Three metal-catalyzed vinyl addition copolymers derived from partially fluorinated norbornenes and tricyclononenes have been synthesized and evaluated for use in formulating photoresists
for 157 nm lithography imaging. The transparency of these polymers at 157 nm, as measured by variable
angle spectroscopic ellipsometry (VASE), is greatly improved over their nonfluorinated counterparts. The
results of preliminary lithographic evaluations of resists formulated from these polymers alone and with
the addition of several new fluorinated dissolution inhibitors are presented. Images as small as 70 nm
have been printed in some formulations.
The crystal structures of five 5,6‐disubstituted benzofurazan 1‐oxides are presented and compared with five previously reported structures: three polymorphs of 5,6‐dichlorobenzofurazan 1‐oxide plus 4,5‐dichloro‐ and 4,5‐dibromophthalic anhydride. All but one of these compounds pack with similar two‐dimensional layers. The benzofurazan oxides all show disorder about a crystallographic twofold or pseudo‐twofold axis. In addition, six complexes of phthalic anhydride and benzofurazan oxides are reported. With the packing in the complexes principally directed by the π complexing, the disorder, invariably found in the uncomplexed benzofurazan oxides, is diminished, and, in two cases, eliminated.
The synthesis and characterization of several new fluoropolymers designed for use in the formulation of photoresists for exposure at 157 nm will be described. The design of these platforms has in some cases been inspired by ab initio quantum mechanical calculations of excited state transition energies and by interpretation of gas phase VUV spectrophotometric data. We have explored anionic polymerizations, free radical polymerizations, metal-catalyzed addition polymerizations and metal-catalyzed copolymerizations with carbon monoxide in these studies. The polymers and resist formulations were characterized by VUV spectrometry and variable angle spectroscopic ellipsometry ͑VASE͒. Resist formulations based on these polymers were exposed at the 157 nm wavelength to produce high-resolution images that will be presented.
The molecular structures of the title compounds, 2,4, 6-trichlorophenylisonitrile (IUPAC name: 2,4,6-trichlorophenyl isocyanide), C(7)H(2)Cl(3)N, and 2,4,6-trichlorobenzonitrile, C(7)H(2)Cl(3)N, are normal. The two structures are not isomorphous, but do contain similar two-dimensional layers in which pairs of molecules are held together by pairs of Cl.CN [3.245 (3) A] or Cl.NC [3.153 (2) A] interactions. The two-dimensional isomorphism is lost through different layer-stacking modes.
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