CN1552943A - Rapid process for producing multilayer barrier coatings - Google Patents

Rapid process for producing multilayer barrier coatings Download PDF

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Publication number
CN1552943A
CN1552943A CNA031275567A CN03127556A CN1552943A CN 1552943 A CN1552943 A CN 1552943A CN A031275567 A CNA031275567 A CN A031275567A CN 03127556 A CN03127556 A CN 03127556A CN 1552943 A CN1552943 A CN 1552943A
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layer
aforementioned
scope
pressure
organic
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CN100381606C (en
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M
M·比克尔
S·贝赫勒
L·克利普
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A·鲁特林豪斯-汉高
G·阿诺德
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Schott AG
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Schott Glaswerke AG
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Priority claimed from PCT/EP2002/008853 external-priority patent/WO2003014415A1/en
Priority claimed from DE10258678A external-priority patent/DE10258678B4/en
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00Processes for applying liquids or other fluent materials
    • B05D1/62Plasma-deposition of organic layers
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02Pretreatment of the material to be coated
    • C23C16/0272Deposition of sub-layers, e.g. to promote the adhesion of the main coating
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02Pretreatment of the material to be coated
    • C23C16/0272Deposition of sub-layers, e.g. to promote the adhesion of the main coating
    • C23C16/029Graded interfaces
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/04Coating on selected surface areas, e.g. using masks
    • C23C16/045Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40Oxides
    • C23C16/401Oxides containing silicon
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40Oxides
    • C23C16/401Oxides containing silicon
    • C23C16/402Silicon dioxide
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/515Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using pulsed discharges
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50Multilayers
    • B05D7/56Three layers or more
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/42Component parts, details or accessories; Auxiliary operations
    • B29C49/64Heating or cooling preforms, parisons or blown articles
    • B29C49/6604Thermal conditioning of the blown article
    • B29C49/6605Heating the article, e.g. for hot fill

Abstract

The method for alternatively depositing layers by the chemical vapor phase deposition includes a processing step of depositing a bonding promoting layer on a base material and a processing step of depositing a barrier layer. The layers include organic and inorganic materials to be alternatively deposited. In the method, the coating time to deposit the bonding promoting layer is 0.05-4.0 seconds, and/or the coating time to deposit the inorganic barrier layer is 0.1-6.0 seconds, and a composite material is also manufactured by using the method.

Description

Produce the fast method of multi-layer isolation layer
The present invention relates to by chemical vapour deposition (CVD) method, especially by plasma enhanced chemical vapour deposition PECVD, particularly plasma pulse chemical vapour deposition PICVD method applies the fast method of alternating layer and relates to the coating that this method of use applies.
For the packing perviousness that can make gas and liquid is reduced and in order to protect wrapping material to exempt from chemical attack or UV radiation, this packing that provides sealing coat (barrier layer) is favourable.In the context of the present invention, as an example, in particular for mass-producted plastics, in order to reduce its perviousness, especially to the perviousness of oxygen and water vapour with meanwhile especially in order to keep the transparency of material, the SiO of deposition of thin on polymeric substrate xCoating or coating system are interesting.In addition, can pass through microwave device usually, heat the content of the material of coating in this way safely.The further advantage of these coatings is that deposition the multiple of them may be selected on polymer surfaces.
Yet,, need understand fully buffer action, morphological property and by the relation between the molecule of layer material migration with need to control the influence of mode of deposition especially to the painting parameter that produced in order to improve the quality of this type coating.
People such as Erlat are at J.Mater.Res., and (2000) 15,704-716 pages or leaves have proposed a kind ofly to show the model that concerns between the morphology of buffer action and layer material, and explained the influence of various processing parameters.
People such as Erlat have described processing parameter based on each side at J.Phys.Chem.B (1999) 103,6047-6055 pages or leaves, with respect to smooth surface, and the morphology of layer material.Yet these two pieces of reference have only been studied independent inorganic barrier.
In order to improve SiO on polymeric substrate xThe bonding performance that connects of layer, people such as Rupertus have proposed pre-treatment ground in oxygen gas plasma at Fresenius J.Anal.Chem. (1997) 358,85-88 pages or leaves.
Use processing parameter power, pressure and time, carry out the improvement of coating process in a usual manner.
According to US5718967A1, by at first avoiding being used for the oxygen of the first layer, when not having oxygen; can produce a kind of adhesion promotor (adhesion-promoter) layer; by introducing oxygen subsequently, under excessive oxygen, on adhesion promoter layer, produce protective layer then.
EP709485 has described a kind ofly to has by HMDSO and TiCl 4The method of the laminated plastics coating of the alternating layer of producing.In the method, use HMDSO to deposit organic sealing coat and use TiCl 4The deposition inorganic barrier.Yet this application do not have open how realize the possibility of rapid processing time and how to finish volume>18ml, typically>and the fast method of the container of 50ml.
In order on ground (as the PET bottle), to finish the sealing coat coating process economically, need to realize very high throughput rate.Throughput rate on production line be 10000-30000 container/hour, wherein said production line comprises charging (filling) device in the stretch blowing machine that is used for plastic containers and downstream.Yet, for the optimum integration of sealing coat apparatus for coating, promptly on this production line, arrange described device according to following order:
1. stretch-blow
2. coating
3. charging
Must realize with carry out throughput rate that sealing coat coating obtained quite or just the same high throughput rate and this be favourable.Yet these framework conditional requests are the sealing coat coating process very fast, in this technology, should be in pure coating time of ground upper strata material growth less than 6 seconds, and preferably less than 3.6 seconds, or even less than 1.0 seconds.
