CN104183712A - Organic light emission diode, display screen and terminal - Google Patents
Organic light emission diode, display screen and terminal Download PDFInfo
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- CN104183712A CN104183712A CN201310192345.7A CN201310192345A CN104183712A CN 104183712 A CN104183712 A CN 104183712A CN 201310192345 A CN201310192345 A CN 201310192345A CN 104183712 A CN104183712 A CN 104183712A
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/865—Intermediate layers comprising a mixture of materials of the adjoining active layers
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/125—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light
- H10K50/13—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light comprising stacked EL layers within one EL unit
- H10K50/131—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light comprising stacked EL layers within one EL unit with spacer layers between the electroluminescent layers
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- 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
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- H—ELECTRICITY
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- 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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- H—ELECTRICITY
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Abstract
The invention discloses an organic light emission diode, a display screen and a terminal. The organic light emission diode includes a transparent substrate, an anode layer, at least two organic function layers, a cathode layer, and a charge generation layer with a transflective characteristic, which is laminated and combined between every two adjacent organic function layers. Each charge generation layer includes an Al layer and an Au layer, which are laminated and combined. In a direction from the anode layer to the cathode layer, the charge generation layer is laminated and combined between every two adjacent organic function layers according to an Al layer/Au layer lamination sequence. The organic light emission diode has a low light reflectivity and a high contrast ratio. The display screen which includes the organic light emission diode, and the terminal have a high contrast ratio and clear display pictures.
Description
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, 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 negative electrode 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 negative electrode 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 transparency carrier, anode layer, at least two organic function layers, the cathode layer that stack gradually combination, described organic function layer is included in luminescent layer luminous under the driving of additional power source, and the stacked charge generating layers with semi-transflective reflective characteristic that is combined with also between adjacent described organic function layer between two; Described charge generating layers comprises Al layer, the Au layer that stacks gradually combination, presses from anode layer to cathode layer direction, and described charge generating layers is combined between adjacent between two described organic function layer according to the lamination order of Al layer/Au layer is stacked.
And a kind of display screen, comprises display module and for controlling the control module of display module, wherein said 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 setting up the charge generating layers that contains Al layer/Au layer structure between the organic function layer adjacent between two, makes electric charge, at this interface, separation effectively occur, and has improved light efficiency, efficiency; In addition, its semi-transparent semi-reflecting characteristic makes the light coming from anode layer end-fire in its interface generating unit sub reflector and part refraction, again due to charge generating layers in Au layer by layer the organic function layer of folded combination can play the effect of dielectric layer, make the single spin-echo at the light of cathode layer reflection and the light of charge generating layers reflection, reach the effect that interference disappears mutually, effectively reduce the total reflection of light, realized low reflectivity.
Above-mentioned display screen is owing to containing above-mentioned 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 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;
Fig. 4 is the resolution chart of Organnic electroluminescent device reflectance spectrum in the Organnic electroluminescent device of embodiment 1 preparation and comparison example 1.
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 provides a kind of Organnic electroluminescent device with antiradar reflectivity, and its structure as shown in Figure 1 to Figure 2.This Organnic electroluminescent device comprises transparency carrier 1, anode layer 2, (organic function layer 3/ charge generating layers 4/ organic function layer 3) n and the cathode layer 5 that stacks gradually combination; Wherein, the natural number of n >=1.
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 materials are transparent conductive oxide.This transparent conductive oxide is preferably at least one in tin oxide film (ITO), indium-zinc oxide (IZO), aluminium zinc oxide (AZO), gallium zinc oxide (GZO).This preferred transparent conductive oxide has excellent light transmission rate, can effectively improve the light emission rate of this Organnic electroluminescent device, and in addition, this preferred transparent conductive oxide electric conductivity is excellent.These anode layer 2 thickness are preferably 70～200nm.Certainly, the material of this anode layer 2 and thickness can also be other materials and the thickness of this area routine.
