CN113186494A - Composite film and preparation method and application thereof - Google Patents

Composite film and preparation method and application thereof Download PDF

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CN113186494A
CN113186494A CN202110467886.0A CN202110467886A CN113186494A CN 113186494 A CN113186494 A CN 113186494A CN 202110467886 A CN202110467886 A CN 202110467886A CN 113186494 A CN113186494 A CN 113186494A
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composite film
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CN113186494B (en
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王奕涵
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Jiangsu First Light Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/12—Organic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/18—Metallic material, boron or silicon on other inorganic substrates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/54—Controlling or regulating the coating process
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/844—Encapsulations
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

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Abstract

The invention belongs to the technical field of organic light emitting diode packaging, and particularly relates to a composite film and a preparation method and application thereof. The invention provides a composite film, which comprises a metal/metal fluoride layer and a fluorine-containing organic layer which are alternately stacked; the material of the metal/metal fluoride layer comprises metal and metal fluoride; the material of the fluorine-containing organic layer comprises copper perfluorophthalocyanine; the particle size of the metal is larger than the particle size of the metal fluoride. The invention combines metal and metal fluoride, which can improve the air isolation effect of the composite film; and meanwhile, the fluorine-containing organic layer is combined, so that the waterproof performance and the oxygen barrier performance of the composite film are further improved. The packaging structure is applied to OLED packaging, the packaging reliability can be improved, and the service life of a device is prolonged.

Description

Composite film and preparation method and application thereof
Technical Field
The invention belongs to the technical field of organic light emitting diode packaging, and particularly relates to a composite film and a preparation method and application thereof.
Background
Organic Light Emitting Diodes (OLEDs), which have characteristics of self-luminescence, wide viewing angle, high contrast, flexibility, fast response speed, and low power consumption, have begun to gradually replace conventional liquid crystal displays as a new generation of display technology. OLEDs employ a coating of an organic material as the light-emitting material, which emits light when an electric current is passed through it. However, these organic light emitting materials are liable to react with water and oxygen, which leads to decrease in luminance and lifetime of the device. Therefore, an encapsulation process for the OLED device is required.
The traditional packaging mode is mainly cover plate packaging, after the device is manufactured, the device is placed in a nitrogen environment, a rigid cover plate is added on the top of the device, sufficient drying agent is fixed on the inner side of the cover plate, and epoxy resin is used as adhesive colloid to package the cover plate and the device. However, since the cover plate itself has no hydrophobicity and the gap between the cover plate and the epoxy resin cannot be avoided, and meanwhile, the epoxy resin itself is fast aged, water and oxygen can still permeate into the device in a long-time use process, so that the packaging reliability is reduced, and the performance of the OLED device is reduced or even loses efficacy.
Disclosure of Invention
The invention provides a composite film which can effectively improve the packaging reliability and effectively avoid the problem of OLED device performance reduction caused by the permeation of water and oxygen when applied to the packaging of OLED devices.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a composite film, which comprises a metal/metal fluoride layer and a fluorine-containing organic layer which are alternately stacked;
the material of the metal/metal fluoride layer comprises metal and metal fluoride;
the material of the fluorine-containing organic layer comprises copper perfluorophthalocyanine;
the particle size of the metal is larger than the particle size of the metal fluoride.
Preferably, the metal comprises gold, silver or aluminum;
the metal fluoride includes one of an alkali metal fluoride and an alkaline earth metal fluoride.
Preferably, the mass ratio of the metal to the metal fluoride is 1-2: 1.
preferably, the thicknesses of the metal/metal fluoride layer and the fluorine-containing organic layer are 10-100 nm independently.
Preferably, the number of the metal/metal fluoride layers and the fluorine-containing organic layer is more than or equal to 1; the metal/metal fluoride layers and the fluorine-containing organic layers are alternately stacked in sequence, and the number of the metal/metal fluoride layers is the same as that of the fluorine-containing organic layers.
The invention also provides a preparation method of the composite film, which comprises the following steps:
simultaneously performing first metal evaporation and metal fluoride on the surface of the substrate to obtain a metal/metal fluoride layer;
and (3) evaporating perfluorinated phthalocyanine copper on the surface of the metal/metal fluoride layer for the second time to obtain the composite film.