Throughput rate also depends on desired workshop section number (number ofstation) on coating machine, this means and to reduce desired workshop section number by the very short coating time, perhaps, can increase throughput rate, thereby cause significant profit for identical workshop section's number.
WO99/49991 has described a kind of barrier coat that comprises decolorizing carbon, has wherein realized the shock processing of coating time in 2-3 scope second.Yet the document not explanation is compared with the uncoated ground with predetermined process period, how to realize infiltration or isolation improvement.Yet these layers material is opaque, but the band brown is to yellow.In particular for applied transparent vessel, this painted be highly inaesthetic, and often cause unacceptable result.Although if apply these layers material with the form of film, painted can the reduction, it still can exist.Yet, if reduce bed thickness, the remarkable deterioration buffer action of result.In addition, only may be very big difficulty ground and expensive these layers material that contains decolorizing carbon of from the PET ground, removing.Owing to these reasons, the recovery of coating container causes problem, and this is because a certain amount of color may be retained in to be reclaimed in the product, in addition when it when uncoated PET mixes.
In patent WO02/09891A1 and WO02/10473, also disclose for SiO xSealing coat, the coating time of 2-4 second.Yet these public publications not explanation reach regulation coating spendable processing parameter of time.Especially, there is not accurately information about the flow velocity aspect of pressure, concentration, microwave power and precursor flow rate and carrier and reactive gas.
In addition, WO02/10473 discloses the method that applies the layer material that is formed by various initial compounds, and described layer material comprises protective layer and towards the frictional belt of ground, and protective layer comprises decolorizing carbon, SiO xLayer and frictional belt are to be produced by the compound of oxygen and " containing organosilicon ".This method high complexity is because apply three layers and the far different initial compounds of necessary use altogether.The claim 1-10 of WO02/09891A1 also discloses a kind of similar complicated approach.
Based on the work of above-mentioned currently known methods, but the purpose of this invention is to provide a kind of on production line the method for optimum integration so that on ground, for example on the internal surface of Plastic Bottle, apply high-quality sealing coat.
In simple mode astoundingly, the feature by claim 1 can realize this purpose.In addition, claim 33 has proposed a kind of matrix material that uses method of the present invention to produce.
In each autocorrelative dependent claims, provided favourable restriction.
In the application PCT/EP/0208853 that is entitled as " Composite material comprising a substrate material anda barrier layer material ", the applicant has proposed a kind of method of producing matrix material, and it has improved buffer action and improved adhesive effect.With reference to this application PCT/EP/0208853 and the application and any subsequently the protection by its deutero-right in, its content all is incorporated herein by reference at this.
In the method for the invention, produce alternating layers by a kind of precursor only or by two kinds of siliceous precursor substances.This makes can be fast and realize a kind of method simply and also make especially realizing the described rapid processing time of claim 1.
Can change the zone of transition between organic and the inorganic layer, in addition, can strengthen buffer action, thereby can apply very slick layer material by the interface between organic and the inorganic layer.
The invention provides the overall flow rate of the overall flow rate of second inorganic layer more than or equal to the first layer organic adhesion promoter layer.Under one situation of back, may advantageously significantly increase the sedimentation rate of the second layer, so that can further reduce total coating time.Under low precursor concentration, the increase of overall flow rate makes may keep the quality of sealing coat and meanwhile, may significantly increase sedimentation rate, and the coating time of second layer inorganic barrier may significantly reduce as a result, keeps identical bed thickness simultaneously.
Therefore, solution of the present invention provides a kind of CVD of passing through first, preferred PECVD, PICVD method especially, alternating layer is provided, promptly two-layer at least method, this method comprises following processing step: fast deposition adhesion promoter layer on ground, and apply sealing coat, the alternating layer of the organic and inorganic materials of alternating deposit wherein.Preferably only deposit two-layer.This makes may realize process period fast.
Only can advantageously deposit alternating layer by a kind of single precursor gases or by two kinds of similar siliceous organic precursor gases, for example two-layer for this, described precursor gases is hexamethyldisiloxane or hexamethyldisilazane, or be hexamethyldisiloxane for first organic layer, or for second inorganic layer hexamethyldisilazane.
The present invention show be characterised in that coating time of applying adhesion promoter layer between 0.05 second-4 seconds and/or coating time of applying sealing coat the fact between 0.1 second-6 seconds.In the context of the present invention, term material " coating time " is meant and deposits material from level to level and continuously or the time length of the plasma body of pulse burning (buring) on ground.
In order effectively to produce sealing coat, on dielectric materials, produce sealing coat especially, need deposit low-density smooth layer at inner boundary or other heterogeneity part.The layer material rate of permeation that highdensity topology or chemical heterogeneity part can cause increasing.
If there is short the evolving path, this is especially true, wherein can occur and the proportional rapid diffusion of volume along the heterogeneity part by this path.As an example, porous layer can not be realized the good isolation effect usually.Therefore, preferably have the low-density layer material of short the evolving path, as have the low-density unformed layer material of inner boundary and/or have the low-density polycrystal layer of crystal grain boundary.
