Method of depositing electrically conductive, infra-red reflective, transparent coatings of stannic oxide

Claim 2

A process for making transparent films of stannic oxide on a heated substrate using a gaseous mixture initially containing (1) a first organotin fluorine-bearing compound which is free of any direct tin-fluorine bond (2) an oxidizable, tin compound, and (3) an oxidizing gas said process comprising the steps of: (a) converting said first organotin fluorine-bearing component of said gaseous mixture into a second organotin fluoride gaseous compound having a direct tin-to-fluorine bond; (b) immediately oxidizing, in immediate proximity to said substrate, the second fluoride compound to obtain a fluorine dopant in the gaseous mixture; (c) and forming a fluorine doped stannic oxide film, on said heated substrate, by simultaneous deposition thereon of said oxidizable tin compound and said fluorine dopant.

Claim 3

A process as defined in claim 1 wherein said first organotin fluorine-bearing gaseous compound is formed by heating a gas mixture containing (a) a gas selected from the group consisting of CF 3 I, CF 3 Br, and CF 3 SF 5 and homologous alkyl alpha-fluorinated compounds of said CF 3 I, CF 3 Br and CF 3 SF 5 , SF 5 Br, and SF 5 Cl; or mixtures thereof and (b) said oxidizable tin compound, and wherein (a) and (b) are substantially inert with respect to one another at temperatures below about 150° F.

Claim 4

A process as in claim 2 in which a mixture of (a) and (b) is stable at about 90° F., but wherein a reaction of (a) and (b) is thermally initiated and forms an organotin monofluoride vapor; said vapor forming a source for controlled addition of fluorine impurity to said film of stannic oxide.

Claim 5

A process as in claim 3 in which the fluorine dopant is formed by reacting trifluoroiodomethane and an organotin compound containing at least one tin-carbon bond per molecule.

Claim 6

A process as in claim 4 in which the fluorine dopant is forming a reacting trifluoroidomethane gas and tetramethyltin.

Claim 7

A process as in claim 5 wherein bromine is substituted for iodine.

Claim 8

A process as in claim 4 in which bromine is substituted for iodine.

Claim 9

A process as in claim 3 in which the fluorine dopant is formed by reacting sulfur chloride pentafluoride gas and an organo-tin compound containing at least one tin-carbon bond per molecule.

Claim 10

A process as in claim 8 in which the fluorine dopant is formed by reacting sulfur chloride pentafluoride gas and tetramethyltin.

Claim 11

A process as in claim 3 in which the fluorine dopant is formed by reacting trifluoromethyl sulfur pentafluoride gas and an organo-tin compound containing at least one tin-carbon bond per molecule.

Claim 12

A process as in claim 10 in which the fluorine dopant is formed by reacting trifluoromethyl sulfur pentafluoride gas and tetramethyltin.

Claim 13

A process as defined in claim 1 wherein said conversion of said first volatile organotin fluorine-bearing compound which is free of any direct tin-fluorine bond, into said organotin fluoride gaseous compound having a direct tin-fluorine bond, takes place on heating by said substrate.

Claim 14

A process as defined in claim 1 wherein said substrate to be coated faces downwardly and said gaseous mixture is directed upwardly toward said surface.

Claim 15

A process as in claim 1 in which tetramethyltin vapor, at concentrations up to about one percent, is the volatile oxidizable tin compound; oxygen gas, at partial pressures up to about one atmosphere, is the oxidizing gas; and said stannic oxide is deposited on a surface heated at about 500° C.

Claim 16

A process as in claim 1 in which said first fluorine-bearing compound is a volatile tin compound which decomposes on heating to form an organotin monofluoride vapor.

Claim 17

A process as in claim 9 in which said volatile tin compound is trimethyl trifluoromethyl tin.

Claim 18

A process as in claim 9 in which the volatile tin compound is trimethyl pentafluoroethyl tin.

