CN104183720A - Organic light emission diode, display screen and terminal - Google Patents

Organic light emission diode, display screen and terminal Download PDF

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Publication number
CN104183720A
CN104183720A CN201310193565.1A CN201310193565A CN104183720A CN 104183720 A CN104183720 A CN 104183720A CN 201310193565 A CN201310193565 A CN 201310193565A CN 104183720 A CN104183720 A CN 104183720A
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China
Prior art keywords
layer
electroluminescent device
organnic electroluminescent
thickness
anode
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CN201310193565.1A
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Inventor
周明杰
冯小明
陈吉星
王平
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Application filed by Oceans King Lighting Science and Technology Co Ltd, Shenzhen Oceans King Lighting Engineering Co Ltd filed Critical Oceans King Lighting Science and Technology Co Ltd
Priority to CN201310193565.1A priority Critical patent/CN104183720A/en
Publication of CN104183720A publication Critical patent/CN104183720A/en
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] 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
    • H10K50/80—Constructional details
    • H10K50/85—Arrangements for extracting light from the devices
    • H10K50/854—Arrangements for extracting light from the devices comprising scattering means
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/85—Arrangements for extracting light from the devices
    • H10K50/856—Arrangements for extracting light from the devices comprising reflective means
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/85—Arrangements for extracting light from the devices
    • H10K50/858—Arrangements for extracting light from the devices comprising refractive means, e.g. lenses
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/86—Arrangements for improving contrast, e.g. preventing reflection of ambient light

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The invention discloses an organic light emission diode, a display screen and a terminal. The organic light emission diode comprises a substrate, an anode layer, an organic function layer and a cathode layer serving as a light-outgoing surface, which are in stack combination in sequence. The anode layer comprises a metal reflection layer, a scattering layer, an interference layer and a semi-permeable metal layer which are in stack combination in sequence, wherein the scattering layer material comprises transparent conducting oxide and metal particles doped in the transparent conducting oxide; and the interference layer material is transparent conducting oxide. The anode of the organic light emission diode reduces reflectivity of the anode of the organic light emission diode on light effectively, and contrast ratio is improved. The display screen comprising the organic light emission diode and the terminal provided with the display screen have high contrast ratio, and the displayed pictures are clear.

Description

Organnic electroluminescent device, display screen and terminal thereof
Technical field
The invention belongs to electric light source technology field, relate to specifically a kind of Organnic electroluminescent device, display screen and terminal thereof.
Background technology
Organic electroluminescence device (Organic Light Emission Diode, hereinafter to be referred as OLED) is a kind of current mode light emitting semiconductor device based on organic material.Its typical structure is that the luminous organic material of making one deck tens nanometer thickness on ito glass is made luminescent layer, and there is the metal electrode of one deck low work function luminescent layer top.
The principle of luminosity of OLED is based under the effect of extra electric field, and electronics is injected into organic lowest unocccupied molecular orbital (LUMO) from negative electrode, and hole is injected into organic highest occupied molecular orbital (HOMO) from anode.Electronics and hole meet at luminescent layer, compound, form exciton, exciton moves under electric field action, and energy is passed to luminescent material, and excitation electron is from ground state transition to excitation state, excited energy, by Radiation-induced deactivation, produces photon, discharges luminous energy.
The advantages such as OLED has that luminous efficiency is high, material range of choice is wide, driving voltage is low, entirely solidifies active illuminating, light, thin, have high definition, wide viewing angle, fast response time, low cost and the advantage such as bright in luster simultaneously, a kind of Display Technique and light source that has potentiality, meet the development trend that information age mobile communication and information show, and the requirement of green lighting technique, therefore, thought to be most likely at by insider the device of new generation that occupies dominance on following illumination and display device market.As a brand-new illumination and Display Technique, the ten years development in the past of OLED technology is swift and violent, has obtained huge achievement.Throw light on because the whole world is increasing and show that producer drops into research and development one after another, having promoted greatly the industrialization process of OLED, making the growth rate of OLED industry surprising, having arrived the eve of scale of mass production at present.
But the negative electrode of existing OLED device is generally the metallic cathode material that uses high reflectance, particularly, the metallic cathode of the high reflectance that the metallic cathode material of this high reflectance is prepared into has the reflectivity that exceedes 90% in visible ray section, therefore this high reflectance negative electrode like this brings obstruction but to the application of OLED on display device.This be because, as display device, high-contrast is the long-term pursuits of people, requirement to Display Contrast is higher, if when the application by the OLED device of existing high reflectance negative electrode on display device, under solar light irradiation, due to the high reflectance effect of its high reflectance negative electrode, make the contrast of display device low, the content of demonstration cannot be seen clearly.Therefore,, when OLED device is applied in display, the reflectivity that how to reduce OLED device is technical barrier to be solved.
Summary of the invention
The object of the invention is to overcome the above-mentioned deficiency of prior art, provide a kind of anode to there is the Organnic electroluminescent device of antiradar reflectivity.
The display screen that provides a kind of contrast high is provided.
Another object of the present invention is to provide a kind of terminal that contains above-mentioned display screen.
