RESUMEN

Chromophore-functionalized copoly(2-oxazoline)s are successfully evaluated as bottom antireflective coatings (BARCs) in high-resolution photolithography. With respect to UV light sources used in photolithographic production routines, anthracene is chosen as a chromophore. For application as polymer in BARCs, the copolymer poly(2-ethyl-2-oxazolin)45 -stat-poly(2-dec-9'-enyl-2-oxazolin)20 -stat-poly(2-(3'-(1"-(anthracen-9-ylmethyl)-1",2",3"-triazol-4-yl)propyl)-2-oxazolin)35 can be synthesized by the Huisgen cycloaddition click reaction of the copolymer poly(2-ethyl-2-oxazolin)45 -stat-poly(2-dec-9'-enyl-2-oxazolin)20 -stat-poly(2-pent-4'-inyl-2-oxazolin)35 and the corresponding azide-functionalized anthracenes. These copolymers can be crosslinked by the thermally induced thiol-ene reaction involving the unsaturated C=C bonds of the poly(2-dec-9'-enyl-2-oxazoline) repetition units and a multifunctional thiol as crosslinker. Tests of this BARC in a clean room under production conditions reveal a significant decrease of the swing-curve of a chemically amplified positive photoresist by more than 50%, hence significantly increasing the resolution of the photoresist.

Asunto(s)

RESUMEN

Poly(2-nonyl-2-oxazoline)80-stat-poly(2-dec-9'-enyl-2-oxazoline)20 and poly(2-dec-9'-enyl-2-oxazoline)100 can be synthesized from the cationic ring-opening polymerization of monomers that can be derived from fatty acids from renewable resources. These (co)poly(2-oxazoline)s can be crosslinked with di- and trifunctional mercapto compounds using the UV-induced thiol-ene reaction. The complex permittivity of the corresponding networks increases with the temperature and decreases with the network density. In a frequency range from 10-2 to 106 Hz and at temperatures ranging from -20 to 40 °C, the changes of the real part of the complex permittivity as well as the loss factor can be explained by interfacial polarization within the material. At a temperature of 20 °C and a frequency of 50 Hz, the permittivity of the crosslinked (co)poly(2-oxazoline)s covers a range from 4.29 to 4.97, and the loss factors are in the range from 0.030 to 0.093. The electrical conductivities of these polymer networks span a range from 5 × 10-12 to 8 × 10-9 S/m, classifying these materials as medium insulators. Notably, the values for the permittivity, loss factor and conductivity of these copoly(2-oxazoline)s are in the same range as for polyamides, and, hence, these copoly(2-oxazoline)-based networks may be referred to as "green" alternatives for polyamides as insulators in electronic applications.

RESUMEN

The single crystal X-ray analysis of the ester-functionalized 2-oxazoline, methyl 3-(4,5-dihydrooxazol-2-yl)propanoate, revealed π-electron delocalization along the N-C-O segment in the 2-oxazoline pentacycle to significant extent, which is comparable to its counterpart along the O-C-O segment in the ester. Quantum chemical calculations based on the experimental X-ray geometry of the molecule supported the conjecture that the N-C-O segment has a delocalized electronic structure similar to an ester group. The calculated bond orders were 1.97 and 1.10 for the N=C and C-O bonds, and the computed partial charges for the nitrogen and oxygen atoms of -0.43 and -0.44 were almost identical. In the ester group, the bond orders were 1.94 and 1.18 for the C-O bonds, while the partial charges of the oxygen atom are -0.49 and -0.41, which demonstrates the similar electronic structure of the N-C-O and O-C-O segments. In 2-oxazolines, despite the higher electronegativity of the oxygen atom (compared to the nitrogen atom), the charges of the hetero atoms oxygen and nitrogen are equalized due to the delocalization, and it also means that a cationic attack on the nitrogen is possible, enabling regioselectivity during the initiation of the cationic ring-opening polymerization of 2-oxazoline monomers, which is a prerequisite for the synthesis of materials with well-defined structures.