Utilize alternating layer, meeting significantly suppresses through the diffusion at interface between organic and the inorganic layer or makes the evolving path significantly elongated.
Both can deposit very slick inorganic layer by the parameter of selecting suitably, can deposit very slick organic layer again.(it has applicant's reference number 02SGL0184DEP in the application of applying on the same day the applicant that is entitled as " Process forproducing smooth barrier layers and composite material with smoothbarrier layer ", after obtaining official's proof with interpolations application number) in, the applicant has proposed the apparatus and method of the very slick isolation alternating layer of production.At this in full with reference to this application.
In order to carry out the present invention's technology very fast, by changing at least a processing parameter, to deposit alternating layer of the present invention in simple mode.
The present inventor finds that by using plasma enhanced CVD method, so-called especially PICVD method may deposit the layer material that has special excellent bonds effect and have good buffer action in very short process period.Can use the PICVD technology on the ground material, to apply extremely thin layer material, and described layer material still have very good isolation performance.In addition, the flexible height of layer material.
The use of PICVD method also makes this method use on multiplex's section apparatus, and described device provides high turnout especially.
In the method for the invention, for the deposition of layer material, advantageously use the plasma body that produces by microwave.In the context of the present invention, preferred frequency of utilization is the microwave of 2.45GHz.In addition, there is the measure that produces plasma body by pulse microwave.
The overall flow rate that increases causes that the flow curve in the container changes.Find,, depend on the flow velocity of gas in particular for inorganic barrier, can advantageously regulate spray gun length (lancelength), wherein, precursor gases can be incorporated in the container to be coated, so that can realize the uniform distribution of component in the processing gas in container by it.In this case, spray gun length is defined as in to be coated and container with respect to atmospheric sealing, and gas flow into described opening in the container to be coated to the distance between the external margin of vessel port from opening.In this regulate process, the layer thickness distribution of organic layer is varied slightly only.
Except spray gun length, the present invention also provides interpulse (interpulse) time period of adopting for the overall flow rate that increases.In the case, for higher overall flow rate, the interpulse time period shortens.
Interpulse time period decision is before the plasma body burning and being coated with, and fresh processing gas can flow into the time in the container.Under optimal flow situation with respect to pressure, overall flow rate, precursor concentration, spray gun length and nozzle diameter, may realize the well distributed of component in the processing gas, even under short relatively interpulse time period situation and still further may quicken processing sequence in such a way.
It should be noted that, when using pulsed plasma, sedimentation rate needn't be lower than the sedimentation rate that is called as " continuous wave plasma body (CW plasma body) " when using, because if use the pulsed plasma parameter of determining rightly, the then in fact conversion fully of generating material in pulse length, with in pulse process next time, the new live gas that transforms fully will flow in the interpulse time period in fact once more.
The sedimentation rate that realizes with pulsed plasma can in addition higher, if fresh processing gas flows at appropriate time place, in pulse process, use high pulse power can take place then than high material inversion quantity under the CW plasma body situation of using lower momentary power.Under the short interpulse time period, sedimentation rate significantly increases, and reaches optimum value, and this is because the ratio of unconverted precursor gases raises until reaching saturation point always.
According to the present invention, the sedimentation rate of organic layer is in the 120nm/min-5000nm/min scope, preferably in the 500nm/min-2000nm/min scope, and/or the sedimentation rate of inorganic layer is in the 60nm/min-2000nm/min scope, preferably in the 100nm/min-1000nm/min scope.
Therefore, by the time period between chopped pulse, may realize the significantly short coating time, form best state simultaneously, this is because of too short as if the interpulse time period, then based on this fact of uniform distribution that can not form the processing gas component, and the deficiency so the uniformity coefficient of coating becomes.
Unevenness is defined as the ratio of minimum bed thickness and maximum bed thickness, wherein determines its numerical value by measuring on above-mentioned ground.
On the other hand, if the interpulse time period is oversize, then the ratio of the processing gas that does not consume raises.According to the present invention, along with overall flow rate increases, spray gun length reduces.Spray gun length is ducted body (hollow body) 5%-80% highly to be coated, preferred 10%-50%.
The further advantage of pulsed plasma is possible produce very pure inorganic barrier, because different with the CW plasma body, can remove non-required organic reaction product in the interpulse time period, therefore mixes the organic composition of remarkable reduction ratio in this layer.
Except the above-mentioned advantage of PICVD method, also may provide further processing parameter, be used to control the fast deposition process of the alternating layer that forms by a kind of single precursor gases or two kinds of similar siliceous precursor compounds.
At least a processing parameter to be changed is selected from precursor concentration, average microwave power, pressure, pulse power, pulse length, the time length of interpulse time period and overall flow rate., these parameters use the very short coating time sealing coat of possibility depositing high-quality although making.
All mentioned processing parameters are meant the coating of single ground.For at the multi-position device, for example in rotation with a plurality of chambers or intermittent type device, be coated with a large amount of grounds, mentioned parameter is meant in each indoor coating under each situation.
Proof is 2ms-100ms for time period scope between the optimum pulse of organic layer, preferred 5ms-60ms, and prove for time period scope between the optimum pulse of inorganic layer to be 5ms-200ms, preferred 20ms-50ms.
According to the present invention, for this purpose with the numerical value of parameter setting for optimizing.
Especially, for applying of the first layer organic adhesion promoter layer, existing measure to make the precursor concentration scope is the 5%-80% of total flux, and/or applying for second layer inorganic barrier, existing measure to make the precursor concentration scope is the 0.5%-4% of total flux, preferred 0.8%-3%.
