Dielectric metal oxide films

The development of film growth processes for large scale multilayer HTS device technologies is crucially dependent not only upon the ability to fabricate large area HTS metal oxide films, but also on the ability to reliably grow HTS lattice-matched, CTE-matched, chemically compatible, low E/tan d metal oxides for use as dielectrics, buffers, substrates, interlayers, and overlayers [282]. (See Fig. 2-11 for an illustration of a complex HTS device). MOCVD processes appear to offer advantages that could be employed to this end, provided that reliable routes to dielectric films can be established. Films of many of the aforementioned lattice-matched metal oxide substrate and/or interlayer materials (Table 2-3) have been grown by MOCVD (see below). 

Highly protective layers can also fonn in gaseous environments at ambient temperatures by a redox reaction similar to that in an aqueous electrolyte, i.e. by oxygen reduction combined with metal oxidation. The thickness of spontaneously fonned oxide films is typically in the range of 1-3 nm, i.e., of similar thickness to electrochemical passive films. Substantially thicker anodic films can be fonned on so-called valve metals (Ti, Ta, Zr,. ..), which allow the application of anodizing potentials (high electric fields) without dielectric breakdown. 

Gate oxide dielectrics are a cmcial element in the down-scaling of n- and -channel metal-oxide semiconductor field-effect transistors (MOSEETs) in CMOS technology. Ultrathin dielectric films are required, and the 12.0-nm thick layers are expected to shrink to 6.0 nm by the year 2000 (2). Gate dielectrics have been made by growing thermal oxides, whereas development has turned to the use of oxide/nitride/oxide (ONO) sandwich stmctures, or to oxynitrides, SiO N. Oxynitrides are formed by growing thermal oxides in the presence of a nitrogen source such as ammonia or nitrous oxide, N2O. Oxidation and nitridation are also performed in rapid thermal processors (RTP), which reduce the temperature exposure of a substrate. 

The contact ends of printed circuit boards are copper. Alloys of nickel and iron are used as substrates in hermetic connectors in which glass (qv) is the dielectric material. Terminals are fabricated from brass or copper from nickel, for high temperature appHcations from aluminum, when aluminum conductors are used and from steel when high strength is required. Because steel has poor corrosion resistance, it is always plated using a protective metal, such as tin (see Tin and tin alloys). Other substrates can be unplated when high contact normal forces, usually more than 5 N, are available to mechanically dismpt insulating oxide films on the surfaces and thereby assure metaUic contact (see Corrosion and corrosion control). 

Similar considerations also apply to the dielectric films formed on the metal surface during anodising, and, for example, in the case of the valve metals (Al, Ti, Ta, Nb, etc.) IR drops of hundreds of volts may be produced by the anodic oxide film formed on the metal surfaces. Paint films applied to a metal surface also exert resistance control see Section 14.3). 

It is somewhat less corrosion resistant than tantalum, and like tantalum suffers from hydrogen embrittlement if it is made cathodic by a galvanic couple or an external e.m.f., or is exposed to hot hydrogen gas. The metal anodises in acid electrolytes to form an anodic oxide film which has a high dielectric constant, and a high anodic breakdown potential. This latter property coupled with good electrical conductivity has led to the use of niobium as a substrate for platinum-group metals in impressed-current cathodic-protection anodes. 

As indicated above, when a positive direct current is impressed upon a piece of titanium immersed in an electrolyte, the consequent rise in potential induces the formation of a protective surface film, which is resistant to passage of any further appreciable quantity of current into the electrolyte. The upper potential limit that can be attained without breakdown of the surface film will depend upon the nature of the electrolyte. Thus, in strong sulphuric acid the metal/oxide system will sustain voltages of between 80 and 100 V before a spark-type dielectric rupture ensues, while in sodium chloride solutions or in sea water film rupture takes place when the voltage across the oxide film reaches a value of about 12 to 14 V. Above the critical voltage, anodic dissolution takes place at weak spots in the surface film and appreciable current passes into the electrolyte, presumably by an initial mechanism involving the formation of soluble titanium ions. 

It is a valve metal and when made anodic in a chloride-containing solution it forms an anodic oxide film of TiOj (rutile form), that thickens with an increase in voltage up to 8-12 V, when localised film breakdown occurs with subsequent pitting. The TiOj film has a high electrical resistivity, and this coupled with the fact that breakdown can occur at the e.m.f. s produced by the transformer rectifiers used in cathodic protection makes it unsuitable for use as an anode material. Nevertheless, it forms a most valuable substrate for platinum, which may be applied to titanium in the form of a thin coating. The composite anode is characterised by the fact that the titanium exposed at discontinuities is protected by the anodically formed dielectric Ti02 film. Platinised titanium therefore provides an economical method of utilising the inertness and electronic conductivity of platinum on a relatively inexpensive, yet inert substrate. 

Anodising the formation of oxide films on metals by anodic oxidation of the metal in an electrolyte solution. The term can be used for thin dielectric films but is more particularly applied to thicker films formed on some metals such as aluminium at higher anodic voltages. 

The origin of the observed correlation was not established, and the relation was not interpreted as causal. It could be argued that a sustained elevated potential due to as-yet unknown microbial processes altered the passive film characteristics, as is known to occur for metals polarized at anodic potentials. If these conditions thickened the oxide film or decreased the dielectric constant to the point where passive film capacitance was on the order of double-layer capacitance (Cji), the series equivalent oxide would have begun to reflect the contribution from the oxide. In this scenario, decreased C would have appeared as a consequence of sustained elevated potential. 

A cross-sectional schematic of a monolithic gas sensor system featuring a microhotplate is shown in Fig. 2.2. Its fabrication relies on an industrial CMOS-process with subsequent micromachining steps. Diverse thin-film layers, which can be used for electrical insulation and passivation, are available in the CMOS-process. They are denoted dielectric layers and include several silicon-oxide layers such as the thermal field oxide, the contact oxide and the intermetal oxide as well as a silicon-nitride layer that serves as passivation. All these materials exhibit a characteristically low thermal conductivity, so that a membrane, which consists of only the dielectric layers, provides excellent thermal insulation between the bulk-silicon chip and a heated area. The heated area features a resistive heater, a temperature sensor, and the electrodes that contact the deposited sensitive metal oxide. An additional temperature sensor is integrated close to the circuitry on the bulk chip to monitor the overall chip temperature. The membrane is released by etching away the silicon underneath the dielectric layers. Depending on the micromachining procedure, it is possible to leave a silicon island underneath the heated area. Such an island can serve as a heat spreader and also mechanically stabihzes the membrane. The fabrication process will be explained in more detail in Chap 4. 

IR spectra measurements as well as variation of the film thickness, shrinkage, and refractive index demonstrated substantial differences in the mechanisms of thermal decomposition of films prepared from the exclusively metal alkoxide precursor and from the metal alkoxides modified by 2-ethylhexanoic acid. These differences affect the evolution of film microstructure and thus determine the different dielectric properties of the obtained films. The dielectric permittivity of the films prepared from metal alkoxide solutions was relatively low (about 100) and showed weak dependence ofthe bias field. This fact may be explained by the early formation of metal-oxide network (mostly in the... 

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