CN110316690A - Flexible device buffer layer and preparation method thereof and flexible device - Google Patents
Flexible device buffer layer and preparation method thereof and flexible device Download PDFInfo
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- CN110316690A CN110316690A CN201910504014.XA CN201910504014A CN110316690A CN 110316690 A CN110316690 A CN 110316690A CN 201910504014 A CN201910504014 A CN 201910504014A CN 110316690 A CN110316690 A CN 110316690A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81B—MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
- B81B3/00—Devices comprising flexible or deformable elements, e.g. comprising elastic tongues or membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00349—Creating layers of material on a substrate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00349—Creating layers of material on a substrate
- B81C1/00373—Selective deposition, e.g. printing or microcontact printing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/206—Insulating
Abstract
The present invention discloses a kind of flexible device buffer layer and preparation method thereof and flexible device, wherein the flexible device buffer layer, including ethylene vinyl alcohol copolymer film layer and inorganic layer, the inorganic layer are set to the ethylene vinyl alcohol copolymer film layer surface.On the one hand buffer layer of the present invention utilizes the characteristics of ethylene vinyl alcohol copolymer film layer low Young's modulus, on the other hand in conjunction with the high gas of inorganic layer and water vapor barrier property and heat-resisting quantity, to efficiently solve individual inorganic layer or individual organic layer as the problems of buffer layer.Buffer layer of the present invention not only has high gas and water vapor rejection performance, effectively prevent gas to generate serious destruction, and high temperature resistant to flexible device through buffer layer, also has good bending performance, the manufacturing suitable for flexible device.
Description
Technical field
The present invention relates to flexible device technical field, in particular to a kind of flexible device buffer layer and preparation method thereof with it is soft
Property device.
Background technique
The substrate of flexible device mostly uses greatly polyimides (Polyimide, PI) or polyethylene naphthalate
(Polyethylene naphthalate, PEN), but this substrate has disadvantages that, such as the barrier to oxygen, vapor
Performance is poor；Non-refractory, it is low using temperature, subsequent thin film can only be prepared at low temperature, this is unfavorable for chemical vapor deposition
(Chemical Vapor Deposition, CVD), physical vapour deposition (PVD) (Physical Vapor Deposition, PVD) with
And plasma enhanced chemical vapor deposition (plasma enhanced chemical vapor deposition, PECVD)
The methods of preparation subsequent thin film when atom diffusion, forming core, growth so that preparation subsequent thin film resistivity it is big, it is seen that
The low and binding force with substrate of light transmission rate is poor.
It for these problems, is mostly used greatly at present in substrate surface buffer layer, gas resistance is improved by buffer layer
Separating performance enhances heat-resisting quantity, improves the matching with subsequent thin film.Existing buffer layer is broadly divided into two classes: one kind is nothing
Machine material buffer layer, such as Si oxide (SiOx), silicon nitride (SiNx) and aluminium oxide (Al2O3) etc.；Another kind of is organic
Material buffer layer, such as polyvinylpyrrolidone (PVP).However, these buffer layers still remain following ask in practical applications
Topic:
(1) organic material buffer layer, such as polyvinylpyrrolidone (PVP), it is poor to the barrier property of oxygen, vapor,
Oxygen, vapor readily penetrate through buffer layer and generate serious destruction, and non-refractory to flexible device, low using temperature, thus
The resistivity that will lead to prepared subsequent thin film is big, it is seen that the low and binding force with substrate of light transmission rate is poor；
(2) inorganic material buffer layer, such as Si oxide (SiOx), silicon nitride (SiNx) and aluminium oxide (Al2O3) etc.,
Young's modulus is big, is unfavorable for repeatedly bending in Flexible Displays.
Summary of the invention
The main object of the present invention is to provide a kind of with high gas and water vapor barrier property, high temperature resistant and low Young's modulus
Flexible device buffer film.
To achieve the above object, flexible device buffer layer proposed by the present invention, including ethylene vinyl alcohol copolymer film layer and
Inorganic layer, the inorganic layer are set to the ethylene vinyl alcohol copolymer film layer surface.
Further, the flexible device buffer layer, the inorganic layer include in siliceous inorganic matter and inorganic matter containing aluminium
One or two.
Further, the flexible device buffer layer, the ethylene vinyl alcohol copolymer film layer arrive with a thickness of 1 μm
10μm；
And/or the inorganic layer with a thickness of 20nm to 100nm.
