Antireflective porogens

• US 20030022953A1
• Filed: 07/11/2002
• Published: 01/30/2003
• Est. Priority Date: 10/10/2000
• Status: Active Grant

• Current Assignee: Shipley Company, LLC (Dow, Inc.)
• Original Assignee: Shipley Company, LLC (Dow, Inc.)
• Inventors: Zampini, Anthony, Gallagher, Michael K.
• Granted Patent: US 6,596,405 B2
• Time in Patent Office: Days
• US Class Current: 521/61
• CPC Class Codes: C08G 77/16 to hydroxyl groups
• CPC Class Codes: C08G 77/18 to alkoxy or aryloxy groups
• CPC Class Codes: C08G 77/20 containing silicon bound to unsaturated aliphatic groups C08G77/045 takes precedence
• CPC Class Codes: C08G 77/70 Siloxanes defined by use of the MDTQ nomenclature
• CPC Class Codes: C08L 2666/04 Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
• CPC Class Codes: C08L 2666/28 Non-macromolecular organic substances
• CPC Class Codes: C08L 83/04 Polysiloxanes
• CPC Class Codes: C09D 183/04 Polysiloxanes
• CPC Class Codes: H01L 21/02126 the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
• CPC Class Codes: H01L 21/02203 the layer being porous
• CPC Class Codes: H01L 21/02216 the compound being a molecule comprising at least one silicon-oxygen bond and the compound having hydrogen or an organic group attached to the silicon or oxygen, e.g. a siloxane
• CPC Class Codes: H01L 21/02282 liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
• CPC Class Codes: H01L 21/31695 Deposition of porous oxides or porous glassy oxides or oxide based porous glass
• CPC Class Codes: H05K 1/0313 Organic insulating material
• CPC Class Codes: H05K 3/0011 Working of insulating substrates or insulating layers
• CPC Class Codes: Y10T 428/249958 Void-containing component is synthetic resin or natural rubbers
• CPC Class Codes: Y10T 428/31663 As siloxane, silicone or silane

Abstract

Disclosed are organo polysilica dielectric materials having low dielectric constants useful in electronic component manufacture are disclosed along with methods of preparing the porous organo polysilica dielectric materials. Also disclosed are methods of forming electronic devices containing such porous organo polysilica dielectric materials without the use of antiretlective coatings.

Claims

1. A composition useful for forming porous organo polysilica dielectric material, comprising removable porogen, wherein the porogen comprises one or more chromophores.

2. The composition of claim 1 wherein the one or more chromophores are selected from monomers containing phenyl, substituted phenyl, naphthyl, substituted naphthyl, anthracenyl, substituted anthracenyl, phenanthrenyl, substituted phenanthrenyl, and one or more (C₄-C₂₄)alkyl groups.

3. The composition of claim 2 wherein the one or more chromophores are monomers of formula I

4. The composition of claim 2 wherein the one or more chromophores are (C₄-C₂₄)alkyl (meth)acrylates.

5. The composition of claim 1 wherein the removable porogen further comprises as polymerized units one or more monomers selected from silyl containing monomers or poly(alkylene oxide) monomers.

6. A composition comprising a B-staged organo polysilica dielectric material and a porogen, wherein the porogen includes one or more chromophores.

7. The composition of claim 6 wherein the one or more chromophores are selected from monomers containing phenyl, substituted phenyl, naphthyl, substituted naphthyl, anthracenyl, substituted anthracenyl, phenanthrenyl, substituted phenanthrenyl, and one or more (C₄-C₂₄)alkyl groups.

8. The composition of claim 6 wherein the removable porogen further comprises as polymerized units one or more monomers selected from silyl containing monomers or poly(alkylene oxide) monomers.

