US6846515B2 — Methods for using porogens and/or porogenated pre…

Claim 1

Independent Claim 181 words

A chemical vapor deposition method for producing a porous organosilica glass film represented by the formula Si v O w C x H y F z , where v+w+x+y+z=100%, v is from 10 to 35 atomic %, w is from 10 to 65 atomic %, x is from 5 to 30 atomic %, y is from 10 to 50 atomic % and z is from 0 to 15 atomic %, said method comprising: providing a substrate within a vacuum chamber; introducing into the vacuum chamber gaseous reagents including at least one precursor gas selected from the group consisting of an organosilane and an organosiloxane, and a porogen distinct from the at least one precursor gas; applying energy to the gaseous reagents in the vacuum chamber to induce reaction of the gaseous reagents to deposit a preliminary film on the substrate, wherein the preliminary film contains the porogen, and the preliminary film is deposited without added oxidants; and removing from the preliminary film substantially all of the porogen to provide the porous film with pores and a dielectric constant less than 2.6.

Claim 2

Dependent Claim 181 words

A chemical vapor deposition method for producing a porous organosilica glass film represented by the formula Si v O w C x H y F z , where v+w+x+y+z=100%, v is from 10 to 35 atomic %, w is from 10 to 65 atomic %, x is from 5 to 30 atomic %, y is from 10 to 50 atomic % and z is from 0 to 15 atomic %, said method comprising: providing a substrate within a vacuum chamber; introducing into the vacuum chamber gaseous reagents including at least one precursor gas selected from the group consisting of an organosilane and an organosiloxane, and a porogen distinct from the at least one precursor gas; applying energy to the gaseous reagents in the vacuum chamber to induce reaction of the gaseous reagents to deposit a preliminary film on the substrate, wherein the preliminary film contains the porogen, and the preliminary film is deposited without added oxidants; and removing from the preliminary film substantially all of the porogen to provide the porous film with pores and a dielectric constant less than 2.6.

Claim 3

Dependent Claim 14 words

The method of claim 1 , wherein the dielectric constant is less than 2.4.

Claim 4

Dependent Claim 14 words

The method of claim 1 , wherein the dielectric constant is less than 2.2.

Claim 5

Dependent Claim 14 words

The method of claim 1 , wherein the dielectric constant is less than 1.9.

Claim 6

Dependent Claim 43 words

The method of claim 1 , wherein v is from 20 to 30 atomic %, w is from 20 to 45 atomic %, x is from 5 to 20 atomic %, y is from 15 to 40 atomic % and z is 0.

Claim 7

Dependent Claim 14 words

The method of claim 1 , wherein z is 0.5 to 7 atomic %.

Claim 8

Dependent Claim 52 words

The method of claim 6 , wherein at least one fluorination agent selected from the group consisting of SiF 4 , NF 3 , F 2 and HF is used to introduce F to the porous film, and substantially all F in the porous film is bonded to Si in Si—F groups.

Claim 9

Dependent Claim 19 words

The method of claim 1 , wherein most of the hydrogen in the porous film is bonded to carbon.

Claim 10

Dependent Claim 17 words

The method of claim 1 , wherein the porous film has a density less than 1.5 g/ml.

Claim 11

Dependent Claim 17 words

The method of claim 1 , wherein the porous film has a density less than 1.25 g/ml.

Claim 12

Dependent Claim 21 words

The method of claim 1 , wherein the pores have an equivalent spherical diameter less than or equal to 5 nm.

Claim 13

Dependent Claim 21 words

The method of claim 1 , wherein the pores have an equivalent spherical diameter less than or equal to 2.5 nm.

Claim 14

Dependent Claim 12 words

The method of claim 1 , wherein the substrate is a semiconductor.

Claim 15

Dependent Claim 43 words

The method of claim 1 , wherein the porous film is an insulation layer, an interlayer dielectric layer, an intermetal dielectric layer, a capping layer, a chemical-mechanical planarization or etch stop layer, a barrier layer or an adhesion layer in an integrated circuit.

Claim 16

Dependent Claim 29 words

The method of claim 1 , wherein the gaseous reagents further include at least one porogenated precursor gas selected from the group consisting of an organosilane and an organosiloxane.

Claim 17

Dependent Claim 44 words

The method of claim 1 , wherein a Fourier transform infrared (FTIR) spectrum of the porous film is substantially identical to a reference FTIR of a reference film prepared by a process substantially identical to the method except for a lack of any porogen.

