CN101031519A - Method of forming a coating on a substrate, and a coating thus formed - Google Patents
Method of forming a coating on a substrate, and a coating thus formed Download PDFInfo
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- CN101031519A CN101031519A CN 200580033058 CN200580033058A CN101031519A CN 101031519 A CN101031519 A CN 101031519A CN 200580033058 CN200580033058 CN 200580033058 CN 200580033058 A CN200580033058 A CN 200580033058A CN 101031519 A CN101031519 A CN 101031519A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
- C03C17/3435—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a nitride, oxynitride, boronitride or carbonitride
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/291—Oxides or nitrides or carbides, e.g. ceramics, glass
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/58—Structural electrical arrangements for semiconductor devices not otherwise provided for, e.g. in combination with batteries
- H01L23/585—Structural electrical arrangements for semiconductor devices not otherwise provided for, e.g. in combination with batteries comprising conductive layers or plates or strips or rods or rings
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/425—Coatings comprising at least one inhomogeneous layer consisting of a porous layer
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/44—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the composition of the continuous phase
- C03C2217/45—Inorganic continuous phases
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
- C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
- C03C2217/475—Inorganic materials
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/113—Deposition methods from solutions or suspensions by sol-gel processes
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/116—Deposition methods from solutions or suspensions by spin-coating, centrifugation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/30—Technical effects
- H01L2924/301—Electrical effects
- H01L2924/3011—Impedance
Abstract
The present invention relates to a method of forming a protective coating on an electronic substrate such as an IC, the protective coating having a good mechanical, chemical and physical resistance and providing a suitable non-transparency. According to the present invention a porous matrix (preferably comprising Ti02) is formed, which is filled with a filler component which can absorb or scatter light, such as TiN particles. After a curing step, a reinforcing precursor component is added. In preparing the protective coating a predetermined amount of the filler component is used in order to obtain at least 40 vol.% of the filler component in the protective coating eventually obtained, based on the porous matrix obtained.
Description
Technical field
The present invention relates on substrate to form the method for coating, described method comprises the step that forms vesicular structure and with the step of partially filled at least this vesicular structure of second solution.
The invention still further relates to the composition that is used to form vesicular structure.The invention further relates to that arrangement can be by the substrate of the coating that obtains according to the inventive method on it.
Background technology
From EP-A 560485, can learn such method and such device.Known coating is the ceramic coating that is filled with siloxane polymer, and for example described ceramic coating is by silicon dioxide compound (SiO for example
2-reticulation) constitutes.Be placed on hydrogen silsesquioxane resin in the oxygen plasma reactor and be heated 250 ℃, used oxygen plasma treatment simultaneously 3 hours, thereby obtain silicon dioxide compound.As pointed such in related application EP-A 775680 (the 4th hurdle, 48-51 is capable), it is that 200nm and porosity are 25 to 30% coating that this technology has produced thickness.Subsequently, the solution with polydimethylsiloxane (PDMS) is penetrated in the vesicular structure.These devices are placed under the vacuum of 84.66kPa, place under atmospheric pressure afterwards, place 3 circulations like this, more excessive fluid is wiped.
The shortcoming of this currently known methods is that it is quite clumsy and technology consuming time that vesicular structure utilizes low pressure and atmospheric circulation to permeate.Such technology may cause yield losses.Table 1 in EP-A 560485 also causes the worry of people to this yield loss, because 250 hours test shows that the productive rate that only just makes functional device under the specific concentrations of second solution is 100%.In view of coating is what to intend as the supercoat of electron device especially unicircuit, so yield loss is very large problem.This supercoat uses as preparation technology's final step, and the yield loss in this step means the lossy of value.
Therefore, it is simpler thereby improving one's methods of better yield arranged to the purpose of this invention is to provide a kind of operation.
Summary of the invention
The realization of this purpose is that vesicular structure obtains by following process: the coating composition that comprises matrix precursor component and particulate filler component is provided, this coating composition is coated on the substrate, and said composition is solidified.
