CN111864094A - Light-emitting device, preparation method and display device - Google Patents
Light-emitting device, preparation method and display device Download PDFInfo
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- CN111864094A CN111864094A CN202010712499.4A CN202010712499A CN111864094A CN 111864094 A CN111864094 A CN 111864094A CN 202010712499 A CN202010712499 A CN 202010712499A CN 111864094 A CN111864094 A CN 111864094A
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- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- H10K50/85—Arrangements for extracting light from the devices
- H10K50/858—Arrangements for extracting light from the devices comprising refractive means, e.g. lenses
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Abstract
The invention provides a light-emitting device, a preparation method and a display device, belongs to the technical field of display, and can solve the problem that the brightness and service life of the conventional OLED light-emitting device are too fast to decay. The light emitting device of the present invention comprises: the organic light-emitting diode comprises a substrate, and a first electrode, an organic functional layer and a second electrode which are sequentially arranged on the substrate; further comprising: the coupling light-emitting layer is positioned on one side of the second electrode, which is far away from the organic functional layer; the coupling light-out layer is made of a first copolymer material; the first copolymer material undergoes photoisomerization under the irradiation of ultraviolet light to form a second copolymer material; the second copolymer material has a refractive index greater than the refractive index of the first copolymer material.
Description
Technical Field
The invention belongs to the technical field of display, and particularly relates to a light-emitting device, a preparation method and a display device.
Background
Organic light-emitting diodes (OLEDs) have the advantages of being light and thin, saving power, full-color, actively emitting light, having a fast response speed, and the like, and show a great application prospect in the display technology field.
The inventor finds that at least the following problems exist in the prior art: in a vehicle-mounted display product, the OLED light-emitting device is often exposed to high temperature, high humidity and ultraviolet light irradiation environments, and particularly under ultraviolet light irradiation, the OLED light-emitting device is easy to age, so that the brightness and the service life of the OLED light-emitting device are easily reduced too fast, and the user experience is affected.
Disclosure of Invention
The invention aims to solve at least one technical problem in the prior art, and provides a light-emitting device, a preparation method and a display device.
The technical scheme adopted for solving the technical problem of the invention is a light-emitting device, which comprises: the organic light-emitting diode comprises a substrate, and a first electrode, an organic functional layer and a second electrode which are sequentially arranged on the substrate; further comprising: a coupling light-emitting layer positioned on one side of the second electrode far away from the organic functional layer;
the coupling light-out layer is composed of a first copolymer material; the first copolymer material undergoes photoisomerization under the irradiation of ultraviolet light to form a second copolymer material; the second copolymer material has a refractive index greater than the refractive index of the first copolymer material.
Optionally, the first copolymer material is formed from polymerization of vinylcarbazole and 4-vinylbenzylthiocyanate.
Alternatively, the ratio of the vinylcarbazole and the 4-vinylbenzylthiocyanate is 8: 1.
Optionally, the ultraviolet light has a wavelength in a range of 250 nanometers to 260 nanometers.
Optionally, the first electrode comprises a reflective electrode; the second electrode includes a translucent electrode.
Optionally, the light emitting device further comprises: a protective layer;
the protective layer is located between the second electrode and the coupling light-out layer.
The technical scheme adopted for solving the technical problem of the invention is a display device which comprises a plurality of light-emitting devices.
Optionally, the display device includes an in-vehicle central control unit or an in-vehicle navigator.
The technical scheme adopted for solving the technical problem of the invention is a preparation method of a light-emitting device, which comprises the following steps:
sequentially forming a first electrode, an organic functional layer and a second electrode on a substrate;
forming a first copolymer material using a plurality of organic materials; the first copolymer material undergoes photoisomerization under the irradiation of ultraviolet light to form a second copolymer material; the second copolymer material has a refractive index greater than the refractive index of the first copolymer material;
curing the first copolymer material on the second electrode using a spin-on or ink-jet printing process to form a coupled light-out layer.
Optionally, the forming a first copolymer material from a plurality of organic materials comprises:
toluene is used as a solvent, and vinyl carbazole and 4-vinylbenzylthiocyanate are used for reacting under the catalytic action of azobisisobutyronitrile at the reaction temperature of 70 ℃ to form the first copolymer material.