Above-mentioned organic function layer 3 at least comprises two-layer, and charge generating layers 4 is stacked is combined between adjacent between two organic function layer 3, and therefore, in the above-described embodiments, charge generating layers 4 at least contains one deck.
Every layer of organic function layer 3 in above-described embodiment comprises hole transmission layer 31, luminescent layer 32, the electron transfer layer 33 that stacks gradually combination.Above-mentioned charge generating layers 4 comprises Al layer 41 and the Au layer 42 of stacked combination.Press from anode layer 2 to cathode layer 5 directions, the hole transmission layer 31 that this organic function layer 3 comprises, luminescent layer 32, electron transfer layer 33 lamination order are hole transmission layer 31/ luminescent layer 32/ electron transfer layers 33, and the Al layer 41 that this charge generating layers 4 comprises and Au layer 42 lamination order are Al layer 41/Au layers 42.Therefore, in the above-described embodiments, be somebody's turn to do in the unit of (organic function layer 3/ charge generating layers 4/ organic function layer 3) n, press from anode layer 2 to cathode layer 5 directions, in unit, each layer of lamination order is: hole transmission layer 31/ luminescent layer 32/ electron transfer layer 33/Al layer 41/Au layer 42/ hole transmission layer 31/ luminescent layer 32/ electron transfer layer 33.
In the specific embodiment as shown in Fig. 1,2, Organnic electroluminescent device comprises organic function layer 3a and organic function layer 3b two-layer organic function layer altogether, and the stacked one deck charge generating layers 4 being combined between this two-layer organic function layer, i.e. n=1 in (organic function layer 3/ charge generating layers 4/ organic function layer 3) n.Wherein, organic function layer 3a comprises hole transmission layer 31a/ luminescent layer 32a/ electron transfer layer 33a, organic function layer 3b comprises hole transmission layer 31b/ luminescent layer 32b/ electron transfer layer 33b, therefore, in this embodiment, the structure of Organnic electroluminescent device is substrate 1/ anode layer 2/ hole transmission layer 31a/ luminescent layer 32a/ electron transfer layer 33a/Al layer 41/Au layer 42/ hole transmission layer 31b/ luminescent layer 32b/ electron transfer layer 33b/ cathode layer 5.In this specific embodiment, ambient light a is during from outside directive Al layer 41 interface, there is first reflection and refraction in its interface, form reflection ray b, refracted ray c sees through Au layer and organic function layer 3b, this refract light reflects at cathode layer 5 interfaces together with organic function layer 3b, form reverberation d, the effect of the dielectric layer simultaneously playing due to organic function layer 3b, make at the light d of cathode layer 5 reflections and the single spin-echo of reflection ray b, reach the effect that interference disappears mutually, effectively reduced the total reflection of light, realize low reflectivity.
It should be understood that; in Fig. 1,2, organic function layer 3 and charge generating layers 4 are only the present invention's one specific embodiments; can be according to this specific embodiment and the Organnic electroluminescent device developing according to invention thinking of the present invention; all, within the scope of protection of the invention, concrete can be the specific embodiment when said n >=2.
Better for the dielectric layer effect that organic function layer 3b is play, make to disappear mutually effect more at the light d of cathode layer 5 reflections with the interference of reflection ray b, the general thickness of this organic function layer 3b is preferably 60nm～100nm.In like manner, in the specific embodiment of said n >=2, all can preferably be set to 60nm～100nm with the general thickness of the organic function layer 3 of Au layer 42 combination, so that each charge generating layers interface 4 reverberation disappear effect more mutually with cathode layer 5 reverberation interference, thereby realize reflectivity and high-contrast that Organnic electroluminescent device is low.
Wherein, above-mentioned hole transmission layer 31 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, two (N, N-bis-(4-methoxyphenyl) amino)-9 of 7-, 9-spiral shell two fluorenes) at least one in.Certainly, these hole transmission layer 31 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.
