Thin films thermal stability

Amorphous Silicon. Amorphous alloys made of thin films of hydrogenated siUcon (a-Si H) are an alternative to crystalline siUcon devices. Amorphous siUcon ahoy devices have demonstrated smah-area laboratory device efficiencies above 13%, but a-Si H materials exhibit an inherent dynamic effect cahed the Staebler-Wronski effect in which electron—hole recombination, via photogeneration or junction currents, creates electricahy active defects that reduce the light-to-electricity efficiency of a-Si H devices. Quasi-steady-state efficiencies are typicahy reached outdoors after a few weeks of exposure as photoinduced defect generation is balanced by thermally activated defect annihilation. Commercial single-junction devices have initial efficiencies of ca 7.5%, photoinduced losses of ca 20 rel %, and stabilized efficiencies of ca 6%. These stabilized efficiencies are approximately half those of commercial crystalline shicon PV modules. In the future, initial module efficiencies up to 12.5% and photoinduced losses of ca 10 rel % are projected, suggesting stabilized module aperture-area efficiencies above 11%. 

BiaxiaHy orieated PPS film is transpareat and nearly colorless. It has low permeability to water vapor, carbon dioxide, and oxygen. PPS film has a low coefficient of hygroscopic expansion and a low dissipation factor, making it a candidate material for information storage devices and for thin-film capacitors. Chemical and thermal stability of PPS film derives from inherent resia properties. PPS films exposed to tolueae or chloroform for 8 weeks retaia 75% of theh original streagth. The UL temperature iadex rating of PPS film is 160°C for mechanical appHcatioas and 180°C for electrical appHcations. Table 9 summarizes the properties of PPS film. 

The advantage of sol-gel technology is the ability to produce a highly pure y-alumina and zirconia membrane at medium temperatures, about 700 °C, with a uniform pore size distribution in a thin film. However, the membrane is sensitive to heat treatment, resulting in cracking on the film layer. A successful crack-free product was produced, but it needed special care and time for suitable heat curing. Only y-alumina membrane have the disadvantage of poor chemical and thermal stability. 

In most of the studies discussed above, except for the meta-linked diamines, when the aromatic content (dianhydride and diamine chain extender), of the copolymers were increased above a certain level, the materials became insoluble and infusible 153, i79, lsi) solution to this problem with minimum sacrifice in the thermal properties of the products has been the synthesis of siloxane-amide-imides183). In this approach pyromellitic acid chloride has been utilized instead of PMDA or BTDA and the copolymers were synthesized in two steps. The first step, which involved the formation of (siloxane-amide-amic acid) intermediate was conducted at low temperatures (0-25 °C) in THF/DMAC solution. After purification of this intermediate thin films were cast on stainless steel or glass plates and imidization was obtained in high temperature ovens between 100 and 300 °C following a similar procedure that was discussed for siloxane-imide copolymers. Copolymers obtained showed good solubility in various polar solvents. DSC studies indicated the formation of two-phase morphologies. Thermogravimetric analysis showed that the thermal stability of these siloxane-amide-imide systems were comparable to those of siloxane-imide copolymers 183>. 

MicrocrystalUne zeolites such as beta zeolite suffer from calcination. The crystallinity is decreased and the framework can be notably dealuminated by the steam generated [175]. Potential Br0nsted catalytic sites are lost and heteroatoms migrate to extra-framework positions, leading to a decrease in catalytic performance. Nanocrystals and ultrafine zeolite particles display aggregation issues, difficulties in regeneration, and low thermal and hydrothermal stabilities. Therefore, calcination is sometimes not the optimal protocol to activate such systems. Application of zeolites for coatings, patterned thin-films, and membranes usually is associated with defects and cracks upon template removal. 

The Langmuir-Blodgett (LB) technique was successfully applied for the deposition of thin protein layers (Langmuir and Schaefer 1938, Tiede 1985, Lvov et al. 1991). LB organization of protein molecules in film not only preserved the structure and functionality of the molecules, but also resulted in the appearance of new, useful properties, such as enhanced thermal stability (Nicolini et al. 1993 Erokhin et al. 1995). 

For technical purposes (as well as in the laboratory) RuOz and Ru based thin film electrodes are prepared by thermal decomposition techniques. Chlorides or other salts of the respective metals are dissolved in an aqueous or alcoholic solution, painted onto a valve metal substrate, dried and fired in the presence of air or oxygen. In order to achieve reasonable thicknesses the procedure has to be applied repetitively with a final firing for usually 1 hour at temperatures of around 450°C. A survey of the various processes can be found in Trasatti s book [44], For such thermal decomposition processes it is dangerous to assume that the bulk composition of the final sample is the same as the composition of the starting products. This is especially true for the surface composition. The knowledge of these parameters, however, is of vital importance for a better understanding of the electrochemical performance including stability of the electrode material. 

Crepaldi, E. L. Soler-Illia, G. Grosso, D. Sanchez, M. 2003. Nanocrystallised titania and zirconia mesoporous thin films exhibiting enhanced thermal stability. New J. Chem. 27 9-13. 

Phthalocyanines (Pc) are attractive materials for their potential functions including the semiconductive behaviours in addition to the thermal and chemical stabilities. In particular, control of orientation of the Pc macrocycles in thin films is expected to provide novel molecular electronic devices. Previously, we have found that copper tetrakis(butoxycarbonyl) Pc is oriented nearly perpendicular to the surface and also the dipping direction in the LB films [46], while octa-alkyl Pc derivatives [H2Pc(R)8, CuPc(R)a R = CnH2n+i. n=7,9,11] take the orientation with Pc macrocycles nearly parallel to the plane of films deposited by the horizontal lifting method to form a non-alternating X-type film [47], as illustrated schematically in... 

In the second area, improvements to the thermal and mechanical stability of nanoporous materials from ordered block copolymers should be targeted. To expand the application base for these materials, high temperature stability is a key requirement. For example, in templating applications that require elevated processing temperatures in either thin films or monolithic materials... 

It has been observed that solid oxide fuel cell voltage losses are dominated by ohmic polarization and that the most significant contribution to the ohmic polarization is the interfacial resistance between the anode and the electrolyte (23). This interfacial resistance is dependent on nickel distribution in the anode. A process has been developed, PMSS (pyrolysis of metallic soap slurry), where NiO particles are surrounded by thin films or fine precipitates of yttria stabilized zirconia (YSZ) to improve nickel dispersion to strengthen adhesion of the anode to the YSZ electrolyte. This may help relieve the mismatch in thermal expansion between the anode and the electrolyte. 

There are a few reports of poly(naphthalene) thin films. Yoshino and co-workers. used electrochemical polymerization to obtain poly(2,6-naphthalene) film from a solution of naphthalene and nitrobenzene with a composite electrolyte of copper(II) chloride and lithium hexafluoroarsenate. Zotti and co-workers prepared poly( 1,4-naphthalene) film by anionic coupling of naphthalene on. platinum or glassy carbon electrodes with tetrabutylammonium tetrafluoroborate as an electrolyte in anhydrous acetonitrile and 1,2-dichloroethane. Recently, Hara and Toshima prepared a purple-colored poly( 1,4-naphthalene) film by electrochemical polymerization of naphthalene using a mixed electrolyte of aluminum chloride and cuprous chloride. Although the film was contaminated with the electrolyte, the polymer had very high thermal stability (decomposition temperature of 546°C). The only catalyst-free poly(naphthalene) which utilized a unique chemistry, Bergman s cycloaromatization, was obtained by Tour and co-workers recently (vide infra). 

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