The present invention also proposes a kind of preparation method of flexible device buffer layer, comprising the following steps:
Ethylene vinyl alcohol copolymer film layer is prepared, ethylene vinyl alcohol copolymer film layer is obtained；
Inorganic layer is prepared in the ethylene vinyl alcohol copolymer film layer surface.
Further, the preparation method of the flexible device buffer layer, " in the ethylene vinyl alcohol copolymer film layer
Surface prepares inorganic layer " the step of include:
The ethylene vinyl alcohol copolymer film layer is put into the reaction chamber of atomic layer deposition apparatus；
First presoma and the second presoma are alternately passed through the reaction chamber in a pulsed fashion and are deposited on described
Ethylene vinyl alcohol copolymer film layer surface, so that first presoma and second presoma are in the ethylene-vinyl alcohol
The reaction of co-polymer membrane layer surface generates inorganic layer.
Further, the preparation method of the flexible device buffer layer, first presoma include silicon source presoma
One or both of with silicon source presoma；
And/or second presoma includes one or both of oxygen source presoma and nitrogen source presoma.
Further, the preparation method of the flexible device buffer layer, first presoma include ethyl orthosilicate,
One of methyl orthosilicate, trim,ethylchlorosilane, tetramethylsilane, trimethyl aluminium, tri-tert aluminium are a variety of.
Further, the preparation method of the flexible device buffer layer, " preparation ethylene vinyl alcohol copolymer film layer, obtains
To ethylene vinyl alcohol copolymer film layer " the step of include:
Ethylene-vinyl acetate copolymer is placed under alkaline condition, to be saponified generation ethylene-vinyl alcohol copolymer；
The ethylene-vinyl alcohol copolymer is coated, ethylene vinyl alcohol copolymer film layer is obtained.
Further, the preparation method of the flexible device buffer layer, " is placed in alkali for ethylene-vinyl acetate copolymer
Property under the conditions of, be saponified generate ethylene-vinyl alcohol copolymer " the step of include:
Ethylene-vinyl acetate copolymer is placed under the first alkaline condition, to carry out first time saponification, obtains intermediary；
The intermediary is placed under the second alkaline condition, and it is total to carry out secondary saponification generation ethylene-vinyl alcohol to heat up
Polymers, wherein the alkalinity of second alkaline condition is higher than the alkalinity of first alkaline condition.
The present invention also provides a kind of flexible devices, including substrate and the flexible device buffer layer, the flexible device
Buffer layer is set to the substrate surface.
Technical solution of the present invention is set to ethylene vinyl alcohol copolymer film layer surface by using inorganic layer and forms buffering
It the characteristics of layer, on the one hand buffer layer of the present invention utilizes ethylene vinyl alcohol copolymer film layer low Young's modulus, on the other hand ties
The high gas and water vapor barrier property and heat-resisting quantity of conjunction inorganic layer, to efficiently solve individual inorganic layer or individual
Organic layer is as the problems of buffer layer.Buffer layer of the present invention not only has high gas and water vapor rejection performance, has
Effect prevents gas from generating serious destruction, and high temperature resistant to flexible device through buffer layer, also has good bending performance, fits
The manufacturing for flexible device.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
Other relevant attached drawings are obtained according to these attached drawings.
Fig. 1 is the structural schematic diagram of one embodiment of flexible device of the present invention；
Fig. 2 is the flow chart of one embodiment of manufacturing method of flexible device in Fig. 1.
The embodiments will be further described with reference to the accompanying drawings for the realization, the function and the advantages of the object of the present invention.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
It is emphasized that occur in text " and/or " meaning be, including three schemes arranged side by side, with " A and/or B
For ", including the scheme that A scheme or B scheme or A and B meet simultaneously.In addition, the technical solution between each embodiment can
It to be combined with each other, but must be based on can be realized by those of ordinary skill in the art, when the combination of technical solution occurs
Conflicting or cannot achieve when, will be understood that the combination of this technical solution is not present, also not the present invention claims guarantor
Within the scope of shield.
The present invention proposes a kind of flexible device buffer layer.
In embodiments of the present invention, a kind of flexible device buffer layer, including ethylene vinyl alcohol copolymer film layer and inorganic
Layer, the inorganic layer are set to the ethylene vinyl alcohol copolymer film layer surface.
