CN112349861A - Light-emitting device, packaging structure thereof and manufacturing method thereof - Google Patents

Light-emitting device, packaging structure thereof and manufacturing method thereof Download PDF

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Publication number
CN112349861A
CN112349861A CN201911380422.5A CN201911380422A CN112349861A CN 112349861 A CN112349861 A CN 112349861A CN 201911380422 A CN201911380422 A CN 201911380422A CN 112349861 A CN112349861 A CN 112349861A
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China
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layer
sub
encapsulation layer
emitting device
package
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李松举
宋晶尧
付东
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Guangdong Juhua Printing Display Technology Co Ltd
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Guangdong Juhua Printing Display Technology Co Ltd
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Priority to CN201911380422.5A priority Critical patent/CN112349861A/en
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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/80Constructional details
    • H10K50/84Passivation; Containers; Encapsulations
    • H10K50/844Encapsulations
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00Manufacture or treatment specially adapted for the organic devices covered by this subclass

Abstract

The invention relates to a light-emitting device, a packaging structure and a manufacturing method thereof, wherein the packaging structure comprises a first packaging layer and a second packaging layer, the second packaging layer is a film layer which is soft in film quality and can be close to zero in film stress during bending, and the effect of buffering action can be achieved, so that the device has better reliability and bending resistance. The materials of the two opposite sides of the first packaging layer are different, and the material of one side of the first packaging layer close to the light-emitting device main body is different from the material of the second packaging layer, so that the adhesion between the two layers can be ensured, the stress of the first packaging layer can be adjusted, the integral bending resistance of the packaging structure can be improved, and the phenomena of interlayer peeling, falling off and the like of the film layer after bending can be reduced.

Description

Light-emitting device, packaging structure thereof and manufacturing method thereof
Technical Field
The invention relates to the field of light-emitting devices, in particular to a light-emitting device and a packaging structure and a manufacturing method thereof.
Background
As the OLED production technology is mature, the OLED manufacturing cost is reduced gradually, and the OLED is a technology that can compete with the liquid crystal display. Also, the advantages of the OLED are gradually highlighted, wherein flexible display is the greatest feature thereof.
The flexible display technology is originallyTwo layers of glass substrates are replaced by a flexible substrate and a thin film packaging layer so as to realize the bendable folding performance. Since the flexible display is often bent in practical use, it is desirable that the stress of the thin film encapsulation film layer is as small as possible when bending. On the other hand, since the OLED is extremely sensitive to water vapor and is easily affected by water vapor to fail, the thin film package needs to have a strong water oxygen barrier capability (generally up to 10 f)-6g/cm2·day)。
The prior art needs to be improved and improved.
Disclosure of Invention
Based on the scheme, the light-emitting device, the packaging structure and the manufacturing method are provided.
The packaging structure of the light-emitting device comprises a light-emitting device main body, the packaging structure comprises a first packaging layer and a second packaging layer, the first packaging layer is arranged on the light-emitting device main body, the second packaging layer is arranged on the first packaging layer, the material of one side, close to the light-emitting device main body, of the first packaging layer is different from the material of one side, close to the second packaging layer, of the first packaging layer, the material of the second packaging layer is one or more of silicon oxycarbide, silicon carbonitride, silicon oxycarbide fluoride, silicon carbonitride fluoride and organic silicon compound, and the material of one side, close to the light-emitting device main body, of the first packaging layer is different from the material of the second packaging layer.
In one embodiment, the material of the side of the first encapsulation layer close to the second encapsulation layer is the same as the material of the second encapsulation layer.
In one embodiment, the material of the side of the first encapsulation layer adjacent to the second encapsulation layer is different from the material of the second encapsulation layer, and the material of the side of the first encapsulation layer adjacent to the second encapsulation layer comprises elemental silicon.
In one embodiment, the material of the side of the first encapsulation layer close to the second encapsulation layer is silicon oxide or silicon nitride.
In one embodiment, the material of the second encapsulation layer is selected from silicon oxycarbide or fluorinated silicon oxycarbide, and the material of the side of the first encapsulation layer adjacent to the second encapsulation layer is selected from silicon oxide; or
The second packaging layer is made of silicon carbonitride or fluorinated silicon carbonitride, and the side, close to the first packaging layer, of the second packaging layer is made of silicon nitride.
In one embodiment, the first encapsulation layer includes a first sub-encapsulation layer and a second sub-encapsulation layer which are stacked, the first sub-encapsulation layer is disposed on the light emitting device body, and the second sub-encapsulation layer is disposed between the first sub-encapsulation layer and the second encapsulation layer;
the material of the first sub-encapsulation layer is different from the material of the second sub-encapsulation layer, and the material of the first sub-encapsulation layer is different from the material of the second encapsulation layer.
In one embodiment, the stress generated by the first sub-package layer and the stress generated by the second sub-package layer are opposite in direction.
In one embodiment, the package structure includes a third package layer disposed on the second package layer, and a side of the third package layer adjacent to the second package layer is made of the same material as a side of the first package layer adjacent to the second package layer.
In one embodiment, a side of the third encapsulation layer distal from the second encapsulation layer is the same material as a side of the first encapsulation layer proximal to the light emitting device body.
In one embodiment, the stress generated by the first encapsulation layer is opposite to the stress generated by the third encapsulation layer.
In one embodiment, the third encapsulating layer includes a third sub-encapsulating layer and a fourth sub-encapsulating layer which are stacked, the third sub-encapsulating layer is disposed on the second encapsulating layer, and the third sub-encapsulating layer is located between the second encapsulating layer and the fourth sub-encapsulating layer.
In one embodiment, the stress generated by the third sub-package layer and the stress generated by the fourth sub-package layer are opposite in direction.
A method of fabricating a package structure of a light emitting device including a light emitting device body, comprising the steps of:
manufacturing a first packaging layer on the light-emitting device main body;
manufacturing a second packaging layer on the first packaging layer;
wherein a material of a side of the first encapsulation layer adjacent to the light emitting device body is different from a material of a side of the first encapsulation layer adjacent to the second encapsulation layer, the material of the second encapsulation layer is one or more of silicon oxycarbide, silicon carbonitride, silicon oxycarbide fluoride, silicon carbonitride fluoride, and an organosilicon compound, and the material of a side of the first encapsulation layer adjacent to the light emitting device body is different from the material of the second encapsulation layer.
