CN101553599A - Multilayered coatings for use on electronic devices or other articles - Google Patents

Abstract

A method of forming a multilayer coating on a surface is disclosed. The method includes providing a source of precursor material and delivering the precursor material to a reaction site adjacent a surface to be coated. Under a first set of reaction conditions, a first layer is deposited over the surface by chemical vapor deposition using a single source of precursor material. Under a second set of reaction conditions, a second layer is deposited over the surface by chemical vapor deposition using a single precursor material source. The first layer can have a predominantly polymeric component, while the second layer can have a predominantly non-polymeric component. Chemical vapor deposition processes can be plasma enhanced and can be performed using reactant gases. The precursor material may be an organosilicon compound such as siloxane. The first and second layers may comprise various types of polymeric materials such as silicone polymers and various types of non-polymeric materials such as silicon oxides. The multilayer coating can have various properties suitable for use with organic light emitting devices, such as optical transparency, impermeability, and/or flexibility.

Description

Multilayer coatings for electronic devices or other articles

The application is by reference Sigurd Wagner and Prashant Mandlik entitled " Mixed Composition Layers for Use as Coatings onElectronic Devices or Other Articles " U.S. Patent Application No._____ is incorporated herein as a whole, and the lawyer's file number of this application is No. 10020/35301 and filed on the same date as this application.

[0002] This invention was made with United States Government support under Contract No. W911QX-06-C-0017 awarded by the Army Research Office. The US Government may have certain rights in this invention.

technical field

[0003] The present invention relates to barrier coatings for electronic devices.

Background technique

[0004] Organic electronic devices such as organic light emitting devices (OLEDs) are prone to degradation when exposed to water vapor or oxygen. Protective barrier coatings on OLEDs that reduce their exposure to water vapor or oxygen can help improve the lifetime and performance of the devices. Silicon oxide films, silicon nitride films, or aluminum oxide films, which are successfully used in food packaging, have been considered as barrier coatings for OLEDs. However, these inorganic films tend to contain microscopic defects that allow water vapor and oxygen to diffuse through the film. In some cases, the defects manifest as cracks in the brittle film. While this amount of diffusion is acceptable for edible products, it is not acceptable for OLEDs. To address this issue, multilayer barrier coatings using alternating inorganic and polymer layers were tested on OLEDs and found to have improved resistance to water vapor and oxygen permeation. But the methods for making these multilayer coatings can be cumbersome and expensive. Therefore, there is a need for other methods of making multilayer coatings suitable for protecting OLEDs.

overview

[0005] In one aspect, the present invention provides a method of forming a coating on a surface comprising: (a) providing a single source of precursor material; (b) delivering the precursor material to a reaction site adjacent to the surface to be coated (c) depositing a first layer over the surface by chemical vapor deposition using the single precursor material source under a first set of reaction conditions, the first layer having a 100:0-75:25 polymeric material and non-polymeric material and (d) depositing a second layer over the surface by chemical vapor deposition using the single precursor material source under a second set of reaction conditions, the second layer having a polymerization ratio of 0:100 to 25:75 The weight ratio of polymer material to non-polymer material.

[0006] The chemical vapor deposition process may be plasma enhanced and may be performed using reactant gases. The precursor material may be an organosilicon compound such as siloxane. The polymer layer may contain various types of polymer materials such as silicone polymers, and the non-polymer layer may contain various types of non-polymer materials such as silicon oxide. The multilayer coating can have various properties suitable for use with organic light emitting devices, such as optical transparency, impermeability, and/or flexibility.

Brief description of the drawings

[0007] Figure 1 shows a schematic diagram of a PE-CVD apparatus that may be used to practice certain embodiments of the present invention.

[0008] FIG. 2 shows a cross-sectional view of a portion of an OLED with a multilayer barrier coating.

[0009] Figure 3 shows the results of experiments comparing the degradation of coated OLEDs to bare OLEDs.

detail

[0010] In one aspect, the invention provides a method of forming a multilayer coating on a surface. The method involves depositing a polymer layer and a non-polymer layer over a surface by chemical vapor deposition. Under the first set of reaction conditions, the non-polymeric layer is deposited using a single precursor material source alone or with the addition of reactant gases. Under a second set of reaction conditions, the same single precursor material source is used to deposit the polymer layer alone or with the addition of reactant gases.

