DLTS and conductance transient investigation on defects in anodic tantalum pentoxide thin films

In this work we report on deep level transient spectroscopy (DLTS) and conductance transient measurements (G-t) carried out on films of tantalum oxide fabricated by anodic oxidation of tantalum nitride and tantalum silicide with thickness ranging from 10 to 450 nm. These films exhibit greatly improved leakage currents, breakdown voltage and very low defect density, thus allowing the fabrication of large area capacitors. Leakage currents in the insulator under thermal stress have been carefully studied in order to determine the nature and physical origin of the dominant conduction mechanisms in the insulator. We have found noticeable differences in the dominant conduction mechanisms for thin and thick anodic tantalum pentoxide films. These differences are explained in terms of the thickness dependence of the insulator layer structure. We have characterized the physical nature of the conduction mechanisms in the dielectric films. The Poole–Frenkel effect and the modified Poole–Frenkel effect are suggested. No DLTS signals have been obtained, because transients do not change for temperatures ranging from 77 to 300 K. Conductance transients have important dependencies on voltage bias pulse amplitude and frequency that seem to be closely related to the physical nature of the anodic tantalum pentoxide.     

5A06铝合金阳极氧化和微弧氧化膜绝缘性能研究

采用阳极氧化和微弧氧化方法对5A06铝合金进行表面绝缘化处理,并对试样膜层的形貌、物相、绝缘电阻、漏电流、击穿电压和抗液氮冲击等性能进行了研究.结果表明,5A06阳极氧化膜为非晶相,而微弧氧化膜主要为晶相γ-Al2O3.无论是阳极氧化膜还是微弧氧化膜,干燥条件下的交流和直流击穿电压均较潮湿条件下的高;相同电流模式下,氧...     

Multilayer structure of tantalum anodic oxide films formed in dilute phosphoric acid

An investigation has been made of the multilayer structure of anodic oxide films on pure tantalum, formed up to various voltages with a constant current density of 1.0 mA cm^-2 in 1.0 × 10^-2 N H₃PO₄ at 20°C. For the study, infrared reflectance spectra (IRRS) were recorded and the optical thickness measuring method was successfully applied using the wavelengths of optical interference maxima and a chemical film stripper (concentrated ammonium hydrogen difluoride aqueous solution).The conclusions are that: (1) tantalum anodic oxide films anodized in dilute phosphoric acid consist of three layers, irrespective of the formation voltage; (2) the innermost layer is uniform whatever the anodization voltage; (3) phosphate anions are incorporated in both the outermost and middle layers but not in the innermost layer; (4) all three layers grow from the initial formation stage and the growth rates are nearly equal; (5) for formation voltages below 100 V the middle layer has an unchanging chemical structure, but above 100 V its chemical structure changes with the voltage; (6) the outermost layer appears to vary in chemical structure over all anodization voltages.     

Titanium oxide films produced on commercially pure titanium by anodic oxidation with different voltages

Titanium oxide films produced on commercially pure Ti by anodic oxidation with different voltages were analyzed. Anodic oxidation was carried out at room temperature using 1.4 M H₃PO₄ electrolyte and a platinum counter-electrode, in potentiostatic mode under the following conditions: 50 V, 100 V, 150 V, 200 V and 250 V. It was observed that porous titanium layers were formed at all voltage values but morphological differences were observed. Initially, the film was thin but with increasing voltage it broke down locally and porous regions became evident due to the dielectric breakdown. The porosity and the pore size increased with the increasing voltage. The surface morphology in samples formed with 200 V had substantially different porous structures than those formed with other voltage values. The anodic film surface displayed pores and craters formed on the relatively flat ground oxide surface. AFM images showed that higher voltages produced thicker titanium oxide films.     

阳极氧化法制备Ta2O5绝缘膜及性能研究

采用阳极氧化法在纯Ta表面制备绝缘性优良的Ta2O5介质膜,分析阳极氧化制备Ta2O5膜的基本机理,讨论不同电解液、阳极氧化电压及热处理等工艺参数对Ta2O5膜性能的影响.利用XRD、EDS和AFM分析薄膜的组织结构和表面形貌,超高阻微电流测试仪测试Ta2O5绝缘膜漏电流特性和耐击穿电压,结果表明,磷酸电解液中添加适当乙二醇溶液能有效地防止"晶化",阳极氧化电压在125～150V范围内制备Ta2O5绝缘膜耐击穿电压能力强,经350℃/60min大气气氛下热处理Ta2O5薄膜,内部结构致密,能有效提高Ta2O5绝缘膜耐击穿电压.     

