Process of curing hydrogen silsesquioxane coating to form silicon oxide layer

• US 5,456,952 A
• Filed: 05/17/1994
• Issued: 10/10/1995
• Est. Priority Date: 05/17/1994
• Status: Expired due to Term

• Current Assignee: LSI Logic Corporation (Broadcom, Inc.)
• Original Assignee: LSI Logic Corporation (Broadcom, Inc.)
• Inventors: Garza, Mario, Chao, Keith
• Primary Examiner(s): Utech, Benjamin L.
• Application Number:
  US08/245,191
• Time in Patent Office: 511 Days
• Field of Search: 427/489, 427/573, 427/574, 427/226, 427/376.2, 427/387
• US Class Current: 427/489
• CPC Class Codes: C08G 77/12 containing silicon bound to hydrogen C08G77/045 takes precedence
• CPC Class Codes: C09D 183/04 Polysiloxanes
• CPC Class Codes: C23C 18/1212 Zeolites, glasses
• CPC Class Codes: C23C 18/122 Inorganic polymers, e.g. silanes, polysilazanes, polysiloxanes
• CPC Class Codes: H01L 21/02134 the material comprising hydrogen silsesquioxane, e.g. HSQ
• CPC Class Codes: H01L 21/02164 the material being a silicon oxide, e.g. SiO2
• 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 21/0234 treatment by exposure to a plasma
• CPC Class Codes: H01L 21/316 composed of oxides or glassy oxides or oxide based glass

Abstract

A process is disclosed for curing a hydrogen silsesquioxane coating material to form SiO₂ by first placing the coating material in a preheated furnace; igniting a plasma ignited in the furnace immediately after insertion of the coating material therein; then raising the temperature of the furnace up to a predetermined curing temperature, while still maintaining the plasma in the chamber; maintaining the coating material at the curing temperature until substantially all of the coating material has cured to form SiO₂ ; and then extinguishing the plasma and cooling the furnace. In another embodiment, the coating material is cured, with or without the assistance of heat and a plasma, in an ultrahigh vacuum, i.e., a vacuum of at least 10^-5 Torr or better, and preferably at least 10^-6 Torr or better.

Claims

1. A process for converting a hydrogen silsesquioxane coating on a substrate to SiO₂ which comprises:

a) coating a substrate with a hydrogen silsesquioxane coating, and then, after drying said coated substrate;

b) inserting said coated substrate into a furnace preheated to a temperature of at least about 300°

C. prior to said inserting of said coated substrate therein;

c) igniting a plasma in said furnace immediately after said insertion of said coated substrate therein;

d) further heating said coated substrate in said furnace in the presence of said plasma to a curing temperature of at least about 400°

C.;

e) maintaining the coated substrate at said curing temperature until substantially all of the hydrogen silsesquioxane coating material has been converted to SiO₂ while still maintaining said plasma in said furnace;

f) then extinguishing said plasma; and

g) subsequently removing said SiO₂ -coated substrate from said furnace.

2. The process of claim 1 wherein said furnace is preheated to a temperature of at least about 400°

C., prior to insertion of said coated substrate into said furnace.

3. The process of claim 1 wherein said furnace temperature is raised, after insertion of said coated substrate therein, to thereby heat said coated substrate to at least about 400°

C. and then maintaining said coated substrate in said furnace for an initial holding period of at least about 5 minutes before raising said furnace to a higher curing temperature.

4. The process of claim 3 wherein said coated substrate is maintained in said preheated furnace at said at least about 400°

C. for an initial holding period of at least about 20 minutes before raising said furnace to a higher curing temperature.

5. The process of claim 3 wherein said furnace temperature is raised to a higher curing temperature of at least about 600°

C. after said initial holding period.

6. The process of claim 5 wherein said furnace temperature is raised to said curing temperature of at least about 600°

C. over a period of at least about 5 minutes.

7. The process of claim 6 wherein said furnace is maintained at said curing temperature of at least about 600°

C. for a period of at least about 5 minutes, after which said plasma is extinguished and said furnace is allowed to cool back at least to said temperature to which said furnace was preheated.