Technical solution of the present invention is set to ethylene vinyl alcohol copolymer film layer surface by using inorganic layer and forms buffering
It the characteristics of layer, on the one hand buffer layer of the present invention utilizes ethylene vinyl alcohol copolymer film layer low Young's modulus, on the other hand ties
The high gas and water vapor barrier property and heat-resisting quantity of conjunction inorganic layer, to efficiently solve individual inorganic layer or individual
Organic layer is as the problems of buffer layer.Buffer layer of the present invention not only has high gas and water vapor rejection performance, has
Effect prevents gas from generating serious destruction, and high temperature resistant to flexible device through buffer layer, also has good bending performance, fits
The manufacturing for flexible device.
Compared with other organic layers, the embodiment of the present invention is using ethylene vinyl alcohol copolymer film layer as organic layer, second
Alkene-ethenol copolymer combines the barrier property of polyvinyl processability and vinyl alcohol polymer, ethylene vinyl alcohol copolymer
Object film not only shows high-flatness, is conducive to inorganic layer uniform deposition, and excellent blocking effect is showed to gas, into
One step prevents oxygen, vapor to readily penetrate through buffer layer and generates serious destroy to flexible device.Also, ethylene-vinyl alcohol is total
Polymers film also has a high mechanical strength, surface hardness, wearability, weatherability, antistatic property and high glaze and low haze,
High performance buffer layer is formed in conjunction with inorganic layer, the manufacturing suitable for flexible device.
Further, the inorganic layer includes one or both of siliceous inorganic matter and inorganic matter containing aluminium.The present invention is real
Example is applied using one or both of siliceous inorganic matter and inorganic matter containing aluminium as inorganic layer, not only have good high gas with
Water vapor rejection performance, and high temperature resistance is excellent, also has good insulating properties, efficiently avoids flexible device electric leakage
Problem.Certainly, siliceous inorganic matter of the present invention includes one or both of Si oxide and silicon nitride；Correspondingly, institute
Stating inorganic matter containing aluminium includes one or both of aluminium oxide and aluminium nitride.Even, the inorganic layer can also be sial oxygen
Compound or silicon aluminum nitrides.
Still further, the chemical composition of the Si oxide is SiOx, wherein 1≤X≤2.Further, the silicon
Oxide is silica (SiO2).Silica (SiO2) not only there is good high gas and water vapor rejection performance, Er Qienai
High-temperature behavior is excellent, good insulation preformance, also has rock-steady structure.Similarly, the chemical composition of the silicon nitride is SiNx, wherein
1≤X<2.Further, the Si oxide is silicon nitride (Si3N4), silicon nitride (Si3N4) it is a kind of superhard substance, itself
It is anti-oxidant when with lubricity, wear-resistant and high temperature, be conducive to the preparation of subsequent thin film layer.
Further, the ethylene vinyl alcohol copolymer film layer with a thickness of 1 μm to 10 μm；And/or the inorganic layer
With a thickness of 20nm to 100nm.Ethylene vinyl alcohol copolymer film layer of the embodiment of the present invention with a thickness of 1 μm to 10 μm, pass through control
The thickness of ethylene vinyl alcohol copolymer film layer processed, reduces the Young's modulus of buffer layer, ensure that buffer layer can be by repeatedly curved
Folding, is conducive to the manufacture of flexible device.In addition, the inorganic layer with a thickness of 20nm to 100nm, guaranteeing buffer layer Young mould
Under the premise of amount, so that prepared buffer layer has high gas and water vapor rejection performance and high temperature resistance.The present invention is real
Example is applied by the thickness of adjusting ethylene vinyl alcohol copolymer film layer and inorganic layer, so that prepared buffer layer not only has height
Gas and water vapor rejection performance can repeatedly be bent, and high temperature resistance is excellent.
The present invention also proposes a kind of preparation method of flexible device buffer layer, including the flexible device buffer layer, described
Flexible device buffer layer is referring to above-described embodiment, since flexible device buffer layer uses whole technologies of above-mentioned all embodiments
Scheme, therefore at least all beneficial effects brought by the technical solution with above-described embodiment, this is no longer going to repeat them.Institute
The preparation method of flexible device buffer layer is stated the following steps are included: preparation ethylene vinyl alcohol copolymer film layer, obtains ethylene-second
Enol copolymer film layer；Inorganic layer is prepared in the ethylene vinyl alcohol copolymer film layer surface.The embodiment of the present invention is prepared soft
Property device buffer layer not only there is high gas and water vapor rejection performance, effectively prevent gas through buffer layer to flexible device generate
It is serious to destroy, and high temperature resistant, also there is good bending performance, the manufacturing suitable for flexible device.
