Insulating film material containing organic silane or organic siloxane compound, method for producing same, and semiconductor device
A material for insulating film suitable as an interlayer insulating material for a semiconductor device, from which an insulating film is formed by chemical vapor deposition, and an insulating film formed from such a material and a semiconductor device employing an insulating film, are provided. A material for insulating film comprising an organosilicon compound which is one of an organosilane compound in which a secondary hydrocarbon group and an alkenyl group, or an alkenyl group, is directly bonded to a silicon atom, or an organosiloxane compound in which a secondary hydrocarbon group and/or an alkenyl group is directly bonded to a silicon atom, represented by the formulae (1) to (4), from which an insulating film is formed by chemical vapor deposition of the organosilicon compound:
1. A method for producing the organosilane compound represented by the formula (2):
wherein
x represents an integer of 3 or above,
each of R 1 and R 2 represents a C 1-20 hydrocarbon group,
R 5 represents a C 1-20 hydrocarbon group or a hydrogen atom,
which comprises reacting a halogenated alkoxysilane compound substituted by a secondary hydrocarbon group, represented by the following formula (8) having such a structure that a secondary hydrocarbon group is directly bonded to a silicon atom:
wherein R 1 , R 2 , R 5 are as defined above,
R 4 represents a C 1-10 hydrocarbon group or hydrogen atom,
X represents a hydrogen atom, a chlorine atom, a bromine atom or an iodine atom; and
s represents an integer of from 0 to 2, with water in the presence of an acid or a base.
2. An insulating film formed by introducing at least one compound selected from the group consisting of compounds of formulae (1), (2) and (4) in a PECVD equipment followed by film formation with plasma:
an organosilane compound represented by the formula (1) having such a structure that a secondary hydrocarbon group and an alkenyl group are directly bonded to a silicon atom:
wherein each of R 1 and R 2 represents a C 1-20 hydrocarbon group, R 3 represents a C 1-20 hydrocarbon group having at least one alkenyl group, R 4 represents a C 1-10 hydrocarbon group or a hydrogen atom, m and n each represent 1;
an organosiloxane compound represented by the formula (2) having such a structure that a secondary hydrocarbon group is directly bonded to a silicon atom:
wherein R 1 and R 2 are as defined above, R 5 represents a C 1-20 hydrocarbon group or a hydrogen atom, and x represents an integer of 3 or above, wherein two substitutents bonded to the Si in formula (2) are different;
an organosiloxane compound represented by the formula (4) having such a structure that a vinyl group is directly bonded to a silicon atom:
wherein R 7 represents a vinyl group and x is as defined above, and,
wherein, the organosiloxane compound of formula (4) is selected from the group consisting of hexavinylcyclotrisiloxane, octavinylcyclotetrasiloxane, and decavinylcyclopentasiloxane.
3. The insulating film according to claim 2 , which has a cyclic siloxane structure of the organosiloxane compound of the formula (2) and/or (4).
4. The insulating film according to claim 2 , which is formed into a porous body by subjecting the insulating film to a heat treatment at a temperature of at least a temperature at which bond between a silicon atom and one of a secondary hydrocarbon group, an alkyl group, an alkenyl group and an aryl group is broken.
5. A semiconductor device comprising the insulating film according to claim 2 .
6. The insulating film according to claim 3 , which is formed into a porous body by subjecting the insulating film to a heat treatment at a temperature of at least a temperature at which bond between a silicon atom and one of a secondary hydrocarbon group, an alkyl group, an alkenyl group and an aryl group is broken.
7. A semiconductor device comprising the insulating film according to claim 3 .
8. A semiconductor device comprising the insulating film according to claim 4 .
9. A material for insulating film comprising an organosilicon compound, from which an insulating film is formed by chemical vapor deposition of the ogranosilicon compound, wherein the organosilicon compound is one of
1,3,5-triisopropyl-1,3,5-trivinylcyclotrisiloxane, 1,3,5,7-tetraisopropyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7,9-pentaisopropyl-1,3,5,7,9-pentavinylcyclopentasiloxane, 1,3,5-tri-sec-butyl-1,3,5-trivinylcyclotrisiloxane, 1,3,5,7-tetra-sec-butyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7,9-penta-sec-butyl-1,3,5,7,9-pentavinylcyclopentasiloxane, 1,3,5-triisopropyl-1,3,5-trimethylcyclotrisiloxane, 1,3,5,7-tetraisopropyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentaisopropyl-1,3,5,7,9-pentamethylcyclopentasiloxane, 1,3,5-triisopropyl-1,3,5-triethylcylotrisiloxane, 1,3,5,7-tetraisopropyl-1,3,5,7-tetraethylcyclotetrasiloxane, 1,3,5,7,9-pentaisopropyl-1,3,5,7,9-pentaethylcyclopentasiloxane,
1,3,5-tri-sec-butyl-1,3,5-trimethylcyclotrisiloxane, 1,3,5,7-tetra-sec-butyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-penta-sec-butyl-1,3,5,7,9-pentamethylcyclopentasiloxane, 1,3,5-tri-sec-butyl-1,3,5-triethylcyclotrisiloxane, 1,3,5,7-tetra-sec-butyl-1,3,5,7-tetraethylcyclotetrasiloxane and 1,3,5,7,9-penta-sec-butyl-1,3,5,7,9-pentaethylcyclopentasiloxane.