[0011] As used herein, the term "non-polymer" refers to a material composed of molecules of a well-defined chemical formula having a single, well-defined molecular weight. "Non-polymeric" molecules can have very large molecular weights. In some cases, non-polymeric molecules may include repeating units. As used herein, the term "polymer" refers to a material composed of molecules having covalently linked repeating subunits, and the molecular weight of said molecules may vary from molecule to molecule, This is because polymerization reactions can produce different numbers of repeat units for each molecule. Polymers include, but are not limited to, homopolymers and copolymers such as block, graft, random or alternating copolymers, and blends and variations thereof. Polymers include, but are not limited to, polymers of carbon or silicon.

[0012] A "polymeric layer" consists essentially of a polymeric material, but may contain incidental amounts (up to 5%) of non-polymeric materials. The residual volume is sufficiently small that a person skilled in the art would still consider the layer to be polymeric. Likewise, a "non-polymeric layer" consists essentially of non-polymeric material, but may contain incidental amounts (up to 5%) of polymeric material. The residual volume is sufficiently small that a person skilled in the art would still consider the layer to be non-polymeric.

[0013] Various techniques can be used to determine the polymer/non-polymer composition of a layer, including wetting contact angle of a water droplet, infrared absorption, hardness, and flexibility. For example, a pure polymer layer formed from HMDSO has a wetting contact angle of about 103°. As such, in some cases, the first layer has a wetting contact angle of 60°-115°, preferably 75°-115°. The wetting contact angle of a pure silicon oxide layer is about 32°. As such, in some cases, the second layer has a wetting contact angle of 0°-60°. It should be noted that the wetting contact angle is a measure of composition if measured on the surface of the film in the as-deposited state. Because wetting contact angles can vary greatly due to post-deposition processing, measurements made after such processing may not accurately reflect layer composition. It is believed that these wetting contact angles are applicable to many layers formed from organosilicon precursors. Preferably, the first layer has a nanoindentation hardness of 1 MPa-3 GPa, more preferably 0.2-2 GPa. Preferably, the second layer has a nanoindentation hardness of 10GPa-200GPa, more preferably 10GPa-20GPa. In some cases, at least one layer has a surface roughness (root mean square) of 0.1 nm to 10 nm, more preferably 0.2 nm to 0.35 nm. In some cases, at least one layer has sufficient flexibility when deposited as a 4 μm thick layer on a 50 μm thick polyimide foil substrate, such that at a tensile strain (ε) of 0.2% No microstructural changes were observed after at least 55000 rolling cycles on diameter rolls. In some cases, at least one layer is sufficiently flexible such that at least 0.35% tensile strain (ε) (a level of tensile strain considered by those skilled in the art to typically crack a 4 μm layer of pure silicon oxide) has no Cracks appear.

[0014] Single-layer barrier coatings made of pure non-polymeric materials such as silicon oxide can have various advantages related to light transmission, good adhesion, and good film stress. However, these non-polymeric layers tend to contain microscopic defects that allow water vapor and oxygen to diffuse through the layer. Alternating polymer and non-polymer layers reduces the permeability of the coating. Without intending to be bound by theory, the inventors believe that the polymer layer masks and/or planarizes defects in adjacent non-polymeric layers, thereby reducing diffusion through the defects.

[0015] As used herein, "single source of precursor material" means providing the precursor material necessary to form both the polymer layer and the non-polymer layer when depositing the precursor material by CVD (with or without the addition of reactant gases). source of all precursor materials. This is intended to exclude methods in which one precursor material is used to form a polymer layer and a different precursor material is used to form a non-polymer layer. The deposition method is simplified by using a single precursor material source. For example, a single source of precursor material can eliminate the need for a separate flow of precursor material and the attendant need to monitor that separate flow.

[0016] The precursor material may be a single compound or a mixture of compounds. In some cases, when the precursor material is a mixture of compounds, each different compound in the mixture can independently serve as the precursor material by itself. For example, the precursor material may be a mixture of hexamethyldisiloxane (HMDSO) and dimethylsiloxane (DMSO).

[0017] In some cases, plasma enhanced CVD (PE-CVD) may be used for the deposition of each layer. PE-CVD can be desirable for a number of reasons including low temperature deposition, uniform coating formation, and controllable process parameters. Various PE-CVD methods suitable for use in the present invention are known in the art, including those that use RF energy to generate a plasma.

