CN104183710A - Inversed organic light emission diode, display screen and terminal - Google Patents
Inversed organic light emission diode, display screen and terminal Download PDFInfo
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- CN104183710A CN104183710A CN201310192343.8A CN201310192343A CN104183710A CN 104183710 A CN104183710 A CN 104183710A CN 201310192343 A CN201310192343 A CN 201310192343A CN 104183710 A CN104183710 A CN 104183710A
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- H—ELECTRICITY
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- H10K50/00—Organic light-emitting devices
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- H—ELECTRICITY
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- H10K50/00—Organic light-emitting devices
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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
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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
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- H10K50/86—Arrangements for improving contrast, e.g. preventing reflection of ambient light
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Abstract
The invention discloses an inversed organic light emission diode, a display screen and a terminal. The inversed organic light emission diode includes a substrate, a cathode layer, an organic function layer and an anode layer used as a light-emitting surface, which are sequentially laminated and combined. The organic function layer includes a light-emitting layer which emits light under the drive of an external power supply. The light emission diode is characterized in that the cathode layer includes a transflective metal layer, an interference layer with light transmission property and a metal reflection layer, which are sequentially laminated and combined, wherein the transflective metal layer and the organic function layer are laminated and combined, and the metal reflection layer and the substrate layer are laminated and combined; and an interference layer material is a metal oxide, the refractive index of which is larger than or equal to 2.0. The cathode of the inversed organic light emission diode effectively reduces a light reflectivity of the cathode of the inversed organic light emission diode and improves the contrast ratio thereof. The display screen which includes the inversed organic light emission diode and the terminal have high contrast ratios and clear display pictures.
Description
Technical field
The invention belongs to electric light source technology field, relate to specifically a kind of inversion 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, by insider, thought to be most likely at 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.Because the whole world is increasing, throw light on 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 surpasses 90% in visible ray section, so 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 during 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, the inversion Organnic electroluminescent device that provides a kind of negative electrode to there is 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 inversion Organnic electroluminescent device, comprise and stack gradually the substrate, cathode layer, organic function layer of combination and as the anode layer of exiting surface, described organic function layer is included in luminescent layer luminous under the driving of additional power source, described cathode layer comprise stack gradually combination semi-transparent metal level, there is interfering layer, metallic reflector to photopermeability, wherein, described semi-transparent metal level and the stacked combination of organic function layer, the stacked combination of described metallic reflector and substrate; Described interfering layer material is that refractive index is more than or equal to 2.0 metal oxide.
And a kind of display screen, comprises display module and for controlling the control module of display module, wherein said display module contains inversion 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 of being inverted Organnic electroluminescent device that contains.
Above-mentioned inversion Organnic electroluminescent device by negative electrode is arranged to stack gradually combination semi-transparent metal level, there is interfering layer, metallic reflector structure to photopermeability, effectively reduce the negative electrode of this inversion Organnic electroluminescent device to reflection of light rate, improved its contrast.Wherein, this semi-transparent metal level can to by from anode tap incident light the effect of semi-transflective reflective; Interfering layer can reach the effect that interference disappears mutually by semi-transparent metal layer reflection light and the catoptrical single spin-echo of metallic reflector, has effectively reduced the total reflection of light, realizes low reflectivity.
Above-mentioned display screen is owing to containing above-mentioned inversion Organnic electroluminescent device, so 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, so the display screen picture of this terminal is clear.
Accompanying drawing explanation
Fig. 1 is that the embodiment of the present invention is inverted Organnic electroluminescent device structural representation;
Fig. 2 is that the embodiment of the present invention is inverted another preferred structure schematic diagram of Organnic electroluminescent device;
Fig. 3 is the schematic flow sheet that the embodiment of the present invention is inverted Organnic electroluminescent device preparation method.