Method of the present invention provides the vesicular structure based on particulate filler component.As in the situation of art methods, matrix precursor is used as sealing agent and tackiness agent simultaneously, rather than is used as vesicular structure itself.Therefore, can select matrix precursor freer and more largo.Its main character is: be fully bonded on the particulate filler, and can fully form reticulation.
Method of the present invention can also be selected porosity, thereby also allows to exist bigger hole.Required porosity can be set according to the mean sizes and the distribution of sizes of particulate filler component.Big mean sizes and narrower distribution of sizes can obtain high porosity.The porosity that obtains is 40 to 90 volume %.Be at least tens microns even may be about several microns supercoat that for thickness mean particle size can suitably be selected in 1 to 3 micron scope; If this coating is a functional layer, then mean particle size can be chosen as littler.
The improvement vesicular structure of Huo Deing allows it to adopt simpler fill process in the methods of the invention.Adopt coating process to replace employed plasma process in the prior art in the methods of the invention.This coating process is simpler and more direct, and seldom depends on the control to pressure.
The gained coating has at least two favourable textural properties; At first, it not necessarily needs to carry out completely filled, but can stay a part of hole.Secondly, its end face is closed, thereby can apply another layer on the top of vesicular structure.And the suitable selection of second solution can make to the bonding of substrate and to bonding all optimizations of arbitrary layer on the vesicular structure top.
In suitable embodiment, matrix precursor component comprises the hydrolyzable compound with melts combine.Typical hydrolysable group comprises but is not limited in the compound: alkoxyl group, such as methoxyl group, oxyethyl group, propoxy-, butoxy and hexyloxy; Acyloxy is such as acetoxyl group; By other organic group of oxygen and melts combine, such as Acetyl Acetone thing or amino.These compounds itself are known in sol-gel processing and the MOCVD technology.Use ethylate, isopropoxide and propyl carbinol salt compound, obtained good result.Suitable metal comprises aluminium, titanium, zirconium, silicon, niobium, tantalum etc.The quantity of hydrolysable group is generally 4, but can use hydrolysable group to be less than 4 component, as long as the reticulation of gained is enough strong.The reticulation of gained for example is the reticulation of oxide compound or the reticulation of carbide.
Show, if matrix precursor component comprises the compound that is selected from the group of being made up of following compounds, then can obtain favourable result: tetraethyl orthotitanate (TEOTi), phthalandione tetra isopropyl ester, ethanol niobium (V), ethanol tantalum (V), propyl carbinol tantalum, zirconium-n-butylate or these mixture.Then the gained vesicular structure comprises and being selected from by TiO
2, Nb
2O
5, Ta
2O
5, ZrO
2Or compound in the group of their mixture composition and other particulate filler component.Also more preferably described compound is TiO
2, and filler component mainly comprises TiN.
Particulate filler component preferably includes crystalline particle, and they can have shape arbitrarily.Amorphous granular can other or alternative use.Example comprises aluminum oxide, zirconium white, silicon oxide, titanium oxide, titanium nitride, titanium carbide, zinc oxide, silicon carbide.These particles not necessarily need only to be made of a kind of material.Use TiN and TiO
2Particle and the mixture that uses them have obtained good result.For thick nontransparent coating, these results are optimized, and also can use other material.Preferably can chemistry or the material of physical bond on the matrix precursor component.In this example, described combination to small part is achieved by hydrogen bond.
In order to obtain the vesicular structure that filler component is at least 40 volume %, only is to use the filler component of predetermined amount.Use diameter when the particle of 1 to 3 micrometer range, the filler component of this amount can produce suitable vesicular structure.Yet the relative volume of filler component shows as the viscosity of the mean size that depends on filler component, employed concrete material and matrix precursor component.The volume % of filler component also preferably is higher than 40 volume %, at least 60 volume % more preferably, and for some application, even 80 volume % most preferably.The coating of thickness is fitted in this high filler component volume production intercrescence.Thickness is suitable for as safety coatings greater than 2 microns coating, and preferred this coating has the thickness at 2 to 10 micrometer ranges.