In one embodiment, the first encapsulation layer includes a first sub-encapsulation layer and a second sub-encapsulation layer which are stacked, the first sub-encapsulation layer is disposed on the light emitting device body, and the second sub-encapsulation layer is disposed on the first sub-encapsulation layer;
the material of the first sub-encapsulation layer is different from the material of the second sub-encapsulation layer, and the material of the first sub-encapsulation layer is different from the material of the second encapsulation layer.
In one embodiment, the first sub-encapsulation layer and the second sub-encapsulation layer are fabricated by an atomic layer deposition process.
In one embodiment, the step of fabricating the first sub-encapsulation layer comprises:
adopting protective gas as carrier gas, and introducing an organic aluminum source into a reaction chamber provided with the light-emitting device main body, wherein the flow rate is 6000sccm/m 2-24000 sccm/m2, and the introduction time is 0.05-1 s;
exhausting to remove the residual organic aluminum source;
introducing a reaction source into the reaction chamber, wherein the flow rate is 6000sccm/m 2-24000 sccm/m2, and the introduction time is 0.2-5 s;
loading radio frequency on an electrode plate of the reaction chamber, wherein the radio frequency power is 30kW/m 2-120 kW/m2, and the duration is 0.5-10 s;
pumping to remove unreacted substances.
In one embodiment, the step of fabricating the second sub-encapsulation layer comprises:
introducing an organic silicon source into the reaction chamber by using protective gas as carrier gas, so that the organic silicon source is deposited on the first packaging layer, wherein the flow rate is 6000sccm/m 2-24000 sccm/m2, and the introduction time is 0.05-1 s;
pumping to remove the residual organic silicon source;
introducing a reaction source into the reaction chamber, wherein the flow rate is 9000sccm/m 2-36000 sccm/m2, and the introduction time is 0.2-5 s;
loading radio frequency on an electrode plate of the reaction chamber, wherein the radio frequency power is 45kW/m 2-180 kW/m2, and the duration is 0.5-10 s;
pumping to remove unreacted substances.
A light emitting device includes a light emitting device body and a package structure;
the packaging structure comprises a first packaging layer and a second packaging layer, wherein the first packaging layer is arranged on the light-emitting device main body, the second packaging layer is arranged on the first packaging layer, the material of one side, close to the light-emitting device main body, of the first packaging layer is different from the material of one side, close to the second packaging layer, of the second packaging layer, the material of the second packaging layer is one or more of silicon oxycarbide, silicon carbonitride, silicon oxycarbide, silicon fluorocarbonnitride and organic silicon compounds, and the material of one side, close to the light-emitting device main body, of the first packaging layer is different from the material of the second packaging layer.
Compared with the prior art, the light-emitting device and the packaging structure and the manufacturing method thereof have the following beneficial effects:
in the above-mentioned packaging structure and the light emitting device having the packaging structure in the embodiment, the second packaging layer is a film layer which is soft in film quality and can be close to zero in film stress when being bent, so that the effect of buffering action can be achieved, and the device has better reliability and bending resistance. The materials of the two opposite sides of the first packaging layer are different, and the material of one side of the first packaging layer close to the light-emitting device main body is different from the material of the second packaging layer, so that the adhesion between the two layers can be ensured, the stress of the first packaging layer can be adjusted, the integral bending resistance of the packaging structure can be improved, and the phenomena of interlayer peeling, falling off and the like of the film layer after bending can be reduced.
Drawings
Fig. 1 is a schematic structural view of a light emitting device of an embodiment;
fig. 2 is a schematic structural view of a light-emitting device of another embodiment;
fig. 3 is a schematic structural view of a light-emitting device of a further embodiment;
fig. 4 is a schematic structural view of a light emitting device body in the light emitting device shown in fig. 3;
FIG. 5 is a schematic diagram of a first sub-package layer formed on a second electrode layer;
FIG. 6 is a schematic diagram of a second sub-package layer fabricated on the first sub-package layer;
FIG. 7 is a schematic diagram of a third packaging layer formed on the second sub-packaging layer;
fig. 8 is a schematic diagram of a fourth sub-package layer fabricated on the third package layer.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
As shown in fig. 1, the present invention provides a light emitting device 10 and a package structure of the light emitting device 10. The light emitting device 10 includes a light emitting device body 1. The packaging structure is arranged on a light-emitting device main body 1 and comprises a first packaging layer 2 and a second packaging layer 3. The first encapsulation layer 2 is disposed on the light emitting device body 1, and the second encapsulation layer 3 is disposed on the first encapsulation layer 2. The first and second sealing layers 2 and 3 are stacked. The material of the side of the first encapsulation layer 2 adjacent to the light emitting device body 1 is different from the material of the side of the first encapsulation layer 2 adjacent to the second encapsulation layer 3. The material of the second encapsulation layer 3 is one or more of silicon oxycarbide, silicon carbonitride, fluorinated silicon oxycarbide, fluorinated silicon carbonitride and organosilicon compound. The material of the side of the first encapsulation layer 2 close to the light emitting device body 1 is different from the material of the second encapsulation layer 3.
In the packaging structure and the light-emitting device with the packaging structure in the embodiment, the second packaging layer is a film layer which is soft in film quality and can be close to zero in film stress during bending, so that the effect of buffering is achieved, and the device has better reliability and bending resistance. The materials of the two opposite sides of the first packaging layer 2 are different, and the material of one side of the first packaging layer 2 close to the light-emitting device main body 1 is different from the material of the second packaging layer 3, so that the adhesion between the two layers can be ensured, the stress of the first packaging layer 2 can be adjusted, the integral bending resistance of the packaging structure can be improved, and the phenomena of interlayer peeling, falling off and the like of the film layer after bending can be reduced.
