CN111384282A - Packaging film, preparation method thereof and light-emitting display device - Google Patents
Packaging film, preparation method thereof and light-emitting display device Download PDFInfo
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- CN111384282A CN111384282A CN201811615764.6A CN201811615764A CN111384282A CN 111384282 A CN111384282 A CN 111384282A CN 201811615764 A CN201811615764 A CN 201811615764A CN 111384282 A CN111384282 A CN 111384282A
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Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/875—Arrangements for extracting light from the devices
- H10K59/879—Arrangements for extracting light from the devices comprising refractive means, e.g. lenses
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biophysics (AREA)
- Optics & Photonics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention belongs to the technical field of display, and particularly relates to a packaging film, a preparation method thereof and a light-emitting display device. The packaging film comprises N layers of inorganic films which are sequentially stacked, wherein in the N layers of inorganic films, the refractive indexes from the 1 st layer of inorganic film to the N layers of inorganic films are sequentially increased, and when the packaging film is used for packaging a photoelectric device, the 1 st layer of inorganic film is adjacent to the top electrode of the light-emitting device; wherein N is an integer equal to or greater than 2. When the packaging film is used for packaging photoelectric devices, the total reflection of light emitted from the devices in the packaging film can be reduced on the premise of effectively preventing water and oxygen in the air from entering the devices, and the luminous efficiency and the service life of the devices can be improved.
Description
Technical Field
The invention belongs to the technical field of display, and particularly relates to a packaging film, a preparation method thereof and a light-emitting display device.
Background
Compared with organic luminescent dyes and inorganic fluorescent powder, the quantum dot light emitting diode (QLED) with the semiconductor quantum dot material as the luminescent layer has wide application space in the fields of photoelectricity, photovoltaics and biological marks due to the excellent characteristics of optics, device stability and the like, and particularly has application in the aspect of light emitting diodes, and the quantum dot light emitting diode can lead the development of new generation products in the display screen and solid-state lighting industries.
Although the performance (including device efficiency and service life) of the QLED is greatly improved by the improvement of the quantum dot material, the light extraction efficiency is far from the requirement of industrial production. Conventional QLED devices include Al + ITO substrate/PEDOT: PSS/poly-TPD/quantum dot luminous layer/ZnO/Mg-Ag alloy + packaging cover plate glass layer, and the traditional photoelectric device packaging technology is completed in a glove box with water and oxygen contents lower than 1 ppm. And transferring the manufactured device into a glove box by a linear manipulator in the glove box. The back cover plate is coated with UV glue by an automatic glue coating machine with a program adjusted, the manufactured photoelectric device substrate is aligned and attached to the back cover plate coated with the UV glue, and a barrier separated from the atmospheric environment is formed after UV exposure, so that water and oxygen in the air can be effectively prevented from entering the photoelectric device, and the reaction with the water and oxygen is avoided. The packaging method can successfully couple the QLED out of the LED in a low proportion, so that the light emitting efficiency of the device is influenced.
Currently, the packaging technology of commercial photoelectric devices is being developed from the conventional cover plate type packaging to the novel thin film integrated packaging. The film package enables the dream of flexible display to be realized, but at the present stage, the package life and stability need to be further improved, the cost advantage is not great, and the advantage is not very obvious compared with the traditional package. In a typical top-emission type QLED device with a planar structure, in order to achieve a QLED device with high illumination efficiency, the light output coupling efficiency must be improved, and a method is devised to couple out the limited light.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, provides a packaging film, a preparation method thereof and a light-emitting display device, and aims to solve the technical problem that the light-emitting efficiency and the service life of a device are influenced due to the fact that the packaging effect of the existing photoelectric device is not ideal.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a packaging film, which comprises N layers of inorganic films which are sequentially stacked, wherein in the N layers of inorganic films, the refractive indexes from a 1 st layer of inorganic film to an N layer of inorganic film are sequentially increased, and when the packaging film is used for packaging a photoelectric device, the 1 st layer of inorganic film is adjacent to a top electrode of the light-emitting device; wherein N is an integer equal to or greater than 2.
