WO2015096336A1 - 一种显示面板及显示装置 - Google Patents
一种显示面板及显示装置 Download PDFInfo
- Publication number
- WO2015096336A1 WO2015096336A1 PCT/CN2014/076434 CN2014076434W WO2015096336A1 WO 2015096336 A1 WO2015096336 A1 WO 2015096336A1 CN 2014076434 W CN2014076434 W CN 2014076434W WO 2015096336 A1 WO2015096336 A1 WO 2015096336A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- light
- display panel
- layer
- emitting diode
- transport layer
- Prior art date
Links
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- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
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- 150000007978 oxazole derivatives Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229960003540 oxyquinoline Drugs 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
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- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- DLJHXMRDIWMMGO-UHFFFAOYSA-N quinolin-8-ol;zinc Chemical compound [Zn].C1=CN=C2C(O)=CC=CC2=C1.C1=CN=C2C(O)=CC=CC2=C1 DLJHXMRDIWMMGO-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/04—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction
- H01L33/06—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction within the light emitting region, e.g. quantum confinement structure or tunnel barrier
-
- 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
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
-
- 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
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/125—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light
-
- 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
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
-
- 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
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
-
- 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
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection layers
- H10K50/171—Electron injection layers
-
- 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
- H10K59/30—Devices specially adapted for multicolour light emission
- H10K59/35—Devices specially adapted for multicolour light emission comprising red-green-blue [RGB] subpixels
-
- 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
- H10K59/30—Devices specially adapted for multicolour light emission
- H10K59/38—Devices specially adapted for multicolour light emission comprising colour filters or colour changing media [CCM]
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/301—Details of OLEDs
- H10K2102/331—Nanoparticles used in non-emissive layers, e.g. in packaging layer
Definitions
- the present invention belongs to the field of display technologies, and in particular, to a display panel and a display device. Background technique
- OLED Organic Light-Emective Diode
- the 0LED comprises at least an anode, a light-emitting layer and a cathode, and the light-emitting layer is generally formed of an organic material.
- a feasible method of color-to-color conversion and blue-light illumination to achieve full-color display is to use an inorganic doping system material that can be excited by blue light, for example:
- Quantum Dot is usually a kind of nano-scale luminescent particle that emits visible fluorescence after absorbing a certain energy. It can be precisely controlled by changing the chemical composition of quantum dots or by adjusting the size of quantum dots. Light of different wavelengths is obtained, thereby obtaining visible light of different colors; compared with the conventional light color conversion material, the fluorescence intensity and stability of the quantum dot are good, and the luminous efficiency is high and the half-peak width of the emission spectrum is narrow, and the color purity is high. A good light color conversion material.
- the organic light emitting diode 20 includes a first electrode 21, a second electrode 25, and an electron transport layer 22 disposed between the first electrode 21 and the second electrode 25, and a light emitting layer.
- 23 blue OLED or ultraviolet OLED
- hole transport layer 24 quantum dots are added to the periphery of the organic light emitting diode 20 Layer 26, quantum dot layer 26, is located above second electrode 25.
- a plurality of quantum dot units 280 are evenly distributed inside the quantum dot layer 26; the red sub-pixel unit and the green sub-pixel unit are respectively red light quantum dots and green light quantum dots; and the color filter 27 (Color Fi l ter ) is used. The color purity is improved by filtering blue or ultraviolet light emitted through the quantum dot layer 26.
- the organic light emitting diode shown in FIG. 1 corresponds to the quantum dot layer 26, and two sets (corresponding to blue light OLED) or three sets (corresponding to ultraviolet light OLED) mask are additionally introduced; In terms of increasing costs, on the other hand, the preparation process is complicated. Summary of the invention
- the technical problem to be solved by the present invention is to provide a display panel and a display device, which are simple in structure, can simplify the corresponding preparation process, and can effectively improve the color purity of the display panel. Improve the carrier migration ability.
- the technical solution adopted to solve the above technical problem is a display panel including a driving substrate and an organic light emitting diode disposed on the driving substrate, the organic light emitting diode including a first electrode and a second electrode, and further including An electron transport layer, a light emitting layer, and a hole transport layer disposed between the first electrode and the second electrode, wherein the electron transport layer, the light emitting layer, or the hole transport layer are hooked There are multiple light color conversion units distributed.
- the light color conversion unit includes a core and a casing (shel l ) coated on the outside of the core, the core includes a quantum dot, and the casing includes a layer formed of an organic substance. Structure, or a laminate structure formed of organic matter and inorganic matter.
- the quantum dots comprise Id-VI CdS, CdSe, CdTe, Zn0, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, and III-V GaAs, GaP, GaSb, InAs, InP , InSb, AlAs, A1P, and AlSb; the organic substance includes mercaptoethanol, and the inorganic substance includes CdS or ZnS.
- the quantum dots comprise red quantum dots, green quantum dots, and blue The quantum dot, the red quantum dot as a core particle size range of 5. 0-5. 5nm, the green quantum dot as the core particle size range of 3. 0-3. 5nm, the blue quantum dot as 5 ⁇ The core particle size range of 2. 0-2. 5nm.
- the electron transporting layer employs a metal complex having a higher electron transporting ability than a hole transporting ability, a carbazole derivative, an imidazole derivative, a pheniramine derivative or a hydrazine derivative;
- the layer is doped with a luminescent material by a matrix material;
- the hole transport layer is an aromatic diamine compound, a triphenylamine compound, an aromatic triamine compound, or a biphenyldiamine derivative having a hole transporting ability stronger than an electron transporting ability.
- a triarylamine polymer is an aromatic diamine compound, a triphenylamine compound, an aromatic triamine compound, or a biphenyldiamine derivative having a hole transporting ability stronger than an electron transporting ability. Or a triarylamine polymer.
- the matrix material in the light-emitting layer is a metal complex having electron transporting ability, a carbazole derivative, an imidazole derivative, a phenanthroline derivative or a derivative of hydrazine, or An aromatic diamine compound, a triphenylamine compound, an aromatic triamine compound, a biphenyldiamine derivative or a triarylamine polymer having a hole transporting ability;
- the luminescent material is Alq (8-hydroxyquinoline aluminum), BAlq (bis(2-indolyl-8-hydroxyquinoline-N1, 08)-biphenyl- 4-hydroxy)aluminum) or
- DPVBi 4, 4'-bis(2,2-distyryl)-1,-biphenyl
- PPV polyparaphenylene vinylene
- the driving substrate is divided into a plurality of sub-pixel regions, each of the sub-pixel regions is provided with the organic light emitting diode, and an electronic control component is further disposed in the sub-pixel region, and the electronic control component is further disposed. And electrically connecting to the first electrode or the second electrode of the organic light emitting diode, wherein the electronic control component is configured to control whether the organic light emitting diode emits light or not.
- the driving substrate is divided into a plurality of sub-pixel regions, the sub-pixel region further includes a color filter, the color filter is disposed on a light emitting side of the organic light emitting diode, and the color filter is The sheet selectively transmits light emitted by the organic light emitting diode out of the display panel.
- the electron transport layer, the light-emitting layer or the hole transport layer of the organic light-emitting diode including the light color conversion unit is thermally evaporated. , formed by spin coating or inkjet printing.
- the color filter comprises a red filter, a green filter and a blue color a color filter, the light emitted by the light emitting layer or the light converted by the light color conversion unit passes through the color matching red color filter, the green color filter, and the blue A color filter is exposed through the display panel.
- the present invention also provides a display device comprising the above display panel.
- the invention has the following advantages: In the display panel of the present invention, the structure of any one of the three layers of the hole transport layer, the light-emitting layer and the electron transport layer which directly dope the light-color conversion unit into the organic light-emitting diode is used. , simplifies the structure of the display panel and the corresponding preparation process, and can effectively improve the color purity and effectively improve the carrier migration ability. DRAWINGS
- FIG. 1 is a schematic structural view of an organic light emitting diode in the prior art
- FIG. 2 is a schematic structural view of a display panel according to Embodiment 1 of the present invention.
- FIG. 2 is a schematic structural view of an organic light emitting diode according to Embodiment 1 of the present invention
- FIG. 3 is a schematic structural view of a light color conversion unit of the organic light emitting diode of FIG.
- FIG. 4 is a schematic structural view of a light color conversion unit in the organic light emitting diode of FIG. 2;
- FIG. 5 is a schematic structural view of an organic light emitting diode according to Embodiment 2 of the present invention
- FIG. 6 is a schematic structural view of an organic light emitting diode according to Embodiment 3 of the present invention.