In this embodiment, a side of the first encapsulation layer 2 close to the light emitting device body 1 and a side of the first encapsulation layer 2 close to the second encapsulation layer 3 are opposite sides of the first encapsulation layer 2. One side of the first encapsulation layer 2 adjacent to the light emitting device body 1 may be disposed to be attached to the light emitting device body 1. That is, the side of the first encapsulation layer 2 adjacent to the light emitting device body 1 may be directly attached to the light emitting device body 1, and the side of the first encapsulation layer 2 adjacent to the second encapsulation layer 3 may be directly attached to the second encapsulation layer 3. The mutual arrangement of the encapsulation layers in the present application can be understood from the above description.
It is understood that the material of the side of the first encapsulation layer 2 adjacent to the light emitting device body 1 and the material of the side of the first encapsulation layer 2 adjacent to the second encapsulation layer 3 may both adopt inorganic materials.
In some embodiments, the material of the side of the first encapsulation layer 2 that is close to the second encapsulation layer 3 is the same as the material of the second encapsulation layer 3. That is, the material on the side of the first encapsulation layer 2 close to the second encapsulation layer 3 may also be one or more of silicon oxycarbide, silicon carbonitride, silicon oxycarbide, silicon carbonitride fluoride, and organosilicon compounds. Therefore, the performance of one side of the first packaging layer 2 close to the second packaging layer 3 is close to that of the second packaging layer 3, the adhesion of the first packaging layer 2 and the second packaging layer 3 can be improved, and the joint corresponding to the first packaging layer 2 and the second packaging layer 3 has better bending resistance.
In some embodiments, the material of the side of the first encapsulation layer 2 adjacent to the second encapsulation layer 3 is different from the material of the second encapsulation layer 3, and the material of the side of the first encapsulation layer 2 adjacent to the second encapsulation layer 3 comprises elemental silicon. The material of the side of the first packaging layer 2 close to the second packaging layer 3 is similar to the material of the second packaging layer 3, so that the adhesion between the first packaging layer 2 and the second packaging layer 3 is large, the integral film quality of the first packaging layer 2 is hard, and the integral structural strength of the packaging structure is improved.
In some embodiments, the material of the side of the first encapsulation layer 2 that is close to the second encapsulation layer 3 is an inorganic material. Specifically, the material of the side of the first encapsulation layer 2 close to the second encapsulation layer 3 is silicon oxide or silicon nitride. Therefore, the first packaging layer 2 is simple to prepare, and materials of one side of the first packaging layer 2 close to the second packaging layer 3 are similar to those of the second packaging layer 3, so that interlayer bonding is facilitated.
In some embodiments, the material of the side of the first encapsulation layer 2 adjacent to the light emitting device body 1 is selected from one or more of alumina, titania, zirconia, cobalt oxide, boron oxide, magnesium oxide, molybdenum oxide, barium oxide, aluminum nitride, titanium nitride, magnesium nitride. The material of the side of the first encapsulation layer 2 close to the second encapsulation layer 3 is silicon oxide or silicon nitride. Thus, the first encapsulation layer 2 has a better water oxygen barrier capability.
In some embodiments, the material of the second encapsulation layer 3 is selected from silicon oxycarbide or fluorinated silicon oxycarbide, and the material of the side of the first encapsulation layer 2 adjacent to the second encapsulation layer 3 is selected from silicon oxide. The components of the silicon oxycarbide and the fluorinated silicon oxycarbide are closer to the silicon oxide, so that the interlayer bonding force between the first packaging layer 2 and the second packaging layer 3 can be improved, and the overall stress of the packaging structure is favorably reduced.
In some embodiments, the material of the second encapsulation layer 3 is selected from silicon carbonitride or fluorinated silicon carbonitride, and the material of the side of the first encapsulation layer 2 adjacent to the second encapsulation layer 3 is selected from silicon nitride. The silicon carbonitride or fluorinated silicon carbonitride is closer to silicon nitride, so that the interlayer bonding force between the first packaging layer 2 and the second packaging layer 3 can be improved, and the overall stress of the packaging structure is reduced.
As shown in fig. 2, in some embodiments, the first encapsulation layer 2 includes a first sub-encapsulation layer 22 and a second sub-encapsulation layer 21 which are stacked. The first sub-encapsulation layer 22 is disposed on the light emitting device body 1. The second sub-encapsulation layer 21 is disposed between the first sub-encapsulation layer 22 and the second encapsulation layer 3. The material of the first sub-encapsulation layer 22 is different from the material of the second sub-encapsulation layer 21. The material of the first sub-encapsulation layer 22 is different from the material of the second encapsulation layer 3. Therefore, the formation of the packaging structure is facilitated, and the overall packaging effect of the packaging structure can be ensured. It is to be understood that the first sub-encapsulation layer 22 is disposed adjacent to the light emitting device body 1 with respect to the second sub-encapsulation layer 21, and the second sub-encapsulation layer 21 is disposed adjacent to the second encapsulation layer 3 with respect to the first sub-encapsulation layer 22.
In some embodiments, the stress generated by the first sub-encapsulation layer 22 and the stress generated by the second sub-encapsulation layer 21 are in opposite directions. It is understood that the two encapsulation layers are oppositely stressed, and that one of the encapsulation layers exhibits tensile stress and the other encapsulation layer exhibits compressive stress. For example, the stress value generated by the first sub-encapsulation layer 22 may be a positive number, which is expressed as tensile stress; the stress value generated by the second sub-encapsulation layer 21 may be negative, and is expressed as compressive stress. In some embodiments, the stress generated by the first sub-package layer 22 and the stress generated by the second sub-package layer 21 may cancel each other out to improve the reliability of the package.
In some embodiments, the encapsulation structure comprises a third encapsulation layer 4. A third encapsulation layer 4 is arranged on the second encapsulation layer 3. The material of the side of the third encapsulation layer 4 adjacent to the second encapsulation layer 3 is the same as the material of the side of the first encapsulation layer 2 adjacent to the second encapsulation layer 3. Therefore, the bonding property of the second packaging layer 3 for connecting the first packaging layer 2 and the third packaging layer 4 is improved, and the overall bending resistance and the water oxygen blocking effect of the packaging structure can be further improved.
In some embodiments, the material of the side of the third encapsulation layer 4 remote from the second encapsulation layer 3 is the same as the material of the side of the first encapsulation layer 2 close to the light emitting device body 1. Therefore, the third packaging layer 4 is integrally hard, and has better water and oxygen blocking effect and bending resistance.