In order to realize foregoing invention object, technical scheme of the present invention is as follows:
A kind of Organnic electroluminescent device, comprise the substrate, anode layer, organic function layer and the cathode layer as exiting surface that stack gradually combination, described organic function layer is included in luminescent layer luminous under the driving of additional power source, described anode layer comprises the metallic reflector, scattering layer, interfering layer, the semi-transparent metal level that stack gradually combination, the stacked combination of described metallic reflector and substrate, described semi-transparent metal level and the stacked combination of organic function layer; Wherein, described scattering layer material comprises transparent conductive oxide and be doped in the metallic in described transparent conductive oxide, and described interfering layer material is transparent conductive oxide.
And a kind of display screen, comprises display module and for controlling the control module of display module, wherein, described display module contains Organnic electroluminescent device described above.
And, a kind of terminal that is provided with display screen, the display screen of described terminal is the above-mentioned display that contains Organnic electroluminescent device.
Above-mentioned Organnic electroluminescent device, by anode being arranged to stack gradually metallic reflector, scattering layer, interfering layer, the semi-transparent metal-layer structure of combination, effectively reduces the anode of this Organnic electroluminescent device to reflection of light rate, has improved its contrast.Wherein, semi-transparent metal level can to by from cathode layer end incident light the effect of semi-transflective reflective; Interfering layer can produce and interfere the light being reflected by semi-transparent metal level, it is reflected again, scattering layer can not only be to interfering effect by the light of interfering layer incident, metallic is wherein to incident light generation scattering process, and therefore, this interfering layer and scattering layer act synergistically, make semi-transparent metal layer reflection light and the catoptrical single spin-echo of metallic reflector, reach the effect that interference disappears mutually, effectively reduced the total reflection of light, realize low reflectivity.
Above-mentioned display screen is owing to containing above-mentioned Organnic electroluminescent device, and therefore it has high-contrast, and its display frame is clear.Due to the display screen that is provided with the terminal of display screen and contains this high-contrast, therefore the display screen picture of this terminal is clear.
Brief description of the drawings
Fig. 1 is embodiment of the present invention Organnic electroluminescent device structural representation;
Fig. 2 is another preferred structure schematic diagram of embodiment of the present invention Organnic electroluminescent device;
Fig. 3 is embodiment of the present invention Organnic electroluminescent device preparation method's schematic flow sheet.
Embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment and accompanying drawing, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Organic electroluminescent pixel contrast=(environmental light brightness of device luminosity (opening)+device reflection)/(environmental light brightness of device luminosity (pass)+device reflection), according to these computational methods, in the OLED of transparent anode device, one of method that improves contrast is exactly to reduce the light reflection of device to environment, namely reduces the reflectivity of reflecting electrode.
Based on above-mentioned theory, the embodiment of the present invention adopts the approach that reduces anode reflectivity to improve organic electroluminescent pixel contrast.Therefore, the Organnic electroluminescent device that the embodiment of the present invention provides a kind of anode to have antiradar reflectivity, its structure is as shown in Figure 1 to Figure 2.This Organnic electroluminescent device comprises the substrate 1, anode layer 2, organic function layer 3 and the cathode layer 4 that stack gradually combination.
Particularly, the material of aforesaid substrate 1 is glass, polymer thin-film material etc., as simple glass, polymer thin-film material substrate etc.Certainly, the material of substrate 1 also can adopt this area other materials to substitute.The thickness of substrate 1 also can adopt the conventional thickness in this area or select flexibly according to the requirement of application.
Above-mentioned anode layer 2 comprises the metallic reflector 21, scattering layer 22, interfering layer 23 and the semi-transparent metal level 24 that stack gradually combination, wherein, and metallic reflector 21 and the stacked combination of substrate 1, semi-transparent metal level 24 and the stacked combination of organic function layer 3.Semi-transparent metal level 24 in the anode layer 2 of this structure can to by from cathode layer 4 end incident lights the effect of semi-transflective reflective, scattering layer 22, interfering layer 23 not only have good conductivity, can make hole inject, the more important thing is can be to semi-transparent metal level 24 reverberation and the catoptrical single spin-echo of metallic reflector 21, reach the effect that interference disappears mutually, effectively reduce the total reflection of light, realized low reflectivity.Wherein, this interfering layer 23 produces and interferes the light being reflected by semi-transparent metal level, it is reflected again, scattering layer can not only be to interfering effect by the light of interfering layer incident, metallic wherein can also be to incident light generation scattering process, therefore, this interfering layer 23 acts synergistically incident light is produced to interference effect with scattering layer 22.Particularly, the light reflection of the anode layer 2 from cathode layer 4 end-fires to this structure and refraction are as shown in Fig. 1,2, ambient light a is during from outside incident, there is first reflection and refraction on semi-transparent metal level 24 surfaces, form reflection ray b, refracted ray c after the collaborative interference effect between interfering layer 23, scattering layer 22, is incident to metallic reflector 21 surfaces and reflects successively, forms reflection ray d.This emission of light b, reflection ray D-shaped become the interference cancellation effect of light, slacken the reverberation that anode layer 2 produces, thereby effectively reduce the reflectivity of anode layer 2.
Wherein, this semi-transparent metal level 24 can make the light being come by cathode layer 4 end incidents reflect at its interface generation part permeation parts.For reflection and the transmitance of better light regulating, as preferred embodiment, the thickness of this semi-transparent metal level 24 is 5nm～10nm.As another preferred embodiment, the material of this semi-transparent metal level 24 is any one or more alloy in Ag, Al, Au, Ni, Cr.Should be appreciated that, can do cathodic metal material and also belong to the framework of the present definition as long as can realize other thickness of this semi-transparent metal level 24 part permeation parts reflections and other.
