Photoresists copolymers

In contrast to HFPO, 2,2-bis(trifluoromethyl)oxirane (2) ring opens with oxygen, nitrogen, sulfur, and carbon nucleophiles at the less hindered carbon, yielding tertiary alcoholsWith diethylamine, for example, 2 affords an aminoalcohol in 83% yield. Oxirane 2 played an important role in the development of monomers from which to build highly transparent, yet readily alkali-soluble photoresist copolymers... 

Miscellaneous Applications. PEIs and their derivatives ate used as cementation auxihaties in cmde oil exploration (459), and for breaking cmde oil emulsions (460) in cmde oil extraction. Seed coatings of water-soluble copolymers containing polyethyleneimine have been developed (461). Polyethyleneimine derivatives have positive photoresist properties (462) amidated polyethyleneimines improve the flow properties of cement (463) and with few exceptions, A/-acyla2iddines act as chemical sterilisers for insects (464). 

Recently, as a further recognition of the importance of multiphase copolymers in specialty applications, siloxane containing block and segmented copolymers have received special attention for applications such as biomaterials, photoresists, gas separation membranes, protective coatings, elastomers and emulsifiers, as we shall... 

With the growing interest for the polynorbomene, photoresist polymer, and cyclic olefin copolymer, the synthesis norbornene or bicyclo[2,2,l]-2-heptene (NBN) has drawn significant attention because it is one of the most important precursor for these materials. Norbornene is produced by the reaction between ethylene and cyclopentadiene (CPD) via the Diels-Alder condensation process at elevated temperature and pressure [1,2]. 

Soluble polydiorganosilane homo and copolymers have recently shown great potential in such areas as precursors for the preparation of silicon carbide fibers (1), as photoinitiators in alkene polymerization (2), as photoconductors (3), and as positive or negative self-developing photoresists for photolithographic applications (4). A number of copolydiorganosilane copolymers have been reported recently (5) in which the copolymer contained equal amounts of both monomers in the feed. 

The photopolymerization of St with catalytic amount of 52 as the pho-toiniferter gave a benzene-soluble polymer that contains a styryl double bond and a DC group at the polymer chain ends. When this macromonomer-iniferter 54 was copolymerized with a second monomer in the presence of an azo initiator, the formation of a high molecular weight graft copolymer was confirmed by GPC data. The monomer iniferter 52 was also used for the preparation of photoresist polymers [189]. 

The incorporation of PDMSX into conventional novolac resins has produced potential bilevel resist materials. Adequate silicon contents necessary for O2 RIE resistance can be achieved without sacrificing aqueous TMAH solubility. Positive resist formulations using an o-cresol novolac-PDMSX (510 g/mole) copolymer with a diazonaphthoquinone dissolution inhibitor have demonstrated a resolution of coded 0.5 pm L/S patterns at a dose of 156 mJ/cm2 upon deep-UV irradiation. A 1 18 O2 etching selectivity versus hard-baked photoresist allows dry pattern transfer into the bilevel structure. 

Polymethacrylates containing 6-cyanouracil or 5-bromouracil units in the side chain of the polymer displayed the highest photosensitivity. Copolymers of butadiene with the methacrylate monomer with pendant 6-cyanouracil are capable of resolving 1 o features and behaved as negative photoresists. 

One attractive possibility is the use of the a-keto-oxime chromophore. It has a strong absorption at 220 nm whose tail, which extends to 240-250 nm, would improve the absorption characteristics of PMMA. Also, the esters possess a N-O bond which is photochemically labile yet sufficiently thermally stable so as to be compatible with the various processing steps. The solution degradation of a-keto oximino methacrylate esters upon irradiation with light of X365 nm has been reported by Delz-enne (2), and we proceeded to investigate the solid state photodegradation of similar copolymers and their possible utility as deep UV photoresists. 

Maeda et al. (3) prepared florinated norbomane copolymers, (VI), which were effective in photoresist compositions. 

It is clear from these results that the relative sensitivity of the copolymers is unchanged in the very thin photoresist films. Quite high quantum yields can be obtained for photoprocesses which do not require large amounts of free volume. 

Research has also been aimed at the development of more-transparent base-soluble matrix resins. For example, novolacs prepared from pure p-cresol absorb less strongly at 250 nm than do typical photoresist novolacs containing a mixture of cresol isomers. Unfortunately, p-cresol novolac is only sparingly soluble in aqueous base and has limited usefulness (28, 57). Other examples of more-transparent matrix resins include poly(dimethyl glutarimide) (PMGI) (58) and copolymers of methyl methacrylate (MMA) and methacrylic acid (MAA) [P(MMA-MAA)]. 

The copolymers of type 67 exhibit the characteristic photochemical depolymerization noted for polysilanes, a source of their potential as photoresist materials. However, the presence of the ferrocenyl substituents results in a significant retardation of this depolymerization, presumably due to the ability of ferrocene to quench the triplet state responsible for the polysilane photochemistry164. Polymers of type 67 can be regarded as polysilanes with reversible redox behaviour. 

Jeong S-J, Moon H-S et al (2010) Ultralarge-area block copolymer lithography enabled by disposable photoresist prepatteming. ACS Nano 4 5181-5186... 

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