Can in every way coating composition be coated on the substrate, as long as on described substrate, form suitable coating compounds.Usually coating composition applies by dip-coating, spin coating or spraying, and these technology all are known in the art.The coating of second solution also can use the known technology that comprises above-mentioned dip-coating, spin coating or spraying to carry out.The optional curing of the curing of coating composition and second solution uses UV-light or elevated temperature (preferably at 100-450 ℃) to carry out usually, but also can use other suitable method.
In another embodiment, second solution comprises the component that has with the hydrolysable group of melts combine, and these constitutional changes reticulate thing.The result produces the inorganic coating with specific microstructure.The second suitable solution comprises the compound that for example is selected from by in tetraethyl orthotitanate (TEOTi), phthalandione four isopropyl esters, ethanol niobium (V), ethanol tantalum (V), propyl carbinol tantalum, zirconium-n-butylate or these the mixture.
This coating is suitable as protectiveness that unicircuit uses ' safety ' coating very much, and can be used to suppress not authorized people near this unicircuit.For this reason, coating must provide the protection of chemistry, optics and physics.Use can absorption, the filler component of scattering or reflect visible light, is achieved the optics protection.In addition, TiN and TiO
2Granular mixture can adequately protect and avoid the injury of UV, IR and electron radiation.By selecting substrate material and being chosen in this case second solution, make the chemoproection optimization.Can use the substrate material of monoaluminum phosphate or based on the substrate material of tetraethoxy ortho-silicate (TEOS).The non-porous coating of protectiveness itself with monoaluminum phosphate substrate material and filler component can be from US-A 6,198, learns in 155.Use the substrate material of Ti-base, obtained excellent result.The hardness of coating can be carried out physical protection.In addition, can be below coating and/or above arrangement can measure the transmitter of impedance.So just can produce identify code uncertain and that physics is expressed, this technology itself can be learned from WO-A 2003/046986.
Yet coating of the present invention is not to be limited to this safety coatings.In an alternative embodiment, this coating is as the supercoat in the packing of semiconductor compound.Normally, adopt mold compound (molding compound) as supercoat.The example of knowing is by the epoxy resin of glass or glass particles filling.Yet supercoat needs to restrain oneself the required comparatively high temps of pb-free solder, and need be than the suitable thermal expansivity of packing composition.
Method of the present invention is very suitable for providing this supercoat.Then, preferably, organic polymer especially mold compound is selected as second solution of partially filled at least vesicular structure.Example comprises epoxy resin, polyimide, polystyrene, polyterephthalate and known other material in the field of transfer molding and injection molding technique.This mold compound can but be not necessarily to need with particles filled.If it is with particles filled, then these particles can suitably have to liken to and are the littler mean diameter of the filler component of a vesicular structure part.If the median size of filler component is between 1 to 2 micron, then Shi Yi mean particle size is less than 0.5 micron, and most preferably less than 0.3 micron.Mold compound is suitable selection, because the gained coating chemically is being similar (although having different on the structure) with the supercoat of current use.
Because the substrate material and second solution have suitable chemical resistant properties, therefore using described coating is favourable as supercoat.Whether another advantage is to choose wantonly vesicular structure by completely filled.This incomplete filling can be compensated with the inherence of doing thermal dilation difference well.Because the precursor component of this material can be transformed into vesicular structure under enough low temperature, therefore can also be used in combination with wire bonding (wire bonding).
In addition, this coating has good binding property to bottom such as passivation layer.Such as the vesicular structure of alkoxide oxidation and nitrided surface had good binding property based on precursor material.Second solution, that is, organic polymer has good binding property to organic and apolar surfaces.By selecting the precursor material and second solution, by selecting to have specific fusible second solution and, can further making bonding optimization by changing precursor material and being used for volume ratio between the compound of filling porous structure.
In the specific embodiments of this mold compound that is used for packing, it is transparent that its component is selected to.In practice, the stability of transparent epoxy resin class is than the stability of standard mold compound even have a bigger problem.And present unicircuit often all produces a large amount of heat, and therefore, coating should be restrained oneself heat and do not produced any adhesion problem.Because coating of the present invention is an inorganic structure, therefore can not produce such problem.
