Hermetic substrate coatings in an inert gas atmosphere

• US 6,171,703 B1
• Filed: 08/22/1994
• Issued: 01/09/2001
• Est. Priority Date: 10/18/1989
• Status: Expired due to Fees

• Current Assignee: Dow, Inc.
• Original Assignee: Dow, Inc.
• Inventors: Haluska, Loren Andrew
• Primary Examiner(s): ROBINSON, ELLIS P
• Application Number:
  US08/293,331
• Time in Patent Office: 2,332 Days
• Field of Search: 428/698, 428/702, 428/704, 428/446, 428/448, 428/450, 428/469, 428/432, 428/433, 428/434, 427/226, 427/228, 427/377, 427/397.7, 427/489, 427/497, 427/503, 427/419.8, 427/407.1
• US Class Current: 428/446
• CPC Class Codes: C09D 183/04 Polysiloxanes
• CPC Class Codes: H01L 21/56 Encapsulations, e.g. encapsulation layers, coatings
• CPC Class Codes: H01L 23/291 Oxides or nitrides or carbides, e.g. ceramics, glass
• CPC Class Codes: H01L 2924/00 Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
• CPC Class Codes: H01L 2924/0002 Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Abstract

The present invention relates to a method of forming a ceramic or ceramic-like coating on a substrate in the absence of oxygen. The method comprises coating the substrate with a solution comprising a solven and one or more preceramic materials selected from the group consisting of hydrogen silsesquioxane and hydrolyzed or partially hydrolyzed R_xSi(OR)_4-x wherein R is independently selected from the group consisting of alkyl, aryl and unsaturated hydrocarbons and x is 0-2. The solvent is evaporated and a preceramic coating thereby deposited on the substrate. The preceramic coating is then ceramified by heating the coated substrate to a temperature of between about 500 up to about 1000° C. under an inert gas atmosphere to thereby produce a ceramic or ceramic-like coating on the substrate. The process of the invention is useful for forming protective coatings on any substrate prone to oxidation at the temperature necessary for ceramification. The present invention also relates to the formation of additional ceramic coatings on the ceramic or ceramic-like coating formed above.

Claims

1. A coated electronic device formed by a method consisting essentially of:

(A) coating the electronic device with a solution consisting essentially of a solvent and hydrogen silsesquioxane resin;

(B) evaporating the solvent to deposit a preceramic coating on the electronic device;

(C) heating the preceramic coating to a temperature of between about 500 up to about 800°

C. under an inert gas atmosphere; and

(D) applying a passivating coating over the coating of step (C), the passivating coating applied by means of (i) coating the electronic device having the coating of step (C) with a second solution comprising a solvent and a preceramic polymer, (ii) evaporating said solvent to thereby deposit a preceramic coating; and

(iii) heating the preceramic coating to a temperature between 200-900°

C. under an ammonia or inert gas atmosphere, whereby a dual layer coating is obtained on the electronic device.

2. A coated electronic device formed by a method consisting essentially of:

(A) coating the electronic device with a solution consisting essentially of a solvent and hydrogen silsesquioxane resin;

(B) evaporating the solvent to deposit a preceramic coating on the electronic device;

(C) heating the preceramic coating to a temperature of between about 500 up to about 800°

C. under an inert gas atmosphere;

(D) applying a silicon containing passivating coating over the coating of step (C), said passivating coating selected from the group consisting of (i) silicon coatings, (ii) silicon carbon-containing coatings, (iii) silicon nitrogen-containing coatings, and (iv) silicon carbon nitrogen-containing coatings, wherein the silicon coating is applied by a means selected from the group consisting of (a) chemical vapor deposition of a silane, halosilane, halodisilane, halopolysilane or mixtures thereof in an inert gas atmosphere, (b) plasma enhanced chemical vapor deposition of a silane, halosilane, halodisilane, halopolysilane or mixtures thereof in an inert gas atmosphere and (c) metal assisted chemical vapor deposition of a silane, halosilane, halodisilane, halopolysilane or a mixture thereof in the presence of an inert gas, and wherein the silicon carbon-containing coating is applied by a means selected from the group consisting of (1) chemical vapor deposition in an inert gas atmosphere 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 in an inert gas atmosphere of an alkylsilane, halosilane, halodisilane, halopolysilane or mixtures thereof in the presence of an alkane of one to six carbon atoms or an alkylsilane and (3) plasma enhanced chemical vapor deposition of a silacyclobutane or disilacyclobutane in an inert gas atmosphere; and

wherein the 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 an ammonia atmosphere, (b′

