Organoaminosilane precursors and methods for depositing films comprising same

A composition comprising:

• (a) at least one organoaminosilane comprising a compound represented by one of following Formulae A through E below:
• wherein R1 is selected from a linear or branched C1 to C10 alkyl group, a linear or branched C3 to C10 alkenyl group, a linear or branched C3 to C10 alkynyl group, a C3 to C10 cyclic alkyl group, and a C5 to C10 aryl group;
• wherein R2 is selected from hydrogen, a linear or branched C1 to C10 alkyl group, a linear or branched C3 to C10 alkenyl group, a linear or branched C3 to C10 alkynyl group, a C3 to C10 cyclic alkyl group, and a C5 to C10 aryl group, R3 and R4 are each independently selected from a linear or branched C1 to C10 alkylene group, a linear or branched C3 to C6 alkenylene group, a linear or branched C3 to C6 alkynylene group, a C3 to C10 cyclic alkylene group, a C3 to C10 hetero-cyclic alkylene group, a C5 to C10 arylene group, and a C5 to C10 hetero-arylene group;
• n in Formula A equals 1 or 2;
• m in Formula A equals 0, 1, 2, or 3;
• p and q in Formula E equal 1 or 2;
• and optionally wherein R3 in Formula D forms a ring selected from a four-membered, five-membered or six-membered ring with the two silicon atoms and at least one nitrogen atom;
• and
• (b) a solvent wherein the solvent has a boiling point and wherein the difference between the boiling point of the solvent and that of the at least one organoaminosilane is 40° C. or less.

A method for forming a silicon-containing film on at least one surface of a substrate by a deposition process selected from a chemical vapor deposition process and an atomic layer deposition process, the method comprising:

• providing the at least one surface of the substrate in a reaction chamber;
• introducing at least one organoaminosilane precursor comprising a compound represented by one of following Formulae A through E below:
• wherein R1 is selected from a linear or branched C1 to C10 alkyl group, a linear or branched C3 to C10 alkenyl group, a linear or branched C3 to C10 alkynyl group, a C3 to C10 cyclic alkyl group, and a C5 to C10 aryl group;
• wherein R2 is selected from hydrogen, a linear or branched C1 to C10 alkyl group, a linear or branched C3 to C10 alkenyl group, a linear or branched C3 to C10 alkynyl group, a C3 to C10 cyclic alkyl group, and a C5 to C10 aryl group, R3 and R4 are each independently selected from a linear or branched C1 to C10 alkylene group, a linear or branched C3 to C6 alkenylene group, a linear or branched C3 to C6 alkynylene group, a C3 to C10 cyclic alkylene group, a C3 to C10 hetero-cyclic alkylene group, a C5 to C10 arylene group, and a C5 to C10 hetero-arylene group;
• n in Formula A equals 1 or 2;
• m in Formula A equals 0, 1, 2, or 3;
• p and q in Formula E equal 1 or 2;
• and optionally wherein R3 in Formula D forms a ring selected from a four-membered, five-membered or six-membered ring with the two silicon atoms and at least one nitrogen atom;
• and
• introducing a nitrogen-containing source into the reactor wherein the at least one organoaminosilane precursor and the nitrogen-containing source react to form the film on the at least one surface.

A method of forming a silicon-containing film via an atomic layer deposition (ALD) process, the method comprising the steps of:

• a. providing a substrate in an ALD reactor;
• b. providing in the ALD reactor at least one organoaminosilane precursor comprising a compound represented by one of following Formulae A through E below:
• wherein R1 is selected from a linear or branched C1 to C10 alkyl group, a linear or branched C3 to C10 alkenyl group, a linear or branched C3 to C10 alkynyl group, a C3 to C10 cyclic alkyl group, and a C5 to C10 aryl group;
• wherein R2 is selected from hydrogen, a linear or branched C1 to C10 alkyl group, a linear or branched C3 to C10 alkenyl group, a linear or branched C3 to C10 alkynyl group, a C3 to C10 cyclic alkyl group, and a C5 to C10 aryl group, R3 and R4 are each independently selected from a linear or branched C1 to C10 alkylene group, a linear or branched C3 to C6 alkenylene group, a linear or branched C3 to C6 alkynylene group, a C3 to C10 cyclic alkylene group, a C3 to C10 hetero-cyclic alkylene group, a C5 to C10 arylene group, and a C5 to C10 hetero-arylene group;
• n in Formula A equals 1 or 2;
• m in Formula A equals 0, 1, 2, or 3;
• p and q in Formula E equal 1 or 2;
• and optionally wherein R3 in Formula D forms a ring selected from a four-membered, five-membered or six-membered ring with the two silicon atoms and at least one nitrogen atom;
• c. purging the ALD reactor with an inert gas;
• d. providing a nitrogen-containing source in the ALD reactor;
• e. purging the ALD reactor with an inert gas;
• and wherein steps b through e are repeated until a desired thickness of the film is obtained.