Above-mentioned luminescent layer 32 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 32 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).
Above-mentioned electron transfer layer 33 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.
In further preferred embodiment, on the basis of organic function layer 3 as shown in Figure 1, 2, above-mentioned every layer of organic function layer 3 can also arrange electronic barrier layer and hole blocking layer (showing without figure).Wherein, this electronic barrier layer is stacked to be combined between hole transmission layer 31 and luminescent layer 32, and hole blocking layer is stacked to be combined between luminescent layer 32 and electron transfer layer 33.Arranging of this electronic barrier layer can stop the electronics that does not form exciton in luminescent layer as much as possible and be trapped in luminescent layer 32, arranging of hole blocking layer can stop the hole that does not form exciton in luminescent layer 32 as much as possible and be trapped in luminescent layer 32, to improve electronics and the hole meeting rate in luminescent layer 32, 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 32.Certainly, this electronic barrier layer and hole blocking layer 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.
In further preferred embodiment, on the basis of organic function layer 3 as shown in Figure 1, 2, at the organic function layer 3 with anode layer 2 direct stacked combinations, also comprise hole injection layer (figure do not show), and this hole injection layer is stacked is combined between anode layer 2 and hole transmission layer 31.Particularly, as Fig. 1,2 organic function layer 3a also comprise hole injection layer, this hole injection layer is stacked to be combined between anode layer 2 and hole transmission layer 31a.
In further preferred embodiment, on the basis of organic function layer 3 as shown in Figure 1, 2, at the organic function layer 3 with cathode layer 5 direct stacked combinations, also comprise electron injecting layer (figure do not show), and this electron injecting layer is stacked is combined between cathode layer 5 and electron transfer layer 33.Particularly, as Fig. 1,2 organic function layer 3b also comprise electron injecting layer, this electron injecting layer is stacked to be combined between cathode layer 5 and electron transfer layer 33b.
Certainly, in the preferred embodiment, electron injecting layer and hole injection layer can also can exist by individualism simultaneously, are preferably simultaneously and exist.The setting of this hole injection layer, can effectively strengthen the ohmic contact of 2 of itself and anode layers, has strengthened electric conductivity, improves the hole injectability of anode layer 2 ends; The arranging of this electron injecting layer can effectively strengthen the ohmic contact between itself and cathode layer 5, strengthened electric conductivity, further improve the electronic injection ability of cathode layer 5 ends, with further equilibrium carrier, control recombination region, in luminescent layer, increase exciton amount, obtained desirable luminosity and luminous efficiency.Wherein, in above-mentioned organic function layer 3, stacked hole injection layer material can be ZnPc (Phthalocyanine Zinc), CuPc(CuPc), at least one in VOPc (ranadylic phthalocyanine), TiOPc (TiOPc); Electronic injection layer material LiF, CsF, NaF, MgF
2, lithium iodide, KI, sodium iodide, cesium iodide, rubidium iodide etc. at least one etc. alkali-metal halide.Certainly, this hole injection layer material, electronic injection layer material can also be selected respectively the conventional other materials in this area.
