CA2069521A1 - Process for coating a substrate with a silica precursor - Google Patents

Process for coating a substrate with a silica precursor

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Publication number
CA2069521A1
CA2069521A1 CA002069521A CA2069521A CA2069521A1 CA 2069521 A1 CA2069521 A1 CA 2069521A1 CA 002069521 A CA002069521 A CA 002069521A CA 2069521 A CA2069521 A CA 2069521A CA 2069521 A1 CA2069521 A1 CA 2069521A1
Authority
CA
Canada
Prior art keywords
coating
silica
substrate
silica precursor
environment
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
CA002069521A
Other languages
French (fr)
Inventor
David S. Ballance
Robert C. Camilletti
Theresa E. Gentle
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Silicones Corp
Original Assignee
David S. Ballance
Robert C. Camilletti
Theresa E. Gentle
Dow Corning Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by David S. Ballance, Robert C. Camilletti, Theresa E. Gentle, Dow Corning Corporation filed Critical David S. Ballance
Publication of CA2069521A1 publication Critical patent/CA2069521A1/en
Abandoned legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/314—Inorganic layers
    • H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
    • H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
    • C04B41/5035—Silica
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1212—Zeolites, glasses
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/122—Inorganic polymers, e.g. silanes, polysilazanes, polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1275—Process of deposition of the inorganic material performed under inert atmosphere
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1279—Process of deposition of the inorganic material performed under reactive atmosphere, e.g. oxidising or reducing atmospheres
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02126—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02126—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
    • H01L21/02134—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC the material comprising hydrogen silsesquioxane, e.g. HSQ
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
    • H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
    • H01L21/02214—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen
    • H01L21/02216—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen the compound being a molecule comprising at least one silicon-oxygen bond and the compound having hydrogen or an organic group attached to the silicon or oxygen, e.g. a siloxane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
    • H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
    • H01L21/02337—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to a gas or vapour
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/312—Organic layers, e.g. photoresist
    • H01L21/3121—Layers comprising organo-silicon compounds
    • H01L21/3122—Layers comprising organo-silicon compounds layers comprising polysiloxane compounds
    • H01L21/3124—Layers comprising organo-silicon compounds layers comprising polysiloxane compounds layers comprising hydrogen silsesquioxane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/324—Thermal treatment for modifying the properties of semiconductor bodies, e.g. annealing, sintering

Abstract

PROCESS FOR COATING A SUBSTRATE WITH A SILICA PRECURSOR

ABSTRACT

The present invention relates to a method of forming a silica coating on a substrate. The method comprises coating a substrate with a silica precursor having a melting point between about 50 and about 450°C. The coating is heated to a temperature above its melting point in an inert environment to allow the coating to melt and flow.
The melted coating is then heated in an environment which facilitates conversion to silica for a time sufficient to convert it to silica.

Description

- 2~32~

PROGESS FOR COATING A SUBSTRATE WITH A SILICA PRECURSOR

The present invention relates to a method of forming a silica coating on a substrate. The method comprises applying a silica precursor coating to the substrate and heating it to a temperature above its melting point in an inert environment. The melted coating is then heated in an environment which facilitates conversion to silica for a time sufficient to convert it to silica.
The use of ceramic coatings for their protective and dielectric effect is known in the electronics art. For instance, Haluska et al. in U.S. Patent No. 4,756,977 disclose silica coatings produced by applying a solution of hydrogen silsesquioxane resin to an electronic device and then ceramifying by heating in air at temperatures of 200-1000C. The ceramic coatings produced thereby have many desirable characteristics such as microhardness, moisture resistance, high adhesion, etc.
The present inventors have now discovered that sequential heating first in an inert environment and then in a reactive environment which faci~itates conversion to silica produces coatings having improved planarity and reduced cracks in comparison to conventionally formed silica coatings.
The present invention relates to a method of forming a silica coating on a substrate. The method comprises forming a preceramic coating comprising a silica precursor having a melting point between about 50 and about 450C. on the substrate. The preceramic coating is then heated above the melting point of the silica precursor in an inert environment for a time sufficient to allow the coating . ., : ~.

- ~: . "

- - . : , , , : ,.