These scattering layer 22 materials comprise transparent conductive oxide and be doped in the metallic in transparent conductive oxide, and interfering layer 23 materials are transparent conductive oxide.In a preferred embodiment, transparent conductive oxide in these scattering layer 22 materials and interfering layer 23 material transparent conductive oxides are identical or not identical indium and tin oxide film (ITO), indium-zinc oxide (IZO) or aluminium zinc oxide (AZO), at least one in gallium zinc oxide (GZO).This preferred transparent conductive oxide has suitable interference effect to light, the metallic being entrained in scattering layer 22 can also play scattering of light effect, realize the collaborative interference effect to light between scattering layer 22 and interfering layer 23, what make the interference between semi-transparent metal level 24 reverberation and metallic reflector 21 reverberation to disappear mutually is effective, effectively reduce the total reflection of light, realized low reflectivity.In addition, this transparent conductive oxide film forming good conductivity, can effectively improve hole injectability.
In order to improve this scattering layer 22 to scattering of light effect, in a preferred embodiment, the metallic doping in these scattering layer 22 materials accounts for 9.1%～16.7% of scattering layer 22 total weights.Wherein, this metallic is preferably at least one in Ag, Cr, Ni, Pt, Cu.In another preferred embodiment, the thickness of this scattering layer 22 is 10nm～20nm, and this preferred thickness has better interference and scattering process to light.
As preferred embodiment, these interfering layer 23 thickness are 60nm～80nm.Realize its raising to interference of light effect by regulating these interfering layer 23 thickness.
As another preferred embodiment, the thickness of scattering layer 22 is 10nm～20nm, and interfering layer 23 thickness are 60nm～80nm.By regulate two-layer thickness simultaneously, make two-layer synergy better, strengthen two-layer to interference of light effect.
The object that this metallic reflector 21 arranges is to reflect at its interface transmit the light coming from scattering layer 22, and the light that this reverberation reflection is occurred to semi-transparent metal level 24 interfaces after by the transmission of scattering layer 22, interfering layer 23 cancels each other, to reduce the reflectivity of anode layer 2.As preferred embodiment, the thickness of this metallic reflector 21 is 70nm～200nm.As another preferred embodiment, above-mentioned metallic reflector 21 metal materials are any one or more alloy in Ag, Al, Au, Ni, Cr.Should be appreciated that, can do anode metal material and also belong to the framework of the present definition as long as can realize other thickness of this metallic reflector 21 reflection action and other, as disregard cost, the thickness of this metallic reflector 21 can also be more than 200nm.
As another preferred embodiment of above-mentioned Organnic electroluminescent device, the thickness of metallic reflector 21 is 70nm～200nm, and the thickness of scattering layer 22 is 10nm～20nm, and the thickness of interfering layer 23 is that 60nm～80nm and semi-transparent metal level 24 thickness are 5nm～10nm.The combination of each layer thickness in the preferred embodiment, the better effects if that can make metallic reflector 21 and semi-transparent metal level 24 reverberation offset, makes anode layer 2 have lower reflectivity.
As a preferred embodiment again of above-mentioned Organnic electroluminescent device, above-mentioned metallic reflector 21 and semi-transparent metal level 24 materials are any one or more alloy in Ag, Al, Au, Ni, Cr; Scattering layer 22 materials are the mixture layer of above-mentioned transparent conductive oxide and the doping of above-mentioned metallic, and metallic doping accounts for 9.1%～16.7% of scattering layer total weight; Interfering layer 23 materials are above-mentioned transparent conductive oxide.The combination of each layer of selected material in the preferred embodiment, gives reflectivity and the hole that anode layer 2 is lower and injects and transmission performance.
As the another preferred embodiment of above-mentioned Organnic electroluminescent device, the thickness of above-mentioned metallic reflector 21 is 70nm～200nm, and its material is any one or more alloy in metal A g, Al, Au, Ni, Cr; Scattering layer 22 thickness are 10nm～20nm, and its material is the mixture layer of above-mentioned transparent conductive oxide and the doping of above-mentioned metallic, and metallic doping accounts for 9.1%～16.7% of scattering layer total weight; Interfering layer 23 thickness are 60nm～80nm, and its material is above-mentioned transparent conductive oxide; Semi-transparent metal level 24 thickness are 5nm～10nm, and its material is any one or more alloy in metal A g, Al, Au, Ni, Cr.The combination of each layer thickness and material in the preferred embodiment, injects and transmission performance reflectivity that anode layer 2 is lower and excellent hole.
Organic function layer 3 in above-mentioned Organnic electroluminescent device embodiment comprises the hole injection layer 31, hole transmission layer 32, luminescent layer 33, electron transfer layer 34, the electron injecting layer 35 that stack gradually combination, and the stacked combination in the relative surface of face that combines with substrate layer 1 of hole injection layer 31 and anode layer 2, electron injecting layer 35 and the stacked combination of cathode layer 4, as shown in Figure 1.