In some embodiments, the stress generated by the first encapsulation layer 2 is in the opposite direction to the stress generated by the third encapsulation layer 4. Thus, the stress of the packaging layer can be buffered, and the bending resistance and the reliability can be improved.
In some embodiments, the third encapsulating layer 4 includes a third sub-encapsulating layer and a fourth sub-encapsulating layer, which are stacked, the third sub-encapsulating layer is disposed on the second encapsulating layer, and the third sub-encapsulating layer is located between the second encapsulating layer and the fourth sub-encapsulating layer. Likewise, in some embodiments, the stress generated by the third sub-package layer is in the opposite direction as the stress generated by the fourth sub-package layer. As shown in fig. 3, the light emitting device 100 of one example includes a first sub-encapsulation layer 131, a second sub-encapsulation layer 132, a third encapsulation layer 133, a fourth sub-encapsulation layer 134, and a fifth sub-encapsulation layer 135.
The first sub-encapsulation layer 131 is disposed on the light emitting device body, the second sub-encapsulation layer 132 is disposed on the first sub-encapsulation layer 131, the third sub-encapsulation layer 133 is disposed on the second sub-encapsulation layer 132, the fourth sub-encapsulation layer 134 is disposed on the third sub-encapsulation layer 133, and the fifth sub-encapsulation layer 135 is disposed on the fourth sub-encapsulation layer 134.
The material of the third encapsulation layer 133 is one or more of silicon oxycarbide, silicon carbonitride, fluorinated silicon oxycarbide, fluorinated silicon carbonitride, and an organosilicon compound, wherein the organosilicon compound may be, but is not limited to, Polydimethylsiloxane (PDMS).
The first sub-package layer 131, the second sub-package layer 132, the fourth sub-package layer 134, and the fifth sub-package layer 135 are all inorganic materials.
In one example, a first stress generated by the first sub-package layer 131 and a second stress generated by the second sub-package layer 132 are opposite in direction, and a fourth stress generated by the fourth sub-package layer 134 and a fifth stress generated by the fifth sub-package layer 135 are opposite in direction.
It is understood that the two encapsulation layers are oppositely stressed, and that one of the encapsulation layers exhibits tensile stress and the other encapsulation layer exhibits compressive stress. For example, the stress value of the first stress may be a positive number, expressed as tensile stress; the stress value of the second stress may be negative, expressed as a compressive stress. In some embodiments, the first stress and the second stress may cancel each other out to improve the reliability of the package. Likewise, the stress value of the fourth stress may be negative, expressed as compressive stress; the stress value of the fifth stress may be a positive number, expressed as tensile stress. The fourth stress and the fifth stress can be mutually offset to improve the reliability of the package.
In one example, the direction of the resultant stress generated by the first sub-packaging layer 131 and the second sub-packaging layer 132 is opposite to the direction of the resultant stress generated by the fourth sub-packaging layer 134 and the fifth sub-packaging layer 135. Thus, the stress of the packaging layer can be buffered, and the bending resistance and the reliability can be improved. It should be understood that the resultant stress described above refers to the stress generated by the two connected package layers as a whole, such as the stress generated by the first sub-package layer 131 and the second sub-package layer 132 as a whole. It will be appreciated that the two package layers being connected may exhibit tensile stress, as well as compressive stress. For example, the stress value of the resultant stress generated by the first sub-package layer 131 and the second sub-package layer 132 may be a positive number, which is expressed as tensile stress; the stress value of the resultant stress generated by the fourth sub-encapsulation layer 134 and the fifth sub-encapsulation layer 135 may be negative, which is expressed as compressive stress. The combined stress generated by the first sub-package layer 131 and the second sub-package layer 132 and the combined stress generated by the fourth sub-package layer 134 and the fifth sub-package layer 135 can be offset to improve the bending resistance and reliability of the package.
In one example, the materials of the first sub-encapsulation layer 131 and the fifth sub-encapsulation layer 135 are independently selected from one or more of aluminum oxide, titanium oxide, zirconium oxide, cobalt oxide, boron oxide, magnesium oxide, molybdenum oxide, barium oxide, silicon oxynitride, aluminum nitride, titanium nitride, and magnesium nitride. The material of the second sub-encapsulation layer 132 and the fourth sub-encapsulation layer 134 is selected from silicon oxide or silicon nitride. In some embodiments, the materials of the first sub-encapsulation layer 131 and the fifth sub-encapsulation layer 135 are independently selected from aluminum oxide, which has a positive stress value and exhibits tensile stress. The material of the second sub-encapsulation layer 132 and the fourth sub-encapsulation layer 134 is selected from silicon oxide, and the stress value is negative and is expressed as compressive stress. Since the stress of the package layer is related to the material used, when the materials of the first sub-package layer 131 and the fifth sub-package layer 135 are different from the materials of the second sub-package layer 132 and the fourth sub-package layer 134, it is more beneficial to reduce the overall stress of the package structure.
In one example, the material of the third encapsulation layer 133 is selected from silicon oxycarbide or fluorinated silicon oxycarbide. The material of the second sub-encapsulation layer 132 and the fourth sub-encapsulation layer 134 is selected from silicon oxide. The silicon oxycarbide and the fluorinated silicon oxycarbide have compositions closer to silicon oxide, which can improve the adhesive force between the second sub-encapsulation layer 132 and the fourth sub-encapsulation layer 134 and the third encapsulation layer 133, and is beneficial to reducing the overall stress of the encapsulation structure.
In one example, the material of the third encapsulation layer 133 is selected from silicon carbonitride or fluorinated silicon carbonitride, and the material of the second sub-encapsulation layer 132 and the fourth sub-encapsulation layer 134 is selected from silicon nitride. The silicon carbonitride or fluorinated silicon carbonitride has the components closer to those of silicon nitride, so that the bonding force between the second sub-packaging layer 132 and the third sub-packaging layer 133 and between the fourth sub-packaging layer 134 and the third packaging layer 133 can be improved, and the overall stress of the packaging structure can be reduced.