The packaging film provided by the invention is a novel packaging cover plate inorganic glass, which is used for packaging photoelectric devices, wherein the packaging film is provided with a plurality of inorganic transparent films with gradient refractive indexes, namely the refractive indexes of the inorganic films from the 1 st layer to the N th layer are sequentially increased in the N layers of inorganic films stacked in the packaging film, so that when the packaging film is used for packaging the photoelectric devices, the total reflection of light emitted by the devices in the packaging film can be reduced on the premise of effectively preventing water and oxygen in the air from entering the devices, thereby increasing the light output, and finally improving the luminous efficiency of the devices.
The invention also provides a preparation method of the packaging film, which comprises the following steps:
providing a substrate;
preparing an encapsulation film on the substrate;
the packaging film comprises N layers of inorganic films which are sequentially stacked, the refractive indexes of the N layers of inorganic films from the 1 st layer of inorganic film to the N layers of inorganic films are sequentially increased, the 1 st layer of inorganic film is adjacent to the substrate, and N is an integer equal to or larger than 2.
The preparation method of the packaging film provided by the invention has simple and feasible process, and the laminated N layers of inorganic films are sequentially prepared on the substrate, so that the packaging film is obtained; when the packaging film obtained by the preparation method is used for packaging photoelectric devices, the total reflection of light emitted from the devices in the packaging film can be reduced on the premise of effectively preventing water and oxygen in the air from entering the devices, and the luminous efficiency and the service life of the devices can be improved.
Finally, the invention also provides a light-emitting display device which comprises a photoelectric device and an encapsulation layer arranged on the photoelectric device, wherein the encapsulation layer is the encapsulation film or the encapsulation film obtained by the preparation method.
The light-emitting display device provided by the invention uses the special packaging film of the invention as a packaging layer for packaging, so that the light-emitting device can effectively prevent water and oxygen in the air from entering the device, and simultaneously reduces the total reflection of light emitted from the device in the packaging film, thereby having good light-emitting efficiency and service life.
Drawings
FIG. 1 is a schematic diagram of light extraction from a packaging film according to the present invention;
FIG. 2 is a schematic view of a light-emitting display device according to an embodiment of the present invention;
fig. 3 is a schematic view of a light-emitting display device according to another embodiment of the invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In one aspect, an embodiment of the present invention provides an encapsulation film, including N sequentially stacked inorganic films, where refractive indexes of the N inorganic films sequentially increase from a 1 st inorganic film to an N th inorganic film, and when the encapsulation film is used for encapsulating a photovoltaic device, the 1 st inorganic film is adjacent to a top electrode of the light emitting device; wherein N is an integer equal to or greater than 2.
The packaging film provided by the embodiment of the invention is a novel packaging cover plate inorganic glass, which is used for packaging photoelectric devices, wherein the packaging film is provided with a plurality of inorganic transparent films with gradient refractive indexes, namely the refractive indexes of the 1 st inorganic film to the N th inorganic film in the N layers of inorganic films stacked in the packaging film are sequentially increased, so that when the packaging film is used for packaging the photoelectric devices, the total reflection of light emitted by the devices in the packaging film can be reduced on the premise of effectively preventing water and oxygen in the air from entering the devices, thereby increasing the light output, and finally improving the luminous efficiency of the devices.
Specifically, the optoelectronic device is a top-emitting light-emitting device.
Further, the encapsulation film provided by the embodiment of the invention comprises 2-10 inorganic films which are sequentially stacked.
Further, when the encapsulating thin film provided by the embodiment of the present invention encapsulates an optoelectronic device, the 1 st inorganic thin film is adjacent to a top electrode of an encapsulated light emitting device, and a material used for the 1 st inorganic thin film may be a material having a refractive index similar to that of the top electrode (the top electrode is typically an AgMg alloy, and the refractive index n is 1); preferably, the refractive index difference between the 1 st inorganic thin film and the top electrode of the photoelectric device is less than or equal to 0.3, so that the refractive index difference between the top electrode and the cathode is small, the change of the incident angle is small when light enters the 1 st inorganic thin film from the device, and the refractive indexes from the top electrode to the 1 st inorganic thin film to the Nth inorganic thin film are sequentially increased, so that the light is easier to be led out.
In the N inorganic thin films in the encapsulation thin film provided in the embodiment of the present invention, the material used for the inorganic thin film of each layer is an inorganic nano material, and specifically, may be a solid nanoparticle or a hollow nanoparticle (such as a nanosphere), a solid nanorod, or a hollow nanorod, as long as the refractive indexes of the 1 st inorganic thin film to the N th inorganic thin film in the N inorganic thin films formed of inorganic materials are sequentially increased.
