PATTERNING PROCESS

• US 20090081595A1
• Filed: 09/23/2008
• Published: 03/26/2009
• Est. Priority Date: 09/25/2007
• Status: Active Grant

• Current Assignee: Shin-Etsu Chemical Company Limited
• Original Assignee: Shin-Etsu Chemical Company Limited
• Inventors: ISHIHARA, Toshinobu, HATAKEYAMA, Jun, YOSHIHARA, Takao
• Granted Patent: US 8,105,764 B2
• Time in Patent Office: Days
• US Class Current: 430/323
• CPC Class Codes: G03F 7/0046 with perfluoro compounds, e.g. for dry lithography G03F7/0048 takes precedence
• CPC Class Codes: G03F 7/0397 the macromolecular compound having an alicyclic moiety in a side chain
• CPC Class Codes: G03F 7/11 having cover layers or intermediate layers, e.g. subbing layers G03F7/091 - G03F7/093, B41N3/03 take precedence
• CPC Class Codes: G03F 7/2024 of the already developed image
• CPC Class Codes: G03F 7/2041 in the presence of a fluid, e.g. immersion; using fluid cooling means
• CPC Class Codes: G03F 7/40 Treatment after imagewise removal, e.g. baking
• CPC Class Codes: H01L 21/0273 characterised by the treatment of photoresist layers
• CPC Class Codes: H01L 21/0337 characterised by the process involved to create the mask, e.g. lift-off masks, sidewalls, or to modify the mask, e.g. pre-treatment, post-treatment
• CPC Class Codes: H05K 2203/0582 Coating by resist, i.e. resist used as mask for application of insulating coating or of second resist
• CPC Class Codes: H05K 3/061 Etching masks

Abstract

A pattern is formed through positive/negative reversal by coating a chemically amplified positive resist composition comprising an acid labile group-bearing resin, a photoacid generator, and an organic solvent onto a substrate, prebaking the resist composition, exposing the resist film to high-energy radiation, post-exposure heating, and developing the exposed resist film with an alkaline developer to form a positive pattern; irradiating or heating the positive pattern to facilitate elimination of acid labile groups and crosslinking for improving alkali solubility and imparting solvent resistance; coating a reversal film-forming composition thereon to form a reversal film; and applying an alkaline wet etchant thereto for dissolving away the positive pattern.

Claims

1. A process for forming a pattern by way of positive/negative reversal, comprising the steps of:

coating a chemically amplified positive resist composition onto a processable substrate, said resist composition comprising a resin comprising recurring units having acid labile groups which are eliminatable with acid, the resin turning to be soluble in an alkaline developer as a result of elimination of the acid labile groups, a photoacid generator capable of generating an acid upon exposure to high-energy radiation and optionally, a thermal acid generator capable of generating an acid upon heating, and an organic solvent, prebaking the resist composition to remove the unnecessary solvent to form a resist film,

exposing the resist film to high-energy radiation in a pattern of exposed and unexposed areas, post-exposure heating for causing the acid generated by the acid generator upon exposure to act on the acid labile groups on the resin whereby the acid labile groups on the resin in the exposed area undergo elimination reaction, and developing the exposed resist film with an alkaline developer to form a positive pattern,

exposing to radiation or heating the positive pattern so that acid or heat acts to eliminate the acid labile groups on the resin in the positive pattern for thereby improving the alkali solubility of the resin, and to induce crosslinking in the resin to such an extent that the resin may not lose a solubility in an alkaline wet etchant, for thereby endowing the positive pattern with resistance to an organic solvent to be used in a reversal film-forming composition,

coating a reversal film-forming composition thereon to form a reversal film, and

applying an alkaline wet etchant thereto for dissolving away the crosslinked positive pattern.

2. The process of claim 1 wherein

in the step of exposing to radiation or heating the positive pattern for endowing the positive pattern with resistance to an organic solvent to be used in a reversal film-forming composition,

the crosslinked positive pattern has a dissolution rate in the alkaline wet etchant corresponding to an etching rate in excess of 2 nm/sec when etched with a 2.38 wt % aqueous solution of tetramethylammonium hydroxide (TMAH),

the reversal film-forming composition comprises an organic solvent selected from propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, propylene glycol monomethyl ether, heptanone, and a mixture of two or more of the foregoing, and

the resistance of the crosslinked positive pattern to the organic solvent used in the reversal film-forming composition is such that the crosslinked positive pattern experiences a thickness reduction of not more than 10 nm when the pattern is kept in contact with the organic solvent for 30 seconds.

3. The process of claim 1 wherein the step of exposing to radiation or heating the positive pattern includes heat treatment at a higher temperature than in both the prebaking and post-exposure heating steps.

4. The process of claim 1 wherein the reversal film formed from the reversal film-forming composition is selectively etchable relative to metallic silicon and silicon oxide.

5. The process of claim 1 wherein the reversal film-forming composition comprises a resin comprising monomeric units of aromatic or alicyclic structure.

6. The process of claim 1, further comprising between the step of coating a reversal film-forming composition to form a reversal film and the step of applying an alkaline wet etchant for dissolving away the crosslinked positive pattern, the step of removing a portion of the reversal film overlying the crosslinked positive pattern.

7. The process of claim 6 wherein the step of removing a portion of the reversal film overlying the crosslinked positive pattern includes wet etching.