- 10-drive substrate 11-electronic control element; 20, 201, 202, 203-organic light-emitting diode; 21-first electrode; 22, IV-electron transport layer; 23, 23'-light-emitting layer; 24, 24' - Hole transport layer; 25-second electrode; 26-quantum dot layer; 27-color filter; 28-light color conversion unit; 280-quantum dot; 281-inorganic layer; 282-organic layer.
- An embodiment of the present invention provides a display panel including a driving substrate and an organic light emitting diode disposed on the driving substrate, the organic light emitting diode including a first electrode and a second electrode, and further comprising An electron transport layer, a light-emitting layer, and a hole transport layer between the first electrode and the second electrode, wherein the electron transport layer, the light-emitting layer, or the hole transport layer are uniformly distributed Light color conversion unit.
- the light emitted by the luminescent layer is blue light, and in order to ensure that each sub-pixel unit can emit corresponding red light and green light, red quantum dots and green quantum dots are usually disposed in each sub-pixel unit simultaneously; It is ensured that the red light and the green light emission state of each sub-pixel unit are the same, and preferably, the plurality of light color conversion units are hook-distributed in any of the electron transport layer, the light-emitting layer or the hole transport layer.
- Another embodiment of the present invention provides a display device including the above display panel.
- Example 1
- the present embodiment provides a display panel.
- the display panel includes a driving substrate 10 and an organic light emitting diode 201 disposed on the driving substrate 10.
- the organic light emitting diode 201 includes a first electrode 21 and a second electrode 25. Also included is an electron transport layer 22, a light-emitting layer 23, and a hole transport layer 24' disposed between the first electrode 21 and the second electrode 25.
- a plurality of light color conversion units 28 are branched in the hole transport layer 24'.
- the driving substrate 10 is divided into a plurality of sub-pixel regions (each sub-pixel region correspondingly forms one sub-pixel unit), and each of the sub-pixel regions is provided with an organic light emitting diode 201, and the sub-pixel region is further provided with
- the electronic control unit 11 is electrically connected to the first electrode 21 or the second electrode 25 of the organic light emitting diode 201.
- the electronic control unit 11 is used to control whether the organic light emitting diode 201 emits light or not.
- the electronic control element 11 is a thin film transistor (Thin Fi lm Transistor: abbreviated as TFT), the TFT for driving the organic light emitting diode 201 in this embodiment may be an a-Si TFT, an oxide TFT, an LTPS-TFT (low temperature polysilicon), and an HTPS-TFT (high temperature polysilicon).
- the driving mode of the OLED 201 can be a Passive Matrix Organic Light Emission Display (PMOLED) driving method and an active matrix (Active).
- PMOLED Passive Matrix Organic Light Emission Display
- AMOLED Matrix Organic Light Emission Display
- the light color conversion unit 28 includes a core and a casing that is wrapped around the outside of the core, that is, the light color conversion unit 28 is a core/shell structure.
- the core includes a quantum dot 280
- the outer casing includes an organic layer 282 structure formed of an organic substance, or a laminated structure of an organic substance layer 282 and an inorganic substance layer 281 formed of an organic substance and an inorganic substance.
- the doped particles i.e., the unmodified photochromic conversion unit 28
- the intrinsic material i.e., the host material used to form the hole transport layer 24'
- the interface between the particles and the intrinsic material is quenched, which will result in a decrease in the properties of the intrinsic material; in this embodiment, in order to ensure the smooth transport of the carriers, the doped particles are surface-modified to form the core shell. structure.
- the shell thickness is on the order of nanometers, i.e., less than 1 micron.
- the quantum dot is usually a kind of nano-scale luminescent particle, which can emit visible fluorescence after absorbing a certain energy, and the luminescence spectrum can be controlled by changing the size of the quantum dot, and the fluorescence intensity and stability are good. At the same time, the efficiency is high, and the half-peak width of the emission spectrum is narrow. It is only necessary to accurately control the excitation of different wavelengths of light by changing the chemical composition of the quantum dots or by adjusting the size of the quantum dots, thereby obtaining visible light of different colors. Light color conversion material. There are many types of quantum dots.
- the quantum dots include CdS, CdSe, CdTe, Zn0, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, and III-V GaAs of the ⁇ -VI family.
- Organic substances that can be used in the outer shell to surface-modify quantum dots include mercaptoethanol, and inorganic substances include CdS or ZnS.
- quantum dots can include red quantum dots, green quantum dots, and blue quantum dots, and red quantum dots as the core have a particle size range of 5-2. 5nm ⁇ 5 nm, 5 nm, the green quantum dot as the core of the particle size range of 3. 0-3. 5nm, the blue quantum dot as the core particle size range of 2. 0-2. 5nm.
- the red quantum dot emitting red light has a particle diameter of 5 nm
- the green light emitting green dot has a particle diameter of 3 nm.
- the advantage of using the light color conversion unit 28 is that even if the same quantum dot is used, by adjusting the size of the quantum dot in the light color conversion unit 28, the purpose of accurately controlling the light emission wavelength can be achieved, thereby obtaining visible light of different colors.
- the display panel can adopt three primary colors of R (red), G (green), and B (blue), so that a light color conversion unit with a red light quantum dot as a core and a green light quantum dot are disposed in the organic light emitting diode. It can be used as a light color conversion unit of the core.
- quantum dots as the core may also include yellow quantum dots, orange quantum dots, or cyan quantum dots, depending on the display application.
- quantum dots according to the luminescent properties of quantum dots, such as: half-width of luminescence spectrum, luminescence peak and luminescence wavelength, etc., by adjusting the ratio of quantum dots of different materials, or adjusting the ratio of quantum dots of different sizes To get different colors of light.
- the quantum dot luminescence spectrum has a narrower half-width, and the higher the color purity, the better the color display effect; by adjusting the distribution ratio of the light color conversion unit, the amplitude of the emitted light can be changed.
- the base shield material of the hole transport layer 24' is usually an organic material, and an aromatic amine fluorescent compound is more commonly used.
- the base shield material of the hole transport layer 24' is derived from an aromatic diamine compound, a triphenylamine compound, an aromatic triamine compound, or a biphenyldiamine derivative having a hole transporting ability stronger than an electron transporting ability.
- a triarylamine polymer for example: NPB (N, ⁇ '-bis(naphthyl)-anthracene, ⁇ '-diphenylbenzidine), TPD ( ⁇ , ⁇ '-bis(3-nonylphenyl)- ⁇ , N'-diphenylbenzidine), TCTA (4, 4', 4"-tris(carbazol-9-yl)triphenylamine), TDATA (4, 4,, 4"-three (N, N -Diphenylamino]triphenylamine) and polyvinylcarbazole or a monomer thereof.
- NPB N, ⁇ '-bis(naphthyl)-anthracene, ⁇ '-diphenylbenzidine
- TPD ⁇ , ⁇ '-bis(3-nonylphenyl)- ⁇ , N'-diphenylbenzidine
- TCTA 4, 4', 4"-tris(carbazol-9-yl)tri
- the hole transporting ability is stronger than the electron transporting ability can be defined as the charge transporting ability when the mobility of holes is greater than the mobility of electrons, and can be measured according to a conventional method such as a time-of-flight method; Stronger than the ability to transport holes, it can be similarly pushed.
- the manner of surface modification of the light color conversion unit in this embodiment includes: As shown in FIG. 3, the surface of the quantum dot 280 which can be used above is coated with an organic substance to form an organic layer 282, and the transport characteristics of the organic layer 282 and the carrier of the host material for forming the hole transport layer 24' are shown. (mainly hole carriers) transmission characteristics are close, for example: coating a surface of ZnS quantum dots with a layer of mercaptoethanol (ME), modified to form a light color conversion unit 28, can effectively improve carrier transport characteristics, improve luminous efficiency And light stability.
- ME mercaptoethanol
- quantum dots have a certain water solubility and can be coupled to organic molecules through reactive groups on the surface.
- a layer of the inorganic layer 281 is coated, and an organic layer 282 is modified on the surface thereof.
- the photochromic conversion unit can be combined with the macromolecular organic substance through the amide bond.
- the quantum dot 280 may be selected from CdSe
- the inorganic material may be selected from ZnS
- the organic material may be selected from thioglycolic acid.
- a surfactant or a polymer can also be used as the organic layer 282 for surface modification of quantum dots.
- styrene, acrylic acid, decyl methacrylate MMA, sodium dodecyl hydride SDS, azobisisobutyronitrile AIBN, thioglycolic acid, mercaptoethanol ME, divinylbenzene) DVB, etc. can also be used as the organic layer 282 for surface modification of quantum dots.