Further, the step of " preparing inorganic layer in the ethylene vinyl alcohol copolymer film layer surface " includes: will be described
Ethylene vinyl alcohol copolymer film layer is put into the reaction chamber of atomic layer deposition apparatus；By the first presoma and the second presoma with
The mode of pulse is alternately passed through the reaction chamber and is deposited on the ethylene vinyl alcohol copolymer film layer surface, so that described
First presoma and second presoma are reacted in the ethylene vinyl alcohol copolymer film layer surface generates inorganic layer.
Atomic layer deposition (atomic layer deposition, ALD) method is a kind of special chemical vapor deposition side
Method is by the way that vaporous precursors pulse to be alternately passed through to reaction chamber and is formed in depositing base surface generation Chemisorption thin
A kind of method of film.Technical solution of the present invention is by using Atomic layer deposition method by inorganic layer deposition in the ethylene-second
In enol copolymer film layer, it on the one hand ensure that the uniformity and compactness of deposition inorganic layer thickness, realize inorganic layer deposition
Thickness it is adjustable, another aspect inorganic layer using high activity presoma as reaction source, can be deposited, be kept away at low temperature
Exempt from high temperature to the destruction of ethylene-ethenol copolymer film layer, ensure that the structural stability of buffer layer.The embodiment of the present invention
It alternately is passed through the reaction chamber by the first presoma and the second presoma pulse, so that the monoatomic layer of inorganic layer gradually sinks
Product, on the one hand realizes the deposition of monoatomic layer, on the other hand also ensures the uniformity of Atomic layer deposition and excellent
Consistency.Also, the embodiment of the present invention can also alternately realize for several times the adjustable of inorganic layer thickness by adjusting pulse.
Still further, first presoma includes one or both of silicon source presoma and silicon source presoma, institute
Stating the second presoma includes one or both of oxygen source presoma and nitrogen source presoma.Silicon atom in first presoma
Either aluminium atom generates monoatomic inorganic layer in conjunction with oxygen atom or nitrogen-atoms in the second presoma, and reactivity is high,
Reaction speed is fast, and the first presoma and the second presoma pass through contact and reaction can be completed, and improves reaction efficiency.
Further, first presoma includes ethyl orthosilicate, methyl orthosilicate, trim,ethylchlorosilane, tetramethyl
One of base silane, trimethyl aluminium, tri-tert aluminium are a variety of.The silicon source presoma includes ethyl orthosilicate, positive silicic acid
Methyl esters, trim,ethylchlorosilane and tetramethylsilane；The nitrogen source presoma includes trimethyl aluminium and tri-tert aluminium.According to deposition
The difference of first presoma, there are two types of different for atomic layer deposition from restriction scheme, i.e. chemisorption is reacted from limitation and sequentially
From limitation.Different from limitation from sequentially reaction, chemisorption does not need active precursor species from limitation deposition process, the
One presoma is directly chemisorbed on ethylene vinyl alcohol copolymer film layer surface, when the second presoma is passed through the reaction chamber,
Second presoma will react with the first presoma adsorbed.First presoma described in the embodiment of the present invention not only has
Volatility can be in ethylene vinyl alcohol copolymer film layer by heating steam easy to form, and activation energy with higher
Surface quickly forms stable chemisorption, and it is good to go back thermal stability.In addition, when being alternately sent into the first different presomas, it will
It can obtain different inorganic layers.For example, the first presoma is alternately passed through silicon source presoma and silicon source presoma, the second presoma is
Oxygen source presoma is then capable of forming the inorganic layer of sieve and silica-sesquioxide.For example, the first presoma is alternately passed through silicon source presoma and aluminium
Source presoma, the second presoma are nitrogen source presoma, then are capable of forming the inorganic layer of silicon aluminum nitrides.
Further, the oxygen source presoma is vapor.Certainly, the second presoma can also use ozone and oxygen
One of or two kinds.Consider from economical and environmentally friendly angle, the second presoma described in the embodiment of the present invention uses vapor.Institute
Stating nitrogen source presoma can be ammonia.
Specifically, it for using aluminium oxide as inorganic layer, " is prepared in the ethylene vinyl alcohol copolymer film layer surface
The step of inorganic layer " includes: that the ethylene vinyl alcohol copolymer film layer is put into the reaction chamber of atomic layer deposition apparatus, and three
Aluminium methyl forms steam and is sent into the reaction chamber with impulse form, and after first time inert gas purge, vapor is with pulse
Form is sent into the reaction chamber, on the trimethyl aluminium of water vapor adsorption to the ethylene vinyl alcohol copolymer film layer, trimethyl aluminium
It is reacted with vapor by atomic layer and generates aluminium oxide, trimethyl aluminium is re-fed into after inert gas purge again, so weight
Complex Alternating pulse cycle 200 times, aluminium oxide is constantly deposited on the ethylene vinyl alcohol copolymer film layer and forms alumina layer.
