CN115148927A - Packaging structure - Google Patents
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- CN115148927A CN115148927A CN202110354742.4A CN202110354742A CN115148927A CN 115148927 A CN115148927 A CN 115148927A CN 202110354742 A CN202110354742 A CN 202110354742A CN 115148927 A CN115148927 A CN 115148927A
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- 238000004806 packaging method and process Methods 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 83
- 238000000605 extraction Methods 0.000 claims abstract description 36
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- 239000010410 layer Substances 0.000 claims description 99
- 150000003384 small molecules Chemical class 0.000 claims description 36
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- 238000005538 encapsulation Methods 0.000 claims description 23
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- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000000304 alkynyl group Chemical group 0.000 claims description 8
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- 125000000623 heterocyclic group Chemical group 0.000 claims description 8
- 125000003282 alkyl amino group Chemical group 0.000 claims description 7
- 125000004414 alkyl thio group Chemical group 0.000 claims description 7
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- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 7
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 claims description 7
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 229910052805 deuterium Inorganic materials 0.000 claims description 6
- 239000002346 layers by function Substances 0.000 claims description 6
- 125000005013 aryl ether group Chemical group 0.000 claims description 5
- 239000008393 encapsulating agent Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000006732 (C1-C15) alkyl group Chemical group 0.000 claims description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
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Images
Classifications
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- 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
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
- G09F9/301—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements flexible foldable or roll-able electronic displays, e.g. thin LCD, OLED
-
- 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
- H10K50/85—Arrangements for extracting light from the devices
-
- 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
- H10K50/85—Arrangements for extracting light from the devices
- H10K50/858—Arrangements for extracting light from the devices comprising refractive means, e.g. lenses
-
- 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
- H10K59/10—OLED displays
Abstract
The invention provides a packaging structure which comprises a composite packaging structure formed by a high-refractive-index inorganic material and a low-refractive-index high polymer material and an interval packaging layer formed by a low-refractive-index organic micromolecule material. The low-refractive-index organic micromolecules are arranged between the high-refractive-index inorganic material of the composite packaging structure and the light extraction layer in the light-emitting device. In addition, the invention also provides an organic low-refractive-index micromolecule material which can be applied to the interval packaging layer. Compared with the prior art, the packaging structure provided by the invention can increase the visual angle, improve the reliability of bending and curling the screen, reduce the process difficulty and possibly improve the luminous efficiency. The packaging structure can be used in various rigid and flexible screens, and can be used for mobile phones, televisions, flat panels, vehicle-mounted displays, tail lamps, illumination, VR, AR and the like.
Description
Technical Field
The invention relates to a packaging structure for an organic light-emitting diode, in particular to a packaging structure which utilizes a low-refractive-index micromolecular material to replace lithium fluoride (LiF) so as to simplify the process flow, mechanically improve the reliability of a screen body on flexibility and optically improve the light extraction efficiency and the visual angle.
Background
An organic light emitting diode is a self-luminous display device, and has the characteristics of lightness, thinness, wide viewing angle, low driving voltage, high-brightness light emission and the like.
Generally, an organic light emitting diode is packaged by using glass, and a thin film packaging technology for a flexible display is attracting attention as the characteristics of the organic light emitting diode in terms of flexibility are recognized by various manufacturers and a flexible display panel is popularized. In the thin film encapsulation technology, since a composite encapsulation structure in which high refractive index inorganic materials and low refractive index polymer materials are alternately arranged is used, it is necessary to add a low refractive index material above a high refractive index cover layer of a conventional organic light emitting diode for optical adjustment. The prior art uses lithium fluoride as the optical encapsulation layer. However, the lithium fluoride material is an inorganic material, and has a higher hardness and a higher brittleness compared with an organic material, and has a problem of reducing the reliability of a screen body when aiming at a flexible display, particularly a foldable and rollable display screen. On the other hand, the sublimation temperature of the lithium fluoride material is too high, and the lithium fluoride material is insoluble in organic solvents and water, so that the pollution of the cavity is easily caused, a special cavity is needed for evaporation, the equipment is expensive, and the waste is caused. In addition, the orientation of the lithium fluoride material results in a limited viewing angle for products using the lithium fluoride material. Some solutions attempt to use a high-molecular low-refractive-index material instead of lithium fluoride, however, the high-molecular film forming mode is generally ink-jet printing, the film forming time is long, and the industrial production rhythm is reduced. In addition, the film thickness after film formation and the film thickness after vapor deposition are not in the same order of magnitude, and it is difficult to control the optical path length when a polymer material is substituted for lithium fluoride. Therefore, there is a need for a material that is "resistant to bending", "simple in manufacturing process", and "easy to adjust optical length" to solve the problems of the prior art.