In further preferred embodiment, the charge generating layers 4 in above-mentioned each preferred embodiment has semi-transparent semi-reflecting characteristic, and it is except comprising the Al layer 41 and Au layer 42 of stacked combination, also comprises electron injecting layer 40, as shown in Figure 2.This electron injecting layer 40 is stacked be combined in described Al layer 41 and with the Au layer 42 relative surface of face that combines.In embodiment as shown in Figure 2, this electron injecting layer 40 is stacked to be combined between Al layer 41 and electron transfer layer 33a.It should be understood that when said n >=2, every layer all charge generating layers 4 all preferably contain this electron injecting layer 40, and in every layer charge generation layer 4, electron injecting layer 40 all the stacked Al of being combined in layer 41 and with the Au layer 42 relative surface of face that combines.In the charge generating layers 4 of this structure, the structural interface that the Al layer 41 of stacked combination and Au layer 42 form, because the Fermi level of two kinds of metal materials is respectively 4.3eV and 5.1eV, under electric field action, electronics can occur separated with hole at the interface of Al/Au, separated electronics anode layer 2 end move, and move to cathode layer 5 ends in separated hole.And the existence of electron injecting layer 40, the electronics that can significantly improve charge generating layers 4 separation is the extreme ability of injecting on the sunny side, thereby improves luminous efficiency and the intensity of Organnic electroluminescent device in the various embodiments described above.In addition, its semi-transparent semi-reflecting characteristic that this charge generating layers 4 has can make the light coming from anode end-fire in its interface generating unit sub reflector and part refraction, with charge generating layers 4 in the organic function layer 3 of Au layer 42 stacked combination play dielectric layer effect, make light and the catoptrical single spin-echo of charge generating layers 4 in cathode layer 5 reflections, reach the effect that interference disappears mutually, effectively reduce the total reflection of light, realize low reflectivity.
Particularly, as preferred embodiment, as described above, its material is LiF, CsF, at least one in NaF in the effect of the electron injecting layer 40 in above-mentioned charge generating layers 4.The prepared electron injecting layer 40 of this preferred material can improve the injectability of electronic high-effective of the interfacial separation of Al/Au.Certainly, should be understood that, these electron injecting layer 40 materials can also be other electron injection materials, as MgF
2, etc. the alkaline-earth metal of fluorine or lithium iodide, KI, sodium iodide, cesium iodide, rubidium iodide etc. at least one etc. alkali-metal iodide.As another preferred embodiment, the thickness of above-mentioned electron injecting layer 40 is preferably 0.2nm～1nm.
As preferred embodiment, the thickness of above-mentioned Al layer 41 is 3nm～7nm.
As preferred embodiment, the thickness of above-mentioned Au layer 42 is 5nm～10nm.
In further preferred embodiment, the thickness of the electron injecting layer 40 in above-mentioned charge generating layers 4 is preferably 0.2nm～1nm, and the thickness of Al layer 41 is 3nm～7nm, and the thickness of Au layer 42 is 5nm～10nm.
About the preferred thickness of electron injecting layer 40, Al layer 41 and Au layer 42 in above-mentioned charge generating layers 4 and the combination of threeply degree, can make charge generating layers 4 there is more excellent semi-transparent semi-reflecting performance, thereby improve the better effects if that reverberation and cathode layer 5 reverberation offset, give reflectivity that in the various embodiments described above, Organnic electroluminescent device is lower and the contrast of Geng Gao.
Above-mentioned cathode layer 5 materials can be selected metal, as one or more the alloy in Ag, Au, Cu, Ni, Pt etc.The thickness of cathode layer 5 can but be not only 70～200nm.Certainly, cathode layer 5 can also be other cathode materials well known in the art, and its thickness also can adopt the conventional thickness in this area.
From the above, between adjacent between two organic function layer, set up the charge generating layers 4 that contains Al layer 41/Au layer 42 structure, make electric charge, at this interface, separation effectively occur, improved light efficiency, efficiency; In addition, its semi-transparent semi-reflecting characteristic makes the light coming from anode end-fire in its interface generating unit sub reflector and part refraction, again due to charge generating layers 4 in the organic function layer 3 of Au layer 42 stacked combination can play the effect of dielectric layer, make the single spin-echo at the light of cathode layer 5 reflections and the light of charge generating layers 4 reflections, reach the effect that interference disappears mutually, effectively reduce the total reflection of light, realized low reflectivity.In addition, by set up electron injecting layer 40 in charge generating layers 4, improve isolated electronic injection ability in charge generating layers 4, thereby realize the light efficiency that further improves Organnic electroluminescent device.By adjusting the charge generating layers 4 that can make of charge generating layers 4 each layers, there is more excellent semi-transparent semi-reflecting performance, thereby improve the better effects if that reverberation and cathode layer 5 reverberation offset, give reflectivity that in the various embodiments described above, Organnic electroluminescent device is lower and the contrast of Geng Gao.