Wherein, the atomic layer reaction principle are as follows:
2Al(CH3)3(g)+3H2O(g)→Al2O3(s)+6CH4(g)；
The embodiment of the present invention is using trimethyl aluminium as the first presoma, and certainly, the first presoma can also be three tertiary fourths
The alkyl aluminums such as base aluminium guarantee that atomic layer reaction sufficiently carries out, the present invention to reduce the influence that steric hindrance reacts atomic layer
Embodiment is using trimethyl aluminium as the first presoma.Also, after trimethyl aluminium pulse feeding, first time inert gas purge
Reaction chamber, it is (including unadsorbed in ethylene vinyl alcohol copolymer film in reaction chamber to take excessive trimethyl aluminium in reaction chamber out of
Trimethyl aluminium on layer), it is therefore prevented that gas phase reaction occurs in the reactor for trimethyl aluminium.Second of inert gas is carried out after reaction
Purging is conducive to the methane byproduct for taking atomic layer reaction out of, has catharsis.Certainly, inert gas includes nitrogen or argon
The inert gases such as gas.It is not difficult to find out that the number of pulse cycle is controllable, according to the number of the thickness control pulse cycle of inorganic layer,
To realize the deposition of different-thickness inorganic layer, the controllable adjustment of inorganic layer thickness is reached.In addition, the embodiment of the present invention three
The aluminium methyl burst length is 0.03s, and the trimethyl aluminium residence time is 5s, and first time inert blowing gas flyback time is 10s, vapor
Burst length is 0.02s, and the vapor residence time is 3s, and second of inert blowing gas flyback time is 5s.The present invention passes through control
Burst length, residence time and purge time ensure that trimethyl aluminium steam is sufficiently reacted with vapor, avoid other because
Influence of the element to reaction.
Further, the step of " preparation ethylene vinyl alcohol copolymer film layer, obtain ethylene vinyl alcohol copolymer film layer "
It include: that ethylene-vinyl acetate copolymer is placed under alkaline condition, to be saponified generation ethylene-vinyl alcohol copolymer；By the second
Alkene-ethenol copolymer is coated, and obtains ethylene vinyl alcohol copolymer film layer.The saponification side of ethylene-vinyl acetate copolymer
Method is divided into two types, and one kind is heterogeneous saponification, and another kind is homogeneous saponification.Heterogeneous saponification is by ethene-vinyl acetate
Copolymer is placed in poor solvent (such as polarity alcohol, water), in the premise for keeping ethylene-vinyl acetate copolymer resin form
The advantages of lower carry out saponification, this method is can to keep ethylene-vinyl acetate copolymer resin original shape, and saponified
Separation and drying are easier.Homogeneous saponification is that ethylene-vinyl acetate copolymer is first dissolved in good solvent appropriate (benzene, first
Benzene, dimethylbenzene etc.) in formed homogeneous phase solution, then under alkaline condition with alcohols carry out saponification, be eventually adding ethylene-vinegar
Saponified ethylene-vinyl alcohol copolymer is precipitated in the poor solvent (such as polarity alcohol, water) of sour ethylene copolymer.Homogeneous saponification
The advantages of be that reaction speed is fast, ethylene-vinyl acetate copolymer can be highly saponified in a short time, can prepare not similar shape
The ethylene-vinyl alcohol copolymer of state.
Still further, " ethylene-vinyl acetate copolymer is placed under alkaline condition, to be saponified generation ethylene-vinyl
The step of alcohol copolymer " includes: that ethylene-vinyl acetate copolymer dissolution is placed under alkaline condition, with homogeneous saponification generation
Ethylene-vinyl alcohol copolymer.After ethylene-vinyl acetate copolymer is dissolved, homogeneous soap occurs for ethylene-acetate ethylene copolymer
Change reaction, ensure that ethylene-vinyl acetate copolymer is saponified by abundant height, the uniformity of saponification is improved, so that second
Alkene-vinyl acetate copolymer resin surface is consistent with internal saponification degree, while being also convenient for the ethylene vinyl alcohol copolymer film layer
Coated and molded.
