Photoresist development with halide chemistries

Patent metadata

Field	Value
Publication number	US-12510825-B2
Application number	US-202418769038-A
Country	US
Kind code	B2
Filing date	Jul 10, 2024
Priority date	Jun 26, 2019
Publication date	Dec 30, 2025
Grant date	Dec 30, 2025

Abstract

Development of resists are useful, for example, to form a patterning mask in the context of high-resolution patterning. Development can be accomplished using a halide-containing chemistry such as a hydrogen halide. A metal-containing resist film may be deposited on a semiconductor substrate using a dry or wet deposition technique. The resist film may be an EUV-sensitive organo-metal oxide or organo-metal-containing thin film resist. After exposure, the photopatterned metal-containing resist is developed using wet or dry development.

First claim

The invention claimed is:

1 . A method of dry developing a photopatterned EUV resist on a semiconductor substrate, comprising:
dry developing the photopatterned EUV resist comprising an unexposed organo-metal-oxide-containing portion with organo-metal-oxide networks and metal-carbon bonds and an EUV-exposed metal-oxide-containing portion with metal-oxide networks that lost the metal-carbon bonds using a dry development chemistry comprising a halide etchant to form a resist mask, wherein the halide etchant selectively removes the unexposed organo-metal-oxide-containing portion relative to the EUV-exposed metal-oxide-containing portion to form the resist mask, wherein the halide etchant breaks metal-oxide bonds in the organo-metal-oxide networks in the unexposed organo-metal-oxide-containing portion to form one or more volatile byproducts while leaving metal-oxide bonds intact in the metal-oxide networks in the EUV-exposed metal-oxide-containing portion to form the resist mask.

2 . The method of claim 1 , wherein the dry development chemistry comprises a hydrogen halide.

3 . The method of claim 2 , wherein the hydrogen halide comprises hydrogen bromide (HBr).

4 . The method of claim 2 , wherein the hydrogen halide comprises hydrogen chloride (HCl).

5 . The method of claim 1 , wherein the dry development chemistry comprises a mixture of HBr and HCl.

6 . The method of claim 1 , wherein the dry development chemistry comprises a mixture of hydrogen iodide (HI) and HBr or HCl.

7 . The method of claim 1 , wherein the dry development chemistry comprises a mixture of a hydrogen halide and boron trichloride (BCl 3 ).

8 . The method of claim 1 , wherein the dry developing the photopatterned EUV resist is with HBr at a temperature between about −60° C. and about 60° C.

9 . The method of claim 1 , wherein the dry developing the photopatterned EUV resist is with HCl at a temperature between about −20° C. and about 120° C.

10 . The method of claim 1 , wherein the dry developing the photopatterned EUV resist is with a mixture of hydrogen halide and BCl 3 at a temperature between about −20° C. and about 120° C.

11 . The method of claim 1 , wherein the dry developing the photopatterned EUV resist is with a mixture of HBr and HCl at a temperature between about −60° C. and about 120° C.

12 . The method of claim 1 , wherein the dry developing the photopatterned EUV resist is at a chamber pressure equal to or greater than about 5 mTorr.

13 . The method of claim 1 , wherein the photopatterned EUV resist comprises an element selected from the group consisting of: tin, hafnium, tellurium, bismuth, indium, antimony, iodine, and germanium.

14 . The method of claim 1 , wherein the halide etchant favors breaking oxygen-metal bonds in the organo-metal-oxide networks that are less dense in the unexposed organo-metal-oxide-containing portion with a lower coordination structure over oxygen-metal bonds in the metal-oxide networks in the EUV-exposed metal-oxide-containing portion with a higher coordination structure.

15 . The method of claim 1 , wherein the halide etchant favors protonating more basic oxygen and breaking the metal-oxide bonds in the organo-metal-oxide networks in the unexposed organo-metal-oxide-containing portion over less basic oxygen in the metal-oxide networks in the EUV-exposed metal-oxide portion.

16 . The method of claim 1 , the one or more volatile byproducts comprise an organo-metal-halide and water.

17 . The method of claim 1 , wherein the dry development comprises a combination of a plasma-less thermal development and a plasma development.