Preferably, the vapor deposition rates of the first vapor deposition and the second vapor deposition are independent
Figure BDA0003044012360000021
Preferably, during the first evaporation, the evaporation current of the metal is 25-160A;
the evaporation current of the metal fluoride is 55-65A;
the current of the second evaporation is 60-70A.
Preferably, after the second evaporation is finished, the first evaporation and the second evaporation are sequentially repeated;
the repetition frequency is more than or equal to 1.
The invention also provides the application of the composite film or the composite film prepared by the preparation method in the technical scheme in OLED device packaging.
The invention provides a composite film, which comprises a metal/metal fluoride layer and a fluorine-containing organic layer which are sequentially stacked; the material of the metal/metal fluoride layer comprises metal and metal fluoride; the material of the fluorine-containing organic layer comprises copper perfluorophthalocyanine; the particle size of the metal is larger than the particle size of the metal fluoride. The present invention combines metal and metal fluoride, controls the grain size of the metal and metal fluoride, and utilizesThe metal fluoride with small particle size is filled between the metals with large particle size to form a more compact composite layer, so that the air isolation effect of the composite film can be improved; and meanwhile, the fluorine-containing organic layer and the metal/metal fluoride layer are combined, so that the waterproof performance and the oxygen barrier performance of the composite film are further improved. The composite film provided by the invention is applied to the encapsulation of the OLED device, the encapsulation reliability can be improved, the infiltration of water and oxygen can be prevented, the performance of the OLED device is further influenced, and the service life of the device is further prolonged. The results of the examples show that the composite film obtained by the invention has the water vapor transmission rate of 3.5-5.2 multiplied by 10-5g/m2And day, the service life of the OLED device packaged by the composite film obtained by the invention can reach 822-1028 hours.
Drawings
Fig. 1 is a schematic structural diagram of a composite film provided by the present invention. Wherein 1, 2, fluorine-containing organic layers, 3, 4, metal fluoride;
FIG. 2 is a life test chart of an OLED device packaged by the composite film obtained in example 1;
fig. 3 is a life test chart of an OLED device obtained by encapsulating the composite film obtained in example 2.
Detailed Description
The invention provides a composite film, which comprises a metal/metal fluoride layer and a fluorine-containing organic layer which are alternately stacked;
the material of the metal/metal fluoride layer comprises metal and metal fluoride;
the material of the fluorine-containing organic layer comprises copper perfluorophthalocyanine;
the particle size of the metal is larger than the particle size of the metal fluoride.
In the present invention, the material of the metal/metal fluoride layer includes metal and metal fluoride. In the present invention, the metal preferably includes gold, silver or aluminum. In the present invention, the metal fluoride preferably includes one of an alkali metal fluoride and an alkaline earth metal fluoride. In the present invention, the alkali metal fluoride further preferably includes lithium fluoride and potassium fluoride; the alkaline earth metal fluoride further preferably comprises magnesium fluoride.
In the present invention, the particle size of the metal is larger than that of the metal fluoride. In the present invention, the particle size of the metal is preferably 0.5 to 1nm, more preferably 0.6 to 0.9nm, and still more preferably 0.7 to 0.8 nm. In the present invention, the particle size of the metal fluoride is preferably 0.1 to 0.2 nm.
In the invention, the mass ratio of the metal to the metal fluoride is preferably 1-2: 1, more preferably 1 to 1.5: 1. in a specific embodiment of the present invention, the mass ratio of the metal and the metal fluoride is specifically 1: 1.
in the present invention, the metal fluoride fills the voids between the metals, forming a densely packed metal/metal fluoride layer.
In the present invention, the material of the fluorine-containing organic layer includes copper perfluorophthalocyanine.
In the invention, the thicknesses of the metal/metal fluoride layer and the fluorine-containing organic layer are independent, preferably 10-100 nm, more preferably 20-90 nm, and even more preferably 30-80 nm.
In the invention, the number of layers of the metal/metal fluoride layer and the fluorine-containing organic layer is more than or equal to 1; the metal/metal fluoride layers and the fluorine-containing organic layers are alternately stacked in sequence, and the number of the metal/metal fluoride layers is the same as that of the fluorine-containing organic layers. In the present invention, when the metal/metal fluoride layer and the fluorine-containing organic layer are multilayered, the thickness of each metal/metal fluoride or each fluorine-containing organic layer is the same as that of the metal/metal fluoride layer or each fluorine-containing organic layer defined above.