Scintillation in anodic Ta2O5 films

The scintillation of anodic tantalum oxide was investigated by counting the number of breakdown events during anodization at a constant current density. A theory is developed which qualitatively explains the variation in the number of breakdown pulses with time and voltage for different current densities and different electrolyte resistivities. The theory also allows definition of a limiting anodization voltage which increases with the logarithm of the current density. Several experiments are presented which are in agreement with the theory.     

Caractéristiques Courant-Tension Des Structures Ti/TiO2/Électrolyte Et Ti/TiO2/Métal: Effet Schottky Et Claquage

Anodic layers of TiO₂ were made with a potentiostatic setting and voltages from 1 to 90 V in 1 N sulphuric acid. The current-applied voltage characteristics of the structures Ti/TiO₂/Au and Ti/TiO₂/electrolyte are compared and analysed with the Schottky mechanism. The barrier heights calculated for the rectifying interfaces TiO₂-Au and TiO₂-electrolyte are respectively 1.2±0.1 eV and 0.88±0.05 eV. Three domains of voltage were distinguished for the anodic oxidation of titanium in the potentiostatic mode as follows: from 1 to 10 V corresponding to a natural oxide thin layer and the beginning of anodic oxidation; from 10 to 90 V corresponding to oxidation with electronic breakdown; beyond 90 V relating to oxidation accompanied by thermal breakdown.     

Transparent nanoporous tin-oxide film electrode fabricated by anodization

A transparent nanoporous tin oxide film electrode was fabricated by anodizing a tin film on a fluorine-doped tin oxide (FTO) film electrode. The resulting anodized nanoporous tin oxide (ANPTO) film has columnar-type pore channels with around 50 nm in diameter and is optically transparent. Electrochemical measurements with Fe(CN)₆³⁻ as a redox probe clearly revealed that the ANPTO film could be used for a working electrode with a large internal surface area. Moreover, it was found that ANPTO film had a wider anodic potential window (> ca. 2.0 V) than conventional metal oxide electrodes, such as FTO and indium tin oxide film electrodes (> ca. 1.3 V). The wide anodic potential window improves applicability of a transparent metal oxide electrode for various electrochemical oxidation reactions, which are often interfered by oxygen evolution in water. These results conclude that the ANPTO film can be used as an advanced transparent nanoporous film electrode.     

Use of anodic tantalum pentoxide for high-density capacitor fabrication

In this work we report on very thin (10 to 100 nm) tantalum oxide fabricated by anodic oxidation of tantalum nitride and tantalum silicide to be used as the dielectric of high density MIM and MIS capacitors. These films exhibit greatly improved leakage currents, breakdown voltage and very low defect density, thus allowing the fabrication of large area capacitors. Several counter and bottom electrodes have been used and compared. The effects of the different processing conditions (top-electrode metals, annealing conditions, bottom electrode stoichiometry) on the capacitor performances are extensively discussed throughout this work. The nitrogen content of tantalum nitride films seems to have an important influence on the insulator quality. Leakage currents in the insulator have been carefully studied in order to determine the nature and physical origin of the dominant conduction mechanisms in the insulator. The electrical behaviour of the resulting high-density MIM capacitors has been extensively characterized. Finally, we describe a new method to fabricate MIS diodes with anodic tantalum oxide as insulator.     