In another embodiment, coating be selected to have competent flexible.Flexible device can be from for example learning the EP-A 1256983.They are applicable to Secure Application, and the data that are stored in the unicircuit herein should obtain suitable protection.As from US-A 6,198,155 learn like that, the safety coatings of prior art does not realize the flexible condition, it is flexible fully but but porous coating optimization of the present invention obtains, and coating of the present invention only is coated on the limited quantity zone of semiconducter substrate, and this limited arrangement can help to realize required flexible.An example of one class suitable material is a polyimide.These materials can be used with the soluble form of polymeric amide, and the soluble form of described polymeric amide is used as second solution that is filled to the small part vesicular structure, and can be transformed into polyimide subsequently.Also can use alternative polymkeric substance or polymerizable material.
In another embodiment, coating can provide specific functional.Herein, it is functional that the vesicular structure and second solution of filling this vesicular structure can have complementary.If a kind of component produces or transmits optical radiation, then another kind of component can be used to be suppressed at the radiation delivery of a certain direction, perhaps the intensity of reduced radiation.If a kind of component has magnetic, then another kind of component can be used as this magnetic field, especially in some direction, shielding.In particular, the vesicular structure of top closure shows and is applicable to this shielding or inhibit feature.In addition, by the formation method of patterning of explaining below, vesicular structure can only be placed in the zone of limited quantity.For example can make like this and only on the zone of limited quantity, transmit light, and can on whole surf zone, produce light.
In another embodiment, coating is used as porous coating, and deposits some coatings subsequently on the top of this porous coating.The character of this coating with and closed top, make it be highly suitable for the duplexer of integrated multi-layer.Porous layer can be applied to various various objectives known to the skilled.In field of semiconductor devices, can be a kind of suitable applications as inter-metal dielectric with them.
In a favourable embodiment of described method, make coating form pattern.Before the application of coatings composition, on substrate, provide figuratum structure.Then, modification is carried out on the surface of substrate and patterning, make substrate surface hydrophilic relatively, and the surface of patterning is hydrophobic relatively.Therefore, when the application of coatings composition, patterning is held does not have coating composition.After the application of coatings composition, remove this patterning.Described removing preferably carried out before coating composition solidifies, and for example carried out after about 100 ℃ prebake step.Surface modification can be undertaken by using some properties-correcting agent.Alternatively, use Cement Composite Treated by Plasma.
It is favourable using following technology.At first, the resist layer that forms pattern is applied on the substrate, and forms pattern, thereby obtain above-mentioned patterning with photolithography.Photo-resist is present in and is held in the zone that does not have coating composition.Then, carry out the fluorine plasma etch step.The exposed surface of substrate, especially oxide compound or nitride layer and resist all are subjected to the influence of this processing.For silicon nitride, be present in lip-deep Si-OH group and all will be replaced by the Si-F group in a large number, thereby make nitride have less wetting ability.Resist is subjected to different influences, and more complicated reaction takes place.This makes basically that the first half of resist is fluoridized, polymerization and be subjected to some damages.These effects provide very high water repellency.After Cement Composite Treated by Plasma, carry out slight oxidation, for example by carrying out in the mixture that is immersed in ammonia, hydrogen peroxide and water formation.In this step, the Si-F group on substrate surface is replaced by the Si-OH group once more, thereby produces hydrophilic nitride surface.Thereby, realized big wetting behavior difference.Apply the aqueous solution subsequently, liquid only is deposited on and is easy on those wetting surfaces.Resist is removed in such as ethanol at organic solvent.Only use the photo-resist layer such as 2 microns limited thickness, this method can make and thickly form pattern to 30 microns even thicker film.
The pattern of coating forms and makes and can and be hidden in pad under this coating near bonding pad (bond pad) or other metallic region.Alternatively, pattern is formed for limiting the appearance of vesicular structure, to be limited to the zone on the substrate surface in advance.Present method has additional advantage, and reason is to remove (lift-off) technology by means of tradition to have in essence problem when removing vesicular structure in view of its inhomogeneous character and bad stability.And in view of the intensity of its reticulation and the differing materials that needs particular etching process, therefore, forming pattern by coating photo-resist on the top of filling coating can have problems.In addition, the particle characteristics of filler component suppresses to form the hole of sharp outline.