As shown in fig. 4, the light emitting device body includes a substrate 110 and a light emitting assembly 120, and the light emitting assembly 120 includes a first electrode layer 121, a light emitting function layer 122, and a second electrode layer 123. The first electrode layer 121 is disposed on the substrate 110, the light emitting function layer 122 is disposed on the first electrode layer 121, and the second electrode layer 123 is disposed on the light emitting function layer 122. The first sub-encapsulation layer 131 is disposed on the second electrode layer 123.
In one example, the thickness of the first sub-encapsulation layer 131 is 50nm to 200nm, the thickness of the second sub-encapsulation layer 132 is 25nm to 100nm, the thickness of the third encapsulation layer 133 is 1 μm to 10 μm, the thickness of the fourth sub-encapsulation layer 134 is 25nm to 100nm, and the thickness of the fifth sub-encapsulation layer 135 is 100nm to 300 nm.
The first sub-package layer 131, the second sub-package layer 132, the fourth sub-package layer 134, and the fifth sub-package layer 135 are hard inorganic film layers with large film stress when being bent, and have ideal water and oxygen blocking capability and high visible light transmittance.
The third packaging layer 133 is a film layer with a relatively soft film quality and a film layer stress of almost zero when the third packaging layer is bent, and mainly has the effects of buffering the stress of the adjacent film layers, so that the display has better reliability and bending resistance, has higher visible light transmittance, can also wrap the dust impurities which possibly fall in the packaging process, has more rounded corners of the wrapped dust impurities, is not easy to form a channel through which water and oxygen permeate, and has certain water and oxygen barrier performance. Meanwhile, the material of the third packaging layer is one or more of silicon oxycarbide, silicon carbonitride, silicon oxycarbide fluoride, silicon carbonitride fluoride and organic silicon compound, and the components of the third packaging layer are similar to those of the inorganic packaging layers on the two sides, so that the interlayer bonding force is strong.
The directions of the stresses generated by the first sub-package layer 131 and the second sub-package layer 132 are opposite, for example, the material of the first sub-package layer 131 is one or more of aluminum oxide, titanium oxide, zirconium oxide, cobalt oxide, boron oxide, magnesium oxide, molybdenum oxide, barium oxide, silicon nitride, silicon oxynitride, aluminum nitride, titanium nitride, and magnesium nitride, the stress value generated by the material may be positive and may be expressed as tensile stress, the material of the second sub-package layer 132 is silicon oxide, the stress value generated by the material may be negative and may be expressed as compressive stress, the properties of the stresses are opposite and may cancel each other out, the stress of the inorganic package layer is buffered, and the bending resistance and the reliability are improved. Likewise, the stress properties of the fourth sub-package layer and the fifth sub-package layer are opposite and can be mutually counteracted. In addition, the direction of the combined stress generated by the first sub-packaging layer and the second sub-packaging layer is opposite to the direction of the combined stress generated by the fourth sub-packaging layer and the fifth sub-packaging layer, so that the overall stress of the packaging structure can be reduced.
Through the integral matching of the technical means, the integral stress of the packaging film layer can be effectively reduced, the interlayer bonding force is improved, the situation that the film is peeled off after the packaging film layer is bent is reduced, and the bending resistance and the reliability of the packaging film layer are improved.
The method for manufacturing the package structure of the light emitting device shown in fig. 3 includes the following steps:
step one, as shown in fig. 5, a first sub-encapsulation layer 131 is fabricated on the light emitting device body.
In step two, as shown in fig. 6, a second sub-package layer 132 is fabricated on the first sub-package layer 131.
Step three, as shown in fig. 7, a third encapsulation layer 133 is fabricated on the second sub-encapsulation layer 132, and the material of the third encapsulation layer 133 is one or more of silicon oxycarbide, silicon carbonitride, silicon oxycarbide fluoride, silicon carbonitride fluoride, and an organic silicon compound.
Step four, as shown in fig. 8, a fourth sub-package layer 134 is fabricated on the third package layer 133.
Step five, fabricating a fifth sub-encapsulation layer 135 on the fourth sub-encapsulation layer 134, so as to obtain the light emitting device 100 shown in fig. 3.
The stress directions generated by the first sub-packaging layer 131 and the second sub-packaging layer 132 are opposite, and the stress directions generated by the fourth sub-packaging layer 134 and the fifth sub-packaging layer 135 are opposite; and/or, the direction of the resultant stress generated by the first sub-packaging layer 131 and the second sub-packaging layer 132 is opposite to the direction of the resultant stress generated by the fourth sub-packaging layer 134 and the fifth sub-packaging layer 135.
In one example, the materials of the first sub-encapsulation layer 131 and the fifth sub-encapsulation layer 135 are independently selected from one or more of aluminum oxide, titanium oxide, zirconium oxide, cobalt oxide, boron oxide, magnesium oxide, molybdenum oxide, barium oxide, silicon nitride, silicon oxynitride, aluminum nitride, titanium nitride, and magnesium nitride. The stress value generated by the above materials can be positive, and the stress can be expressed as tensile stress. The material of the second sub-encapsulation layer 132 and the fourth sub-encapsulation layer 134 is selected from silicon oxide, and the generated stress value may be negative and may be expressed as compressive stress. In one example, the material of the third encapsulation layer 133 is selected from silicon oxycarbide or fluorinated silicon oxycarbide. The composition of silicon oxycarbide and fluorinated silicon oxycarbide is closer to that of silicon oxide, and can improve the adhesion between the second and fourth sub-encapsulation layers 132 and 134 and the third encapsulation layer 133.
In one example, the material of the third encapsulation layer 133 is selected from silicon carbonitride or fluorinated silicon carbonitride, and the material of the second sub-encapsulation layer 132 and the fourth sub-encapsulation layer 134 is selected from silicon nitride. The silicon carbonitride or fluorinated silicon carbonitride has the components closer to those of silicon nitride, so that the bonding force between the second sub-packaging layer 132 and the third sub-packaging layer 133 and between the fourth sub-packaging layer 134 and the third packaging layer 133 can be improved, and the overall stress of the packaging structure can be reduced.
In one example, the first sub-encapsulation layer 131, the second sub-encapsulation layer 132, the fourth sub-encapsulation layer 134, and the fifth sub-encapsulation layer 135 are fabricated by Atomic Layer Deposition (ALD).