The invention also provides a preparation method of the composite film, which comprises the following steps:
simultaneously performing first metal evaporation and metal fluoride on the surface of the substrate to obtain a metal/metal fluoride layer;
and (3) evaporating perfluorinated phthalocyanine copper on the surface of the metal/metal fluoride layer for the second time to obtain the composite film.
In the present invention, all the raw materials are commercially available products well known to those skilled in the art unless otherwise specified.
The invention simultaneously carries out first metal evaporation and metal fluoride evaporation on the surface of a substrate to obtain a metal/metal fluoride layer.
The present invention does not require a particular substrate, and may be used as is well known to those skilled in the art. In a particular embodiment of the invention, the substrate to be evaporated is further preferably an OLED device to be evaporated.
In the present invention, it is preferable to preheat the metal and the metal fluoride before the first evaporation. In the present invention, the preheating is preferably performed by supplying current.
In the invention, the preheating current of the metal is preferably 25-160A. In the invention, when the metal is gold, the preheating current of the gold is preferably 150-160A; when the metal is silver, the preheating current of the silver is preferably 130-150A; when the metal is aluminum, the preheating current of the aluminum is preferably 25-35A.
In the invention, the preheating mode of the metal is specifically that the metal is placed on a boat source, and the boat source is preheated until the metal can volatilize.
In the invention, the preheating current of the metal fluoride is preferably 55-65A. In the invention, when the metal fluoride is magnesium fluoride, the preheating current of the magnesium fluoride is preferably 55-65A; when the metal fluoride is lithium fluoride, the preheating current of the lithium fluoride is preferably 60-65A; when the metal fluoride is potassium fluoride, the preheating current of the potassium fluoride is preferably 55-65A. In the invention, the preheating mode of the metal fluoride is specifically to put the metal fluoride on a crucible, and preheat the crucible until the metal fluoride can volatilize.
In the present invention, the first vapor deposition preferably has a vapor deposition rate
Figure BDA0003044012360000051
Further preferred is
Figure BDA0003044012360000052
More preferably
Figure BDA0003044012360000053
In the present invention, the deposition rates of the metal and the metal fluoride are preferably the same.
In the first evaporation, the metal and the metal fluoride are preferably kept in a state capable of being volatilized by supplying an electric current. The current is preferably the same as the preheat current and will not be described further herein.
According to the invention, metal and metal fluoride are simultaneously evaporated under the above conditions, and the metal fluoride with small particles is filled among the metal with large particles, so that a more compact composite layer is formed, and the air isolation effect of the composite film is further improved.
After the metal/metal fluoride layer is obtained, the perfluorinated phthalocyanine copper is evaporated on the surface of the metal/metal fluoride layer for the second time to obtain the composite film.
The present invention also preferably includes preheating the copper perfluorophthalocyanine before the second evaporation. In the present invention, the preheating is preferably performed by supplying current. In the invention, the preheating current of the perfluorinated copper phthalocyanine is preferably 60-70A, more preferably 62-68A, and even more preferably 63-65A. In the invention, the preheating mode of the perfluorinated phthalocyanine copper is specifically that the perfluorinated phthalocyanine copper is placed on a crucible, and the crucible is preheated until the perfluorinated phthalocyanine copper can volatilize.
In the second evaporation, the present invention preferably maintains the perfluorophthalocyanine copper in a volatile state by supplying an electric current. The current is preferably the same as the preheat current and will not be described further herein.
In the present invention, the second vapor deposition preferably has a vapor deposition rate
Figure BDA0003044012360000054
Further preferred is
Figure BDA0003044012360000055
More preferably
Figure BDA0003044012360000056
In the present invention, in the second vapor deposition, the current of the second vapor deposition is preferably 60 to 70A, more preferably 62 to 68A, and still more preferably 63 to 65A. According to the invention, the perfluorinated phthalocyanine copper is subjected to second evaporation under the conditions, so that the obtained fluorine-containing organic layer is combined with the metal/metal fluoride, and the water resistance of the composite film is improved, and the oxygen barrier property is further improved.
After the composite film is obtained, the method preferably comprises the steps of sequentially repeating the first evaporation and the second evaporation; the number of repetitions is preferably ≧ 1.
In the present invention, the first vapor deposition and the second vapor deposition are preferably performed in a vacuum atmosphere.