[0018] A precursor material is a material capable of forming both polymeric and non-polymeric materials when deposited by chemical vapor deposition. A variety of such precursor materials are suitable for use in the present invention and are selected for their various properties. For example, the precursor material can be selected with respect to its chemical element content, its stoichiometric ratio of chemical elements, and/or the polymeric and non-polymeric materials formed under CVD. For example, organosilicon compounds such as siloxanes are a class of compounds suitable for use as precursor materials. Representative examples of silicone compounds include hexamethyldisiloxane (HMDSO) and dimethylsiloxane (DMSO). These siloxane compounds are capable of forming polymeric materials such as silicone polymers and non-polymeric materials such as silicon oxide when deposited by CVD. Precursor materials can also be selected for various other characteristics such as cost, non-toxicity, handling characteristics, ability to maintain a liquid phase at room temperature, volatility, molecular weight, and the like.

[0019] Other organosilicon compounds suitable for use as precursor materials include methylsilane; dimethylsilane; vinyltrimethylsilane; trimethylsilane; tetramethylsilane; disilanomethane); bis(methyl-silano)methane); 1,2-disilanoethane; 1,2-bis(methyl-silano)ethane Alkane (1,2-bis(methylsilano)ethane); 2,2-disilanopropane (2,2-disilanopropane); 1,3,5-trisilyl-2,4,6-trimethylene (1 , 3,5-trisilano-2,4,6-trimethylene), and fluorinated derivatives of these compounds. Phenyl-containing organosilicon compounds suitable for use as precursor materials include: dimethylphenylsilane and diphenylmethylsilane. Oxygen-containing organosilicon compounds suitable for use as precursor materials include: dimethyldimethoxysilane; 1,3,5,7-tetramethylcyclotetrasiloxane; 1,1,3,3-tetramethyl 1,3-bis(silylmethylene)disiloxane (1,3-bis(silanomethylene)disiloxane); bis(1-methylsilyl ether)methane; 2,2 -Bis(1-methylsilyl)propane; 2,4,6,8-Tetramethylcyclotetrasiloxane; Octamethylcyclotetrasiloxane; 2,4,6,8,10- Pentamethylcyclopentasiloxane; 1,3,5,7-tetrasilyl-2,6-dioxo-4,8-dimethylene (1,3,5,7-tetrasilano-2,6 -dioxy-4,8-dimethylene); Hexamethylcyclotrisiloxane; 1,3-Dimethyldisiloxane; 1,3,5,7,9-Pentamethylcyclopentasiloxane; Hexamethoxydisiloxane, and fluorinated derivatives of these compounds. Nitrogen-containing organosilicon compounds suitable for use as precursor materials include: hexamethyldisilazane; divinyltetramethyldisilazane; hexamethylcyclotrisilazane; dimethylbis(N-methyldisilazane; Dimethylbis-(N-ethylacetamido)silane; Methylvinylbis(N-methylacetamido)silane; Methylvinylbis(N-butylacetamido)silane ; Methyltris(N-phenylacetamido)silane; Vinyltris(N-ethylacetamido)silane; Tetrakis(N-methylacetamido)silane; Diphenylbis(diethylaminooxy) silane; methyltris(diethylaminooxy)silane; and bis(trimethylsilyl)carbodiimide.

[0020] When using PE-CVD, a precursor material may be used in conjunction with a reactant gas that reacts with the precursor material during the PE-CVD process. The use of reactant gases in PE-CVD is known in the art, and a variety of reactant gases are suitable for use in the present invention, including oxygen-containing gases (e.g. _O2 , ozone, water) and nitrogen-containing gases (e.g. ammonia) . The reactant gases can be used to alter the stoichiometric ratios of the chemical elements present in the reaction mixture. For example, when a siloxane precursor material is used with an oxygen- or nitrogen-containing reactant gas, the reactant gas will alter the stoichiometric ratio of oxygen or nitrogen relative to silicon and carbon in the reaction mixture. This stoichiometric relationship between the various chemical elements (eg, silicon, carbon, oxygen, nitrogen) in the reaction mixture can be varied in several ways. One way is to vary the concentration of precursor material or reactant gas in the reaction. Another way is to vary the flow rate of precursor material or reactant gas into the reaction. Yet another way is to vary the type of precursor material or reactant gas used for the reaction.

