown. These results indicate, that with LSCF as a cathode in ambient (humid) air in SOFC stacks containing various Si-sources, such as glass or glass-ceramic seals, and thermal insulation materials a significant decrease of the surface oxygen exchange coefficient can occur, even at temperatures as low as 600 °C. In order to prevent a severe Si-induced degradation, dry air should be used as an oxidant. However, even in dry atmosphere a minor decrease of k_chem can occur during long-term operation due to changes in the relative cation and oxygen content at the surface.     

Surface studies on the low work function surface complex of barium on an osmium-ruthenium substrate

Barium and oxygen on an osmium-ruthenium (Os/Ru) surface is the surface complex responsible for the excellent electron emission properties of commercial M-type thermionic cathodes. A computerized Auger technique was used to study the surface properties of this surface complex and compare it with results obtained earlier for Ba-O-W surfaces, which characterize the properties of commercial barium impregnated tungsten thermionic cathodes. Barium desorption, electron emission and barium, barium oxide evaporation were measured at elevated temperatures for this experimental surface study. Desorption measurements, at 1100°C, on the barium on osmium-ruthenium substrate show that the energy for desorption was higher than that for the lowest work function Ba-O-W surface (5.4 to 4.8 eV). Oxygen was always present on the sputtered Os/Ru substrate and contributed to the strong bonding of barium to the Os/Ru surface. The barium and barium oxide evaporative products from such a surface at 1100°C were found to be mainly barium with the Ba/BaO ratio equal to approximately 100.     

A model of dispenser cathode activity

A semiquantitative model of dispenser cathode activity based on recent work on the co-adsorption of Ba and O onto W surfaces is presented. The co-adsorption studies have determined the shape of a three-dimensional surface of work function as a function of θ_O and θ_Ba, the surface coverages of O and Ba, respectively. Compositions of a variety of pedigreed dispenser cathodes were fitted to this surface and their composition changes during lifetime were modeled. Changes of surface composition with temperature and of workfunction, φ, with temperature were also found to fit these curves. The concept of a patchy surface implied by the co-adsorption measurements was used to explain earlier results on the shape of the X-ray excited Ba MNN Auger feature. Finally, SIMS measurements under UHV conditions was found to provide an extremely sensitive measurement of surface composition in the region of surface coverages of interest in the study of cathode phenomena. Extensions of this work to other types of cathodes such as M-types, and rhenium substrate cathodes is also discussed.     

Characterization of scandia doped pressed cathode fabricated by spray drying method

Scandia doped pressed cathode was prepared by a new method of spray drying combined with two-step hydrogen reduction process. The Sc₂O₃ and barium-calcium aluminate co-doped powders have sub-micrometer size in the range of 0.1-1 μm and scandium oxide and barium-calcium aluminate are distributed evenly in the powders. The cathodes sintered by powder metallurgy at 1600 °C_b have a smooth surface and sub-micrometer grain structure with homogeneous distribution of scandium, barium, calcium and aluminum which are dispersed over and among the tungsten grains. This cathode has good emission, e.g., the current density of this cathode reaches 31.50 A/cm² at 850 °C_b. After proper activation, the cathode surface is covered by a Ba-Sc-O active substances layer with a preferable atomic ratio, leading to its good emission property. The evaporation activation energy of SDP cathode with 4.58 eV is the highest among the Ba-W, M-type and SDP cathodes, and the average evaporation velocity v_t of SDP cathode with 1.28 × 10⁻⁸ g cm⁻² s⁻¹ at 1150 °C_b is the lowest one.     

Application of novel SIMS technique for imaging the active sites of oxygen reduction at the SOFC cathode/electrolyte interfaces

The oxygen reduction active sites were visualized around the O₂/SOFC cathode/electrolyte triple phase boundaries (TPB) by the¹⁶O/¹⁸O exchange techniques and secondary ion mass spectrometry (SIMS) analysis. The higher¹⁸O concentration is observed on the cathode top surfaces (La_0.9Sr_0.1MnO₃-mesh, Au-mesh, and Ag-porous), which suggested the promotion of oxygen adsorption and oxygen surface exchange at the cathode. The oxygen diffusion through the bulk of cathode occurred at the La_0.9Sr_0.1MnO₃-mesh and the Ag-porous cathodes, not at the Au-mesh cathode. On the YSZ surfaces after removing the cathode, the active sites for oxygen incorporation were analyzed by SIMS. The active sites for oxygen incorporation were at the La_0.9Sr_0.1MnO₃/YSZ interface as well as the TPB. On the other hand, the active sites for oxygen incorporation are limited to the TPB in the case of the Au-mesh removed YSZ surface. From the SIMS analysis, the expansion of the active sites for oxygen incorporation is less than a few μm from the TPB lines. Paper presented at the 8th EuroConference on Ionics, Carvoeiro, Algarve, Portugal, Sept. 16–22, 2001.     