A method of forming a silicon-containing film onto at least a surface of a substrate using a deposition process selected from a plasma enhanced atomic layer (PEALD) process and a PECCVD process, the method comprising:

• a. providing a substrate in an ALD reactor;
• b. providing in the ALD reactor at least one organoaminosilane precursor comprising a compound represented by one of following Formulae A through E below:
• wherein R1 is selected from a linear or branched C1 to C10 alkyl group, a linear or branched C3 to C10 alkenyl group, a linear or branched C3 to C10 alkynyl group, a C3 to C10 cyclic alkyl group, and a C5 to C10 aryl group;
• wherein R2 is selected from hydrogen, a linear or branched C1 to C10 alkyl group, a linear or branched C3 to C10 alkenyl group, a linear or branched C3 to C10 alkynyl group, a C3 to C10 cyclic alkyl group, and a C5 to C10 aryl group, R3 and R4 are each independently selected from a linear or branched C1 to C10 alkylene group, a linear or branched C3 to C6 alkenylene group, a linear or branched C3 to C6 alkynylene group, a C3 to C10 cyclic alkylene group, a C3 to C10 hetero-cyclic alkylene group, a C5 to C10 arylene group, and a C5 to C10 hetero-arylene group;
• n in Formula A equals 1 or 2;
• m in Formula A equals 0, 1, 2, or 3;
• p and q in Formula E equal 1 or 2;
• and optionally wherein R3 in Formula D forms a ring selected from a four-membered, five-membered or six-membered ring with the two silicon atoms and at least one nitrogen atom;
• c. purging the ALD reactor with an inert gas;
• d. providing a plasma nitrogen-containing source in the ALD reactor;
• e. purging the ALD reactor with an inert gas;
• and wherein the steps b through e are repeated until a desired thickness of the silicon-containing film is obtained.

A method for forming a silicon oxide or a carbon doped silicon oxide film on a substrate comprising:

• reacting an oxygen-containing source with a precursor comprising at least one organoaminosilane precursor comprising a compound represented by one of following Formulae A through E below:
• wherein R1 is selected from a linear or branched C1 to C10 alkyl group, a linear or branched C3 to C10 alkenyl group, a linear or branched C3 to C10 alkynyl group, a C3 to C10 cyclic alkyl group, and a C5 to C10 aryl group;
• wherein R2 is selected from hydrogen, a linear or branched C1 to C10 alkyl group, a linear or branched C3 to C10 alkenyl group, a linear or branched C3 to C10 alkynyl group, a C3 to C10 cyclic alkyl group, and a C5 to C10 aryl group, R3 and R4 are each independently selected from a linear or branched C1 to C10 alkylene group, a linear or branched C3 to C6 alkenylene group, a linear or branched C3 to C6 alkynylene group, a C3 to C10 cyclic alkylene group, a C3 to C10 hetero-cyclic alkylene group, a C5 to C10 arylene group, and a C5 to C10 hetero-arylene group;
• n in Formula A equals 1 or 2;
• m in Formula A equals 0, 1, 2, or 3;
• p and q in Formula E equal 1 or 2;
• and optionally wherein R3 in Formula D forms a ring selected from a four-membered, five-membered or six-membered ring with the two silicon atoms and at least one nitrogen atom in a vapor deposition to form the film on the substrate.

A method for forming a silicon oxide or carbon doped silicon oxide film on a substrate comprising:

• forming via vapor deposition the film on the substrate from a composition comprising at least one organoaminosilane precursor comprising a compound represented by one of following Formulae A through E below:
• wherein R1 is selected from a linear or branched C1 to C10 alkyl group, a linear or branched C3 to C10 alkenyl group, a linear or branched C3 to C10 alkynyl group, a C3 to C10 cyclic alkyl group, and a C5 to C10 aryl group;
• wherein R2 is selected from hydrogen, a linear or branched C1 to C10 alkyl group, a linear or branched C3 to C10 alkenyl group, a linear or branched C3 to C10 alkynyl group, a C3 to C10 cyclic alkyl group, and a C5 to C10 aryl group, R3 and R4 are each independently selected from a linear or branched C1 to C10 alkylene group, a linear or branched C3 to C6 alkenylene group, a linear or branched C3 to C6 alkynylene group, a C3 to C10 cyclic alkylene group, a C3 to C10 hetero-cyclic alkylene group, a C5 to C10 arylene group, and a C5 to C10 hetero-arylene group;
• n in Formula A equals 1 or 2;
• m in Formula A equals 0, 1, 2, or 3;
• p and q in Formula E equal 1 or 2;
• and optionally wherein R3 in Formula D forms a ring selected from a four-membered, five-membered or six-membered ring with the two silicon atoms and at least one nitrogen atom, and at least one oxygen-containing source,
• wherein the vapor deposition is at least one selected from chemical vapor deposition, low pressure vapor deposition, plasma enhanced chemical vapor deposition, cyclic chemical vapor deposition, plasma enhanced cyclic chemical vapor deposition, atomic layer deposition, and plasma enhanced atomic layer deposition.

A method for forming a silicon oxide or carbon doped silicon oxide film on a substrate comprising:

• introducing at least one organoaminosilane precursor comprising a compound represented by one of following Formulae A through E below:
• wherein R1 is selected from a linear or branched C1 to C10 alkyl group, a linear or branched C3 to C10 alkenyl group, a linear or branched C3 to C10 alkynyl group, a C3 to C10 cyclic alkyl group, and a C5 to C10 aryl group;
• wherein R2 is selected from hydrogen, a linear or branched C1 to C10 alkyl group, a linear or branched C3 to C10 alkenyl group, a linear or branched C3 to C10 alkynyl group, a C3 to C10 cyclic alkyl group, and a C5 to C10 aryl group, R3 and R4 are each independently selected from a linear or branched C1 to C10 alkylene group, a linear or branched C3 to C6 alkenylene group, a linear or branched C3 to C6 alkynylene group, a C3 to C10 cyclic alkylene group, a C3 to C10 hetero-cyclic alkylene group, a C5 to C10 arylene group, and a C5 to C10 hetero-arylene group;
• n in Formula A equals 1 or 2;
• m in Formula A equals 0, 1, 2, or 3;
• p and q in Formula E equal 1 or 2;
• and optionally wherein R3 in Formula D forms a ring selected from a four-membered, five-membered or six-membered ring with the two silicon atoms and at least one nitrogen atom, into a reactor;
• introducing at least one oxygen-containing source into the reactor wherein the at least one oxygen-containing source reacts with the organoaminosilane to provide the film on the substrate.

A method for forming a silicon oxide or carbon doped silicon oxide film on a substrate wherein the film comprises a thickness, the method comprising:

• a. introducing at least one organoaminosilane precursor comprising a compound represented by one of following Formulae A through E below:
• wherein R1 is selected from a linear or branched C1 to C10 alkyl group, a linear or branched C3 to C10 alkenyl group, a linear or branched C3 to C10 alkynyl group, a C3 to C10 cyclic alkyl group, and a C5 to C10 aryl group;
• wherein R2 is selected from hydrogen, a linear or branched C1 to C10 alkyl group, a linear or branched C3 to C10 alkenyl group, a linear or branched C3 to C10 alkynyl group, a C3 to C10 cyclic alkyl group, and a C5 to C10 aryl group, R3 and R4 are each independently selected from a linear or branched C1 to C10 alkylene group, a linear or branched C3 to C6 alkenylene group, a linear or branched C3 to C6 alkynylene group, a C3 to C10 cyclic alkylene group, a C3 to C10 hetero-cyclic alkylene group, a C5 to C10 arylene group, and a C5 to C10 hetero-arylene group;
• n in Formula A equals 1 or 2;
• m in Formula A equals 0, 1, 2, or 3;
• p and q in Formula E equal 1 or 2;
• and optionally wherein R3 in Formula D forms a ring selected from a four-membered, five-membered or six-membered ring with the two silicon atoms and at least one nitrogen atom;
• b. chemisorbing the at least one organoaminosilane precursor onto the substrate;
• c. purging away the unreacted at least one organoaminosilane precursor using a purge gas;
• d. providing an oxygen-containing source to the organoaminosilane precursor onto the heated substrate to react with the sorbed at least one organoaminosilane precursor;
• and
• e. optionally purging away any unreacted oxygen-containing source.