Drawings
Fig. 1 is a schematic structural diagram of a light emitting device according to an embodiment of the present invention;
fig. 2 is a graph showing refractive index profiles corresponding to a first copolymer material and a second copolymer material in a light emitting device according to an embodiment of the present invention;
fig. 3 is a graph showing spectra corresponding to a first copolymer material and a second copolymer material in a light-emitting device according to an embodiment of the present invention;
fig. 4 is a schematic flow chart of a manufacturing method of a light emitting device according to an embodiment of the present invention.
Detailed Description
In order to make the technical solutions of the present invention better understood, the present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
Example one
Fig. 1 is a schematic structural diagram of a light emitting device according to an embodiment of the present invention, and as shown in fig. 1, the light emitting device includes: the organic light-emitting diode comprises a substrate 101, and a first electrode 102, an organic functional layer 103 and a second electrode 104 which are sequentially arranged on the substrate 101; further comprising: a coupling-out layer 105 on the side of the second electrode 104 remote from the organic functional layer 103; the coupling-out layer 105 is composed of a first copolymer material; the first copolymer material undergoes photoisomerization under the irradiation of ultraviolet light to form a second copolymer material; the second copolymer material has a refractive index greater than the refractive index of the first copolymer material.
In the light emitting device provided by the embodiment of the present invention, the first electrode 102 and the second electrode 103 on the substrate 101 are oppositely disposed, when an electrical signal is applied between the first electrode 102 and the second electrode 104, an electric field is generated between the first electrode 102 and the second electrode 104, the organic functional layer 103 generates a hole-electron pair under the driving of the electric field, and excites the optical material in the organic functional layer 103 to emit light, and light can be emitted from the direction toward the second electrode 104 and through the coupling light emitting layer 105, thereby realizing the light emitting and displaying functions. In the embodiment of the present invention, the coupling light-out layer 105 is made of the first copolymer material, and the first copolymer material has a higher refractive index, so that the coupling light-out layer 105 made of the first copolymer material can improve the light-emitting efficiency of the whole light-emitting device, and thus can improve the light emission and display brightness. After a period of time and ultraviolet irradiation, the refractive index of the first copolymer material in the coupling light-emitting layer 105 is attenuated, which affects the light-emitting efficiency of the whole light-emitting device, at this time, the first copolymer material is photoisomerized after ultraviolet irradiation, the first copolymer material with the attenuated refractive index is converted into the second copolymer material, the second copolymer material has a higher refractive index and is greater than the refractive index of the first copolymer material, so the coupling light-emitting layer 105 made of the second copolymer material can ensure that the whole light-emitting device has higher light-emitting efficiency, thereby improving the light-emitting and display brightness, and further improving the display effect. In addition, a higher refractive index can be maintained in the process of converting the first copolymer material into the second copolymer material, so that the attenuation speed of the material in the coupling light-emitting layer 105 can be reduced, the material in the coupling light-emitting layer 105 is prevented from being attenuated too fast, and the service life of the whole light-emitting device can be prolonged.
In some embodiments, the first electrode 102 may be an anode of the light emitting device, the anode may be made of ITO (indium tin oxide), Indium Zinc Oxide (IZO), zinc oxide (ZnO), or the like, the anode may be made of one metal material of aluminum (Al), magnesium (Mg), and silver (Ag), or a mixture of aluminum (Al), magnesium (Mg), and silver (Ag), and it is understood that the anode may have a single-layer structure or a multi-layer structure, such as a multi-layer structure of ITO (indium tin oxide)/silver (Ag)/ITO (indium tin oxide). An organic functional layer 103 is formed on the first electrode 102, and the organic functional layer 103 may include a small molecule organic material or a polymer molecule organic material, may be a fluorescent light emitting material or a phosphorescent light emitting material, may emit red light, green light, blue light, or may emit white light, etc. In addition, according to different actual needs, in different examples, the organic functional layer 103 may further include functional layers such as a hole injection layer, a hole transport layer, an organic light emitting layer, an electron transport layer, and an electron injection layer. The second electrode 104 covers the organic functional layer 103, and the polarity of the second electrode 104 is opposite to that of the first electrode 102; the second electrode 104 may be a cathode made of a metal material such as lithium (Li), aluminum (Al), magnesium (Mg), silver (Ag), etc. When a plurality of light emitting devices are formed on the same substrate 101, the first electrodes 102 may be disconnected, each first electrode 102 corresponds to one organic functional layer 103, the second electrode 104 may be a full-surface electrode, and the same second electrode 104 may correspond to a plurality of organic functional layers 103. It is understood that the light emitting device provided by the embodiments of the present invention may further include, in addition to the above structures, a barrier layer, a buffer layer, a pixel defining layer, a spacer, and an encapsulation layer, which may be prepared by using materials and methods in the related art, and the implementation principle is the same as that of each structure in the related art, and will not be described in detail here.
