Single and multilayer coatings containing aluminum nitride

• US 5,183,684 A
• Filed: 11/20/1989
• Issued: 02/02/1993
• Est. Priority Date: 11/20/1989
• Status: Expired due to Fees

• Current Assignee: The Dow Chemical Company (Dow, Inc.)
• Original Assignee: Dow, Inc.
• Inventors: Carpenter, Leslie E.
• Primary Examiner(s): BELL, JANYCE A
• Application Number:
  US07/438,859
• Time in Patent Office: 1,170 Days
• Field of Search: 427/226, 427/38, 427/39, 427/126.2, 427/255.2, 427/255, 427/380, 427/419.2, 427/431, 427/420, 427/419.7, 427/421, 427/126.1, 427/343, 427/344, 437/231, 437/235, 437/241, 428/689, 428/698, 428/699, 428/701
• US Class Current: 427/574
• CPC Class Codes: C23C 18/1204 inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
• CPC Class Codes: C23C 18/1208 Oxides, e.g. ceramics
• CPC Class Codes: C23C 18/1225 Deposition of multilayers of inorganic material

Abstract

Ceramic or ceramic-like single, two, or multilayer coatings having aluminum nitride as one of the layers are provided, including methods for the preparation of such coatings which produce planarizing, passivating and hermetic barrier coatings on temperature sensitive substrates such as semiconductors and electronic devices. The aluminum nitride ceramic or ceramic-like coating is provided by applying a liquid alkylaluminum amide having the formula (R₂ AlNH₂)₃, where R is an alkyl group containing from 1 to 4 carbon atoms, neat or diluted in an organic solvent. The liquid coating is then dried, followed by heating the coating to a temperature of between about 400° to about 100° C. in the presence of ammonia to produce an aluminum nitride-containing ceramic coating.

Claims

1. A process for the formation of an aluminum nitride ceramic or ceramic-like coating on a substrate comprising the steps of:

(a) coating said substrate with a liquid containing an alkylaluminum amide having the formula (R₂ AlNH₂)₃, where R is an alkyl group containing from 1 to 4 carbon atoms;

(b) drying said liquid and thereby depositing a preceramic coating on said substrate; and

(c) ceramifying said preceramic coating to an aluminum nitride-containing ceramic by heating said preceramic coating to a temperature of between about 400°

to about 1000°

C. in the presence of ammonia.

2. The process of claim 1 in which said liquid containing said alkylaluminum amide is coated onto said substrate by spray coating, dip coating, flow coating, or spin coating.

3. The process of claim 1 in which said substrate is an electronic device.

4. The process of claim 1 in which said coating has a thickness of between about 50 to about 500 nanometers.

5. The process of claim 1 in which said alkylaluminum amide is diluted in a solution of an organic solvent.

6. A process for the formation of a multilayer ceramic or ceramic-like protective coating on a substrate comprising the steps of:

(I) (a) coating said substrate with a planarizing coating comprising a liquid containing an alkylaluminum amide having the formula (R₂ AlNH₂)₃, where R is an alkyl group containing from 1 to 4 carbon atoms;

(b) drying said liquid and thereby depositing a preceramic coating on said substrate; and

(c) ceramifying said preceramic coating to an aluminum nitride-containing ceramic by heating said preceramic coating to a temperature of between about 400°

to about 1000°

C. in the presence of ammonia to form said planarizing coating;

(II) applying to said planarizing coating a passivating coating selected from the group consisting of (i) a silicon nitrogen-containing coating, (ii) a silicon carbon-containing coating, and (iii) a silicon carbon nitrogen-containing coating; and

(III) applying to said passivating coating a protective coating selected from the group consisting of (i) a silicon-containing coating, (ii) a silicon nitrogen-containing coating, (iii) a silicon carbon-containing coating, and (iv) a silicon carbon nitrogen-containing coating, whereby a multilayer ceramic or ceramic-like coating on said substrate is obtained.