The preparation process of the second sub-encapsulation layer 132 is an atomic layer deposition process, which can obtain a dense thin film with less defects, provide an ideal and appropriate deposition environment for the third encapsulation layer, reduce the possibility of dust generation on the deposition surface of the third encapsulation layer 133, and because the second layer is made of a silicon oxide material with higher affinity, the process parameter range that the third encapsulation layer 133 can use can be wider.
In one example, the step of fabricating the first sub-encapsulation layer 131 includes:
step S11, placing the light-emitting device main body in a reaction chamber, and introducing an organic aluminum source by taking protective gas as carrier gasDepositing an organic aluminum source on the second electrode layer at a flow rate of 6000sccm/m2~24000sccm/m2The feeding time is 0.05 s-1 s. Wherein the protective gas is argon and the organoaluminum source is Trimethylaluminum (TMA).
And step S12, exhausting and removing the residual organic aluminum source.
Step S13, introducing a reaction source into the reaction chamber with a flow rate of 6000sccm/m2~24000sccm/m2The feeding time is 0.2 s-5 s. The reaction source can be selected from H2O、O2、N2O and O3One or more of (a).
Step S14, loading radio frequency on the electrode plate of the reaction chamber, wherein the radio frequency power is 30kW/m2~120kW/m2The duration is 0.5 s-10 s.
In step S15, unreacted materials are removed by evacuation.
The steps S11 to S15 are repeated a plurality of times to obtain a first sub-encapsulation layer 131 with a certain thickness. In one example, the number of repetitions is 360 to 1440, and the thickness of the first sub-encapsulation layer 131 is 50 to 200 nm.
In one example, the step of fabricating the second sub-encapsulation layer 132 includes:
step S21, introducing an organic silicon source into the reaction chamber by using a protective gas as a carrier gas to deposit the organic silicon source on the first sub-packaging layer 131, wherein the flow rate is 6000sccm/m2~24000sccm/m2The introduction time is 0.05-1 s. Wherein the protective gas is argon, and the organosilicon source is Diisopropylaminosilane (DIPAS).
And step S22, exhausting to remove the residual organic silicon source.
Step S23, introducing a reaction source into the reaction chamber with a flow rate of 9000sccm/m2~36000sccm/m2The introduction time is 0.2-5 s. The reaction source can be selected from H2O、O2、N2O and O3One or more of (a).
Step S24, loading radio frequency on the electrode plate of the reaction chamber, wherein the radio frequency power is 45kW/m2~180kW/m2The duration is 0.5 s-10 s。
In step S25, unreacted materials are removed by evacuation.
The steps S21 to S25 are repeated a plurality of times to obtain a second sub-encapsulation layer 132 with a certain thickness. In one example, the number of repetitions is 226 to 905 times, and the thickness of the first sub-encapsulation layer 131 is 25nm to 100 nm.
In one example, the third encapsulation layer 133 is fabricated by a Plasma Enhanced Chemical Vapor Deposition (PECVD) process, including:
step S31, introducing hexamethyldisiloxane, nitrous oxide and nitrogen into the reaction chamber, wherein the flow rate of hexamethyldisiloxane is 3000sccm/m2~15000sccm/m2The flow rate of nitrous oxide is 60000sccm/m2~300000sccm/m2The flow rate of nitrogen gas is 150000sccm/m2~750000sccm/m2The introduction time is 5 s-120 s.
Step S32, loading radio frequency on the electrode plate of the reaction chamber, wherein the radio frequency power is 45kW/m2~225kW/m2For a duration of 160s to 1600s, to obtain a third encapsulation layer 133 having a thickness of 1 μm to 10 μm.
In one example, the step of fabricating the fourth sub-encapsulation layer 134 includes:
step S41, introducing an organic silicon source into the reaction chamber using the protective gas as a carrier gas to deposit the organic silicon source on the third encapsulation layer 133 at a flow rate of 6000sccm/m2~24000sccm/m2The feeding time is 0.05 s-1 s. Wherein the protective gas is argon, and the organosilicon source is Diisopropylaminosilane (DIPAS).
And step S42, exhausting to remove the residual organic silicon source.
Step S43, introducing a reaction source into the reaction chamber with a flow rate of 9000sccm/m2~36000sccm/m2The feeding time is 0.2 s-5 s.
Step S44, loading radio frequency on the electrode plate of the reaction chamber, wherein the radio frequency power is 45kW/m2~180kW/m2The duration is 0.5 s-10 s.
In step S45, unreacted materials are removed by evacuation.
The steps S41-S45 are repeated a plurality of times to obtain a thickness of the fourth sub-encapsulation layer 134. In one example, the number of repetitions is 226 to 905 times, and the thickness of the first sub-encapsulation layer 131 is 25nm to 100 nm.
In one example, the step of fabricating the fifth sub-encapsulation layer 135 includes:
step S51, introducing an organic aluminum source into the reaction chamber by taking protective gas as carrier gas to deposit the organic aluminum source on the second electrode layer, wherein the flow rate is 6000sccm/m2~24000sccm/m2The feeding time is 0.05 s-1 s.
And step S52, exhausting and removing the residual organic aluminum source.
Step S53, introducing a reaction source into the reaction chamber with a flow rate of 6000sccm/m2~24000sccm/m2The feeding time is 0.2 s-5 s.
Step S54, loading radio frequency on the electrode plate of the reaction chamber, wherein the radio frequency power is 30kW/m2~120kW/m2The duration is 0.5 s-10 s.
In step S55, unreacted materials are removed by evacuation.
Steps S51 to S55 are repeated a plurality of times. In one example, the thickness of the fifth sub-encapsulation layer 135 is 100nm to 300 nm.
The magnitude of the stress of the encapsulation layer has a correlation with the magnitude of the rf power used by the ald process. In the above example, the stress of the deposited encapsulation layer is regulated and controlled by adjusting the radio frequency power used by the atomic layer deposition process, so that the stresses between the first sub-encapsulation layer and the second sub-encapsulation layer and between the fourth sub-encapsulation layer and the fifth sub-encapsulation layer are similar or identical on the basis of opposite stress properties, and thus the stresses can be mutually offset and the stress of the inorganic encapsulation layer can be buffered.