Further, the material of the 1 st inorganic film is selected from magnesium fluoride nano-materials; and the materials of the 2 nd to Nth inorganic films (i.e. the rest inorganic films except the 1 st inorganic film) in the packaging films are respectively and independently selected from titanium oxide (TiO)2,n-2.3) nanomaterial and zirconium oxide (ZrO)2N 2.0 nanomaterial, zinc oxide (ZnO, n 2.0) nanomaterial, and silicon oxide (SiO)2And N is 1.4), and therefore, according to the selection of different materials from the 1 st inorganic thin film and the 2 nd to nth inorganic thin films, the difference between the refractive indexes of the nth inorganic thin film and the N-1 st inorganic thin film can be in the range of 0.1 to 1.0, and it can be understood that the difference between the refractive indexes of the nth inorganic thin film and the N-1 st inorganic thin film can be in the range of 0.1 to 1.0.
Further, the encapsulation film includes 3 inorganic films stacked in sequence; wherein, the material of the 1 st layer of inorganic film is magnesium fluoride nano-rod (preferably magnesium fluoride hollow nano-rod, the lowest refractive index is 1.3), the material of the 2 nd layer of inorganic film is hollow nano-particle, the material of the 3 rd layer of inorganic film is solid nano-particle; more preferably, the hollow nanoparticles and the solid nanoparticles are the same in chemical composition. The hollow nanoparticles are generally larger than the solid nanoparticles in particle size, so that the porosity of a film made of the hollow nanoparticles is larger than that of a film made of the solid nanoparticles, and the larger the porosity of the material is, the lower the corresponding refractive index is, and the refractive index of the film layer can be reduced to a great extent by the antireflection film material with the hollow structure, so that the refractive indexes of the 2 nd inorganic film and the 3 rd inorganic film can be sequentially increased; the interfaces of three layers of inorganic films in the optimized packaging film can be better matched to form a good covering step, so that the corrosion of water and oxygen to the device can be effectively prevented, and the service life of the device can be better prolonged; meanwhile, because the chemical components of the 2 nd inorganic film composed of hollow nanoparticles and the 3 rd inorganic film composed of solid nanoparticles are the same, the interfaces of the two films are matched, the gaps between film interfaces are reduced, and the stability of the packaging film is improved.
In a preferred embodiment of the present invention, as shown in fig. 1 and 2, the encapsulation film includes 3 inorganic films stacked in sequence; wherein the 1 st inorganic film is MgF2The nanorod film (with a refractive index of 1.3) and the 2 nd inorganic film are H-SiO2The film (i.e., hollow silica nanoparticle film, refractive index of about 1.35) and the 3 rd inorganic thin film are SiO2The film (i.e., the solid silica nanoparticle film has a refractive index of about 1.4, and a refractive index difference of 0.05 from layer 2). The encapsulation film is formed from MgF2Nanorod film to SiO2The refractive index n of the film increases in turn, so that, when used to encapsulate an optoelectronic device, total reflection of light emitted in the device in the encapsulating film can be reduced, thereby increasing light extraction.
Further, in the encapsulation film provided by the embodiment of the present invention, the nth inorganic film is subjected to surface hydrophobic modification treatment by a modifier. The N-th inorganic film on the surface of the packaging film is subjected to surface hydrophobic modification, so that the self-cleaning capability of the packaging film is improved, and the scattering of dust to emergent light and the permeation of moisture are reduced. The modifier is preferably Hexamethyldisilazane (HMDS).
Further, in the encapsulation film provided by the embodiment of the present invention, the thickness of each inorganic film in the encapsulation film is independently 50 to 150 nm. That is, the thickness of the 1 st inorganic film may be 50-150nm, the thickness of the 2 nd inorganic film may be 50-150nm, the thickness of the 3 rd inorganic film may be 50-150nm, and so on.
On the other hand, the embodiment of the invention also provides a preparation method of the packaging film, which comprises the following steps:
s01: providing a substrate;
s02: preparing an encapsulation film on the substrate;
the packaging film comprises N layers of inorganic films which are sequentially stacked, the refractive indexes of the N layers of inorganic films from the 1 st layer of inorganic film to the N layers of inorganic films are sequentially increased, the 1 st layer of inorganic film is adjacent to the substrate, and N is an integer equal to or larger than 2.
