# US 9,006,373 B2 · Photo-patternable dielectric materials curable to porous dielectric materials, formulations, precursors and methods of use thereof

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- Number: US 9,006,373 B2
- Document ID: US9006373B2
- Status: Granted
- Kind: B2
- Application number: 13/742,490
- Filed: 2013-01-16
- Published: 2013-08-15
- Granted: 2015-04-14
- Earliest claimed: 2009-10-08
- Assignees: International Business Machines Corporation
- Applicants: International Business Machines Corporation
- Inventors: Phillip J. Brock; Qinghuang Lin; Robert D. Miller; Alshakim Nelson; Jitendra S. Rathore; Ratnam Sooriyakumaran
- Web page: https://patentgrep.com/patent/US9006373B2

## CPC

- H10W 20/48: Insulating materials thereof
- C07F 7/21: Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
- C08L 83/14: in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms (C08L83/10 takes precedence)
- G03F 7/0755: {Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds (G03F7/0752 takes precedence)}
- G03F 7/0757: {Macromolecular compounds containing Si-O, Si-C or Si-N bonds (G03F7/0752 takes precedence)}
- G03F 7/40: Treatment after imagewise removal, e.g. baking
- H10P 14/60: of insulating materials
- H10P 14/6342: {Liquid deposition, e.g. spin-coating, sol-gel techniques or spray coating}
- H10P 14/665: {Porous materials}
- H10P 14/6922: {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}
- H10P 14/6926: {the material comprising alkyl silsesquioxane, e.g. MSQ}
- H10W 20/081: {by forming openings in the dielectric parts}
- H10W 20/085: {involving intermediate temporary filling with material}
- C08G 77/50: by carbon linkages
- G03F 7/0045: {with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors}
- H10W 20/0886: {involving forming a via in a via-level dielectric prior to deposition of a trench-level dielectric}
- Y10T 428/31663: As siloxane, silicone or silane
- H10W: GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- G03F: PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR; (phototypographic composing devices B41B; photosensitive materials or processes for photographic purposes G03C; electrophotography, sensitive layers or processes therefor G03G)
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

Silsesquioxane polymers that cure to porous silsesquioxane polymers, silsesquioxane polymers that cure to porous silsesquioxane polymers in negative tone photo-patternable dielectric formulations, methods of forming structures using negative tone photo-patternable dielectric formulations containing silsesquioxane polymers that cure to porous silsesquioxane polymers, structures containing porous silsesquioxane polymers and monomers and method of preparing monomers for silsesquioxane polymers that cure to porous silsesquioxane polymers.

## Claims

### Claim 1

A structure, comprising:
a porous cross-linked layer of a silsesquioxane polymer on a substrate, said porous cross-linked layer comprises three monomers of the structural formulas (1), (7) and (3):
wherein R1 is selected from the group consisting of linear alkyl, branched alkyl, cycloalkyl, aromatic, arene and ester moieties, each containing 1 to 20 carbon atoms;
wherein R3 is selected from the group consisting of linear alkyl, branched alkyl and cycloalkyl moieties, each containing 1 to 20 carbon atoms;
wherein m, q, and o, represent the mole percent (mol %) of repeating units with m+q+o equal to or greater than about 40 mol %;
said porous cross-linked layer including an additive silsesquioxane polymer of structure (5):
wherein R4 is selected from the group consisting of cycloalkyl and aryl moieties; and
wherein s is an integer between about 10 and about 1000;
a trench in said porous cross-linked layer;
an electrically conductive material filling said trench and contacting said substrate in a bottom of said trench;
an additional porous cross-linked layer of an additional silsesquioxane polymer directly on a top surface of said porous cross-linked layer;
an additional trench in said additional porous cross-linked layer, a top of said trench open to a bottom of said additional trench; and
said electrically conductive material additionally filling said additional trench.

### Claim 2 (depends on 1)

The structure of claim 1, wherein said additional porous cross-linked layer comprises three monomers of the structural formulas (1), (7) and (3)):
wherein R1 is selected from the group consisting of linear alkyl, branched alkyl, cycloalkyl, aromatic, arene and ester moieties, each containing 1 to 20 carbon atoms;
wherein R3 is selected from the group consisting of linear alkyl, branched alkyl and cycloalkyl moieties, each containing 1 to 20 carbon atoms; and
wherein m, q, and o, represent the mole percent (mol %) of repeating units with m+q+o equal to or greater than about 40 mol %.

### Claim 3 (depends on 1)

The structure of claim 1, wherein said porous cross-linked layer has a dielectric constant of 3.0 or less.

### Claim 4 (depends on 1)

The structure of claim 1, wherein said porous cross-linked layer consists essentially of a cross-linked polymer of structural formulas (1), (7), and (3), R1 is a methyl moiety and m is between about 40 mol % and about 70 mol %, R3 is an ethyl moiety and o is between about 10 mol % and about 30 mol %, and q is between about 5 mol % and about 15 mol %.

### Claim 5 (depends on 1)

The structure of claim 1, wherein said additional porous cross-linked layer consists essentially of a cross-linked polymer of structural formulas (1), (7), (3), R1 is a methyl moiety and m is between about 40 mol % and about 70 mol %, R3 is an ethyl moiety and o is between about 10 mol % and about 30 mol %, and q is between about 5 mol % and about 15 mol %.

### Claim 6 (depends on 1)

The structure of claim 1, wherein said additional porous cross-linked layer has a dielectric constant of about 3.0 or less.

### Claim 7 (depends on 1)

The structure of claim 1, wherein said porous cross-linked layer has a dielectric constant of 2.5 or less.

### Claim 8 (depends on 1)

The structure of claim 1, said additional porous cross-linked layer including:
an additive silsesquioxane polymer of structure (5):
wherein R4 is selected from the group consisting of cycloalkyl and aryl moieties; and
wherein s is an integer between about 10 and about 1000.

### Claim 9 (depends on 1)

The structure of claim 1, wherein said additional porous cross-linked layer has a dielectric constant of 2.5 or less.

### Claim 10

A structure comprising:
a porous cross-linked layer of a silsesquioxane polymer on a substrate, said porous cross-linked layer consists essentially of a cross-linked polymer of structural formulas (1), (7), and (3),
R1 is a methyl moiety and m is between about 40 mol % and about 70 mol %, R3 is an ethyl moiety and o is between about 10 mol % and about 30 mol %, and q is between about 5 mol % and about 15 mol %;
a trench in said porous cross-linked layer;
an electrically conductive material filling said trench and contacting said substrate in a bottom of said trench;
an additional porous cross-linked layer of an additional silsesquioxane polymer directly on a top surface of said porous cross-linked layer;
an additional trench in said additional porous cross-linked layer, a top of said trench open to a bottom of said additional trench; and
said electrically conductive material additionally filling said additional trench.