Disclosure of Invention
As described above, in the prior art, lithium fluoride or a high-molecular material with a low refractive index is used as an optical encapsulation layer between an organic light emitting diode and a composite encapsulation structure manufactured by a thin film encapsulation technology, so as to adjust the optical performance between the composite encapsulation structure and a high-refractive-index cover layer material of the organic light emitting diode. However, lithium fluoride has problems of reliability reduction in flexible display, requirement of a dedicated chamber, and increase of equipment load, and polymer materials have problems of process reduction in production efficiency and excessive film thickness.
The invention provides a technical scheme for replacing lithium fluoride by low-refractive-index organic vapor deposition micromolecules, which aims to improve the visual angle, reduce the process difficulty, and improve the screen reliability in the aspects of flexibility, bending and curling while conveniently adjusting the optical path.
The invention provides a packaging structure, which is characterized by comprising a composite packaging structure formed by a high-refractive-index material with a refractive index of more than 2.0 and a low-refractive-index material with a refractive index of less than 1.7, wherein the high-refractive-index material with a refractive index of more than 2.0 is an inorganic high-refractive-index material, the low-refractive-index material with a refractive index of less than 1.7 is selected from a group formed by an organic high-molecular low-refractive-index material and an organic small-molecular low-refractive-index material, and the packaging structure further comprises an interval packaging layer formed by a low-refractive-index organic small-molecular material with a refractive index of less than 1.7. The number of layers used for the inorganic high refractive index material and the organic high molecular low refractive index material in the composite package structure is not particularly limited. The polymer material is a compound having at least one repeating unit repeating 4 times or more, and cannot be formed by an evaporation method but can be formed only by an inkjet printing method. The small molecule organic material refers to a compound in which a repeating unit repeated 4 times or more is not present. Such a small-molecule organic material can be formed into a film by vapor deposition.
With this organic encapsulation structure, a light emitting device can be made, which is protected by the above encapsulation structure and which comprises a first electrode and a second electrode with a light emitting layer between the two electrodes and a functional layer that can be used to perform functions related to electron or hole transport. The light extraction layer is made of a small molecule organic material and has one or more layers on the light emitting side, except for the two electrodes. The light extraction layer has a high refractive index small molecule organic material layer having a refractive index higher than 2.0 and/or a low refractive index small molecule organic material layer having a refractive index lower than 1.7. The number of functional layers and light extraction layers in the light-emitting device is not particularly limited. The method for forming the functional layer may be vapor deposition ink jet printing or spin coating, and is not particularly limited. The light extraction layer may be formed by evaporation.
In terms of the manufacturing process, the light extraction layer of the light emitting device is manufactured by using an evaporation method, the low refractive index organic small molecules are also manufactured by evaporation, and the layer manufactured in the same manner can be continuously manufactured, so that the burden on the manufacturing process is less. On the other hand, the optical path can be adjusted by adding the low-refractive-index material between the high-refractive-index covering layer material and the high-refractive-index packaging material, so that the low-refractive-index organic small molecule material of the packaging structure is directly attached to the light-emitting side of the light-emitting structure.
Recently, some documents have pointed out that the microcavity can be increased and the light extraction efficiency can be improved by using a composite light extraction layer technology with a high refractive index and a low refractive index. In the case of applying this technique, a low refractive index organic small molecule material is used, and in consideration of the difference in the purpose of use of the two low refractive index organic small molecule layers, it should be considered independently, and therefore the low refractive index organic small molecule material of the light extraction layer of the light emitting device may be the same as or different from the low refractive index organic small molecule material in the spacer sealing layer. It can be understood that the low refractive index small molecule organic material of the light extraction layer of the light emitting device is independent of the spacer encapsulation layer, and is not the same layer, in the case of the same material.
In some embodiments, the light extraction layer is composed of two or more layers of small molecule organic materials, wherein the difference in refractive index is 0.3 or more for any two adjacent layers, wherein the refractive index of the material with the higher refractive index is 1.8 or more and the refractive index of the material with the lower refractive index is 1.7 or less.
