1. Polyimides having improved thermal-oxidative stability derived from the polymerization of effective amounts of at least one polyamine, at least one tetracarboxylic dianhydride and a dicarboxylic endcap having a formula:
wherein R1 is selected from the group consisting of an alkyl, fluoroalkyl, aryl, fluoroaryl, OR, carboxy, nitro, cyano, R\u2014N\u2014R, SO3R, PO4R, F and Cl radicals where R is selected from the group consisting of hydrogen, an aryl radical, and an alkyl radical of 1 to 6 carbons; and wherein R2, R3, R4, R5, R6, R7, and R8 are the same or different radicals selected from the group consisting of hydrogen, alkyl, fluoroalkyl, aryl, fluoroaryl, OR, carboxy, nitro, cyano, R\u2014N\u2014R, SO3R, PO4R, F and Cl radicals where R is selected from the group consisting of hydrogen, an aryl radical, and an alkyl radical of 1 to 6 carbon atoms.
2. Polyimides having improved thermal-oxidative stability derived from the polymerization of effective amounts of at least one polyamine, at least one tetracarboxylic dianhydride and a dicarboxylic endcap having a formula:
wherein R2 and R3 are the same or different radicals selected from the group consisting of alkyl, fluoroalkyl, aryl, fluoroaryl, OR, carboxy, nitro, cyano, R\u2014N\u2014R, SO3R, PO4R, F and Cl radicals where R is selected from the group consisting of hydrogen, an aryl radical, and an alkyl radical of 1 to 6 carbons; and wherein, R1, R4, R5, R6, R7, R8 are the same or different radicals selected from the group consisting of hydrogen, alkyl, fluoroalkyl, aryl, fluoroaryl, OR, carboxy, nitro, cyano, R\u2014N\u2014R, SO3R, PO4R, F and Cl radicals where R is selected from the group consisting of hydrogen, an aryl radical, and an alkyl radical of 1 to 6 carbons.
3. The polyimide of claim 1 wherein the dicarboxylic endcap is 2,3-dimethyl-1,2,3,6-tetrahydrophthalic anhydride.
4. The polyimide of claim 1 wherein the dicarboxylic endcap is 1,3-dimethyl-1,2,3,6-tetrahydrophthalic anhydride.
5. The polyimide of claim 1 wherein the dicarboxylic endcap is 3,3-dimethyl-1,2,3,6-tetrahydrophthalic anhydride.
6. The polyimides of claim 1 wherein the polyamine is an aromatic polyamine.
7. The polyimide of claim 6 wherein the aromatic polyamine is an aromatic diamine.
8. The polyimide of claim 6 wherein the aromatic polyamine is 4,4\u2032-methylene dianiline.
9. The polyimide of claim 8 wherein the tetracarboxylic dianhydride is 3,3\u2032,4,4\u2032-benzophenonetetracarboxylic dianhydride.
10. The polyimide of claim 9 wherein the dicarboxylic endcap is 2,3-dimethyl-1,2,3,6-tetrahydrophthalic anhydride.
11. The polyimides of claim 2 wherein the polyamine is 4,4\u2032-methylene dianiline.
12. The polyimides of claim 11 wherein the tetracarboxylic dianhydride is 3,3\u2032,4,4\u2032-benzophenonetetracarboxylic dianhydride.
13. The polyimides of claim 12 wherein the dicarboxylic endcap is 2,3-dimethyl-1,2,3,6-tetrahydrophthalic anhydride.
14. The process of preparing polyimides having improved thermal-oxidative stability derived from the polymerization of effective amounts of at least one aromatic polyamine, at least one tetracarboxylic dianhydride and a dicarboxylic endcap having a formula:
wherein R1 is a radical selected from the group consisting of an alkyl, fluoroalkyl, aryl, fluoroaryl, OR, carboxy, nitro cyano, R\u2014N\u2014R, SO3R, PO4R, F and Cl radicals where R is selected from the group consisting of hydrogen, aryl radicals and alkyl radicals of 1 to 6 carbons; and wherein R2, R3, R4, R5, R6, R7, and R8 are the same or different radicals selected from the group consisting of hydrogen, alkyl, fluoroalkyl, aryl, fluoroaryl, OR, carboxy, nitro, cyano, R\u2014N\u2014R, SO3R, PO4R, F and Cl radicals where R is selected from the group consisting of hydrogen, aryl radicals and alkyl radicals of 1 to 6 carbons.
15. The process of claim 14 wherein the aromatic polyamine is 4,4\u2032-methylene dianiline.
16. The process of claim 15 wherein the tetracarboxylic dianhydride is 3,3\u2032,4,4\u2032-benzophenonetetracarboxylic dianhydride.
17. The process of claim 16 wherein the dicarboxylic endcap is 2,3-dimethyl-1,2,3,6-tetrahydrophthalic anhydride.
18. The process of claim 14 wherein R2 and R3 are the same or different radicals selected from the group consisting of alkyl, fluoroalkyl, aryl, fluoroaryl, OR, carboxy, nitro, cyano, R\u2014N\u2014R, SO3R, PO4R, F and Cl radicals where R is selected from the group consisting of hydrogen, aryl radicals and alkyl radicals of 1 to 6 carbons, and wherein R1, R4, R5, R6, R7, R8, are the same or different radicals selected from the group consisting of hydrogen, alkyl, fluoroalkyl, aryl, fluoroaryl, OR, carboxy, nitro, cyano, R\u2014N\u2014R, SO3R, PO4R, F and Cl radicals where R is selected from the group consisting of hydrogen, aryl radicals and alkyl radicals of 1 to 6 carbons.