The preparation method of the packaging film provided by the embodiment of the invention has simple and feasible process, and the packaging film is obtained by sequentially preparing the laminated N layers of inorganic films on the substrate; when the packaging film obtained by the preparation method is used for packaging photoelectric devices, the total reflection of light emitted from the devices in the packaging film can be reduced on the premise of effectively preventing water and oxygen in the air from entering the devices, and the luminous efficiency and the service life of the devices can be improved.
Specifically, the photoelectric device is prepared on the substrate, namely the packaging film is directly prepared on the photoelectric device. The optoelectronic device may be a quantum dot light emitting diode or an organic light emitting diode. Further, the above encapsulation film includes 2 to 10 inorganic films stacked in this order. The choice of materials and thicknesses and refractive indices of the above-described encapsulation films are set forth in detail above.
In the preparation method of the packaging film, each layer of inorganic film can be prepared by adopting a vacuum coating method or a solution method. Specifically, taking the structure of the encapsulation film in fig. 2 as an example, the refractive indexes of the three-layer structure are respectively prepared into films from small to large by vacuum coating and printing methods, so as to ensure the sharpness of the interface of each layer of film and improve the bonding force between the layers, and the 1 st inorganic film is prepared into MgF by vacuum coating2Nanorod film, or MgF prepared by solution method2Rod-like solutions and then prepare MgF by printing2A nanorod film; the 2 nd layer inorganic film and the 3 rd layer inorganic film are both prepared by a solution method, namely, solid silica particle sol and hollow silica particle sol are prepared firstly, and then the corresponding films are prepared by a printing or lifting method.
In particular, the 1 st inorganic film is MgF2The thickness of the nano-rod film is about 50-150nm, the vacuum coating method comprises a radio frequency magnetron sputtering method, the sputtering pressure is 1-1.5Pa, and the sputtering powerIs 80-300W. The thicknesses of the 2 nd inorganic film and the 3 rd inorganic film are both 50-150 nm.
Finally, after the packaging film is prepared on the substrate, the method further comprises the following steps: and placing the packaging film in a modifier atmosphere to carry out surface hydrophobic modification treatment. By carrying out surface hydrophobic treatment on the packaging film, the hydrophobic property of the film is improved, the packaging film can be kept in a self-cleaning state, and the scattering of dust to emergent light is reduced. The modifying agent is preferably hexamethyldisilazane, and the specific process is that the packaging film is placed in hexamethyldisilazane atmosphere, modified for 48 hours at 50 ℃, and naturally cooled to room temperature.
Finally, the embodiment of the present invention further provides a light emitting display device, as shown in fig. 2, including a photoelectric device and an encapsulation layer disposed on the photoelectric device, where the encapsulation layer is the encapsulation film according to the embodiment of the present invention or the encapsulation film obtained by the preparation method according to the embodiment of the present invention.
The light-emitting display device provided by the embodiment of the invention uses the special packaging film of the embodiment of the invention as the packaging layer for packaging, so that the light-emitting device can effectively prevent water and oxygen in the air from entering the device, and simultaneously reduces the total reflection of the light emitted by the device in the packaging film, thereby having good light-emitting efficiency and service life.
In a preferred embodiment, as shown in fig. 3, the light emitting display device sequentially includes a substrate, a bottom electrode, a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), a light emitting layer (R, G, B), an Electron Transport Layer (ETL), a top electrode, and an encapsulation layer.
Wherein, the bottom electrode adopts a magnetron sputtering Al electrode and an ITO film, and the thickness of the Al/ITO electrode is about 30-50 nm; one embodiment is as follows: preparing a hole injection material PEDOT on an Al/ITO substrate: PSS with thickness of 30-40nm and hole transport material poly-TPD with thickness of 30-50nm, and preparing a luminescent layer with thickness of 30-60 nm. And after the luminescent layer is annealed, preparing an electron transport layer ZnO on the luminescent layer, wherein the thickness of the electron transport layer is about 50-150nm, the top electrode is made of Ag/Mg alloy, the evaporation thickness is 30-50nm, and the evaporation speed is 0.1-0.3 nm/s.