7. The process of claim 6 in which said alkylaluminum amide is diluted in a solution of an organic solvent.

8. The process of claim 6 wherein in said passivating coating said silicon nitrogen-containing coating is applied onto said planarizing coating by a means selected from the group consisting of (a) chemical vapor deposition of a silane, halosilane, halodisilane, halopolysilane or mixtures thereof in the presence of ammonia, (b) plasma enhanced chemical vapor deposition of a silane, halosilane, halodisilane, halopolysilane or mixtures thereof in the presence of ammonia, (c) ceramification of a silicon and nitrogen-containing polymer;

and wherein said silicon carbon nitrogen-containing coating is applied onto said planarizing coating by a means selected from the group consisting of (1) chemical vapor deposition of hexamethyldisilazane, (2) plasma enhanced chemical vapor deposition of hexamethyldisilazane, (3) chemical vapor deposition of a silane, halosilane, halodisilane, halopolysilane or mixture thereof in the presence of an alkane of one to six carbon atoms or an alkylsilane, and further in the presence of ammonia, and (4) plasma enhanced chemical vapor deposition of a silane, halosilane, halodisilane, halopolysilane or mixture thereof in the presence of an alkane of one to six carbon atoms or an alkylsilane, and further in the presence of ammonia; and

wherein said silicon carbon-containing coating is deposited by a means selected from the group consisting of (i) chemical vapor deposition of a silane, halosilane, halopolysilane, or mixtures thereof in the presence of an alkane of one to six carbon atoms or an alkylsilane, and (ii) plasma enhanced chemical vapor deposition of a silane, alkylsilane, halosilane, halodisilane, halopolysilane, or mixtures thereof in the presence of an alkane of one to six carbon atoms or an alkylsilane, to produce said passivating coating.

9. The process of claim 6 wherein in said protective coating, said silicon-containing coating is applied onto said passivating coating by a means selected from the group consisting of (a) chemical vapor deposition of a silane, halosilane, halopolysilane, or mixtures thereof, (b) plasma enhanced chemical vapor deposition of a silane, halosilane, halopolysilane, or mixtures thereof, or (c) metal assisted chemical vapor deposition of a silane, halosilane, halopolysilane, or mixtures thereof;

and wherein said silicon carbon-containing coating is applied by a means selected from the group consisting of (1) chemical vapor deposition of a silane, alkylsilane, halosilane, halodisilane, halopolysilane, or mixtures thereof in the presence of an alkane of one to six carbon atoms or an alkylsilane, (2) plasma enhanced chemical vapor deposition of a silane, alkylsilane, halosilane, halodisilane, halopolysilane, or mixtures thereof in the presence of an alkane of one to six carbon atoms or an alkylsilane; and

wherein said silicon nitrogen-containing coating is deposited by a means selected from the group consisting of (A) chemical vapor deposition of a silane, halosilane, halodisilane, halopolysilane, or mixtures thereof in the presence of ammonia, (B) plasma enhanced chemical vapor deposition of a silane, halosilane, halodisilane, halopolysilane or mixtures thereof in the presence of ammonia, and (C) ceramification of a silicon and nitrogen-containing preceramic polymer; and

wherein said silicon carbon nitrogen-containing coating is deposited by a means selected from the group consisting of (i) chemical vapor deposition of hexamethyldisilazane, (ii) plasma enhanced chemical vapor deposition of hexamethyldisilazane, (iii) chemical vapor deposition of a silane, alkylsilane, halosilane, halodisilane, halopolysilane, or mixtures thereof in the presence of an alkane of one to six carbon atoms or an alkylsilane and further in the presence of ammonia, and (iv) plasma enhanced chemical vapor deposition of a silane, alkylsilane, halosilane, halodisilane, halopolysilane, or mixtures thereof in the presence of an alkane of one to presence of ammonia, to produce said protective coating.

10. The process of claim 6 in which said liquid containing said alkylaluminum amide is coated onto said substrate by spray coating, dip coating, flow coating, or spin coating.