The light-emitting structure is widely applied, and has the effects of reducing the process difficulty, improving the visual angle and the like for all existing OLED panels and all OLED panels newly developed in the future, so that the light-emitting structure can be applied to transparent, rigid, flexible, foldable or rollable OLED panels, and the panels can be applied to mobile phones, televisions, flat panels, vehicle-mounted displays, tail lamps, illumination, VR, AR and the like.
In particular, the above light emitting structure has an effect of improving reliability for a flexible, foldable or rollable screen, and thus the light emitting structure can be applied to flexible, foldable or rollable OLED panels, which can be applied to mobile phones, televisions, flat panels, vehicle displays, tail lamps, lighting, VR, AR, and the like.
In order to realize the packaging structure, the invention provides two systems of low-refractive-index organic micromolecular materials. Selected from the following formula 1 or formula 2,
wherein Ar is 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 Each independently is: substituted or unsubstituted aryl or heteroaryl, or substituted or unsubstituted aryl or heteroaryl wherein two or more aryl or heteroaryl groups are bonded in a non-fused manner,
Ar 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 when substituted, the substituents are independently selected from one or more of hydrogen, deuterium, an alkyl group which may be substituted, a cycloalkyl group which may be substituted, a heterocyclic group which may be substituted, an alkenyl group which may be substituted, a cycloalkenyl group which may be substituted, an alkynyl group which may be substituted, an alkoxy group which may be substituted, an alkylthio group which may be substituted, an aryl ether group which may be substituted, an aryl thioether group which may be substituted, an aryl group which may be substituted, a heteroaryl group which may be substituted, a carbonyl group which may be substituted, a carboxyl group which may be substituted, an oxycarbonyl group which may be substituted, a carbamoyl group which may be substituted, a silane group which may be substituted, an alkylamino group which may be substituted, or an arylamino group which may be substituted,
n 1 、n 2 independently an integer of from 1 to 5,
wherein Ar is 6 ～Ar 17 Are the same or different and are respectively and independently selected from hydrogen, deuterium,One or more of trifluoromethyl, an alkyl group which may be substituted, a cycloalkyl group which may be substituted, a heterocyclic group which may be substituted, an alkenyl group which may be substituted, a cycloalkenyl group which may be substituted, an alkynyl group which may be substituted, an alkoxy group which may be substituted, an alkylthio group which may be substituted, an aryl ether group which may be substituted, an aryl thioether group which may be substituted, an aryl group which may be substituted, a heteroaryl group which may be substituted, a carbonyl group which may be substituted, a carboxyl group which may be substituted, an oxycarbonyl group which may be substituted, a carbamoyl group which may be substituted, an alkylamino group which may be substituted, or a silyl group which may be substituted; n3 is an integer of 1 to 3; ar (Ar) 16 And Ar 17 May be bonded to form a ring; ar (Ar) 7 And Ar 8 Can be bonded to form a ring, ar 10 And Ar 11 Can be bonded into a ring,
Ar 6 ～Ar 17 when substituted, the substituents are independently selected from one or more of deuterium, halogen, C1-C15 alkyl, C3-C15 cycloalkyl, C3-C15 heterocyclic group, C2-C15 alkenyl, C4-C15 cycloalkenyl, C2-C15 alkynyl, C1-C15 alkoxy, C1-C15 alkylthio, C6-C55 aryl ether group, C6-C55 aryl thioether group, C6-C55 aryl, C5-C55 aromatic heterocyclic group, carbonyl, carboxyl, oxycarbonyl, carbamoyl, C1-C40 alkylamino group or C3-C15 silyl group with 1-5 silicon atoms.
Drawings
The following presents a detailed description of embodiments of the present application in conjunction with the accompanying drawings to illustrate the technical solutions and their advantages.
Fig. 1 is a schematic structural diagram of a package structure according to the present application.
FIG. 2 is a view of one embodiment of the present application structure schematic diagram of the OLED structure.
Detailed Description
The technical solution of the present application will be clearly and completely described below with reference to the accompanying drawings. It should be apparent that the described embodiments are only some embodiments of the present application, and not all embodiments. All other embodiments obtained by a person skilled in the art based on the embodiments in the present application without making creative efforts belong to the protection scope of the present application.