18 . A method of developing a photopatterned EUV resist on a semiconductor substrate, comprising:
dry developing the photopatterned EUV resist on the semiconductor substrate using an etch gas in a plasma-free thermal process to form a resist mask on the semiconductor substrate, wherein the photopatterned EUV resist comprises an unexposed organo-metal-oxide-containing portion with organo-metal-oxide networks and metal-carbon bonds and an EUV-exposed metal-oxide-containing portion with metal-oxide networks that lost the metal-carbon bonds, wherein the etch gas comprises a halide etchant that breaks metal-oxide bonds in the organo-metal-oxide networks in the unexposed organo-metal-oxide-containing portion to form one or more volatile byproducts while leaving metal-oxide bonds intact in the metal-oxide networks in the EUV-exposed metal-oxide-containing portion to form the resist mask.

19 . The method of claim 18 , wherein the photopatterned EUV resist is exposed to EUV light under vacuum prior to the dry developing the photopatterned EUV resist.

20 . The method of claim 18 , wherein the etch gas comprises a hydrogen halide.

21 . The method of claim 18 , wherein the etch gas comprises hydrogen bromide (HBr).

22 . The method of claim 18 , wherein the etch gas comprises hydrogen chloride (HCl).

23 . The method of claim 18 , wherein the etch gas comprises a mixture of a hydrogen halide and boron trichloride (BCl 3 ).

24 . The method of claim 18 , wherein the etch gas selectively removes the unexposed organo-metal-oxide-containing portion relative to the EUV-exposed metal-oxide-containing portion to form the resist mask.

25 . The method of claim 18 , further comprising:
after the dry developing the photopatterned EUV resist in a plasma-free thermal process, descumming or smoothing the resist mask by exposure to plasma.

26 . The method of claim 18 , wherein the dry developing the photopatterned EUV resist is with HBr at a temperature between about −60° C. and about 60° C.

27 . The method of claim 18 , wherein the dry developing the photopatterned EUV resist is with HCl at a temperature at a temperature between about −20° C. and about 120° C.

28 . The method of claim 18 , wherein the dry developing the photopatterned EUV resist is with a mixture of a hydrogen halide and BCl 3 at a temperature between about −20° C. and about 20° C.

29 . The method of claim 18 , wherein the dry developing the photopatterned EUV resist is at a chamber pressure equal to or greater than about 5 mTorr.

30 . The method of claim 18 , wherein the photopatterned EUV resist comprises an element selected from the group consisting of: tin, hafnium, tellurium, bismuth, indium, antimony, iodine, and germanium.

31 . The method of claim 18 , wherein the halide etchant favors breaking oxygen-metal bonds in the organo-metal-oxide networks that are less dense in the unexposed organo-metal-oxide-containing portion with a lower coordination structure over oxygen-metal bonds in the metal-oxide networks in the EUV-exposed metal-oxide-containing portion with a higher coordination structure.

32 . The method of claim 18 , wherein the halide etchant favors protonating more basic oxygen and breaking the metal-oxide bonds in the organo-metal-oxide networks in the unexposed organo-metal-oxide-containing portion over less basic oxygen in the metal-oxide networks in the EUV-exposed metal-oxide portion.

33 . The method of claim 18 , wherein the one or more volatile byproducts comprise an organo-metal-halide and water.

Assignees

• Lam Res Corp

Inventors

• Tan Samantha Siamhwa
• Yu Jengyi
• Li Da
• Fan Yiwen
• Pan Yang
• Marks Jeffrey
• Gottscho Richard A
• Peter Daniel
• Weidman Timothy William
• Volosskiy Boris
• Yang Wenbing

Classifications

• H10P72/0604

  Process monitoring, e.g. flow or thickness monitoring · CPC title

• H10P72/0606

  Position monitoring, e.g. misposition detection or presence detection · CPC title

• H10P72/0466

  characterised by the construction of the load-lock chamber · CPC title

• H10P72/0448

  Apparatus for applying a liquid, a resin, an ink or the like · CPC title

• H10P76/204

  of organic photoresist masks · CPC title