The holes described in embodiments of the present invention may be, but are not limited to, PEDOT: PSS. The hole transport material in the embodiment of the invention can be but is not limited to organic transport materials such as poly-TPD, TFB and the like, NiO, MoO and the like3And inorganic transport materials and composites thereof. The material of the light emitting layer (R, G, B) described in the embodiments of the present invention may be, but is not limited to, core-shell quantum dots, graded-shell based quantum dots, phosphorescent or fluorescent light emitting materials. The electron transport layer described in the embodiments of the present invention may be, but is not limited to, ZnO, Cs2CO3Etc. or an inorganic material or an organic transport material such as Alq 3.
The invention is described in further detail with reference to a part of the test results, which are described in detail below with reference to specific examples.
Example 1
The embodiment provides an electronic device. The QLED packaging film comprises a substrate, a QLED electronic element combined on the substrate and a packaging film used for packaging the QLED electronic element. The structure of the electronic device is as follows: al + ITO substrate (50 nm)/PEDOT: PSS (50nm)/poly-TPD (30 nm)/quantum dot luminescent layer (20nm)/ZnO (30nm)/Mg-Ag alloy (50 nm)/encapsulating layer (300 mm).
Forming layers in sequence on an AL + ITO substrate according to the QLED structure of the embodiment, thereby forming a QLED;
wherein the material of the packaging layer is MgF2film/H-SiO2film/SiO2Film of said MgF2The film thickness is 100nm, the film is prepared by adopting a radio frequency magnetron sputtering method, and the background vacuum is 1 x 10-4Pa, sputtering pressure of 0.8Pa, sputtering power of 80W, sputtering time of 180s, sputtering thickness of 100nm, and the thickness of the H-SiO film2Film and SiO2The film is prepared into sol by a solution method and then printed to form the film.
Solid SiO2Preparation of the solution: 2.02mL of Ammonia (NH)3·H2O, 28%) into 65.5mL of absolute ethanol (EtOH, 99.9%), stirring in a 30 ℃ water bath, dropwise adding into 6.67mL of tetraethoxysilane (TEOS, 99%), reacting for 6h, aging for 4d, removing ammonia to dilute SiO2Mass fraction of 1 wt%, to obtain corresponding solid SiO2A solution;
hollow SiO2Preparation of the solution: 0.12g polyacrylic acid (PAA, Mw. apprxeq.5000, 30 wt.%) was dissolved in 6mL NH3·H2Adding 120mL of EtOH into O, mixing and stirring uniformly, dropwise adding 0.36mL of TEOS every 10min for 5 times, violently stirring for 10H, removing ammonia, adjusting H-SiO2The mass fraction is 2wt percent, and the corresponding H-SiO is obtained2A solution;
adding a certain amount of solvent (n-octane), surfactant, adhesive and the like to prepare ink, controlling the thickness of a corresponding film layer by the number of printing drops, and preparing H-SiO by printing 15 drops2film/SiO2The thickness of the film was 100 nm.
And after the preparation of the three-layer packaging film is finished, placing the packaging film in Hexamethyldisilazane (HMDS) atmosphere, modifying for 48 hours at the temperature of 50 ℃, and naturally cooling to room temperature to finish the preparation of the packaging layer.
Example 2
The embodiment provides an electronic device. The QLED packaging film comprises a substrate, a QLED electronic element combined on the substrate and a packaging film used for packaging the QLED electronic element. The structure of the electronic device is as follows: al + ITO substrate (50 nm)/PEDOT: PSS (50nm)/poly-TPD (30 nm)/quantum dot luminescent layer (20nm)/ZnO (30nm)/Mg-Ag alloy (50 nm)/encapsulating layer (300 nm). Forming layers in sequence on an AL + ITO substrate according to the QLED structure of the embodiment, thereby forming a QLED;
wherein the material of the packaging layer is MgF2film/H-TiO2film/TiO2Film of said MgF2The film thickness is 100nm, the film is prepared by adopting a radio frequency magnetron sputtering method, and the background vacuum is 1 x 10-4Pa, sputtering pressure of 0.8Pa, sputtering power of 80W, sputtering time of 180s and sputtering thickness of 100 nm; the H-TiO2Film and TiO2The film is prepared into sol by a solution method and then printed to form the film.