In the description of the present application, it is to be understood that the terms "center," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," and the like are used in the orientations and positional relationships indicated in the drawings for convenience in describing the present application and for simplicity in description, and are not intended to indicate or imply that the referenced devices or elements must have a particular orientation, be constructed in a particular orientation, and be operated in a particular manner, and are not to be construed as limiting the present application. Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, features defined as "first", "second", may explicitly or implicitly include one or more of the described features. In the description of the present application, "a plurality" means two or more unless specifically limited otherwise. In the description of the present application, it should be noted that, unless otherwise explicitly stated or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be, for example, a fixed connection, a detachable connection, or an integral connection; may be mechanically connected, may be electrically connected or may be in communication with each other; either directly or indirectly through intervening media, either internally or in any other relationship. The specific meaning of the above terms in the present application can be understood by those of ordinary skill in the art as appropriate.
In this application, unless expressly stated or limited otherwise, the first feature "on" or "under" the second feature may comprise direct contact of the first and second features, or may comprise contact of the first and second features not directly but through another feature in between. Also, the first feature being "on," "above" and "over" the second feature includes the first feature being directly on and obliquely above the second feature, or merely indicating that the first feature is at a higher level than the second feature. A first feature being "under," "below," and "beneath" a second feature includes the first feature being directly under and obliquely below the second feature, or simply meaning that the first feature is at a lesser elevation than the second feature.
The following disclosure provides many different embodiments or examples for implementing different features of the application. In order to simplify the disclosure of the present application, specific example components and arrangements are described below. Of course, they are merely examples and are not intended to limit the present application. Moreover, the present application may repeat reference numerals and/or letters in the various examples, such repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed. In addition, examples of various specific processes and materials are provided herein, but one of ordinary skill in the art will recognize applications of other processes and/or use of other materials.
References to "a plurality" in this specification include all instances of more than one, i.e., "one or more" includes one, two, three, … …, and so forth. In the present specification, when an upper limit and a lower limit are described for a certain numerical range, or when a certain numerical range is described in combination of an upper limit and a lower limit, the upper limit and the lower limit described therein may be arbitrarily combined into a new numerical range, and it should be considered that the same forms as the numerical ranges in which combinations are explicitly described are described. Variations and modifications of the present invention may be effected by those of ordinary skill in the art without departing from the spirit of the invention, which is also within the scope of the invention. In the present application, the number of carbon atoms in the alkyl group is not limited, and may be a C1 to C15 alkyl group. The number of carbon atoms of the cycloalkyl group is not limited, and the cycloalkyl group may be a C3-C15 cycloalkyl group. The number of carbon atoms of the heterocyclic group is not limited, and it may be a C3-C15 heterocyclic group. The number of carbon atoms of the alkenyl group is not limited, and it may be a C2-C15 alkenyl group. The number of carbon atoms of the cycloalkenyl group is not limited, and the cycloalkenyl group may be a C4-C15 cycloalkenyl group. The number of carbon atoms of the alkynyl group is not limited, and it may be a C2-C15 alkynyl group. The number of carbon atoms of the alkoxy group is not limited, and may be a C1-C15 alkoxy group. One or more of C1-C15 alkylthio, C6-C55 aryl ether, C6-C55 aryl thioether, C6-C55 aryl, C5-C55 aromatic heterocyclic group, carbonyl, carboxyl, oxycarbonyl, carbamoyl, C1-C40 alkylamino or C3-C15 silane group with 1-5 silicon atoms.
The present application is further described below with reference to the accompanying drawings and examples.
(1) Implementation of the Package Structure
As shown in fig. 1, one embodiment of the present application provides a package structure including composite package structures 121-123 and a spacing package layer 110. The composite package structure includes:
high refractive index inorganic materials 121, 123;
a low refractive index polymer material 122; disposed between 121 and 123;
in these, 121 and 123 may be the same material or different materials, but both films are formed by a PECVD (Plasma Enhanced Chemical Vapor Deposition) method. 121 The high refractive index material and the low refractive index material of type 122 may be repeatedly arranged, the number of repetition thereof is not particularly limited, and when there is repetition, a plurality of layers of the high refractive index material or a plurality of layers of the low refractive index material are not necessarily the same material.