Claim 19

A process as defined in claim 1 wherein the ratio of fluorine dopant and oxidizable tin compound are selected that the free .[.election.]. .Iadd.electron .Iaddend.concentration of the films is within about a range of from 10 20 cm -3 to 10 21 cm -3 .

Claim 20

A process as defined in claim 1 wherein fluorine dopant levels in said stannic oxide film are about 1% to 3% fluorine substituted for oxygen.

Claim 21

A process for depositing transparent, fluorine-doped, tin-oxide films, on a heated substrate said process comprising the steps of (1) supplying a continuous stream of a reagent gas to the vicinity of said substrate, said reagent gas containing reagents which are convertible to an organotin fluoride compound having a direct tin-fluorine bond in the immediate proximity of said heated substrate, and (2) depositing said organotin fluoride compound with an oxidizable tin component of said reagent gas at the surface of said substrate and thereby achieving a fluorine-doped, tin oxide coating upon said surface.

Claim 22

A process for depositing transparent, fluorine-doped, tin-oxide films, on a heated substrate said process comprising the steps of (1) supplying a continuous stream of a reagent gas to the vicinity of said substrate, said reagent gas containing reagents which are convertible to an organotin fluoride compound having a direct tin-fluorine bond in the immediate proximity of said heated substrate, and (2) depositing said organotin fluoride compound with an oxidizable tin component of said reagent gas at the surface of said substrate and thereby achieving a fluorine-doped, tin oxide coating upon said surface.

Claim 23

A process for depositing films of fluorine-doped stannic oxide on a heated substrate, said process comprising mixing (a) a gaseous, fluorine-bearing component, and (b) a gaseous, oxidizable tin-bearing component, and (c) a gaseous, oxygen-bearing component, and, optionally, (d) inert carrier gas these components being selected so that they remain in the gas phase at the temperature of mixing and wherein component (a) forms a compound with a tin-fluorine bond only as the gas mixture is heated to about the temperature of said heated substrate, said compound with a tin-fluorine bond and said oxygen bearing component then reacting to deposit said film of fluorine-doped stannic oxide on said heated substrate, and wherein said component (a) contains a volatile organotin fluorine-bearing compound which is free of any direct tine-fluorine bond but which rearranges on heating to form a direct tin-fluorine bond at temperatures high enough so that the newly-formed compound with a direct tin-fluorine bond remains in the vapor phase until it reacts along with the oxidizable tin compound to deposit a film of fluorine-doped tin oxide.

Claim 24

A process for depositing films of fluorine-doped stannic oxide on a heated substrate, said process comprising mixing (a) a gaseous, fluorine-bearing component, and (b) a gaseous, oxidizable tin-bearing component, and (c) a gaseous, oxygen-bearing component, and, optionally, (d) inert carrier gas these components being selected so that they remain in the gas phase at the temperature of mixing and wherein component (a) forms a compound with a tin-fluorine bond only as the gas mixture is heated to about the temperature of said heated substrate, said compound with a tin-fluorine bond and said oxygen bearing component then reacting to deposit said film of fluorine-doped stannic oxide on said heated substrate, and wherein said component (a) contains a volatile organotin fluorine-bearing compound which is free of any direct tine-fluorine bond but which rearranges on heating to form a direct tin-fluorine bond at temperatures high enough so that the newly-formed compound with a direct tin-fluorine bond remains in the vapor phase until it reacts along with the oxidizable tin compound to deposit a film of fluorine-doped tin oxide.

Claim 25

A process as in claim 21, in which component (a) contains a fluoroalkyl group or substituted fluoralkyl group, bonded to a tin atom.

Claim 26

A process as in claim 22 in which component (a) contains trimethyl trifluoromethyl tin.

Claim 27

A process as in claim 23 in which component (b) contains an organometallic tin compound.

Claim 28

A process as in claim 24 in which component (b) contains tetramethyl tin.

Claim 29

A process as in claim 22 in which component (a) contains trimethyl pentafluoroethyl tin.