Solid TiO 22Preparation of the solution: 1.7mL of Ammonia (NH)3·H2O, 28%) was added to 40mL of absolute ethanol (EtOH, 99.9%) and water at 50 deg.CStirring the solution, dropwise adding the solution into 5.7mL of butyl titanate, reacting for 4 hours, then aging for 4 days, removing ammonia and diluting TiO2Mass fraction of 2 wt%, to obtain the corresponding solid TiO2A solution;
hollow TiO 22Preparation of the solution: 0.2g of polyacrylic acid (PAA, Mw. apprxeq.5000, 30 wt.%) is dissolved in 8mLNH3·H2Adding 100mL of EtOH into O, uniformly mixing and stirring, dropwise adding 0.5mL of butyl titanate every 10min for 5 times, violently stirring for 10H, removing ammonia, and adjusting H-TiO2The mass fraction is 3wt percent to obtain the corresponding H-TiO2A solution;
adding a certain amount of solvent (water), surfactant, adhesive and the like to prepare ink, controlling the thickness of a corresponding film layer by the number of printing drops, and preparing H-TiO by printing 15 drops2film/TiO2The thickness of the film is 100 nm;
and after the preparation of the three-layer packaging film is finished, placing the packaging film in Hexamethyldisilazane (HMDS) atmosphere, modifying for 48 hours at the temperature of 50 ℃, and naturally cooling to room temperature to finish the preparation of the packaging layer.
Example 3
The embodiment provides an electronic device. The QLED packaging film comprises a substrate, a QLED electronic element combined on the substrate and a packaging film used for packaging the QLED electronic element. The structure of the electronic device is as follows: al + ITO substrate (50 nm)/PEDOT: PSS (50nm)/poly-TPD (30 nm)/quantum dot luminescent layer (20nm)/ZnO (30nm)/Mg-Ag alloy (50 nm)/encapsulating layer (210 nm). Forming layers in sequence on an AL + ITO substrate according to the QLED structure of the embodiment, thereby forming a QLED;
wherein the material of the packaging film is MgF2film/H-SiO2film/SiO2Film of said MgF2The thickness of the film was 50nm,
hollow rod-shaped MgF2Preparing sol: 1.73g magnesium acetate tetrahydrate (Mg (CH)3COO)2·4H2O, 99%) in 38g of anhydrous methanol (CH)3OH, 99.9%), 9.3gCH was slowly added dropwise30.645g of hydrofluoric acid (HF,40 wt%) solution diluted by OH reacts for 30min at normal temperature, and then the reaction is carried out in an oven at 240 ℃ for 24h to obtain MgF2Solutions of,
Adding certain amount of solvent (ethanol), surfactant, adhesive, etc. to obtain MgF2Ink, the thickness of the corresponding film layer is controlled by the number of printing drops, and when the number of printing drops is 7, MgF2The film is about 50nm thick;
solid SiO2Preparation of the solution: 2.02mL of Ammonia (NH)3·H2O, 28%) into 65.5mL of absolute ethanol (EtOH, 99.9%), stirring in a 30 ℃ water bath, dropwise adding into 6.67mL of tetraethoxysilane (TEOS, 99%), reacting for 6h, aging for 4d, removing ammonia to dilute SiO with the mass fraction of 1 wt% to obtain the corresponding solid SiO2A solution;
hollow SiO2Preparation of the solution: 0.12g polyacrylic acid (PAA, Mw. apprxeq.5000, 30 wt.%) was dissolved in 6mL NH3·H2Adding 120mL of EtOH into O, mixing and stirring uniformly, dropwise adding 0.36mL of TEOS every 10min for 5 times, violently stirring for 10H, removing ammonia, adjusting H-SiO2The mass fraction is 2wt percent, and the corresponding H-SiO is obtained2A solution;
adding a certain amount of solvent (water), surfactant, adhesive and the like to prepare ink, controlling the thickness of a corresponding film layer by the number of printing drops, and preparing the H-TiO through printing 12 drops2film/TiO2The thickness of the film was 80 nm.
And after the preparation of the three-layer packaging film is finished, placing the packaging film in Hexamethyldisilazane (HMDS) atmosphere, modifying for 48 hours at the temperature of 50 ℃, and naturally cooling to room temperature to finish the preparation of the packaging layer.