The high refractive index material is inorganic material with refractive index higher than 2.0, and can be selected from SiNx and SiO x 、SiON x 、SiCN x 、Al 2 O 3 、TiO 2 And ZrO 2 Is not particularly limited.
The refractive index of the low refractive index material may be lower than 1.7. The low refractive index material may be polymer material such as acryl, epoxy resin or polyimide, or organic small molecule material, and is not particularly limited.
The spacer encapsulant layer 110 uses low refractive index organic small molecules with a refractive index of less than 1.7. The organic small molecule refers to a compound in which a repeating unit repeating 4 times or more is not present. Such small organic molecules can be formed into a film by vapor deposition.
In the prior art, the interval encapsulation layer 110 uses lithium fluoride for dimming, the low refractive index organic small molecules used in the embodiment not only have the dimming function of lithium fluoride, but also have the advantages of low sublimation temperature and easy cleaning, and compared with the lithium fluoride which needs to occupy equipment such as a special chamber in the preparation process of an evaporation process and the like, the low refractive index organic small molecules can share the chamber with other evaporation materials, the number of materials which can be evaporated can be increased for the existing evaporation machine, and the cost of the special chamber can be reduced for the newly manufactured evaporation machine. The reliability of small organic molecules on non-rigid screens is improved compared to hard inorganic materials. In terms of dimming, the refractive index of the low refractive index organic small molecules (less than 1.7) is lower than that of the high refractive index inorganic layer 121, and dimming can be performed between two high refractive index materials as with lithium fluoride. On the other hand, the viewing angle is limited due to the problem of orientation of lithium fluoride, and the use of small organic molecules allows more free orientation and an expanded viewing angle. Preferably, the refractive index of the small organic molecules may be adjusted according to the structure thereof, and when the refractive index of the small organic molecules is higher than that of lithium fluoride, the light extraction efficiency is also higher than that of lithium fluoride. Meanwhile, considering that the refractive index of lithium fluoride is too low, there is a high possibility that the refractive index of small organic molecules exceeds that of lithium fluoride.
Some solutions use polymeric materials instead of lithium fluoride. Since a polymer material is required to be formed into a film by ink jet printing, the film thickness is often on the order of millimeters, and lithium fluoride, which is an inorganic material, cannot be formed into a thick film during vapor deposition. The film thickness of the conventional vapor deposition technique is on the order of several tens of nanometers, and the film thickness of lithium fluoride is also a very thin film thickness in this case. Since the optical path is affected by the film thickness, the film thickness in millimeter order is completely different from the optical path in ten nanometer order, and the peripheral material needs to be adjusted greatly to fit the structure. It should be noted in particular that a too thick low refractive index material reduces the light extraction efficiency, which is detrimental for the organic light emitting diode technology, which still has difficulties with the light extraction efficiency. However, the film thickness is naturally on the nanometer level by using a small molecule organic material and also using an evaporation process. Compared with inorganic materials with difficult film thickness accumulation, the film thickness adjustment of the organic material during vapor deposition is more free, and the packaging structure close to the prior art can be manufactured more conveniently. In addition, inkjet printing techniques require a drying process, which is time consuming and often becomes a speed control step. In fact, one of the major issues in the technological innovation of composite encapsulation layers is to reduce the number of layers of low refractive index polymer materials to reduce the number of drying times of inkjet printing and improve the production efficiency. Therefore, the production efficiency can be improved by using the evaporation technology to form the film.
In summary, the package structure of the present application uses the spacer package layer 110 containing low refractive index organic small molecules, which not only replaces the realization of the optical characteristics and effects of the original lithium fluoride film, but also simplifies the manufacturing process, improves the viewing angle, improves the reliability of the non-rigid screen, and does not cause the reduction of light extraction efficiency (light emitting efficiency) and even increases the possibility of light extraction efficiency as when using high polymer low refractive index materials.
(2) Fabrication of organic light-emitting device
According to the above object of the present application, there is also provided a method for fabricating an OLED structure, which is described by taking the OLED structure of fig. 2 as an example:
it should be noted at the outset that the OLED structure of FIG. 2 is a top-emitting single layer device, but the application is not limited to application to this device structure, and the application is also applicable to device structures including, but not limited to, top-emitting devices, bottom-emitting devices, single layer devices, multilayer stack devices, evaporation devices, ink jet printing devices, and the like.
