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 method for manufacturing a micro-structure comprising the stages of (i) processing a sacrificial film on a substrate to form a sacrificial film pattern, (ii) forming an inorganic material film on the sacrificial film pattern, (iii) providing a portion of the inorganic material film with an aperture for etching, and (iv) etching away the sacrificial film pattern through the aperture to form a space having the contour of the sacrificial film pattern, wherein
the stage (i) of forming a sacrificial film pattern includes the steps of:
(A) coating the substrate with a sacrificial film-forming composition comprising (A-1) (i) a cresol novolac resin having 0.5 to 30 mol % of phenolic hydroxyl groups esterified with 1,2-naphthoquinonediazidosulfonic acid halide, or (ii) a mixture of a cresol novolac resin having 0.5 to 30 mol % of phenolic hydroxyl groups esterified with 1,2-naphthoquinonediazidosulfonic acid halide and a cresol novolac resin having phenolic hydroxyl groups non-esterified, or (A-2) the novolac resin (i) or novolac resin mixture (ii) as component (A-1) and a 1,2-naphthoquinonediazidosulfonic acid ester, 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,
(B) heating the sacrificial film-forming composition on the substrate to form an optically patternable sacrificial film of 2 to 20 μm thick,
(C) exposing the sacrificial film to first high-energy radiation in accordance with a pattern layout image,
(D) developing the sacrificial film in an alkaline developer to form a positive sacrificial film pattern, and
(E) exposing the sacrificial film pattern to second high-energy radiation which is ultraviolet radiation covering a wavelength of 254 nm, for thereby forming crosslinks within the cresol novolac resin in the sacrificial film pattern.
2. The method of claim 1 wherein step (E) includes exposing the sacrificial film pattern to ultraviolet radiation covering a wavelength of 254 nm while heating at a temperature in the range of 30 to 220° C., or exposing the sacrificial film pattern to ultraviolet radiation covering a wavelength of 254 nm and then heating at a temperature in the range of 100 to 220° C., or exposing the sacrificial film pattern to ultraviolet radiation covering a wavelength of 254 nm while heating at a temperature in the range of 30 to 220° C., and further heating at a temperature in the range of 100 to 220° C.
3. The method of claim 1 wherein the cresol novolac resin used in said sacrificial film-forming composition or a cresol novolac resin from which the cresol novolac resin having phenolic hydroxyl groups esterified is derived is a cresol novolac resin containing at least 40 mol % of p-cresol and having a weight average molecular weight of 2,000 to 30,000 and a melting temperature of at least 130° C.
4. The method of claim 1 wherein said sacrificial film-forming composition comprises 45 to 98% by weight of component (A-1) or (A-2), 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) or (A-2).
5. The method of claim 1 wherein said crosslinker is a melamine compound or glycoluril compound and is present in an amount of 2 to 30% by weight based on the total solids weight of said sacrificial film-forming composition.
6. The method of claim 5 wherein the melamine compound comprises at least 80% by weight of a hexamethoxymethylmelamine monomer.
7. The method 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 method of claim 1 wherein said sacrificial film-forming composition is such that the sacrificial film pattern resulting from step (E) of the pattern forming stage (i) has a sidewall which is forward tapered at an angle from 85° to less than 90° relative to the substrate.
9. An optically patternable sacrificial film-forming composition comprising
(A-1) (i) a cresol novolac resin having 0.5 to 30 mol % of phenolic hydroxyl groups esterified with 1,2-naphthoquinonediazidosulfonic acid halide, or (ii) a mixture of a cresol novolac resin having 0.5 to 30 mol % of phenolic hydroxyl groups esterified with 1,2-naphthoquinonediazidosulfonic acid halide and a cresol novolac resin having phenolic hydroxyl groups non-esterified, or (A-2) the novolac resin (i) or novolac resin mixture (ii) as component (A-1) and a 1,2-naphthoquinonediazidosulfonic acid ester,
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.
10. The composition of claim 9 wherein the cresol novolac resin in (A-1) or (A-2) or a cresol novolac resin from which the cresol novolac resin having phenolic hydroxyl groups esterified is derived is a cresol novolac resin containing at least 40 mol % of p-cresol and having a weight average molecular weight of 2,000 to 30,000 and a melting temperature of at least 130° C.
11. The composition of claim 9 wherein said sacrificial film-forming composition comprises 45 to 98% by weight of component (A-1) or (A-2), 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) or (A-2).
12. The composition of claim 9 wherein said crosslinker is a melamine compound and said sacrificial film-forming composition comprises 2 to 30% by weight of the melamine compound based on the total solids weight of the composition.
13. The composition of claim 12 wherein the melamine compound comprises at least 80% by weight of a hexamethoxymethylmelamine monomer.
14. The composition of claim 9 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.