19. Fiber-reinforced high-temperature polyimide matrix composites comprising a fibrous material impregnated with an effective amount of a polyimide having improved thermal-oxidative stability; said polyimide derived from the polymerization of at least one polyamine, at least one tetracarboxylic dianhydride and a dicarboxylic endcap having the formula:
wherein R1 is selected from the group consisting of an alkyl, fluoroalkyl, aryl, fluoroaryl, OR, carboxy, nitro, cyano, R\u2014N\u2014R, SO3R, PO4R, F and Cl radicals where R is selected from the group consisting of hydrogen, an aryl radical, and an alkyl radical of 1 to 6 carbons; and wherein R2, R3, R4, R5, R6, R7, and R8 are the same or different radicals selected from the group consisting of hydrogen, alkyl, fluoroalkyl, aryl, fluoroaryl, OR, carboxy, nitro, cyano, R\u2014N\u2014R, SO3R, PO4R, F and Cl radicals, where R is selected from the group consisting of hydrogen, an aryl radical, and an alkyl radical of 1 to 6 carbon atoms.
20. The composites of claim 19 wherein the fiberous material comprises carbon fibers.
21. The composites of claim 19 wherein the fiberous materials comprises glass fibers.
22. A process of preparing a fiber-reinforced prepreg which comprises impregnating a fiberous material with an effective amount of a polyimide prepolymer derived from at least one polyamine, at least one tetracarboxylic dianhydride and a dicarboxylic endcap having the formula:
wherein R1 is selected from the group consisting of an alkyl, fluoroalkyl, aryl, fluoroaryl, OR, carboxy, nitro, cyano, R\u2014N\u2014R, SO3R, PO4R, F and Cl radicals where R is selected from the group consisting of hydrogen, an aryl radical, and an alkyl radical of 1 to 6 carbons; and wherein R2, R3, R4, R5, R6, R7, and R8 are the same or different radicals selected from the group consisting of hydrogen, alkyl, fluoroalkyl, aryl, fluoroaryl, OR, carboxy, nitro, cyano, R\u2014N\u2014R, SO3R, PO4R, F and Cl radicals, where R is selected from the group consisting of hydrogen, an aryl radical, and an alkyl radical of 1 to 6 carbon atoms.
23. The prepreg obtained by the process of claim 22
The claims below are in addition to those above.
All refrences to claim(s) which appear below refer to the numbering after this setence.
1. A CMOS compatible method for manufacturing a Group III-nitride HEMT having a gate electrode and Au-free source and drain ohmic contacts, comprising:
a) providing a substrate;
b) forming a stack of Group III-nitride layers on the substrate;
c) forming a first passivation layer comprising silicon nitride overlying and in contact with an upper layer of the stack of Group III-nitride layers, wherein the first passivation layer is deposited at a temperature between 900\xb0 C. and 1250\xb0 C. by a first chemical vapor deposition technique, and wherein the first passivation layer is deposited in-situ with the stack of Group III-nitride layers;
d) forming a dielectric layer overlying and in contact with the first passivation layer, the dielectric layer comprising a high-k dielectric material;
e) forming a second passivation layer comprising silicon nitride overlying and in contact with the dielectric layer, wherein the second passivation layer is deposited at a temperature higher than 450\xb0 C. by a second chemical vapor deposition technique; and thereafter
f) forming source and drain ohmic contacts, and a gate electrode in such a way that a gate dielectric is formed comprising the first passivation layer and at least part of the dielectric layer, wherein forming source and drain ohmic contacts comprises patterning source and drain ohmic contact regions by selectively etching the second passivation layer, the dielectric layer, and the first passivation layer, and forming ohmic contacts by deposition of an Au-free metal layer, patterning the metal layer, and forming an ohmic alloy at a temperature between 500\xb0 C. and 850\xb0 C. and below a crystallization temperature of the high-k material of the gate dielectric, wherein forming the gate electrode comprises patterning a gate trench by selective etching of the second passivation layer towards the dielectric layer and forming the gate electrode in the gate trench by deposition of a metal gate layer and patterning the metal gate layer such that the second passivation layer is thinner in an exposed region between an edge of the gate electrode and the source and drain contacts when compared to an original thickness as-deposited in regions covered by the gate electrode.
2. The method of claim 1, wherein at least one of the first passivation layer and the second passivation layer comprises Si3N4.
3. The method of claim 1, wherein the second chemical vapor deposition technique is selected from the group consisting of low pressure chemical vapor deposition and metal organic chemical vapor deposition.
4. The method of claim 1, wherein patterning the metal layer comprises a dry-etch process of the metal layer wherein the dry-etch process of the metal layer consumes partially the second passivation layer.
5. The method of claim 1, wherein patterning the metal gate layer comprises a dry-etch process of the metal gate layer wherein the dry-etch process of the metal gate layer consumes partially the second passivation layer.
6. The method of claim 1, further comprising: forming a dielectric cap layer on whichever is formed first of the source and drain ohmic contacts or the gate electrode, thereby protecting the source and drain ohmic contacts or the gate electrode during a subsequent metal layer or metal gate layer deposition.
7. The method of claim 1, wherein the dielectric layer comprises Al.
8. The method of claim 7, wherein the dielectric layer comprises Al2O3.
9. The method of claim 1, wherein the first passivation layer has a thickness of at least 0.5 nm.
10. The method of claim 1, wherein the second passivation layer has a thickness of at least 50 nm.
11. The method of claim 1, wherein the first passivation layer is deposited at a temperature of 1100\xb0 C.