In addition, for organic layer, exist measure to make pulse power in the 100W-5000W scope, preferably in the 400W-1500W scope, and/or, exist measure to make pulse power in the 100W-5000W scope, preferably in the 400W-1500W scope for second inorganic layer.
According to the present invention, the average microwave power that is used for organic layer is in the 10W-5000W scope, and preferably in the 10W-500W scope, and/or the average microwave power that is used for inorganic layer is in the 10W-5000W scope, preferably in the 30W-2000W scope.
Barrier coat also can advantageously have structure or the composition perpendicular to the coating surface variation of ground.Variation in this case can be continuous or fractionated.
Changed in stages causes the multilayer barrier coat.As an example, the bottom that contacts with substrate surface can be used as the adhesion promoter layer of coating subsequently.For example, in coating process,, can produce this class layer material or layer material system by the continuous or changed in stages of precursor concentration.
In this case, use multilayer alternating layer (being called multilayer) can realize good especially coating performance.
Ground material to be coated also can comprise ducted body especially.Therefore, method of the present invention is feasible may be at the inboard and/or the outside deposited coatings of ducted body.
The application's applicant on the same day in the application that is entitled as " Process for producing smooth barrier layers and compositematerial with smooth barrier layer " of German Patent and trademark office application (applicant's reference number 02SGL0184DEP) device that applies sealing coat to the ducted body as ground is disclosed.In the disclosure and theme in the application of this full text with reference to this application, the content of this application is incorporated herein by reference in full.
The present invention also advantageously provides the ducted body as ground, and the wherein preferred while is evacuated down to pressure P in the outside 1Be evacuated to pressure of foundation P in the inboard 2<P 1, pressure P wherein 1Be about 50 mbar and pressure of foundation P especially 2Especially less than 0.1mbar.
In addition, for method of the present invention, exist measure to make and contain the gaseous mixture of precursor with pressure P 3Flow into the inside of ground, wherein P 2<P 3<P 1, in particular for first organic layer, pressure P 3Scope be 0.1mbar-1.0mbar, preferably in the 0.2mbar-0.5mbar scope and for second inorganic layer, pressure P 3Scope be 0.1mbar-1.0mbar, preferably in the 0.25mbar-0.6mbar scope.The advantageous results of this measure is that the pressure reduction that works on the hollow body wall is not excessive, and under the situation of thin-walled material, excessive pressure reduction may cause the deformation of ducted body.
In addition, for only coating is inner, can be advantageously externally there not to be this mode of plasma body incendiary to select external pressure.For fear of high pressure reduction, even in the evacuation process, can advantageously evenly carry out evacuation at first, so that reach above-mentioned external pressure, the inside of further only finding time then is until the pressure of foundation that reaches in described scope.
In the method, in the deposition process of inorganic barrier, overall flow rate and/or pressure P in ground inside 3At least equal and be higher than in the deposition process of organic adhesion promoter layer overall flow rate and/or pressure P especially in ground inside 3Be favourable.Therefore,, compare, the invention enables and to realize significantly higher sedimentation rate with using lower overall flow rate applying in the process of inorganic barrier.
According to the present invention, layer material uses processing gas with pressure P 4Enter, wherein pressure P 4Be higher than the just pressure P before the plasma body burning 5In such a way, can be rapidly and carry out loading operation effectively.Then, applying in the process of layer material, continue to reduce operation pressure until beginning to apply down one deck and at the lasting elevated temperature in the process that applies of coating.
According to the present invention, the overall flow rate of organic adhesion promoter layer in the 10sccm-250sccm scope, preferably in the 40sccm-100sccm scope and the overall flow rate of inorganic layer in the 200sccm-1000sccm scope, preferably in the 250sccm-400sccm scope.
In addition, the present invention shows in the transient process be characterised in that between two application step, along with changes in process parameters, and plasma body or burn away, or in transit time, interrupt.As a result, the invention enables smooth, the continuous transition that may realize the gradual change form, or the sharp transition of hierarchical form, in addition, the invention enables may be energy-conservation.Especially, the transit time of pulsed plasma is greater than the interpulse time period.
Do not need the pre-treatment ground on the methodological principle of the present invention.Yet, requiring under the ground situation of extra-high-speed, and for example forming the bonding unsatisfactory of the material of described ground and coating, according to the present invention, also may before applying coating, carry out the plasma body pre-treatment.Yet in order to ensure not reducing the high-speed of the inventive method, the pretreated time length of plasma body is less than 5 seconds, preferably less than 1 second.
In addition, in order to widen may selecting and, having the measure of the combination of processing parameter to be changed of technology controlling and process in order to utilize synergy.
Depend on requirement, can use method production of the present invention to have layer material of different nature coating.For example, a condition can be to produce the border of determining in coating, is used for improved buffer action especially.Therefore, solution of the present invention comprises the various selections that change processing parameter.Can be continuously or change at least one parameter discontinuously, but perhaps partial continuous or part change at least one parameter discontinuously.
Under the situation of the inventive method, at first the deposition organic layer is favourable as adhesion promoter layer on ground.This provides the improvement of further layer material bonding, and the improvement of sealing coat is bonding especially.