Further, " ethylene-vinyl acetate copolymer is placed under alkaline condition, to be saponified generation ethylene-vinyl
The step of alcohol copolymer " includes: that ethylene-vinyl acetate copolymer is placed under the first alkaline condition, to carry out first time saponification, is obtained
To intermediary；The intermediary is placed under the second alkaline condition, and it is total to carry out secondary saponification generation ethylene-vinyl alcohol to heat up
Polymers, wherein the alkalinity of second alkaline condition is higher than the alkalinity of first alkaline condition.The embodiment of the present invention is for the first time
Saponification is added in weak alkali alcosol after dissolving ethylene-vinyl acetate copolymer, is heated to carrying out in 30 DEG C to 80 DEG C
It is saponified for the first time, the saponification degree of saponification reaches as high as 98% for the first time.If higher saponification degree need to be reached, secondary soap is carried out
Change, i.e., by strong base solution be added to it is above-mentioned it is saponified in, be warming up under conditions of 50 DEG C to 150 DEG C and stir, can obtain in this way
99.5% or more ethylene-vinyl alcohol copolymer is up to saponification degree.The embodiment of the present invention be added after primary saponification with
On the one hand strong alkali aqueous solution based on water, strong alkali aqueous solution are used as reaction solution to make ethylene-vinyl acetate copolymer further
Sufficiently saponification, the ethylene-vinyl alcohol copolymer on the other hand as precipitated liquid saponification being generated precipitates and particlized, guarantees it
Will not be coalesced again in secondary saponification process it is agglomerating so that secondary saponification uniformly sufficiently carries out.In addition, the present invention passes through
Increase the saponification degree of ethylene-vinyl acetate copolymer, so that ethylene-vinyl acetate copolymer generates ethylene-second by abundant reaction
Enol copolymer, to ensure that the gas barrier property of ethylene vinyl alcohol copolymer film layer.
Specifically, the step of " preparation ethylene vinyl alcohol copolymer film layer, obtain ethylene vinyl alcohol copolymer film layer "
It include: firstly, ethylene-vinyl acetate copolymer is dissolved in the tert-butyl alcohol；Then, the alcoholic solution of acetate is added, is heated to
30 DEG C to 80 DEG C progress first step saponification；Then, the aqueous solution of highly basic is added, and is warming up to 50 DEG C to 100 DEG C and carries out secondary soap
Change；It will be dissolved in the tert-butyl alcohol after saponified washing again；Finally, saponified solution is spin-coated on substrate surface, ethylene-vinyl is obtained
Alcohol copolymer film layer.
The lysate of ethylene-vinyl acetate copolymer can be using benzene, toluene or dimethylbenzene etc..The embodiment of the present invention is adopted
Use the tert-butyl alcohol as the lysate of ethylene-vinyl acetate copolymer, the one side tert-butyl alcohol can sufficiently dissolve ethene-vinyl acetate
Copolymer, another aspect tert-butyl alcohol small toxicity are small to the harm of environment and human body.Certainly, ethene-vinyl acetate is total in the present invention
The lysate of polymers is also conceivable to other low polar alcohols.In addition, the embodiment of the present invention using acetate as weak base into
Row first step saponification, it is obvious that weak base can also include ammonium hydroxide, aluminium hydroxide etc..It is envisioned that acetate includes acetic acid
Sodium and potassium acetate etc., as long as guaranteeing weak basic condition.Aqueous solution by the way that highly basic is added carries out secondary saponification, the water of highly basic
On the one hand solution is used as reaction solution that ethylene-vinyl acetate copolymer is further sufficiently saponified, be on the other hand used as precipitated liquid
So that ethylene-vinyl alcohol copolymer precipitating and particlized that saponification generates, guarantee that it will not gather again in secondary saponification process
It clumps together, so that secondary saponification uniformly sufficiently carries out.The highly basic includes sodium hydroxide, hydrogen-oxygen in embodiments of the present invention
Change potassium and barium hydroxide etc..The product of secondary saponification is emulsion form, and the product of emulsion form passes through highly polar solvent (such as methanol, second
Alcohol etc.) washing, it is ethylene-second that liquid separation, which removes highly polar impurity, ensure that the purity of the ethylene-vinyl alcohol copolymer product,
Enol copolymer film forming provides guarantee.Good solvent (such as tert-butyl alcohol) is added in ethylene-vinyl alcohol copolymer after washing, passes through
Good solvent dissolution ethylene-vinyl alcohol copolymer and the surface formation ethylene-ethenol copolymer film layer for being spin-coated on substrate, it is ensured that
The flatness of ethylene vinyl alcohol copolymer film layer, is conducive to the uniform deposition of inorganic layer.