Claim 18

Dependent Claim 27 words

The method of claim 16 , wherein the porous film has a dielectric constant at least 0.3 less than a reference dielectric constant of the reference film.

Claim 19

Dependent Claim 25 words

The method of claim 16 , wherein the porous film has a density at least 10% less than a reference density of the reference film.

Claim 20

Dependent Claim 29 words

The method of claim 1 , wherein the porous film has an average weight loss of less than 1.0 wt %/hr isothermal at 425° C. under N 2 .

Claim 21

Dependent Claim 27 words

The method of claim 1 , wherein the porous film has an average weight loss of less than 1.0 wt %/hr isothermal at 425° C. under air.

Claim 22

Dependent Claim 71 words

The method of claim 1 , wherein the porous film is adapted to adhere to silicon, SiO 2 , Si 3 N 4 , OSG, FSG, silicon carbide, hydrogenated silicon carbide, silicon nitride, hydrogenated silicon nitride, silicon carbonitride, hydrogenated silicon carbonitride, boronitride, antireflective coatings, photoresists, organic polymers, porous organic and inorganic materials, copper, aluminum, TiN, Ti(C)N TaN, Ta(C)N, Ta, W and WN sufficiently to pass ASTM Standard D3359-95a tape pull test.

Claim 23

Dependent Claim 97 words

The method of claim 1 , wherein the at least one precursor gas is represented by the formula R 1 n (OR 2 )4−n Si where R 1 is independently H or a linear or branched, saturated, singly or multiply unsaturated, cyclic, partially or fully fluorinated C 1 to C 4 hydrocarbon, R 2 is independently a C 1 to C 6 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, and n is 1 to 3, with the proviso that there is not more than one Si—H per Si atom.

Claim 24

Dependent Claim 113 words

The method of claim 1 , wherein the at least one precursor gas is represented by the formula R 1 n (OR 2 ) 3−n Si—O—SiR 3 m (OR 4 ) 3−m where R 1 and R 3 are independently H or C 1 to C 4 linear or branched, saturated, singly or multiply unsaturated, cyclic, partially or fully fluorinated hydrocarbon; R 2 and R 4 are independently C 1 to C 6 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, n is 1 to 3 and m is 1 to 3, with the proviso that there is not more than one Si—H per Si atom.

Claim 25

Dependent Claim 113 words

The method of claim 1 , wherein the at least one precursor gas is represented by the formula R 1 n (OR 2 ) 3−n Si—SiR 3 m (OR 4 ) 3−m where R 1 and R 3 are independently H or C 1 to C 4 linear or branched, saturated, singly or multiply unsaturated, cyclic, partially or fully fluorinated hydrocarbon; R 2 and R 4 are independently C 1 to C 6 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, n is 1 to 3 and m is 1 to 3, with the proviso that there is not more than one Si—H per Si atom.

Claim 26

Dependent Claim 98 words

The method of claim 1 , wherein the at least one precursor gas is represented by the formula R 1 n (O(O)CR 2 ) 4−n Si where R 1 is independently H or a linear or branched, saturated, singly or multiply unsaturated, cyclic, partially or fully fluorinated C 1 to C 4 hydrocarbon, R 2 is independently H, C 1 to C 6 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, and n is 1 to 3, with the proviso that there is not more than one Si—H per Si atom.

Claim 27

Dependent Claim 114 words

The method of claim 1 , wherein the at least one precursor gas is represented by the formula R 1 n (O(O)CR 2 ) 3−n Si—O—SiR 3 m (O(O)CR 4 ) 3−m where R 1 and R 3 are independently H or C 1 to C 4 linear or branched, saturated, singly or multiply unsaturated, cyclic, partially or fully fluorinated hydrocarbon; R 2 and R 4 are independently H, C 1 to C 6 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, n is 1 to 3 and m is 1 to 3, with the proviso that there is not more than one Si—H per Si atom.

Claim 28

Dependent Claim 114 words

The method of claim 1 , wherein the at least one precursor gas is represented by the formula R 1 n (O(O)CR 2 ) 3−n Si—SiR 3 m (O(O)CR 4 ) 3−m where R 1 and R 3 are independently H or C 1 to C 4 linear or branched, saturated, singly or multiply unsaturated, cyclic, partially or fully fluorinated hydrocarbon; R 2 and R 4 are independently H, C 1 to C 6 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, n is 1 to 3 and m is 1 to 3, with the proviso that there is not more than one Si—H per Si atom.