) plasma enhanced chemical vapor deposition of a silane, halosilane, halodisilane, halopolysilane, or mixtures thereof in an ammonia atmosphere and (c′

) coating the coating of step (C) with a second solution comprising a solvent and a preceramic polymer, evaporating said solvent to thereby deposit a preceramic coating and heating the preceramic coating to a temperature between 200-900°

C. under an ammonia or inert gas atmosphere, and wherein the silicon carbon nitrogen-containing coating is deposited by a means selected from the group consisting of (i) chemical vapor deposition of hexamethyl disilazane in an ammonia or inert gas atmosphere, (ii) plasma enhanced chemical vapor deposition of hexamethyldisilazane in an ammonia or inert gas atmosphere, (iii) chemical vapor deposition of a silane, alkylsilane, halosilane, halodisilane, halopolysilane or a 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 (iv) plasma enhanced chemical vapor deposition of a silane, alkylsilane, halosilane, halodisilane, halopolysilane or a mixture thereof in the presence of an alkane of one to six carbon atoms or an alkylsilane and further in the presence of ammonia, whereby a dual layer coating is obtained on the electronic device.

3. A coated electronic device formed by a method consisting essentially of:

(A) coating the electronic device with a solution consisting essentially of a solvent and hydrogen silsesquioxane resin;

(B) evaporating the solvent to deposit a preceramic coating on the electronic device;

(C) heating the preceramic coating to a temperature of between about 500 up to about 800°

C. under an inert gas atmosphere;

(D) applying a passivating coating over the coating of step (C), the passivating coating applied by means of (i) coating the electronic device having the coating of step (C) with a second solution comprising a solvent and a preceramic polymer, (ii) evaporating said solvent to thereby deposit a preceramic coating; and

(iii) heating the preceramic coating to a temperature between 200-900°

C. under an ammonia or inert gas atmosphere; and

(E) applying a silicon containing barrier coating to said passivating coating, said barrier coating selected from the group consisting of (i) silicon coatings, (ii) silicon carbon-containing coatings, (iii) silicon nitrogen-containing coatings, and (iv) silicon carbon nitrogen-containing coatings, wherein the silicon coating is applied by a means selected from the group consisting of chemical vapor deposition of a silane, halosilane, halodisilane, halopolysilane or mixtures thereof in an inert gas atmosphere, (b) plasma enhanced chemical vapor deposition of a silane, halosilane, halodisilane;

halopolysilane or mixtures thereof in an inert gas atmosphere and (c) metal assisted chemical vapor deposition of asilane, halosilane, halodisilane, halopolysilane or a mixture thereof in the presence of an inert gas, and wherein the silicon carbon-containing coating is applied by a means selected from the group consisting of (1) chemical vapor deposition in an inert gas atmosphere 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 in an inert gas atmosphere of an alkylsilane, halosilane, halodisilane, halopolysilane or mixtures thereof in the presence of an alkane of one to six carbon atoms or an alkylsilane and (3) plasma enhanced chemical vapor deposition of a silacyclobutane or disilacyclobutane in an inert gas atmosphere; and

wherein the 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 an ammonia atmosphere, (b′

) plasma enhanced chemical vapor deposition of a silane, halosilane, halodisilane, halopolysilane, or mixtures thereof in an ammonia atmosphere and (c′

) coating the passivating coating with a third solution comprising a solvent and a preceramic polymer, evaporating said solvent to thereby deposit a preceramic coating and heating the preceramic coating to a temperature between 200-900°

C. under an ammonia or inert gas atmosphere, and wherein the silicon carbon nitrogen-containing coating is deposited by a means selected from the group consisting of (i) chemical vapor deposition of hexamethyl disilazane in an ammonia or inert gas atmosphere, (ii) plasma enhanced chemical vapor deposition of hexamethyldisilazane in an ammonia or inert gas atmosphere, (iii) deposition of a silane, alkylsilane, halosilane, halopolysilane or a mixture thereof in the presence one to six carbon atoms or an alkylsilane and presence of ammonia, and (iv) plasma enhanced deposition of a silane, alkylsilane, halosilane halopolysilane or a mixture thereof in the presence one to six carbon atoms or an alkylsilane and presence of ammonia, whereby a multilayer coating is obtained on the electronic device.