- the light color conversion unit formed by the above two methods, or the color light conversion unit formed by modifying the quantum dots forms a surface close to the carrier transport characteristic in the hole transport layer, so It can effectively improve carrier transport characteristics, improve luminous efficiency and light stability. More specifically, the reason is: Under normal circumstances, the hole transport layer is mostly formed by organic matter, and when the surface is modified by the surface of the quantum dots, the light color is made.
- the conversion unit can be more effectively combined with the organic material, and the carriers will be smoothly transported inside the organic light emitting diode 201, and the carrier migration will be correspondingly improved.
- the driving substrate 10 serves as an adhesion layer of the organic light emitting diode 201, has good light transmission performance in the visible light region, has a certain ability to penetrate water vapor and oxygen, has good surface flatness, and may be glass or flexible.
- the substrate or the TFT back sheet, wherein the flexible substrate may be made of one of a polyester type, a polyimide compound or a thin metal, and the transparent area corresponding to the display panel is set to be transparent.
- the anode serves as a connection layer of the forward voltage of the organic light emitting diode 201, and has a comparison Good electrical conductivity and high work function (High work funct ion).
- the anode is usually made of an inorganic metal oxide (for example, a high work function of 4. 5 eV to 5.
- a stable and transparent indium tin oxide, IT0, zinc oxide, etc. or an organic conductive polymer (such as PED0T (poly( 3, 4 - ethylenedioxy-thiophene)): the PSS (poly (4 - styrenesulfonate)), ⁇ (polyaniline), etc.) or a metallic material of high work function value (for example: gold, copper, silver, , platinum, etc.).
- PED0T poly( 3, 4 - ethylenedioxy-thiophene)
- PSS poly (4 - styrenesulfonate
- ⁇ polyaniline
- a metallic material of high work function value for example: gold, copper, silver, , platinum, etc.
- the cathode serves as a connection layer for the negative voltage of the organic light emitting diode 201, and has better electrical conductivity and a lower work function (Low work funct ion).
- the cathode is usually made of a metal material having a low work function value, such as lithium Li, magnesium Mg, calcium Ca, strontium Sr, aluminum Al, indium In, etc., or copper.
- the first electrode 21 is generally a cathode, and may be a metal layer.
- the metal layer may be translucent or opaque according to the light-emitting direction of the organic light-emitting diode;
- the second electrode 25 is generally an anode, and is transparent.
- the IT0 material is formed such that the cathode is above the drive substrate 10 and the anode is above the cathode. In this embodiment, FIG.
- the second electrode 25 is a light emitting side of the organic light emitting diode 201, and since light emitted from the light emitting layer is emitted from a side of the second electrode 25,
- the second electrode 25 is generally a transparent conductive material capable of transmitting light, such as a transparent IOK film, and the first electrode 21 is an opaque metal capable of reflecting light.
- the first electrode 21 may be an anode and the second electrode 25 may be a cathode, which are not limited in the present invention.
- the arrangement of the materials of the first electrode 21 and the second electrode 25 in the bottom emission type organic light emitting diode 201 is opposite to that of Fig. 2A.
- the sub-pixel region further includes a color filter 27 disposed on the light-emitting side of the organic light-emitting diode 201, and the color filter 27 selectively illuminates the light emitted from the organic light-emitting diode 201.
- the display panel is displayed.
- the color filter 27 includes a red filter, a green filter, and a blue filter.
- the light emitted by the light-emitting layer 23 in the organic light-emitting diode 201 or the light converted by the light-color conversion unit 28 is color-compatible. Red filter, green filter and blue The color filter is exposed through the display panel.
- the light color conversion unit 28 in the hole transport layer 24' is distributed over a pixel area constituting a full color color, and the pixel area of the full color color includes a plurality of sub-pixel areas having different colors.
- FIG. 2B uses only one sub-pixel region as an example.
- a sub-pixel region that emits green light is taken as an example, and a structure of a sub-pixel region that emits red light and a sub-pixel region that emits blue light can be analogously inferred.
- the green sub-pixel region, the red sub-pixel region, and the blue sub-pixel region form one pixel region.
- one or more pixels may be used to form one pixel region, which is not limited herein.
- the color gamut of the display panel can be improved relative to the pixel region formed by the green sub-pixel region, the red sub-pixel region, and the blue sub-pixel region, and the light transmission of the display panel is improved. Rate, enhance color saturation, and improve the display quality of the display panel.
- the intensity of the light emitted by each of the organic light emitting diodes 201 can be independently controlled, thereby independently adjusting the R, G, and B light effects.
- the electron transport layer, the light emitting layer and the light color conversion unit in the organic light emitting diode are included in the plurality of sub-pixel regions.
- the hole transport layer is formed by three layers of thermal evaporation (therma l evaporat ion), respectively, without using a patterning process, and it is not necessary to use different processes to complete the holes corresponding to different color regions doped with the light color conversion unit. Transport layer.
- the material of the pre-formed light color conversion unit 28 and the intrinsic material for forming the hole transport layer are respectively placed in the vacuum reaction chamber, and the evaporation process is adopted.
- the evaporation process is adopted.
- Formed above the light-emitting layer 23 shown in FIG. 2B that is, a plurality of sub-pixel regions corresponding to the red sub-pixel region, a plurality of sub-pixel regions corresponding to the green sub-pixel region, and a hole transport layer corresponding to the blue sub-pixel region It is formed by one evaporation process, and it is not necessary to form pixel regions of three colors separately in three patterning processes, thereby effectively simplifying the preparation process of the display panel and saving the mask.
- the pre-fabricated light color conversion unit 28 is uniformly distributed in a solution for forming a hole transport layer, and then spin-coating is used in FIG. 2B. A coating film is formed on the luminescent layer 23.
- the hole transport layer including the light color conversion unit can be formed by using the above-described thermal evaporation method (for small molecule OLED) and by spin coating (for macromolecular OLED).
- the inkjet printing method (inkje t ) forms a corresponding OLED film layer.
- the principle of illumination of the display panel is: when a voltage is applied between the anode and the cathode, the hole injected by the anode enters the light through the hole transport layer 24' under the driving of the voltage.
- the layer 23 electrons injected from the cathode enter the luminescent layer 23 through the electron transport layer 22, and holes and electrons entering the luminescent layer 23 are combined to form excitons in the recombination region, and the exciton radiation illuminates to emit luminescence, that is, Blue light is formed; since the light color conversion unit 28 is doped into the hole transport layer 24', the blue light emitted by the light emitting layer 23 is irradiated onto the red light quantum dots and the green light quantum dots in the hole transport layer 24', and the stimulated emission is red. Light and green light, the red and green light emitted by the excitation and the blue light not acting on the light color conversion unit are mixed together, and the full color display is realized after the color filter 27.
- the above organic light emitting diode may further include other layers such as one or more of an electron blocking layer, a hole and exciton blocking layer, an electron injecting layer or a hole injecting layer.
- Example 2
- the embodiment provides a display panel.
- the display panel includes a driving substrate (not shown in FIG. 5) and an organic light emitting diode 202 disposed on the driving substrate.
- the organic light emitting diode 202 includes a first electrode 21
- the second electrode 25 further includes an electron transport layer 22, a light emitting layer 23', and a hole transport layer 24 disposed between the first electrode 21 and the second electrode 25.
- a plurality of light color conversion units 28 are uniformly distributed in the light-emitting layer 23', and the light-emitting layer 23' is excited to emit blue light (monochromatic light), and the blue light emits green light or red light to the illumination light color conversion unit 28. , through the color filter 27, to achieve full color.
- the light-emitting layer is formed of an organic substance having strong fluorescence in a solid state, good carrier transport performance, good thermal stability and chemical stability, and quantum efficiency. High and vacuum evaporation characteristics.
- the luminescent layer 23' is doped with a luminescent material using a base shield material.
- the matrix material in the light-emitting layer 23' may be a metal complex, an oxazole derivative, an imidazole derivative, a phenanthroline derivative or a hydrazine derivative having an electron transporting ability stronger than a hole transporting ability, or
- An aromatic diamine compound, a triphenylamine compound, an aromatic triamine compound, a biphenyldiamine derivative or a triarylamine polymer having a hole transporting ability stronger than an electron transporting ability can be used;
- a luminescent material a low molecular OLED Luminescent materials often use A lq as a green material, using BAlq (bis(2-mercapto-8-hydroxyquinoline-N1, 08)-(1,1'-biphenyl-4-hydroxy)aluminum) and DPVB i (4, 4'-bis(2,2-distyryl)-1,1'-biphenyl) is a blue light material, and PPV and its derivatives are often used in high mole
- the surface modification of the doped particles may be carried out by referring to Embodiment 1, that is, the organic layer structure formed by modifying the organic substance on the surface of the quantum dot, or the modification of the organic substance and the inorganic substance on the surface of the quantum dot.