Claim 29

Dependent Claim 136 words

The method of claim 1 , wherein the at least one precursor gas is represented by the formula R 1 n (O(O)CR 2 ) 3−n Si—O—SiR 3 m (OR 4 ) 3−m where R 1 and R 3 are independently H or C 1 to C 4 linear or branched, saturated, singly or multiply unsaturated, cyclic, partially or fully fluorinated hydrocarbon; R 2 is independently H, C 1 to C 6 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon; and R 4 is independently C 1 to C 6 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, n is 1 to 3 and m is 1 to 3, with the proviso that there is not more than one Si—H per Si atom.

Claim 30

Dependent Claim 136 words

The method of claim 1 , wherein the at least one precursor gas is represented by the formula R 1 n (O(O)CR 2 ) 3−n Si—SiR 3 m (OR 4 ) 3−m where R 1 and R 3 are independently H or C 1 to C 4 linear or branched, saturated, singly or multiply unsaturated, cyclic, partially or fully fluorinated hydrocarbon; R 2 is independently H, C 1 to C 6 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon; and R 4 is independently C 1 to C 6 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, n is 1 to 3 and m is 1 to 3, with the proviso that there is not more than one Si—H per Si atom.

Claim 31

Dependent Claim 130 words

The method of claim 1 , wherein the at least one precursor gas is represented by the formula R 1 n (OR 2 ) p (O(O)CR 3 ) 4−(n+p) Si where R 1 is independently H or C 1 to C 4 linear or branched, saturated, singly or multiply unsaturated, cyclic, partially or fully fluorinated hydrocarbon; R 2 is independently C 1 to C 6 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, R 3 is independently H, C 1 to C 6 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, n is 1 to 3 and p is 1 to 3, with the proviso that there is not more than one Si—H per Si atom.

Claim 32

Dependent Claim 159 words

The method of claim 1 , wherein the at least one precursor gas is represented by the formula R 1 n (OR 2 ) p (O(O)CR 4 ) 3−n−p Si—O—SiR 3 m (O(O)CR 5 ) q (OR 6 ) 3−m−q where R 1 and R 3 are independently H or C 1 to C 4 linear or branched, saturated, singly or multiply unsaturated, cyclic, partially or fully fluorinated hydrocarbon; R 2 and R 6 are independently C 1 to C 6 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, R 4 and R 5 are independently H, C 1 to C 6 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, n is 1 to 3, m is 1 to 3, q is 1 to 3 and p is 1 to 3, with the proviso that there is not more than one Si—H per Si atom.

Claim 33

Dependent Claim 158 words

The method of claim 1 , wherein the at least one precursor gas is represented by the formula R 1 n (OR 2) p (O(O)CR 4 ) 3−n−p Si—SiR 3 m (O(O)CR 5 ) q (OR 6 ) 3−m−q where R 1 and R 3 are independently H or C 1 to C 4 linear or branched, saturated, singly or multiply unsaturated, cyclic, partially or fully fluorinated hydrocarbon; R 2 and R 6 are independently C 1 to C 6 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, R 4 and R 5 are independently H, C 1 to C 6 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, n is 1 to 3, m is 1 to 3, q is 1 to 3 and p is 1 to 3, with the proviso that there is not more than one Si—H per Si atom.

Claim 34

Dependent Claim 81 words

The method of claim 1 , wherein the at least one precursor gas is represented by cyclic siloxanes of the formula (OSiR 1 R 3 ) x , where R 1 and R 3 can be independently H, C 1 to C 4 , linear or branched, saturated, singly or multiply unsaturated, cyclic, partially or fully fluorinated, and x may be any integer from 2 to 8, with the proviso that there is not more than one Si—H per Si atom.

Claim 35

Dependent Claim 38 words

The method of claim 1 , wherein the at least one precursor gas is a member selected from the group consisting of diethoxymethylsilane, dimethoxymethylsilane, di-isopropoxymethylsilane, di-t-butoxymethylsilane, methyltriethoxysilane, methyltrimethoxysilane, methyltri-isopropoxysilane, methyltri-t-butoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-isopropoxysilane, dimethyidi-t-butoxysilane, 1,3,5,7-tetramethylcyclotatrasiloxane, octamethyl-cyclotetrasiloxane and tetraethoxysilane.

Claim 36

Dependent Claim 15 words

The method of claim 1 , wherein a mixture of organosilanes or organosiloxanes are used.