Second purpose of the present invention provides a kind of coating composition, and uses this coating composition can form improved porous coating.This purpose realizes in the following way, make this coating composition comprise matrix precursor component and filler component, and described matrix precursor component is transformed into substrate material when heat treated, and the amount of described filler component is at least 30 volume %, and its mean particle size is at least 1 μ m.Provide after coating composition of the present invention can prepare at the scene or provide afterwards by another company's supply.Can see, can have alternative compositions, can use it to form porous coating in the methods of the invention.Yet the advantage of coating composition is owing to have good rheological property, thereby has good workability.
According to observations, contain precursor material monoaluminum phosphate and can be from US 6,759, learn in 736 at the coating composition of the filler particles of sub-micrometer range.Yet the use of this coating composition does not produce porous coating.Preferably, mean particle size is in 1 to 3 micron scope, more preferably between 1.2 to 2.8 microns, most preferably between 1.5 to 2.5 microns.
The preferred matrix precursor material of selecting makes it be lower than 500 ℃, more preferably be lower than 450 ℃ or also more preferably be lower than in 400 ℃ the thermal treatment and be transformed into matrix.Therefore, allow it in interconnection structure of semiconductor device, to use.The example of this material comprises mixture that orthosilicic acid four ethyls (TEOS) for example and monoaluminum phosphate (MAP), tetraethyl orthotitanate (TEOTi), phthalandione four isopropyl esters, ethanol niobium (V), ethanol tantalum (V), propyl carbinol tantalum, zirconium-n-butylate or more than one described precursor material form each other or the mixture that forms with other precursor material.For the application in package semiconductor, thermal treatment is most preferably carried out being lower than under 300 ℃ the temperature.A lot of precursor materials can both be changed under such temperature.Suitable example for example is TEOS, itself in addition also can change being lower than 100 ℃ of following thermal treatments.
Most preferably, select filler component and precursor matrix material, so that the matrix of filler and transformation is bonded to each other.Chemical bond is a kind of very strong key.Because filler component comprises precursor group such as alkoxide on its surperficial at least a portion, therefore, can realize such key.Alternatively, can use the key that forms with acrylate-based polycondensation by for example.Alternatively, the substrate material of filler and transformation utilizes physical bond to be together with each other, and described physical bond comprises capillary force, Van der Waals force and hydrogen bond.The latter's mechanism estimation is to utilize at the intramatrical TiN particle that also comprises hydroxyl to produce.
The 3rd purpose of the present invention provides a kind of substrate, and this substrate comprises and has high yield and enough porous coating is arranged.This purpose is to realize by the vesicular structure that comprises the filler particles of being sealed by one deck matrix components and be filled to the fixedly component of small part vesicular structure.
Except described method is obtained also observing the observations, fixedly component provides the coating with intensity.Because term ' fixedly component ' meaning is the not homonymy extension of the object of filling porous structure at vesicular structure, therefore obtains mechanical fixed effect.Coating can have any concrete application of describing in claim to a method.It is particularly useful for being integrated into electron device.Its suitable example is a semiconducter device, such as unicircuit.Yet, do not discharge the application in relevant art certainly, such as (biological medicine) transmitter and optics yet.
These and other aspect of the present invention all will become clear from the limiting examples of hereinafter describing, and be described with reference to the limiting examples of hereinafter describing.
Embodiment
Embodiment 1:
Use tetraethyl orthotitanate (TEOTi) (to produce TiO as matrix precursor component
2Porous matrix), the TiN particle is as filler component, and then TEOTi (produced TiO
2) as the precursor enhancement component, to prepare according to porousness supercoat of the present invention.
For this reason, 1g TEOTi is joined 0.3g HCl (6M) in 14.5g ethanol in the formed solution.In this solution, add 4.58g TiN, (obtain TiO thus based on last acquisition thereby obtain 4.4 volume % solution
2Porous matrix is the filler component TiN of 91 volume %).