In the deposition process of adhesion promoter layer, make preceding fragmentation body.The suitable selection of processing parameter influences the cracked of precursor, and its influence mode makes the single fragment of atom, molecule, ion or radical form and ground molecular reaction to be coated, and forms chemical bond (chemisorption).This keyed jointing has precedence over physical adsorption.The strong bond that comes from the precursor molecule fragment connects and has improved the bonding of layer material.The cracked formation that especially causes carbon content greater than 10% organic adhesion promoter layer.
In addition, the growth of effects of process parameters adhesion promoter layer, its influence mode makes organic layer advantageously be deposited on the defective that only has on the ground and in the inner boundary structure seldom by monolayer growth.So adhesion promoter layer is very smooth and himself can even have buffer action, and this is because it only has very small amount of interface of serving as diffusion path.
In addition, under appropriate condition, can use adhesion promoter layer, on coarse plastic bottom material, realize slick effect.In the context of the present invention, reference is with the full text of the application 02SGL0184DEP of the applicant's name.An advantage of smooth adhesion promoter layer is the inorganic layer with good buffer action can be applied on it, and has under the coarse morphologic adhesion promoter layer situation, only may apply the inorganic layer with remarkable reduction buffer action.Employed inorganic barrier is bonding for good layer material to be fully, even under nonpolar plastics such as polypropylene situation.In the context of the invention, a process engineering advantage is that method of the present invention does not require that plasma body pre-treatment consuming time is used for activating surface, and this may take place when using oxygen gas plasma for example according to the above document of quoting as proof.
The method according to this invention is with sealing coat form deposition inorganic layer.Because the interface between the same slick inorganic layer of organic layer and densification causes this sealing coat advantageously to improve buffer action.For example from the monolayer growth to the columnar growth or to the morphology of island growth sudden change significant prolongation along the evolving path on border.In addition, be different from a layer material inside at the interface keyed jointing condition, this makes more difficult infiltration in these zones.
Can use various precursors to carry out method of the present invention, especially, exist measure to make gaseous mixture containing oxygen gas and at least a precursor that is selected from organic siliceous or metallic organic compound, especially, HMDSN, HMDSO, TMDSO, the silane in nitrogen, TEOS or TIPT or metal chloride, TiCl especially 4, or silicon chlorides and hydrocarbon, alkane, alkene or alkynes, acetylene especially especially.Preferred in this case precursor is HMDSN and/or HMDSO.
Repeat to apply the processing step of the first layer and the second layer, wherein alternating layer is deposited on the dielectric materials and/or on the plastics especially, this makes method of the present invention can apply the barrier coat with long especially the evolving path, in this case, can advantageously use this method to be used for packing, especially plastic wrapping.
Except this method, the present invention also comprises a kind of matrix material, and it contains the alternating layer of alternately being made up of organic and inorganic materials, and described alternating layer is formed by a kind of single precursor gases deposition.
In addition, matrix material advantageously have the buffer action of increase, bonding, stretchiness, the mechanical stability that under compressive load, increases that increases that increases with ground and/or the mechanical stability that under tension load, increases.Comprise length variations greater than 4% stretching and/or plastic deformation after, under matrix material situation of the present invention, isolation improvement still keeps, wherein the isolation improvement factor of oxygen is preferably greater than 2.0 greater than 1.5.
Another advantage of matrix material is especially under excessive pressure, and under the tension load that is caused by carbonic liquids, it has high mechanical stability.Container by matrix material manufacturing of the present invention is specially adapted to this class I liquid I.Therefore, especially when comprising or forming foamed products or have when using coating of the present invention on the ground of container for product of solubilising gas that it provides advantage usually.
It is the inorganic barrier of one deck at least in the 5nm-200nm scope that coating has at least one deck organic adhesion promoter layer and the thickness of thickness in the 1nm-200nm scope.
The present invention makes first may be less than 6 seconds rapid processing productive zone material in the time, its quality is so good, so that even under the bed thickness situation in above-mentioned scope, can satisfy requirement to buffer action, bonding, stretchiness and the mechanical stability under compressive load.
Because desired bed thickness is little, so may economical with materials.In addition, the desired coating time reduces, because layer material is thin more, then can select the short more coating time.In such a way, coating process of the present invention makes may use coating process very fast, has high-quality astoundingly buffer action simultaneously.
In addition, matrix material is heat-stable.By in addition after molten charge, especially under the thermal load that causes by molten charge, still exist bonding and fact buffer action of layer material to determine thermotolerance.Therefore, advantage provided by the invention be not exist basically the barrier coat that causes because of thermal load separation and even after thermal load, still have the good isolation effect.
In addition, coating of the present invention is to having good thermotolerance with hot liquid charging, and this is requirement for the other products that HOT-FILL bottle or molten charge are used for example.Also in these containers, in the very short coating time, can finish this method.
Except the alternating layer of one deck at least that comprises organic and inorganic coating, matrix material also can comprise tectum.For example, depend on requirement, protective layer may be provided coated substrates.
In addition, tectum can be included in literal notation or other this appearance on the coated substrates.
Different with the carbon-Ji technology of routine, matrix material of the present invention is transparent on substantially.Term " transparent " is illustrated in layer material transparent in the visible wavelength region, and it means that vision transparence (the type D65 of light) is not less than the transmissivity of uncoated bottle.Therefore, can use the present invention to produce container, at first, can see the product that exists with form of distortion not clearly from the outside, the second, naked eyes content visible thing.This is to medical skill or biotechnology applications, and for example photometric measurement is important.