In a word, the multilayer inorganic film of the layered film structure forms good covering steps, the shell reduces the defects of the film layer, the permeation of water and oxygen to the device can be well blocked, and meanwhile, the visible light transmittance is improved for the top light-emitting device through the preparation of the packaging film of the multilayer film with the gradient refractive index; and the surface of the packaging film is subjected to hydrophobic treatment, so that the packaging film has self-cleaning capacity and water and oxygen isolation capacity. In addition, compared with the traditional cover plate packaging, the packaging film has the characteristics of light weight, thinness, high efficiency and the like, overcomes the defect of fragility of glass, and can prolong the service life of a photoelectric device to the maximum extent, so that the self-luminous display technology is more widely applied.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A packaging film is characterized by comprising N layers of inorganic films which are sequentially stacked, wherein in the N layers of inorganic films, the refractive indexes from a 1 st layer of inorganic film to an N layer of inorganic film are sequentially increased, and when the packaging film is used for packaging a photoelectric device, the 1 st layer of inorganic film is adjacent to a top electrode of the light-emitting device; wherein N is an integer equal to or greater than 2.
2. The encapsulation film according to claim 1, wherein the encapsulation film comprises 2 to 10 inorganic films stacked in this order; and/or
The absolute value of the difference between the refractive indexes of the 1 st inorganic film and the top electrode of the photoelectric device is less than or equal to 0.3; and/or the presence of a gas in the gas,
the refractive index difference between the N-th inorganic thin film and the N-1 th inorganic thin film is in the range of 0.05-1.0.
3. The encapsulation film according to claim 1, wherein the material of the layer 1 inorganic film is selected from the group consisting of magnesium fluoride nanomaterials; and/or the presence of a gas in the gas,
the materials from the 2 nd layer inorganic film to the Nth layer inorganic film in the packaging film are respectively and independently selected from at least one of titanium oxide nano material, zirconium oxide nano material, zinc oxide nano material and silicon oxide nano material.
4. The encapsulation film according to any one of claims 1 to 3, wherein the encapsulation film comprises 3 inorganic films laminated in this order; the material of the 1 st layer of inorganic film is magnesium fluoride nano-rods, the material of the 2 nd layer of inorganic film is hollow nano-particles, and the material of the 3 rd layer of inorganic film is solid nano-particles.
5. The encapsulation film of claim 4, wherein the hollow nanoparticles and the solid nanoparticles are chemically the same.
6. The encapsulation film according to any one of claims 1 to 3, wherein the N-th inorganic film is surface-hydrophobically modified with a modifier; and/or the presence of a gas in the gas,
the thickness of each layer of inorganic film in the packaging film is 50-150nm respectively and independently.
7. The preparation method of the packaging film is characterized by comprising the following steps:
providing a substrate;
preparing an encapsulation film on the substrate;
the packaging film comprises N layers of inorganic films which are sequentially stacked, the refractive indexes of the N layers of inorganic films from the 1 st layer of inorganic film to the N layers of inorganic films are sequentially increased, the 1 st layer of inorganic film is adjacent to the substrate, and N is an integer equal to or larger than 2.
8. The production method according to claim 7, wherein the encapsulation film comprises 2 to 10 inorganic films laminated in this order; and/or the presence of a gas in the gas,
the absolute value of the difference between the refractive indexes of the 1 st inorganic film and the top electrode of the photoelectric device is less than or equal to 0.3; and/or the presence of a gas in the gas,
the material of the 1 st layer of inorganic film is selected from magnesium fluoride nano material; and/or the presence of a gas in the gas,
the materials from the 2 nd layer inorganic film to the Nth layer inorganic film in the packaging film are respectively and independently selected from at least one of titanium oxide nano material, zirconium oxide nano material, zinc oxide nano material and silicon oxide nano material; and/or the presence of a gas in the gas,
the packaging film comprises 3 layers of inorganic films which are sequentially stacked; the material of the 1 st layer of inorganic film is magnesium fluoride nano-rods, the material of the 2 nd layer of inorganic film is hollow nano-particles, and the material of the 3 rd layer of inorganic film is solid nano-particles.
9. The method of manufacturing according to claim 7, further comprising, after manufacturing an encapsulation film on the substrate, the steps of: and placing the packaging film in a modifier atmosphere to carry out surface hydrophobic modification treatment.
10. A light-emitting display device comprising an optoelectronic device and an encapsulation layer provided on the optoelectronic device, wherein the encapsulation layer is the encapsulation film according to any one of claims 1 to 6 or the encapsulation film obtained by the production method according to any one of claims 7 to 9.
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