[0021] The type of material formed by chemical vapor deposition of the precursor material will depend on the reaction conditions under which the CVD process is performed. The reaction conditions may be defined by the composition of the reaction mixture, including the types of precursor materials and reactant gases used and the amounts of these materials. For example, the reaction mixture may contain a siloxane gas (such as HMDSO or DMSO) as a precursor material and oxygen as a reactant gas. The amount of reaction mixture materials can be adjusted by varying the flow rates of these materials. For example, by varying the flow rates of precursor materials and reactant gases, different types of materials can be deposited. In some cases, no reactant gas is present in the reaction mixture (eg, the flow rate of the reactant gas is set to zero). Other parameters defining reaction conditions include various process parameters such as RF power and frequency, deposition pressure, temperature and deposition time.

[0022] In the method of the present invention, a first layer having a predominantly polymeric component is deposited by CVD using a first set of reaction conditions. Depending on the reaction conditions used, the precursor materials can form various types of non-polymeric materials. Non-polymeric materials can be inorganic or organic. For example, when an organosilicon compound is used as the precursor material and combined with an oxygen-containing reactant gas, the non-polymeric material may include silicon oxides such as SiO, _SiO2 , and mixed valence oxides _SiOx . When deposition is performed with a nitrogen-containing reactant gas, the non-polymeric material may include silicon nitride ( _SiNx ). Other non-polymeric materials that may be formed include silicon carbide, silicon oxycarbide, and silicon oxynitride. Preferably, the first layer has a polymer to non-polymer weight ratio of 100:0 to 75:25.

[0023] A second layer having a predominantly non-polymeric component is deposited by CVD using a second set of reaction conditions. Depending on the reaction conditions used, the precursor materials can form various types of polymeric materials. Polymeric materials can be inorganic or organic. For example, when organosilicon compounds are used as precursor materials, the deposited hybrid layer can include Si-O bonds, Si-C bonds, or polymer chains of Si-O-C bonds to form polysiloxanes, polycarbosilanes, and polysilanes. and organic polymers. Preferably, the second layer has a polymer to non-polymer weight ratio of 0:100 to 25:75.

[0024] Thus, by using the method of the present invention, multilayer coatings can be formed having alternating predominantly polymeric layers and predominantly non-polymeric layers. The coating can have properties suitable for a variety of uses. Such properties include light transmission, impermeability, flexibility, thickness, adhesion and other mechanical properties. For example, one or more of these properties can be adjusted by varying the overall thickness of the coating, the thickness of the polymeric layer relative to the thickness of the non-polymeric layer, and the number of alternating layers. For example, the coating may have 3 to 5 polymer/non-polymer layer pairs to achieve the desired level of impermeability. In some cases, the polymeric layer may have a thickness of 0.1 μm-10 μm, and the non-polymeric layer may have a thickness of 0.05 μm-10 μm. Other numbers and thicknesses of layers are also possible and the thickness of each layer can be varied independently.

[0025] One method by which a layer can be characterized is the wetting contact angle of a water drop, a technique well known in the art. One way to determine if a multilayer coating has alternating layers having a predominantly polymeric component and a predominantly non-polymeric component is to measure the wetting angle. For example, if the first layer has a wetting angle greater than 60° (or 60°-115°) and the second layer has a wetting angle less than 60° (or 60°-0°), the first layer can be considered Has significantly more polymer than the second layer. As an example, the contact angle of the polymer pp-HMDSO is 103°, while _that of the non-polymer SiO is 32°. In some cases, a multilayer coating may be considered to have alternating layers if the wetting contact angles differ by a certain amount between the first layer and the second layer. For example, a multilayer coating can be characterized as having alternating layers, with the first layer being more polymeric, wherein the first layer has a wetting contact angle that is at least 15° greater than the second layer.

[0026] The polymeric and non-polymeric layers may be deposited in any order. In some cases, the non-polymeric layer is deposited before depositing the polymeric layer. In other cases, the polymeric layer is deposited prior to depositing the non-polymeric layer. For example, a polymer layer may first be deposited on the surface to act as a planarization layer.

[0027] The multilayer coating can be deposited on various types of articles. In some cases, the article can be an organic electronic device such as an OLED. For OLEDs, this multilayer coating acts as a barrier coating against water vapor and oxygen penetration. For example, a multilayer coating having a water vapor transmission rate of less than 10 ⁻⁶ g/m ² /day and/or an oxygen transmission rate of less than 10 ⁻³ g/m ² /day may be suitable for protecting OLEDs. In some cases, the thickness of the multilayer coating may be 0.5-10 μm, but other thicknesses may also be used depending on the application. In addition, multilayer coatings with thicknesses and material compositions that impart light transmission may be suitable for use with OLEDs. For use with flexible OLEDs, multilayer coatings can be engineered to have the desired amount of flexibility. In some cases, the multilayer coatings can be used on other articles that are sensitive to degradation when exposed to the environment, such as pharmaceuticals, medical devices, biological reagents, biological samples, biosensors, or other sensitive measurement devices.