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 negative electrode reflectivity to improve organic electroluminescent pixel contrast.Therefore, the inversion Organnic electroluminescent device that the embodiment of the present invention provides a kind of negative electrode to have antiradar reflectivity, its structure is as shown in Figure 1 to Figure 2.This inversion Organnic electroluminescent device comprises substrate 1, cathode layer 2, organic function layer 3 and the anode layer 4 that stacks 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 cathode layer 2 comprise stack gradually combination metallic reflector 21, have the interfering layer 22 of photopermeability and semi-transparent metal level 23, wherein, this metallic reflector 21 and the stacked combination of substrate 1, semi-transparent metal level 23 and the stacked combination of organic function layer 3.Semi-transparent metal level 23 in the cathode layer 2 of this structure can to from anode layer 4 end incident lights the effect of semi-transflective reflective, interfering layer 22 can play to the light at its interface of incident the interference effect of refraction, make semi-transparent metal level 23 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.Therefore, when this Organnic electroluminescent device is connected to additional power source, the negative pole of additional power source is connected on semi-transparent metal level 23, and its positive pole is connected on anode layer 4.Particularly, from organic function layer 3, the light reflection of the cathode layer 2 of this structure of directive and refraction are as shown in Fig. 1,2, ambient light a is during from outside incident, on semi-transparent metal level 23 surfaces, there is reflection and refraction, form reflection ray b, refracted ray c sees through interfering layer 22 and arrives metallic reflector 21 surfaces, reflects, and forms reflection ray d.Under the effect of interfering layer 22, reflection ray b becomes the interference of light to disappear mutually with reflection ray D-shaped, weakens the reverberation that cathode layer 2 produces, thereby effectively reduces the reflectivity of cathode layer 2.
Wherein, this semi-transparent metal level 23 and the stacked combination of organic function layer 3, this semi-transparent metal level 23 can make the light that anode layer 4 end-fires come that the reflection of part permeation parts occurs at its interface.For reflection and the transmitance of better light regulating, as preferred embodiment, the thickness of this semi-transparent metal level 23 is 5～10nm, and its thickness can also be adjusted flexibly according to the difference of material.As another preferred embodiment, above-mentioned semi-transparent metal level 23 metal materials are any or both the above alloys in Mg, Ag, Al, Ca, and this preferred material not only has good semi permeability, also has excellent electronic injection performance.Should be appreciated that, as long as can realize other thickness of this semi-transparent metal level 23 part permeation parts reflections and other, can do cathodic metal material and also belong to the framework of the present definition.
This interfering layer 22 is layered between semi-transparent metal level 23 and metallic reflector 21, the single spin-echo of the light of two-layer reflection can be reached to the effect that interference disappears mutually, has effectively reduced the total reflection of light.In order to realize, the light at its interface of incident is played to effective interference effect, interfering layer 22 materials are that refractive index is more than or equal to 2.0 metal oxide.In a preferred embodiment, this metal oxide TiO
2, CeO
2, Ta
2o
5, ZrO
2in at least one.TiO
2, CeO
2, Ta
2o
5, ZrO
2these materials have the refractive index that is greater than 2.0, and all can see through in visible region, therefore being prepared interfering layer 22 can obtain extraordinary interference and disappear mutually, to realize antireflecting effect, the light that concrete is makes to see through from semi-transparent metal level 23 is passed to its interface, light is reflected, after this refract light is incident to metallic reflector 21 and reflects, the effect offseting to realize semi-transparent metal level 23 and metallic reflector 21 reverberation.Therefore, adopt TiO
2, CeO
2, Ta
2o
5, ZrO
2prepare interfering layer 22 and give the high-contrast that the embodiment of the present invention is inverted Organnic electroluminescent device excellence.
By regulating the thickness of interfering layer 22, can effectively improve the effect that semi-transparent metal level 23 and metallic reflector 21 reverberation offset.Therefore, as preferred embodiment, material is that these interfering layer 22 thickness that refractive index is more than or equal to 2.0 metal oxide are 60nm～80nm, and in specific embodiment, its thickness can be 60nm, 65nm, 70nm, 75nm, 80nm etc.