9. The composition of claim 8 wherein the silyl containing monomer is selected from vinyltrimethylsilane, vinyltriethylsilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ

-trimethoxysilyipropyl (meth)acrylate. divinylsilane, trivinylsilane, dimethyldivinylsilane, divinylmethylsilane, methyltrivinylsilane, diphenyldivinylsilane, divinylphenylsilane, trivinylphenylsilane, divinylmethylphenylsilane, tetravinylsilane, dimethylvinyldisiloxane, poly(methylvinylsiloxane), poly(vinylhydrosiloxane), poly(phenylvinylsiloxane), allyloxy-tert-butyldimethylsilane, allyloxytrimethylsilane, allyltriethoxysilane, allyltri-iso-propylsilane, allyltrimethoxysilane, allyltrimethylsilane, allyltriphenylsilane, diethoxy methylvinylsilane, diethyl methylvinylsilane, dimethyl ethoxyvinylsilane, dimethyl phenylvinylsilane, ethoxy diphenylvinylsilane, methyl bis(trimethylsilyloxy)vinylsilane, triacetoxyvinylsilane, triethoxyvinylsilane, triethylvinylsilane, triphenylvinylsilane, tris(trimethylsilyloxy)vinylsilane, vinyloxytrimethylsilane or mixtures thereof.

10. The composition of claim 8 wherein the poly(alkylene oxide) monomers are selected from poly(propylene oxide) monomers, poly(ethylene oxide) monomers, poly(ethylene oxide/propylene oxide) monomers, poly(propylene glycol) (meth)acrylates, poly(propylene glycol) alkyl ether (meth)acrylates, poly(propylene glycol) phenyl ether (meth)acrylates, poly(propylene glycol) 4-nonylphenol ether (meth)acrylates, poly(ethylene glycol) (meth)acrylates, poly(ethylene glycol) alkyl ether (meth)acrylates, poly(ethylene glycol) phenyl ether (meth)acrylates, poly(propylene/ethylene glycol) alkyl ether (meth)acrylates or mixtures thereof.

11. The composition of claim 6 wherein the porogen further comprises as polymerized units one or more fluorinated monomers.

12. The composition of claim 6 wherein the B-staged organo polysilica dielectric matrix material has the formula:

((RR¹SiO)_a(R²SiO_1.5)_b(R³SiO_1.5)_c(SiO₂)_d)_n

wherein R, R¹, R² and R³ are independently selected from hydrogen, (C₁-C₆)alkyl, aryl, and substituted aryl;

a, c and d are independently a number from 0 to 1;

b is a number from 0.2 to 1;

n is integer from about 3 to about 10,000;

provided that a+b+c+d=1; and

provided that at least one of R, R¹ and R² is not hydrogen.

13. The composition of claim 6 wherein the porogen has a particle size in the range of from about 0.5 to about 1000 nm.

14. The composition of claim 13 wherein the particle size is in the range of from about 0.5 to about 200 nm.

15. The composition of claim 6 wherein the porogen is substantially compatible with the B-staged organo polysilica dielectric matrix material.

16. A method of manufacturing an electronic device comprising the steps of;

a) disposing on the substrate a B-staged organo polysilica dielectric material comprising porogen;

b) curing the B-staged organo polysilica dielectric material to form an organo polysilica dielectric matrix material without substantially degrading the porogen; and

c) thereafter subjecting the organo polysilica dielectric matrix material to conditions which at least partially remove the porogen to form a porous organo polysilica dielectric material without substantially degrading the organo polysilica dielectric material;

wherein the porogen comprises one or more chromophores.

17. A method of manufacturing an electronic device comprising the steps of:

a) disposing on the substrate a B-staged organo polysilica dielectric material comprising porogen;

b) curing the B-staged organo polysilica dielectric material to form an organo polysilica dielectric matrix material without substantially degrading the porogen;

c) disposing a photoresist on the organo polysilica dielectric matrix material;

d) exposing the photoresist; and

e) thereafter subjecting the organo polysilica dielectric matrix material to conditions which at least partially remove the porogen to form a porous organo polysilica dielectric material without substantially degrading the organo polysilica dielectric material;

wherein the porogen comprises one or more chromophores.

18. The method of claim 17 wherein the one or more chromophores are selected from monomers containing phenyl, substituted phenyl, naphthyl, substituted naphthyl, anthracenyl, substituted anthracenyl, phenanthrenyl, substituted phenanthrenyl, and one or more (C₄-C₂₄)alkyl groups.

19. The method of claim 17 wherein the removable porogen further comprises as polymerized units one or more monomers selected from silyl containing monomers or poly(alkylene oxide) monomers.