8. The process of claim 6 wherein said furnace is maintained at said curing temperature of at least about 600°

C. for a period of at least about 10 minutes, after which said plasma is extinguished and said furnace is allowed to cool back at least to said temperature to which said furnace was preheated.

9. The process of claim 6 wherein said furnace is maintained at said curing temperature of at least about 600°

C. for a period of at least about 20 minutes, after which said plasma is extinguished and said furnace is allowed to cool back to at least said temperature to which said furnace was preheated.

10. The process of claim 3 wherein said furnace and said coated substrate therein are subsequently heated to a curing temperature of at least about 700°

C. after said initial holding period.

11. The process of claim 1 wherein the temperature of said furnace, after insertion of said coated substrate therein, is maintained at a curing temperature of about 400°

C. for a period of at least about 20 minutes.

12. A process for converting substantially all of a hydrogen silsesquioxane coating on a substrate to SiO₂ which comprises:

a) coating a substrate with a hydrogen silsesquioxane coating, and then, after drying said coated substrate;

b) inserting said coated substrate into a furnace preheated to a temperature of at least about 300°

C.;

c) igniting a plasma in said furnace immediately after inserting said coated substrate therein;

d) maintaining said coated substrate in said furnace at said preheated temperature and in the presence of said plasma for a period of at least about 5 minutes before raising the temperature in said furnace;

e) then raising the temperature of the furnace to a curing temperature of at least about 600°

over a period of at least about 5 minutes;

f) maintaining the coated substrate at said curing temperature for a period of at least about 20 minutes while maintaining said plasma in said furnace to permit substantially all of said hydrogen silsesquioxane coating material to convert to SiO₂ ;

g) then extinguishing said plasma and cooling said furnace back to said preheated temperature; and

h) subsequently removing said SiO₂ -coated substrate from said furnace.

13. The process of claim 12 wherein said furnace is preheated to a temperature of at least about 400°

C., prior to insertion of said coated substrate into said furnace.

14. The process of claim 12 wherein said furnace temperature is raised to a curing temperature of at least about 700°

C.

15. The process of claim 12 wherein said SiO₂ -coated substrate is allowed to cool in said furnace for a period of at least about 20 minutes before said coated substrate is removed from said furnace.

16. The process of claim 12 wherein said plasma is maintained at a power level ranging from about 25 watts to about 2000 watts.

17. The process of claim 12 wherein said plasma power is maintained at a duty cycle ranging from about 40% to about 90%.

18. The process of claim 12 wherein said furnace is maintained at a pressure not exceeding 1 Torr.

19. A process for converting substantially all of a hydrogen silsesquioxane coating on a substrate to SiO₂ which comprises:

a) coating a substrate with a hydrogen silsesquioxane coating, and then, after drying said coated substrate;

b) inserting said coated substrate into a furnace preheated to a temperature of at least about 400°

C. and maintained at a pressure not exceeding 1 Torr;

c) igniting a plasma in said chamber immediately after inserting said coated substrate therein, said plasma having a power ranging from about 25 watts to about 2000 watts and a duty cycle ranging from about 40% to about 90%;

d) preheating said coated substrate for a period of at least about 10 minutes in said preheated furnace in the presence of said plasma;

e) then raising the temperature of said furnace to a curing temperature of at least about 700°

over a period of at least about 5 minutes;

f) maintaining said coated substrate at said curing temperature for a period of at least about 20 minutes to convert substantially all of said hydrogen silsesquioxane coating material to SiO₂ while still maintaining said plasma in said furnace;

g) then extinguishing said plasma and cooling said furnace back to at least said preheated temperature;

h) maintaining said coated substrate in said furnace for a period of at least about 10 minutes after said cooling step commences; and

i) subsequently removing said SiO₂ -coated substrate from said furnace.