Radiation-sensitive compositions and patterning and metallization processes

Patent metadata

Field	Value
Publication number	US-2018188648-A1
Application number	US-201715848006-A
Country	US
Kind code	A1
Filing date	Dec 20, 2017
Priority date	Dec 31, 2016
Publication date	Jul 5, 2018
Grant date	—

Abstract

A patterning process, comprises: (i) forming a radiation-sensitive film on a substrate, wherein the radiation-sensitive film comprises: (a) a resin, (b) a photoacid generator, (c) a first quencher, and (d) a second quencher; (ii) patternwise exposing the radiation-sensitive film to activating radiation; and (iii) contacting the radiation-sensitive film with an alkaline developing solution to form a resist pattern; wherein the resin comprises the following repeat units:

wherein: R 1 is selected from a hydrogen atom, an alkyl group having from 1 to 4 carbon atoms, a cyano group or a trifluoromethyl group; Z is a non-hydrogen substituent that provides an acid-labile moiety; n is from 40 to 90 mol %; m is from 10 to 60 mol %; and the total combined content of the two repeat units in the resin is 80 mol % or more based on all repeat units of the resin; and the first quencher is selected from benzotriazole or a derivative thereof.

First claim

What is claimed is:

1 . A patterning process, comprising:
(i) forming a radiation-sensitive film on a substrate, wherein the radiation-sensitive film comprises: (a) a resin, (b) a photoacid generator, (c) a first quencher, and (d) a second quencher; (ii) patternwise exposing the radiation-sensitive film to activating radiation; and (iii) contacting the radiation-sensitive film with an alkaline developing solution to form a resist pattern; wherein the resin comprises the following repeat units:

wherein: R 1 is selected from a hydrogen atom, an alkyl group having from 1 to 4 carbon atoms, a cyano group or a trifluoromethyl group; Z is a non-hydrogen substituent that provides an acid-labile moiety; n is from 40 to 90 mol %; m is from 10 to 60 mol %; and the total combined content of the two repeat units in the resin is 80 mol % or more based on all repeat units of the resin; and
the first quencher is selected from benzotriazole or a derivative thereof.

2 . The process of claim 4 , wherein the activating radiation has a wavelength of 365 nm.

3 . The patterning process of claim 1 , further comprising depositing a metal on the substrate in regions defined by the resist pattern.

4 . A process for depositing a metal on a metal layer, comprising the steps of:
(i) forming a radiation-sensitive film on a metal layer, wherein the film comprises: (a) a resin, (b) a photoacid generator, (c) a first quencher, and (d) a second quencher; (ii) patternwise exposing the radiation-sensitive film to activating radiation; and (iii) contacting the radiation-sensitive film with an alkaline developing solution to remove exposed portions of the radiation-sensitive film; and (iv) immersing the metal layer in a metal plating solution and depositing a metal on the metal layer in the exposed portions of the radiation-sensitive film; wherein the resin comprises the following two repeat units:

wherein: R 1 is selected from a hydrogen atom, an alkyl group having from 1 to 4 carbon atoms, a cyano group or a trifluoromethyl group; Z is a non-hydrogen substituent that provides an acid-labile moiety; n is from 40 to 90 mol %; m is from 10 to 60 mol %; and the total combined content of the two repeat units in the resin is 80 mol % or more based on all repeat units of the resin; and

the first quencher is selected from benzotriazole or a derivative thereof.

5 . The process of claim 4 , wherein the resin has a weight average molecular weight of from 10,000 to 30,000 Daltons.

6 . The process of claim 4 , wherein the photoacid generator of the radiation-sensitive film is selected from one or more of N-hydroxynaphthalimide trifluoromethanesulfonate, N-hydroxynaphthalimide perfluoro-1-butanesulfonate, N-hydroxynaphthalimide camphor-10-sulfonate, N-hydroxynaphthalimide 2-trifluoromethylphenylsulfonate, N-hydroxy-5-norbornene-2,3-dicarboximide perfluoro-1-butanesulfonate, N-(trifluoromethylsulfonyloxy)phthalimide and N-hydroxysuccinimide perfluorobutanesulfonate.

7 . The process of claim 4 , wherein the second quencher is selected from amine compounds other than tertiary alkyl amines.

8 . The process of claim 7 , wherein the second quencher is selected from N,N-diethyldodecanamide, 2,8-dimethyl-6H,12H-5,11-methanodibenzo[b,f]diazocine, 1,1-dimethylethyl 4-hydroxypiperidine-1-carboxylate and N-allylcaprolactam.

9 . The process of claim 4 , wherein the amount of the first quencher is from 0.001 to 1.0 wt % based on the weight of the resin.

10 . The process of claim 4 , wherein the amount of the second quencher is from 0.001 to 1.0 wt % based on the weight of the resin.

11 . The process of claim 4 , wherein the metal deposition is in the form of a pillar having a diameter of 200 microns or less and a height of 20 micron or more.

12 . The process of claim 4 , wherein the metal layer comprises copper.

13 . The process of claim 4 , wherein the activating radiation has a wavelength of 365 nm.

14 . A radiation-sensitive composition, comprising: (a) a resin; (b) two or more photoacid generators; (c) a first quencher; (d) a second quencher; and (e) a solvent;
wherein the resin comprises the following two repeat units:

wherein: R 1 is selected from a hydrogen atom, an alkyl group having from 1 to 4 carbon atoms, a cyano group or a trifluoromethyl group; Z is a non-hydrogen substituent that provides an acid-labile moiety; n is from 40 to 90 mol %; m is from 10 to 60 mol %; and the total combined content of the two repeat units in the resin is 80 mol % or more based on all repeat units of the resin;

wherein the photoacid generators are selected from N-hydroxynaphthalimide trifluoromethanesulfonate, N-hydroxynaphthalimide perfluoro-1-butanesulfonate, N-hydroxynaphthalimide camphor-10-sulfonate, N-hydroxynaphthalimide 2-trifluoromethylphenylsulfonate, N-hydroxy-5-norbornene-2,3-dicarboximide perfluoro-1-butanesulfonate, N-(trifluoromethylsulfonyloxy)phthalimide and N-hydroxysuccinimide perfluorobutanesulfonate;
wherein the first quencher is selected from benzotriazole or its derivatives;
wherein the second quencher is selected from N,N-diethyldodecanamide, 2,8-dimethyl-6H,12H-5,11-methanodibenzo[b,f][1,5]diazocine,1,1-dimethylethyl 4-hydroxypiperidine-1-carboxylate and N-allylcaprolactam; and
wherein the solid content of the composition is from 10 to 60 weight %.

Assignees

• Rohm & Haas Elect Mat

Inventors

• Haga Mitsuru
• Kushida Shugaku
• Kainuma Kunio
• Cameron James F

Classifications

• H10P14/40

  of conductive or resistive materials · CPC title

• G03F7/039

  Macromolecular compounds which are photodegradable, e.g. positive electron resists (G03F7/075 takes precedence; macromolecular quinonediazides G03F7/023) · CPC title

• G03F7/2006

  using coherent light; using polarised light · CPC title

• G03F7/322

  Aqueous alkaline compositions · CPC title

• C23C18/1667

  Radiant energy, e.g. laser · CPC title