~&~

to flow yet insufficient to allow the coating to ceramify.
The melted coating is then heated in an environment which facilitates conversion to silica for a time sufficient to convert the melted preceramic coating to silica.
The present invention is based on the discovery that silica precursors having melting~points between about 50 and about 450C. will reproducibly melt and ~low under an inert environment prior to ceramification. This discovery is used in this invention to cause the silica precursor to controllably melt and evenly flow across the surface of a substrate prior to its conversion to silica. This process is particularly advantageous over the prior art which suggest heating the coating in an oxidizing environment since such a process results in either no or vary erratic flow due to the simultaneous initiation of melting along with oxidation and cross-linking in the coating. Similarly, this process is also advantageous over the prior art which completes the conversion of the precursor to silica entirely in an inert environment since high temperatures are often necessary in such a process. The sequential use of an inert environment and an oxidative enviromnent as described herein thus allows for desirable flow characteristics and low temperature ceramification.
The coatings taught herein are useful as protective and dielectric layers on a variety of substrates. For instance, the planarizing and dielectric properties of these coatings make them ideally suited for use on electronic devices as interlevel dielectrics in multilayered devices.
Similarly, the high density and low defect rate of these coatings makes them useful for protecting electronic devices from environmental contaminants such as moisture and ionic impurities.

-: :.~ . :

~0~9~21 Despite the specific applications set forth above, however~ it is contemplated that the coatings taught herein can be used on any substrate requiring such a coating.
Moreover, the choice of such substrates and devices is limited only by the need for thermal and chemical stability of the substrate at the temperature and in the environment utilized in the present invention.
As used in the present invention, the expression "silica" refers to those pyrolyzed materials containing Si-O-Si bonds which may or may not be fully free of residual Si-C, Si-H, Si-OH and/or Si-OC but which are otherwise ceramic in character; the expression "planarizing coating"
refers to a coating which is less irregular than the surface prior to application of the coating; and the expressions "electronic device" or "electronic circuit" include, but are not limited to silicon based devices, gallium arsenide based devices, f~cal plane arrays, opto-electronic devices, photovoltaic cells and optical devices. Specific examples o~
such devices include transistor-like devices, capacitor and capacitor~ e devices, multilayer devices, 3-D devices, silicon on insulator devices, super lattice devices and the ?
like~
The silica coatings taught herein are produced by a process which comprises applying a preceramic coating comprising a silica precursor having a melting point between about S0 and about 450C. to the substrate. The preceramic coating is then heated above the melting point of the silica precursor in an inert environment for a tiloe su~ficient to allow the coating to flow but at a temperature and for a time insufficient to cause the coating to ceramify. The melted coating is then heated in an environment which facilitates conversion to silica for a time and at a temperature . . , ~ . .
: ~' : ,' ;. ', .' ' : ' .. . , , ,., : ~ '.
'' I ' ' ,' . .. ,' ' ;',~ ' . ~ ' , ,; `~

2 ~ ~ 3 3 2 ~

~i sufficient to convert the melted preceramic coating to silica.
The silica precursor materials which are useful herein are any which have a melting point between about 50 and about 450C. under an inert atmosphere and which can be converted to silica at temperatures less than about 1000C.
Examples of such materials include hydridosilane resins, hydrolyzed or partially hydrolyzed RXSi(OR)4 x' wherein R is independently selected from the group consisting of alkyl, aryl and unsaturated hydrocarbons and x is 0-2 and conventional spin-on-glasses such as those produced by Allied Chemical and marketed under the trade name AccuglassTM.
Preferred herein, however, is the use of the hydridosilane resins with the use of hydrogen silsesquioxane resin being particularly preferred.
The term hydrogen silsesquioxane resin or H-resin is used in this application to describe various hydridosilane resins of the formula HSi(OH) (OR)yO /2' in which each R is independently an organic group or a substituted organic group which, when bonded to silicon through the oxygen atom, forms a hydrolyzable substituent, x - 0-2, y = 0-2, z = 1-3, x + y ~ z - 3. Though not represented by this structure, these resins may contain a small number of silicon atoms which have either O or 2 hydrogen atoms attached thereto due to various factors involved in their formation or handling.
The above hydridosilane resins are generally produced by a process comprising the hydrolysis and condensation of silanes of the formula HSiX3, wherein X is a hydrolyzable group. These reactions may result in a fully condensed (~SiO3/2)n resin or the hydrolysis and/or condensation may be interrupted at an intermediate point such that partial hydrolyzates (containing Si-OR groups) and/or ;l' : .
- .
, . .
,.