The light emitting device 100 can be applied to the fields of flat panel displays, television displays, electronic paper, logic and memory circuits, flexible displays, and the like, such as mobile phones, televisions, tablet computers, displays, VR/AR devices, computers, vehicle-mounted displays, or any other products or components with display functions.
The present invention will be further described below by taking a specific exemplary method for manufacturing a package structure of a light emitting device as an example.
A specific example of the method for manufacturing a light-emitting device includes the steps of:
step S110, providing a light emitting device main body, where the light emitting device main body includes a substrate, a first electrode layer, a light emitting function layer and a second electrode layer, the first electrode layer is disposed on the substrate, the light emitting function layer is disposed on the first electrode layer, and the second electrode layer is disposed on the light emitting function layer. And conveying the light-emitting device main body needing to deposit the packaging film into the reaction chamber by using a vacuum mechanical arm or a manual conveying method and the like.
In step S120, as shown in fig. 5, a first sub-encapsulation layer 131 is formed on the light emitting device body through an atomic layer deposition process.
Specifically, the pressure of the reaction chamber is kept at 0.2 to 1.5Torr, the distance between the substrates is kept at 20 to 50mm, and the specific deposition steps are as follows:
firstly, introducing an organic aluminum source. Taking Ar gas as carrier gas, and introducing Trimethylaluminum (TMA) in a steel cylinder into the reaction chamber for 1s at a flow rate of 20000sccm/m2The TMA and the second electrode layer of the light-emitting device main body are chemically reacted by surface adsorption.
And step two, air exhaust process. Pumping away residual TMA in the chamber environment, and only keeping the reaction TMA adsorbed on the substrate and the chamber wall; the air extraction time was 3 s.
And step three, introducing a reaction source. Mixing O with2Introducing into a reaction chamber as a reaction source with a flow rate of 20000sccm/m2The passage time was 3 seconds.
And fourthly, generating reaction plasma. This example uses O2Plasma as a reaction source in O2After the reaction chamber is filled, radio frequency is loaded on an electrode plate of the reaction chamber, and the power is 70kW/m2And the duration is 5 s.
And fifthly, air exhaust process. And pumping to remove unreacted substances, wherein the pumping time is 4 s.
Repeating the first step to the fifth step for 1000 times to obtain the aluminum oxide packaging film with the thickness of 120 nm.
In step S130, as shown in fig. 6, a second sub-encapsulation layer 132 is deposited on the first sub-encapsulation layer 131 by an atomic layer deposition process.
The specific deposition steps are as follows:
firstly, an organic silicon source is introduced. Ar gas is used as carrier gas, Diisopropylaminosilane (DIPAS) in a steel cylinder is brought into a reaction chamber, the introducing time is 1s, and the flow rate is 15000sccm/m2
And step two, air exhaust process. Pumping away residual DIPAS in the chamber environment, and only keeping the reaction DIPAS adsorbed on the substrate and the chamber wall, wherein the pumping time is 3 s.
And step three, introducing a reaction source. This example employs N2O is used as a reaction source, and the flow rate is 10000sccm/m2The passage time was 5 s.
And fourthly, generating reaction plasma. More, this example employs N2O plasma as a reaction source in N2After O is introduced into the chamber, radio frequency is loaded on an electrode plate of the reaction chamber, and the power is 100kW/m2And the duration is 6 s.
And fifthly, air exhaust process. And pumping to remove unreacted substances, wherein the pumping time is 4 s.
Repeating the first step to the fifth step for 500 times to obtain the silicon oxide film with the thickness of 50 nm.
In step S140, as shown in fig. 7, the device is kept still in the reaction chamber, and a third encapsulating layer 133 is formed on the second sub-encapsulating layer 132 by using a plasma chemical vapor deposition process. The pressure in the reaction chamber is maintained at 0.4 to 1.8Torr, and the substrate pitch is 20 to 50 mm.
The specific deposition steps are as follows:
firstly, reaction gas is introduced to stabilize deposition conditions. The reaction gases used in this example were HMDSO, N2O、N2. The HMDSO flow is 9000sccm/m2、N2The flow rate of O was 180000sccm/m2、N2The flow rate of (2) was 450000sccm/m2The passage time was 10 seconds.
Second, load shootingFrequency. Loading 100kW/m into electrode plate of reaction chamber2The radio frequency of the radio frequency is 13.56MHz, so that the reaction gas in the chamber is dissociated and plasma polymerization reaction occurs, and the reacted plasma polymer can continuously deposit the silicon oxycarbide film close to the polymer property on the second sub-encapsulation layer 132 for 9s, so as to obtain the silicon oxycarbide film with the thickness of 6 μm.
Step S150, as shown in fig. 8, the device is kept still in the reaction chamber, and a fourth sub-encapsulation layer 134 of silicon oxide is deposited on the third encapsulation layer 133 by an atomic layer deposition process, where the process method is the same as that of the second encapsulation layer.
Step S160, keeping the device in the reaction chamber, and depositing the aluminum oxide fifth sub-encapsulation layer 135 on the fourth sub-encapsulation layer 134 by an atomic layer deposition process, with the same process as the first encapsulation layer, so as to obtain the light emitting device 100 shown in fig. 3.
In conclusion, through the overall matching of the technical means, the overall stress of the packaging film layer can be effectively reduced, the interlayer bonding force can be improved, the situation that the film is peeled off after the packaging film layer is bent can be reduced, and the bending resistance and the reliability of the packaging film layer can be improved.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (18)

1. An encapsulation structure of a light-emitting device, the light-emitting device comprises a light-emitting device body, and the encapsulation structure comprises a first encapsulation layer and a second encapsulation layer, the first encapsulation layer is arranged on the light-emitting device body, the second encapsulation layer is arranged on the first encapsulation layer, the material of one side, close to the light-emitting device body, of the first encapsulation layer is different from the material of one side, close to the second encapsulation layer, of the first encapsulation layer, the material of the second encapsulation layer is one or more of silicon oxycarbide, silicon carbonitride, silicon oxycarbide fluoride, silicon carbonitride fluoride and organosilicon compound, and the material of one side, close to the light-emitting device body, of the first encapsulation layer is different from the material of the second encapsulation layer.