The present invention also proposes a kind of flexible device, as shown in Figure 1, including the flexible device buffer layer and the flexible device
The preparation method of the preparation method of part buffer layer, the flexible device buffer layer and the flexible device buffer layer is referring to above-mentioned reality
Example is applied, since flexible device uses whole technical solutions of above-mentioned all embodiments, at least with above-described embodiment
All beneficial effects brought by technical solution, this is no longer going to repeat them.The flexible device, including substrate and flexible device
Buffer layer 100, the flexible device buffer layer 100 include ethylene vinyl alcohol copolymer film layer 110 and inorganic layer 120, the second
Alkene-ethenol copolymer film layer 110 is set to 200 surface of substrate, and the inorganic layer 120 is set to the ethylene-vinyl alcohol copolymer
110 surface of film layer, 120 surface of inorganic layer are equipped with film layer 300, and the film layer 300 includes that active layer 310 and grid are exhausted
Edge layer 330, the active layer 310 is set to 220 surface of inorganic layer, between the active layer 310 and the gate insulation layer 330
Equipped with source-drain electrode layer 320, the source-drain electrode layer 320 is located at 310 both ends of active layer, 330 surface of gate insulation layer
Equipped with gate electrode layer 340.The embodiment of the present invention by substrate 200 be arranged ethylene vinyl alcohol copolymer film layer 110, then
Inorganic layer 120 is arranged in the ethylene vinyl alcohol copolymer film layer 110, is not only reduced by ethylene vinyl alcohol copolymer film layer
Young's modulus enhances the barrier property to gas and steam, effectively prevent gas to generate through buffer layer to flexible device tight
It destroys, and inorganic layer high temperature resistant, is can adapt in chemical vapor deposition, physical vapour deposition (PVD) and plasma enhancing again
Diffusion, forming core, the growth of atom, ensure that resistivity, the transmitance of film layer when learning the methods of vapor deposition preparation film layer
And the binding force with substrate.
The present invention also proposes a kind of manufacturing method of flexible device, as shown in Figure 2, comprising the following steps: S1, in substrate
Upper coating ethylene-vinyl alcohol copolymer forms ethylene vinyl alcohol copolymer film layer；S2, using Atomic layer deposition method described
Inorganic layer is deposited on ethylene vinyl alcohol copolymer film layer；S3 successively sputters active layer on the inorganic layer by sputtering method
With source-drain electrode layer and patterned process；S4, using Atomic layer deposition method or chemical vapor deposition method in the active layer
With deposition gate insulation layer and patterned process on source-drain electrode layer；S5, the depositing gate electrode layer on the gate insulation layer form institute
State flexible device.The flexible device of the embodiment of the present invention enhances the barrier property to gas and steam, it is therefore prevented that gas penetrates
Buffer layer generates serious destroy to flexible device.
To further illustrate the technical scheme of the present invention combined with specific embodiments below.It should be understood that this place is retouched
It states that the specific embodiments are only for explaining the present invention, is not intended to limit the scope of the present invention..
Embodiment 1
(1) preparation of ethylene vinyl alcohol copolymer film layer
Firstly, ethylene-vinyl acetate copolymer is dissolved in the tert-butyl alcohol；Then, the alcoholic solution of acetate is added, heats
It is tentatively saponified to 30 DEG C to 80 DEG C；Then, the aqueous solution of highly basic is added, and is warming up to 50 DEG C to 100 DEG C and carries out secondary soap
Change；Again by saponified by being dissolved in the tert-butyl alcohol after ethanol washing；Finally, saponified solution is spin-coated on to the surface of substrate,
Ethylene vinyl alcohol copolymer film layer is formed, ethylene-ethenol copolymer film layer is with a thickness of 1 μm to 10 μm.
(2) deposition of inorganic layer
The ethylene vinyl alcohol copolymer film layer is put into the reaction chamber of atomic layer deposition apparatus, trimethyl aluminium is formed
Steam is sent into the reaction chamber with impulse form, and the burst length of trimethyl aluminium is 0.03s, and the trimethyl aluminium residence time is 5s,
After argon gas purges, argon gas purge time is 10s, and vapor is sent into the reaction chamber, the pulse of vapor with impulse form
Time is 0.02s, and the residence time of vapor is 3s, front three of the water vapor adsorption to the ethylene vinyl alcohol copolymer film layer
On base aluminium, while trimethyl aluminium hydrolysis generates aluminium oxide, is re-fed into trimethyl aluminium, second of argon after second of argon gas purges
Air-blowing flyback time is 5s, so repeats ALT pulse and recycles 200 times, aluminium oxide is constantly deposited on the ethylene vinyl alcohol copolymer
In object film layer, alumina layer with a thickness of 20nm to 100nm.