The object that this metallic reflector 21 arranges is that the light that will come from interfering layer 22 transmission reflect at its interface, and the light that this reverberation is occurred to reflect with semi-transparent metal level 23 interfaces after by the transmission of interfering layer 22 cancels each other, to reduce the reflectivity of cathode layer 2.As preferred embodiment, the thickness of this metallic reflector 21 is 70～200nm.As another preferred embodiment, above-mentioned metallic reflector 21 metal materials are Al, Au, any in Ag or both above alloys.Should be appreciated that, as long as can realize other thickness and other energy metal materials of the reflection action of this metallic reflector 21, also belong to the framework of the present definition, as disregard cost, the thickness of this metallic reflector 21 can also be more than 200nm.
As another preferred embodiment of above-mentioned inversion Organnic electroluminescent device, the thickness of above-mentioned semi-transparent metal level 23 is 5～10nm, and the thickness of interfering layer 22 is 60～80nm, and the thickness of metallic reflector 21 is 70～200nm.The combination of each layer thickness in the preferred embodiment, the better effects if that can make the interference of light of semi-transparent metal level 23 and metallic reflector 21 reflections disappear mutually, makes the reflectivity that cathode layer 2 is lower.
As a preferred embodiment again of above-mentioned inversion Organnic electroluminescent device, above-mentioned semi-transparent metal level 23 materials are any or both the above alloys in Mg, Ag, Al, Ca, and interfering layer 22 materials are TiO
2, CeO
2, Ta
2o
5, ZrO
2in at least one, metallic reflector 21 materials are Al, Au, any in Ag or both above alloys.The combination of each layer of selected material in the preferred embodiment, gives reflectivity and electronic injection performance that cathode layer 2 is lower.
As the another preferred embodiment of above-mentioned inversion Organnic electroluminescent device, above-mentioned semi-transparent metal level 23 materials are any or both the above alloys in Mg, Ag, Al, Ca, and its thickness is 5～10nm; Interfering layer 22 materials are TiO
2, CeO
2, Ta
2o
5, ZrO
2in at least one, and its thickness is 60～80nm; Metallic reflector 21 materials are Al, Au, and any in Ag or both above alloys, and its thickness is 70～200nm.The combination of each layer thickness and material in the preferred embodiment, the better effects if that can make the interference of light of semi-transparent metal level 23 and metallic reflector 21 reflections disappear mutually, makes cathode layer 2 have lower reflectivity and excellent electronic injection performance.
Organic function layer 3 in above-mentioned inversion Organnic electroluminescent device embodiment comprises electron injecting layer 31, electron transfer layer 32, luminescent layer 33, hole transmission layer 34, the hole injection layer 35 that stacks gradually combination, and electron injecting layer 31 and the stacked combination of cathode layer 2, particularly, the surface stacked combination relative with interfering layer 22 faying faces of semi-transparent metal level 23 in 2 layers of electron injecting layer 31 and cathode layers, as shown in Figure 1.
In specific embodiment, above-mentioned electron injecting layer 31 materials can LiF, CsF, NaF, MgF
2deng at least one etc. alkali-metal halide, certainly, these electron injecting layer 31 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 31 also can arrange according to the thickness of this area routine.The arranging of this electron injecting layer 31 can effectively strengthen the ohmic contact between itself and cathode layer 2, strengthened electric conductivity, further improve the electronic injection ability of cathode layer 2 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 31 can not arrange according to the actual needs yet, that is to say, electron transfer layer 32 can be directly and the direct stacked combination of cathode layer 2.
Above-mentioned electron transfer layer 32 materials can be 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole (PBD), (oxine)-aluminium (Alq3), 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, in 10-phenanthrolene (BCP) at least one.Certainly, electron transfer layer 32 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 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 (Alq3), 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), 4,4'-two [4-(di-p-tolyl is amino) styryl] biphenyl (DPAVBi), 5,6, 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 hole transmission layer 34 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) at least one-9,9-spiral shell two fluorenes).Certainly, these hole transmission layer 34 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 34 also can arrange according to the thickness of this area routine.