- the laminated structure of the formed organic layer and the inorganic layer enhances carrier transport characteristics, improves luminous efficiency, and photostability.
- the blue light emitted by the light-emitting layer 23' of the organic light-emitting diode 202 is irradiated onto the red light quantum dots and the green light quantum dots in the light-emitting layer 23', and the red light and the green light are excitedly emitted, and the red light is excited.
- the light and green light and the blue light that is not applied to the light color conversion unit are subjected to full color display via the color filter 27.
- the above organic light emitting diode may further include other layers such as one or more of an electron blocking layer, a hole and exciton blocking layer, an electron injecting layer or a hole injecting layer.
- the above organic light emitting diode may alternatively include only the light emitting layer.
- Example 3 the structure of the other layers of the display panel and the corresponding preparation method can be set by referring to Embodiment 1, and details are not described herein again.
- Example 3 the structure of the other layers of the display panel and the corresponding preparation method can be set by referring to Embodiment 1, and details are not described herein again.
- the embodiment provides a display panel.
- the display panel includes a driving substrate (not shown in FIG. 6 ) and an organic light emitting diode 203 disposed on the driving substrate.
- the organic light emitting diode 203 includes a first electrode 21 .
- the second electrode 25 Also included is an electron transport layer 22', a light-emitting layer 23, and a hole transport layer 24 disposed between the first electrode 21 and the second electrode 25.
- a plurality of light color conversion units 28 are evenly distributed in the electron transport layer 22'.
- the electron transport layer and the hole transport layer in the organic light emitting diode use different organic materials.
- the materials most commonly used to fabricate electron transport layers are generally characterized by high film stability, thermal stability, and good electron transport properties.
- the electron transport layer 22' uses electron transport capability better than hole transport.
- fluorescent dye compounds such as: Alq (8-hydroxyquinoline aluminum), Znq ( 8-hydroxyquinoline zinc), Gaq (8-hydroxyquinoline gallium), Bebq (bis(10-hydroxybenzo[H]quinoline) ⁇ ), BA lq (bis(2-mercapto- 8-hydroxyquinoline) Porphyrin- ⁇ 1, 08) - ( ⁇ , -biphenyl-4-hydroxy)aluminum), DPVBi (4,4'-bis(2,2-distyryl)-1,1'-biphenyl), ZnSPB , PBD (2-(4-diphenyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole), OXD (derivative of 1,3,4-oxadiazole) , BB0T (di-benzoxazolylthiophene)
- the surface modification of the doped particles may be carried out by referring to Embodiment 1, that is, the organic layer structure formed by modifying the organic substance on the surface of the quantum dot, or the modification of the organic substance and the inorganic substance on the surface of the quantum dot.
- the laminated structure of the formed organic layer and the inorganic layer enhances carrier transport characteristics, improves luminous efficiency, and photostability.
- the electron transport layer 22' is located between the light-emitting layer 23 and the first electrode 21, and the first electrode 21 is formed of an opaque metal to emit the light-emitting layer 23 and convert the light color in the electron transport layer 22'.
- the light converted by unit 28 is emitted to improve light utilization.
- the blue light emitted by the light-emitting layer 23 of the organic light-emitting diode 203 is irradiated onto the red light quantum dots and the green light quantum dots in the electron transport layer 22', and the red light and the green light are excitedly emitted, and the red light is excited.
- the light and green light and the blue light that is not applied to the light color conversion unit are reflected upward through the opaque metal of the first electrode 21, and the full color display is realized by the color filter 27.
- the above organic light emitting diode may further include other layers, for example: One or more of the sub-barrier layer, the hole and exciton blocking layer, the electron injecting layer or the hole injecting layer.