Claim 37

Dependent Claim 52 words

The method of claim 1 , wherein said at least one precursor gas is a mixture of a first organosilicon precursor with two or fewer Si—O bonds with a second organosilicon precursor with three or more Si—O bonds, and the mixture is provided to tailor a chemical composition of the porous film.

Claim 38

Dependent Claim 67 words

The method of claim 1 , wherein the porogen is at least one cyclic hydrocarbon having a cyclic structure and the formula C n H 2n , where n is 4 to 14, a number of carbons in the cyclic structure is between 4 and 10, and the at least one cyclic hydrocarbon optionally contains a plurality of simple or branched hydrocarbons substituted onto the cyclic structure.

Claim 39

Dependent Claim 95 words

The method of claim 1 , wherein the porogen is at least one singly or multiply unsaturated cyclic hydrocarbon having a cyclic structure and the formula C n H 2n−2x , where x is a number of unsaturated sites, n is 4 to 14, a number of carbons in the cyclic structure is between 4 and 10, and the at least one singly or multiply unsaturated cyclic hydrocarbon optionally contains a plurality of simple or branched hydrocarbons substituents substituted onto the cyclic structure, and contains unsaturation inside endocyclic or on one of the hydrocarbon substituents.

Claim 40

Dependent Claim 67 words

The method of claim 1 , wherein the porogen is at least one bicyclic hydrocarbon having a bicyclic structure and the formula C n H 2n−2 , where n is 4 to 14, a number of carbons in the bicyclic structure is from 4 to 12, and the at least one bicyclic hydrocarbon optionally contains a plurality of simple or branched hydrocarbons substituted onto the bicyclic structure.

Claim 41

Dependent Claim 91 words

The method of claim 1 , wherein the porogen is at least one multiply unsaturated bicyclic hydrocarbon having a bicyclic structure and the formula C n H 2n−(2+2x) , where x is a number of unsaturated sites, n is 4 to 14, a number of carbons in the bicyclic structure is from 4 to 12, and the at least one multiply unsaturated bicyclic hydrocarbon optionally contains a plurality of simple or branched hydrocarbons substituents substituted onto the bicyclic structure, and contains unsaturation inside endocyclic or on one of the hydrocarbon substituents.

Claim 42

Dependent Claim 67 words

The method of claim 1 , wherein the porogen is at least one tricyclic hydrocarbon having a tricyclic structure and the formula C n H 2n−4 , where n is 4 to 14, a number of carbons in the tricyclic structure is from 4 to 12, and the at least one tricyclic hydrocarbon optionally contains a plurality of simple or branched hydrocarbons substituted onto the cyclic structure.

Claim 43

Dependent Claim 30 words

The process of claim 1 , wherein the porogen is a member selected from the group consisting of alpha-terpinene, limonene, cyclohexane, 1,2,4-trimethylcyclohexane, 1,5-dimethyl-1,5-cyclooctadiene, camphene, adamantane, 1,3-butadiene, substituted dienes and decahydronaphthelene.

Claim 44

Dependent Claim 26 words

The method of claim 1 , wherein the at least one precursor and at least one porogen are introduced into the vacuum chamber from distinct sources.

Claim 45

Dependent Claim 26 words

The method of claim 1 , wherein the at least one precursor and at least one porogen are introduced into the vacuum chamber as a mixture.

Claim 46

Dependent Claim 32 words

The method of claim 1 , wherein the energy provides the gaseous reagents in a plasma, pulsed plasma, helicon plasma, high density plasma, inductively coupled plasma, capacitively coupled plasma or remote plasma.

Claim 47

Dependent Claim 24 words

The method of claim 45 , wherein a secondary rf frequency source is used to modify plasma characteristics at a surface of the substrate.

Claim 48

Dependent Claim 23 words

The method of claim 1 , wherein the gaseous reagents are carried in the vacuum chamber by a carrier gas containing carbon dioxide.

Claim 49

Dependent Claim 32 words

The method of claim 1 , wherein the porogen removing is accomplished by at least one member selected from the group consisting of thermal annealing, plasma treating, photocuring, chemical treating and microwaving.

Claim 50

Dependent Claim 30 words

The method of claim 1 , wherein the porogen removing is accomplished by thermal treatment between 250 and 450° C. in a nitrogen atmosphere with less than 50 ppm oxygen.

Claim 51

Dependent Claim 53 words

The method of claim 1 , wherein the porogen removing is accomplished by at least one member selected from the group consisting of thermal annealing, plasma treating, photocuring and microwaving in an inert atmosphere comprising at least one inert gas, wherein a concentration of oxidizing gases is less than 50 parts per million.

