A kind of preparation method of flexible OLED display film
Technical field
The present invention relates to display technology field, and in particular to a kind of preparation method of flexible OLED display film.
Background technology
Organic light emitting display is that one kind applies Organic Light Emitting Diode (OLED) as the display screen of luminescent device, is compared
Present main flow flat panel display Thin Film Transistor-LCD (TFT-LCD), organic light emitting display has high contrast
The advantages of degree, wide viewing angle, low-power consumption, thinner volume, it is expected to turn into the flat panel display of future generation after LCD, is current
Attract attention one of most technologies in flat panel display.
OLED is very sensitive to steam, oxygen, it is easy to decay, and effective encapsulation can prevent steam and oxygen
The immersion of gas, prevents organic material aging, extends the OLED life-span.At present, flexible OLED mainly has cover plate to encapsulate and film
Encapsulation (TFE) two kinds of packaged types, cover plate encapsulation is packaged using prefabricated cover plate, mainly there is glass material and membrane material, thin
Film encapsulates main adopter's single thin film or plural layers are packaged.
It is to the method that flexible display apparatus are packaged in conventional art:The moon of OLED is completed on flexible substrates
After the manufacture of pole, one layer of protective layer for being used to cover OLED negative electrode is first made, then attach protecting film on protective layer again.
Wherein, mainly protective layer plays encapsulation effect, prevents the immersion of steam and oxygen;Protecting film is mainly used in preventing protective layer from being drawn
Wound.However, such protective layer is easily broken off in bending flexible display apparatus, so that water oxygen obstructing capacity significantly drops
It is low, influence display effect, in some instances it may even be possible to cause OLED to fail.
Chinese invention patent application number 201410727845.0 discloses a kind of flexible OLED substrates and flexibility OLED encapsulation
Method, the flexible OLED substrates include:Polymeric layer, tinsel and insulation glue material layer.The flexible OLED substrates have good
Good pliability and waterproof, oxygen permeability.Substrate is prepared and is combined together with encapsulation process by the invention, simplifies encapsulation work
Skill, and the stress produced and substrate between during device bend will improve the reliability of packaging technology by whole devices share.
But, between each layer that the invention is used, especially between tinsel and insulation glue material layer, the bonding of chemical bond is not made
With, therefore after flexibility bending repeatedly, easily splitting, causes its potential safety hazard big.
Chinese invention patent application number 201510700071.7 discloses a kind of encapsulating structure of flexible OLED devices.This is soft
Property OLED encapsulating structures, by flexible conductive substrate, feature organic electronic and flexible is sealed complete covering water oxygen encapsulated layer for it
Lid film composition.Wherein intactly water oxygen encapsulated layer is to use one or more potting resin glue and sealant to entirety
OLED carries out comprehensive liquid covering packaging technology, sets up one efficiently to water and the barrier of Oxygen permeation.But, the method
When one or more potting resin glue and sealant for using are chronically exposed in ultraviolet lighting or the environment that drenches with rain, resin
Aging situation, defencive function reduction just occurs.
Chinese invention patent application number 201610431035.X discloses a kind of flexible OLED devices and its method for packing.Should
Invention is provided with the first barrier layer and the second barrier layer, is additionally provided with cushion, optimizes barrier film structures, specific good water oxygen
Barrier property, makes that flexible OLED display is more frivolous, bending performance more preferably, and extends the use longevity of flexible OLED display
Life.However, program complex operation, cost is improved, and the thickness of OLED increases, and weight increases, and have lost it light
The characteristics of.
In sum, the method being packaged to flexible display apparatus in currently available technology is substantially similar, is all
After completing the negative electrode manufacture of OLED on flexible substrates, one layer of protective layer for being used to cover OLED negative electrode is first made,
Then protective filmy layer is then covered with protective layer again.Wherein, mainly protective layer plays encapsulation effect, prevents steam and oxygen
Immersion, and protecting film thereon is mainly used in preventing protective layer to be scratched.However, such protective layer is in bending Flexible Displays
It is easily broken off during device, so that water oxygen obstructing capacity is greatly reduced, influences display effect, in some instances it may even be possible to cause OLED to lose
Effect.If protective organic film and inorganic dielectric film combined, it would be possible to for the solution of above mentioned problem provides a kind of effective approach.