11. The process of claim 6 in which said substrate is an electronic device.

12. A process for the formation of a multilayer ceramic or ceramic-like protective coating on a substrate comprising the steps of:

(I) coating said substrate with a planarizing coating of a silicon dioxide containing ceramic or ceramic-like composition;

(II) (a) applying to said planarizing coating a passivating coating comprising a liquid containing an alkylaluminum amide having the formula (R₂ AlNH₂)₃, where R is an alkyl group containing from 1 to 4 carbon atoms;

(b) drying said liquid and thereby depositing a preceramic coating on said substrate; and

(c) ceramifying said preceramic coating to an aluminum nitride-containing ceramic by heating said preceramic coating to a temperature of between about 400°

to about 1000°

C. in the presence of ammonia to form said passivating coating; and

(III) applying to said passivating coating a protective coating selected from the group consisting of (i) a silicon-containing coating, (ii) a silicon nitrogen-containing coating, (iii) a silicon carbon-containing coating, and (iv) a silicon carbon nitrogen-containing coating, whereby a multilayer ceramic or ceramic-like coating on said substrate is obtained.

13. The process of claim 12 in which said alkylaluminum amide is diluted in a solution of an organic solvent.

14. The process of claim 12 wherein in said planarizing coating, said silicon dioxide containing ceramic or ceramic-like composition is applied onto said substrate by a means selected from the group consisting of (a) deposition of a hydrogen silsesquioxane resin from a solvent solution, with or without a catalyst, drying, and ceramification, (b) deposition of a mixture of a hydrogen silsesquioxane resin and one or more metal oxides from a solvent solution, with or without a catalyst, drying, and ceramification, (c) deposition of a silicate ester from a solvent solution, drying, and ceramification, (d) deposition of a mixture of a silicate ester and one or more metal oxides from a solvent solution, drying, and ceramification, (e) deposition of a nitrided hydrogen silsesquioxane resin from a solvent solution, with or without a catalyst, drying, and ceramification, and (f) deposition of a mixture of a nitrided hydrogen silsesquioxane resin and one or more metal oxides from a solvent solution, with or without a catalyst, drying, and ceramification.

15. The process of claim 12 wherein in said protective coating, said silicon-containing coating is applied onto said passivating coating by a means selected from the group consisting of (a) chemical vapor deposition of a silane, halosilane, halopolysilane, or mixtures thereof, (b) plasma enhanced chemical vapor deposition of a silane, halosilane, halopolysilane, or mixtures thereof, or (c) metal assisted chemical vapor deposition of a silane, halosilane, halopolysilane, or mixtures thereof;

and wherein said silicon carbon-containing coating is applied by a means selected from the group consisting of (1) chemical vapor deposition of a silane, alkylsilane, halosilane, halodisilane, halopolysilane, or mixtures thereof in the presence of an alkane of one to six carbon atoms or an alkylsilane, (2) plasma enhanced chemical vapor deposition of a silane, alkylsilane, halosilane, halodisilane, halopolysilane, or mixtures thereof in the presence of an alkane of one to six carbon atoms or an alkylsilane; and

wherein said silicon nitrogen-containing coating is deposited by a means selected from the group consisting of (A) chemical vapor deposition of a silane, halosilane, halodisilane, halopolysilane or mixtures thereof in the presence of ammonia, (B) plasma enhanced chemical vapor deposition of a silane, halosilane, halodisilane, halopolysilane or mixtures thereof in the presence of ammonia, and (C) ceramification of a silicon and nitrogen-containing preceramic polymer; and

wherein said silicon carbon nitrogen-containing coating is deposited by a means selected from the group consisting of (i) chemical vapor deposition of hexamethyldisilazane, (ii) plasma enhanced chemical vapor deposition of hexamethyldisilazane, (iii) chemical vapor deposition of a silane, alkylsilane, halosilane, halodisilane, halopolysilane, or mixtures thereof in the presence of an alkane of one to six carbon atoms or an alkylsilane and further in the presence of ammonia, and (iv) plasma enhanced chemical vapor deposition of a silane, alkylsilane, halosilane, halodisilane, halopolysilane, or mixtures thereof in the presence of an alkane of one to six carbon atoms or an alkylsilane and further in the presence of ammonia, to produce said protective coating.