Above-mentioned hole injection layer 35 materials can be ZnPc (Phthalocyanine Zinc), CuPc(CuPc), at least one in VOPc (ranadylic phthalocyanine), TiOPc (TiOPc).Certainly, these hole injection layer 35 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 35 also can arrange according to the thickness of this area routine.The setting of this hole injection layer 35, can effectively strengthen the ohmic contact of 4 of itself and anode layers, has strengthened electric conductivity, improves the hole injectability of anode layer 4 ends.Just because of this, this hole injection layer 35 can not arrange according to the actual needs yet, that is to say, hole transmission layer 34 can be directly and the direct stacked combination of anode 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 hole blocking layer 36 and electronic barrier layer 37 Hes, as shown in Figure 2.Wherein, this electronic barrier layer 37 is stacked to be combined between hole transmission layer 34 and luminescent layer 33, and hole blocking layer 36 is stacked to be combined between luminescent layer 33 and electron transfer layer 32.Arranging of this electronic barrier layer 37 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 36 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 37 and hole blocking layer 36 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 anode layer 4 is as the exiting surface of above-mentioned inversion Organnic electroluminescent device, and therefore, it is 18～35nm that its thickness is preferably.These anode layer 4 materials are preferably in arbitrary in Ag, Au, Al or two or more alloys, and this preferred anode material electric conductivity is excellent.Certainly, these anode layer 4 materials and thickness can also be other materials and the thickness of this area routine.
From the above, above-mentioned inversion Organnic electroluminescent device by negative electrode is arranged to stack gradually combination metallic reflector 21, there are the interfering layer 22 to photopermeability, semi-transparent metal level 23 structures, by the light reflection negative function of cathode layer 2, thereby effectively reduce the negative electrode of this inversion Organnic electroluminescent device to reflection of light rate, improved its contrast.In addition, by selecting metallic reflector 21, thering is the interfering layer 22 to photopermeability, material and the thickness of semi-transparent metal level 23, can further reduce the negative electrode of above-mentioned inversion Organnic electroluminescent device to reflection of light rate, improve its contrast.
Correspondingly, so above-described embodiment inversion 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 cathode layer 2: in vacuum coating system, metallic reflection layer material is sputtered to substrate 1 one outer surface film forming, form metallic reflector 21; Again interfering layer material is sputtered to these metallic reflector 21 outer surfaces, form interfering layer 22; Then the substrate 1 that is coated with reflector 21 and interfering layer 22 is placed in to vacuum thermal evaporation system, by semi-transparent metal layer material evaporation at interfering layer 22 outer surfaces, form semi-transparent metal level 23, this metallic reflector 21, interfering layer 22 and semi-transparent metal level 23 form cathode layer 2;
S03. prepare organic function layer 3: at step S02, prepare cathode layer 2 with substrate 1 the combine relative surface of face evaporation electronic injection layer material, electric transmission layer material, luminescent layer material, hole transport layer material and hole injection layer material successively, prepare respectively electron injecting layer 31, electron transfer layer 32, luminescent layer 33, hole transmission layer 34 and hole injection layer 35, form organic function layer 3;
S04. prepare anode layer 4: in vacuum coating system, at organic function layer 3 outer surface evaporation anode materials, form anode layer 4.
Particularly, in above-mentioned S01 step, the structure of substrate 1, material and specification 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, the material that the semi-transparent metal level 23 of splash-proofing sputtering metal reflector 21 and interfering layer 22 and evaporation is selected and even thickness are as described above.Wherein, the process conditions of splash-proofing sputtering metal reflector 21 and interfering layer 22 can be sputtering technology conditions in embodiment 1-4 below, and certainly, the process conditions of splash-proofing sputtering metal reflector 21 and interfering layer 22 also can adopt the sputtering technology condition of this area routine.The operating pressure that the process conditions of the semi-transparent metal level 23 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.This preferred sputtering technology condition, can obtain metallic reflector 21 and the interfering layer 22 of densification and homogeneous.