In some embodiments, the first copolymer material is formed from the polymerization of vinylcarbazole and 4-vinylbenzylthiocyanate.
It should be noted that the first copolymer material can be formed by polymerizing vinylcarbazole and 4-vinylbenzylthiocyanate, the reaction formula of which is shown below,
toluene (Toluene) is used as a solvent, and Vinyl Carbazole (VC) and 4-Vinylbenzylthiocyanoate (VBT) react under the catalysis of Azobisisobutyronitrile (AIBN) at the reaction temperature of 70 ℃ to form a first copolymer material (VC-co-VBT). Under Ultraviolet (UV) radiation, thiocyanate (-SCN) groups in the first copolymer material may be photoisomerized to isothiocyanate (-NCS) groups, forming a second copolymer material.
Fig. 2 is a graph showing refractive index curves corresponding to the first copolymer material and the second copolymer material in the light emitting device provided in the embodiment of the present invention, and as shown in fig. 2, in a visible light wavelength range, the refractive index of the second copolymer material formed by ultraviolet light irradiation is significantly greater than the refractive index of the first copolymer material not irradiated by ultraviolet light, so that the coupled light-emitting layer 105 formed by the second copolymer material can ensure that the whole light emitting device has higher light-emitting efficiency, thereby improving light-emitting and display brightness, and further improving display effect.
Fig. 3 is a graph showing the spectra corresponding to the first copolymer material and the second copolymer material in the light emitting device provided by the embodiment of the invention, as shown in fig. 3, the second electrode 104 is Mg; ag, for example, the light generated by the organic functional layer 105 is blue light, the coupling light-emitting layer 105 is formed on the second electrode 104, and the coupling light-emitting layer 105 made of the second copolymer material formed by ultraviolet light irradiation significantly increases the light-emitting intensity of the whole light-emitting device, and improves the light-emitting efficiency of the light-emitting device by about 4%, so that the attenuation speed of the material in the coupling light-emitting layer 105 can be slowed down, the material in the coupling light-emitting layer 105 is prevented from being attenuated too fast, and the service life of the whole light-emitting device can be prolonged.
In some embodiments, the ratio of vinylcarbazole to 4-vinylbenzylthiocyanate is 8: 1.
It should be noted that, in practical applications, the ratio of Vinylcarbazole (VC) to 4-Vinylbenzylthiocyanate (VBT) is 8:1 when they are polymerized, which ensures that the first copolymer material with higher refractive index is formed by polymerization.
In some embodiments, the ultraviolet light has a wavelength in the range of 250 nanometers to 260 nanometers.
It is noted that the first copolymer material may undergo photoisomerization under the irradiation of ultraviolet light having a wavelength ranging from 250 nm to 260 nm. Preferably, in the above reaction formula, under the irradiation of ultraviolet light with a wavelength of 254 nm, the first copolymer material can undergo photo-isomerization and be converted into the second copolymer material. The refractive index of the second copolymer material is greater than that of the first copolymer material, so that the coupling light-emitting layer 105 made of the second copolymer material can ensure that the whole light-emitting device has higher light-emitting efficiency, thereby improving the light-emitting and display brightness and further improving the display effect. In addition, a higher refractive index can be maintained in the process of converting the first copolymer material into the second copolymer material, so that the attenuation speed of the material in the coupling light-emitting layer 105 can be reduced, the material in the coupling light-emitting layer 105 is prevented from being attenuated too fast, and the service life of the whole light-emitting device can be prolonged.
In some embodiments, the first electrode 102 comprises a reflective electrode; the second electrode 104 includes a translucent electrode.
It should be noted that, in the embodiment of the present invention, the light emitting device is a top emission type light emitting device, the first electrode 102 includes a reflective electrode, the second electrode 104 includes a translucent electrode, light generated by the organic functional layer 103 can be reflected by the first electrode 102, and then passes through the second electrode 104 and exits through the coupling light-emitting layer 105, and a material in the coupling light-emitting layer 105 has a higher refractive index, so that the light-emitting efficiency can be improved, and the light-emitting and display effects can be improved. It is understood that the light emitting device may also be a bottom emission type light emitting device, and the light generated by the organic functional layer 103 may be emitted from the first electrode 102, and in this case, the coupling light-emitting layer 105 should be located between the substrate 101 and the first electrode 102 to couple the emitted light, so as to improve the light-emitting efficiency. In practical applications, different types of light emitting devices can be selected according to actual needs, and the position of the coupling light-emitting layer 105 is reasonably set, so as to achieve higher light-emitting efficiency.