- the structure of the other layers of the display panel and the corresponding preparation method can be set by referring to Embodiment 1, and details are not described herein again.
- the materials of the electron transport layer 22 and the electron transport layer 22' are the same except that the electron transport layer 22' is doped with the light color conversion unit; except that the light emitting layer 23' is doped with
- the light-emitting layer 23 and the light-emitting layer 23' are made of the same material except for the light-color conversion unit; the hole transport layer 24' and the hole transport layer 24 are provided except that the hole-transport layer 24' is doped with a light-color conversion unit.
- the materials are the same.
- a display device comprising any of the display panels of Embodiments 1-3.
- the display device can be: any product or component having display function such as electronic paper, mobile phone, tablet computer, television, display, notebook computer, digital photo frame, navigator, and the like.
- the organic light emitting diodes of Embodiments 1-3 are not only applicable to the top of Embodiments 1-3 by providing the structure of the light color conversion unit in any one of the electron transporting layer, the light emitting layer and the hole transporting layer.
- the emitter type organic light emitting diode is also suitable for the bottom emission type organic light emitting diode.
- the structure of any one of the three layers of the hole transport layer, the light emitting layer and the electron transport layer which directly dope the light color conversion unit into the organic light emitting diode is used, which simplifies the structure and corresponding of the display panel.
- the quantum dots forming the light color conversion unit are surface-modified, which can effectively enhance the carrier mobility; and, because the quantum dots have high luminous efficiency and a narrow spectrum of emitted light, the color purity of the corresponding sub-pixel region can be improved, and further The color purity of the combined pixel regions is improved, and the color purity is better than other light conversion materials, and the color purity of the display panel is correspondingly improved.
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- Electroluminescent Light Sources (AREA)
Abstract
一种显示面板及显示装置。该显示面板包括驱动基板(10)以及设置于该驱动基板(10)上的有机发光二极管(201),该有机发光二极管(201)包括第一电极(21)和第二电极(25),还包括设置于该第一电极(21)和该第二电极(25)之间的电子传输层(22)、发光层(23)和空穴传输层(24'),该电子传输层(22)、该发光层(23)或该空穴传输层(24')中均匀分布有多个光色转换单元(28)。采用将光色转换单元(28)直接掺杂到有机发光二极管(201)中的空穴传输层(24')、发光层(23)、电子传输层(22)这三层中的任意一层的结构,简化了显示面板的结构和相应的制备工艺流程,并能有效提高显示面板的色纯度、有效提升载流子迀移能力。
Description
一种显示面板及显示装置 技术领域
本发明属于显示技术领域, 具体涉及一种显示面板及显示装 置。 背景技术
OLED ( Organic Light-Emi t t ing Diode, 有机发光二极管) 由于具备轻薄、 宽视角、 响应速度快、 高对比度等优点, 近年来 越来越多地被应用于平板显示装置中。
随着显示技术的发展, 目前出现了采用光色转换 ( Color Convers ion )材料配合蓝光发光实现 0LED显示装置全彩显示的方 式。 其中, 0LED至少包括阳极、 发光层和阴极, 发光层一般采用 有机材料形成。 一种可行的光色转换与蓝光发光配合实现全彩显 示的方式是, 采用能被蓝光激发的无机掺杂体系材料, 例如: 掺
Ce钇铝石榴石、掺 Eu碱土金属硅酸盐、稀土离子掺杂的硅基氮化 物或氮氧化物, 但是, 这些光色转换材料通常存在色纯度低及效 率低的问题。
随着材料技术的发展, 目前有人提出了采用量子点 (一种纳 米结构)作为光色转换材料的观点。 量子点 ( Quantum Dot )通常 是一种纳米级的发光颗粒, 在吸收一定能量受激后可以发射可见 的荧光, 只需通过更换量子点的化学组成或通过调整量子点的尺 寸就能精确控制激发出不同波长的光线, 从而得到不同颜色的可 见光; 相对于传统光色转换材料, 量子点荧光强度和稳定性都很 好, 同时其发光效率高且发射光谱半峰宽窄, 色纯度高, 是一种 很好的光色转换材料。
图 1所示为一种有机发光二极管的结构示意图: 有机发光二 极管 20包括第一电极 21、第二电极 25及设置于第一电极 21和第 二电极 25之间的电子传输层 22、 发光层 23 (蓝光 0LED或紫外光 0LED )和空穴传输层 24; 有机发光二极管 20的外围添加有量子点
层 26 , 即量子点层 26位于第二电极 25上方。在量子点层 26内部 均匀分布有多个量子点单元 280;对应于红色子像素单元及绿色子 像素单元分别为红光量子点及绿光量子点; 彩色滤光片 27 ( Color Fi l ter ) , 用于过滤通过量子点层 26出射的蓝光或紫外光, 提高 色纯度。
可以发现, 图 1所示的有机发光二极管在制备过程中, 对应 量子点层 26 , 需额外引入两套(对应于蓝光 0LED )或三套(对应 于紫外光 0LED )掩模板 ( Mask ) ; 一方面增加成本, 另一方面, 制备工艺流程复杂。 发明内容
本发明所要解决的技术问题是针对现有技术中存在的上述不 足, 提供一种显示面板及显示装置, 该显示面板结构简单, 能简 化相应的制备工艺流程, 并能有效提高显示面板的色纯度、 有效 提升载流子迁移能力。
解决上述技术问题所采用的技术方案是这样的显示面板, 该 显示面板包括驱动基板以及设置于所述驱动基板上的有机发光二 极管, 所述有机发光二极管包括第一电极和第二电极, 还包括设 置于所述第一电极和所述第二电极之间的电子传输层、 发光层和 空穴传输层, 其中, 所述电子传输层、 所述发光层或所述空穴传 输层中均勾分布有多个光色转换单元。
优选的是, 所述光色转换单元包括内核 (core ) 以及包覆在 所述内核外部的外壳 (shel l ) , 所述内核包括量子点 (quantum dot ) , 所述外壳包括采用有机物形成的层结构, 或采用有机物与 无机物形成的叠层结构。
优选的是, 所述量子点包括 I I- VI族的 CdS、 CdSe、 CdTe、 Zn0、 ZnS、 ZnSe、 ZnTe、 HgS、 HgSe、 HgTe, 以及 I I I— V族的 GaAs、 GaP、 GaSb、 InAs、 InP、 InSb、 AlAs、 A1P和 AlSb; 所述有机物 包括巯基乙醇, 所述无机物包括 CdS或 ZnS。
优选的是, 所述量子点包括红色量子点、 绿色量子点和蓝色