Claim 52

Dependent Claim 52 words

The method of claim 1 , wherein the porogen removing is accomplished by at least one member selected from the group consisting of thermal annealing, plasma treating, photocuring and microwaving in an oxidizing atmosphere comprising at least one gas, wherein a concentration of oxidizing gases is greater than 50 parts per million.

Claim 53

Dependent Claim 220 words

A chemical vapor deposition method for producing an organosilica glass film represented by the formula Si v O w C x H y F z , where v+w+x+y+z=100%, v is from 10 to 35 atomic %, w is from 10 to 65 atomic %, x is from 5 to 30 atomic %, y is from 10 to 50 atomic % and z is from 0 to 15 atomic %, said method comprising: providing a substrate within a vacuum chamber; introducing into the vacuum chamber gaseous reagents including at least one precursor gas selected from the group consisting of a organosilane and an organosiloxane, wherein the at least one precursor gas contains at least one porogen bonded thereto; applying energy to the gaseous reagents in the vacuum chamber to induce reaction of the gaseous reagents to deposit a preliminary film on the substrate, wherein the preliminary film contains the at least one porogen and a first quantity of methyl groups bonded to silicon atoms; and removing from the preliminary film at least a portion of the at least one porogen to provide the porous film with pores and a dielectric constant less than 2.6, wherein the porous film contains a second quantity of methyl groups bonded to silicon atoms, and the second quantity is more than 50% of the first quantity.

Claim 54

Dependent Claim 220 words

A chemical vapor deposition method for producing an organosilica glass film represented by the formula Si v O w C x H y F z , where v+w+x+y+z=100%, v is from 10 to 35 atomic %, w is from 10 to 65 atomic %, x is from 5 to 30 atomic %, y is from 10 to 50 atomic % and z is from 0 to 15 atomic %, said method comprising: providing a substrate within a vacuum chamber; introducing into the vacuum chamber gaseous reagents including at least one precursor gas selected from the group consisting of a organosilane and an organosiloxane, wherein the at least one precursor gas contains at least one porogen bonded thereto; applying energy to the gaseous reagents in the vacuum chamber to induce reaction of the gaseous reagents to deposit a preliminary film on the substrate, wherein the preliminary film contains the at least one porogen and a first quantity of methyl groups bonded to silicon atoms; and removing from the preliminary film at least a portion of the at least one porogen to provide the porous film with pores and a dielectric constant less than 2.6, wherein the porous film contains a second quantity of methyl groups bonded to silicon atoms, and the second quantity is more than 50% of the first quantity.

Claim 55

Dependent Claim 29 words

The method of claim 52 , wherein the gaseous reagents further include at least one porogen-free precursor gas selected from the group consisting of an organosilane and an organosiloxane.

Claim 56

Dependent Claim 19 words

The method of claim 52 , wherein the removing step removes from the film substantially all of the porogen.

Claim 57

Dependent Claim 23 words

The method of claim 52 , wherein the removing step leaves a methyl group attached to Si where the porogen was previously attached.

Claim 58

Dependent Claim 14 words

The method of claim 52 , wherein the dielectric constant is less than 2.4.

Claim 59

Dependent Claim 14 words

The method of claim 52 , wherein the dielectric constant is less than 2.2.

Claim 60

Dependent Claim 14 words

The method of claim 52 , wherein the dielectric constant is less than 1.9.

Claim 61

Dependent Claim 43 words

The method of claim 52 , wherein v is from 20 to 30 atomic %, w is from 20 to 45 atomic %, x is from 5 to 20 atomic %, y is from 15 to 40 atomic % and z is 0.

Claim 62

Dependent Claim 14 words

The method of claim 52 , wherein z is 0.5 to 7 atomic %.

Claim 63

Dependent Claim 59 words

The method of claim 60 , wherein at least one fluorination agent selected from the group consisting of SiF 4 , NF 3 , F 2 COF 2 , CO 2 F 2 and HF is used to introduce F to the porous film, and substantially all F in the porous film is bonded to Si in Si—F groups.

Claim 64

Dependent Claim 19 words

The method of claim 52 , wherein most of the hydrogen in the porous film is bonded to carbon.

Claim 65

Dependent Claim 17 words

The method of claim 52 , wherein the porous film has a density less than 1.5 g/ml.

Claim 66

Dependent Claim 17 words

The method of claim 52 , wherein the porous film has a density less than 1.25 g/ml.