For obtaining basically coating liquid uniformly, it is used ZrO
2Mill pearl (2mm diameter) was ground 21 hours in the PE-of 60ml bottle, and the per minute rotation is about 120 commentaries on classics (rpm).Add ZrO
2The amount of mill pearl makes these mill pearls just in time under the coating liquid surface.
By spin coating, resulting suspension is deposited in order on the glass substrate.When substrate rotates with 450rpm, applied excessive liquid 18 seconds.Afterwards, sample rotated 60 seconds under 620rpm.After the rotation, sample was kept 1 minute on 100 ℃ hot plate, kept 2 minutes down at 200 ℃ afterwards.At last, porous coating solidified 1 hour down at 400 ℃.
Porous coating comprises based on TiO
2Porous matrix is the filler component TiN of 91 volume %.
After porous coating solidifies, fill with strengthening precursor component, at the TiO of present embodiment
2In, use TEOTi-solution as precursor.For this reason, in the solution of 30g ethanol and the formation of 3.53g acetate, add 30g TEOTi.Under vacuum (300mbar), will contain porous TiN-TiO
2The glass substrate of coating was flooded 10 minutes in the latter's TEOTi-solution.In order to remove excessive TEOTi-solution, sample was rotated 2 minutes under 5400rpm.After the rotation, sample was kept 1 minute on 100 ℃ hot plate, kept 2 minutes down at 200 ℃ afterwards.At last, porous coating solidified 1 hour down at 400 ℃.Resulting supercoat has the thickness of 3 μ m.
Show, this coating also can be easy to be applied to replace above-mentioned shown on the IC of glass substrate.This supercoat has the character of excellent anti-machinery, physics and chemistry, and suitable non-transparency.
Those skilled in the art should be understood that and can much improve under the situation of the scope that does not deviate from appended claim.As an example, when needing,, can further improve the chemical resistant properties of supercoat by on supercoat, further being coated with application layer.For example, it can apply TiO in addition
2, ZrO
2, Nb
2O
5, Ta
2O
5Deng or use TiO
2, ZrO
2, Nb
2O
5, Ta
2O
5Deng dipping.In addition, in case of necessity, above-mentioned coating can form pattern.
Claims (16)
1. method that on substrate, forms coating, described method comprises at least:
The coating composition that comprises matrix precursor component and particulate filler component is provided;
Coating composition is coated on the substrate, and described composition is solidified, thereby obtain vesicular structure;
Second solution is coated on the substrate, and partially filled at least thus vesicular structure also obtains described coating.
2. as in the method described in the claim 1, wherein said filler component is included in the particle in the predetermined size range.
3. as in the method described in claim 1 or 2, wherein said matrix precursor component comprises the hydrolysable group with melts combine, and described component is transformed into reticulation in described curing schedule, and described reticulation is sealed described particulate filler component basically.
4. as in the method described in the claim 1, wherein said second solution comprises alkoxide, and described alkoxide is transformed into oxide net shape thing in described curing schedule.
5. as in the method described in the claim 1, wherein said second solution comprises polymkeric substance or polymerisable compound.
6. as in the method described in the claim 1, wherein, use the filler component of predetermined amount in order to obtain the vesicular structure of filler component at least 40 volume %.
7. as in the method described in the claim 3, wherein said matrix precursor component comprises the compound that is selected from the group of being made up of tetraethyl orthotitanate (TEOTi), phthalandione tetra isopropyl ester, ethanol niobium (V), ethanol tantalum (V), propyl carbinol tantalum, zirconium-n-butylate or its mixture.
8. as in the method described in claim 1 or 2, wherein said filler component comprises and is selected from by TiO
2, the compound in the group formed of TiN or its mixture.
9. as in the method described in the claim 1, the porosity of wherein said vesicular structure is 40-90%, be preferably＞50%.
