Method for manufacturing micro-structure and optically patternable sacrificial film-forming composition
A micro-structure is manufactured by patterning a sacrificial film, forming an inorganic material film on the pattern, and etching away the sacrificial film pattern through an aperture to define a space having the contour of the pattern. The patterning stage includes the steps of (A) coating a substrate with a composition comprising a cresol novolac resin, a crosslinker, and a photoacid generator, (B) heating to form a sacrificial film, (C) patternwise exposure, (D) development to form a sacrificial film pattern, and (E) forming crosslinks within the cresol novolac resin.
1. A sacrificial film pattern having a sidewall which is forward tapered at an angle from 85° to less than 90° relative to the substrate, and formed from a positive novolac resist composition comprising
(A-1) (i) a cresol novolac resin consisting of at least 40 mol % of p-cresol and the remainder of m-cresol and having some or all phenolic hydroxyl groups esterified with 1,2-naphthoquinonediazidosulfonic acid halide, or (ii) a mixture of a cresol novolac resin consisting of at least 40 mol % of p-cresol and the remainder of m-cresol and having some or all phenolic hydroxyl groups esterified with 1,2-naphthoquinonediazidosulfonic acid halide and a cresol novolac resin having phenolic hydroxyl groups non-esterified,
a crosslinker capable of forming crosslinks within the cresol novolac resin in the presence of an acid catalyst, and
a photoacid generator having the highest absorption peak in the wavelength range of 200 to 300 nm and selected from the group consisting of sulfonium salts, iodonium salts, sulfonyldiazomethane and N-sulfonyloxyimide compounds.
2. The pattern of claim 1 wherein the cresol novolac resin in (A-1) has a weight average molecular weight of 2,000 to 30,000 and a melting temperature of at least 130° C.
3. The pattern of claim 1 wherein the cresol novolac resin having some or all phenolic hydroxyl groups esterified with 1,2-naphthoquinonediazidosulfonic acid halide is a cresol novolac resin in which 0.5 to 30 mol % of phenolic hydroxyl groups are esterified with 1,2-naphthoquinonediazidosulfonic acid halide.
4. The pattern of claim 1 wherein the composition comprises 45 to 98% by weight of component (A-1), based on the total solids weight of the composition, and
the total of the esterified cresol novolac resin and the non-esterified cresol novolac resin is at least 67% by weight of component (A-1).
5. The pattern of claim 1 wherein said crosslinker is a melamine compound and the composition comprises 2 to 30% by weight of the melamine compound based on the total solids weight of the composition.
6. The pattern of claim 5 wherein the melamine compound comprises at least 80% by weight of a hexamethoxymethylmelamine monomer.
7. The pattern of claim 1 wherein said photoacid generator having the highest absorption peak in the wavelength range of 200 to 300 nm comprises a photoacid generator having an absorption coefficient ratio A <300 /A >300 of at least 2.0 wherein A <300 is an absorption coefficient at a wavelength providing the highest light absorption in the wavelength range of 200 to 300 nm and A >300 is an absorption coefficient at a wavelength providing a maximum light absorption in a wavelength range in excess of 300 nm.
8. The pattern of claim 1 wherein the sacrificial film has a thickness of 2 to 20 μm.
9. A sacrificial film pattern having a sidewall which is forward tapered at an angle from 85° to less than 90° relative to the substrate, and formed from a positive novolac resist composition consisting essentially of
70 to less than 98% by weight of (A-1) (i) a cresol novolac resin consisting of at least 40 mol % of p-cresol and the remainder of m-cresol and having some or all phenolic hydroxyl groups esterified with 1,2-naphthoquinonediazidosulfonic acid halide,
2 to 25% by weight of a crosslinker capable of forming crosslinks within the cresol novolac resin in the presence of an acid catalyst,
0.001 to 15% by weight of a photoacid generator having the highest absorption peak in the wavelength range of 200 to 300 nm and selected from the group consisting of sulfonium salts, iodonium salts, sulfonyldiazomethane and N-sulfonyloxyimide compounds, and
0 to 0.5% by weight of a surfactant.
10. A sacrificial film pattern having a sidewall which is forward tapered at an angle from 85° to less than 90° relative to the substrate, and formed from a positive novolac resist composition consisting essentially of
70 to less than 98% by weight of (A-1) (i) a cresol novolac resin consisting of at least 40 mol % of p-cresol and the remainder of m-cresol and having some or all phenolic hydroxyl groups esterified with 1,2-naphthoquinonediazidosulfonic acid halide,
2 to 25% by weight of a crosslinker capable of forming crosslinks within the cresol novolac resin in the presence of an acid catalyst,
0.001 to 15% by weight of a photoacid generator having the highest absorption peak in the wavelength range of 200 to 300 nm and selected from the group consisting of sulfonium salts, iodonium salts, sulfonyldiazomethane and N-sulfonyloxyimide compounds, and
0 to 0.5% by weight of a surfactant,
wherein the cresol novolac resin in (A-1) has a weight average molecular weight of 2,000 to 30,000 and a melting temperature of at least 130° C., and
the cresol novolac resin having some or all phenolic hydroxyl groups esterified with 1,2-naphthaoquinonediazidosulfonic acid halide is a cresol novolac resin in which 0.5 to 30 mol % of phenolic hydroxyl groups are esterified with 1,2-naphthoquinonediazidosulfonic acid halide, and
wherein said crosslinker is a melamine compound and the composition comprises 2 to 30% by weight of the melamine compound based on the total solids weight of the composition.