In the device structure of fig. 2, the light emitting device 200 includes: an anode 210, a hole transport layer 220, an emissive layer 230, an electron transport layer 240, a cathode 250, and a light extraction layer 260. Note that the names of the respective layers are based on the functions thereof, but the types of materials contained in the respective layers are not limited, and one or more materials may be contained in the same functional layer. When a plurality of materials are contained in the same layer, the materials may be layered vertically in the direction shown in the figure, may be layered horizontally, may be layered at a certain angle, may be layered in a certain cross-sectional structure, may be co-evaporated and mixed, or may be mixed at a molecular level or an atomic level in a manner other than co-evaporation, and the layering and/or mixing manner of the materials is not limited to the above-described manner.
The following compounds are used in the examples:
TBDB
JG1
JG2
JG3
JG4
wherein TBDB is a high refractive index material for the light extraction layer. JG1-JG4 are low refractive index materials used in the spacer encapsulation layer or as low refractive index materials in the light extraction layer.
Example 1
After the alkali-free glass was ultrasonically washed in isopropyl alcohol for 15 minutes, UV ozone washing treatment was performed in the atmosphere for 30 minutes. The reflective anode 210 was formed by sequentially forming films of 100nm silver (Ag) and 10nm ITO on alkali-free glass by a sputtering method. After the reflective anode was subjected to UV ozone cleaning treatment for 10 minutes, a 130nm hole transport layer 220, a 20nm blue light emitting layer 230, and a 36nm electron transport layer 240 were sequentially deposited on the anode by vacuum deposition, and then 15nm Mg and Ag (weight ratio 10. A50 nm compound [ TBDB ] was deposited on the translucent cathode as a light extraction layer 260.
After the light-emitting device is completed, a compound JG1 with the thickness of 10nm and corresponding to the interval packaging layer is continuously evaporated, then a film 121 made of high-refractive-index inorganic material SiNx is sequentially formed by PECVD, a low-refractive-index polymer film 122 is formed by ink-jet printing, and finally a high-refractive-index inorganic material film 123 is formed by PECVD.
It should be noted that the light extraction layer is the last ring of the light emitting device process in both the top emitting device and the low emitting device, and the fabrication of the package structure is performed after the light emitting device process. Therefore, the spacer encapsulation layer 110 is used as a starting point of the encapsulation structure, and the manufacturing process can be simplified by adopting the same film forming process as the light extraction layer.
The light-emitting structure is added with 10mA/cm in the atmosphere at room temperature 2 The luminance and color purity of the light emitted from the sealing plate were measured by a spectral emission luminance meter using a direct current. The measured values were: luminous efficiency is 90 degrees: 3.4cd/A,45 °:1.5cd/A, color purity CIE (x, y) = (0.138,0.050). In addition, the light-emitting structure was subjected to 7 ten thousand bending experiments, and the condition of the spacer encapsulating layer was confirmed by a microscope without significant cracks.
Example 2
The same as example 1 except that the spacer encapsulating layer was the compound JG 2.
An organic light-emitting element using the compound JG2 was evaluated. The evaluation results are shown in Table 1.
Example 3
The same as example 1 except that the spacer encapsulating layer was the compound JG 3.
An organic light-emitting element using the compound JG3 was evaluated. The evaluation results are shown in Table 1.
Example 4
The same as example 1 except that the spacer encapsulating layer was the compound JG 4.
An organic light-emitting element using the compound JG4 was evaluated. The evaluation results are shown in Table 1.
Example 5
The same as example 1 was repeated, except that the spacer encapsulating layer was a double-layer structure of the compound JG4, the compound JG4 and the compound TBDB were provided in this order from the light-emitting device to the spacer encapsulating layer.
The organic light-emitting element was evaluated. The evaluation results are shown in Table 1.
Example 6
The same as example 1 was repeated, except that the spacer encapsulating layer was the compound JG4, and the light extraction layer had a two-layer structure of TBDB and JG4 in this order from the light-emitting device to the spacer encapsulating layer.
The organic light-emitting element was evaluated. The evaluation results are shown in Table 1.
Comparative example 1
The same procedure as in example 1 was repeated, except that the spacer sealing layer was formed of lithium fluoride.
Organic light-emitting elements using lithium fluoride were evaluated. The evaluation results are shown in Table 1.
Comparative example 2
The same as example 1 except that no spacer encapsulating layer was used.