2. The package structure of the light emitting device according to claim 1, wherein a side of the first package layer adjacent to the second package layer is made of the same material as the second package layer.
3. The package structure of the light emitting device according to claim 1, wherein a material of a side of the first package layer adjacent to the second package layer is different from a material of the second package layer, and the material of the side of the first package layer adjacent to the second package layer comprises silicon element.
4. The light emitting device package structure of claim 3, wherein a material of a side of the first encapsulation layer adjacent to the second encapsulation layer is silicon oxide or silicon nitride.
5. The light emitting device package structure of claim 4, wherein the material of the second encapsulation layer is selected from silicon oxycarbide or fluorinated silicon oxycarbide, and the material of the side of the first encapsulation layer adjacent to the second encapsulation layer is selected from silicon oxide; or
The second packaging layer is made of silicon carbonitride or fluorinated silicon carbonitride, and the side, close to the first packaging layer, of the second packaging layer is made of silicon nitride.
6. The package structure of the light emitting device according to claim 1, wherein the first package layer comprises a first sub-package layer and a second sub-package layer stacked, the first sub-package layer being disposed on the light emitting device body, the second sub-package layer being disposed between the first sub-package layer and the second package layer;
the material of the first sub-encapsulation layer is different from the material of the second sub-encapsulation layer, and the material of the first sub-encapsulation layer is different from the material of the second encapsulation layer.
7. The package structure of the light emitting device according to claim 6, wherein the stress generated by the first sub-package layer is opposite to the stress generated by the second sub-package layer.
8. The package structure of the light emitting device according to claim 1, wherein the package structure comprises a third package layer disposed on the second package layer, and a side of the third package layer adjacent to the second package layer is the same material as a side of the first package layer adjacent to the second package layer.
9. The light emitting device package structure of claim 8, wherein a side of the third encapsulation layer distal from the second encapsulation layer is the same material as a side of the first encapsulation layer proximal to the light emitting device body.
10. The package structure of a light emitting device according to claim 8, wherein the stress generated by the first package layer is opposite in direction to the stress generated by the third package layer.
11. The package structure of the light emitting device according to claim 8, wherein the third encapsulating layer comprises a third sub-encapsulating layer and a fourth sub-encapsulating layer, the third sub-encapsulating layer is disposed on the second encapsulating layer, and the third sub-encapsulating layer is disposed between the second encapsulating layer and the fourth sub-encapsulating layer.
12. The package structure of the light emitting device according to claim 11, wherein the stress generated by the third sub-package layer and the stress generated by the fourth sub-package layer are in opposite directions.
13. A method for manufacturing a packaging structure of a light emitting device, wherein the light emitting device comprises a light emitting device main body, and the method comprises the following steps:
manufacturing a first packaging layer on the light-emitting device main body;
manufacturing a second packaging layer on the first packaging layer;
wherein a material of a side of the first encapsulation layer adjacent to the light emitting device body is different from a material of a side of the first encapsulation layer adjacent to the second encapsulation layer, the material of the second encapsulation layer is one or more of silicon oxycarbide, silicon carbonitride, silicon oxycarbide fluoride, silicon carbonitride fluoride, and an organosilicon compound, and the material of a side of the first encapsulation layer adjacent to the light emitting device body is different from the material of the second encapsulation layer.
14. The method of manufacturing according to claim 13, wherein the first encapsulation layer includes a first sub-encapsulation layer and a second sub-encapsulation layer which are stacked, the first sub-encapsulation layer being disposed on the light emitting device body, the second sub-encapsulation layer being disposed on the first sub-encapsulation layer;
the material of the first sub-encapsulation layer is different from the material of the second sub-encapsulation layer, and the material of the first sub-encapsulation layer is different from the material of the second encapsulation layer.
15. The method of claim 14, wherein the first sub-encapsulation layer and the second sub-encapsulation layer are fabricated by an atomic layer deposition process.
16. The method of manufacturing of claim 15, wherein the step of manufacturing the first sub-encapsulation layer comprises:
adopting protective gas as carrier gas, and introducing an organic aluminum source into the reaction chamber provided with the light-emitting device main body, wherein the flow rate is 6000sccm/m2~24000sccm/m2The feeding time is 0.05 s-1 s;
exhausting to remove the residual organic aluminum source;
introducing a reaction source into the reaction chamber at a flow rate of 6000sccm/m2~24000sccm/m2The feeding time is 0.2 s-5 s;
loading radio frequency on an electrode plate of the reaction chamber, wherein the radio frequency power is 30kW/m2~120kW/m2The duration is 0.5 s-10 s;
pumping to remove unreacted substances.
17. The method of manufacturing of claim 15, wherein the step of manufacturing the second sub-encapsulation layer comprises:
adopting protective gas as carrier gas, and introducing an organic silicon source into the reaction chamber to deposit the organic silicon source on the first packaging layer at a flow rate of 6000sccm/m2~24000sccm/m2The feeding time is 0.05 s-1 s;
pumping to remove the residual organic silicon source;
introducing a reaction source into the reaction chamber with the flow rate of 9000sccm/m2~36000sccm/m2The feeding time is 0.2 s-5 s;
loading radio frequency to the electrode plate of the reaction chamber, wherein the radio frequency power is 45kW/m2~180kW/m2The duration is 0.5 s-10 s;
pumping to remove unreacted substances.
18. A light emitting device is characterized by comprising a light emitting device main body and a packaging structure;
the packaging structure comprises a first packaging layer and a second packaging layer, wherein the first packaging layer is arranged on the light-emitting device main body, the second packaging layer is arranged on the first packaging layer, the material of one side, close to the light-emitting device main body, of the first packaging layer is different from the material of one side, close to the second packaging layer, of the second packaging layer, the material of the second packaging layer is one or more of silicon oxycarbide, silicon carbonitride, silicon oxycarbide, silicon fluorocarbonnitride and organic silicon compounds, and the material of one side, close to the light-emitting device main body, of the first packaging layer is different from the material of the second packaging layer.
CN201911380422.5A 2019-12-27 2019-12-27 Light-emitting device, packaging structure thereof and manufacturing method thereof Pending CN112349861A (en)

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