量子点, 所述红色量子点作为内核的粒径范围为 5. 0-5. 5nm, 所述 绿色量子点作为内核的粒径范围为 3. 0-3. 5nm,所述蓝色量子点作 为内核的粒径范围为 2. 0-2. 5nm。
优选的是, 所述电子传输层采用电子传输能力强于空穴传输 能力的金属配合物、 咔唑类衍生物、 咪唑类衍生物、 邻菲罗林衍 生物或蒽的衍生物; 所述发光层采用基质材料掺杂发光材料; 所 述空穴传输层采用空穴传输能力强于电子传输能力的芳香族二胺 类化合物、 三苯胺化合物、 芳香族三胺类化合物、 联苯二胺衍生 物或三芳胺聚合物。
优选的是, 所述发光层中的基质材料采用具有电子传输能力 的金属配合物、 咔唑类衍生物、 咪唑类衍生物、 邻菲罗林衍生物 或蒽的衍生物, 或者, 采用具有空穴传输能力的芳香族二胺类化 合物、 三苯胺化合物、 芳香族三胺类化合物、 联苯二胺衍生物或 三芳胺聚合物; 所述发光材料采用 Alq ( 8-羟基喹啉铝) 、 BAlq (双(2-曱基- 8-羟基喹啉- N1, 08) - 联苯- 4-羟基)铝) 或
DPVBi ( 4, 4' - 二(2, 2-二苯乙烯基) - 1, -联苯) , 或者 PPV (聚对亚苯基亚乙烯基)及其衍生物。
优选的是, 所述驱动基板划分为多个子像素区域, 每一所述 子像素区域内均设置有所述有机发光二极管, 所述子像素区域内 还设置有电子控制元件, 所述电子控制元件与所述有机发光二极 管的第一电极或所述第二电极电连接, 所述电子控制元件用于对 所述有机发光二极管发光与否进行控制。
优选的是, 所述驱动基板划分为多个子像素区域, 所述子像 素区域内还包括彩色滤光片, 所述彩色滤光片设置于所述有机发 光二极管的出光侧, 所述彩色滤光片使所述有机发光二极管发出 的光线选择性地透出所述显示面板。
进一步优选的是, 多个所述子像素区域内, 包含有所述光色 转换单元的所述有机发光二极管的所述电子传输层、 所述发光层 或所述空穴传输层采用热蒸镀、 旋转涂布或喷墨打印方式形成。 优选的是, 所述彩色滤光片包括红色滤光片、 绿色滤光片和蓝色
滤光片, 所述有机发光二极管中所述发光层发出的光线或所述光 色转换单元转换的光线通过颜色相适配的所述红色滤光片、 所述 绿色滤光片和所述蓝色滤光片透出所述显示面板。
本发明还提供一种显示装置, 其包括上述的显示面板。
本发明的有益效果是: 本发明的显示面板中, 采用将光色转 换单元直接掺杂到有机发光二极管中的空穴传输层、 发光层、 电 子传输层这三层中的任意一层的结构, 简化了显示面板的结构和 相应的制备工艺流程, 并能有效提高色纯度、 有效改善载流子迁 移能力。 附图说明
图 1为现有技术中有机发光二极管的结构示意图;
图 2Α为本发明实施例 1中显示面板的结构示意图;
图 2Β为本发明实施例 1中有机发光二极管的结构示意图; 图 3为图 2Β中有机发光二极管中一种光色转换单元的结构示 意图;
图 4为图 2Β中有机发光二极管中一种光色转换单元的结构示 意图;
图 5为本发明实施例 2中有机发光二极管的结构示意图; 图 6为本发明实施例 3中有机发光二极管的结构示意图; 图中:
10-驱动基板; 11-电子控制元件; 20, 201 , 202 , 203-有机 发光二极管; 21-第一电极; 22 , IV -电子传输层; 23, 23' -发 光层; 24 , 24' -空穴传输层; 25-第二电极; 26-量子点层; 27- 彩色滤光片; 28-光色转换单元; 280-量子点; 281-无机物层; 282- 有机物层。
另外, 需要指出的是, 各图仅为示意图, 图中的尺寸并非是 按比例绘制的。 具体实施方式
为使本领域技术人员更好地理解本发明的技术方案, 下面结 合附图和具体实施方式对本发明显示面板及显示装置作进一步详 细描述。
本发明的一个实施方案提供了一种显示面板, 其包括驱动基 板以及设置于所述驱动基板上的有机发光二极管, 所述有机发光 二极管包括第一电极和第二电极, 还包括设置于所述第一电极和 所述第二电极之间的电子传输层、 发光层和空穴传输层, 其中, 所述电子传输层、 所述发光层或所述空穴传输层中均勾分布有多 个光色转换单元。 其中, 优选发光层发出的光为蓝光, 为确保每 一子像素单元均能发出相应的红光及绿光, 通常在每一子像素单 元中同时设置红色量子点及绿色量子点; 同时, 为了确保各子像 素单元红光及绿光发光状况相同, 优选多个光色转换单元在所述 电子传输层、 所述发光层或所述空穴传输层的任一层中均勾分布。
本发明的另一个实施方案提供了一种显示装置, 其包括上述 的显示面板。 实施例 1 :
本实施例提供一种显示面板, 如图 2A所示, 该显示面板包括 驱动基板 10以及设置于驱动基板 10上的有机发光二极管 201 ,有 机发光二极管 201包括第一电极 21和第二电极 25 ,还包括设置于 第一电极 21和第二电极 25之间的电子传输层 22、发光层 23和空 穴传输层 24' 。 在本实施例中, 空穴传输层 24' 中均勾分布有多 个光色转换单元 28。
在本实施例中, 驱动基板 10划分为多个子像素区域(每一子 像素区域对应形成一个子像素单元) , 每一子像素区域内均设置 有有机发光二极管 201 , 子像素区域内还设置有电子控制元件 11 , 电子控制元件 11与有机发光二极管 201的第一电极 21或第二电 极 25电连接, 电子控制元件 11用于对有机发光二极管 201发光 与否进行控制。
通常情况下, 电子控制元件 11 为薄膜晶体管 (Thin Fi lm
Transistor: 简称 TFT) , 在本实施例中驱动有机发光二极管 201 的 TFT可以为 a- Si TFT、 氧化物 TFT ( oxide TFT)、 LTPS-TFT (低 温多晶硅)及 HTPS- TFT (高温多晶硅) 。 对有机发光二极管 201 的驱动方式可以为无源矩阵 ( Passive Matrix Organic Light Emission Display, 简称 PMOLED )驱动方式和有源矩阵 (Active
Matrix Organic Light Emission Display, 简称 AMOLED )驱动方 式。
在本实施例中,光色转换单元 28包括内核以及包覆在内核外 部的外壳, 即光色转换单元 28为核壳(core/shell)结构。 其中, 内核包括量子点 280, 外壳包括采用有机物形成的有机物层 282 结构,或采用有机物与无机物形成的有机物层 282与无机物层 281 的叠层结构。 在通常情况下, 将掺杂粒子 (即未经修饰的光色转 换单元 28)直接引入本征材料(即用于形成空穴传输层 24' 的基 质材料) 中, 载流子会在掺杂粒子与本征材料的界面发生湮灭, 这将导致本征材料相关特性的降低; 在本实施例中, 为了保证载 流子顺利传输, 对掺杂粒子进行表面修饰, 从而形成所述的核壳 结构。 优选的是, 壳层厚度在纳米量级, 即小于 1微米。
其中, 量子点通常是一种纳米级的发光颗粒, 在吸收一定能 量受激后可以发射可见的荧光, 发光光谱可以通过改变量子点的 尺寸来控制, 且其荧光强度和稳定性都很好, 同时其效率高、 发 射光谱半峰宽窄, 只需通过更换量子点的化学组成或通过调整量 子点的尺寸就能精确控制激发出不同波长的光线, 从而得到不同 颜色的可见光, 是一种很好的光色转换材料。 量子点的种类很多, 优选的是,在本实施例中量子点包括 Π- VI族的 CdS、 CdSe、 CdTe、 Zn0、 ZnS、 ZnSe、 ZnTe、 HgS、 HgSe、 HgTe, 以及 III- V族的 GaAs、
GaP、 GaSb、 InAs、 InP、 InSb、 AlAs、 AlP和 AlSb等。 可用于外 壳以对量子点进行表面修饰的有机物包括巯基乙醇, 无机物包括 CdS或 ZnS。
当应用到显示技术领域时, 量子点可以包括红色量子点、 绿 色量子点和蓝色量子点, 红色量子点作为内核的粒径范围为
5. 0-5. 5nm, 绿色量子点作为内核的粒径范围为 3. 0-3. 5nm, 蓝色 量子点作为内核的粒径范围为 2. 0-2. 5nm。 以 ZnS为例,发射红光 的红色量子点粒径为 5nm, 发射绿光的绿光量子点粒径为 3nm。 采 用光色转换单元 28的优点在于, 即使是采用同一种量子点, 通过 调整光色转换单元 28中量子点的尺寸, 就可以达到精确控制发光 波长的目的, 从而得到不同颜色的可见光。 在本实施例中, 显示 面板可以采用 R (红) 、 G (绿) 、 B (蓝)三原色, 因而在该有机 发光二极管中设置以红光量子点作为内核的光色转换单元和以绿 光量子点作为内核的光色转换单元即可。
当然, 根据显示应用的不同, 作为内核的量子点还可以包括 黄色量子点、 橙色量子点或青色量子点。 在实际应用中, 可根据 量子点的发光特性, 例如: 发光光谱半峰宽、 发光波峰及发光波 长等, 通过调节不同材料的量子点的配比, 或者, 调节不同尺寸 的量子点的配比来得到不同颜色的光。 一般的, 量子点发光光谱 半峰宽越窄, 色纯度越高, 色彩显示效果越好; 通过调整光色转 换单元的分布率, 可以改变发出光的波幅大小。
空穴传输层 24' 的基盾材料通常为有机物, 较常采用的是芳 香胺荧光化合物。 在本实施例中, 空穴传输层 24' 的基盾材料采 用空穴传输能力强于电子传输能力的芳香族二胺类化合物、 三苯 胺化合物、 芳香族三胺类化合物、 联苯二胺衍生物或三芳胺聚合 物,例如: NPB (N, Ν' -双(卜萘基)- Ν, Ν' -二苯基联苯胺)、 TPD (Ν, Ν' - 双 ( 3-曱基苯基) - Ν, N' -二苯基联苯胺)、 TCTA (4, 4' , 4" -三(咔 唑- 9-基)三苯胺)、 TDATA (4, 4,, 4 "-三 (N, N-二苯基氨基]三苯胺) 以及聚乙烯咔唑或者其单体。
这里应该理解的是, 空穴传输能力强于电子传输能力可被定 义为空穴的迁移率大于电子的迁移率时的电荷传输能力, 并且可 按照常规方法如飞行时间法进行测定; 电子传输能力强于空穴传 输能力可同理推之。
具体的, 本实施例中对光色转换单元进行表面修饰的方式包 括:
如图 3所示, 在上述可采用的量子点 280表面包覆一层有机 物以形成有机物层 282 ,且有机物层 282的传输特性与用于形成空 穴传输层 24' 的基质材料的载流子 (主要是空穴载流子)传输特 性接近, 例如: 在 ZnS量子点表面包覆一层巯基乙醇 (ME ) , 修 饰形成光色转换单元 28 , 可以有效提高载流子传输特性、 提高发 光效率及光稳定性。
经研究表明, 量子点具有一定水溶性, 可以通过表面的活性 基团与有机分子相偶联。 如图 4所示, 在量子点 280表面包覆一 层无机物层 281的基础上, 在其表面再次修饰一层有机物层 282 , 该光色转换单元可通过酰胺键与大分子有机物相结合。 此处, 作 为一种可选择方式, 量子点 280可选择 CdSe, 无机物可选择 ZnS, 有机物可选择巯基乙酸。 此处, 表面活性剂或聚合物 (苯乙烯、 丙烯酸、 曱基丙烯酸曱酯 MMA、 十二烷基蹟酸钠 SDS、 偶氮二异丁 腈 AIBN、 巯基乙酸、 巯基乙醇 ME、 二乙烯基苯 DVB等)通常也可 以作为有机物层 282用来对量子点进行表面修饰。
在本实施例中, 上述两种方式形成的光色转换单元, 或者说 对量子点进行修饰形成的光色转换单元, 由于形成了与空穴传输 层中载流子传输特性接近的表面, 所以可有效提高载流子传输特 性、 提高发光效率及光稳定性, 更具体的原因在于: 在通常情况 下, 空穴传输层多采用有机物形成, 当通过对量子点进行表面修 饰时, 使得光色转换单元可与有机物更有效结合, 载流子将顺利 地在有机发光二极管 201 内部传输, 载流子迁移会得到相应地提 高。
此外, 驱动基板 10作为有机发光二极管 201的附着层, 在可 见光区域有着良好的透光性能, 并具有一定的防水汽和氧气渗透 的能力, 有较好的表面平整性, 其可以是玻璃或柔性基片或 TFT 背板, 其中柔性基片可采用聚酯类、 聚酰亚胺化合物中的一种材 料或者较薄的金属制成, 对应着显示面板的透光区域设置为透明 的。
阳极作为该有机发光二极管 201正向电压的连接层, 具有较
好的导电性能及较高功函数值 (High work funct ion ) 。 阳极通 常采用无机金属氧化物 (比如: 具有 4. 5eV- 5. 3eV的高功函数、 性质稳定且透光的氧化铟锡 IT0、氧化锌 ΖηΟ等)或有机导电聚合 物 (如 PED0T (聚(3, 4-亚乙二氧基噻吩) ) : PSS (聚(4-苯乙 烯磺酸盐) ), ΡΑΝΙ (聚苯胺)等)或高功函数值的金属材料(比 如: 金、 铜、 银、 铂等)制成。
阴极作为该有机发光二极管 201 负向电压的连接层, 具有较 好的导电性能和较低功函数值(Low work funct ion ) 。 为了增加 有机发光二极管的发光效率, 阴极通常采用低功函数值的金属材 料, 比如: 锂 Li、 镁 Mg、 钙 Ca、 锶 Sr、 铝 Al、 铟 In等, 或铜
Cu、 金 Au、 银 Ag等金属材料及其合金制成。
在图 2A中, 第一电极 21—般为阴极, 可以为金属层, 根据 有机发光二极管的出光方向的不同, 金属层可以为半透明或者不 透明; 第二电极 25—般为阳极, 采用透明的 IT0材料形成, 即阴 极位于驱动基板 10的上方,阳极位于阴极的上方。在本实施例中, 图 2A以顶发射型有机发光二极管作为示例, 即第二电极 25为有 机发光二极管 201 的出光侧, 由于发光层发出的光线从第二电极 25所在一侧出射, 因此, 第二电极 25—般为能够透光的透明导电 材料, 例如透明的 IT0薄膜, 而第一电极 21为能够反射光的不透 明金属。
当然, 在其他一些结构的变型中, 第一电极 21可以为阳极, 第二电极 25可以为阴极,这些本发明均不做限定。同时容易推知, 底发射型有机发光二极管 201 中第一电极 21和第二电极 25材料 的设置与图 2A相反。
在本实施例中, 子像素区域内还包括彩色滤光片 27 , 彩色滤 光片 27设置于有机发光二极管 201的出光侧, 彩色滤光片 27使 有机发光二极管 201发出的光线选择性地透出显示面板。
其中, 彩色滤光片 27包括红色滤光片、 绿色滤光片和蓝色滤 光片, 有机发光二极管 201中发光层 23发出的光线或光色转换单 元 28转换的光线通过颜色相适配的红色滤光片、绿色滤光片和蓝
色滤光片透出显示面板。 在本实施例中, 空穴传输层 24' 中的光 色转换单元 28的分布范围遍及构成全彩颜色的像素区域, 该全彩 颜色的像素区域包括多个具有不同颜色的子像素区域。
在本实施例中, 图 2B仅以一个子像素区域作为示例, 例如以 出射绿光的子像素区域为例, 出射红光的子像素区域及出射蓝光 的子像素区域的结构可类比推知。 上述绿色子像素区域、 红色子 像素区域以及蓝色子像素区域形成一个像素区域; 当然, 也可以 由三个以上的颜色组成一个像素区域, 在此不做限定。 在采用三 个以上的颜色组成一个像素区域时, 相对于由绿色子像素区域、 红色子像素区域以及蓝色子像素区域形成的像素区域, 可以提高 显示面板的色域, 提高显示面板的透光率, 增强色彩饱和度, 提 高显示面板的显示品质。
通过调节各 R、 G、 B子像素区域内电子控制元件 11的输入电 压 (调节电流) , 可独立控制各有机发光二极管 201发射光线的 强度, 从而独立调节 R、 G、 B光效。
为简化制备工艺, 当采用小分子 0LED时, 在形成本实施例中 的有机发光二极管 201 时, 在多个子像素区域内将有机发光二极 管中的电子传输层、 发光层和包含有光色转换单元的空穴传输层 分三层热蒸镀 ( therma l evaporat ion )分别形成, 无需采用构图 工艺, 且不必采用不同的工艺来完成掺杂有光色转换单元的对应 着不同的颜色区域的空穴传输层。 其中, 在空穴传输层的热蒸镀 过程中, 将提前预制好的光色转换单元 28的材料及用于形成空穴 传输层的本征材料分别放置于真空反应腔中, 采用蒸镀工艺形成 于图 2B所示发光层 23上方, 即可以将对应着红色子像素区域的 多个子像素区域、 对应着绿色子像素区域的多个子像素区域和对 应着蓝色子像素区域的空穴传输层采用一次蒸镀工艺形成, 而不 必分三次构图工艺分别形成三个颜色的像素区域, 从而有效简化 显示面板的制备工艺流程, 节省掩模板。 当采用大分子 0LED时, 将提前预制好的光色转换单元 28均勾分布于用于形成空穴传输层 的溶液中, 之后采用旋转涂布( spin- coat ing )的方式在图 2B所
示发光层 23上方涂膜。
可以理解的是, 包含有光色转换单元的空穴传输层除采用上 述的热蒸镀方式 (针对小分子 0LED )形成, 以及采用旋转涂布方 式(针对大分子 0LED )形成外,还可以采用喷墨打印方式( inkje t ) 形成相应 OLED膜层。
在本实施例中, 以蓝光 0LED为例, 显示面板的发光原理为: 当阳极和阴极之间施加电压时, 在电压的驱动下, 由阳极注入的 空穴通过空穴传输层 24' 进入发光层 23中,由阴极注入的电子通 过电子传输层 22进入发光层 23中, 进入到发光层 23中的空穴和 电子在复合区复合形成激子, 激子辐射跃迁发光而产生发光现象, 即形成蓝光; 由于光色转换单元 28掺杂到空穴传输层 24' 中,发 光层 23发出的蓝光照射到空穴传输层 24' 内的红光量子点及绿 光量子点上, 将受激发射出红光及绿光, 受激发射出的红光和绿 光以及未与光色转换单元作用的蓝光混合在一起, 经彩色滤光片 27之后实现全彩显示。
当然, 上述有机发光二极管中还可以包括其他层, 例如: 电 子阻挡层、 空穴与激子阻挡层、 电子注入层或空穴注入层中的一 层或多层。 实施例 2 :
本实施例提供一种显示面板, 如图 5所示, 该显示面板包括 驱动基板(图 5 中未示出) 以及设置于驱动基板上的有机发光二 极管 202 , 有机发光二极管 202包括第一电极 21和第二电极 25 , 还包括设置于第一电极 21和第二电极 25之间的电子传输层 22、 发光层 23' 和空穴传输层 24。在本实施例中,发光层 23' 中均匀 分布有多个光色转换单元 28 , 发光层 23' 受激发射出蓝光(单色 光) , 蓝光将照射光色转换单元 28发出绿光或红光, 经彩色滤光 片 27 , 从而实现全彩。
通常, 发光层采用有机物形成, 该有机物具备固态下有较强 荧光、 载流子传输性能好、 热稳定性和化学稳定性佳、 量子效率
高且能够真空蒸镀的特性。 在本实施例中, 发光层 23' 采用基盾 材料掺杂发光材料。 其中, 发光层 23' 中的基质材料可以采用电 子传输能力强于空穴传输能力的金属配合物、 咔唑类衍生物、 咪 唑类衍生物、 邻菲罗林衍生物或蒽的衍生物, 或者, 可以采用空 穴传输能力强于电子传输能力的芳香族二胺类化合物、 三苯胺化 合物、 芳香族三胺类化合物、 联苯二胺衍生物或三芳胺聚合物; 对于发光材料, 低分子 0LED发光材料常采用 A lq为绿光材料, 采 用 BAlq (双(2-曱基- 8-羟基喹啉- N1, 08) - (1, 1' -联苯- 4-羟基)铝) 与 DPVB i ( 4, 4' -二(2, 2-二苯乙烯基)-1, 1' -联苯) 为蓝光材料, 而高分子 0LED发光材料常采用 PPV及其衍生物。
同样, 为了保证载流子顺利传输, 可以参考实施例 1对掺杂 粒子进行表面修饰, 即采用在量子点的表面修饰有机物形成的有 机物层结构, 或采用在量子点的表面修饰有机物与无机物形成的 有机物层与无机物层的叠层结构, 从而提高载流子传输特性、 提 高发光效率及光稳定性。
在本实施例中, 有机发光二极管 202的发光层 23' 所发射的 蓝光照射到发光层 23' 内的红光量子点及绿光量子点上, 受激发 射出红光及绿光, 受激发射出的红光和绿光以及未与光色转换单 元作用的蓝光, 经彩色滤光片 27实现全彩显示。
当然, 上述有机发光二极管中还可以包括其他层, 例如: 电 子阻挡层、 空穴与激子阻挡层、 电子注入层或空穴注入层中的一 层或多层。 或者, 可替代地, 上述有机发光二极管也可以只包括 发光层。
在本实施例中, 该显示面板的其他各层的结构以及相应的制 备方法可参考实施例 1进行设置, 这里不再赘述。 实施例 3:
