IP Library › Granted Patent US 12,547,075
Granted Patent B2
US 12,547,075 · App. 17/098,238 · Granted Feb 10, 2026

Method of forming photoresist pattern

Inventors: Yu-Chung Su (Hsinchu, TW); Tsung-Han Ko (New Taipei, TW); Ching-Yu Chang (Yuansun Village, TW)
Assignee: TAIWAN SEMICONDUCTOR MANUFACTURING COMPANY, LTD.
G03F7/11G03F7/0045G03F7/38
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Quick Facts
Patent No.
US 12,547,075
App. No.
17/098,238
Granted
Feb 10, 2026
Kind
B2
Abstract

A method of forming a photoresist pattern includes forming a protective layer over a photoresist layer formed on a substrate. The protective layer and the photoresist layer are selectively exposed to actinic radiation. The photoresist layer is developed to form a pattern in the photoresist layer. The protective layer includes a polymer without a nitrogen-containing moiety, and a basic quencher, an organic acid, a photoacid generator, or a thermal acid generator.

Claims (43)

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

forming a protective layer over a photoresist layer formed on a substrate,

wherein the protective layer consists essentially of a polymer without a nitrogen-containing moiety and without acid labile groups, and a basic quencher,

wherein the polymer is a polyfluoroalcohol;

selectively exposing the protective layer and the photoresist layer to actinic radiation;

generating a base from the basic quencher,

wherein the basic quencher is a photobase generator selected from the group consisting of quaternary ammonium dithiocarbamates, oxime-urethane containing molecules, dibenzophenoneoxime hexamethylene diurethan, ammonium tetraorganylborate salts, N-(2-nitrobenzyloxycarbonyl) cyclic amines, and α aminoketones, and combinations thereof; and

developing the photoresist layer to form a pattern in the photoresist layer.

2 . The method according to claim 1 , wherein a concentration of the basic quencher in the protective layer ranges from 0.1 wt. % to 10 wt. % based on a weight of the polymer and the basic quencher.

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

forming a photoresist layer comprising a photoresist composition over a substrate;

forming a protective layer consisting essentially of a basic quencher and a polymer without a nitrogen-containing moiety and without acid labile groups over the photoresist layer,

wherein the polymer is a polyfluoroalcohol, and

wherein the basic quencher is a photobase generator selected from the group consisting of quaternary ammonium dithiocarbamates, oxime-urethane containing molecules, dibenzophenoneoxime hexamethylene diurethan, ammonium tetraorganylborate salts, N-(2-nitrobenzyloxycarbonyl) cyclic amines, and a aminoketones, and combinations thereof;

forming a latent pattern in the photoresist layer by selectively exposing the photoresist layer to actinic radiation;

generating a base in the protective layer from the photobase generator and diffusing the base in the protective layer into the photoresist layer;

removing the protective layer; and

developing the photoresist layer to form a pattern in the photoresist layer.

4 . The method according to claim 3 , wherein portions of the photoresist layer exposed to the actinic radiation are removed during the developing the photoresist layer.

5 . The method according to claim 3 , wherein the base generated in the protective layer is generated by exposing the protective layer to the actinic radiation.

6 . The method according to claim 3 , wherein the base is diffused from the protective layer into the photoresist layer by heating the protective layer and the photoresist layer.

7 . The method according to claim 3 , wherein the protective layer is heated at temperature ranging from 50° C. to 150° C.

8 . The method according to claim 3 , wherein the protective layer and the photoresist layer are heated at temperature ranging from 50° C. to 150° C.

9 . A method, comprising:

forming a first layer comprising a photoresist composition over a substrate;

forming a second layer consisting essentially of a polymer without a nitrogen-containing moiety and without acid labile groups and a photobase generator over the first layer,

wherein the polymer is a polyfluoroalcohol, and

wherein the photobase generator is selected from the group consisting of quaternary ammonium dithiocarbamates, oxime-urethane containing molecules, dibenzophenoneoxime hexamethylene diurethan, ammonium tetraorganylborate salts, N-(2-nitrobenzyloxycarbonyl) cyclic amines, and a aminoketones, and combinations thereof;

patternwise exposing the first layer to actinic radiation to form a latent pattern in the first layer;

heating the second layer to diffuse base in the second layer into the first layer;

removing the second layer; and

developing the latent pattern to form a pattern in the first layer.

10 . The method according to claim 9 , wherein the second layer is heated at temperature ranging from 50° C. to 150° C.

11 . The method according to claim 9 , wherein portions of the first layer patternwise exposed to the actinic radiation are removed during the developing the latent pattern.

12 . The method according to claim 1 , wherein the base is diffused from the protective layer into the photoresist layer by heating the protective layer and the photoresist layer.

13 . The method according to claim 1 , wherein the protective layer is heated at temperature ranging from 50° C. to 150° C.

14 . The method according to claim 1 , wherein the protective layer and the photoresist layer are heated at temperature ranging from 50° C. to 150° C.

15 . The method according to claim 3 , wherein a concentration of the basic quencher in the protective layer ranges from 0.1 wt. % to 10 wt. % based on a weight of the polymer and the basic quencher.

16 . The method according to claim 9 , wherein a concentration of the photobase generator in the protective layer ranges from 0.1 wt. % to 10 wt. % based on a weight of the polymer and the photobase generator.

17 . The method according to claim 1 , wherein portions of the photoresist layer exposed to the actinic radiation are removed during the developing the photoresist layer.

18 . The method according to claim 1 , wherein the photobase generator is selected from the group consisting of quaternary ammonium dithiocarbamates and a aminoketones, and combinations thereof.

19 . The method according to claim 3 , wherein the photobase generator is selected from the group consisting of quaternary ammonium dithiocarbamates and a aminoketones, and combinations thereof.

20 . The method according to claim 9 , wherein the photobase generator is selected from the group consisting of quaternary ammonium dithiocarbamates and a aminoketones, and combinations thereof.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Sep 21, 2021
From: SU, YU-CHUNG; KO, TSUNG-HAN; CHANG, CHING-YU
To: TAIWAN SEMICONDUCTOR MANUFACTURING COMPANY, LTD.
Reel/Frame 057545/0506 →
Continuity (2)
Provisional Application 62956018 · Dec 31, 2019
Related Publication 20210200092A1 · Jul 1, 2021
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