In food or cosmetic package field, at first, transparent packing attracts the human consumer, the second, can be easily and the content that detects reliably in this packing whether rotten.
Below based on the embodiment that exemplifies and with reference to appended claim the present invention is described, wherein:
Fig. 1 shows the sedimentation rate that second layer inorganic barrier changes with oxygen gas flow rate.
The embodiment that first exemplifies
Coated inside with 0.4L PET bottle of adhesion promotor/isolation matrix material
The stocking volume of being made by polyethylene terephthalate (PET) is the bottle of 0.4L is evacuated down to 50mbar simultaneously in the outside pressure and the initial pressure of foundation that is lower than 0.1mbar that is evacuated in the inboard.
Then, under the pressure of 0.3mbar, make the mixture of oxygen and hexamethyldisilazane (HMDSN) enter into bottle interior.
Then, pull-in frequency is the pulse microwave energy of 2.45GHz and at this container internal combustion plasma body.
At first, in less than 1 second coating time, under HMDSN concentration 40% and the overall flow rate of 40sccm, apply first thick organic sealing coat of 10nm.
Pulse power is 800W, and preferred 0.7ms of pulse length and interpulse time period are 40ms.
Then fast gas is changed to 1.2% low HMDSN concentration.Under identical setting pressure, apply second layer inorganic barrier.
In the examination test of using constant HMDSN concentration and constant pressure, according to the statistical test method of planning, running parameter bed thickness and/or coating time and further processing parameter oxygen gas flow rate and pulse power, pulse length and interpulse time period and device parameter spray gun length.
Fig. 1 shows the comparison between the sedimentation rate of the oxygen gas flow rate of setting and measurement.
When oxygen gas flow rate increases, can significantly improve the sedimentation rate of second inorganic layer.
Table 1 shows the processing parameter selection that second inorganic layer is tested, and under described selection, the matrix material that contains first and second layers produces high buffer action.
In addition, just show after coating and afterwards in loading test (using the creep test of the carbonic acid gas of 4% volume), the coating time of second inorganic layer and sedimentation rate be with the variation of processing parameter and device parameter, and this is the sign of isolation improvement that contains the double-layer composite material of first organic layer and second inorganic layer.
Table 1: in loading test (using the creep test of the carbonic acid gas of 4% volume) afterwards, the coating time of second inorganic layer and sedimentation rate are with the variation of the technology isolation improvement (BIF) of the double-layer composite material that contains first organic coating and second inorganic coating
Method 1 2 3 4
Spray gun length (mm) 120 50 50 50
The thickness of the second layer (mm) 20 20 17.5 12
Oxygen gas flow rate (sccm) 100 220 380 450
Pulse power (W) 800 800 850 900
Pulse length is isolated (ms) 3 3.5 3.5 4
The interpulse time period is isolated (ms) 50 40 40 40
The coating time (s) 14 6 3 2
Sedimentation rate (nm/min) 86 200 318 360
The O of double-layer composite material 2-BIF >40 >40 >40 ..30
O after 4% creep test 2-BIF 4 5 5 4
In last table, isolation improvement factor B IF is defined as the ratio of the infiltration of uncoated ground with respect to the infiltration of coated substrates.
Can find out that from the data of method 1 oxygen gas flow rate is 100sccm, the interpulse time period is 50ms and spray gun length when being 102mm, has realized the sedimentation rate of 86nm/min.
The coating time is long relatively, is 14 seconds.As a comparison, because 220,380 and the higher oxygen gas velocity of 450sccm and,, be respectively 200,318 and 360nm/min so the sedimentation rate of method 2,3 and 4 is significantly higher because the interpulse time period shortens to 40ms and improved spray gun length is 50mm.
Therefore, can significantly reduce the coating time.
In addition, in order further to shorten process period, reduced the thickness of the second layer.This causes the gained coating time totally to be reduced to 2-6 second.
Coating makes to produce to have the high oxygen isolation improvement factor (O 2-BIF) adhesion promotor/isolation matrix material, for method 1,2 and 3, its numerical value substantially exceeds 40.
The infiltration of uncoated bottle is 0.1955cm 3/ (packing day bar).The infiltration of coating bottle is so low, so that reach the resolving limit of employed Mocon-Oxtran measuring apparatus.
The O of measuring method 4 2-BIF is 30, and for the second layer, it has 2 seconds the shortest coating time.
These layers material has good bonding and stretch-resistance, and this proves by following creep test.
As for creep test, be the bottle that 4% carbonic liquids is filled coating with the 0.4L carbon dioxide content, and isolate with plastic cover.At room temperature store charging bottle 24 hours then at first, then store 24 hours down at 38 ℃.
In this test method, in bottle, built up the interior pressure that reaches 5bar, this causes a layer material/composite substrates local elongation to surpass 4.5% and even cause plastics deformation.The stretching of height and/or plastics deformation meeting reduce isolation improvement, and this can trace back to the variation of range of stretch extremely high in layer material matrix material.
Yet although this high-load, matrix material is so stable, so that kept the buffer action that can detect easily.Although this effect is owing to high elongation and/or plastic deformation, but because good bondingly cause not occurring layer material and separate, with most surfaces, in layer material matrix material, do not form the fact of crackle, and crackle will have negative impact to buffer action for coated substrates.