关于热电子发射理论的评述(Ⅰ)——对氧化物阴极的半导体模型的批判

二十多年来,我们从实践中发现,氧化物阴极的理论与实际之间存在着很多矛盾。本文从逸出功测量、吸收光谱、超额钡浓度、晶格结构、表面能级、涂层导电率、涂层电位分布、薄膜和厚涂层发射的比较、中间层电阻、发射的不均性、闪变噪声、脉冲电流不稳定性、电火花等方面的实验和论证,说明氧化物阴极并不是以超额钡为施主的电子型半导体。提出了表面发射中心的观点,并用它解释了氧化物阴极中的许多现象。     

Methods for evaluating the performance of emitters in plane parallel diodes

The curvature seen in Child's law plots of current-voltage characteristics measured using plane parallel diodes may be analysed in a number of ways to give information about the work function distribution of a cathode. This paper suggests a simple technique for characterising a cathode based on the assumption it has a “top-hat” work function distribution. The technique allows synthetic current/voltage characteristics to be generated which agree well with the practical characteristics from which the parameters of the work function distribution were derived. The parameters of the “top-hat” model may also be used to obtain an equivalent Gaussian work function distribution which gives almost identical synthetic characteristics and Schottky enhancement may be modelled in a rather empirical manner. Since either model gives good predictions, synthetic characteristics may be used to investigate other methods used to characterise cathodes. It is found that there is generally reasonable agreement which could be improved, for most practical work function distributions, by the choice of parameters slightly different from those normally used.     

Temperature-dependent electrical properties of organic light-emitting diodes depending on cathodes

We have studied temperature-dependent electrical properties of organic light-emitting diodes with a variation of cathode materials; Al, LiAl, and LiF/Al. The organic light-emitting diodes emit a light by a recombination of injected charge carriers such as holes and electrons. Thus, the charge transport is affected by the injection barrier at the interface. By varying the cathode materials, the electron injection at the interface could be controlled because of the work-function change at the cathode. Temperature-dependent current–voltage luminance characteristics of the organic light-emitting diodes were measured in the temperature range from 10 to 300 K. The current-voltage characteristics were analyzed in terms of Fowler–Nordheim tunneling model, and the energy-barrier height was obtained. A measured lifetime of device with LiF/Al cathode is relatively longer than the other cathodes at room temperature: 4.5 h for Al cathode, 12.4 h for LiAl, and 29.6 h for LiF/Al. The device with LiAl and LiF/Al cathode, in the aspect of lifetime and luminous efficiency, is superior to one of other cathodes.     

XPS on impregnated cathodes: Surface concentrations and thermal stability

Photoelectron spectra are presented for S, M and scandate cathodes before and after the activation procedure. Using the calculatory method and the Ba deposition method the Ba coverages for the S, M and Sc cathodes have been established as 4.0×10¹⁴, 5.8×10¹⁴ and 5.8×10¹⁴ Ba atoms cm^-2 respectively. On the Os-Ru cathode an enhancement of the Ru concentration is found which may be due to segregation. Further a short investigation was made into the thermal stability of the Ba overlayer and its regeneration. It appears that after a heating cycle to 1200 °C the S and M cathodes recover very well whereas the Sc cathode suffers from the loss of Sc which is inherently connected with the fine emission properties of this cathode.     

Reaction mechanisms of the copper-manganese spinel cathode in a solid oxide fuel cell

Cu_1.25Mn_1.75O₄ spinel (CMO) was studied as a potential solid oxide fuel cell (SOFC) cathode material at intermediate temperatures. The reaction mechanism of a composite cathode consisting of Cu_1.25Mn_1.75O₄ and yttria-stabilized zirconia (YSZ) was investigated by impedance spectroscopy. The influence of the CMO/YSZ ratio, time exposed to current passage and temperature on the impedance spectra was examined. Activation energy of the corresponding processes was calculated to be near 1 eV and between 1.32 and 1.96 eV for the high and low frequency arcs in the impedance spectra. Comparison between CMO-YSZ and Sr-doped LaMnO₃ (LSM)-YSZ composite cathodes showed they had similar reaction mechanisms. The transport or transfer of oxygen intermediates or oxide ions between the catalyst and electrolyte was suggested to be the rate determining steps between 700 and 800 °C, whereas dissociative adsorption, mass transfer and surface diffusion were rate controlling between 600 and 700 °C.