In above-mentioned steps S03, the material that evaporation electron injecting layer 31, electron transfer layer 32, luminescent layer 33, hole transmission layer 34 and hole injection 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 electron injecting layer 31 that stacks gradually combination, electron transfer layer 32, hole blocking layer 36, luminescent layer 33, electronic barrier layer 37, when hole transmission layer 34 and hole injection layer 35, or it only includes the electron transfer layer 32 that stacks gradually combination, hole blocking layer 36, luminescent layer 33, when electronic barrier layer 37 and hole transmission layer 34, or it comprises the electron transfer layer 32 that stacks gradually combination, when luminescent layer 33 and hole transmission layer 34, the method of preparing organic function layer 3 is in this each layer of structure of cathode layer 2 outer surfaces successively evaporation.
In above-mentioned steps S04, the thickness of the anode material that evaporation anode layer 4 is used and the anode 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 the preparation method about embodiment of the present invention inversion Organnic electroluminescent device also should comprise the method for packing that this inversion 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 inversion Organnic electroluminescent device described above, and particularly, in display module, inversion Organnic electroluminescent device mentioned above is arranged according to matrix.Because this display screen contains above-mentioned inversion Organnic electroluminescent device, so 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 of being inverted Organnic electroluminescent device that contains.Certainly, should be appreciated that, different according to the type 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 large-scale household electrical appliances (as television set, desktop computer display, the air-conditioning that is provided with display screen, washing machine etc.), factory lathe of being provided with 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 above-mentionedly to contain the display screen of being inverted Organnic electroluminescent device, so the display screen contrast of electronic device is high, and picture is clear.
Certainly, inversion Organnic electroluminescent device mentioned above can also be applied in characteristic lighting field, as applied in requiring the lighting field that reflectivity is low.As the embodiment of the present invention also be can be applicable to illumination panel, at specific lighting condition, do not need illumination panel to have mirror-reflection particularly, the organic electroluminescence device of low reflection provided by the invention just can meet this demand.
By a plurality of embodiment, illustrate below the aspects such as above-mentioned inversion Organnic electroluminescent device.
Embodiment 1
That negative electrode has an antiradar reflectivity and anode is as an inversion Organnic electroluminescent device for exiting surface, and its structure is: glass substrate/Ag (70nm)/TiO
2(60nm)/Mg (10nm)/electron injecting layer (LiF, 0.5nm)/electron transfer layer (TPBi, 30nm)/luminescent layer (DPVBi, 10nm)/hole transmission layer (NPB, 30nm)/hole injection layer (CuPc, 10nm)/Ag (20nm).Wherein, Ag (70nm)/TiO
2(60nm)/Mg (10nm) forms negative electrode.
Its preparation method is as follows:
(1) glass substrate is cleaned with cleaning agent, then use distilled water, acetone is ultrasonic cleaning successively;
(2) in vacuum degree, be 10
-4in the vacuum coating system of Pa, prepare negative electrode on substrate, in its preparation technology parameter, base target spacing is 60mm, and working gas is that argon flow amount is 25sccm; Particularly, first reflective metal layer is prepared in sputter, and target is Ag, and thickness is 70nm, and sputtering rate is 0.5nm/s, is then interfering layer, and target is TiO
2, thickness is 60nm, and sputtering rate is 0.2nm/s, finally substrate is transferred in vacuum thermal evaporation system, at substrate surface, prepares semi-transflective reflective layer, and material is Mg, and thickness is 10nm, forms negative electrode;
(3) at cathode surface, prepare organic function layer and be followed successively by electron injecting layer, electron transfer layer, luminescent layer, hole transmission layer and hole injection layer, form organic function layer, material is followed successively by LiF, TPBi, DPVBi, NPB, CuPc, thickness is followed successively by 0.5nm, 30nm, 10nm, 30nm, 10nm;
(4) at organic function layer outer surface, prepare anode, material is metal A g, and thickness is 20nm;
(5), after preparation, adopt glass cover-plate to encapsulate.
Embodiment 2
Negative electrode has an inversion Organnic electroluminescent device for antiradar reflectivity, and its structure is: glass substrate/Ag (70nm)/CeO
2(75nm)/Al (5nm)/electron injecting layer (CsF, 1nm)/electron transfer layer (Bphen, 30nm)/luminescent layer (Ir (ppy)
3: TPBi (10%), 10nm)/hole transmission layer (TPD, 40nm)/hole injection layer (ZnPc, 15nm)/Au (35nm).Wherein, Ag (70nm)/CeO
2(75nm)/Al (5nm) forms negative electrode.