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 systems, transparent conductive oxide magnetron sputtering is prepared to anode layer 2 on substrate 1 one surfaces of step S01;
S03. according to (organic function layer 3/ charge generating layers 4/ organic function layer 3) n structure, prepare organic function layer 3 and charge generating layers 4: at step S02, prepare anode layer 2 with light-transmissive substrates layer 1 the combine relative surface of face each layer of evaporation organic function layer 3 and each layer of charge generating layers 4 successively;
S04. prepare cathode layer 5: in vacuum coating system, at organic function layer 3 outer surface cathode materials, form cathode layer 5.
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, transparent conductive oxide and anode layer 2 thickness all as described above, do not repeat them here.Preferably, to become the sputtering technology condition of anode layer 2 be that base vacuum degree is 1 * 10 to sputter transparent conductive oxide
-5～1 * 10
-3pa, the evaporation rate of magnetron sputtering is 0.2～2nm/s.Certainly, the process conditions of preparing anode layer 2 also can be carried out according to existing processing parameter setting.
Preferably, before carrying out following step S03, also comprise the anode layer 2 in step S02 is carried out to plasma treatment: the substrate that this is coated with to anode layer 2 is placed in plasma processing chamber, carries out plasma treatment.This plasma treatment condition adopts the process conditions of this area routine.After plasma treatment, anode layer 2 can effectively improve anode work function, reduces the injection barrier in hole.
Certainly, also can directly select and be coated with anode as being coated with the transparent substrates of ITO, the transparent substrates that this is coated with to anode is carried out the preliminary treatment in early stage, as carried out following step S03 after the PROCESS FOR TREATMENT such as cleaning, plasma treatment.
In above-mentioned steps S03, when n=1, as shown in Figure 1, at the material of anode layer 2 outer surfaces successively evaporation hole transmission layer 31a, luminescent layer 32a, electron transfer layer 33a, Al layer 41, Au layer 42, hole transmission layer 31b, luminescent layer 32b, electron transfer layer 33b, prepare corresponding each layer.The like, when n >=2, according to the structure of (organic function layer 3/ charge generating layers 4/ organic function layer 3) n successively each layer of evaporation.Wherein, the material of each layer 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, organic function layer 3 also comprises while stacking gradually the hole injection layer, electron injecting layer, electronic barrier layer of combination and/or hole blocking layer, when charge generating layers 4 also comprises electron injecting layer 40, according to the layer structure mentioned above successively corresponding material of evaporation, prepare each layer.Concrete layers of material and thickness are as described above.
In above-mentioned steps S04, the thickness of the cathode material that evaporation cathode layer 5 is used and the cathode layer 5 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 Organnic electroluminescent device 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, 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 that contains Organnic electroluminescent device.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 the above-mentioned display screen that contains Organnic electroluminescent device, so 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 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 above-mentioned Organnic electroluminescent device aspect below.
Embodiment 1
A kind of that have an antiradar reflectivity and substrate is as the Organnic electroluminescent device of exiting surface, its structure is: glass substrate/ITO (100nm)/hole injection layer (CuPc, 10nm)/hole transmission layer (NPB, 20nm)/luminescent layer (DPVBi, 10nm)/electron transfer layer (TPBi, 20nm)/LiF (0.5nm)/Al (5nm)/Au (7nm)/hole transmission layer (NPB, 40nm)/luminescent layer (DPVBi, 20nm)/electron transfer layer (Bphen, 30nm)/Ag (100nm).Wherein, hole injection layer (CuPc, 10nm)/hole transmission layer (NPB, 20nm)/luminescent layer (DPVBi, 10nm)/electron transfer layer (TPBi, 20nm) form the first organic function layer, hole transmission layer (NPB, 40nm)/luminescent layer (DPVBi, 20nm)/electron transfer layer (Bphen, 30nm) form the second organic function layer, LiF (0.5nm)/Al (5nm)/Au (7nm) forms charge generating layers.