Claim 67

Dependent Claim 21 words

The method of claim 52 , wherein the pores have an equivalent spherical diameter less than or equal to 5 nm.

Claim 68

Dependent Claim 21 words

The method of claim 52 , wherein the pores have an equivalent spherical diameter less than or equal to 2.5 nm.

Claim 69

Dependent Claim 12 words

The method of claim 52 , wherein the substrate is a semiconductor.

Claim 70

Dependent Claim 43 words

The method of claim 52 , wherein the porous film is an insulation layer, an interlayer dielectric layer, an intermetal dielectric layer, a capping layer, a chemical-mechanical planarization or etch stop layer, a barrier layer or an adhesion layer in an integrated circuit.

Claim 71

Dependent Claim 42 words

The method of claim 52 , wherein a Fourier transform infrared (FTIR) spectrum of the porous film is identical to a reference FTIR of a reference film prepared by a process identical to the method except for a lack of any porogen.

Claim 72

Dependent Claim 27 words

The method of claim 69 , wherein the porous film has a dielectric constant at least 0.3 less than a reference dielectric constant of the reference film.

Claim 73

Dependent Claim 25 words

The method of claim 69 , wherein the porous film has a density at least 10% less than a reference density of the reference film.

Claim 74

Dependent Claim 29 words

The method of claim 52 , wherein the porous film has an average weight loss of less than 1.0 wt %/hr isothermal at 425° C. under N 2 .

Claim 75

Dependent Claim 27 words

The method of claim 52 , wherein the porous film has an average weight loss of less than 1.0 wt %/hr isothermal at 425° C. under air.

Claim 76

Dependent Claim 119 words

The method of claim 52 , wherein the at least one precursor gas is represented by the formula R 1 n (OR 2 ) 4−n Si where R 1 is independently H or a linear or branched, saturated, singly or multiply unsaturated, cyclic, partially or fully fluorinated C 1 to C 12 hydrocarbon, R 2 is independently a C 1 to C 12 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, and n is 1 to 3, with the provisos that there is not more than one Si—H per Si atom and that one of R 1 and R 2 is substituted with a C 3 or larger hydrocarbon as the porogen.

Claim 77

Dependent Claim 133 words

The method of claim 52 , wherein the at least one precursor gas is represented by the formula R 1 n (OR 2) 4−n Si—O—SiR 3 m (OR 4 ) 4−m where R 1 and R 3 are independently H or C 1 to C 12 linear or branched, saturated, singly or multiply unsaturated, cyclic, partially or fully fluorinated hydrocarbon; R 2 and R 4 are independently C 1 to C 12 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, n is 1 to 3 and m is 1 to 3, with the provisos that there is not more than one Si—H per Si atom and that one of R 1 and R 3 is substituted with a C 3 or larger hydrocarbon as the porogen.

Claim 78

Dependent Claim 134 words

The method of claim 52 , wherein the at least one precursor gas is represented by the formula R 1 n (OR 2 ) 4−n Si—SiR 3 m (OR 4 ) 4−m where R 1 and R 3 are independently H or C 1 to C 12 linear or branched, saturated, singly or multiply unsaturated, cyclic, partially or fully fluorinated hydrocarbon; R 2 and R 4 are independently C 1 to C 12 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, n is 1 to 3 and m is 1 to 3, with the provisos that there is not more than one Si—H per Si atom and that one of R 1 and R 3 is substituted with a C 3 or larger hydrocarbon as the porogen.

Claim 79

Dependent Claim 119 words

The method of claim 52 , wherein the at least one precursor gas is represented by the formula R 1 n (O(O)CR 2 ) 4−n Si where R 1 is independently H or a linear or branched, saturated, singly or multiply unsaturated, cyclic, partially or fully fluorinated C 1 to C 12 hydrocarbon, R 2 is independently a C 1 to C 12 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, and n is 1 to 3, with the provisos that there is not more than one Si—H per Si atom and that one of R 1 and R 3 is substituted with a C 3 or larger hydrocarbon as the porogen.

Claim 80

Dependent Claim 134 words

The method of claim 52 , wherein the at least one precursor gas is represented by the formula R 1 n (O(O)CR 2 ) 4−n Si—O—SiR 3 m (O(O)CR 4 ) 4−m where R 1 and R 3 are independently H or C 1 to C 12 linear or branched, saturated, singly or multiply unsaturated, cyclic, partially or fully fluorinated hydrocarbon; R 2 and R 4 are independently C 1 to C 12 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, n is 1 to 3 and m is 1 to 3, with the provisos that there is not more than one Si—H per Si atom and that one of R 1 and R 3 is substituted with a C 3 or larger hydrocarbon as the porogen.