A method for forming a silicon containing film using a deposition method selected from ALD or cyclic CVD that comprises the steps of:

• a. placing a substrates into a reactor which is heated to one or more temperatures ranging from about ambient temperature to about 700° C.;
• b. introducing at least one organoaminosilane precursor comprising a compound represented by one of following Formulae A through E below:
• wherein R1 is selected from a linear or branched C1 to C10 alkyl group, a linear or branched C3 to C10 alkenyl group, a linear or branched C3 to C10 alkynyl group, a C3 to C10 cyclic alkyl group, and a C5 to C10 aryl group;
• wherein R2 is selected from hydrogen, a linear or branched C1 to C10 alkyl group, a linear or branched C3 to C10 alkenyl group, a linear or branched C3 to C10 alkynyl group, a C3 to C10 cyclic alkyl group, and a C5 to C10 aryl group, R3 and R4 are each independently selected from a linear or branched C1 to C10 alkylene group, a linear or branched C3 to C6 alkenylene group, a linear or branched C3 to C6 alkynylene group, a C3 to C10 cyclic alkylene group, a C3 to C10 hetero-cyclic alkylene group, a C5 to C10 arylene group, and a C5 to C10 hetero-arylene group;
• n in Formula A equals 1 or 2;
• m in Formula A equals 0, 1, 2, or 3;
• p and q in Formula E equal 1 or 2;
• and optionally wherein R3 in Formula D forms a ring selected from a four-membered, five-membered or six-membered ring with the two silicon atoms and at least one nitrogen atom;
• c. optionally purging away the unreacted at least one organoaminosilane precursor using a purge gas;
• d. providing a reducing agent into the reactor to at least partially react with the absorbed organoaminosilane;
• e. optionally purging away any unreacted reducing agent wherein the steps b to e are repeated until a desired thickness is obtained.

A method of depositing an amorphous or a crystalline silicon film via a deposition process selected from an atomic layer deposition, a cyclic chemical vapor deposition process and a chemical vapor deposition, the method comprising the steps of:

• a. providing a substrate in a reactor;
• b. introducing into the reactor at least one organoaminosilane precursor comprising a compound represented by one of following Formulae A through E below:
• wherein R1 is selected from a linear or branched C1 to C10 alkyl group, a linear or branched C3 to C10 alkenyl group, a linear or branched C3 to C10 alkynyl group, a C3 to C10 cyclic alkyl group, and a C5 to C10 aryl group;
• wherein R2 is selected from hydrogen, a linear or branched C1 to C10 alkyl group, a linear or branched C3 to C10 alkenyl group, a linear or branched C3 to C10 alkynyl group, a C3 to C10 cyclic alkyl group, and a C5 to C10 aryl group, R3 and R4 are each independently selected from a linear or branched C1 to C10 alkylene group, a linear or branched C3 to C6 alkenylene group, a linear or branched C3 to C6 alkynylene group, a C3 to C10 cyclic alkylene group, a C3 to C10 hetero-cyclic alkylene group, a C5 to C10 arylene group, and a C5 to C10 hetero-arylene group;
• n in Formula A equals 1 or 2;
• m in Formula A equals 0, 1, 2, or 3;
• p and q in Formula E equal 1 or 2;
• and optionally wherein R3 in Formula D forms a ring selected from a four-membered, five-membered or six-membered ring with the two silicon atoms and at least one nitrogen atom;
• and
• c. purging the reactor with a purge gas or pumping the reactor;
• wherein the steps b through c are repeated until a desired thickness of film is obtained.

A method of forming a silicon-containing film onto at least a surface of a substrate using a deposition process selected from a plasma enhanced atomic layer (PEALD) process and a plasma enhanced cyclic chemical vapor deposition (PECCVD) process, the method comprising:

• a. providing a substrate in an ALD reactor;
• b. providing in the ALD reactor at least one organoaminosilane precursor comprising a compound represented by one of following Formulae A through E below:
• wherein R1 is selected from a linear or branched C1 to C10 alkyl group, a linear or branched C3 to C10 alkenyl group, a linear or branched C3 to C10 alkynyl group, a C3 to C10 cyclic alkyl group, and a C5 to C10 aryl group;
• wherein R2 is selected from hydrogen, a linear or branched C1 to C10 alkyl group, a linear or branched C3 to C10 alkenyl group, a linear or branched C3 to C10 alkynyl group, a C3 to C10 cyclic alkyl group, and a C5 to C10 aryl group, R3 and R4 are each independently selected from a linear or branched C1 to C10 alkylene group, a linear or branched C3 to C6 alkenylene group, a linear or branched C3 to C6 alkynylene group, a C3 to C10 cyclic alkylene group, a C3 to C10 hetero-cyclic alkylene group, a C5 to C10 arylene group, and a C5 to C10 hetero-arylene group;
• n in Formula A equals 1 or 2;
• m in Formula A equals 0, 1, 2, or 3;
• p and q in Formula E equal 1 or 2;
• and optionally wherein R3 in Formula D forms a ring selected from a four-membered, five-membered or six-membered ring with the two silicon atoms and at least one nitrogen atom;
• c. purging the ALD reactor with an inert gas;
• d. providing a plasma source in the ALD reactor;
• e. purging the ALD reactor with an inert gas;
• and wherein the steps b through e are repeated until a desired thickness of the silicon-containing film is obtained.