The content of the invention
It is essentially identical for the method for packing in currently available technology to flexible display apparatus, all it is basic in OLED
After structure is completed, one layer of protective layer for being used to cover OLED negative electrode is first made, be then then covered with protective layer again
Protective filmy layer.Wherein, protective layer plays encapsulation effect, prevents the immersion of steam and oxygen, and protecting film thereon is mainly used in
Protective layer is prevented to be scratched.However, such protective layer is easily broken off in bending flexible display apparatus, so that water oxygen hinders
It is greatly reduced every ability, influences display effect, in some instances it may even be possible to cause OLED to fail.The present invention proposes a kind of flexible OLED display
The preparation method of film, methods described uses acrylic acid and derivatives monomer as organic film raw material, by acrylic acid and derivative
Monomer is evaporated in plastic supporting base, by the method polymerization film formation for solidifying, improves the surface condition of plastic supporting base, is allowed to surface light
It is sliding, then inorganic medium compact film is prepared using the method for rf magnetron sputtering over an organic film, thus it is prepared for flexibility
OLED display screen film.The present invention is evaporated acrylic acid and derivatives monomer is evenly laid out on substrate using the method for evaporation, former
The organic film formed after the solidification of position is finer and close, and preparing inorganic medium over an organic film using the method for rf magnetron sputtering causes
Close film layer, this inorganic medium compact film has certain compression, it is to avoid repeatedly bending is ftractureed, it is ensured that steam and oxygen
Iris action, whole preparation process has good industrial foundation, reduces process costs, while protectiveness is lifted simultaneously
Advantage without destruction OLED itself, with industrial application value very high.
The present invention provides a kind of preparation method of flexible OLED display film, and methods described uses acrylic acid and derivative
Monomer prepares inorganic medium compact film over an organic film as organic film raw material using the method for rf magnetron sputtering, including
Following steps:
(1)Cleaning plastic supporting base, obtains the plastic supporting base of cleaning;
(2)In the cleaning plastic supporting base, using 100-120 DEG C of evaporating temperature, vacuum under, evaporation 50-200nm's
Acrylic acid and derivatives monomer, underlayer temperature are set to 50-80 DEG C so that be evaporated to acrylic acid and the derivatives monomer warp of substrate
Polymerizing curable is crossed, a kind of film of flexible and transparent is condensed into;
(3)Then in the method that inorganic medium compact film is passed through into radio-frequency sputtering, deposit in film layer, as stop steam and
The barrier of oxygen.
Preferably, the cleaning plastic supporting base is comprised the following steps:
It is cleaned by ultrasonic 10-15 minutes in ethanol solution, the grease on removal plastic supporting base surface, then with deionized water rinsing,
The salt on removal plastic supporting base surface, plastic supporting base is dried under 40-50 DEG C of argon gas protection;
The argon gas is that purity is 99.9%, and the ambient pressure of argon gas is 100-1000Pa.
Preferably, the acrylic acid and derivatives monomer include:Acrylic acid, methyl acrylate, ethyl acrylate, acrylic acid
Any one of N-butyl, methyl methacrylate, n-BMA.Preferably, it is 30-50 points in the hardening time
Clock.
Preferably, the inorganic medium compact film is that material is SiO2、Al2O3、TiO2、VO2, one or more of h-BN
Combination.
Preferably, the parameter of the inorganic medium compact film radio-frequency sputtering is sputtering power 100-140W, sputtering pressure
It is 0.2-2.0Pa, depositing temperature is 20-50 DEG C.
Preferably, the thickness of the inorganic medium compact film is 100-500nm.
Prepared flexible OLED display film of the invention and the conventional the performance test results contrast for encapsulating OLED, such as table 1
It is shown.