The organic light-emitting element was evaluated. The evaluation results are shown in Table 1.
Comparative example 3
The same as example 1 except that the spacer sealing layer was an ink-jet printed acryl resin.
Table 1: luminous element Performance (examples and comparative examples)
In the examples and comparative examples, since the same device structure was used and the light emission efficiency was the same before passing through the light extraction layer and the encapsulation layer, the comparison of the actual light emission efficiency was equivalent to the comparison of the light extraction efficiency.
In the light extraction layer entries of examples 5 and 6 in the table, the light extraction layer material near the electrodes is on the left and the light extraction layer material near the spacer encapsulant layer is on the right.
As can be seen from the table, comparative example 1 is a conventional technique, and examples 1 to 6 are improved in the luminous efficiency of 90 ° and significantly improved in the luminous efficiency of 45 ° compared to comparative example 1. In addition, after 7 ten thousand bending experiments of comparative example 1, since the inorganic material was more brittle than the organic material, the spacer encapsulation layer of comparative example 1 had small cracks, whereas examples 1 to 6 had no significant cracks, and thus it was seen that the use of the organic small molecule material could improve the reliability of bending. In addition, although not shown in the table, comparative example 1 uses a special chamber to evaporate lithium fluoride, whereas examples 1 to 6 enable evaporation of organic small molecule materials using one evaporation source in any chamber. Meanwhile, because lithium fluoride is insoluble in organic solvents and insoluble in water, cleaning of a lithium fluoride cavity after evaporation is very difficult, and the spacer packaging layer material adopted in the application, such as organic small molecules, can be simply wiped by using common solvents (including but not limited to benzenes, amines and the like). It is noted that in examples 5 and 6, the light extraction layers having a two-layer structure were used, and the light emission efficiency at 90 ° was further improved as compared with example 4 (in which the same spacer encapsulant layer was used, but the light extraction layers had a single-layer structure), and the light emission efficiency at 45 ° was slightly decreased, but the light emission efficiency at 45 ° was still significantly improved as compared with that at comparative example 1. In comparative example 2, the 90 ° luminous efficiency was approximately equivalent to that of comparative example 1 without using a spacer encapsulating layer, and lithium fluoride as a low refractive index material had the effect of scattering light and was lower in the 45 ° luminous efficiency than that of comparative example 1. Comparative example 3 using an acryl resin as a spacer encapsulation layer, the film of the acryl resin prepared by ink-jet printing was thicker than the evaporated lithium fluoride film and had a stronger ability to scatter light, and thus the 45 ° luminous efficiency was substantially the same as the 90 ° luminous efficiency, but the 90 ° luminous efficiency was significantly reduced compared to comparative example 1.
Claims (9)
1. A package structure is characterized in that a plurality of semiconductor chips are arranged in a package,
comprising:
a composite package structure composed of a high refractive index material having a refractive index of 2.0 or more and a low refractive index material having a refractive index of 1.7 or less, the high refractive index material having a refractive index of 2.0 or more being an inorganic high refractive index material, the low refractive index material having a refractive index of 1.7 or less being selected from the group consisting of an organic high polymer low refractive index material and an organic small molecule low refractive index material, and
and the interval packaging layer is made of low-refractive-index organic small molecule materials with the refractive index of 1.7 or less.
2. The encapsulation structure according to claim 1, wherein the organic small molecule material constituting the spacer encapsulation layer is a compound having no repeating unit repeated 4 times or more.
3. A light emitting structure characterized in that it has a light emitting device protected by the encapsulation structure of claim 1,
the light emitting device includes a first electrode and a second electrode,
a luminescent layer and a functional layer are arranged between the two electrodes, the functional layer is used for realizing the function of electron transmission or hole transmission,
outside the two electrodes, there is one or more light extraction layers made of small molecule organic material on the side emitting light,
the light extraction layer has a high refractive index small molecule organic material layer having a refractive index higher than 2.0 and/or a low refractive index small molecule organic material layer having a refractive index lower than 1.7.
4. A light emitting structure according to claim 3, wherein the light extraction layer is composed of two or more layers of small molecule organic materials, wherein a difference in refractive index is 0.3 or more for any two adjacent layers, and wherein a refractive index of a material having a higher refractive index is 1.8 or more and a refractive index of a material having a lower refractive index is 1.7 or less.