In some embodiments, the light emitting device further comprises: a protective layer 106; the protective layer 106 is located between the second electrode 104 and the coupling-out layer 105.
It should be noted that, in the embodiment of the present invention, the protection layer 106 may protect the second electrode 104, and prevent the coupling light-emitting layer 105 from damaging the second electrode 104 during the preparation process. Meanwhile, the protection layer 106 may also protect the coupling light-emitting layer 105 from being damaged by the second electrode 104 during the preparation process. The material of the protective layer 106 may be the same as the material of the coupling light-emitting layer in the related art, which not only can play a role in protection, but also can improve the light-emitting efficiency of the whole light-emitting device, thereby improving the light-emitting and display functions.
Example two
Embodiments of the present invention provide a display apparatus including a plurality of light emitting devices as provided in the above embodiments. The display device can be a mobile phone, a tablet personal computer, a smart television and other terminal equipment, and particularly is a vehicle-mounted display device which is often exposed in high-temperature high-humidity and ultraviolet irradiation environments. Specifically, the display device may be a vehicle-mounted central control unit or a vehicle-mounted navigator. It should be noted that the display device provided in the embodiment of the present invention may further include other devices and structures such as a switching transistor, a driving transistor, a data line, a scan line, and the like, besides the light emitting device provided in the above embodiment, and the operation principle and the manufacturing method thereof are consistent with those of the related art. It is understood that the implementation principle of the display device provided by the embodiment of the present invention is the same as that of the light emitting device provided by the above embodiment, and is not described herein again.
EXAMPLE III
Fig. 4 is a schematic flow chart of a method for manufacturing a light emitting device according to an embodiment of the present invention, and as shown in fig. 4, the method for manufacturing the light emitting device includes the following steps:
s401, forming a first electrode, an organic functional layer and a second electrode on a substrate in sequence.
It should be noted that the first electrode may be an anode of the light emitting device, the anode may be made of ITO (indium tin oxide), Indium Zinc Oxide (IZO), zinc oxide (ZnO), or the like, the anode may be made of one metal material of aluminum (Al), magnesium (Mg), and silver (Ag), or a mixture of aluminum (Al), magnesium (Mg), and silver (Ag), and it is understood that the anode may have a single-layer structure or a multi-layer structure, for example, a multi-layer structure of ITO (indium tin oxide)/silver (Ag)/ITO (indium tin oxide). An organic functional layer is formed on the first electrode, and the organic functional layer may include a small molecule organic material or a polymer molecule organic material, may be a fluorescent light emitting material or a phosphorescent light emitting material, may emit red light, green light, blue light, or may emit white light, etc. In addition, according to different actual needs, in different examples, the organic functional layer may further include functional layers such as a hole injection layer, a hole transport layer, an organic light emitting layer, an electron transport layer, and an electron injection layer. The second electrode is covered with an organic functional layer, and the polarity of the second electrode is opposite to that of the first electrode; the second electrode can be a cathode made of a metal material such as lithium (Li), aluminum (Al), magnesium (Mg), silver (Ag), etc.
S402, forming a first copolymer material by using a plurality of organic materials; the first copolymer material undergoes photoisomerization under the irradiation of ultraviolet light to form a second copolymer material; the second copolymer material has a refractive index greater than the refractive index of the first copolymer material.
It should be noted that the first copolymer material has a higher refractive index, so that the light-coupling layer formed by the first copolymer material can improve the light-emitting efficiency of the whole light-emitting device, and thus can improve the light emission and display brightness. After a period of time and ultraviolet irradiation, the refractive index attenuation of the first copolymer material can influence the light-emitting efficiency of the whole light-emitting device, at the moment, the first copolymer material is subjected to photoisomerization after the ultraviolet irradiation, the first copolymer material with the attenuated refractive index is converted into the second copolymer material, the second copolymer material has a higher refractive index, and is greater than the refractive index of the first copolymer material, the coupling light-emitting layer formed by the second copolymer material can ensure that the whole light-emitting device has higher light-emitting efficiency, thereby the light-emitting and display brightness can be improved, and the display effect can be improved. And the higher refractive index can be kept in the process of converting the first copolymer material into the second copolymer material, so that the attenuation speed of the material in the light coupling-out layer can be reduced, the material in the light coupling-out layer is prevented from being attenuated too fast, and the service life of the whole light-emitting device can be prolonged.
