IP Library Granted Patent US 12,449,728
Granted Patent B2
US 12,449,728 · App. 17/727,133 · Granted Oct 21, 2025

High quantum efficiency dry resist for low exposure dose of EUV radiation

Inventors: Tse-An Yeh (Taipei, TW); Montray Leavy (Singapore, SG); Chun Kuang Chen (Zhubei, TW)
Assignee: ENTEGRIS, INC.
G03F7/0042H01L21/0274G03F7/2004
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Quick Facts
Patent No.
US 12,449,728
App. No.
17/727,133
Granted
Oct 21, 2025
Kind
B2
Abstract

The present disclosure provides a module for creating a metal-containing film, including a reactor chamber; an inlet for providing an organo-metallic precursor to the reactor chamber; and an inlet for providing a reactive gaseous species to react with the organo-metallic precursor to form a metal-containing film. The reactive gaseous species includes an element having three to five valence electrons and one or more radicals selected from hydrogen, C 1 -C 3 alkyl, and C 1 -C 3 alkoxyl. The present disclosure further relates to a method of creating the metal-containing film and a semiconductor structure associated therewith.

Claims (19)

1. A method, comprising

creating a metal-containing film by reacting an organo-metallic precursor with a reactive gaseous species, wherein the reactive gaseous species comprises an element having three to five valence electrons and one or more radicals selected from hydrogen, C 1 -C 3 alkyl, and C 1 -C 3 alkoxyl to produce a reaction product and depositing the reaction product onto a substrate using vapor deposition to form the metal-containing film.

2. The method according to claim 1 , wherein the metal-containing film is sensitive to extreme ultraviolet (EUV).

3. The method according to claim 1 , wherein the element having three to five valence electrons is selected from elements of Group IIIA, elements of Group IVA and elements of Group VA.

4. The method according to claim 1 , wherein the element having three to five valence electrons is B, Al, Ga, In, C, Si, Ge, Sn, N, P, As or Sb.

5. The method according to claim 1 , wherein the radical is H, CH 3 or OCH 3 .

6. The method according to claim 1 , wherein the reactive gaseous species is B 2 H 6 , CH 4 , SiH 4 , GeH 4 , SnH 4 , NH 3 , PH 3 , AsH 3 or SbH 3 .

7. The method according to claim 1 , wherein the organo-metallic precursor has the following formula: M(R 1 ) w (R 2 ) x (R 3 ) y (R 4 ) z , in which

M denotes a metal element having a valence of 2 to 4,

R 1 to R 4 , each independently, denote a halogen element, C 1 -C 6 alkyl, C 1 -C 6 alkoxyl, an amido group, a C 1 -C 6 alkylamino group, or a (di-C 1 -C 6 alkyl) amino group,

w, x, y and z, each independently, denote an integer of 0 to 4,

wherein 2≤w+x+y+z≤4, and at least one of R 1 , R 2 , R 3 and R 4 denotes C 1 -C 6 alkyl, C 1 -C 6 alkoxyl, an amido group, a C 1 -C 6 alkylamino group, or a (di-C 1 -C 6 alkyl) amino group.