[0028] Any of various types of CVD reactors can be used to practice the method of the present invention. As an example, Figure 1 shows a PE-CVD apparatus 10 that may be used to practice certain embodiments of the present invention. The PE-CVD apparatus 10 includes a reaction chamber 20 in which an electronic device 30 is loaded on a fixture 24 . The reaction chamber 20 is designed to contain a vacuum and a vacuum pump 70 is connected to the reaction chamber 20 to generate and/or maintain an appropriate pressure. The N ₂ gas tank 50 provides N ₂ gas to purify the device 10 . The reaction chamber 20 may also include a cooling system to reduce the heat generated by the reaction.

[0029] To manipulate gas flow, apparatus 10 also includes various flow control mechanisms (eg, mass flow controller 80, shutoff valve 82, and check valve 84), which may be under manual or automatic control. A precursor material source 40 provides a precursor material (eg, HMDSO in liquid form) that is vaporized and filled into the reaction chamber 20 . In some cases, the precursor material may be delivered to reaction chamber 20 using a carrier gas, such as argon. A reactant gas tank 60 provides a reactant gas (eg, oxygen) which is also charged into the reaction chamber 20 . The precursor materials and reactant gases flow into reaction chamber 20 to generate reaction mixture 42 near electronic device 30 . The pressure inside the reaction chamber 20 may be additionally adjusted to obtain a deposition pressure. Reaction chamber 20 includes a set of electrodes 22 mounted on electrode standoffs 26, which may be conductors or insulators. Various configurations of device 30 and electrodes 22 are possible. Diode or triode electrodes, or remote electrodes may be used. Device 30 may be remotely located as shown in FIG. 1, or may be mounted on one or both electrodes of the diode structure.

[0030] RF power is provided to the electrode 22 to create plasma conditions in the reaction mixture 42. The plasma generated reaction products are deposited onto electronic device 30 . The reaction is allowed to proceed for a period of time sufficient to deposit a layer on electronic device 30 . Reaction times will depend on factors such as the position of device 30 relative to electrode 22, the type of layer to be deposited, reaction conditions, desired layer thickness, precursor materials, and reactant gases. The reaction time can last from 5 seconds to 5 hours, but longer or shorter times can be used depending on the application. The previous steps can then be repeated under different reaction condition settings to deposit different types of layers. Device 30 may require heating or cooling to bring its temperature or maintain its temperature at a desired value.

[0031] FIG. 2 shows a cross-sectional view of a portion of an OLED 100 comprising an OLED body 140 on a substrate 150 and a polyol deposited by PE-CVD using HMDSO as the precursor material and oxygen as the reactant gas. layer barrier coating 160 . In Table 1 below are shown the properties of the layers in the multilayer coating and the reaction conditions for their deposition. A silicon oxide layer 110 was deposited on OLED body 140 using the reaction conditions shown. Silicon polymer layer 120 was deposited over layer 110 using different reaction condition settings including a higher HMDSO flow rate and a reduced oxygen flow rate. Finally, a silicon oxide layer 130 is deposited over layer 120 using the same reaction conditions as layer 110 .

Table 1

[0032] FIG. 3 shows the results of an experiment comparing the degradation of the coated OLED in FIG. 2 with that of the bare OLED. Both OLEDs were operated at room temperature in ambient air for 17 days at 6.5 V DC. Coated OLEDs suffer significantly less degradation than bare OLEDs. These results demonstrate that the method of the present invention can provide coatings that are effective in protecting against the degrading effects of environmental exposure.

[0033] FIG. 4 shows a layer of 6 μm deposited using HMDSO at a source temperature of 33° C. and a flow rate of 1.5 sccm with _an O flow rate of 50 sccm, a deposition pressure of 150 mTorr, an RF power of 60 W, and a deposition time of 135 minutes optical transmission spectrum. The layer has a transmittance greater than 90% in the spectrum from near ultraviolet to near infrared.