4. A coated electronic device formed by a method consisting essentially of:

(A) coating the electronic device with a solution consisting essentially of a solvent and hydrogen silsesquioxane resin;

(B) evaporating the solvent to deposit a preceramic coating on the electronic device;

(C) heating the preceramic coating to a temperature of between about 500 up to about 800°

C. under an inert gas atmosphere;

(D) applying a silicon containing passivating coating to the coating of step (C), said passivating coating selected from the group consisting of (i) silicon carbon-containing coatings, (ii) silicon nitrogen-containing coatings, and (iii) silicon carbon nitrogen containing coatings, wherein the silicon carbon-containing coating is applied by a means selected from the group consisting of (1) chemical vapor deposition in an inert gas atmosphere 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 in an inert gas atmosphere of an alkylsilane, halosilane, halodisilane, halopolysilane or mixtures thereof, in the presence of an alkane of one to six carbon atoms or an alkylsilane and (3) plasma enhanced chemical vapor deposition of a silacyclobutane or disilacyclobutane in an inert gas atmosphere; and

wherein the 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 an ammonia atmosphere, (b′

) plasma enhanced chemical vapor deposition of a silane, halosilane, halodisilane, halopolysilane, or mixtures thereof in an ammonia atmosphere and (c′

) coating the first coating with a second solution comprising a solvent and a preceramic polymer, evaporating said solvent to thereby deposit a preceramic coating and heating the preceramic coating to a temperature between 200-900°

C. under an ammonia or inert gas atmosphere, and wherein the silicon carbon nitrogen-containing coating is deposited by a means selected from the group consisting of (i) chemical vapor deposition of hexamethyldisilazane in an ammonia or inert gas atmosphere, (ii) plasma enhanced chemical vapor deposition of hexamethyl disilazane in an ammonia or inert gas atmosphere, (iii) chemical vapor deposition of a silane, alkylsilane, halosilane, halodisilane, halopolysilane or a 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 (iv) plasma enhanced chemical vapor deposition of a silane, alkylsilane, halosilane, halodisilane, halopolysilane or a mixture 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 the silicon containing passivating coating; and

(E) applying a silicon containing barrier coating to the passivating coating, the barrier coating selected from the group consisting of (i) silicon coatings, (ii) silicon carbon-containing coatings, (iii) silicon nitrogen-containing coatings, and (iv) silicon carbon nitrogen-containing coatings, wherein the silicon coating is applied by a means selected from the group consisting of (a) chemical vapor deposition of a silane, halosilane, halodisilane, halopolysilane or mixtures thereof in an inert gas atmosphere, (b) plasma enhanced chemical vapor deposition of a silane, halosilane, halodisilane, halopolysilane or mixtures thereof in an inert gas atmosphere and (c) metal assisted chemical vapor deposition of a silane, halosilane, halodisilane, halopolysilane or a mixture thereof in the presence of an inert gas, and wherein the silicon carbon-containing coating is applied by a means selected from the group consisting of (1) chemical vapor deposition in an inert gas atmosphere 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 in an inert gas atmosphere of an alkylsilane, halosilane, halodisilane, halopolysilane or mixtures thereof in the presence of an alkane of one to six carbon atoms or an alkylsilane and (3) plasma enhanced chemical vapor deposition of a silacyclobutane or disilacyclobutane in an inert gas atmosphere; and

wherein the 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 an ammonia atmosphere, (b′

) plasma enhanced chemical vapor deposition of a silane, halosilane, halodisilane, halopolysilane, or mixtures thereof in an ammonia atmosphere and (c′

) coating the passivating coating with a second solution comprising a solvent and a preceramic polymer, evaporating said solvent to thereby deposit a preceramic coating and heating the preceramic coating to a temperature between 200-900°

C. under an ammonia or inert gas atmosphere, and wherein the silicon carbon nitrogen-containing coating is deposited by a means selected from the group consisting of (i) chemical vapor deposition of hexamethyldisilazane in an ammonia or inert gas atmosphere, (ii) plasma enhanced chemical vapor deposition of hexamethyldisilazane in an ammonia or inert gas atmosphere, (iii) chemical vapor deposition of a silane, alkylsilane, halosilane, halodisilane, halopolysilane or a 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 (iv) plasma enhanced chemical vapor deposition of a silane, alkylsilane, halosilane, halodisilane, halopolysilane or a mixture thereof in the presence of an alkane of one to six carbon atoms or an alkylsilane and further in the presence of ammonia, whereby a multilayer coating is obtained on the electronic device.