A study of Eu2O3, Sc2O3 co-doped tungsten matrix impregnated cathode

Eu₂O₃ and Sc₂O₃ co-doped W matrix impregnated cathodes have been prepared by the powder metallurgy method. The constitution of active elements on activated cathode surface is analyzed by in-situ Auger electron spectroscopy. It is found that although Eu exists in the matrix, no Eu is found on the cathode surface due to the formation of a stable Eu containing compound. Sc, Ba and O diffuse to the surface of the cathode and form an active surface layer during the activation period whereas the stable Eu-compound cannot liberate free Eu, which can diffuse from the cathode to the surface. The active substance of Sc, Ba and O on the cathode surface contribute to the emission property.     

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.     

Properties and manufacture of top-layer scandate cathodes

The life and/or the staying power against ion bombardment of scandate cathodes can be improved by using a top layer of W + Sc₂O₃ or W + W/ScH₂ on a tungsten matrix. The latter is impregnated with the usual 4-1-1 impregnant. Even at high voltage pulses the current densities are so high that the deviation from space charge limitation is small. The manufacture is discussed and the cathode life at the operating temperature of 1220 K is shown to be very long. Moreover, the relationship between processing parameters and emission recovery after ion bombardment is examined with the aid of combined sputter- and scanning-Auger measurements. It is shown that thin-layer coverage of tungsten by scandia is important to the high emission. This coverage is related to the impregnation process. After extended sputtering it cannot be completely recovered by reactivation. Consequently, the top layer cathodes cannot withstand sufficiently the usual processing and operation of television display tubes. On the other hand, they can improve the life and performance of electron devices with good vacuum and/or relatively low accelerating potentials. Moreover, activated top-layer scandate cathodes are relatively insensitive to exposure to (moist) air.     

Degradation factors of a new long life cathode

This paper analyses the degradation factors of a new long life coated impregnated cathode after accelerated life test. The surface state of the cathode is investigated with scanning electron microscope (SEM) as well as the content and variation of the various elements on the surface and the longitudinal section of the cathode are analyzed with Auger electron spectroscopy (AES) before and after the life test. The analyzing results with SEM show that the cathode coating shrinks at the life end and leads to a rise in its work function. The analyzing results with AES show that the percent of the W increases and the active materials Ba decreases on the cathode surface at the life end. Furthermore, there is less Ba underneath the cathode surface but still a lot of Ba in the tungsten matrix at the life end.     

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.     

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.     

“Alternative” auger analysis reveals important properties of M-type and scandate cathodes

It is shown that in the evaluation of Auger spectra, as measured on cathode surfaces, the elemental sensitivities have to be corrected for differences in elemental number density. The substrate and the surface covering material have to be treated differently in the analysis. The result for normal M-type cathodes is that — besides the Ba---O cover — there is an excess oxygen concentration on the surface of about two times the Ba---O concentration. This in spite of the fact that the oxygen to barium peak-to-peak height ratio in the measured spectra is about equal to 2. For a degraded M-cathode the excess oxygen level is found to be much higher than for the normal cathodes. A new type of scandate cathode is described and discussed. Its analysis shows more Ba and, relatively, much less excess oxygen than for the M-type cathodes. This may account for the substantially higher emission.     

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.     

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.     

Interactions of BaO with mixed-metal substrates: W---Ir

Surface studies of BaO on W---Ir alloy substrates of different composition show work functions lower for the alloys than on either pure W or pure Ir. In particular, the lowest work function ( 1.8 eV) appears near the 50% W, 50% Ir concentration. Peak height characterizations and energy shifts of interatomic Auger lines indicate an adsorbate-substrate interaction is responsible for the function lowering. The interaction consists of the O of the adsorbed Ba⁺O⁻ molecule receiving electrons from the W and the Ba from the same molecule contributing electrons to the Ir. The resulting increase in surface dipole (as observed from interatomic O 2p and Ba 6s peak heights) is in very good agreement with the actual work function lowering. If the substrate consists of significant “patches” of W and Ir, then the Ba and O from the same molecule cannot interact with the different substrate components. When this happens, neither is the adsorbate-substrate interaction seen in the interatomic Auger spectra nor is any work function-lowering observed. The minimum in work function near 50% W, 50% Ir is the point where the dipole lowering (i.e., charge transfer) is most efficient because at thatconcentration there is one Ir atom available for each Ba atom and one W atom available for each O atom on the surface.     