This is inverted Organnic electroluminescent device preparation method with reference to the inversion Organnic electroluminescent device preparation method of embodiment 1.Wherein, preparing in negative electrode step, is that first reflective metal layer is prepared in sputter, and target is Ag, and thickness is 70nm, and sputtering rate is 0.5nm/s, is then interfering layer, and target is CeO
2, thickness is 75nm, and sputtering rate is 0.1nm/s, finally substrate is transferred in vacuum thermal evaporation system, at substrate surface, prepares semi-transflective reflective layer, and material is Al, and thickness is 5nm, forms negative electrode.
Embodiment 3
Negative electrode has an inversion Organnic electroluminescent device for antiradar reflectivity, and its structure is: glass substrate/Ag (200nm)/ZrO
2(80nm)/Ag (7nm)/electron injecting layer (NaF, 0.8nm)/electron transfer layer (PBD, 50nm)/luminescent layer (DCJTB:Alq
3(1%), 20nm)/hole transmission layer (MeO-Sprio-TPD, 40nm)/hole injection layer (TiOPc, 15nm)/Al (18nm).Wherein, Ag (200nm)/ZrO
2(80nm)/Ag (7nm) forms negative electrode.
This is inverted Organnic electroluminescent device preparation method with reference to the inversion Organnic electroluminescent device preparation method of embodiment 1.Wherein, preparing in negative electrode step, is that first reflective metal layer is prepared in sputter, and target is Ag, and thickness is 200nm, and sputtering rate is 0.5nm/s, is then interfering layer, and target is ZrO
2, thickness is 80nm, and sputtering rate is 0.2nm/s, finally substrate is transferred in vacuum thermal evaporation system, at substrate surface, prepares semi-transflective reflective layer, and material is Ag, and thickness is 7nm, forms negative electrode.
Embodiment 4
Negative electrode has an inversion Organnic electroluminescent device for antiradar reflectivity, and its structure is: glass substrate/Ag (200nm)/Ta
2o
5(65nm)/Ca (10nm)/electron injecting layer (MgF
2, 0.5nm)/electron transfer layer (PBD, 40nm)/luminescent layer (Ir (piq)
3: NPB (10%), 12nm)/hole transmission layer (MeO-TPD, 15nm)/hole injection layer (VOPc, 35nm)/Au (30nm).Wherein, Ag (200nm)/Ta
2o
5(65nm)/Ca (10nm) forms negative electrode.
This is inverted Organnic electroluminescent device preparation method with reference to the inversion Organnic electroluminescent device preparation method of embodiment 1.Wherein, preparing in negative electrode step, is that first reflective metal layer is prepared in sputter, and target is Ag, and thickness is 200nm, and sputtering rate is 0.5nm/s, is then interfering layer, and target is Ta
2o
5, thickness is 65nm, and sputtering rate is 0.2nm/s, finally substrate is transferred in vacuum thermal evaporation system, at substrate surface, prepares semi-transflective reflective layer, and material is Ca, and thickness is 10nm, forms negative electrode.
Comparison example 1
Anode is as an inversion Organnic electroluminescent device for exiting surface, and its structure is: glass substrate/Ag (100nm)/TiO
2(60nm)/Mg (10nm)/electron injecting layer (LiF, 0.5nm)/electron transfer layer (TPBi, 30nm)/luminescent layer (DPVBi, 10nm)/hole transmission layer (NPB, 30nm)/hole injection layer (CuPc, 10nm)/Ag (20nm).Wherein, Ag (100nm) forms negative electrode.
Be inverted Organnic electroluminescent device and carry out correlated performance test
When the inversion Organnic electroluminescent device of existing cathode construction in the inversion Organnic electroluminescent device of above-described embodiment 1 to embodiment 4 preparation and comparison example 1 is not lighted, do not carry out reflectance test, test result is as following table 1.