20~2~

partial condensates (containing SiOH groups) are formed.
Such methods include that of Collins et al. in U.S. Patent No. 3 615 272. It is described therein that a nearly fully condensed H-resin twhich may contain up to 100-300 ppm silanol) can be produced by hydrolyzing trichlorosilane in a benzenesulfonic acid hydrate hydrolysis medium and then washing the resultant resin with water or aqueous sulfuric acid. Bank et al. in U.S. Patent No. 5 010 159 teach an alternative method comprising hydrolyzing hydridosilanes in an arylsulfonic acid hydrate hydrolysis medium to form a resin which is then contacted with a neutralizing agent. A
preferred embodiment of this latter process uses an acid to silane ratio of about 6/1.
Other resins such as those described by ~rye et al. in U.S. Patent No. 4 999 397 those produced by hydrolyzing an alkoxy or acyloxy silane in an acidic alcoholic hydrolysis medium those described in Kokai Patent Nos. 59-178749 60-86017 and 63-107122 or any other equivalent hydridosilane are also functional herein.
The desired silica precursor is first applied to the substrate to form a preceramic coating. Although any conventional technique înay be used it is particularly preferred to coat the substrate with a solution comprising a solvent and the silica precursor. Removai of the solvent by evaporation or a similar technique yields the preceramic coating. Other equivalent methods however are also contemplated herein. In an alternative embodiment of this invention, the silica precursor may be applied to the substrate in an inert environment to prevent early cross-linking of the polymer.
If the above solution method is used the silica precursor is first dissolved in a solvent. ~arious facilitating measures such as stirring and/or heating may be . : ., . . . ................ . . .
' ' - . ' ' , ~ .

2~S~52~

used to aid in the dissolution. Solvents which may be used include any which will dissolve the silica precursor to form a solution or suspension without affecting the coating.
These solvents can include, for example, alcohols such as ethyl or isopropyl, aromatic hydrocarbons such as benzene or toluene, alkanes such as n-heptane or dodecane, ketones, esters, glycol ethers or cyclic dimethylpolysiloxanes, in an amount sufficient to dissolve the above materials to low solids. Generally, enough of the above solvent is used to form a 0.1-50 weight percent solution.
If a hydridosilane resin is used in the coating solution, a platinum, rhodium or copper catalyst may also be added herein to increase the rate and extent of conversion to silica. Generally, any platinum, rhodium or copper compound or complex which can be solubilized wi]l be functional. For instance, a composition such as platinum acetylacetonate, rhodium catalyst RhCl3[S(CH2CH2CH2C~3)2]3, obtained from Dow Corning Corporation, Midland, Michigan, U.S.A., or cupric naphthenate are all within the scope of this invention.
These catalysts are generally added in an amount of between about 5 to lO00 ppm platinum, rhodiuln or copper based on the weight of hydridosilane.
If the above solution method is used, the coating solution is applied by techniques such as spin coating, dip coating, spray coating or flow coating. Evaporation of the solvent by any suitable means such as sitnple air drying by exposure to an ambient enviromnent or by the application of a vacuum or mild heat yields the desired preceramic coating.
As noted, an alternative embodiment of this invention comprises coating the substrate with the silica precursor in an inert environment to prevent early cross-linking of the polymer.

