Double promoter process

The double promoter process involves the successive application of liquid promoter solutions of vinyltrichlorosilane (VTS) and 3-chloropropyltrimethoxy-silane followed by successive cure cycles in dry N2 at 90°C after each application and before photoresist application. The double promoter process evolved because it was felt that the silane reaction with the SiOH surface groups of low temperature oxides was incomplete for a single promoter application, and because vapor silane equipment did not exist at that time. Interestingly, a double HMDS liquid promoter process failed to yield adequate adhesion as well. Later in time, the successful but somewhat complex double promoter process was replaced by the vapor phase HMDS process in the Star 1000 (or 2000) then superior resist image adhesion was obtained on all four oxide substrates with all the photoresists tested. Before the advent of the HMDS vapor priming in standalone or wafer track equipment module chambers, liquid priming solutions were widely used, especially in development areas. 

The double promoter process is felt to approach the same quality of surface preparation as that for the vapor HMDS treatment through improved surface cleaning capability. Furthermore, it must be concluded that the Star 1000 in situ dehydration baking and vapor phase processing is of great importance. If this were not so, then suitable adhesion should have been achieved on Si02 substrates by a simple double HMDS (liquid) treatment. 

The double promoter process involves the successive application of liquid promoter solutions of vinyltrichlorosilane (VTS) and 3-chloroprop ltrimethoxysilane, followed by successive cure cycles in dry at 90 C before photoresist application. 

Later, the successful but somewhat complex double promoter process was replaced by the "vapor phase" HMDS process in the Star 2000. Then superior resist image adhesion was obtained on all four oxide substrates with all the photoresists tested. 

In one study, PLG microspheres bound to DNA using a cryogenic double emulsion process and injected intramuscularly into mice were found to promote transgene expression for up to 174 days after injection, dependent upon microsphere mass. More recently nanoparticles were constructed from carboxy terminated, PEG modified PGL polymers. These particles were conjugated with an aptamer to the prostate specific membrane antigen and evaluated for in vivo biodistribution in an LNCaP (PSMA+) xenograft mouse model of prostate cancer. In this study, the aptamer caused a 3.77-fold increase in polymer concentration in the tumor tissue after retro-orbital injection (79). 

Adhesion has been achieved on these oxides through a variety of processes. Conventional liquid phase application of HMDS, however, was not adequate for the latter three substrates listed above. However, it did provide adequate photoresist adhesion for thermal oxides. For the last three substrates, a double adhesion promoter process was needed and developed. This process has been incorporated into actual device fabrication processing. 

Alkyl halides are usually considered to be less suitable for double carbonylation because of the possibility of the direct reaction of alkyl halides with nucleophiles and of instability of alkyl-transition metal complexes involved in the catalytic process. However, allylic halides were found amenable to double carbonylation promoted by zerovalent palladium complex. It is well known that allylic halides undergo ready oxidative addition with a Pd(0) species to produce Tj -allylpalladium halide complexes. Thus, it was reasoned that the double carbonylation process might be realized if CO insertion into the aUyl-palladium bond proceeds before attack of amine on the 17 -allylpaUadium halide takes place. On the basis of fundamental studies on the behavior of i7 -allylpalladium halide complexes with CO and secondary amines, double carbonylation processes of substituted aUyl halides to give a-keto amides in high yields have recently been achieved (Eqs. 15 and... 

As we mentioned in Sect. A, the first catalytic double carbonylation reaction was found to take place by using cobalt carbonyl complex as catalyst. In fact, there are a few other transition metals that can promote the double carbonylation process in addition to palladium complexes. The following is a brief description of the double carbonylation process promoted by transition metals other than palladium. 

In studies toward the synthesis of the antibacterial natural product pleuromutilin (Scheme 25.66), Procter et al. reported a cascade double annulation process using Sml2 to generate an initial ketyl radical from 137. After a subsequent cyclization, the resulting new ketyl radical was reduced to form the organosamarium (III) intermediate 138, which in turn promoted a diastereoselective intramolecular aldol reaction to give 139. ° ... 

The dehydration reaction leads by an Ea process to 8 and is promoted by the tertiary, benzylic nature of the OH group at Ce and its antiperiplanar trans relationship to the H atom at Csg. Furthermore, one of the cannonical forms of the enolizable 0-dicarbonyl system present at Cn and Cia has a double bond in the C ring. Thus, dehydration leads to aromatization of the C ring, and this factor must provide some of the driving force for the reaction. 

Ferrocen-l,l -diylbismetallacycles are conceptually attractive for the development of bimetal-catalyzed processes for one particular reason the distance between the reactive centers in a coordinated electrophile and a coordinated nucleophile is self-adjustable for specific tasks, because the activation energy for Cp ligand rotation is very low. In 2008, Peters and Jautze reported the application of the bis-palladacycle complex 56a to the enantioselective conjugate addition of a-cyanoacetates to enones (Fig. 31) [74—76] based on the idea that a soft bimetallic complex capable of simultaneously activating both Michael donor and acceptor would not only lead to superior catalytic activity, but also to an enhanced level of stereocontrol due to a highly organized transition state [77]. An a-cyanoacetate should be activated by enolization promoted by coordination of the nitrile moiety to one Pd(II)-center, while the enone should be activated as an electrophile by coordination of the olefinic double bond to the carbophilic Lewis acid [78],... 

The calculations were performed using a double-zeta basis set with addition of a polarization function and lead to the results reported in Table 5. The notation used for each state is of typical hole-particle form, an asterisc being added to an orbital (or shell) containing a hole, a number (1) to one into which an electron is promoted. In the same Table we show also the frequently used Tetter symbolism in which K indicates an inner-shell hole, L a hole in the valence shell, and e represents an excited electron. The more commonly observed ionization processes in the Auger spectra of N2 are of the type K—LL (a normal process, core-hole state <-> double-hole state ) ... 

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