A vessel which is used to deliver a precursor for the deposition of a silicon-containing film, the vessel comprising:

• at least one organoaminosilane precursor comprising a compound represented by one of following Formulae A through E below:
• wherein R1 is selected from a linear or branched C1 to C10 alkyl group, a linear or branched C3 to C10 alkenyl group, a linear or branched C3 to C10 alkynyl group, a C3 to C10 cyclic alkyl group, and a C5 to C10 aryl group;
• wherein R2 is selected from hydrogen, a linear or branched C1 to C10 alkyl group, a linear or branched C3 to C10 alkenyl group, a linear or branched C3 to C10 alkynyl group, a C3 to C10 cyclic alkyl group, and a C5 to C10 aryl group, R3 and R4 are independently selected from a linear or branched C1 to C10 alkylene group, a linear or branched C3 to C6 alkenylene group, a linear or branched C3 to C6 alkynylene group, a C3 to C10 cyclic alkylene group, a C3 to C10 hetero-cyclic alkylene group, a C5 to C10 arylene group, and a C5 to C10 hetero-arylene group;
• n in Formula A equals 1 or 2;
• m in Formula A equals 0, 1, 2, or 3;
• p and q equal 1 or 2 in Formula E and optionally wherein R3 in Formula D forms a ring selected from a four-membered, five-membered or six-membered ring with the two silicon atoms and at least one nitrogen atom, and
• wherein the purity of the precursor is about 98% or greater.

A method for preparing an organoaminosilane comprising a compound represented by one of following Formulae A through E below:

• wherein R1 is selected from a linear or branched C1 to C10 alkyl group, a linear or branched C3 to C10 alkenyl group, a linear or branched C3 to C10 alkynyl group, a C3 to C10 cyclic alkyl group, and a C5 to C10 aryl group;
• wherein R2 is selected from hydrogen, a linear or branched C1 to C10 alkyl group, a linear or branched C3 to C10 alkenyl group, a linear or branched C3 to C10 alkynyl group, a C3 to C10 cyclic alkyl group, and a C5 to C10 aryl group, R3 and R4 are each independently selected from a linear or branched C1 to C10 alkylene group, a linear or branched C3 to C6 alkenylene group, a linear or branched C3 to C6 alkynylene group, a C3 to C10 cyclic alkylene group, a C3 to C10 hetero-cyclic alkylene group, a C5 to C10 arylene group, and a C5 to C10 hetero-arylene group;
• wherein n in Formula A equals 1 or 2;
• m in Formula A equals 0, 1, 2, or 3;
• p and q equal 1 or 2 in Formula E and optionally wherein R3 in Formula D forms a ring selected from a four-membered, five-membered or six-membered ring with the two silicon atoms and at least one nitrogen atom, the method comprising the steps of:
• reacting an amine having a formula selected from R1R2NH and R1NH2 wherein R1 in the amine is selected from a linear or branched C1 to C10 alkyl group, a linear or branched C3 to C10 alkenyl group, a linear or branched C3 to C10 alkynyl group, a C3 to C10 cyclic alkyl group, and a C5 to C10 aryl group;
• wherein R2 in the amine is selected from hydrogen, a linear or branched C1 to C10 alkyl group, a linear or branched C3 to C10 alkenyl group, a linear or branched C3 to C10 alkynyl group, a C3 to C10 cyclic alkyl group, and a C5 to C10 aryl group with a silicon source comprising at least one compound selected from the:
• wherein R3 and R4 in the silicon source are independently selected from a linear or branched C1 to C10 alkylene group, a linear or branched C3 to C6 alkenylene group, a linear or branched C3 to C6 alkynylene group, a C3 to C10 cyclic alkylene group, a C3 to C10 hetero-cyclic alkylene group, a C5 to C10 arylene group, and a C5 to C10 hetero-arylene group in the presence of a catalyst under reaction conditions sufficient for at least a portion of the silicon source and at least a portion of the amine to react and provide the organoaminosilane.