Claim 81

Dependent Claim 134 words

The method of claim 52 , wherein the at least one precursor gas is represented by the formula R 1 n (O(O)CR 2 ) 4−n Si—SiR 3 m (O(O)CR 4 ) 4−m where R 1 and R 3 are independently H or C 1 to C 12 linear or branched, saturated, singly or multiply unsaturated, cyclic, partially or fully fluorinated hydrocarbon; R 2 and R 4 are independently C 1 to C 12 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, n is 1 to 3 and m is 1 to 3, with the provisos that there is not more than one Si—H per Si atom and that one of R 1 and R 3 is substituted with a C 3 or larger hydrocarbon as the porogen.

Claim 82

Dependent Claim 134 words

The method of claim 52 , wherein the at least one precursor gas is represented by the formula R 1 n (O(O)CR 2 ) 4−n Si—O—SiR 3 m (OR 4 ) 4−m where R 1 and R 3 are independently H or C 1 to C 12 linear or branched, saturated, singly or multiply unsaturated, cyclic, partially or fully fluorinated hydrocarbon; R 2 and R 4 are independently C 1 to C 12 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, n is 1 to 3 and m is 1 to 3, with the provisos that there is not more than one Si—H per Si atom and that one of R 1 and R 3 is substituted with a C 3 or larger hydrocarbon as the porogen.

Claim 83

Dependent Claim 134 words

The method of claim 52 , wherein the at least one precursor gas is represented by the formula R 1 n (O(O)CR 2 ) 4−n Si—SiR 3 m (OR 4 ) 4−m where R 1 and R 3 are independently H or C 1 to C 12 linear or branched, saturated, singly or multiply unsaturated, cyclic, partially or fully fluorinated hydrocarbon; R 2 and R 4 are independently C 1 to C 12 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, n is 1 to 3 and m is 1 to 3, with the provisos that there is not more than one Si—H per Si atom and that one of R 1 and R 3 is substituted with a C 3 or larger hydrocarbon as the porogen.

Claim 84

Dependent Claim 129 words

The method of claim 52 , wherein the at least one precursor gas is represented by the formula R 1 n (OR 2 ) p (O(O)CR 3 ) 4−(n+p) Si where R 1 is independently H or C 1 to C 12 linear or branched, saturated, singly or multiply unsaturated, cyclic, partially or fully fluorinated hydrocarbon; R 2 and R 3 are independently C 1 to C 12 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, n is 1 to 3 and p is 1 to 3, with the provisos that there is not more than one Si—H per Si atom and that one of R 1 and R 3 is substituted with a C 3 or larger hydrocarbon as the porogen.

Claim 85

Dependent Claim 158 words

The method of claim 52 , wherein the at least one precursor gas is represented by the formula R 1 n (OR 2 ) p (O(O)CR 4 ) 4−n−p Si—O—SiR 3 m (O(O)CR 5 ) q (OR 6 ) 4−m−q where R 1 and R 3 are independently H or C 1 to C 12 linear or branched, saturated, singly or multiply unsaturated, cyclic, partially or fully fluorinated hydrocarbon; R 2 , R 4 , R 5 and R 6 are independently C 1 to C 12 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, n is 1 to 3, m is 1 to 3, q is 1 to 3 and p is 1 to 3, with the provisos that there is not more than one Si—H per Si atom and that one of R 1 and R 3 is substituted with a C 3 or larger hydrocarbon as the porogen.

Claim 86

Dependent Claim 158 words

The method of claim 52 , wherein the at least one precursor gas is represented by the formula R 1 n (OR 2 ) p (O(O)CR 4 ) 4−n−p Si—SiR 3 m (O(O)CR 5 ) q (OR 6 ) 4−m−q where R 1 and R 3 are independently H or C 1 to C 12 linear or branched, saturated, singly or multiply unsaturated, cyclic, partially or fully fluorinated hydrocarbon; R 2 , R 4 , R 5 and R 6 are independently C 1 to C 12 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, n is 1 to 3, m is 1 to 3, q is 1 to 3 and p is 1 to 3, with the provisos that there is not more than one Si—H per Si atom and that one of R 1 and R 3 is substituted with a C 3 or larger hydrocarbon as the porogen.

