Inorganic-polymer-derived dielectric films

• US 4,652,467 A
• Filed: 02/25/1985
• Issued: 03/24/1987
• Est. Priority Date: 02/25/1985
• Status: Expired due to Fees

• Current Assignee: Sandia Corporation (Martin Marietta Corporation)
• Original Assignee: United States Department of Energy
• Inventors: Lenahan, Patrick M., Keefer, Keith D., Brinker, C. Jeffrey
• Primary Examiner(s): LAWRENCE, EVAN
• Application Number:
  US06/704,697
• Time in Patent Office: 757 Days
• Field of Search: 427/93, 427/246, 427/162, 427/168, 427/243, 427/165, 427/169, 427/247
• US Class Current: 427/246
• CPC Class Codes: B05D 5/12 to obtain a coating with specific electrical properties
• CPC Class Codes: C08G 77/02 Polysilicates
• CPC Class Codes: C08G 79/00 Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
• CPC Class Codes: C09D 4/00 Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
• CPC Class Codes: H01B 3/30 plastics; resins; waxes
• CPC Class Codes: H01L 21/02203 the layer being porous
• CPC Class Codes: H01L 21/02282 liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
• CPC Class Codes: H01L 21/3121 Layers comprising organo-silicon compounds

Abstract

A method of coating a substrate with a thin film of a polymer of predetermined porosity comprises depositing the thin film on the substrate from a non-gelled solution comprising at least one hydrolyzable metal alkoxide of a polymeric network forming cation, water, an alcohol compatible with the hydrolysis and the polymerization of the metal alkoxide, and an acid or a base, prior to depositing the film, controlling the structure of the polymer for a given composition of the solution exclusive of the acid or base component and the water component, (a) by adjusting each of the water content, the pH, and the temperature to obtain the desired concentration of alkoxide, and then adjusting the time of standing of the solution prior to lowering the temperature of the solution, and (b) lowering the temperature of the solution after the time of standing to about 15 degrees C. or lower to trap the solution in a state in which, after the depositing step, a coating of the desired porosity will be obtained, and curing the deposited film at a temperature effective for curing whereby there is obtained a thin film of a polymer of a predetermined porosity and corresponding pore size on the substrate.

Claims

1. A method of coating a substrate with a thin film of a polymer of predetermined porosity, comprising:

depositing the thin film on the substrate from a dilute non-gelled solution comprising at least one hydrolyzable metal alkoxide of a polyermic network-forming cation, water, an alochol or other solvent compatible with the hydrolysis and the polymerization of the metal alkoxide, and an acid or a base, wherein the concentration of the alkoxide in said solution is about 1 to 12 equivalent weight %, and

prior to the depositing said film, controlling the structure of said polymer for a given composition of said solution exclusive of the acid or base component and the water component,

(a) by adjusting each of the water content, the pH, and the temperature to obtain the desired concetration of alkoxide, and then adjusting the time of standing of said solution prior to lowering the temperature of said solution, and

(b) lowering the temperature of the solution after said time of standing to about 15 degrees C or lower to trap said solution in a state in which, after said depositing step, a coating of the desired porosity will be obtained, and

curing said deposited film by removing a sufficient quantity of solvent to cause gelation, and heating said film at a temperature compatible with the substrate and effective for crosslinking and densifying said film, whereby there is obtained on the substrate a thin film of a polymer of predetermined porosity and corresponding pore size.

2. A method of claim 1, for forming a film of intermediate and large pores, wherein the amount of water in said solution is greater than about 10 moles per mole of total alkoxides, and said pH is greater than about 2.5.

3. A method of claim 2, wherein said pH is greater than about 7 and said time of standing is up to about one week.

4. A method of claim 3, wherein said pores are about 100 to about 500 Å

in diameter.

5. A method of claim 1, wherein the amount of water in said solution is 4 to 10 moles per mole of total alkoxides, and said pH is greater than about 4.

6. A method of claim 5, wherein the pH is 4 to about 7 and said time of standing is about 2 to about 3 weeks.

7. A method of claim 1, for coating a film of small pores wherein the amount of water in said solution is less than about 4 moles per mole of total alkoxides, and said pH is greater than about 5.

8. A method of claim 7, wherein said pH is about 8 to about 9.

9. A method of claim 7, wherein said time of standing is up to about one month.

10. A method of claim 1, for coating a film of small pores wherein the amount of water in said solution is less than about 4 moles per mole of total alkoxides, said pH is less than about 4 and said time of standing is up to about one month.

11. A method of claim 1, wherein the temperature of the solution during said time of standing is about 40°

-80°

C.

12. A method of claim 1 wherein the temperature of the solution during said time of standing is about 40°

-80°

C.

13. A method of claim 12, wherein the solution is maintained at said lowered temperature for storage purposes.

14. A method of claim 1, wherein said film is of a thickness of about 100-10,000 Å

.

15. A method of claim 1, wherein the metal in the alkoxide is silicon and the alcohol is a C_2-3 -alkanol and the acid is HCl or the base is NH₄ OH.