8. The method according to claim 6 , wherein the metal element is Ti, Zn, Zr, Ru, Sn, Sb, or Hf.

9. The method according to claim 6 , wherein the organo-metallic precursor is Ti(CH 3 ) 4 , TiCl(CH 3 ) 3 , TiCl 2 (CH 3 ) 2 , TiCl 3 CH 3 , ZnClCH 3 , Zn(CH 3 ) 2 , Zr(CH 3 ) 4 , ZrCl(CH 3 ) 3 , ZrCl 2 (CH 3 ) 2 , ZrCl 3 CH 3 , Ru(CH 3 ) 4 , RuCl(CH 3 ) 3 , RuCl 2 (CH 3 ) 2 , RuCl 3 CH 3 , Sn(CH 3 ) 4 , SnCl(CH 3 ) 3 , SnCl 2 (CH 3 ) 2 , SnCl 3 CH 3 , SbCl(CH 3 ) 2 , SbCl 2 CH 3 , Sb(CH 3 ) 3 , Hf(CH 3 ) 4 , HfCl(CH 3 ) 3 , HfCl 2 (CH 3 ) 2 , HfCl 3 CH 3 , Ti(OCH 3 ) 4 , TiCl(OCH 3 ) 3 , TiCl 2 (OCH 3 ) 2 , TiCl 3 OCH 3 , ZnClOCH 3 , Zn(OCH 3 ) 2 , Zr(OCH 3 ) 4 , ZrCl(OCH 3 ) 3 , ZrCl 2 (OCH 3 ) 2 , ZrCl 3 OCH 3 , Ru(OCH 3 ) 4 , RuCl(OCH 3 ) 3 , RuCl 2 (OCH 3 ) 2 , RuCl 3 OCH 3 , Sn(OCH 3 ) 4 , SnCl(OCH 3 ) 3 , SnCl 2 (OCH 3 ) 2 , SnCl 3 OCH 3 , SbCl(OCH 3 ) 2 , SbCl 2 OCH 3 , Sb(OCH 3 ) 3 , Hf(OCH 3 ) 4 , HfCl(OCH 3 ) 3 , HfCl 2 (OCH 3 ) 2 , HfCl 3 OCH 3 , Ti(NH 2 ) 4 , TiCl(NH 2 ) 3 , TiCl 2 (NH 2 ) 2 , TiCl 3 NH 2 , ZnClNH 2 , Zn(NH 2 ) 2 , Zr(NH 2 ) 4 , ZrCl(NH 2 ) 3 , ZrCl 2 (NH 2 ) 2 , ZrCl 3 NH 2 , Ru(NH 2 ) 4 , RuCl(NH 2 ) 3 , RuCl 2 (NH 2 ) 2 , RuCl 3 NH 2 , Sn(NH 2 ) 4 , SnCl(NH 2 ) 3 , SnCl 2 (NH 2 ) 2 , SnCl 3 NH 2 , SbCl(NH 2 ) 2 , SbCl 2 NH 2 , Sb(NH 2 ) 3 , Hf(NH 2 ) 4 , HfCl(NH 2 ) 3 , HfCl 2 (NH 2 ) 2 , HfCl 3 NH 2 , Ti(NHCH 3 ) 4 , TiCl(NHCH 3 ) 3 , TiCl 2 (NHCH 3 ) 2 , TiCl 3 NHCH 3 , ZnClNHCH 3 , Zn(NHCH 3 ) 2 , Zr(NHCH 3 ) 4 , ZrCl(NHCH 3 ) 3 , ZrCl 2 (NHCH 3 ) 2 , ZrCl 3 NHCH 3 , Ru(NHCH 3 ) 4 , RuCl(NHCH 3 ) 3 , RuCl 2 (NHCH 3 ) 2 , RuCl 3 NHCH 3 , Sn(NHCH 3 ) 4 , SnCl(NHCH 3 ) 3 , SnCl 2 (NHCH 3 ) 2 , SnCl 3 NHCH 3 , SbCl(NHCH 3 ) 2 , SbCl 2 NHCH 3 , Sb(NHCH 3 ) 3 , Hf(NHCH 3 ) 4 , HfCl(NHCH 3 ) 3 , HfCl 2 (NHCH 3 ) 2 , HfCl 3 NHCH 3 , Ti[N(CH 3 ) 2 ] 4 , TiCl[N(CH 3 ) 2 ] 3 , TiCl 2 [N(CH 3 ) 2 ] 2 , TiCl 3 N(CH 3 ) 2 , ZnClN(CH 3 ) 2 , Zn[N(CH 3 ) 2 ] 2 , Zr[N(CH 3 ) 2 ] 4 , ZrCl[N(CH 3 ) 2 ] 3 , ZrCl 2 [N(CH 3 ) 2 ] 2 , ZrCl 3 N(CH 3 ) 2 , Ru[N(CH 3 ) 2 ] 4 , RuCl[N(CH 3 ) 2 ] 3 , RuCl 2 [N(CH 3 ) 2 ] 2 , RuCl 3 N(CH 3 ) 2 , Sn[N(CH 3 ) 2 ] 4 , SnCl[N(CH 3 ) 2 ] 3 , SnCl 2 [N(CH 3 ) 2 ] 2 , SnCl 3 N(CH 3 ) 2 , SbCl[N(CH 3 ) 2 ] 2 , SbCl 2 N(CH 3 ) 2 , Sb[N(CH 3 ) 2 ] 3 , Hf[N(CH 3 ) 2 ] 4 , HfCl[N(CH 3 ) 2 ] 3 , HfCl 2 [N(CH 3 ) 2 ] 2 or HfCl 3 N(CH 3 ) 2 .

10. The method according to claim 1 , further comprising exposing at least a portion of the metal-containing film to extreme ultraviolet (EUV) radiation.

11. The method according to claim 10 , further comprising developing the exposed metal-containing film to remove a portion of the metal-containing film.

12. The method according to claim 1 , wherein the absorption efficiency of the metal-containing film at 13.5 nm EUV is at least 25%, 50%, 75%, 100, 125, 150, 175, 200 or 250% greater than the absorption efficiency of a metal-containing film formed with carbon dioxide as the reactive gaseous species at 13.5 nm EUV.

13. The method according to claim 1 , wherein the metal-containing film is an element of a semiconductor structure.

14. The method according to claim 1 , wherein the metal-containing film is an EUV photoresist.

Assignments (2)
SECURITY INTEREST Recorded Jun 2, 2023
From: ENTEGRIS, INC.; CMC MATERIALS LLC
To: MORGAN STANLEY SENIOR FUNDING, INC., AS COLLATERAL AGENT
Reel/Frame 063857/0199 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 12, 2022
From: YEH, TSE-AN; LEAVY, MONTRAY; CHEN, CHUN KUANG
To: ENTEGRIS, INC.
Reel/Frame 060481/0617 →
Continuity (2)
Provisional Application 63178911 · Apr 23, 2021
Related Publication 20220350242A1 · Nov 3, 2022
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