Claim 87

Dependent Claim 171 words

The method of claim 52 , wherein the at least one precursor gas is represented by the formula R 1 n (OR 2 ) 4−n Si—R 5 —SiR 3 m (OR 4 ) 4−m where R 1 and R 3 are independently H or C 1 to C 12 linear or branched, saturated, singly or multiply unsaturated, cyclic, partially or fully fluorinated hydrocarbon; R 2 and R 4 are independently C 1 to C 12 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, R 5 is independently C 1 to C 12 , linear or branched, saturated, singly or multiply unsaturated, cyclic, partially or fully fluorinated hydrocarbon, and bridges the two Si atoms, n is 1 to 3 and m is 1 to 3, with the provisos that there is not more than one Si—H per Si atom and that at least one of R 1 , R 3 and R 5 is substituted with a C 3 or larger hydrocarbon as the porogen.

Claim 88

Dependent Claim 80 words

The method of claim 52 , wherein the at least one precursor gas is represented by cyclic siloxanes of the formula (OSiR 1 R 3 ) x , where R 1 and R 3 are independently H or C 1 to C 12 linear or branched, saturated, singly or multiply unsaturated, cyclic, partially or fully fluorinated hydrocarbon, and x is any integer from 2 to 8, with the proviso that there is not more than one Si—H per Si atom.

Claim 89

Dependent Claim 30 words

The method of claim 52 , wherein the at least one precursor gas is a member selected from the group consisting of 1-neohexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1-neopentyl-1,3,5,7-tetramethylcyclotetrasiloxane, neopentyldiethoxysilane, neohexyldiethoxysilane, neohexyltriethoxysilane, neopentyltriethoxysilane and neopentyl-di-t-butoxysilane.

Claim 90

Dependent Claim 15 words

The method of claim 52 , wherein a mixture of organosilanes or organosiloxanes are used.

Claim 91

Dependent Claim 51 words

The method of claim 52 , wherein said at least one an precursor gas is a mixture of an organosilicon precursor with two or fewer Si—O bonds with an organosilicon precursor with three or more Si—O bonds, and the mixture is provided to tailor a chemical composition of the porous film.

Claim 92

Dependent Claim 24 words

The method of claim 52 , wherein the porogen is at least one member selected from the group consisting of tert-butyl, neopentyl and neohexyl.

Claim 93

Dependent Claim 32 words

The method of claim 52 , wherein the energy provides the gaseous reagents in a plasma, pulsed plasma, helicon plasma, high density plasma, inductively coupled plasma, capacitively coupled plasma or remote plasma.

Claim 94

Dependent Claim 24 words

The method of claim 91 , wherein a secondary rf frequency source is used to modify plasma characteristics at a surface of the substrate.

Claim 95

Dependent Claim 23 words

The method of claim 52 , wherein the gaseous reagents are carried in the vacuum chamber by a carrier gas containing carbon dioxide.

Claim 96

Dependent Claim 32 words

The method of claim 52 , wherein the porogen removing is accomplished by at least one member selected from the group consisting of thermal annealing, plasma treating, photocuring, chemical treating and microwaving.

Claim 97

Dependent Claim 25 words

The method of claim 52 , wherein the porogen removing is accomplished by thermal treatment in a nitrogen atmosphere with less than 50 ppm oxygen.

Claim 98

Dependent Claim 53 words

The method of claim 52 , wherein the porogen removing is accomplished by at least one member selected from the group consisting of thermal annealing, plasma treating, photocuring and microwaving in an inert atmosphere comprising at least one inert gas, wherein the concentration of oxidizing gases is less than 50 parts per million.

Claim 99

Dependent Claim 52 words

The method of claim 52 , wherein the porogen removing is accomplished by at least one member selected from the group consisting of thermal annealing, plasma treating, photocuring and microwaving in an oxidizing atmosphere comprising at least one gas, wherein the concentration of oxidizing gases is greater than 50 parts per million.

Claim 100

Dependent Claim 32 words

The method of claim 52 , wherein process conditions are altered during said method to provide the porous film with at least one of a porosity gradient and layers of differing porosities.

Claim 101

Dependent Claim 32 words

The method of claim 1 , wherein process conditions are altered during said method to provide the porous film with at least one of a porosity gradient and layers of differing porosities.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	2008-01-25	2008-07-26	2009-01-25	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	2012-01-25	2012-07-26	2013-01-25	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	2016-01-25	2016-07-26	2017-01-25	$7700.00	Window Closed / Lapsed

Methods for using porogens and/or porogenated precursors to provide porous organosilica glass films with low dielectric constants

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