The invention also provides the application of the composite film or the composite film prepared by the preparation method in the technical scheme in OLED device packaging. In the invention, the packaging process of the composite film for the OLED device preferably refers to the preparation process of the composite film, and the difference is only that the substrate is replaced by the OLED device to be packaged. The packaged OLED device obtained by the method has excellent air isolation performance and hydrophobic performance, the packaging reliability is further improved, and the service life of the OLED device is prolonged.
For further illustration of the present invention, the following detailed description of the composite film provided by the present invention, its preparation method and application are provided in conjunction with the accompanying drawings and examples, which should not be construed as limiting the scope of the present invention.
Example 1
Putting silver on a boat source for preheating, wherein the preheating current is 135A;
putting magnesium fluoride on a crucible for preheating, wherein the preheating current is 65A;
after reaching the volatilization temperature, continuously electrifying the boat source with the silver and the crucible with the magnesium fluoride,the silver and the magnesium fluoride are always kept in a volatile state, the silver and the magnesium fluoride are evaporated and plated on the surface of the OLED device to be evaporated and plated simultaneously, and the evaporation speeds of the silver and the magnesium fluoride are both
Figure BDA0003044012360000061
Obtaining a silver/magnesium fluoride layer with a thickness of 30nm, wherein the particle size of the silver is 0.5 nm; the grain diameter of the magnesium fluoride is 0.1 nm; the mass ratio of the silver to the magnesium fluoride is 1: 1;
placing the perfluorinated phthalocyanine copper on a crucible for preheating, wherein the preheating current is 65A;
after reaching the volatilization temperature, continuously electrifying to ensure that the perfluorinated phthalocyanine is always in a volatilization state, and evaporating the perfluorinated phthalocyanine copper on the surface of the silver/magnesium fluoride layer at the evaporation speed of
Figure BDA0003044012360000062
A fluorine-containing organic layer having a thickness of 30nm was obtained.
And repeating the first evaporation process and the second evaporation process in sequence for 4 times to obtain the composite film with the thickness of 300 nm.
Example 2
Putting silver on a boat source for preheating, wherein the preheating current is 140A;
placing lithium fluoride on a crucible for preheating, wherein the preheating current is 60A;
after reaching the volatilization temperature, the boat source with silver and the crucible with lithium fluoride are continuously electrified to keep the silver and the lithium fluoride in a volatilization state all the time, silver and the lithium fluoride are firstly evaporated on the surface of the OLED device to be evaporated, and the evaporation speed of the silver and the lithium fluoride is equal to that of the silver and the lithium fluoride
Figure BDA0003044012360000071
Obtaining a silver/lithium fluoride layer with a thickness of 60nm, wherein the particle size of the silver is 0.5 nm; the particle size of the lithium fluoride is 0.1 nm; the mass ratio of the silver to the lithium fluoride is 1: 1;
placing the perfluorinated phthalocyanine copper on a crucible for preheating, wherein the preheating current is 65A;
after reaching the volatilization temperature, continuously electrifyingThe perfluoro phthalocyanine is always kept in a volatile state, and the perfluoro phthalocyanine copper is evaporated on the surface of the silver/lithium fluoride layer at the evaporation speed of
Figure BDA0003044012360000072
A fluorine-containing organic layer having a thickness of 60nm was obtained.
And repeating the first evaporation process and the second evaporation process in sequence for 3 times to obtain a composite film with the thickness of 480 nm.
Example 3
Placing aluminum on a boat source for preheating, wherein the preheating current is 30A;
putting potassium fluoride on a crucible for preheating, wherein the preheating current is 60A;
after reaching volatilization temperature, continuously electrifying the boat source with the potassium fluoride crucible to keep the aluminum and the potassium fluoride in a volatile state all the time, and evaporating aluminum and potassium fluoride simultaneously on the surface of the OLED device to be evaporated, wherein the evaporation speed of the aluminum and the potassium fluoride is equal to that of the OLED device to be evaporated
Figure BDA0003044012360000073
Obtaining an aluminum/potassium fluoride layer with the thickness of 30nm, wherein the particle size of the aluminum is 0.5 nm; the particle size of the potassium fluoride is 0.1 nm; the mass ratio of the aluminum to the potassium fluoride is 1: 1;
placing the perfluorinated phthalocyanine copper on a crucible for preheating, wherein the preheating current is 65A;
continuously electrifying after reaching the volatilization temperature to keep the perfluoro phthalocyanine in a volatile state all the time, and evaporating the perfluoro phthalocyanine copper on the surface of the aluminum/potassium fluoride layer at the evaporation speed of
Figure BDA0003044012360000074
A fluorine-containing organic layer having a thickness of 30nm was obtained.