8. The process of claim 7 wherein in the step of applying an alkaline wet etchant to the reversal film, the reversal film is dissolvable therein, but has a slower dissolution rate than the crosslinked positive pattern, and

the wet etching in the step of removing a portion of the reversal film overlying the crosslinked positive pattern uses an alkaline wet etchant, so that the step of removing a portion of the reversal film overlying the crosslinked positive pattern and the step of applying an alkaline wet etchant for dissolving away the crosslinked positive pattern are simultaneously carried out.

9. The process of claim 8 wherein said reversal film has a dissolution rate of 0.02 nm/sec to 2 nm/sec when etched with a 2.38 wt % aqueous solution of tetramethylammonium hydroxide (TMAH).

10. The process of claim 3 wherein the chemically amplified positive resist composition comprises a component capable of generating an acid in response to the heat in the step of exposing to radiation or heating the positive pattern.

11. The process of claim 10 wherein the component capable of generating an acid in response to the heat is the thermal acid generator added separately from the photoacid generator.

12. The process of claim 11 wherein said thermal acid generator has the general formula (P1a-2):

wherein K⁻

is a sulfonate having at least one a-position fluorinated, perfluoroalkylimidate or perfluoroalkylmethidate, R^101d, R^101e, R^101f, and R^101g are each independently hydrogen, a straight, branched or cyclic alkyl, alkenyl, oxoalkyl or oxoalkenyl group of 1 to 12 carbon atoms, an aryl group of 6 to 20 carbon atoms, or an aralkyl or aryloxoalkyl group of 7 to 12 carbon atoms, in which some or all hydrogen atoms may be substituted by alkoxy groups, or R^101d and R^101e, or R^101d, R^101e and R^101f may bond together to form a ring with the nitrogen atom to which they are attached, and each of R^101d and Role, or R^101d, R^101e and R^101f is an alkylene group of 3 to 10 carbon atoms or a group forming a hetero-aromatic ring having the nitrogen atom therein when they form a ring.

13. The process of claim 1 wherein in said chemically amplified positive resist composition, the resin comprises recurring units having an electrophilicity structure and recurring units having an acid labile group which is eliminatable with acid.

14. The process of claim 1 wherein in said chemically amplified positive resist composition, the resin comprises recurring units having a lactone ring and recurring units having an acid labile group which is eliminatable with acid.

15. The process of claim 14 wherein

in said chemically amplified positive resist composition, the resin comprises recurring units having a 7-oxanorbornane ring and recurring units having an acid labile group which is eliminatable with acid, and

the step of exposing to radiation or heating the positive pattern includes acid generation in and heat application to the positive pattern whereby elimination of acid labile groups and crosslinking of the resin simultaneously take place.

16. The process of claim 15 wherein the recurring units having a 7-oxanorbornane ring are recurring units (a) having the general formula (1):

wherein R¹ is hydrogen or methyl, R² is a single bond or a straight, branched or cyclic C₁-C₆ alkylene group which may have an ether or ester group, and which has a primary or secondary carbon atom through which it is linked to the ester group in the formula, R³, R⁴, and R⁵ are each independently hydrogen or a straight, branched or cyclic C₁-C₆ alkyl group, and “

a”

is a number in the range;

0<

a<

1.0.

17. The process of claim 14 wherein the recurring units having an acid labile group which is eliminatable with acid are recurring units (b) having the general formula (b):

wherein R¹² is hydrogen or methyl, R¹³ is an acid labile group, and b is a number in the range;

0<

b≦

0.8.

18. The process of claim 17 wherein the acid labile group of R¹³ is an acid labile group of alicyclic structure which is eliminatable with acid.

19. The process of claim 1 wherein the positive pattern comprises a dot pattern, and the pattern resulting from positive/negative reversal comprises a hole pattern.

20. A process for forming a pattern by way of positive/negative reversal, comprising the steps of:

coating a chemically amplified positive resist composition onto a processable substrate, said resist composition comprising a resin comprising recurring units having acid labile groups which are eliminatable with acid, a photoacid generator capable of generating an acid upon exposure to high-energy radiation and a solvent, and heat drying to form a resist film,

coating a protective film-forming composition onto the resist film, and heating to remove an unnecessary solvent to form a protective film,

exposing the resist film to high-energy radiation in a pattern of exposed and unexposed areas from a projection lens, while water or a transparent liquid having a refractive index of at least 1 intervenes between the resist film and the projection lens, post-exposure heating for causing the acid generated by the acid generator upon exposure to act on the acid labile groups on the resin whereby the acid labile groups on the resin in the exposed area undergo elimination reaction, and developing the exposed resist film with an alkaline developer to form a positive pattern,

treating the positive pattern so as to eliminate the acid labile groups on the resin in the positive pattern resulting from the previous step, and to induce crosslinking in the resin to such an extent that the resin may not lose a solubility in an alkaline wet etchant, for thereby endowing the positive pattern with resistance to an organic solvent to be used in a reversal film-forming composition,

coating a reversal film-forming composition thereon to form a reversal film, and

applying an alkaline wet etchant thereto for dissolving away the positive pattern.

21. The process of claim 20 wherein said protective film-forming composition is based on a copolymer comprising amino-containing recurring units.

22. The process of claim 20 wherein said protective film-forming composition further comprises an amine compound.