钡钨阴极优化与热电子发射性能

分别从基体和铝酸盐两方面优化了钡钨阴极.在基体方面,首先采用窄粒度钨粉结合放电等离子体烧结获得了孔径分布窄的基体;再利用射频等离子体球化技术制备了球形钨粉,采用球形钨粉制备了多孔基体,获得了孔通道光滑、内孔连通性好、孔径分布更加窄的基体.与窄粒度钨粉基体相比,球形钨粉制备的阴极,空间电荷限制区的斜率由1.25增加至1.37,发射均匀性得到提高,拐点电流密度由6.6 A·cm^–2增至6.96 A·cm^–2.在此基础上,采用液相法改善了铝酸盐物相组成,发现空间电荷限制区的斜率增加至1.44,拐点电流密度增加至21.2 A·cm^–2.通过理论计算对钡钨阴极发射的物理本质进行了研究,发现钡钨阴极发射规律遵循偶极子理论.     

Rare earth oxide doping in oxide cathodes

The effect on life performance and poisoning with O₂ by doping oxide cathodes with rare earth oxides and pseudo rare earth oxides, notably yttria, is qualitatively explained in terms of electrolysis of BaO during emission of electrons. Doped cathodes show less electrolysis and consume therefore less Ba during life: consequently, doped cathodes have a better life performance. However, the lower Ba-production makes doped cathodes more sensitive to oxygen poisoning. The experimentally found relation between conductivity and yttria concentration was the motive to propose a new model for the crystal imperfections in BaO. In this new imperfection model most Y³⁺-ions will combine with barium vacancies, therefore, the increase of the conductivity is modest and also the effect on the position of the Fermi level is modest. By assuming a combination of bulk and surface conductivity, the agreement between experiment and theory can be improved further.     

Sc2O3-W matrix impregnated cathode with spherical grains

Sc₂O₃-W matrix cathodes have been prepared by using a liquid-liquid doping method combined with high-temperature sintering. The microstructure and physical behavior of active substances of scandia-doped tungsten matrix and impregnated cathode has been studied by SEM and AES methods. The results show that the matrix has a homogeneous structure composed of W grains with spherical shape and superfine Sc₂O₃ particles dispersed uniformly over and among W grains. After impregnation, this Sc-type impregnated cathode has high emission capability. Space-charge-limited current density could reach 52 A/cm² at 850 °C_b. The high emission results from a Ba-Sc-O active layer with a thickness of about 80 nm, which is formed at the cathode surface during the activation period. Both the decrease of the thickness of active surface layer and the decrease of the content of Sc at the surface could lead to the degradation of current density during operation.     

Study on anti-emission materials for non-emitting grid applications in microwave power tubes

Hafnium and platinum were deposited onto molybdenum grids by ion-beam assisted deposition method. Electron-emission characteristics from molybdenum grids with Hf and Pt films, which were contaminated by active electron-emission substances (Ba, BaO) of the cathode, were measured using analogous diode method. The surfaces of grids were analyzed by X-ray diffraction. The results revealed that the reaction between BaO and Hf formed BaHfO₃ compound, which greatly reduced the accumulation of BaO on the surface and accordingly decreased grid emission. In contrast, Ba were formed by the decomposition of BaO on the surface of Pt film under high temperature and re-evaporated from its surface, which reduced the active electron-emission substances on the surface of the grid and effectively restrained grid emission. Their mechanisms for grid-emission suppression are discussed and a good method to develop new grid-coating materials is suggested.     