本实施例提供一种显示面板, 如图 6所示, 该显示面板包括 驱动基板(图 6 中未示出) 以及设置于驱动基板上的有机发光二 极管 203 , 有机发光二极管 203包括第一电极 21和第二电极 25 ,
还包括设置于第一电极 21和第二电极 25之间的电子传输层 22' 、 发光层 23和空穴传输层 24。 在本实施例中, 电子传输层 22' 中 均匀分布有多个光色转换单元 28。
一般的, 有机发光二极管中的电子传输层和空穴传输层采用 不同的有机材料。 目前最常被用来制作电子传输层的材料通常具 有制膜稳定性高、 热稳定且电子传输性佳的特性, 在本实施例中, 电子传输层 22' 采用电子传输能力强于空穴传输能力的金属配合 物、 咔唑类衍生物、 咪唑类衍生物、 邻菲罗林衍生物或蒽的衍生 物, 一般通常采用荧光染料化合物, 例如: Alq ( 8-羟基喹啉铝)、 Znq ( 8-羟基喹啉锌) 、 Gaq ( 8-羟基喹啉镓) 、 Bebq (双(10-羟 基苯并 [H]喹啉)铍) 、 BA lq ( 双 (2-曱基- 8-羟基喹啉 - Ν1 , 08) - (Ι, -联苯- 4-羟基)铝) 、 DPVBi ( 4, 4' -二(2, 2-二苯乙 烯基) -1 , 1' -联苯) 、 ZnSPB、 PBD ( 2- (4-二苯基) -5- (4-叔丁苯 基) -1 , 3, 4-噁二唑) 、 OXD ( 1, 3, 4-噁二唑的衍生物) 、 BB0T (二 -苯并噁唑基噻吩)等。
同样, 为了保证载流子顺利传输, 可以参考实施例 1对掺杂 粒子进行表面修饰, 即采用在量子点的表面修饰有机物形成的有 机物层结构, 或采用在量子点的表面修饰有机物与无机物形成的 有机物层与无机物层的叠层结构, 从而提高载流子传输特性、 提 高发光效率及光稳定性。
在本实施例中, 电子传输层 22' 位于发光层 23 与第一电极 21之间, 第一电极 21采用不透明金属形成, 以将发光层 23发出 并经电子传输层 22' 中的光色转换单元 28转换的光线射出,提高 光利用率。
在本实施例中,有机发光二极管 203的发光层 23所发射的蓝 光照射到电子传输层 22' 内的红光量子点及绿光量子点上, 受激 发射出红光及绿光, 受激发射出的红光和绿光以及未与光色转换 单元作用的蓝光经第一电极 21的不透明金属反射向上出射, 经彩 色滤光片 27实现全彩显示。
当然, 上述有机发光二极管中还可以包括其他层, 例如: 电
子阻挡层、 空穴与激子阻挡层、 电子注入层或空穴注入层中的一 层或多层。
在本实施例中, 该显示面板的其他各层的结构以及相应的制 备方法可参考实施例 1进行设置, 这里不再赘述。 上述实施例 1至实施例 3中, 除了电子传输层 22' 中掺杂有 光色转换单元之外, 电子传输层 22 和电子传输层 22' 的材料相 同; 除了发光层 23' 中掺杂有光色转换单元之外,发光层 23和发 光层 23' 的材料相同; 除了空穴传输层 24' 中掺杂有光色转换单 元之外, 空穴传输层 24' 和空穴传输层 24的材料相同。
对按照实施例 1-3制备的显示面板进行性能测试。 其中, 各 实施例的显示面板的结构如图 2A所示, 不同之处仅在于光色转换 单元 28分别位于空穴传输层 24' (实施例 1 )、 发光层 23' (实 施例 2 )、 电子传输层 22' (实施例 3 )中。 作为对照例的现有技 术显示面板的结构如图 1所示。 结果显示, 实施例 1-3的显示面 板相对于对照例表现出提高的色纯度和载流子迁移能力。 实施例 4:
一种显示装置, 其包括实施例 1-3任一种显示面板。
该显示装置可以为: 电子纸、 手机、 平板电脑、 电视机、 显 示器、 笔记本电脑、 数码相框、 导航仪等任何具有显示功能的产 品或部件。
这里应该理解的是, 实施例 1-3 中有机发光二极管通过在电 子传输、 发光层和空穴传输层任意一层中设置光色转换单元的结 构, 不仅适用于实施例 1-3 中的顶发射型有机发光二极管, 也同 时适用于底发射型有机发光二极管。 在本发明中, 采用将光色转换单元直接掺杂到有机发光二极 管中的空穴传输层、 发光层、 电子传输层这三层中的任意一层的 结构, 简化了显示面板的结构和相应的制备工艺流程; 同时, 对
形成光色转换单元的量子点做表面修饰, 能有效地提升载流子迁 移能力; 而且, 由于量子点的发光效率高且发射光线的光谱窄, 因此能提高相应子像素区域的色纯度, 进一步提高组合成的像素 区域的色纯度, 与其他的光转换材料相比色纯度更好, 也相应地 提高了显示面板的色纯度。 可以理解的是, 以上实施方式仅仅是为了说明本发明的原理 而采用的示例性实施方式, 然而本发明并不局限于此。 对于本领 域内的普通技术人员而言, 在不脱离本发明的精神和实质的情况 下, 可以做出各种变型和改进, 这些变型和改进也视为本发明的 保护范围。
Claims
1. 一种显示面板, 包括驱动基板以及设置于所述驱动基板上 的有机发光二极管, 所述有机发光二极管包括第一电极和第二电 极, 还包括设置于所述第一电极和所述第二电极之间的电子传输 层、 发光层和空穴传输层, 其特征在于, 所述电子传输层、 所述 发光层或所述空穴传输层中均勾分布有多个光色转换单元。
2. 根据权利要求 1所述的显示面板, 其特征在于, 所述光色 转换单元包括内核以及包覆在所述内核外部的外壳, 所述内核包 括量子点, 所述外壳包括采用有机物形成的层结构。
3. 根据权利要求 1所述的显示面板, 其特征在于, 所述光色 转换单元包括内核以及包覆在所述内核外部的外壳, 所述内核包 括量子点, 所述外壳包括采用有机物与无机物形成的叠层结构。
4. 根据权利要求 2所述的显示面板, 其特征在于, 所述量子 点包括 CdS、 CdSe、 CdTe、 Zn0、 ZnS、 ZnSe、 ZnTe、 GaAs、 GaP、 GaSb、 HgS、 HgSe、 HgTe、 InAs、 InP、 InSb、 AlAs、 A1P或 Al Sb; 所述有机物包括巯基乙醇。
5. 根据权利要求 3所述的显示面板, 其特征在于, 所述量子 点包括 CdS、 CdSe、 CdTe、 Zn0、 ZnS、 ZnSe、 ZnTe、 GaAs、 GaP、 GaSb、 HgS、 HgSe、 HgTe、 InAs、 InP、 InSb、 AlAs、 A1P或 Al Sb; 所述有机物包括巯基乙醇, 所述无机物包括 CdS或 ZnS。
6. 根据权利要求 4或 5所述的显示面板, 其特征在于, 所述 量子点包括红色量子点、 绿色量子点和蓝色量子点, 所述红色量 子点作为内核的粒径范围为 5. 0-5. 5nm,所述绿色量子点作为内核 的粒径范围为 3. 0-3. 5nm,所述蓝色量子点作为内核的粒径范围为 2. 0-2. 5nm。
7. 根据权利要求 1至 6中任意一项所述的显示面板,其特征 在于, 所述电子传输层采用电子传输能力强于空穴传输能力的金 属配合物、 咔唑类衍生物、 咪唑类衍生物、 邻菲罗林衍生物或蒽 的衍生物; 所述发光层采用基质材料掺杂发光材料; 所述空穴传 输层采用空穴传输能力强于电子传输能力的芳香族二胺类化合 物、 三苯胺化合物、 芳香族三胺类化合物、 联苯二胺衍生物或三 芳胺聚合物。
8. 根据权利要求 7所述的显示面板, 其特征在于, 所述发光 层中的基质材料采用具有电子传输能力的金属配合物、 咔唑类衍 生物、 咪唑类衍生物、 邻菲罗林衍生物或蒽的衍生物, 或者, 采 用具有空穴传输能力的芳香族二胺类化合物、 三苯胺化合物、 芳 香族三胺类化合物、 联苯二胺衍生物或三芳胺聚合物; 所述发光 材料采用 Alq、 BAlq或 DPVBi , 或者 PPV或其衍生物。
9. 根据权利要求 1至 8中任意一项所述的显示面板,其特征 在于, 所述驱动基板划分为多个子像素区域, 每一所述子像素区 域内均设置有所述有机发光二极管, 所述子像素区域内还设置有 电子控制元件, 所述电子控制元件与所述有机发光二极管的第一 电极或所述第二电极电连接, 所述电子控制元件用于对所述有机 发光二极管发光与否进行控制。
10. 根据权利要求 1至 9中任意一项所述的显示面板, 其特 征在于, 所述驱动基板划分为多个子像素区域, 所述子像素区域 内还包括彩色滤光片, 所述彩色滤光片设置于所述有机发光二极 管的出光侧, 所述彩色滤光片使所述有机发光二极管发出的光线 选择性地透出所述显示面板。
11. 根据权利要求 1至 10中任意一项所述的显示面板,其特
征在于, 所述有机发光二极管的所述电子传输层、 所述发光层或 所述空穴传输层采用热蒸镀、 旋转涂布或喷墨打印方式形成。
12. 根据权利要求 1至 11中任意一项所述的显示面板,其特 征在于, 所述彩色滤光片包括红色滤光片、 绿色滤光片和蓝色滤 光片, 所述有机发光二极管中所述发光层发出的光线或所述光色 转换单元转换的光线通过颜色相适配的所述红色滤光片、 所述绿 色滤光片和所述蓝色滤光片透出所述显示面板。
13.—种显示装置, 其特征在于, 包括权利要求 1-12任一项 所述的显示面板。
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CN113299866A (zh) * | 2021-05-24 | 2021-08-24 | 合肥福纳科技有限公司 | 膜层及其制备方法和发光器件及其制备方法 |
CN113631000A (zh) * | 2021-08-19 | 2021-11-09 | Oppo广东移动通信有限公司 | 壳组件和电子装置 |
Also Published As
Publication number | Publication date |
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EP3091588A1 (en) | 2016-11-09 |
CN103730584A (zh) | 2014-04-16 |
US9379344B2 (en) | 2016-06-28 |
US20160028035A1 (en) | 2016-01-28 |
EP3091588A4 (en) | 2017-09-20 |
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