Table 1:
The present invention proposes a kind of preparation method of flexible OLED display film, compared with prior art, the characteristics of its protrusion and
Excellent effect is:
1st, the present invention is combined using organic crylic acid resinoid protecting film and inorganic medium dense film, this inorganic medium dense film
Layer has certain compression, it is to avoid repeatedly bending is ftractureed, it is ensured that the iris action of steam and oxygen, is extremely efficiently solved
Bending fracture failure.
2nd, the present invention reduces lower floor's organic resin contact ultraviolet using the larger inorganic medium compact film covering of band gap
The ratio of line, is protected resin, is more stablized.
3rd, present invention employs conventional sputtering technology, industrial foundation is strong, for display screen industry, equipment extensively into
This is cheap.
4th, the present invention is using acrylic resin as organic protection layer, and raw material sources are extensive.
Specific embodiment
Below by way of specific embodiment, the present invention is described in further detail, but this should not be interpreted as into the present invention
Scope be only limitted to following example.In the case where above method thought of the present invention is not departed from, according to ordinary skill
Various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
The present embodiment is comprised the following steps:
(1)It is cleaned by ultrasonic 10 minutes in ethanol solution, the grease on removal plastic supporting base surface, then with deionized water rinsing,
The salt on removal plastic supporting base surface, is 99.9% in 40 DEG C of purity, and ambient pressure is the lower drying plastics of the argon gas protection of 100Pa
Substrate, obtains the plastic supporting base of cleaning;
(2)In the cleaning plastic supporting base, using 100 DEG C of evaporating temperature, under vacuum, evaporation thickness is the propylene of 50nm
Sour methylmethacrylate monomer, underlayer temperature is set to 50 DEG C so that be evaporated to the methacrylate monomer of substrate by polymerizing curable, solidification
Time is 30 minutes, and a kind of film of flexible and transparent is condensed into after solidification;
(3)Then by SiO2The method that inorganic medium compact film passes through radio-frequency sputtering, controls the parameter of radio-frequency sputtering to splash
Power 100W is penetrated, sputtering pressure is 0.2Pa, and depositing temperature is deposited on polymer film layer for 50 DEG C, control SiO2Inorganic Jie
The thickness of matter compact film is 100nm, used as the barrier for stopping steam and oxygen.
By test, the performance of the flexible OLED display film prepared in embodiment 1 is as shown in table 2.
Embodiment 2
The present embodiment is comprised the following steps:
(1)It is cleaned by ultrasonic 10 minutes in ethanol solution, the grease on removal plastic supporting base surface, then with deionized water rinsing,
The salt on removal plastic supporting base surface, is 99.9% in 45 DEG C of purity, and ambient pressure is the lower drying plastics of the argon gas protection of 300Pa
Substrate, obtains the plastic supporting base of cleaning;
(2)In the cleaning plastic supporting base, using 100 DEG C of evaporating temperature, under vacuum, evaporation thickness is the third of 100nm
Olefin(e) acid acetate monomer, underlayer temperature is set to 60 DEG C so that be evaporated to the acrylic acid ethyl ester monomer of substrate by polymerizing curable, Gu
The change time is 40 minutes, and a kind of film of flexible and transparent is condensed into after solidification;
(3)Then by TiO2The method that inorganic medium compact film passes through radio-frequency sputtering, controls the parameter of radio-frequency sputtering to splash
Power 140W is penetrated, sputtering pressure is 2.0Pa, and depositing temperature is deposited on polymer film layer for 50 DEG C, control TiO2Medium is caused
The thickness of close film layer is 200nm, used as the barrier for stopping steam and oxygen.
By test, the performance of the flexible OLED display film prepared in embodiment 2 is as shown in table 2.