In specific embodiment, above-mentioned hole injection layer 31 materials can be ZnPc (Phthalocyanine Zinc), CuPc(CuPc), at least one in VOPc (ranadylic phthalocyanine), TiOPc (TiOPc).Certainly, these hole injection layer 31 materials can also be the conventional other materials in this area, as WO 3, VO x, WO xor MoO 3deng oxide, or the dopant mixture of inorganic hole injection layer material and organic hole implanted layer material.The thickness of hole injection layer 31 also can arrange according to the thickness of this area routine.The setting of this hole injection layer 31, can effectively strengthen the ohmic contact between itself and anode layer 2, has strengthened electric conductivity, improves the hole injectability of anode layer 2 ends.Just because of this, this hole injection layer 31 also can not arrange according to the actual needs, that is to say, hole transmission layer 32 can be directly and the direct stacked combination of anode layer 2.
Above-mentioned hole transmission layer 32 materials can be NPB (N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines), TPD (N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4,4'-diamines), MeO-TPD (N, N, N', N '-tetramethoxy phenyl)-benzidine), MeO-Sprio-TPD(2, the two (N of 7-, N-bis-(4-methoxyphenyl) amino)-9,9-spiral shell two fluorenes) at least one.Certainly, these hole transmission layer 32 materials can also be the conventional other materials in this area, as 4,4', and 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA) etc.The thickness of hole transmission layer 32 also can arrange according to the thickness of this area routine.
Above-mentioned luminescent layer 33 materials can be guest materials and material of main part dopant mixture.Wherein, guest materials is luminescent material, it comprises 4-(dintrile methyl)-2-butyl-6-(1, 1, 7, 7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), two (4, 6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium (FIrpic), two (4, 6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium (FIr6), two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) close iridium (Ir (MDQ) 2 (acac)), three (1-phenyl-isoquinolin) close iridium (Ir (piq) 3), three (2-phenylpyridines) close at least one in iridium (Ir (ppy) 3), material of main part comprises 4,4'-bis-(9-carbazole) biphenyl (CBP), oxine aluminium (Alq 3), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4, at least one in 4'-diamines (NPB).Main, guest materials can carry out according to the needs of actual production and application compound flexibly, and the mass ratio of guest materials and material of main part can be 1～10:100.
In addition, these luminescent layer 33 materials can also be selected fluorescent material 4,4'-bis-(2,2-diphenylethyllene)-1,1'-biphenyl (DPVBi), 4, two [4-(di-p-tolyl amino) styryl] biphenyl (DPAVBi), 5,6 of 4'-, at least one in the materials such as 11,12-tetraphenyl naphthonaphthalene (Rubrene), dimethylquinacridone (DMQA).The thickness of this luminescent layer 33 also can arrange according to the thickness of this area routine.
Above-mentioned electron transfer layer 34 materials can be 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole (PBD), (oxine)-aluminium (Alq 3), 4,7-diphenyl-o-phenanthroline (Bphen), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP), 1,2, in 4-triazole derivative (TAZ) at least one.Certainly, electron transfer layer 34 materials can also be other electron transport materials well known in the art, and its thickness also can adopt the conventional thickness in this area.
Above-mentioned electron injecting layer 35 materials can LiF, CsF, NaF, MgF 2deng at least one etc. alkali-metal halide, certainly, these electron injecting layer 35 materials can also be selected the alkali-metal halide such as at least one in lithium iodide, KI, sodium iodide, cesium iodide, rubidium iodide.The thickness of electron injecting layer 35 also can arrange according to the thickness of this area routine.The arranging of this electron injecting layer 35 can effectively strengthen the ohmic contact between itself and cathode layer 4, strengthen electric conductivity, further improve the electronic injection ability of cathode layer 4 ends, with further equilibrium carrier, control recombination region, in luminescent layer, increase exciton amount, obtained desirable luminosity and luminous efficiency.Just because of this, this electron injecting layer 35 also can not arrange according to the actual needs, that is to say, electron transfer layer 34 can be directly and the direct stacked combination of cathode layer 4.
In further preferred embodiment, on the basis of organic function layer 3 as shown in Figure 1, above-mentioned organic function layer 3 can also arrange electronic barrier layer 36 and hole blocking layer 37, as shown in Figure 2.Wherein, this electronic barrier layer 36 is stacked to be combined between hole transmission layer 32 and luminescent layer 33, and hole blocking layer 37 is stacked to be combined between luminescent layer 33 and electron transfer layer 34.Arranging of this electronic barrier layer 36 can stop the electronics that does not form exciton in luminescent layer 33 as much as possible and be trapped in luminescent layer 33, arranging of hole blocking layer 37 can stop the hole that does not form exciton in luminescent layer 33 as much as possible and be trapped in luminescent layer 33, to improve electronics and the hole meeting rate in luminescent layer 33, to improve both exciton amounts compound and that form, and exciton energy is passed to luminescent material, thereby the electronics of excitation light-emitting material is from ground state transition to excitation state, excited energy passes through Radiation-induced deactivation, produce photon, discharge luminous energy, to reach the object of the luminous intensity that strengthens luminescent layer 33.Certainly, this electronic barrier layer 36 and hole blocking layer 37 can according to the situation of actual production and application need to select a setting, the material that it is selected and thickness can arrange according to the conventional material in this area and conventional thickness.