16. The process of claim 12 in which said liquid containing said alkylaluminum amide is coated onto said planarizing coating by spray coating, dip coating, flow coating, or spin coating.

17. The process of claim 12 in which said substrate is an electronic device.

18. A process for the formation of a multilayer ceramic or ceramic-like protective coating on a substrate comprising the steps of:

(I) coating said substrate with a planarizing coating of a silicon dioxide containing ceramic or ceramic-like composition;

(II) (a) applying to said planarizing coating a passivating coating selected from the group consisting of (i) a silicon nitrogen-containing coating, (ii) a silicon carbon-containing coating, and (iii) a silicon carbon nitrogen-containing coating; and

(III) applying to said passivating coating a protective coating of aluminum nitride by the chemical vapor deposition of a preceramic composition containing an alkylaluminum amide having the formula (R₂ AlNH₂)₃, where R is an alkyl group containing from 1 to 4 carbon atoms at a temperature of between about 400°

to about 1000°

C. in the presence of ammonia to form said protective coating.

19. The process of claim 18 wherein in said planarizing coating, said silicon dioxide containing ceramic or ceramic-like composition is applied onto said substrate by a means selected from the group consisting of (a) deposition of a hydrogen silsesquioxane resin from a solvent solution, with or without a catalyst, drying, and ceramification, (b) deposition of a mixture of a hydrogen silsesquioxane resin and one or more metal oxides from a solvent solution, with or without a catalyst, drying, and ceramification, (c) deposition of a silicate ester from a solvent solution, drying, and ceramification, (d) deposition of a mixture of a silicate ester and one or more metal oxides from a solvent solution, drying, and ceramification, (e) deposition of a nitrided hydrogen silsesquioxane resin from a solvent solution, with or without a catalyst, drying, and ceramification, and (f) deposition of a mixture of a nitrided hydrogen silsesquioxane resin and one or more metal oxides from a solvent solution, with or without a catalyst, drying, and ceramification.

20. The process of claim 18 wherein in said

The process of claim 24 wherein in said passivating coating said silicon nitrogen-containing coating is applied onto said planarizing coating by a means selected from the group consisting of (a) chemical vapor deposition of a silane, halosilane, halodisilane, halopolysilane or mixtures thereof in the presence of ammonia, (b) plasma enhanced chemical vapor deposition of a silane, halosilane, halodisilane, halopolysilane or mixtures thereof in the presence of ammonia, (c) ceramification of a silicon and nitrogen-containing polymer;

and wherein said silicon carbon nitrogen-containing coating is applied onto said planarizing coating by a means selected from the group consisting of (1) chemical vapor deposition of hexamethyldisilazane, (2) plasma enhanced chemical vapor deposition of hexamethyldisilazane, (3) chemical vapor deposition of a silane, halosilane, halodisilane, halopolysilane or mixture thereof in the presence of an alkane of one to six carbon atoms or an alkylsilane, and further in the presence of ammonia, and (4) plasma enhanced chemical vapor deposition of a silane, halosilane, halodisilane, halopolysilane or mixture thereof in the presence of an alkane of one to six carbon atoms or an alkylsilane, and further in the presence of ammonia; and

wherein said silicon carbon-containing coating is deposited by a means selected from the group consisting of (i) chemical vapor deposition of a silane, halosilane, halopolysilane, or mixtures thereof in the presence of an alkane of one to six carbon atoms or an alkylsilane, and (ii) plasma enhanced chemical vapor deposition of a silane, alkylsilane, halosilane, halodisilane, halopolysilane, or mixtures thereof in the presence of an alkane of one to six carbon atoms or an alkylsilane, to produce said passivating coating.