20. The method of claim 19 wherein the silyl containing monomer is selected from vinyltrimethylsilane, vinyltriethylsilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ

-trimethoxysilylpropyl (meth)acrylate, divinylsilane, trivinylsilane, dimethyldivinylsilane, divinylmethylsilane, methyltrivinylsilane, diphenyldivinylsilane, divinylphenylsilane, trivinylphenylsilane, divinylmethylphenylsilane, tetravinylsilane, dimethylvinyldisiloxane, poly(methylvinylsiloxane), poly(vinylhydrosiloxane), poly(phenylvinylsiloxane), allyloxy-tert-butyldimethylsilane, allyloxytrimethylsilane, allyltriethoxysilane, allyltri-iso-propylsilane, allyltrimethoxysilane, allyltrimethylsilane, allyltriphenylsilane, diethoxy methylvinylsilane, diethyl methylvinylsilane, dimethyl ethoxyvinylsilane, dimethyl phenylvinylsilane, ethoxy diphenylvinylsilane, methyl bis(trimethylsilyloxy)vinylsilane, triacetoxyvinylsilane, triethoxyvinylsilane, triethylvinylsilane, triphenylvinylsilane, tris(trimethylsilyloxy)vinylsilane, vinyloxytrimethylsilane or mixtures thereof.

21. The method of claim 19 wherein the poly(alkylene oxide) monomers are selected from poly(propylene oxide) monomers, poly(ethylene oxide) monomers, poly(ethylene oxide/propylene oxide) monomers, poly(propylene glycol) (meth)acrylates, poly(propylene glycol) alkyl ether (meth)acrylates, poly(propylene glycol) phenyl ether (meth)acrylates, poly(propylene glycol) 4-nonylphenol ether (meth)acrylates, poly(ethylene glycol) (meth)acrylates, poly(ethylene glycol) alkyl ether (meth)acrylates, poly(ethylene glycol) phenyl ether (meth)acrylates, poly(propylene/ethylene glycol) alkyl ether (meth)acrylates or mixtures thereof.

22. The method of claim 17 wherein the porogen further comprises as polymerized units one or more fluorinated monomers.

23. The method of claim 17 wherein the B-staged organo polysilica dielectric matrix material has the formula:

((RR¹SiO)_a(R²SiO_1.5)_b(R³SiO_1.5)_c(SiO₂)_d)_n

wherein R, R¹, R² and R³ are independently selected from hydrogen, (C₁-C₆)alkyl, aryl, and substituted aryl;

a, c and d are independently a number from 0 to 1;

b is a number from 0.2 to 1;

n is integer from about 3 to about 10,000;

provided that a+b+c+d=1; and

provided that at least one of R, R¹ and R² is not hydrogen.

24. The method of claim 17 wherein the porogen has a particle size in the range of from about 0.5 to about 1000 nm.

25. The method of claim 24 wherein the particle size is in the range of from about 0.5 to about 200 nm.

26. A method of preparing porous organo polysilica dielectric materials comprising the steps of:

a) disposing removable porogen in a B-staged organo polysilica dielectric material;

b) curing the B-staged organo polysilica dielectric material to form an organo polysilica dielectric matrix material without substantially degrading the porogen; and

c) subjecting the organo polysilica dielectric matrix material to conditions which at least partially remove the porogen to form a porous organo polysilica dielectric material without substantially degrading the organo polysilica dielectric material;

wherein the porogen comprises one or more chromophores.

27. An electronic device including a layer of organo polysilica dielectric material comprising porogen wherein the porogen includes one or more chromophores.

28. The device of claim 27 wherein the organo polysilica dielectric material organo polysilica dielectric matrix material has the formula:

((RR¹SiO)_b(R³SiO_1.5)_b(R³SiO_1.5)_c(SiO₂)_d)_n

wherein R, R¹, R² and R³ are independently selected from hydrogen, (C₁-C₆)alkyl, aryl, and substituted aryl;

a, c and d are independently a number from 0 to 1;

b is a number from 0.2 to 1;

a is integer from about 3 to about 10,000;

provided that a+b+c+d=1; and

provided that at least one of R, R¹ and R² is not hydrogen.

29. The device of claim 27 wherein the one or more chromophores are selected from monomers containing phenyl, substituted phenyl, naphthyl, substituted naphthyl, anthracenyl, substituted anthracenyl, phenanthrenyl, substituted phenanthrenyl, and one or more (C₄-C₂₄)alkyl groups.

30. A method of manufacturing an electronic device comprising the step of forming a relief image on an organo polysilica dielectric material, wherein the relief image is formed without the use of an antireflective coating layer.