Above-mentioned cathode layer 4 materials are any one or more alloy in Ag, Al, Sm, Yb, and its thickness is 18nm～35nm.This preferred cathode material and thickness have excellent light transmission rate, can effectively improve the light emission rate of this Organnic electroluminescent device, in addition, and this preferred cathode material electric conductivity excellence.Certainly, the material of this galactic pole layer 4 and thickness can also be other materials and the thickness of this area routine.
From the above, above-mentioned Organnic electroluminescent device is by being arranged to anode stack gradually metallic reflector 21, scattering layer 22, interfering layer 23, semi-transparent metal level 24 structures of combination, light reflection by anode layer 2 is offset, thereby effectively reduce the anode of this Organnic electroluminescent device to reflection of light rate, improved its contrast.In addition, by selecting the material of metallic reflector 21, scattering layer 22, interfering layer 23, semi-transparent metal level 24 and regulating the thickness of each layer, particularly thickness and the material of scattering layer 22, interfering layer 23, realize two-layer synergy, can further reduce the negative electrode of above-mentioned Organnic electroluminescent device to reflection of light rate, improve its contrast.
Correspondingly, so above-described embodiment Organnic electroluminescent device preparation method can be according to showing as Fig. 3.Technological process preparation, simultaneously referring to Fig. 1～2, its preparation method comprises the steps:
S01., substrate 1 is provided;
S02. prepare anode layer 2: in vacuum coating system, adopt magnetron sputtering technique, the metallic reflector 21, scattering layer 22, interfering layer 23 and the semi-transparent metal level 24 that stack gradually combination are prepared in substrate 1 one surfaces that metallic reflection layer material, scattering layer material, interfering layer material, semi-transparent metal layer material sputtered at successively to step S01, form anode layer 2;
S03. prepare organic function layer 3: prepare anode layer 2 at step S02 with light-transmissive substrates layer 1 relative surface evaporation hole injection layer material, hole transport layer material, luminescent layer material, electric transmission layer material and the electronic injection layer material successively of face that combine, prepare respectively hole injection layer 31, hole transmission layer 32, luminescent layer 33, electron transfer layer 34, electron injecting layer 35, form organic function layer 3;
S04. prepare cathode layer 4: in vacuum coating system, at organic function layer 3 outer surface cathode materials, form cathode layer 4.
Particularly, in above-mentioned S01 step, structure, material and the specification of substrate 1 as described above, for length, do not repeat them here.In addition, in this S01 step, also comprise the treatment step in early stage to substrate 1, as cleaned the step of decontamination, the step of specifically cleaning decontamination is as the step 1 of embodiment 1 below.
In above-mentioned steps S02, in the process conditions of splash-proofing sputtering metal reflector 21, scattering layer 22, interfering layer 23 and semi-transparent metal level 24, base target spacing when each layer of sputter is preferably 60mm, and working gas is that argon flow amount is preferably 25sccm.Particularly, in the time of splash-proofing sputtering metal reflector 21, using metallic reflector mentioned above 21 metal materials as target, sputtering rate is 0.02～1nm/s; When sputter scattering layer 22, simultaneously, using scattering layer mentioned above 22 transparent conductive oxides and metal material as target, the sputtering rate of metal material is 0.1～0.2nm/s, and the speed of the sputter of oxide is 0.5～1nm/s; When sputter interfering layer 23, using interfering layer mentioned above 23 transparent conductive oxides, separately as target, sputtering rate is 0.1～0.5nm/s; When the semi-transparent metal level 24 of sputter, using semi-transparent metal level 24 metal materials mentioned above as target, sputtering rate is 0.02～0.1nm/s.In sputter anode layer 2, the sputtering time of each layer is determined according to the thickness of each layer.
In above-mentioned steps S03, the material that evaporation hole injection layer 31, hole transmission layer 32, luminescent layer 33, electron transfer layer 34, electron injecting layer 35 are selected and even thickness are as described above.The operating pressure that each layer of involved process conditions of evaporation are preferably vacuum moulding machine film forming is 1 × 10 -5～1 × 10 -3pa, the evaporation rate of organic material is 0.01～1nm/s.
When organic function layer 3 as described above, it comprises the hole injection layer 31 that stacks gradually combination, hole transmission layer 32, electronic barrier layer 36, luminescent layer 33, hole blocking layer 37, electron transfer layer 34, when electron injecting layer 35, or it comprises the hole transmission layer 32 that stacks gradually combination, electronic barrier layer 36, luminescent layer 33, hole blocking layer 37, when electron transfer layer 34, or it comprises the hole transmission layer 32 that stacks gradually combination, luminescent layer 33, when electron transfer layer 34, the method of preparing organic function layer 3 is in this each layer of structure of anode layer 2 outer surfaces successively evaporation.
In above-mentioned steps S04, the thickness of the cathode material that evaporation cathode layer 4 is used and the cathode layer 4 preparing all as described above, does not repeat them here.Its evaporation condition adopts the process conditions of this area routine, and as the evaporation rate of metal is preferably 0.2～2nm/s, the operating pressure of vacuum moulding machine film forming is 1 × 10 -5～1 × 10 -3pa.
Certainly, it is also understood that about the preparation method of embodiment of the present invention Organnic electroluminescent device and also should comprise the method for packing that this Organnic electroluminescent device is follow-up.