Claim 30

A process as in claim 22 in which component (b) contains an organometallic tin compound.

Claim 31

A process as in claim 27 in which component (b) contains tetramethyl tin.

Claim 32

A process as in claim 21 in which component (b) contains a compound containing at least one carbon-tin bond.

Claim 33

A process as in claim 29 in which component (b) contains tetramethyl tin.

Claim 34

A process as in claim 29 in which component (b) contains dimethyl tin dichloride.

Claim 35

A process as in claim 21, in which component (b) contains an organometallic tin compound.

Claim 36

A process as in claim 32 in which component (b) contains tetramethyl tin.

Claim 37

A process for depositing films of fluorine-doped stannic oxide on a heated .Iadd.substrate .Iaddend.said process comprising mixing (a) a gaseous, fluorine-bearing component, and (b) a gaseous, oxidizable tin-bearing component, and (c) a gaseous, oxygen-bearing component, and, optionally, (d) inert carrier gas these components being selected so that they remain in the gas phase at the temperature of mixing and wherein component (a) and component (b) react to form a compound with a tin-fluorine bond only as the gas mixture is heated to about the temperature of said heated substrate, said compound with a tin-fluorine bond and said oxygen bearing component then reacting to deposit said film of fluorine-doped stannic oxide on said heated substrate in which component (a) contains reactive fluoroalkyl groups and in which component (b) contains an organometallic tin compound.

Claim 38

A process for depositing films of fluorine-doped stannic oxide on a heated .Iadd.substrate .Iaddend.said process comprising mixing (a) a gaseous, fluorine-bearing component, and (b) a gaseous, oxidizable tin-bearing component, and (c) a gaseous, oxygen-bearing component, and, optionally, (d) inert carrier gas these components being selected so that they remain in the gas phase at the temperature of mixing and wherein component (a) and component (b) react to form a compound with a tin-fluorine bond only as the gas mixture is heated to about the temperature of said heated substrate, said compound with a tin-fluorine bond and said oxygen bearing component then reacting to deposit said film of fluorine-doped stannic oxide on said heated substrate in which component (a) contains reactive fluoroalkyl groups and in which component (b) contains an organometallic tin compound.

Claim 39

A process as in claim 34 in which component (a) contains fluoroalkyl halides, or mixtures thereof.

Claim 40

A process as in claim 35 in which component (a) contains a gas selected from the group consisting of CF 3 Br, CF 3 I and homologous or substituted fluorinated compounds, or mixtures thereof.

Claim 41

A process as in claim 36 in which component (b) contains an organometallic tin compound.

Claim 42

A process as in claim 37 in which component (b) contains tetramethyltin.

Claim 43

A process as in claim 37 in which component (b) contains dimethyl tin dichloride.

Claim 44

A process as in claim 35 in which component (b) contains an organometallic tin compound.

Claim 45

A process as in claim 40 in which component (b) contains tetramethyl tin.

Claim 46

A process as in claim 34, in which component (a) contains reactive fluorosulfur groups.

Claim 47

A process as in claim 34 in which component (b) contains tetramethyl tin.

Claim 48

A process for depositing films of fluorine-doped stannic oxide on a heated substrate said process comprising mixing (a) a gaseous, fluorine-bearing component, and (b) a gaseous, oxidizable tin-bearing component, and (c) a gaseous, oxygen-bearing component, and, optionally, (d) inert carrier gas these components being selected so that they remain in the gas phase at the temperature of mixing and wherein component (a) and component (b) react to form a compound with a tin-fluorine bond only as the gas mixture is heated to about the temperature of said heated substrate, said compound with a tin-fluorine bond and said oxygen bearing component then reacting to deposit said film of fluorine-doped stannic oxide on said heated substrate; in which component (a) contains reactive fluorosulfur groups; and in which component (b) contains an organometallic tin compound.

