Granted Patent B2

US 12,607,929 · App. 18/314,566 · Granted Apr 21, 2026

Inventors: Jui-Hsiung Liu (Taipei City, TW); Pin-Chia Liao (Taoyuan City, TW); Ting-An Lin (Taoyuan City, TW); Ting-An Shih (Taichung City, TW); Yu-Fang Tseng (New Taipei City, TW); Burn Jeng Lin (Hsinchu City, TW); Tsai-Sheng Gau (Hsinchu City, TW); Po-Hsiung Chen (Taichung City, TW); Po-Wen Chiu (Hsinchu City, TW)

Assignees: TAIWAN SEMICONDUCTOR MANUFACTURING COMPANY, LTD.; NATIONAL TSING HUA UNIVERSITY

G03F7/0043G03F7/027H01L21/0274H10D30/024H10D64/017

Abstract

Claims (46)

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

forming a photoresist layer over a material layer on a substrate, wherein the photoresist layer has a composition comprising:

a solvent; and

a first photo-active compound dissolved in the solvent, the first photo-active compound is represented by the following formula (A1) or formula (A2):

Zr 12 O 8 (OH) 14 (RCO 2 ) 18   Formula (A1); or

Hf 6 O 4 (OH) 6 (RCO 2 ) 10   Formula (A2),

and R in the formula (A1) and R in the formula (A2) each include one of the following formulae (1) to (6):

wherein an OH group and a CO 2 group of the Formula (A1) have a ratio of 14:18, an OH group and a CO 2 group of the Formula (A2) have a ratio of 6:10;

patterning the photoresist layer; and

etching the material layer using the photoresist layer as an etch mask.

2 . The method of claim 1 , wherein the photoresist layer includes the following formula (A1-1):

Zr 2 O 8 (OH) 14 (C 4 H 9 CO 2 ) 18   Formula (A1-1).

3 . The method of claim 1 , wherein the photoresist layer includes the following formula (A2-1):

Hf 6 O 4 (OH) 6 (C 4 H 9 CO 2 ) 10   Formula (A2-1).

4 . The method of claim 1 , wherein the solvent includes 4-methyl-2-pentanol.

5 . The method of claim 1 , wherein the photoresist layer further comprises:

a second photo-active compound dissolved in the solvent, the second photo-active compound includes the following formula (E1):

and R in the formula (E1) includes the formulae (1) to (6).

6 . The method of claim 1 , wherein the photoresist layer further comprises:

a third photo-active compound dissolved in the solvent, the third photo-active compound includes the following formula (F1):

and R in the formula (F1) includes the formulae (1) to (6).

7 . A method of forming a first photo-active compound, comprising:

reacting an M(OBu) 4 with at least one reactant having a carboxylic acid group to form a second photo-active compound, wherein M is Hf or Zr; and

decarboxylating the second photo-active compound to form the first photo-active compound, wherein the first photo-active compound comprises an OH group and a CO 2 group, a ratio of the OH group and the CO 2 group is 14:18 or 6:10.

8 . The method of claim 7 , wherein decarboxylating the second photo-active compound is performed using a base comprising M′OH or M′ 2 CO 3 , M′ is Li, Na, K, Rb, Cs or R 4 N, and R of R 4 N is an alkyl group having 1 to 4 carbon atoms.

9 . The method of claim 7 , wherein the second photo-active compound includes the following formula (B1) or formula (B2):

Zr 12 O 8 (OH) 8 (RCO 2 ) 24

●6RCO 2 H  Formula (B1); or

Hf 6 O 4 (OH) 4 (RCO 2 ) 12 H 2 O

●3R CO 2 H  Formula (B2),

and R in the formula (B1) and R in the formula (B2) each include the following formulae (1) to (6):

10 . The method of claim 7 , wherein the at least one reactant has a first compound and a second compound including the following formula (C1-a) and formula (C2-a), respectively:

11 . The method of claim 7 , wherein the at least one reactant has a first compound and a second compound including the following formula (C1-b) and formula (C2-b), respectively:

12 . The method of claim 7 , wherein the at least one reactant has a first compound and a second compound including the following formula (C1-c) and formula (C2-c), respectively:

13 . The method of claim 7 , wherein the at least one reactant has a first compound and a second compound including the following formula (C1-d) and formula (C2-d), respectively:

14 . The method of claim 7 , wherein the at least one reactant has a first compound and a second compound including the following formula (C1-e) and formula (C2-e), respectively:

15 . The method of claim 7 , wherein the at least one reactant has a first compound and a second compound including the following formula (C1-f) and formula (C2-f), respectively:

16 . The method of claim 7 , wherein the at least one reactant has a first compound and a second compound including the following formula (C1-g) and formula (C2-g), respectively:

17 . The method of claim 7 , wherein reacting the M(OBu) 4 with the at least one reactant is performed in toluene.

18 . A photoresist layer, comprising:

a solvent; and

a first photo-active compound, wherein the first photo-active compound comprises a decarboxylated 6-Hf-oxo cluster, a decarboxylated 12-Zr-oxo cluster, or a combination thereof, wherein the first photo-active compound comprises an OH group and a CO 2 group, a ratio of the OH group and the CO 2 group is 14:18 or 6:10.

19 . The photoresist layer of claim 18 , further comprising:

an inorganic photo-active compound different from the first photo-active compound, an organic photo-active compound, or a combination thereof.

20 . The photoresist layer of claim 19 , wherein the inorganic photo-active compound includes the following formula (E1) or formula (F1):

and R in the formula (E1) and formula (F1) each includes the following formulae (1) to (6):

Assignments (1)

Continuity (2)

References Cited (46)