Hybrid polymer networks as ultra low ‘k’ dielectric layers

• US 9,260,571 B2
• Filed: 05/20/2013
• Issued: 02/16/2016
• Est. Priority Date: 05/24/2012
• Status: Active Grant

• Current Assignee: Lawrence Livermore National Security LLC (Government of the United States of America)
• Original Assignee: Lawrence Livermore National Security LLC (Government of the United States of America)
• Inventors: Lewicki, James, Worsley, Marcus A.
• Primary Examiner(s): Gulakowski, Randy
• Assistant Examiner(s): Rodd, Christopher M
• Application Number:
  US13/898,397
• Publication Number:
  US 20130317183A1
• Time in Patent Office: 1,002 Days
• Field of Search: 525474-479
• US Class Current: 1/1
• CPC Class Codes: C08G 77/38 Polysiloxanes modified by chemical after-treatment C08G77/045 takes precedence

Abstract

According to one embodiment, a polymeric material includes at least one polydimethylsiloxane (PDMS) polymer, and at least one polyhedral oligomericsilsequioxane (POSS) molecule. According to another embodiment, a method includes providing at least one polydimethylsiloxane (PDMS) polymer, providing at least one polyhedral oligomericsilsequioxane (POSS) molecule, and coupling the at least one PDSM polymer to the at least one POSS molecule to form a hybrid polymeric material.

Claims

1. A polymeric material, comprising:

a network of polydimethylsiloxane (PDMS) polymers; and

at least one polyhedral oligomericsilsequioxane (POSS) molecule chemically coupled to at least one PDMS polymer,

wherein the polymeric material has a porosity in a range from about 15% to about 80%,

wherein a molar ratio of the at least one POSS molecule to the at least one PDMS molecule is in a range from about 8;

1 to about 1;

1,

wherein the at least one POSS molecule is represented by R_n(SiO_1.5)_n, wherein n is an even integer from 6 to 16, wherein at least one of the R_n groups is a reactive functional group for co-polymerization, wherein the reactive functional group is selected from the group consisting of;

a carboxylic acid halide, a sulphonic acid ester, a nitrile, a sulphonic acid, a sulphonic acid halide, a phosphine, and combinations thereof.

2. The polymeric material of claim 1, wherein the at least one POSS molecule is covalently coupled to the at least one PDMS polymer and to at least another PDMS polymer as a cross linking site.

3. The polymeric material of claim 1, wherein the at least one POSS molecule is covalently coupled to the at least one PDMS polymer as a free chain end moiety.

4. The polymeric material of claim 1, wherein the at least one POSS molecule is covalently coupled to the at least one PDMS polymer as a chain pendent moiety.

5. The polymeric material of claim 1, wherein the polymeric material includes a plurality of POSS molecules covalently coupled to the network, wherein at least one of the POSS molecules is covalently coupled to the network as a crosslinking site, wherein at least one of the POSS molecules is covalently coupled to the network as a free chain end moiety, and wherein at least one of the POSS molecules is covalently coupled to the network as a chain pendant moiety.

6. The polymeric material of claim 1, wherein the polymeric material is characterized as exhibiting a dielectric constant in a range from greater than about 1 to about 4.

7. A method for forming the polymeric material of claim 1, comprising:

providing the network of polydimethylsiloxane (PDMS) polymers;

providing the at least one polyhedral oligomericsilsequioxane (POSS) molecule; and

chemically coupling at least one PDMS polymer to the at least one POSS molecule,

wherein the polymeric material is characterized as exhibiting a dielectric constant in a range from about 1.2 to about 1.5.

8. The method of claim 7, wherein the providing at least one PDMS polymer and/or the providing at least one POSS molecule includes modifying one or more chemical and/or structural properties thereof for affecting one or more physical properties of the polymeric material.

11. The polymeric material of claim 1, the polymeric material includes a plurality of POSS molecules covalently coupled to the network, wherein each POSS molecule is represented by R_n(SiO_1.5)_n, n being even integer from 6 to 16, wherein at least one of the R_n groups is a reactive functional group for co-polymerization, wherein at least one of the POSS molecules has a different integer value for n than at least another of the POSS molecules.

12. The polymeric material of claim 1, wherein the polymeric material is in a form of a film having a thickness in a range from about 100 nm to about 200 nm, wherein the polymeric material is positioned on a substrate comprising a fluoroalkane.

13. The polymeric material of claim 1, wherein the molar ratio of the at least one POSS molecule to the at least one PDMS molecule is in a range from about 8:

1 to about 2;

1.

14. The polymeric material of claim 1, wherein the molar ratio of the at least one POSS molecule to the at least one PDMS molecule is about 8:

1.

15. The polymeric material of claim 1, wherein the polymeric material includes a plurality of POSS molecules covalently coupled to the network, wherein each POSS molecule is represented by R_n(SiO_1.5)_n, n being even integer from 6 to 16, wherein at least one of the R_n groups of each POSS molecule is a reactive functional group for co-polymerization, wherein the reactive functional group of at least one of the POSS molecules is different than the reactive functional group of at least another of the POSS molecules.

16. The polymeric material of claim 15, wherein the reactive functional group of each POSS molecule is different.

17. The polymeric material of claim 11, wherein the integer value n of each POSS molecule is different.

9. A polymeric material, comprising:

a network of polydimethylsiloxane (PDMS) polymers;

at least one polyhedral oligomericsilsequioxane (POSS) molecule chemically coupled to at least one of the PDMS polymers,

wherein the at least one POSS molecule is present in an amount from about 10% to about 40% by weight,

wherein the at least one POSS molecule comprises at least one reactive functional group selected from the group consisting of;

a carboxylic acid halide, a sulphonic acid ester, a nitrile, a sulphonic acid, a sulphonic acid halide, a phosphine, and combinations thereof; and

a third material coupled to at least one of the PDMS polymers, wherein the third material comprises at least one of an inorganic aerogel and a zeolite.

10. A polymeric material, comprising:

a network of polydimethylsiloxane (PDMS) polymers; and

a plurality of POSS molecules covalently coupled to the network, wherein each POSS molecule comprises a reactive functional group,

wherein the reactive functional group of at least two of the POSS molecules is different from the reactive functional group of at least another of the POSS molecules,

wherein at least one of the POSS molecules is represented by R_n(SiO_1.5)_n, wherein n is an even integer from 6 to 16, wherein at least one of the R_n groups is a reactive functional group for co-polymerization, wherein the reactive functional group is selected from the group consisting of;

a carboxylic acid halide, a sulphonic acid ester, a nitrile, a sulphonic acid, a sulphonic acid halide, a phosphine, and combinations thereof,

wherein the polymeric material has a porosity in a range from about 15% to about 80%.

18. the polymeric material of claim 10, wherein at least one of the POSS molecules has a partially open cage structure, and wherein at least one of the POSS molecules has a closed cage structure.

19. The polymeric material of claim 10, wherein at least one of the POSS molecules is covalently coupled to the network as a crosslinking site, wherein at least one of the POSS molecules is covalently coupled to the network as a free chain end moiety, and wherein at least one of the POSS molecules is covalently coupled to the network as a chain pendant moiety.