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.     

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     

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.     

BaxOy小团簇修饰Ru(0001)表面的结构稳定性和氮分子吸附性质

为了说明钡助剂的存在形式, 本文采用第一性原理方法研究了Ba_xO_y小团簇修饰Ru(0001)表面的结构稳定性和氮分子吸附性质. 基于总能的热力学分析发现, 在实验条件下(500 K, P_H2O/P_H2<10^-3), Ba₂O团簇比BaO₂, BaO, Ba和O等团簇(原子)更加稳定. 这证实含有金属性钡原子的团簇也是氧化钡助剂可能的工作状态. 表面电荷差分密度说明Ba₂O团簇的氧和钡原子与衬底的作用不同. 不过Ba₂O团簇氧和钡原子附近的氮分子吸附行为相似, Ba₂O团簇增强了氮分子和衬底的相互作用. Ba₂O团簇氧和钡原子附近的氮分子吸附能分别为0.78 和0.88 eV, 均大于清洁表面的0.67 eV. 氮分子间距和氮分子的拉伸振动频率都表明Ba₂O团簇在一定程度上活化了吸附氮分子. Ba₂O团簇氧和钡原子附近的N–N键长分别为0.117和0.116 nm, 大于清洁表面的0.114 nm. 氧和钡原子附近氮分子的拉伸振动频率分别为 1888 和1985 cm^-1, 小于清洁表面的2193 cm^-1. 电荷差分密度的计算结果说明, 削弱作用主要来自于Ba₂O团簇中钡离子和氮分子间的静电作用. 两者间的静电作用增加了氮分子π 反键轨道的占据数, 促进了氮分子极化, 从而削弱氮分子键.     

Comparison of autoemission properties of tungsten/n-and p-type semiconductor systems

W/Cs₃Sb and W/TiO₂ field-emission cathodes have been produced and investigated. The emission characteristics obtained for both cathode types were better than for standard tungsten cathode. Physical models of these emitters have been proposed and experimentally confirmed.     

DFT study of BaTiO<Subscript>3</Subscript> (001) surface with O and O<Subscript>2</Subscript> adsorption

Progress of scanning tunneling microscopy (STM) allowed to handle various molecules adsorbed on a given surface. New concepts emerged with molecules on surfaces considered as nano machines by themselves. In this context, a thorough knowledge of surfaces and adsorbed molecules at an atomic scale is thus particularly invaluable. In this work, within the framework of density functional theory (DFT), we present an electronic and structural ab initio study of a BaTiO₃ (001) surface (perovskite structure) in its paraelectric phase. As far as we know the atomic and molecular adsorption of oxygen at surface is then analyzed for the first time in the literature. Relaxation is taken into account for several layers. Its analysis for a depth of at least four layers enables us to conclude that a reasonable approximation for a BaTiO₃ (001) surface is provided with a slab made up of nine plans. The relative stability of two possible terminations is considered. By using a kinetic energy cut off of 400 eV, we found that a surface with BaO termination is more stable than with TiO₂ termination. Consequently, a surface with BaO termination was chosen to adsorb either O atom or O₂ molecule and the corresponding calculations were performed with a coverage 1 on a (1×1) cell. A series of cases with O₂ molecule adsorbed in various geometrical configurations are also analyzed. For O₂, the most favorable adsorption is obtained when the molecule is placed horizontally, with its axis, directed along the Ba-Ba axis and with its centre of gravity located above a Ba atom. The corresponding value of the adsorption energy is -9.70 eV per molecule (-4.85 eV per O atom). The molecule is then rather extended since the O–O distance measures 1.829 ?. By comparison, the adsorption energy of an O atom directly located above a Ba atom is only -3.50 eV. Therefore we are allowed to conclude that the O–O interaction stabilizes atomic adsorption. Also the local densities of states (LDOS) corresponding to various situations are discussed in the present paper. Up to now, we are not aware of experimental data to be compared to our calculated results.