[0034] Figure 5 shows how the contact angle of a water drop on a film is measured. Figure 6 is a graph of the contact angles of several layers formed at various _O2 /HMDSO gas flow ratios compared to that of pure _SiO2 films and pure polymers. As the oxygen flow rate in the deposition process increases, the contact angle of the layer approaches that of a pure _SiO2 film.

[0035] FIG. 7 is a graph of the contact angles of several layers formed during PE-CVD processing at various power levels applied. At increasing power levels, the contact angle of the layer approaches that of the pure _SiO2 film, possibly due to _O2 being a stronger oxidizing agent at higher power levels. Figure 8 shows the infrared absorption spectra of layers formed using relatively high _O2 flow and relatively low _O2 flow compared to films of pure _SiO2 (thermal oxide) or films of pure polymer. The high O _layer shows strong peaks in the Si-O-Si band. The nominal peaks in the Si- _CH3 bands of thermal oxide (pure _SiO2 ) films are believed to be related to Si-O vibrations. Figure 9 is a graph of the nanoindentation hardness of various layers formed at various _O2 /HMDSO gas flow ratios compared to the hardness of pure _SiO2 films. The hardness of this layer increases with the oxygen flow rate in the deposition process, and these layers can be almost as hard as pure _SiO2 films, yet are tough and very soft.

[0036] FIG. 10 is a graph of surface roughness (root mean square) measured by atomic force microscopy for several layers formed at various _O2 /HMDSO gas flow ratios, and shows that the surface roughness varies with The O ₂ flow rate for the deposition process was increased and decreased. Figure 11 is a graph of the surface roughness (root mean square) measured by atomic force microscopy for several layers formed at various power levels and shows that the surface roughness decreases with increasing power levels used for the deposition process .

[0037] FIGS. 12A and 12B show source temperature at 33°C, HMDSO gas flow rate of 1.5 sccm, _O flow rate of 50 sccm, pressure of 150 mTorr and RF power of 60 W on a 50 μm thick Kapton polyimide foil Optical micrograph of the surface under the deposited 4 μm layer. In Figure 12A, images were taken before and after subjecting the coated foil to cyclic rolling (tensile strain ε = 0.2%) on a 1 inch diameter roll. No microstructural changes were observed after 58600 rolling cycles. In FIG. 12B , the coated foil was subjected to increasing tensile strain and images were acquired after the first cracking (14 mm roll diameter) and after extensive cracking (2 mm roll diameter). These flexibility results demonstrate that the method of the present invention can provide highly flexible coatings.

Claims (33)

1. form the method for coating from the teeth outwards, comprising:

The single precursor material source is provided;

Precursor material is transported to response location with surperficial adjacency to be coated;

Under the first group reaction condition, use this single precursor material source to deposit the first layer in this surface by chemical vapour deposition, this first layer has 100: 0-75: 25 polymer materials and non-polymer material weight ratio; With

Under the second group reaction condition, use this single precursor material source to deposit the second layer in this surface by chemical vapour deposition, this second layer has 0: 100-25: 75 polymkeric substance and non-polymer material weight ratio.

2. the process of claim 1 wherein that the chemical vapour deposition under the described first and second group reaction conditions is the plasma body enhanced.

3. the method for claim 2, also being included in the first group reaction condition, the second group reaction conditioned disjunction its both provides reactant gas and this reactant gas is transported to response location.

4. the method for claim 3, wherein reactant gas is an oxygen.

5. wherein there is reactant gas in the method for claim 3 under two group reaction conditions, and the flow velocity of this reactant gas greatly at least 10% in the velocity ratio second group reaction condition of this reactant gas in the first group reaction condition wherein.

6. the process of claim 1 wherein that the described first group reaction condition and the second group reaction condition comprise independently of one another is selected from following parameter: gas flow rate, gaseous tension, processing pressure, DC power, RF power, RF frequency, underlayer temperature and depositing time.

7. the process of claim 1 wherein that described precursor material includes organic silicon compound.

8. the method for claim 7, wherein said precursor material comprises single silicoorganic compound.

9. the method for claim 7, wherein said precursor material comprises the mixture of multiple silicoorganic compound.

10. the method for claim 7, wherein said silicoorganic compound are hexamethyldisiloxane or dimethyl siloxane.