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The resultant preceramic coating is then heated above the melting point of the silica precursor in an inert environment for a time su~ficient to a]low the coating to flow but at a temperature and for a time insufficien~ to cause the coating to ceramify. The expression "melting point" is used herein to describe that temperature at which an amorphous solid is converted to a viscoelastic resin which will flow across the surface of the substrate. This process allows the silica precursor to evenly distribute on the surface of the substrate and planarize any uneven topography.
In addition, it allows the surface of the substrate to be sealed and assists in healing and/or preventing pinholes, cracks or other surface anomalies.
Generally, any inert environment which does not react with the coating can be used during this heating step. For instance, environments comprising argon, helium or nitrogen are all functional herein. Similarly, the use of vacuum will also provide the necessary environment for flow.
The temperature used during this step should be one which melts the silica precursor without initiating ceramification during the required flow time. Temperatures in the range of about 50 to about 450C. are generally sufficient. If hydrogen silsesquioxane resin is used as the silica precursor, temperatures of about 150 to abo~t 400C.
are generally functional.
The heating time necessary cluring this step should be one which allows the resin to flow and yet does not initiate ceramification at the chosen temperature.
Generally, this time can vary from a fraction of a second to several hours. For practical reasons, it is preferred that the time be less than about 1 hour and more preferred that the time be less than about 15 minutes.

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After the resin has melted and flowed, the environment is altered to facilitate conversion of the melted silica precursor to silica. Reactive environments such as those comprising air, 2' oxygen plasma, ammonia, amines, etc. may be used. It is especially prefe~red, however, to heat under a wet ammonia atmosphere to hydrolyze the Si-H
bonds and then under a dry ammonia atmosphere to effect removal of any remaining Si-OH groups.
The melted preceramic coating is subjected to such reactive environments at a temperature sufficient for ceramification. Generally, this temperature is about 20 to about 1000C. depending on the reactive atmosphere.
Preferred temperatures are in the range of about 50 to about 800C. Higher temperatures usually result in quicker and more complete ceramification, but said temperatures also may have detrimental effects on various temperature sensitive substrates. For temperature sensitive substrates, temperatures in the range of about 100 to about 400C. are often preferred. The preceramic coatings are usually subjected to these temperatures for a time sufficient to ceramify the coating, generally up to about 6 hours, with a range of up to about 2 hours being preferred.
Any source of heat such as a hot plate, a convection oven, rapid thermal processing or radiant or microwave energy can be used during either pyrolysis step.
By the above methods a silica planari~ing coating is produced on the substrate. The coating smooths the -irregular surfaces of various substrates and has excellent adhesion. This coating may also be covered by other coatings such as further SiO2 coatings, SiO2/modifying ceramic oxide layers, silicon containing coatings, silicon carbon containing coatings, silicon nitrogen containing coatings, silicon nitrogen carbon containing coatings and/or diamond ,.

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, : ~ :

2 ~ 2 1 like carbon coatings. Such multilayer coatings are taught in U.S. Patent No. 4,973,526.
Example 1 Patterned silicon wafers were coated with 6 mL of a 25 weight percent solution of hydrogen silsesquioxane resin (as in Example 1) in methyl isobutyl ketone and spun at 2000 rpm for 10 seconds in air. The coated wafers were then placed in a nitrogen environment and heated on a hot plate at 150C. for 1 minute, 200C. for 1 minute and 300C. for 1 minute. The wafers with the melted coating were then heated by rapid thermal processing in oxygen at 400C. for 10 minutes.
The resultant coating was a completely planar silica coating as shown in Figure 1. By contrast, Figure 2 shows a cross-section of a commercially available device coated with AccuglassTM spin-on glass and processed according to the instructions provided in the product literature. It is evident that the process of the present invention provides a more planar surface.

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Claims

Claim:
1. A method of forming a silica coating on a substrate comprising forming a coating on a substrate where the coating comprises a silica precursor having a melting point between about 50 and about 450°C.; heating the coating to a temperature above the melting point of the silica precursor in an inert environment for a time sufficient to allow the coating to flow; and after the coating has flowed, exposing the coating to a reactive environment for a time and at a temperature sufficient to convert the coating to silica.
CA002069521A 1991-06-05 1992-05-26 Process for coating a substrate with a silica precursor Abandoned CA2069521A1 (en)

Applications Claiming Priority (2)

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US710,627 1991-06-05
US07/710,627 US5145723A (en) 1991-06-05 1991-06-05 Process for coating a substrate with silica

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DE69232607T2 (en) 2002-12-05
JPH05146755A (en) 1993-06-15
US5145723A (en) 1992-09-08
EP0517475A2 (en) 1992-12-09
ES2176184T3 (en) 2002-12-01
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JP3317998B2 (en) 2002-08-26

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