PROTECTIVE COMPOSITION AND METHOD OF FORMING PHOTORESIST PATTERN

• US 20200135451A1
• Filed: 10/16/2019
• Published: 04/30/2020
• Est. Priority Date: 10/31/2018
• Status: Active Grant

• Current Assignee: Taiwan Semiconductor Manufacturing Company Limited
• Original Assignee: Taiwan Semiconductor Manufacturing Company Limited
• Inventors: ZI, An-Ren, CHANG, Ching-Yu, LIN, Chin-Hsiang
• Granted Patent: US 11,605,538 B2
• Time in Patent Office: Days
• CPC Class Codes: G03F 1/22 Masks or mask blanks for imaging by radiation of 100nm or shorter wavelength, e.g. X-ray masks, extreme ultraviolet [EUV] masks; Preparation thereof
• CPC Class Codes: G03F 7/0042 with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists G03F7/075 takes precedence
• CPC Class Codes: G03F 7/038 Macromolecular compounds which are rendered insoluble or differentially wettable G03F7/075 takes precedence; macromolecular azides G03F7/012; macromolecular diazonium compounds G03F7/021
• 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 7/168 Finishing the coated layer, e.g. drying, baking, soaking
• CPC Class Codes: G03F 7/38 Treatment before imagewise removal, e.g. prebaking G03F7/265 takes precedence
• CPC Class Codes: H01L 21/0274 Photolithographic processes

Abstract

A method includes forming protective layer over substrate edge and photoresist over substrate. Protective layer removed and photoresist exposed to radiation. Protective layer made of composition including acid generator and polymer having pendant acid-labile groups. Pendant acid-labile groups include polar functional groups; acid-labile groups including polar switch functional groups; acid-labile groups, wherein greater than 5% of pendant acid-labile groups have structure

wherein R1 is C6-C30 alkyl group, cycloalkyl group, hydroxylalkyl group, alkoxy group, alkoxyl alkyl group, acetyl group, acetylalkyl group, carboxyl group, alkyl carboxyl group, cycloalkyl carboxyl group, saturated or unsaturated hydrocarbon ring, or heterocyclic group; and R2 is C4-C9 alkyl group, cycloalkyl group, hydroxylalkyl group, alkoxy group, alkoxyl alkyl group, acetyl group, acetylalkyl group, carboxyl group, alkyl carboxyl group, or cycloalkyl carboxyl group; polymer having pendant acid-labile groups and lactone pendant groups; or polymer having pendant acid-labile groups and carboxylic acid groups.

Claims

1. A method of manufacturing a semiconductor device, comprising:

forming a first protective layer over an edge portion of a first main surface of a semiconductor substrate;

forming a photoresist layer over the first main surface of the semiconductor substrate;

removing the first protective layer;

selectively exposing the photoresist layer to actinic radiation,

wherein the first protective layer is made of a composition comprising;

an acid generator; and

a polymer having pendant acid-labile groups, wherein the pendant acid-labile groups include one or more polar functional groups;

a polymer having pendant acid-labile groups, wherein the pendant acid-labile groups include one or more polar switch functional groups;

a polymer having pendant acid-labile groups, wherein greater than 5% of the pendant acid-labile groups have a structure

2. The method according to claim 1, wherein the acid generator is a thermal acid generator.

3. The method according to claim 1, further comprising a first heating of the first protective layer at a temperature of 100°

C. to 200°

C. for 10 seconds to 5 minutes before forming the photoresist layer.

4. The method according to claim 1, wherein the photoresist is a metal-containing photoresist.

5. The method according to claim 1, further comprising forming a second protective layer over the edge portion of the first main surface of the semiconductor substrate after selectively exposing the photoresist layer to actinic radiation.

6. The method according to claim 5, wherein the second protective layer is made of a composition comprising:

a thermal acid generator; and

a polymer having pendant acid-labile groups, wherein the pendant acid-labile groups include one or more polar functional groups;

a polymer having pendant acid-labile groups, wherein the acid-labile groups include one or more polar switch functional groups;

a polymer having pendant acid-labile groups, wherein greater than 5% of the pendant acid-labile groups have a structure

7. The method according to claim 6, further comprising a second heating of the selectively exposed photoresist layer and the second protective layer at a temperature of 100°

C. to 200°

C. for 10 seconds to 5 minutes.

8. The method according to claim 6, further comprising developing the selectively exposed photoresist layer to form a patterned photoresist layer;

9. The method according to claim 8, further comprising removing the second protecting layer after the developing the selectively exposed photoresist layer.

10. The method according to claim 1, further comprising a third heating of the first protective layer and the photoresist layer at a temperature between about 40°

C. and 120°

C. for about 10 seconds to about 10 minutes before removing the first protective layer.

11. The method according to claim 1, wherein the polymer includes a connecting group connecting the pendant acid-labile group to the polar functional group or the polar switch functional groups, wherein the connecting group is selected from substituted and unsubstituted, branched and unbranched aliphatic groups, substituted and unsubstituted, branched and unbranched aromatic groups, and substituted and unsubstituted 1-9 carbon cyclic and non-cyclic groups.

12. The method according to claim 1, wherein the one or more polar functional groups are selected from one or more of —

OH, ═

O, —

S—

, —

P—

P(O₂)—

, —

C(═

O)SH, —

C(═

O)OH, —

C(═

O)O—

, —

O—

, —

N—

, —

C(═

O)NH, —

SO₂OH, —

SO₂SH, —

SOH, and —

SO₂—

.

13. The method according to claim 1, wherein the acid-labile group is selected from the group consisting of

14. The method according to claim 1, wherein the polar switch functional groups are selected from one or more of acetal groups, acetonide groups, and anhydride groups.

15. The method according to claim 1, wherein the pendant acid-labile group is selected from the group consisting of

16. The method according to claim 1, wherein the pendant acid-labile group is selected from the group consisting of

17. The method according to claim 1, wherein the composition further comprises a base generator.

18. The method according to claim 17, wherein the pendant lactone groups are selected from

19. A method of forming a photoresist pattern, comprising:

forming a first protective layer over a substrate,

heating the first protective layer;

forming a photoresist layer over the first protective layer;

removing the first protective layer;

selectively exposing the photoresist layer to actinic radiation;

forming a second protective layer over the substrate;

developing the photoresist layer to form a pattern in the photoresist layer; and

removing the second protective layer,

wherein the first the and second protective layers are made of a composition comprising;

an acid generator; and

a polymer having pendant acid-labile groups, wherein the pendant acid-labile groups include one or more polar functional groups;

a polymer having pendant acid-labile groups, wherein the acid-labile groups include one or more polar switch functional groups;

a polymer having pendant acid-labile groups, wherein greater than 5% of the pendant acid-labile groups have a structure

20. A wafer protective composition, comprising:

an acid generator; and

a polymer having pendant acid-labile groups,

wherein the pendant acid-labile groups are selected from the group consisting of