Compared with prior art, flexible device buffer film prepared by the embodiment of the present invention, not only to oxygen, vapor
Good barrier property, it is seen that light transmission rate is high, good with the binding force of substrate, and Young's modulus is small, can repeatedly bend, and high temperature resistant changes
The matching with subsequent deposition film has been apt to it, the diffusion of atom, forming core, growth when being conducive to prepare subsequent deposition film guarantee
The low-resistivity of subsequent deposition film.
The above description is only a preferred embodiment of the present invention, is not intended to limit the scope of the invention, all at this
Under the inventive concept of invention, using equivalent structure transformation made by description of the invention and accompanying drawing content, or directly/use indirectly
It is included in other related technical areas in scope of patent protection of the invention.
Claims (10)
1. a kind of flexible device buffer layer, which is characterized in that including ethylene vinyl alcohol copolymer film layer and inorganic layer, the nothing
Machine layer is set to the ethylene vinyl alcohol copolymer film layer surface.
2. flexible device buffer layer as described in claim 1, which is characterized in that the inorganic layer includes siliceous inorganic matter and contains
One or both of aluminium inorganic matter.
3. flexible device buffer layer as described in claim 1, which is characterized in that the ethylene vinyl alcohol copolymer film layer
With a thickness of 1 μm to 10 μm；
And/or the inorganic layer with a thickness of 20nm to 100nm.
4. a kind of preparation method of flexible device buffer layer, which comprises the following steps:
Ethylene vinyl alcohol copolymer film layer is prepared, ethylene vinyl alcohol copolymer film layer is obtained；
Inorganic layer is prepared in the ethylene vinyl alcohol copolymer film layer surface.
5. the preparation method of flexible device buffer layer as claimed in claim 4, which is characterized in that " in the ethylene-vinyl alcohol
Co-polymer membrane layer surface prepares inorganic layer " the step of include:
The ethylene vinyl alcohol copolymer film layer is put into the reaction chamber of atomic layer deposition apparatus；
First presoma and the second presoma are alternately passed through the reaction chamber in a pulsed fashion and are deposited on the ethylene-
Ethenol copolymer film surface, so that first presoma and second presoma are in the ethylene vinyl alcohol copolymer
The reaction of object film surface generates inorganic layer.
6. the preparation method of flexible device buffer layer as claimed in claim 5, which is characterized in that first presoma includes
One or both of silicon source presoma and silicon source presoma；
And/or second presoma includes one or both of oxygen source presoma and nitrogen source presoma.
7. the preparation method of flexible device buffer layer as claimed in claim 6, which is characterized in that first presoma includes
One of ethyl orthosilicate, methyl orthosilicate, trim,ethylchlorosilane, tetramethylsilane, trimethyl aluminium, tri-tert aluminium are more
Kind.
8. the preparation method of flexible device buffer layer as claimed in claim 4, which is characterized in that " it is total to prepare ethylene-vinyl alcohol
Copolymer film layer obtains ethylene vinyl alcohol copolymer film layer " the step of include:
Ethylene-vinyl acetate copolymer is placed under alkaline condition, to be saponified generation ethylene-vinyl alcohol copolymer；
The ethylene-vinyl alcohol copolymer is coated, ethylene vinyl alcohol copolymer film layer is obtained.
9. the preparation method of flexible device buffer layer as claimed in claim 8, which is characterized in that " be total to ethene-vinyl acetate
Polymers is placed under alkaline condition, be saponified generate ethylene-vinyl alcohol copolymer " the step of include:
Ethylene-vinyl acetate copolymer is placed under the first alkaline condition, to carry out first time saponification, obtains intermediary；
The intermediary is placed under the second alkaline condition, and is heated up to carry out secondary saponification and generate ethylene-vinyl alcohol copolymer,
Wherein, the alkalinity of second alkaline condition is higher than the alkalinity of first alkaline condition.
10. a kind of flexible device, which is characterized in that slow including flexible device described in substrate and any one of claims 1 to 9
Layer is rushed, the flexible device buffer layer is set to the substrate surface.
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