Correspondingly, the embodiment of the present invention also provides a kind of display screen, and it comprises display module and for controlling the control module of display module, certainly also comprises other necessary modules of application and display screen.Wherein, this display module comprises Organnic electroluminescent device described above, and particularly, in display module, Organnic electroluminescent device mentioned above is arranged according to matrix.Because this display screen contains above-mentioned Organnic electroluminescent device, therefore it has high-contrast, and its display frame is clear.
Correspondingly, the embodiment of the present invention further provides a kind of terminal that is provided with display screen, and the display screen of this terminal is the above-mentioned display that contains Organnic electroluminescent device.Certainly, should be appreciated that, according to the type difference of this terminal, this terminal, except containing display screen mentioned above, also contains other necessary modules or/and device.Therefore, this terminal can be non-portable terminal and portable terminal.Non-portable terminal can be that large-scale household electrical appliances (as television set, desktop computer display, be provided with air-conditioning, the washing machine etc. of display screen), factory are provided with lathe of display screen etc.; Portable terminal can be mobile phone, panel computer, notebook, personal digital assistant, game machine and e-book etc.Like this, because the display screen of this terminal is the above-mentioned display screen that contains Organnic electroluminescent device, therefore the display screen contrast of electronic device is high, and picture is clear.
Certainly, Organnic electroluminescent device mentioned above can also be applied in characteristic lighting field, as applied in the lighting field that reflectivity is low requiring.
Illustrate above-mentioned Organnic electroluminescent device aspect by multiple embodiment below.
Embodiment 1
That a kind of anode has an antiradar reflectivity and negative electrode is as the Organnic electroluminescent device of exiting surface, its structure is: glass substrate/Al (70nm)/ITO:Ni (10nm)/ITO (50nm)/Al (5nm)/hole injection layer (CuPc, 10nm)/hole transmission layer (NPB, 30nm)/luminescent layer (DPVBi, 10nm)/electron transfer layer (TPBi, 30nm)/electron injecting layer (LiF, 0.5nm)/Ag (18nm).Wherein, Al (70nm)/ITO:Ni (10nm)/ITO (50nm)/Al (5nm) forms anode.
Its preparation method is as follows:
(1) glass substrate is cleaned with cleaning agent, then use distilled water, acetone is ultrasonic cleaning successively;
(2) be 10 in vacuum degree -4in the vacuum coating system of Pa, adopt magnetron sputtering technique, prepare anode at glass baseplate surface, in its preparation technology parameter, base target spacing is 60mm, and working gas is that argon flow amount is 25sccm:
First prepare reflective metal layer: using metal A l material as target, sputtering rate is 0.02nm/s, and thickness is 70nm;
Prepare again scattering layer: first prepare the scattering layer of thickness 10nm, wherein metal material is Ni, and sputtering rate is 0.1nm/s, and the material of inorganic oxide is ITO target, and the speed of sputter is 0.5nm/s; Wherein, at the scattering layer of preparation, the doping of this Ni accounts for 16.7% of scattering layer total weight;
Then prepare dielectric layer: thickness is 50nm, material is ITO target, and sputtering rate is 0.1nm/s;
Finally prepare half reflection metal layer: material is Al, thickness is 5nm, and sputtering rate is 0.02nm/s;
(3) be followed successively by hole injection layer, hole transmission layer, luminescent layer in the preparation of anode surface evaporation, electron transfer layer, electron injecting layer, forms organic function layer, material is followed successively by CuPc, NPB, DPVBi, TPBi, LiF, and thickness is followed successively by 10nm, 30nm, 10nm, 30nm, 0.5nm;
(4) prepare Ag layer at organic function layer outer surface and form negative electrode; Thickness is 18nm;
(5), after preparation, adopt glass cover-plate to encapsulate.
Embodiment 2
That a kind of anode has an antiradar reflectivity and negative electrode is as the Organnic electroluminescent device of exiting surface, its structure is: glass substrate/Ag (200nm)/IZO:Ag (20nm)/IZO (60nm)/Ag (7nm)/hole injection layer (ZnPc, 15nm)/hole transmission layer (TPD, 30nm)/luminescent layer (Ir (ppy) 3: TPBi (10%), 10nm)/electron transfer layer (Bphen, 40nm)/electron injecting layer (CsF, 1nm)/Sm (35nm).Wherein, Ag (200nm)/IZO:Ag (20nm)/IZO (60nm)/Ag (7nm) forms anode.
Its preparation method is as follows:
(1) glass substrate is cleaned with cleaning agent, then use distilled water, acetone is ultrasonic cleaning successively;
(2) be 10 in vacuum degree -4in the vacuum coating system of Pa, adopt magnetron sputtering technique, prepare anode at glass baseplate surface, in its preparation technology parameter, base target spacing is 60mm, and working gas is that argon flow amount is 25sccm:
First prepare reflective metal layer: using metal A g material as target, sputtering rate is 1nm/s, and thickness is 200nm;
Prepare again scattering layer: first prepare the scattering layer of thickness 20nm, wherein metal material is Ag, and sputtering rate is 0.15nm/s, and the material of inorganic oxide is IZO target, and the speed of sputter is 1nm/s; Wherein, at the scattering layer of preparation, the doping of this Ag accounts for 13.0% of scattering layer total weight;
Then prepare dielectric layer: thickness is 60nm, material is IZO target, and sputtering rate is 0.05nm/s;
Finally prepare half reflection metal layer: material is Ag, thickness is 7nm, and sputtering rate is 0.05nm/s;
(3) be followed successively by hole injection layer in the preparation of anode surface evaporation, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, forms organic function layer;
(4) prepare Sm layer at organic function layer outer surface and form negative electrode; Thickness is 35nm;
(5), after preparation, adopt glass cover-plate to encapsulate.