Its preparation method is as follows:
(1) in vacuum degree, be 10
-4in the vacuum coating system of Pa, prepare, glass substrate is cleaned with cleaning agent, then use distilled water, acetone is ultrasonic cleaning successively, then in coating system;
(2) evaporation ITO layer successively on substrate, thickness is 100nm;
(3) at anode surface successively evaporation hole injection layer (CuPc, 10nm)/hole transmission layer (NPB, 20nm)/luminescent layer (DPVBi, 10nm)/electron transfer layer (TPBi, 20nm)/LiF (0.5nm)/Al (5nm)/Au (7nm)/hole transmission layer (NPB, 40nm)/luminescent layer (DPVBi, 20nm)/electron transfer layer (Bphen, 30nm), each layer of evaporation rate is 0.2nm/s;
(4) at organic function layer outer surface, prepare Ag layer and form negative electrode; Thickness is 100nm;
(5), after preparation, adopt glass cover-plate to encapsulate.
Embodiment 2
A kind of that have an antiradar reflectivity and substrate is as the Organnic electroluminescent device of exiting surface, its structure is: glass substrate/ITO (100nm)/hole injection layer (ZnPc, 10nm)/hole transmission layer (TPD, 20nm)/luminescent layer (Ir (ppy)
3: TPBi (10%), 10nm)/electron transfer layer (PBD, 20nm)/CsF (0.2nm)/Al (7nm)/Au (5nm)/hole transmission layer (MeO-TPD, 30nm)/luminescent layer (Rubrene, 10nm)/electron transfer layer (Alq
3, 20nm)/Ag (100nm).Wherein, hole injection layer (ZnPc, 10nm)/hole transmission layer (TPD, 20nm)/luminescent layer (Ir (ppy)
3: TPBi (10%), 10nm)/electron transfer layer (TPBi, 20nm) forms the first organic function layer, hole transmission layer (MeO-TPD, 30nm)/luminescent layer (Rubrene, 10nm)/electron transfer layer (Alq
3, 20nm) forming the second organic function layer, CsF (0.2nm)/Al (7nm)/Au (5nm) forms charge generating layers.
This Organnic electroluminescent device preparation method is with reference to the Organnic electroluminescent device preparation method of embodiment 1.
Embodiment 3
A kind of that have an antiradar reflectivity and substrate is as the Organnic electroluminescent device of exiting surface, its structure is: glass substrate/ITO (100nm)/hole injection layer (TiOPc, 10nm)/hole transmission layer (MeO-Sprio-TPD, 20nm)/luminescent layer (DCJTB:Alq
3(1%), 10nm)/electron transfer layer (PBD, 20nm)/NaF (1nm)/Al (3nm)/Au (10nm)/hole transmission layer (MeO-TPD, 60nm)/luminescent layer (DMQA, 30nm)/electron transfer layer (Alq
3, 10nm)/Ag (100nm).Wherein, hole injection layer (TiOPc, 10nm)/hole transmission layer (MeO-Sprio-TPD, 20nm)/luminescent layer (DCJTB:Alq
3(1%), 10nm)/electron transfer layer (PBD, 20nm) forms the first organic function layer, hole transmission layer (MeO-TPD, 60nm)/luminescent layer (DMQA, 30nm)/electron transfer layer (Alq
3, 10nm) forming the second organic function layer, NaF (1nm)/Al (3nm)/Au (10nm) forms charge generating layers.
This Organnic electroluminescent device preparation method is with reference to the Organnic electroluminescent device preparation method of embodiment 1.