After creep test, measure O once more 2-BIF.Measured value sees Table 1: method 2 and 3, and this numeric ratio method 1 shortens widely, and this makes compares with method 1, can realize suitable good isolation effect and after creep test even slightly improved buffer action.
After coating, the fastest method has slightly and to reduce but still very high isolation improvement and after creep test, has just in time and slower method 1 the same good isolation improvement.
The embodiment 2 that exemplifies
The alternating layer that contains the organic and inorganic layer of alternative
Repeatedly repeat the method for first embodiment that exemplifies, so that apply the alternating layer that contains the organic and inorganic layer of alternative.
After having applied organic sealing coat, carry out the quick variation of gas and apply inorganic barrier, carry out further gas and change, in this process, establish the painting parameter of organic layer.
Then, repeat once to contain the operation of above cited step at least.Sedimentary alternating layer has high buffer action and unusual favorable mechanical load-tolerance.
The embodiment 3 that exemplifies
The quick coating of HOT-FILL bottle
Method 2 employed same process parameters in the embodiment 1 of using and exemplifying, coating is the HOT-FILL bottle of 0.5L by the volume of crystalline PET manufacturing.In the case, according to common practice, use the HOT-FILL bottle to represent the charging of available heat liquid and when the liquid filling bottle that with temperature is 85 ℃-95 ℃, do not experience the bottle of dimensional change basically.
Yet based on the bottle shape that changes, sedimentation rate is constant.
In order to be coated with the bottle of substantially the same bed thickness in the embodiment 1 that has and exemplify, the result is to be that coating time of 1.3 seconds and second inorganic layer is 5.3 seconds the coating time of first organic layer.
Just after coating, container has high buffer action.The oxygen infiltration of uncoated HOT-FILL bottle is 0.192cm 3The oxygen infiltration of the bottle of/(packing day bar) and coating is lower than 0.04cm 3The detection lower limit of/(packing day bar), so O 2-BIF is greater than 40.
In loading test, at first under 35 ℃ and 95% relative atmospheric moisture, stored the bottle that is coated with 1 hour.Then, fill the degree of bottle to 0.5L at 95 ℃ of following waters, insulation is 5 minutes under this degree, in cooling bath, the container of feeding is arrived room temperature at 20 minutes internal cooling then.
In the loading test of this heat-charging, the infiltration of the oxygen of working sample.
After loading test, result in this case is O 2-BIF is 9.This evidence coating ability is subjected to molten charge, because do not observe the separation of layer material and keep the good isolation effect after molten charge.
The embodiment 4 that exemplifies
Quick coated inside with 0.6L PP bottle of adhesion promotor/isolation matrix material
Method 2 employed same process parameters in the embodiment 1 of using and exemplifying, the stocking volume that coating is made by polypropylene (PP) is the bottle of 0.6L.Change sedimentation rate based on the bottle shape that changes.
In order to be coated with the bottle of identical bed thickness in the embodiment 1 that has and exemplify, the coating time of first organic layer is that the coating time of 1 second and second inorganic layer is 5.6 seconds as a result.This coating may be produced has the high oxygen isolation improvement factor (O 2-BIF) adhesion promotor/isolation matrix material.
The bonding very firm and ability of layer material is stretched.In this case, do not need plasma body pre-treatment or activation ground, and use oxygen gas plasma that the activation of ground may take place.

Claims (39)

1. method that applies alternating layer by chemical vapour deposition, it comprises following processing step: the organic adhesion promoter layer of deposition on ground, with apply inorganic barrier, the alternating layer of the organic and inorganic materials of alternating deposit wherein, and the organic adhesion promoter layer applies as the first layer, and inorganic layer applies as the second layer, and in the method, the coating time that applies organic adhesion promoter layer is that 0.05 second-4.0 seconds and/or coating time of applying inorganic barrier are 0.1 second-6.0 seconds.
2. the process of claim 1 wherein by changing at least one, preferably at least two processing parameter deposition alternating layers.
3. claim 1 or 2 method wherein will be by microwaves, and optimized frequency is the deposition that plasma body that the microwave of 2.45GHz produces is used for layer material.
4. the method for claim 3, wherein the plasma body that produces by microwave is pulse.
5. the method for one of aforementioned claim wherein applies alternating layer by PECVD (plasma enhanced chemical vapour deposition) method.
6. the method for one of aforementioned claim, processing parameter wherein to be changed are selected from precursor concentration, average microwave power, pressure, overall flow rate, pulse power, pulse length and the time length of interpulse time period.
7. the method for one of aforementioned claim, wherein applying precursor concentration that organic adhesion promoter layer uses and be the 5%-80% of total flux and/or wherein applying the precursor concentration that sealing coat uses is the 0.5%-4% of total flux, preferred 0.8%-3%.
8. the method for one of aforementioned claim, the interpulse time period that wherein is used for organic layer in the 2ms-100ms scope, preferably in the 5ms-60ms scope and the interpulse time period that is used for inorganic layer in the 5ms-200ms scope, preferably in the 20ms-50ms scope.
9. the method for one of aforementioned claim, the pulse power that wherein is used for organic layer is in the 100W-5000W scope, preferably in the 400W-1500W scope, and/or the pulse power that is used for second inorganic layer is in the 100W-5000W scope, preferably in the 400W-1500W scope.