Table 1
From above-mentioned table 1, the inversion Organnic electroluminescent device of preparing in above-described embodiment 1-4 is owing to adopting semi-transparent metal level/have to form black negative electrode to the structure of the interfering layer/metallic reflector of photopermeability, by the synergy of three layers, make semi-transparent metal layer reflection light and the catoptrical single spin-echo of metallic reflector, reach the effect that interference disappears mutually, effectively reduce the total reflection of light, realized low reflectivity.The reflectivity of inversion Organnic electroluminescent device prepared by embodiment 1-4 with in comparison example 1, be inverted Organnic electroluminescent device and compare, the reflectivity of inversion Organnic electroluminescent device prepared by embodiment 1-4 is reduced to 20.2%, well below the reflectivity 80.5% of being inverted Organnic electroluminescent device in comparison example 1.Hence one can see that, and inversion Organnic electroluminescent device prepared by embodiment 1-4 is during as display screen, and its contrast is the contrast when being inverted Organnic electroluminescent device 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 modifications 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. be inverted Organnic electroluminescent device for one kind, comprise and stack gradually the substrate, cathode layer, organic function layer of combination and as the anode layer of exiting surface, described organic function layer is included in luminescent layer luminous under the driving of additional power source, it is characterized in that: described cathode layer comprise stack gradually combination semi-transparent metal level, there is interfering layer, metallic reflector to photopermeability, wherein, described semi-transparent metal level and the stacked combination of organic function layer, the stacked combination of described metallic reflector and substrate; Described interfering layer material is that refractive index is more than or equal to 2.0 metal oxide.
2. inversion Organnic electroluminescent device as claimed in claim 1, is characterized in that: described metal oxide is TiO
2, CeO
2, Ta
2o
5, ZrO
2in at least one.
3. inversion Organnic electroluminescent device as claimed in claim 1 or 2, is characterized in that: the thickness of described interfering layer is 60nm～80nm.
4. inversion Organnic electroluminescent device as claimed in claim 1, is characterized in that: the thickness of described semi-transparent metal level is 5nm～10nm.
5. the inversion Organnic electroluminescent device as described in claim 1 or 4, is characterized in that: described semi-transparent metal level is any or both the above alloys in Mg, Ag, Al, Ca.
6. inversion Organnic electroluminescent device as claimed in claim 1, is characterized in that: the thickness of described metallic reflector is 70～200nm.
7. the inversion Organnic electroluminescent device as described in claim 1 or 6, is characterized in that: described metallic reflector is Al, Au, any in Ag or both above alloys.
8. inversion Organnic electroluminescent device as claimed in claim 1, is characterized in that:
The thickness of described semi-transparent metal level is 5～10nm;
The thickness of described interfering layer is 60～80nm;
The thickness of described metallic reflector is 70～200nm.
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 inversion 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.
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|---|---|---|---|---|
| US20020043931A1 (en) * | 2000-10-18 | 2002-04-18 | Kiyoshi Minoura | Luminous display element |
| US20070046183A1 (en) * | 2005-08-29 | 2007-03-01 | Kwok Hoi S | Metallic anode treated by carbon tetrafluoride plasma for organic light emitting device |
| CN102185111A (en) * | 2011-04-21 | 2011-09-14 | 河北工业大学 | Transition metal oxide inverted organic LED (light emitting diode) |
| CN102714281A (en) * | 2009-11-05 | 2012-10-03 | 韩国科学技术院 | Black organic light-emitting diode device |
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2013
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020043931A1 (en) * | 2000-10-18 | 2002-04-18 | Kiyoshi Minoura | Luminous display element |
| US20070046183A1 (en) * | 2005-08-29 | 2007-03-01 | Kwok Hoi S | Metallic anode treated by carbon tetrafluoride plasma for organic light emitting device |
| CN102714281A (en) * | 2009-11-05 | 2012-10-03 | 韩国科学技术院 | Black organic light-emitting diode device |
| CN102185111A (en) * | 2011-04-21 | 2011-09-14 | 河北工业大学 | Transition metal oxide inverted organic LED (light emitting diode) |
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Application publication date: 20141203 |