Claim 49

A process for depositing films of fluorine-doped stannic oxide on a heated substrate said process comprising mixing (a) a gaseous, fluorine-bearing component, and (b) a gaseous, oxidizable tin-bearing component, and (c) a gaseous, oxygen-bearing component, and, optionally, (d) inert carrier gas these components being selected so that they remain in the gas phase at the temperature of mixing and wherein component (a) and component (b) react to form a compound with a tin-fluorine bond only as the gas mixture is heated to about the temperature of said heated substrate, said compound with a tin-fluorine bond and said oxygen bearing component then reacting to deposit said film of fluorine-doped stannic oxide on said heated substrate; in which component (a) contains reactive fluorosulfur groups; and in which component (b) contains an organometallic tin compound.

Claim 50

A process as in claim 44 in which component (b) contains tetramethyl tin.

Claim 51

A process for depositing films of fluorine-doped stannic oxide on a heated substrate said process comprising mixing (a) a gaseous, fluorine-bearing component, and (b) a gaseous, oxidizable tin-bearing component, and (c) a gaseous, oxygen-bearing component, and, optionally, (d) inert carrier gas these components being selected so that they remain in the gas phase at the temperature of mixing and wherein component (a) and component (b) react to form a compound with a tin-fluorine bond only as the gas mixture is heated to about the temperature of said heated substrate, said compound with a tin-fluorine bond and said oxygen bearing component then reacting to deposit said film of fluorine-doped stannic oxide on said heated substrate; in which component (a) contains reactive fluorosulfur groups selected from SF 5 Cl, SF 5 Br, or SF 5 CF 3 , and homologous or substituted compounds or mixtures thereof; and in which component (b) contains organometallic tin compound.

Claim 52

A process for depositing films of fluorine-doped stannic oxide on a heated substrate said process comprising mixing (a) a gaseous, fluorine-bearing component, and (b) a gaseous, oxidizable tin-bearing component, and (c) a gaseous, oxygen-bearing component, and, optionally, (d) inert carrier gas these components being selected so that they remain in the gas phase at the temperature of mixing and wherein component (a) and component (b) react to form a compound with a tin-fluorine bond only as the gas mixture is heated to about the temperature of said heated substrate, said compound with a tin-fluorine bond and said oxygen bearing component then reacting to deposit said film of fluorine-doped stannic oxide on said heated substrate; in which component (a) contains reactive fluorosulfur groups selected from SF 5 Cl, SF 5 Br, or SF 5 CF 3 , and homologous or substituted compounds or mixtures thereof; and in which component (b) contains organometallic tin compound.

Claim 53

A process as in claim 46 in which component (b) contains tetramethyl tin. .Iadd.48. A process as defined in claim 34 wherein the amounts of said fluorine bearing component and said oxidizable tin compound are selected so that said films have a free electron concentration within about the range of from 10 20 cm -3 to 10 21 cm -3 . .Iaddend. .Iadd.49. A process as defined in claim 34 wherein levels of said fluorine dopant in said stannic oxide film are about 1% to 3%

Claim 54

fluorine substituted for oxygen. .Iaddend. .Iadd.50. A process as in claim 48 in which component (a) contains fluoroalkyl halides, or mixtures thereof. .Iaddend. .Iadd.51. A process as in claim 48 in which component (a) contains a gas selected from the group consisting of CF 3 Br,CF 3 I and homologous or substituted fluorinated compounds or mixtures thereof. .Iaddend. .Iadd.52. A process as in claim 48 in which component (b) contains an organometallic tin compound. .Iaddend. .Iadd.53. A process as in claim 49 in which component (a) contains fluoroalkyl halides, or mixtures thereof. .Iaddend. .Iadd.54. A process as in claim 49 in which component (a) contains a gas selected from the group consisting of CF 3 Br,CF 3 I and homologous or substituted fluorinated compounds or mixtures thereof. .Iaddend. .Iadd.55. A process as in claim 49 in which component (b) contains an organometallic tin compound. .Iaddend.