11. the method for claim 7, wherein said silicoorganic compound are selected from: methyl-monosilane; Dimethylsilane; Vinyl trimethylsilane; Trimethyl silane; Tetramethylsilane; Ethylsilane; The disilane methylmethane; Two (methyl-monosilane base) methane; 1,2-disilane base ethane; 1, two (methyl-monosilane base) ethane of 2-; 2,2-disilane base propane; 1,3,5-three silylation-2,4,6-trimethylene; Dimethylphenylsilaneand; Diphenylmethylsilane; Dimethyldimethoxysil,ne; 1,3,5, the 7-tetramethyl-ring tetrasiloxane; 1,3-dimethyl sily oxide; 1,1,3, the 3-tetramethyl disiloxane; 1, two (silylation methylene radical) sily oxide of 3-; Two (1-methyl disiloxanyl-) methane; 2, two (the 1-methyl disiloxanyl-) propane of 2-; 2,4,6, the 8-tetramethyl-ring tetrasiloxane; Octamethylcyclotetrasiloxane; 2,4,6,8,10-pentamethyl-D5; 1,3,5,7-tetrasilane base-2,6-dioxy-4,8-dimethylene; Hexamethyl cyclotrisiloxane; 1,3,5,7,9-pentamethyl-D5; The hexa methoxy sily oxide; Hexamethyldisilazane; The divinyl tetramethyl-disilazane; Pregnancy basic ring three silazane; Two (the N-methyl kharophen) silane of dimethyl; Dimethyl is two-(N-ethyl kharophen) silane; Two (the N-methyl kharophen) silane of methyl ethylene; Two (the N-butyl kharophen) silane of methyl ethylene; Methyl three (N-phenyl kharophen) silane; Vinyl three (N-ethyl kharophen) silane; Four (N-methyl kharophen) silane; Two (diethyl aminooxy) silane of phenylbenzene; Methyl three (diethyl aminooxy) silane; With two (trimethyl silicon based) carbodiimide.

12. the process of claim 1 wherein that described non-polymer material is made of inorganic materials substantially.

13. the method for claim 12, wherein said inorganic materials is a silicon oxide.

14. the process of claim 1 wherein that described polymer materials is made of silicone polymer substantially.

15. the method for claim 1 also is included under the 3rd group reaction condition, uses this single precursor material source to deposit the 3rd layer by chemical vapour deposition above the first layer and the second layer.

16. the process of claim 1 wherein and before the deposition the first layer, deposit the second layer.

17. the method for claim 1, also comprise and repeat following steps in an alternating manner at least one time: deposition has 100: 0-75: the layer of 25 polymer materials and non-polymer material weight ratio and have 0: 100-25: the layer of 75 polymer materials and non-polymer material weight ratio, wherein selection is used to deposit the reaction conditions of each layer independently.

18. the process of claim 1 wherein at the material of the transition period deposition of deposition between each layer less than 10nm.

19. the process of claim 1 wherein that described surface is the surface that is used for the substrate of electron device.

20. the method for claim 19, wherein said electron device is an organic luminescent device.

21. the method for claim 19, wherein said electron device is a solar cell.

22. the process of claim 1 wherein that described surface is the surface of electron device.

23. the method for claim 22, wherein said electron device is an organic luminescent device.

24. the method for claim 22, wherein said electron device is a solar cell.

25. the process of claim 1 wherein that the first layer of firm sedimentation state has 60 °-115 ° water droplet moisten contact angle.

26. the process of claim 1 wherein that the first layer of firm sedimentation state has 75 °-115 ° water droplet moisten contact angle.

27. the process of claim 1 wherein that the second layer of firm sedimentation state has 0 °-60 ° water droplet moisten contact angle.

28. the process of claim 1 wherein that the first layer of firm sedimentation state and the just moisten contact angle of the second layer of sedimentation state differ at least 15 °.

29. the process of claim 1 wherein that described the first layer has the nano-indentation hardness of 0.2-2GPa.

30. the process of claim 1 wherein that the described second layer has the nano-indentation hardness of 10-20GPa.

31. the process of claim 1 wherein that at least one has the surfaceness (rootmean-square) of 0.1-10nm in the described layer.

32. the method for claim 1, have enough snappinesies during the 4 μ m layers of at least one in the wherein said layer on being deposited as 50 μ m thick polyimide paper tinsels, make not change after at least 55000 rollings circulations under 0.2% stretching strain (ε), observing microstructure on the 1 inch diameter roll.

33. have enough snappinesies when the process of claim 1 wherein 4 μ m layers on being deposited as 50 μ m thick polyimide paper tinsels of in the described layer at least one, make under at least 0.35% stretching strain (ε), crackle not occur.

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