10. the method for one of aforementioned claim, the average microwave power that wherein is used for organic layer is in the 10W-5000W scope, preferably in the 10W-500W scope, and/or the average microwave power that is used for inorganic layer is in the 10W-5000W scope, preferably in the 30W-2000W scope.
11. the method for one of aforementioned claim, wherein ground is a ducted body, the wherein preferred pressure P that is evacuated down to outside it simultaneously 1Side is evacuated to pressure of foundation P within it 2<P 1, pressure P wherein 1Especially in the 10-50mbar scope and pressure of foundation P 2Especially less than 1mbar, preferably less than 0.5mbar.
12. the method for one of aforementioned claim wherein makes the gaseous mixture that contains precursor with pressure P 3Flow into the inside of ground, wherein P 2<P 3<P 1, pressure P 3Scope be 0.2mbar-1.0mbar especially.
13. the method for one of aforementioned claim, wherein in the deposition process of inorganic barrier, overall flow rate and/or pressure P in ground inside 3At least equal and be higher than in the deposition process of organic adhesion promoter layer overall flow rate and/or pressure P especially in ground inside 3
14. the method for one of aforementioned claim wherein is used for the pressure P of first organic layer 3Scope be 0.1mbar-1.0mbar, 0.2mbar-0.5mbar and be used for the pressure P of second inorganic layer preferably 3Scope be 0.1mbar-1.0mbar, 0.25mbar-0.6mbar preferably.
15. the method for one of aforementioned claim, wherein spray gun length is the 5%-80% of ground height to be coated, preferred 10%-50%.
16. the method for one of aforementioned claim, the overall flow rate that wherein is used for the organic adhesion promoter layer is in the 10sccm-250sccm scope, preferably in the 40sccm-100sccm scope, with the overall flow rate that is used for inorganic layer in the 200sccm-1000sccm scope, preferably in the 250sccm-400sccm scope.
17. the method for one of aforementioned claim, the processing gas that wherein is used for layer material under each situation with pressure P 4Enter described pressure P 4Be higher than the just pressure P before the plasma body burning 5
18. the method for one of aforementioned claim, wherein the operation pressure that applies in the process at layer material continues to reduce, until beginning to apply down one deck material.
19. the method for one of aforementioned claim, wherein the temperature that applies in the process in coating continues to raise.
20. the method for one of aforementioned claim, wherein in the transient process between two application step, in changes in process parameters, the plasma body sustained combustion.
21. the method for one of claim 1-19, wherein in the transient process between two application step, in changes in process parameters, in transit time, interrupt plasma body, described transit time especially in 0-1.0 scope second, preferred 0.005 second-0.5 second.
22. the method for one of aforementioned claim, wherein the transit time of pulsed plasma is greater than the interpulse time period.
23. the method for one of aforementioned claim wherein before applying coating, is carried out the plasma body pre-treatment, the wherein pretreated time length is lower than 5 seconds, preferably is lower than 1 second.
24. the method for one of aforementioned claim wherein changes at least a processing parameter continuously.
25. the method for one of aforementioned claim wherein changes at least a processing parameter discontinuously.
26. the method for one of aforementioned claim, wherein partial continuous and part change at least a processing parameter discontinuously.
27. the method for one of aforementioned claim wherein realizes buffer action by prolonging the evolving path.
28. the method for one of aforementioned claim, wherein gaseous mixture containing oxygen gas and at least a siliceous organic compound, preferably hexamethyldisilazane HMDSN and/or hexamethyldisiloxane HMDSO.
29. the method for one of aforementioned claim wherein repeats to apply the processing step of the first layer and the second layer.
30. the method for one of aforementioned claim wherein deposits alternating layer on dielectric materials.
31. the method for claim 30 wherein deposits alternating layer on plastics.
32. the method for one of aforementioned claim, wherein the sedimentation rate of organic layer is in the 120nm/min-5000nm/min scope, preferably in the 500nm/min-2000nm/min scope, and/or the sedimentation rate of inorganic layer is in the 60nm/min-2000nm/min scope, preferably in the 100nm/min-1000nm/min scope.
33. a matrix material, it comprise ground and at least one deck contain organic and alternating layer inorganic coating, wherein use the method for one of aforementioned claim 1-32 to apply this matrix material.
34. the matrix material of claim 33, wherein with uncoated and other identical materials is compared, it is characterized in that having bonding, the stretchiness that increases of the buffer action of increase and/or increase, in the mechanical stability of the increase of compressive load lower floor material-ground matrix material and/or the mechanical stability that under tension load, increases and/or among load and plastic deformation afterwards.
35. the matrix material of claim 34, wherein comprise length variations greater than 4% stretching and/or plastic deformation after, isolation improvement still keeps, wherein the isolation improvement factor of oxygen is preferably greater than 2.0 greater than 1.5.
36. the matrix material of claim 33 or 35, wherein the thickness of organic adhesion promoter layer is 1nm-200nm, and preferred thickness is 2nm-50nm, and/or wherein the thickness of inorganic barrier is 5nm-200nm, and preferred thickness is 5nm-50nm.
37. the matrix material of one of claim 33-36, wherein matrix material is heat-staple, especially under the temperature loading that causes by molten charge.
38. the matrix material of one of claim 33-37, wherein except comprising that one deck includes the alternating layer of machine and inorganic coating at least, matrix material also comprises tectum.
39. the matrix material of one of claim 33-37, wherein matrix material is transparent on substantially.
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