5. A light emitting structure according to claim 3 wherein the low refractive index small organic molecule material of the spacing encapsulant layer is directly attached to the light emitting side of the light emitting structure.
6. A light-emitting structure according to claim 3, wherein the low refractive index small molecule organic material of the light extraction layer of the light-emitting device is the same as or different from the low refractive index organic small molecule material in the spacing encapsulation layer, and in the case where the materials are the same, the low refractive index small molecule organic material layer in the light extraction layer is different from the spacing encapsulation layer composed of the low refractive index organic small molecule material.
7. Light-emitting structure according to claim 3, characterized in that
The light emitting structure is applied to a transparent, rigid, flexible, foldable or rollable OLED panel, which is an OLED panel applied to mobile phone, television, flat panel, vehicle display, tail lamp, lighting, VR or AR applications.
8. Light-emitting structure according to claim 3, characterized in that
The light emitting structure is applied to a flexible, foldable or rollable OLED panel, which is an OLED panel applied to mobile phones, televisions, flat panels, vehicle displays, tail lights, lighting, VR or AR applications.
9. The package structure of claim 1, wherein the package structure further comprises a plurality of conductive pads
Wherein the low-refractive-index organic small molecule material of the interval packaging layer is selected from the following general formula 1 or general formula 2,
wherein Ar is 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 Each independently is: substituted or unsubstituted aryl or heteroaryl, or substituted or unsubstituted aryl or heteroaryl wherein two or more aryl or heteroaryl groups are bonded in a non-fused manner,
Ar 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 when substituted, the substituents are independently selected from one or more of hydrogen, deuterium, an alkyl group which may be substituted, a cycloalkyl group which may be substituted, a heterocyclic group which may be substituted, an alkenyl group which may be substituted, a cycloalkenyl group which may be substituted, an alkynyl group which may be substituted, an alkoxy group which may be substituted, an alkylthio group which may be substituted, an aryl ether group which may be substituted, an aryl thioether group which may be substituted, an aryl group which may be substituted, a heteroaryl group which may be substituted, a carbonyl group which may be substituted, a carboxyl group which may be substituted, an oxycarbonyl group which may be substituted, a carbamoyl group which may be substituted, a silane group which may be substituted, an alkylamino group which may be substituted, or an arylamino group which may be substituted,
n 1 、n 2 independently an integer of from 1 to 5,
wherein Ar is 6 ～Ar 17 The same or different, each independently selected from one or more of hydrogen, deuterium, trifluoromethyl, an alkyl group which may be substituted, a cycloalkyl group which may be substituted, a heterocyclic group which may be substituted, an alkenyl group which may be substituted, a cycloalkenyl group which may be substituted, an alkynyl group which may be substituted, an alkoxy group which may be substituted, an alkylthio group which may be substituted, an aryl ether group which may be substituted, an aryl thioether group which may be substituted, an aryl group which may be substituted, a heteroaryl group which may be substituted, a carbonyl group which may be substituted, a carboxyl group which may be substituted, an oxycarbonyl group which may be substituted, a carbamoyl group which may be substituted, an alkylamino group which may be substituted, or a silyl group which may be substituted; n is 3 Is an integer from 1 to 3; ar (Ar) 16 And Ar 17 May be bonded to form a ring; ar (Ar) 7 And Ar 8 Can be bonded to form a ring, ar 10 And Ar 11 Can be bonded into a ring,
Ar 6 ～Ar 17 when substituted, the substituents are each independently selected from deuterium, halogen, C1-C15 alkyl, C3-C15 cycloalkyl, C3-C15 heterocyclyl, C2-C15 alkenyl, and C4-C15 ringOne or more of alkenyl, alkynyl of C2-C15, alkoxy of C1-C15, alkylthio of C1-C15, aryl ether of C6-C55, aryl thioether of C6-C55, aryl of C6-C55, aromatic heterocyclic radical of C5-C55, carbonyl, carboxyl, oxycarbonyl, carbamoyl, alkylamino of C1-C40 or silyl of C3-C15 with 1-5 silicon atoms.
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| CN115548235A (en) * | 2022-10-13 | 2022-12-30 | 京东方科技集团股份有限公司 | Light extraction film, light emitter module, and display device |
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| CN115548235A (en) * | 2022-10-13 | 2022-12-30 | 京东方科技集团股份有限公司 | Light extraction film, light emitter module, and display device |
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