Embodiment 3
That a kind of anode has an antiradar reflectivity and negative electrode is as the Organnic electroluminescent device of exiting surface, its structure is: glass substrate/Au (100nm)/GZO:Pt (15nm)/GZO (60nm)/Au (10nm)/hole injection layer (TiOPc, 20nm)/hole transmission layer (MeO-Sprio-TPD, 40nm)/luminescent layer (DCJTB:Alq 3(1%), 15nm)/electron transfer layer (PBD, 50nm)/electron injecting layer (NaF, 0.8nm)/Yb (30nm).Wherein, Au (100nm)/GZO:Pt (15nm)/GZO (60nm)/Au (10nm) forms anode.
Its preparation method is as follows:
(1) glass substrate is cleaned with cleaning agent, then use distilled water, acetone is ultrasonic cleaning successively;
(2) be 10 in vacuum degree -4in the vacuum coating system of Pa, adopt magnetron sputtering technique, prepare anode at glass baseplate surface, in its preparation technology parameter, base target spacing is 60mm, and working gas is that argon flow amount is 25sccm:
First prepare reflective metal layer: using metal A u material as target, sputtering rate is 0.5nm/s, and thickness is 100nm;
Prepare again scattering layer: first prepare the scattering layer of thickness 15nm, wherein metal material is Pt, and sputtering rate is 0.1nm/s, and the material of inorganic oxide is GZO target, and the speed of sputter is 1nm/s; Wherein, at the scattering layer of preparation, the doping of this Pt accounts for 9.1% of scattering layer total weight;
Then prepare dielectric layer: thickness is 60nm, material is GZO target, and sputtering rate is 0.5nm/s;
Finally prepare half reflection metal layer: material is Au, thickness is 10nm, and sputtering rate is 0.1nm/s;
(3) be followed successively by hole injection layer in the preparation of anode surface evaporation, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, forms organic function layer;
(4) prepare Yb layer at organic function layer outer surface and form negative electrode; Thickness is 30nm;
(5), after preparation, adopt glass cover-plate to encapsulate.
Embodiment 4
That a kind of anode has an antiradar reflectivity and negative electrode is as the Organnic electroluminescent device of exiting surface, its structure is: glass substrate/Cr (70nm)/AZO:Pt (10nm)/AZO (50nm)/Cr (5nm)/hole injection layer (VOPc, 15nm)/hole transmission layer (MeO-TPD, 35nm)/luminescent layer (Ir (piq) 3:NPB (10%), 12nm)/electron transfer layer (PBD, 40nm)/electron injecting layer (MgF 2, 0.5nm) and/Ag (18nm).Wherein, Cr (70nm)/AZO:Pt (10nm)/AZO (50nm)/Cr (5nm) forms anode.
Its preparation method is as follows:
(1) glass substrate is cleaned with cleaning agent, then use distilled water, acetone is ultrasonic cleaning successively;
(2) be 10 in vacuum degree -4in the vacuum coating system of Pa, adopt magnetron sputtering technique, prepare anode at glass baseplate surface, in its preparation technology parameter, base target spacing is 60mm, and working gas is that argon flow amount is 25sccm:
First prepare reflective metal layer: using Metal Cr material as target, sputtering rate is 0.02nm/s, and thickness is 70nm;
Prepare again scattering layer: first prepare the scattering layer of thickness 10nm, wherein metal material is Pt, and sputtering rate is 0.1nm/s, and the material of inorganic oxide is AZO target, and the speed of sputter is 0.5nm/s; Wherein, at the scattering layer of preparation, the doping of this Pt accounts for 16.7% of scattering layer total weight;
Then prepare dielectric layer: thickness is 50nm, material is AZO target, and sputtering rate is 0.1nm/s;
Finally prepare half reflection metal layer: material is Cr, thickness is 5nm, and sputtering rate is 0.02nm/s;
(3) be followed successively by hole injection layer in the preparation of anode surface evaporation, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, forms organic function layer;
(4) prepare Ag layer at organic function layer outer surface and form negative electrode; Thickness is 18nm;
(5), after preparation, adopt glass cover-plate to encapsulate.
Embodiment 5
That a kind of anode has an antiradar reflectivity and negative electrode is as the Organnic electroluminescent device of exiting surface, its structure is: glass substrate/Ni (100nm)/ITO:Cu (10nm)/ITO (50nm)/Ni (5nm)/hole injection layer (VOPc, 15nm)/hole transmission layer (MeO-TPD, 35nm)/luminescent layer (Ir (piq) 3:NPB (10%), 12nm)/electron transfer layer (PBD, 40nm)/electron injecting layer (MgF 2, 0.5nm) and/Ag (18nm).Wherein, Ni (100nm)/ITO:Cu (10nm)/ITO (50nm)/Ni (5nm) forms anode.