And S403, curing the first copolymer material on the second electrode by utilizing a spin coating or ink-jet printing process to form a coupling light-emitting layer.
It should be noted that the first copolymer material may be dissolved in an organic solution, and a solution film forming manner, such as a spin coating or spray printing process, may be adopted to cure the first copolymer material on the second electrode, so as to form the coupling light-emitting layer.
In some embodiments, the step S402 specifically includes: toluene is used as a solvent, and vinyl carbazole and 4-vinylbenzylthiocyanate are used for reacting under the catalytic action of azobisisobutyronitrile at the reaction temperature of 70 ℃ to form a first copolymer material.
It should be noted that the first copolymer material (VC-co-VBT) can be formed by reacting Vinylcarbazole (VC) and 4-Vinylbenzylthiocyanate (VBT) at a certain ratio under certain conditions. Under Ultraviolet (UV) radiation, thiocyanate (-SCN) groups in the first copolymer material may be photoisomerized to isothiocyanate (-NCS) groups, forming a second copolymer material. The second copolymer material has a higher refractive index and is larger than the refractive index of the first copolymer material, so that the coupling light-emitting layer formed by the second copolymer material can ensure that the whole light-emitting device has higher light-emitting efficiency, thereby improving the light-emitting and display brightness and further improving the display effect.
It should be noted that the first polymer material may be formed by polymerization of the above two organic materials, and certainly, may be formed by reaction of other multiple organic materials, as long as the first polymer material has a higher refractive index, and can undergo photoisomerization after being irradiated by ultraviolet light to form a second polymer material having a higher refractive index. Similarly, besides the spin coating or spray coating process, other processes may be used to form the coupling light-emitting layer, and the specific processes may be selected according to the properties of the material, which are not listed here.
It will be understood that the above embodiments are merely exemplary embodiments taken to illustrate the principles of the present invention, which is not limited thereto. It will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit and substance of the invention, and these modifications and improvements are also considered to be within the scope of the invention.
Claims (10)
1. A light emitting device comprising: the organic light-emitting diode comprises a substrate, and a first electrode, an organic functional layer and a second electrode which are sequentially arranged on the substrate; it is characterized by also comprising: a coupling light-emitting layer positioned on one side of the second electrode far away from the organic functional layer;
the coupling light-out layer is composed of a first copolymer material; the first copolymer material undergoes photoisomerization under the irradiation of ultraviolet light to form a second copolymer material; the second copolymer material has a refractive index greater than the refractive index of the first copolymer material.
2. The light-emitting device of claim 1, wherein the first copolymer material is polymerized from vinylcarbazole and 4-vinylbenzylthiocyanate.
3. The light-emitting device of claim 2, wherein the ratio of vinylcarbazole to 4-vinylbenzylthiocyanate is 8: 1.
4. The light emitting device of claim 1, wherein the ultraviolet light has a wavelength in a range of 250 nm to 260 nm.
5. The light-emitting device according to claim 1, wherein the first electrode comprises a reflective electrode; the second electrode includes a translucent electrode.
6. The light-emitting device according to claim 1, further comprising: a protective layer;
the protective layer is located between the second electrode and the coupling light-out layer.
7. A display device comprising a plurality of light-emitting devices according to any one of claims 1 to 6.
8. The display device according to claim 7, wherein the display device comprises an in-vehicle central control unit or an in-vehicle navigator.
9. A method of making a light emitting device, comprising:
sequentially forming a first electrode, an organic functional layer and a second electrode on a substrate;
forming a first copolymer material using a plurality of organic materials; the first copolymer material undergoes photoisomerization under the irradiation of ultraviolet light to form a second copolymer material; the second copolymer material has a refractive index greater than the refractive index of the first copolymer material;
curing the first copolymer material on the second electrode using a spin-on or ink-jet printing process to form a coupled light-out layer.
10. The method of claim 9, wherein the forming the first copolymer material from a plurality of organic materials comprises:
toluene is used as a solvent, and vinyl carbazole and 4-vinylbenzylthiocyanate are used for reacting under the catalytic action of azobisisobutyronitrile at the reaction temperature of 70 ℃ to form the first copolymer material.
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