Comparison example 1
A kind of substrate is as the Organnic electroluminescent device of exiting surface, its structure is: glass substrate/ITO (100nm)/hole injection layer (CuPc, 10nm)/hole transmission layer (NPB, 20nm)/luminescent layer (DPVBi, 10nm)/electron transfer layer (TPBi, 20nm)/Ag (100nm).Wherein, hole injection layer (CuPc, 10nm)/hole transmission layer (NPB, 20nm)/luminescent layer (DPVBi, 10nm)/electron transfer layer (TPBi, 20nm) forms organic function layer.
Organnic electroluminescent device carries out correlated performance test
Existing Organnic electroluminescent device in the Organnic electroluminescent device of above-described embodiment 1 to embodiment 3 preparation and comparison example 1 is carried out to reflectance test when not lighting, and test result is as shown in following table 1 and accompanying drawing 4.
Table 1
From above-mentioned table 1 by reference to the accompanying drawings 4, the Organnic electroluminescent device of preparing in above-described embodiment 1-3 makes the light coming from anode end-fire in its interface generating unit sub reflector and part refraction owing to setting up between the organic function layer adjacent between two containing Al layer/Au layer structure with its semi-transparent semi-reflecting characteristic, again due to charge generating layers in Au layer by layer the organic function layer of folded combination can play the effect of dielectric layer, make the single spin-echo at the light of cathode layer reflection and the light of charge generating layers reflection, reach the effect that interference disappears mutually, effectively reduced the total reflection of light, realize low reflectivity.Therefore,, by this charge generating layers and the Au synergy of the organic function layer of folded combination layer by layer, make in above-described embodiment Organnic electroluminescent device reflectivity low.The reflectivity of Organnic electroluminescent device prepared by embodiment 1-3 is compared with Organnic electroluminescent device in comparison example 1, the reflectivity of Organnic electroluminescent device prepared by embodiment 1-3 is reduced to 12.5%, well below the reflectivity 88.5% of Organnic electroluminescent device in comparison example 1.Hence one can see that, and Organnic electroluminescent device prepared by embodiment 1-3 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 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. an Organnic electroluminescent device, comprise the transparency carrier, anode layer, at least two organic function layers, the cathode layer that stack gradually combination, described organic function layer is included in luminescent layer luminous under the driving of additional power source, and the stacked charge generating layers with semi-transflective reflective characteristic that is combined with also between adjacent described organic function layer between two; Described charge generating layers comprises Al layer, the Au layer that stacks gradually combination, presses from anode layer to cathode layer direction, and described charge generating layers is combined between adjacent between two described organic function layer according to the lamination order of Al layer/Au layer is stacked.
2. Organnic electroluminescent device as claimed in claim 1, is characterized in that: described charge generating layers also comprises electron injecting layer, described electron injecting layer is stacked be combined in described Al layer and with the Au layer relative surface of face that combines.
3. Organnic electroluminescent device as claimed in claim 2, is characterized in that: described electronic injection layer material is LiF, CsF, at least one in NaF.
4. Organnic electroluminescent device as claimed in claim 2 or claim 3, is characterized in that: the thickness of described electron injecting layer is 0.2nm～1nm.
5. Organnic electroluminescent device as claimed in claim 1 or 2, is characterized in that: the thickness of described Al layer is 3nm～7nm.
6. Organnic electroluminescent device as claimed in claim 1 or 2, is characterized in that: the thickness of described Au layer is 5nm～10nm.
7. Organnic electroluminescent device as claimed in claim 2, is characterized in that: the thickness of described electron injecting layer is 0.2nm～1nm, and the thickness of described Al layer is 3nm～7nm, and the thickness of described Au layer is 5nm～10nm.
8. the Organnic electroluminescent device as described in claim 1～5, is characterized in that: the thickness of the described organic function layer of being combined with described Au layer is 60nm～100nm.
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.
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