Electrochemical characteristics of surface of titanium formed by electrolytic polishing and anodizing

A clear surface was polished using electrolytic polishing (EP). The mean roughness (Rz) of the polished surface was 1.966 nm, as measured by atomic force microscopy (AFM) over a 2 × 2 um² scan area. The various directions of the grains could be observed clearly following EP. The multiple beam interference effect generated various colors of the grains after anodic treatment at constant anodic voltage. A template with ordered nanochannel-array of anodic titanium oxide (ATO) was formed at 20 V. The template formed by self-assembly. The long-range ordered nanochannel had a thickness of 170 nm film, a pore size of 100 nm, an inter-pore distance of 120 nm, pore walls with a thickness of 25 nm, a pore density of 8× 10⁹ pores/cm², and a porosity of 68.2%, after anodizing for 90 s. When the applied voltage exceeded the breakdown voltage (90 V) of titania, the corrosion rate increased and the color of the titanium became as measured electrochemically by Tafel polarization and AC impedance methods, and observed by optical microscopy.     

Ta-Ta2O5-电解液导电体系界面特性的实验研究

分析了阀金属钽氧化膜的形成过程,伏安特性测试结果表明Ta-Ta2O5-电解液体系具有单向导电性.电场作用下,电解液中O2-跃过氧化膜/电解液界面,在氧化膜中形成定向迁移,同时引发膜内二次电子场助发射是该体系的主要导电机理.实验表明,大量二次电子导致介质膜雪崩式击穿是该体系闪火的主要原因,在电解液中添加适量有机物,可以屏蔽O2-使电解液的闪火电压提高30V以上,从而提高液体钽电解电容器的性能.     

Measurements of the thermal conductivity of aqueous LiBr solutions at pressures up to 40 MPa

This paper describes absolute measurements of the thermal conductivity of aqueous LiBr solutions in the concentration range 5 to 15m (molality), the temperature range 30 to 100°C, and the pressure range 0.1 to 40 MPa. The measurements have been performed with the aid of a transient hot-wire apparatus employing a thin tantalum wire coated with an anodic tantalum pentoxide insulation layer. In using the tantalum wire, a modification of the bridge circuit has been made to keep the electric potential of the wire always higher than the ground level in order to protect the insulation layer from breakdown. The experimental data, which have an estimated accuracy of ±0.5%, have been correlated in terms of the polynomials of concentration, temperature, and pressure for practical use. Also, it has been found that the pressure coefficient of the thermal conductivity decreases with increasing concentrations.     

Temperature stability of thin anodic oxide films in metal/insulator/metal structures: A comparison between tantalum and aluminium oxide

The dielectric breakdown of thin (d = 3–4 nm) aluminium and tantalum oxide films was investigated by means of current voltage plots in metal/insulator/metal systems. Dielectric breakdown field strengths, E_DB, of 0.6 GV m^− 1 were found for both oxide types at room temperature. Differences appear in the temperature dependence of E_DB. Tantalum oxide films show an unchanged breakdown behaviour for temperatures up to 420 K while aluminium oxide films lose already 80% of their E_DB value in the same temperature range. Time-resolved investigations of the electric breakdown revealed intermediate states of both oxide types which were stable for several ms being characterized by an enhanced tunnel current. The breakdown voltage clearly scales with the oxide thickness for both oxide types.     

电容器用钽阳极失效分析与研究

利用扫描电镜进行电容器用钽阳极失效原因分析,造成单支阳极块漏电流异常偏大甚至被击穿的主要原因为:局部存在的夹杂物质引起氧化膜生长异常导致颗粒表面局部钽氧化物薄膜不连续,大量的电子通过造成漏流偏大甚至击穿。阳极块中出现的异物为原料钽锭中存在的钽的碳化物夹杂,由于其高熔点、耐酸蚀的特点使得钽粉后续处理过程中无法去除而保留在了钽粉中。背散射电子成像可应用于钽样品检测。      

LED绝缘铝基板的制备与散热性能研究

采用硬质阳极氧化工艺制备LED封装用铝基板绝缘层,通过实验分析了制备铝基板过程中氧化时间、草酸浓度、硫酸浓度和电流密度等因素对其氧化膜厚度、击穿电压的影响,得到了制备低热阻铝基板的最佳工艺参数:电流密度3A/dm2,草酸浓度为10g/L,H2SO4浓度150g/L,氧化时间45min。利用原子力显微镜(AFM)观察热冲击后裂纹萌生的情况,结果表明铝基板有微小裂纹,但仍满足绝缘要求,通过对氧化铝膜热阻的测试发现,铝基板与氧化膜的复合热阻在1～3℃/W之间。结果表明用阳极氧化法制备的铝氧化膜满足LED基板对散热及绝缘性的要求。     