Embodiment 3
The present embodiment is comprised the following steps:
(1)It is cleaned by ultrasonic 12 minutes in ethanol solution, the grease on removal plastic supporting base surface, then with deionized water rinsing,
The salt on removal plastic supporting base surface, is 99.9% in 45 DEG C of purity, and ambient pressure is the lower drying plastics of the argon gas protection of 300Pa
Substrate, obtains the plastic supporting base of cleaning;
(2)In the cleaning plastic supporting base, using 110 DEG C of evaporating temperature, under vacuum, evaporation thickness is the third of 140nm
Olefin(e) acid acetate monomer, underlayer temperature is set to 70 DEG C so that be evaporated to the acrylic acid ethyl ester monomer of substrate by polymerizing curable, Gu
The change time is 40 minutes, and a kind of film of flexible and transparent is condensed into after solidification;
(3)Then by Al2O3The method that inorganic medium compact film passes through radio-frequency sputtering, controls the parameter of radio-frequency sputtering to splash
Power 120W is penetrated, sputtering pressure is 1.5Pa, and depositing temperature is deposited on polymer film layer for 50 DEG C, control Al2O3Inorganic Jie
The thickness of matter compact film is 250nm, used as the barrier for stopping steam and oxygen.
By test, the performance of the flexible OLED display film prepared in embodiment 3 is as shown in table 2.
Embodiment 4
The present embodiment is comprised the following steps:
(1)It is cleaned by ultrasonic 15 minutes in ethanol solution, the grease on removal plastic supporting base surface, then with deionized water rinsing,
The salt on removal plastic supporting base surface, is 99.9% in 50 DEG C of purity, and ambient pressure is the lower drying plastics of the argon gas protection of 500Pa
Substrate, obtains the plastic supporting base of cleaning;
(2)In the cleaning plastic supporting base, using 120 DEG C of evaporating temperature, under vacuum, evaporation thickness is the first of 150nm
Base methyl acrylate, underlayer temperature is set to 60 DEG C so that be evaporated to the methyl methacrylate of substrate by polymerizing curable, Gu
The change time is 40 minutes, and a kind of film of flexible and transparent is condensed into after solidification;
(3)Then by Al2O3The method that inorganic medium compact film passes through radio-frequency sputtering, controls the parameter of radio-frequency sputtering to splash
Power 120W is penetrated, sputtering pressure is 0.5Pa, and depositing temperature is deposited on polymer film layer for 50 DEG C, control Al2O3Inorganic Jie
The thickness of matter compact film is 200nm, then by VO2The method that inorganic medium compact film passes through radio-frequency sputtering, control radio frequency splashes
The parameter penetrated is sputtering power 100W, and sputtering pressure is 0.6Pa, and depositing temperature deposits to Al for 50 DEG C2O3On layer, VO is controlled2Nothing
The thickness of machine medium compact film is 100nm, used as the barrier for stopping steam and oxygen.
By test, the performance of the flexible OLED display film prepared in embodiment 4 is as shown in table 2.
Embodiment 5
The present embodiment is comprised the following steps:
(1)It is cleaned by ultrasonic 10 minutes in ethanol solution, the grease on removal plastic supporting base surface, then with deionized water rinsing,
The salt on removal plastic supporting base surface, is 99.9% in 50 DEG C of purity, and ambient pressure is the lower drying plastics of the argon gas protection of 1000Pa
Substrate, obtains the plastic supporting base of cleaning;
(2)In the cleaning plastic supporting base, using 120 DEG C of evaporating temperature, under vacuum, evaporation thickness is the third of 200nm
Olefin(e) acid N-butyl monomer mixture, underlayer temperature is set to 80 DEG C so that the n-butyl acrylate monomer for being evaporated to substrate passes through
Polymerizing curable, hardening time is 50 minutes, and a kind of film of flexible and transparent is condensed into after solidification;
(3)Then in the method that h-BN inorganic mediums compact film is passed through into radio-frequency sputtering, the parameter of radio-frequency sputtering is controlled to splash
Power 140W is penetrated, sputtering pressure is 2.0Pa, and depositing temperature is deposited on polymer film layer for 50 DEG C, control inorganic Jie of h-BN
The thickness of matter compact film is 500nm, used as the barrier for stopping steam and oxygen.
By test, the performance of the flexible OLED display film prepared in embodiment 5 is as shown in table 2.
Table 2:
The OLED display screen film obtained by above-described embodiment, effectively prevents the immersion of steam and oxygen, and its flexibility function is prevented
In the fracture of bending display device, the service life of OLED display screen is greatly improved.