Molecular glass photoresists containing bisphenol a framework and method for preparing the same and use thereof

Patent metadata

Field	Value
Publication number	US-9454076-B2
Application number	US-201214385238-A
Country	US
Kind code	B2
Filing date	May 18, 2012
Priority date	Mar 16, 2012
Publication date	Sep 27, 2016
Grant date	Sep 27, 2016

Abstract

The present invention provides a class of molecular glass photoresist (I and II) comprising bisphenol A as a main structure and their preparation. The molecular glass photoresist is formulated with a photoacid generator, a cross-linking agent, a photoresist solvent, and other additives into a positive or negative photoresist. A photoresist with a uniform thickness is formed on a silicon wafer by spin-coating. The photoresist formulation can be used in modern lithography, such as 248 nm photolithography, 193 nm photolithography, extreme-ultraviolet (EUV) lithography, nanoimprint lithography, electron beam lithography, and particularly in the EUV-lithography technique.

First claim

The invention claimed is:

1. A compound of the general formula (I) or (II):

wherein X is independently chosen from H, C 1-8 alkyl, —COOC 1-8 alkyl,

R is independently chosen from H, —OH, —OC 1-8 alkyl, —OCOOC 1-8 alkyl,

wherein 2-bis (3,5-diphenyl-4-hydroxyphenyl) propane is excluded.

2. A preparation method of a compound of the general formula (I) according to claim 1 , comprising the steps of:
(i) reacting tetrabromobisphenol A of formula (III) with Z—Y or SO 2 (O—Y) 2 to form a compound of formula (I-A), wherein Y is a C 1-8 alkyl and Z is a halogen;
(ii) reacting the compound of formula (I-A) with

to form a compound of formula (I-B), wherein R 1 is independently chosen from H or —OC 1-8 alkyls; and
(iii) converting the compound of formula (I-B) to a compound of formula (I) via dealkylation, wherein R is independently chosen from H or —OH, X is H, wherein formula (III), (I-A), (I-B) and steps (i), (ii), and (iii) are shown below:

3. The method of claim 2 , further comprising: (iv) reacting the compound of general formula (I) obtained in step (iii) with (COOR 3 ) 2 O or R 4 Z, wherein R 3 is a C 1-8 alkyl, R 4 is a C 1-8 alkyl, and Z is a halogen.

4. A preparation method of a compound of the general formula (II) according to claim 1 , comprising the steps of:
(1) reacting dibromobisphenol A of formula (IV) or a derivative thereof with Z—Y or SO 2 (O—Y) 2 to form a compound of formula (II-A), wherein Y is a C 1-8 alkyl and Z is a halogen;
(2) reacting the compound of formula (II-A) with

to form a compound of formula (II-B), wherein R 1 is independently chosen from H or —OC 1-8 alkyls; and
(3) converting the compound of formula (II-B) to a compound of the general formula (II) via dealkylation reaction, wherein R is independently chosen from H or —OH, X is H, wherein formula (IV), (II-A), (II-B) and steps (1), (2), and (3) are shown below:

5. The method of claim 4 , further comprising: (4) reacting the compound of the general formula (II) obtained in step (3) reacts with (COOR 3 ) 2 O or R 4 Z, wherein R 3 is a C 1-8 alkyl, R 4 is a C 1-8 alkyl,

and Z is a halogen.

6. A method of using a compound of claim 1 , comprising applying the compound of claim 1 on a surface.

7. A negative photoresist composition comprising: a compound of general formula (I) or (II) of claim 1 with none or some of phenolic hydroxyl groups in said compound being protected, a photoacid generator, a cross-linking agent, and a photoresist solvent.

8. The negative photoresist composition of claim 7 , wherein said compound of general formula (I) or (II) is present in an amount ranging from 0.1 to 10 wt. %, a cross-linking agent from 0.01 to 1 wt. %, and a photoacid generator from 0.01 to 1 wt. %, wherein the wt % is based on the total amount of components of the negative photoresist composition.

9. The negative photoresist composition of claim 7 , wherein the photoacid generator is an ionic or non-ionic compound selected from the group consisting of triphenylsulfonium triflate, bis(4-tert-butylphenyl)iodonium triflate, and N-hydroxynaphthalimide triflate; the cross-linking agent is tetramethoxy methyl glycoluril, or 2,4-bis(hydroxymethyl)-6-methylphenol (2,4-DMMP); and the photoresist solvent is selected from the group consisting of propylene glycol methyl ether acetate (PGMEA), ethyl lactate, ethylene glycol monomethyl ether, and cyclohexanone.

10. A positive photoresist composition, comprising: a compound of general formula (I) or (II) of claim 1 with some or all of phenolic hydroxyl groups in said compound being protected, a photoacid generator, and a photoresist solvent.

11. A photoresist coating layer on a silicon wafer, comprising a positive photoresist composition of claim 10 or a negative photoresist composition of claim 5 spin-coated onto the silicon wafer.

12. The positive photoresist composition of claim 10 , wherein said compound of the general formula (I) or (II) is present in an amount ranging from 1 to 10 wt. %, and said photoacid generator is present in an amount ranging from 0.01 to 1 wt. %, wherein the wt % is based on the total amount of components of the positive photoresist composition.

13. The positive photoresist composition of claim 10 , wherein the photoacid generator is an ionic or non-ionic compound selected from the group consisting of triphenylsulfonium triflate, bis(4-tert-butylphenyl)iodonium triflate, and N-hydroxynaphthalimide triflate; and the photoresist solvent is selected from the group consisting of propylene glycol methyl ether acetate (PGMEA), ethyl lactate, ethylene glycol monomethyl ether, and cyclohexanone.

14. A method of using a compound of claim 1 , comprising applying the compound of claim 1 on a surface, wherein the surface is subject to 248 nm photolithography, 193 nm photolithography, extreme-ultraviolet (EUV) lithography, nanoimprint lithography, or electron beam lithography.

Assignees

• Yang Guoqiang
• Xu Jian
• Chen Li
• Wang Shuangqing
• Li Shayu
• Inst Chemistry Cas

Inventors

• Yang Guoqiang
• Xu Jian
• Chen Li
• Wang Shuangqing
• Li Shayu

Classifications

• C07C37/16

  by condensation involving hydroxy groups of phenols or alcohols or the ether or mineral ester group derived therefrom · CPC title

• C07C69/96 Primary

  Esters of carbonic or haloformic acids · CPC title

• C07C2103/92

  Chemistry & Metallurgy · mapped topic

• G03F7/0045 Primary

  with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors · CPC title

• G03F7/0382

  the macromolecular compound being present in a chemically amplified negative photoresist composition · CPC title