And repeating the first evaporation process and the second evaporation process in sequence for 5 times to obtain the composite film with the thickness of 360 nm.
Example 4
Placing gold on a boat source for preheating, wherein the preheating current is 155A;
putting potassium fluoride on a crucible for preheating, wherein the preheating current is 65A;
after reaching the volatilization temperature, the boat source with gold and the crucible with potassium fluoride are continuously electrified to keep gold and potassium fluoride in a volatilization state all the time, the surface of an OLED device to be evaporated is subjected to first evaporation plating of gold and potassium fluoride simultaneously, and the evaporation plating speed of gold and potassium fluoride is equal to that of the gold and potassium fluoride
Figure BDA0003044012360000081
Obtaining a gold/potassium fluoride layer with the thickness of 40nm, wherein the grain size of the gold is 0.5 nm; the particle size of the potassium fluoride is 0.1 nm; the mass ratio of gold to potassium fluoride is 1: 1;
placing the perfluorinated phthalocyanine copper on a crucible for preheating, wherein the preheating current is 65A;
continuously electrifying after reaching the volatilization temperature to keep the perfluoro phthalocyanine in a volatile state, and evaporating the perfluoro phthalocyanine copper on the surface of the gold/potassium fluoride layer at the evaporation speed of
Figure BDA0003044012360000082
A fluorine-containing organic layer having a thickness of 40nm was obtained.
And repeating the first evaporation process and the second evaporation process in sequence for 3 times to obtain a composite film with the thickness of 320 nm.
Example 5
Placing aluminum on a boat source for preheating, wherein the preheating current is 35A;
placing lithium fluoride on a crucible for preheating, wherein the preheating current is 60A;
after reaching volatilization temperature, the boat source with aluminum and the crucible with lithium fluoride are continuously electrified to keep aluminum and lithium fluoride in a volatile state all the time, the surface of an OLED device to be evaporated is simultaneously plated with aluminum and lithium fluoride, and the evaporation speed of the aluminum and the lithium fluoride is equal to that of the OLED device to be evaporated
Figure BDA0003044012360000083
Obtaining an aluminum/lithium fluoride layer with a thickness of 40nm, wherein the particle size of the aluminum is 0.5 nm; the particle size of the lithium fluoride is 0.1 nm; the aluminum and fluorineThe mass ratio of lithium is 1: 1;
placing the perfluorinated phthalocyanine copper on a crucible for preheating, wherein the preheating current is 65A;
after reaching the volatilization temperature, continuously electrifying to ensure that the perfluoro phthalocyanine is always in a volatilization state, and evaporating the perfluoro phthalocyanine copper on the surface of the aluminum/lithium fluoride layer at the evaporation speed of
Figure BDA0003044012360000084
A fluorine-containing organic layer having a thickness of 40nm was obtained.
And repeating the first evaporation process and the second evaporation process in sequence for 4 times to obtain the composite film with the thickness of 400 nm.
Comparative example 1
A composite film, which does not include a fluorine-containing organic layer, was prepared in the same manner as in example 1.
Comparative example 2
A composite film was prepared in the manner described in reference to example 1, except that the silver/magnesium fluoride layer was not included.
Comparative example 3
A composite film was prepared in the manner referred to in example 1, wherein the silver-magnesium fluoride layer was replaced with a silver layer.
Comparative example 4
A composite film was prepared in the manner referred to in example 1, in which the silver-magnesium fluoride layer was replaced with a magnesium fluoride layer.
Performance testing
And (3) carrying out a water vapor transmittance test on the composite films obtained in the examples 1-5 and the comparative examples 1-4, wherein the test conditions are as follows: under the standard atmospheric pressure, the temperature is 25 ℃, and the relative humidity is 20-30%. The test results are shown in table 1.
