Ion-assisted processes

Ion-Assisted Processes An alternative use of ion beams generated from low cost sources is to assist particular chemical reactions, or vapour deposition. An example here is in etching processes (Figure 16). The simultaneous use of an argon beam with XeFp gas compared with the use of either separately, to etch silicon produces an etch rate of a factor of at least fourteen. The use of ion beams can also increase the directionality (23) of the process (Figure 17). Examples are given in Table IV of how ion bombardment during film formation modifies the final film. 

Dry etching techniques permit etch processes to be carried out in various modes. These can be described as purely chemical, purely physical, and a mixture of chemical and physical. With plasma etching and RIE, we have concentrated on chemical and ion assisted processes. In this section, etching methods that depend either solely or primarily on physical processes (momentum transfer) will be discussed briefly. 

Because the ion-assisted processes enable deposition at temperatures less than 100°C, deposition of diamond like coatings has been attempted on a wide range of substrates, e.g., stainless steel, Copper, ceramics,optical materials (plastics, polymers and polycarbonates),glasses,quartz, sapphire,infrared-transmitting optical materials such as germanium, zinc sulfide and zinc selenide, and a variety of electronic grade materials. Although thin films can be produced... 

To resolve this problem and establish a successful fiber-coating system, the coating chamber is set up with either a broad-band, high-current, low-voltage ion gun or a suitable plasma system to density the coating. This is known as an ion-assisted process and can produce dense films on cold substrates, such as fibers. 

Radiation Sources. Ordinarily, electron beams are produced from soHds in vacuo by thermal or field-assisted processes. Plasmas also serve as electron sources, but are more uniquely used as ion sources. Whereas ions can be produced by sputtering and field assisted processes in the absence of plasmas, most ion sources involve plasmas (75). 

Barton, H., Ivadizing Ion Vapour Deposition of Aluminium , in Ion Assisted Surface Treatments, Techniques and Processes, The Metal Society, London, pp. 1-6 (1982)... 

A group of techniques employing differential selection of solute ions relies on nebulisation and ionisation of the eluent, with some discrimination of ion selection in favour of the solute. Main representatives are APCI [544] and thermospray [545]. In a thermospray interface a supersonic jet of vapour and small droplets is generated out of a heated vaporiser tube. Controlled, partial vaporisation of the HPLC solvent occurs before it enters the ion source. Ionisation of nonvolatile analytes takes place by means of solvent-mediated Cl reactions and ion evaporation processes. Most thermospray sources are fitted with a discharge electrode. When this is used, the technique is called plasmaspray (PSP) or discharge-assisted thermospray. In practice, many... 

As noted above, amorphous carbon films can be produced from carbon-containing gas phases (physical vapour deposition, PVD). They can also be produced from hydrocarbon-containing gases (chemical vapour deposition, CVD), Both PVD and CVD processes can be thermally-activated or can be plasma- and/or electric field-assisted processes (e.g., microwave assisted CVD and ion beam deposition). As a consequence a wide range of processes have been developed to form amorphous carbon films and a correspondingly complex nomenclature has evolved [70, 71],... 

Figure 15.24 shows the fabrication process of the optical filter on a fluorinated polyimide substrate. First, the low-thermal-expansion-coefficient PMDA/TFDB poly(amic acid) solution was spin-coated onto a Si substrate and baked. Then alternate TiO2 and SiO2 layers were formed on the polyimide film by ion-assisted deposition. The multilayered polyimide film was diced and peeled off from the Si substrate. In this way, thin optical filters on a fluorinated polyimide substrate are easily fabricated. 

For A n — lOOeV-lOkeV, sputtering of the solid state film surface probably can be element selective, and this reduces the growth rate of ion beam assisted processes and PLD. 

Ion-assisted gas-surface chemistry mechanism is probably the best terminology to describe the plasma processing of a surface. A remarkable illustration of the effect of ion bombardment is reported in Fig. 16 [66]. The reaction rate of XeF2 with Si increases drastically upon the simultaneous combination of chemical species (XeF ) and ions (Ar+) on the surface. Obviously chemical reaction and some sputtering processes are expected to occur and to be responsible of the ablation of the material, but the combined effect of active neutral species and ion bombardment is more efficient than the sum of the individual processes. 

Terpene synthases, also known as terpene cyclases because most of their products are cyclic, utilize a carbocationic reaction mechanism very similar to that employed by the prenyltransferases. Numerous experiments with inhibitors, substrate analogues and chemical model systems (Croteau, 1987 Cane, 1990, 1998) have revealed that the reaction usually begins with the divalent metal ion-assisted cleavage of the diphosphate moiety (Fig. 5.6). The resulting allylic carbocation may then cyclize by addition of the resonance-stabilized cationic centre to one of the other carbon-carbon double bonds in the substrate. The cyclization is followed by a series of rearrangements that may include hydride shifts, alkyl shifts, deprotonation, reprotonation and additional cyclizations, all mediated through enzyme-bound carbocationic intermed iates. The reaction cascade terminates by deprotonation of the cation to an olefin or capture by a nucleophile, such as water. Since the native substrates of terpene synthases are all configured with trans (E) double bonds, they are unable to cyclize directly to many of the carbon skeletons found in nature. In such cases, the cyclization process is preceded by isomerization of the initial carbocation to an intermediate capable of cyclization. 

The fundamental processes involved in the nucleation of diamond like films during the ion beam deposition processes, the critical role of the impinging ion energy and the differences in the basic mechanisms of depositing carbon ions versus the use of argon ions (in the case of ion assisted deposition) are still not well understood. In the following sections some of the established concepts are reviewed and discussed. 

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