10. the process of claim 1 wherein and make described coating form pattern by following process:
Before the coating coating composition, (a) on substrate, provide the structure that forms pattern, and (b) modification is carried out on the surface of substrate and the surface that forms the structure of pattern, make substrate surface hydrophilic relatively, and the surface of the structure of formation pattern is hydrophobic relatively, thereby when the described coating composition of coating, the structure that forms pattern keeps not having coating composition, and
After the described coating composition of coating, the structure of described formation pattern is removed.
11. a coating composition, it is used for forming porous coating on substrate, and it comprises matrix precursor component and filler component, and described matrix precursor component is transformed into substrate material when heat treated, and the amount that described filler component exists is at least 40 volume %.
12. as the desired coating composition of claim 11, the median size of wherein said filler component is between 1～3 μ m.
13. as the desired coating composition of claim 11, wherein said matrix precursor component comprises metal alkoxide, and described metal alkoxide is transformed into metal-oxide matrix under described heat treated.
14. as claim 11 or 13 desired coating compositions, wherein said filler component and described substrate material are bonded to each other.
15. the coating on substrate, it comprises:
Vesicular structure, it contains the filler particles of being sealed by one deck matrix components, and
Fixing component, its filling porous at least in part structure.
16. an electron device, it comprises coating as claimed in claim 15.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP04104791.1 | 2004-09-30 | ||
| EP04104791 | 2004-09-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101031519A true CN101031519A (en) | 2007-09-05 |
Family
ID=36119265
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200580033058 Pending CN101031519A (en) | 2004-09-30 | 2005-09-20 | Method of forming a coating on a substrate, and a coating thus formed |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP1797016A2 (en) |
| JP (1) | JP2008514415A (en) |
| CN (1) | CN101031519A (en) |
| TW (1) | TW200626519A (en) |
| WO (1) | WO2006035360A2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112517352A (en) * | 2020-10-13 | 2021-03-19 | 江苏大学 | Nano-particle loaded porous ultra-wide spectrum absorption coating and preparation method thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140105430A (en) * | 2011-08-02 | 2014-09-01 | 다우 글로벌 테크놀로지스 엘엘씨 | Optoelectronic devices with thin barrier films with crystalline characteristics that are conformally coated onto complex surfaces to provide protection against moisture |
| CN107188616B (en) * | 2017-05-23 | 2019-08-23 | 佛山欧神诺陶瓷有限公司 | A kind of crack brick and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5665422A (en) * | 1991-03-19 | 1997-09-09 | Hitachi, Ltd. | Process for formation of an ultra fine particle film |
| US5711987A (en) | 1996-10-04 | 1998-01-27 | Dow Corning Corporation | Electronic coatings |
| DE69935064T2 (en) * | 1998-06-10 | 2008-01-03 | Koninklijke Philips Electronics N.V. | SEMICONDUCTOR ARRANGEMENT WITH AN INTEGRATED CIRCUIT AND CERAMIC SAFETY LAYER AND METHOD FOR PRODUCING SUCH A LAYOUT |
| WO2004031445A1 (en) * | 2002-10-03 | 2004-04-15 | Alberta Research Council Inc. | Protective ceramic coating |
-
2005
- 2005-09-20 WO PCT/IB2005/053090 patent/WO2006035360A2/en active Application Filing
- 2005-09-20 CN CN 200580033058 patent/CN101031519A/en active Pending
- 2005-09-20 JP JP2007534130A patent/JP2008514415A/en not_active Withdrawn
- 2005-09-20 EP EP05798271A patent/EP1797016A2/en not_active Withdrawn
- 2005-09-27 TW TW094133543A patent/TW200626519A/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112517352A (en) * | 2020-10-13 | 2021-03-19 | 江苏大学 | Nano-particle loaded porous ultra-wide spectrum absorption coating and preparation method thereof |
| CN112517352B (en) * | 2020-10-13 | 2022-07-22 | 江苏大学 | Nano-particle loaded porous ultra-wide spectrum absorption coating and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2006035360A2 (en) | 2006-04-06 |
| JP2008514415A (en) | 2008-05-08 |
| EP1797016A2 (en) | 2007-06-20 |
| WO2006035360A3 (en) | 2006-08-03 |
| TW200626519A (en) | 2006-08-01 |
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