Table 1 test results of water vapor transmission rates of composite films obtained in examples 1 to 5 and comparative examples 1 to 4
Figure BDA0003044012360000091
As can be seen from Table 1, the composite film provided by the invention has lower water vapor transmission rate, which shows that the composite film provided by the invention has excellent hydrophobic property.
The OLED devices packaged by the composite films obtained in the embodiments 1-5 and the comparative examples 1-4 are subjected to service life test by adopting a ZJZCL-2 type OLED aging tester, wherein the test mode is that the time length of the brightness attenuation of the devices to 50% of the initial brightness is measured, and the test conditions are as follows: under the standard atmospheric pressure, the temperature is 25 ℃, and the relative humidity is 20-30%. The test results are shown in table 2. Fig. 2 is a service life test chart of the OLED device obtained by encapsulating the composite film obtained in example 1, and as can be seen from fig. 2, the service life of the OLED device obtained by encapsulating the composite film obtained in example 1 can reach 1028 hours; fig. 3 is a service life test chart of the OLED device obtained by encapsulating the composite film obtained in example 2, and as can be seen from fig. 3, the service life of the OLED device obtained by encapsulating the composite film obtained in example 2 can reach 955h, which has a long service life.
Table 2 life test results of the composite thin film packaged devices obtained in examples 1 to 5 and comparative examples 1 to 4
Example 1 Example 2 Example 3 Example 4 Example 5
Service life/h 1028 955 873 850 822
Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4
Service life/h 320 285 471 512
As can be seen from Table 2, when the composite film provided by the invention is used for packaging an OLED, the service life of a packaging device can reach 822-1028 hours.
In summary, the metal and the metal fluoride are combined, and particles with different particle sizes are mutually filled to obtain a more compact metal/metal fluoride layer, so that the air insulation performance is improved; the fluorine-containing organic layer and the metal/metal fluoride layer are combined, and under the synergistic effect of the fluorine-containing organic layer and the metal/metal fluoride layer, the water resistance is improved, and meanwhile, the oxygen barrier performance of the composite film is further improved. The composite film obtained by the invention is used for packaging the OLED, the service life of a packaging device is further prolonged, and the packaging reliability is improved.
Although the above embodiments have been described in detail, they are only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and all of the embodiments belong to the protection scope of the present invention.

Claims (10)

1. A composite film is characterized by comprising metal/metal fluoride layers and fluorine-containing organic layers which are alternately stacked;
the material of the metal/metal fluoride layer comprises metal and metal fluoride;
the material of the fluorine-containing organic layer comprises copper perfluorophthalocyanine;
the particle size of the metal is larger than the particle size of the metal fluoride.
2. The composite film of claim 1 wherein the metal comprises gold, silver or aluminum;
the metal fluoride includes one of an alkali metal fluoride and an alkaline earth metal fluoride.
3. The composite film according to claim 1 or 2, wherein the mass ratio of the metal to the metal fluoride is 1-2: 1.
4. the composite film according to claim 1, wherein the thicknesses of the metal/metal fluoride layer and the fluorine-containing organic layer are independently 10 to 100 nm.
5. The composite film according to claim 1, wherein the number of layers of the metal/metal fluoride layer and the fluorine-containing organic layer is equal to or greater than 1; the metal/metal fluoride layers and the fluorine-containing organic layers are alternately stacked in sequence, and the number of the metal/metal fluoride layers is the same as that of the fluorine-containing organic layers.
6. A method for producing the composite film according to any one of claims 1 to 5, comprising the steps of:
simultaneously performing first metal evaporation and metal fluoride on the surface of the substrate to obtain a metal/metal fluoride layer;
and (3) evaporating perfluorinated phthalocyanine copper on the surface of the metal/metal fluoride layer for the second time to obtain the composite film.
7. The method according to claim 6, wherein the first evaporation and the second evaporation are performed at evaporation speeds independent of each other
Figure FDA0003044012350000011
8. The production method according to claim 6 or 7, wherein, in the first evaporation, an evaporation current of the metal is 25 to 160A;
the evaporation current of the metal fluoride is 55-65A;
the current of the second evaporation is 60-70A.
9. The method according to claim 6, further comprising repeating the first evaporation and the second evaporation in sequence after the second evaporation is completed;
the repetition frequency is more than or equal to 1.
10. The composite film according to any one of claims 1 to 5 or the composite film prepared by the preparation method according to any one of claims 6 to 9 is applied to packaging of OLED devices.
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