Its preparation method is as follows:
(1) glass substrate is cleaned with cleaning agent, then use distilled water, acetone is ultrasonic cleaning successively;
(2) be 10 in vacuum degree -4in the vacuum coating system of Pa, adopt magnetron sputtering technique, prepare anode at glass baseplate surface, in its preparation technology parameter, base target spacing is 60mm, and working gas is that argon flow amount is 25sccm:
First prepare reflective metal layer: using metal Ni material as target, sputtering rate is 0.02nm/s, and thickness is 100nm;
Prepare again scattering layer: first prepare the scattering layer of thickness 10nm, wherein metal material is Cu, and sputtering rate is 0.1nm/s, and the material of inorganic oxide is ITO target, and the speed of sputter is 0.5nm/s; Wherein, at the scattering layer of preparation, the doping of this Cu accounts for 16.7% of scattering layer total weight;
Then prepare dielectric layer: thickness is 50nm, material is ITO target, and sputtering rate is 0.1nm/s;
Finally prepare half reflection metal layer: material is Ni, thickness is 5nm, and sputtering rate is 0.02nm/s;
(3) be followed successively by hole injection layer in the preparation of anode surface evaporation, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, forms organic function layer;
(4) prepare Ag layer at organic function layer outer surface and form negative electrode; Thickness is 18nm;
(5), after preparation, adopt glass cover-plate to encapsulate.
Comparison example 1
A kind of negative electrode is as the Organnic electroluminescent device of exiting surface, its structure is: glass substrate/Ag (100nm)/hole injection layer (CuPc, 10nm)/hole transmission layer (NPB, 30nm)/luminescent layer (DPVBi, 10nm)/electron transfer layer (TPBi, 30nm)/electron injecting layer (LiF, 0.5nm)/Ag (18nm).Wherein, Ag (100nm) is anode.
Organnic electroluminescent device carries out correlated performance test
When the Organnic electroluminescent device of existing anode construction is not lighted in Organnic electroluminescent device prepared by above-described embodiment 1 to embodiment 5 and comparison example 1, carry out reflectance test, test result is as following table 1.
Table 1
From above-mentioned table 1, the Organnic electroluminescent device of preparing in above-described embodiment 1-5 is owing to adopting metallic reflector, scattering layer, interfering layer, semi-transparent metal level to form black anode, by the synergy of each layer, make the single spin-echo of metallic reflector, semi-transparent metallic reflection light, reach the effect that interference disappears mutually, effectively reduce the total reflection of light, realized low reflectivity.The anode that particularly can further reduce above-mentioned Organnic electroluminescent device to scattering layer, interfering layer thickness and material adjustment, to reflection of light rate, has improved its contrast.The reflectivity of Organnic electroluminescent device prepared by embodiment 1-5 is compared with Organnic electroluminescent device in comparison example 1, the reflectivity of Organnic electroluminescent device prepared by embodiment 1-5 is reduced to 15.9%, well below the reflectivity 80.5% of Organnic electroluminescent device in comparison example 1.Hence one can see that, and Organnic electroluminescent device prepared by embodiment 1-5 is during as display screen, and its contrast is the contrast when Organnic electroluminescent device is as display screen in comparison example 1 far away.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.

Claims (10)

1. an Organnic electroluminescent device, comprise the substrate, anode layer, organic function layer and the cathode layer as exiting surface that stack gradually combination, described organic function layer is included in luminescent layer luminous under the driving of additional power source, it is characterized in that: described anode layer comprises the metallic reflector, scattering layer, interfering layer, the semi-transparent metal level that stack gradually combination, the stacked combination of described metallic reflector and substrate, described semi-transparent metal level and the stacked combination of organic function layer; Wherein, described scattering layer material comprises transparent conductive oxide and be doped in the metallic in described transparent conductive oxide, and described interfering layer material is transparent conductive oxide.
2. Organnic electroluminescent device as claimed in claim 1, is characterized in that: the transparent conductive oxide in described scattering layer material and interfering layer material transparent conductive oxide are at least one in identical or not identical indium and tin oxide film, indium-zinc oxide or aluminium zinc oxide, gallium zinc oxide.
3. Organnic electroluminescent device as claimed in claim 1 or 2, is characterized in that: the metallic doping in described scattering layer material accounts for 9.1%～16.7% of scattering layer total weight, and described metallic is at least one in Ag, Cr, Ni, Pt, Cu.
4. Organnic electroluminescent device as claimed in claim 1 or 2, is characterized in that: the thickness of described scattering layer is 10nm～20nm.
5. Organnic electroluminescent device as claimed in claim 1 or 2, is characterized in that: the thickness of described interfering layer is 60nm～80nm.
6. Organnic electroluminescent device as claimed in claim 1, is characterized in that: the thickness of described metallic reflector is 70nm～200nm.
7. Organnic electroluminescent device as claimed in claim 1, is characterized in that: described semi-transparent metal layer thickness is 5nm～10nm.
8. the Organnic electroluminescent device as described in claim 1 or 6 or 7, is characterized in that: described metallic reflection layer material is or/and semi-transparent metal layer material is any one or more alloy in metal A g, Al, Au, Ni, Cr.
9. a display screen, comprises display module and for controlling the control module of display module, it is characterized in that: described display module contains just like the Organnic electroluminescent device described in claim 1～8 any one.
10. be provided with a terminal for display screen, the display screen of described terminal is display screen as claimed in claim 9.
CN201310193565.1A 2013-05-22 2013-05-22 Organic light emission diode, display screen and terminal Pending CN104183720A (en)

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Application publication date: 20141203