A transient hot-wire instrument for thermal conductivity measurements in electrically conducting liquids at elevated temperatures

This paper describes a novel type of transient hot-wire cell for thermal conductivity measurements on electrically conducting liquids. A tantalum wire of 25 m. diameter is used as the sensing element in the cell, and it is insulated from the conducting liquids by an anodic film of tantalum pentoxide, 70 nm thick. The cell is suitable for measurements on conducting liquids at elevated temperatures. The results of test measurements on liquid water at its saturation vapor pressure are reported in order to confirm the correct operation of the thermal conductivity cell. The data, which have an estimated accuracy of ±3%, depart by less than ±1.8% from the correlation proposed by the International Association for the Properties of Steam. Results are also presented for concentrated aqueous solutions of lithium bromide, which are frequently used in absorption refrigerator cycles.     

Nonlinear<Emphasis Type="Italic">I-V</Emphasis> characteristics study of doped SnO<Subscript>2</Subscript>

When tin oxide is doped with Sb₂O₃ and CoO, it shows highly nonlinear current (I)-voltage (V) characteristics. Addition of CoO leads to creation of oxygen vacancies and helps in sintering of SnO₂. Antimony oxide acts as a donor and increases the conductivity. The results are nearly the same when antimony oxide is replaced by tantalum oxide. The observed nonlinear coefficient, α = 30 and the breakdown voltage is 120 V/mm.     

Enhanced electrical characteristics of sol–gel-derived amorphous SrTiO<Subscript>3</Subscript> films

Amorphous SrTiO₃ thin films were fabricated on Pt (100)/Ti/SiO₂/Si substrates by sol–gel and spin-coating technology and their surface and cross-section morphology were characterized by using field emission scanning electron microscopy. A broad absorption band at about 3390 cm^?1 owing to the stretching vibrations of hydroxyl groups in the absorbed water was observed from fourier transform infrared spectroscopy. J–E measurements were used to investigate the electrical characteristics of SrTiO₃ films. The breakdown characteristics and leakage current are strongly dependent upon their electrode materials. SrTiO₃ films with Al top electrodes exhibit significantly higher breakdown strength and much lower leakage current than those with Au top electrodes. Moreover, samples with Al electrodes exhibit distinct electrical characteristics when a negative voltage was applied under different testing conditions. The surface chemical state of aluminum was analyzed by using X-ray photoelectron spectroscopy, indicating that the 45 nm thick Al electrode was completely transformed into aluminum oxide layer when a positive voltage was applied. These results show that the anodic oxidation of the Al electrodes and films is suggested to be responsible for the enhanced electrical characteristics of SrTiO₃ thin films.     

Electrical conduction phenomena in thin tetracene films

Thin film aluminium oxide capacitors using anodic Al₂O₃ as the dielectric are described. The dependence of oxide thickness and dielectric loss on anodization voltage was studied. Variation of capacitance with temperature and frequency was also investigated. The capacitors were used in conjunction with tantalum resistors to fabricate an astable multivibrator circuit and the waveforms were recorded. The combination of aluminium oxide capacitors and tantalum resistors has some advantages over all-tantalum RC networks.     

乙醇和磁搅拌对高压制备阳极氧化铝膜的影响

硬质阳极氧化(HA)过程中添加乙醇和使用磁搅拌能够有效抑制烧穿现象的发生。将0.3mol/L草酸电解液的溶剂设置为体积比分别为1:1、2:1、3:1和4:1的去离子水与乙醇混合溶液,同时使用磁搅拌进行二次高压阳极氧化。通过分析电流时间曲线和原子力显微镜(AFM)表征的表面形貌,研究了乙醇添加量和磁搅拌对高压阳极氧化的影响。结果表明:溶剂中水与乙醇体积比的大小对制备出模板的孔径和孔间距几乎没有影响;氧化过程中及时改变磁搅拌速度可以有效抑制烧穿现象,使用变速磁搅拌也可制备出高有序度的阳极氧化铝模板。