21. The process of claim 18 in which said substrate is an electronic device.

22. A process for the formation of a multilayer ceramic or ceramic-like protective coating on a substrate comprising the steps of:

(I) coating said substrate with an initial coating of a ceramic or ceramic-like composition selected from the group consisting of (i) a silicon nitrogen-containing coating, (ii) a silicon carbon-containing coating, and (iii) a silicon carbon nitrogen-containing coating and;

(II) (a) applying to said initial coating a passivating coating comprising a liquid containing an alkylaluminum amide having the formula (R₂ AlNH₂)₃, where R is an alkyl group containing from 1 to 4 carbon atoms;

(b) drying said liquid and thereby depositing a preceramic coating on said substrate; and

(c) ceramifying said preceramic coating to an aluminum nitride-containing ceramic by heating said preceramic coating to a temperature of between about 400°

to about 1000°

C. in the presence of ammonia to form said passivating coating; and

(III) applying to said passivating coating a protective coating selected from the group consisting of (i) a silicon-containing coating, (ii) a silicon nitrogen-containing coating, (iii) a silicon carbon-containing coating, and (iv) a silicon carbon nitrogen-containing coating, whereby a multilayer ceramic

23. The process of claim 22 in which said alkylaluminum amide is diluted in a solution of an organic solvent.

24. The process of claim 22 wherein in said protective coating, said silicon-containing coating is applied onto said passivating coating by a means selected from the group consisting of (a) chemical vapor deposition of a silane, halosilane, halopolysilane, or mixtures thereof, (b) plasma enhanced chemical vapor deposition of a silane, halosilane, halopolysilane, or mixtures thereof, or (c) metal assisted chemical vapor deposition of a silane, halosilane, halopolysilane, or mixtures thereof;

and wherein said silicon carbon-containing coating is applied by a means selected from the group consisting of (1) chemical vapor deposition of a silane, alkylsilane, halosilane, halodisilane, halopolysilane, or mixtures thereof in the presence of an alkane of one to six carbon atoms or an alkylsilane, (2) plasma enhanced chemical vapor deposition of a silane, alkylsilane, halosilane, halodisilane, halopolysilane, or mixtures thereof in the presence of an alkane of one to six carbon atoms or an alkylsilane; and

wherein said silicon nitrogen-containing coating is deposited by a means selected from the group consisting of (A) chemical vapor deposition of a silane, halosilane, halodisilane, halopolysilane or mixtures thereof in the presence of ammonia, (B) plasma enhanced chemical vapor deposition of a silane, halosilane, halodisilane, halopolysilane or mixtures thereof in the presence of ammonia, and (C) ceramification of a silicon and nitrogen-containing preceramic polymer; and

wherein said silicon carbon nitrogen-containing coating is deposited by a means selected from the group consisting of (i) chemical vapor deposition of hexamethyldisilazane, (ii) plasma enhanced chemical vapor deposition of hexamethyldisilazane, (iii) chemical vapor deposition of a silane, alkylsilane, halosilane, halodisilane, halopolysilane, or mixtures thereof in the presence of an alkane of one to six carbon atoms or an alkylsilane and further in the presence of ammonia, and (iv) plasma enhanced chemical vapor deposition of a silane, alkylsilane, halosilane, halodisilane, halopolysilane, or mixtures thereof in the presence of an alkane of one to six carbon atoms or an alkylsilane and further in the presence of ammonia, to produce said protective coating.

25. The process of claim 22 in which said liquid containing said alkylaluminum amide is coated onto said planarizing coating by spray coating, dip coating, flow coating, or spin coating.

26. The process of claim 22 in which said substrate is an electronic device.

27. A process for the formation of a two layer ceramic or ceramic-like coating on a substrate comprising the steps of:

(I) (a) coating said substrate with a planarizing coating comprising a liquid containing an alkylaluminum amide having the formula (R₂ AlNH₂)₃, where R is an alkyl group containing from 1 to 4 carbon atoms;

(b) drying said liquid and thereby depositing a preceramic coating on said substrate; and

(c) ceramifying said preceramic coating to an aluminum nitride-containing ceramic by heating said preceramic coating to a temperature of between about 400°

to about 1000°

C. in the presence of a ammonia to form said planarizing coating; and

(II) applying to said planarizing coating a passivating coating selected from the group consisting of (i) silicon nitrogen-containing coating, (ii) a silicon-containing coating, (iii) a silicon nitrogen-containing coating, and (iv) a silicon carbon nitrogen-containing coating, whereby a two layer ceramic or ceramic-like coating is obtained.