10. A material comprising an organosilicon compound, wherein the compounds are represented by the following formula (2):
an organosiloxane compound represented by the formula (2) having such a structure that a secondary hydrocarbon group is directly bonded to a silicon atom:
wherein each of R 1 and R 2 represents a C 1-20 hydrocarbon group, R 5 represents a C 1-20 hydrocarbon group or a hydrogen atom, and x represents an integer of 3 or above, wherein the two substituents bonded to the Si in formula (2) are different; and are selected from the group consisting of:
a hexaalkyltricyclotrisiloxane whose two substituents bonded to the Si atom are different alkyl groups,
a cyclotrisiloxane having, as a substituent, an alkenyl group or an aryl group bonded to the Si atom, and
a cyclosiloxane which is a four or more Si—O unit membered ring including a cyclotetrasiloxane.
11. A method for forming an insulating film, which is formed by introducing at least one compound of the formulae (2) and (4) in a PECVD equipment, followed by film formation with plasma;
an organosiloxane compound represented by the formula (2) having such a structure that a secondary hydrocarbon group is directly bonded to a silicon atom:
wherein each of R 1 and R 2 represents a C 1-20 hydrocarbon group, R 5 represents a C 1-20 hydrocarbon group or a hydrogen atom, and x represents an integer of 3 or above, wherein two substitutents bonded to the Si in formula (2) are different;
an organosiloxane compound represented by the formula (4) having such a structure that a vinyl group is directly bonded to a silicon atom:
wherein R 7 represents a vinyl group and x is as defined above, and,
wherein, the organosiloxane compound of formula (4) is selected from the group consisting of hexavinylcyclotrisiloxane, octavinylcyclotetrasiloxane, and decavinylcyclopentasiloxane.
12. A compound selected from a group consisting of:
(i) 1,3,5-triisopropyl-1,3,5-trivinylcyclotrisiloxane, 1,3,5,7-tetraisopropyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7,9-pentaisopropyl-1,3,5,7,9-pentavinylcyclopentasiloxane, 1,3,5-tri-sec-butyl-1,3,5-trivinylcyclotrisiloxane, 1,3,5,7-tetra-sec-butyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7,9-penta-sec-butyl-1,3,5,7,9-pentavinylcyclopentasiloxane, 1,3,5-triisopropyl-1,3,5-trimethylcyclotrisiloxane, 1,3,5,7-tetraisopropyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentaisopropyl-1,3,5,7,9-pentamethylcyclopentasiloxane, 1,3,5-triisopropyl-1,3,5-triethylcyclotrisiloxane, 1,3,5,7-tetraisopropyl-1,3,5,7-tetraethylcyclotetrasiloxane, 1,3,5,7,9-pentaisopropyl-1,3,5,7,9-pentaethylcyclopentasiloxane,
(ii) 1,3,5-tri-sec-butyl-1,3,5-trimethylcyclotrisiloxane, 1,3,5,7-tetra-sec-butyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-penta-sec-butyl-1,3,5,7,9-pentamethylcyclopentasiloxane, 1,3,5-tri-sec-butyl-1,3,5-triethylcyclotrisiloxane, 1,3,5,7-tetra-sec-butyl-1,3,5,7-tetraethylcyclotetrasiloxane and 1,3,5,7,9-penta-sec-butyl-1,3,5,7,9-pentaethylcyclopentasiloxane.
13. A method for forming an insulating film which is formed by introducing the compound of formula (9) in a PECVD equipment followed by film formation with plasma,
wherein R 1 and R 2 represents a C 1-20 hydrocarbon group, and R 4 represents a C 1-10 hydrocarbon group or a hydrogen atom.
14. An insulating film formed by introducing the compound of the formula (9) in a PECVD equipment followed by film formation with plasma,
wherein R 1 and R 2 represents a C 1-20 hydrocarbon group, and R 4 represents a C 1-10 hydrocarbon group or a hydrogen atom.
15. The method according to claim 13 , wherein the compound of the formula (9) is isopropylvinyldimethoxysilane, isopropylvinyldiethoxysilane, isopropylvinyl-di-tert-butoxysilane, sec-butylvinyldimethoxysilane, sec-butylvinyldiethoxysilane or sec-butylvinyl-di-tert-butoxysilane.
16. The insulating film according to claim 14 , wherein the compound of the formula (9) is isopropylvinyldimethoxysilane, isopropylvinyldiethoxysilane, isopropylvinyl-di-tert-butoxysilane, sec-butylvinyldimethoxysilane, sec-butylvinyldiethoxysilane or sec-butylvinyl-di-ter-butoxysilane.