28. The process of claim 27 in which said alkylaluminum amide is diluted in a solution of an organic solvent.

29. The process of claim 27 wherein in said passivating coating said silicon-containing coating is applied onto said passivating coating by a means selected from the group consisting of (a) chemical vapor deposition of a silane, halosilane, halopolysilane, or mixtures thereof, (b) plasma enhanced chemical vapor deposition of a silane, halosilane, halopolysilane, or mixtures thereof, or (c) metal assisted chemical vapor deposition of a silane, halosilane, halopolysilane, or mixtures thereof;

said silicon nitrogen-containing coating is applied onto said planarizing coating by a means selected from the group consisting of (a) chemical vapor deposition of a silane, halosilane, halodisilane, halopolysilane or mixtures thereof in the presence of ammonia, (b) plasma enhanced chemical vapor deposition of a silane, halosilane, halodisilane, halopolysilane or mixtures thereof in the presence of ammonia, (c) ceramification of a silicon and nitrogen-containing polymer; and

wherein said silicon carbon nitrogen-containing coating is applied onto said planarizing coating by a means selected from the group consisting of (1) chemical vapor deposition of hexamethyldisilazane, (2) plasma enhanced chemical vapor deposition of hexamethyldisilazane, (3) chemical vapor deposition of a silane, halosilane, halodisilane, halopolysilane or mixture thereof in the presence of an alkane of one to six carbon atoms or an alkylsilane, and further in the presence of ammonia, and (4) plasma enhanced chemical vapor deposition of a silane, halosilane, halodisilane, halopolysilane or mixture thereof in the presence of an alkane of one to six carbon atoms or an alkylsilane, and further in the presence of ammonia; and

wherein said silicon carbon-containing coating is deposited by a means selected from the group consisting of (i) chemical vapor deposition of a silane, halosilane, halopolysilane, or mixtures thereof in the presence of an alkane of one to six carbon atoms, to produce said passivating coating.

30. The process of claim 27 in which said solution containing said alkylaluminum amide is coated onto said substrate by spray coating, dip coating, flow coating, or spin coating.

31. The process of claim 27 in which said substrate is an electronic device.

32. A process for the formation of a two layer ceramic or ceramic-like protective coating on a substrate comprising the steps of:

(I) coating said substrate with a planarizing coating of a silicon dioxide containing ceramic or ceramic-like composition; and

(II) applying to said passivating coating a protective coating of aluminum nitride by the chemical vapor deposition of a preceramic composition containing an alkylaluminum amide having the formula (R₂ AlNH₂)₃, where R is an alkyl group containing from 1 to 4 carbon atoms at a temperature of between about 400°

to about 1000°

C. in the presence of ammonia to form said protective coating.

33. The process of claim 32 wherein in said planarizing coating, said silicon dioxide containing ceramic or ceramic-like composition is applied onto said substrate by a means selected from the group consisting of (a) deposition of a hydrogen silsesquioxane resin from a solvent solution, with or without a catalyst, drying, and ceramification, (b) deposition of a mixture of a hydrogen silsesquioxane resin and one or more metal oxides from a solvent solution, with or without a catalyst, drying, and ceramification, (c) deposition of a silicate ester from a solvent solution, drying, and ceramification, (d) deposition of a mixture of a silicate ester and one or more metal oxides from a solvent solution, drying, and ceramification, (e) deposition of a nitrided hydrogen silsesquioxane resin from a solvent solution, with or without a catalyst, drying, and ceramification, and (f) deposition of a mixture of a nitrided hydrogen silsesquioxane resin and one or more metal oxides from a solvent solution, with or without a catalyst, drying, and ceramification.

34. The process of claim 32 in which said substrate is an electronic device.