A kind of organic molecule or macromolecule top emission light-emitting device
Technical field
The present invention relates to a kind of novel top emission light-emitting device, particularly a kind of organic/polymer top emission light-emitting device.
Background technology
Nineteen ninety, research troop of univ cambridge uk is that luminescent layer has been made first polymeric light-emitting element with conjugated structure PPV macromolecular material at first.Because the luminous high polymer device has lower cost for material, is easy to the large tracts of land moulding, driving voltage is low, and energy consumption is little, and emission wavelength can pass through the outstanding advantage of the tuning grade of material structure, is considered to and might be applied in the large-area flat-plate TV.
Along with the process of progress on the display application of plane of global organic/polymer luminescent device, developing efficiently, top emission light-emitting device more and more becomes one of problem that needs urgent research.Because with respect to general luminescent device, end emission just (the electroluminescence screen sends by substrate) device, the top emission has a sequence advantage, and the most outstanding a bit is exactly to adopt emission structure at top to realizing that the large-area flat-plate display is significant efficiently.To using active driving (TFT) with the large-area flat-plate TV, but the TFT switching device itself occupies certain area of substrate, cause the aperture opening ratio (area and Substrate Area ratio that electroluminescence can be passed through generally only are Substrate Area 50~70%) of TFT substrate to reduce.And the employing emission structure at top because only from the upper surface emission of substrate, can be realized nearly 100% aperture opening ratio in theory.
But realize that the emission structure at top device acquires a certain degree of difficulty, electrode material and structure there is new requirement, particularly when adopting negative electrode to place on the substrate, more difficult when luminous by anode surface, therefore at present (on the substrate) was anode bottom the top emission light-emitting device of the most of report of institute was limited to more in the document, and top (on the luminescent layer) is the device of semitransparent cathode.Micromolecule luminous aspect, the V. of Princeton university
Utilized the metallic cathode thin layer of printing opacity to make the transparent dual emission device of micromolecule that a kind of emergent light is launched simultaneously from upper and lower surface in 1996 Deng the people, over-all quantum efficiency is 0.75%, wherein bottom-face luminous efficient than end face luminous efficiency high by about 10% (
, G.Gu, P.E.Burrows, S.R.Forrest and M.E.Thompson, Nature, 380,29 (1996)).Aspect phosphorescence, people such as C.Kwong reported the phosphor material top emission light-emitting device in 2003, at 10mA/cm
2Following upper surface current efficiency is 23.1cd/A, and lower surface current efficiency is 20.3cd/A, and working life surpasses 5000 hours (Raymond C.Kwong, Michael S.Weaver, Min-Hao Michael Lu, Yeh-Jiun Tung, Anna B.Chwang, Theodore X.Zhou, Michael Hack, Julie J.Brown, Organic Electronics, 4,155 (2003)).
At present, the top emission light-emitting device overwhelming majority of most of report is that anode is on substrate, the structure of transparent cathode evaporation on luminescent layer, having only seldom, the part report adopts structure (V.Bulovic, P.Tian, the P.E.Burrows of transparent anode on luminescent layer, M.R.Gokhale, S.R.Forrest and M.E.Thompson, Appl.Phys.Lett.70,2954 (1997); Samil KHO, Sunyoung SOHN andDonggeun JUNG, Jpn.J.Appl.Phys.42,552 (2003)).Bibliographical information cathodic modification layer generally adopts the alkali metal of low work function (as potassium, lithium, or alkaline-earth metal (as calcium, barium etc.) caesium),, but the alkalies and alkaline earth of this class low work function is easy and water, the oxygen reaction causes processing difficulties, and device needs tight sealing (L.H.Smith, J.A.E.Wasey and W.L.Barnes simultaneously, Appl.Phys.Lett.84,2986 (2004); R.B.Pode, C.J.Lee, D.G.Moon and J.I.Han, Appl.Phys.Lett.84,4614 (2004)).Perhaps, sputtering ITO layer (indium tin oxide) again after having plated thin metal layer, but the sputtering ITO energy is very big, causes the damage of luminescent layer easily, influences the luminous (G.Gu of device, V.Bulovic, P.B.Burrows, S.R.Forrest and M.E.Thompson, Appl.Phys, Left.68,2606 (1996); L.S.Hung, C.W.Tang, Appl.Phys.Lett.74,3209 (1999)).Simultaneously, also by the compound no metal level that adopts transparent ITO and micromolecule electron transfer layer to form as the top emission light-emitting device negative electrode, same because the sputtering ITO layer is to carry out under high-energy, and the micromolecule electron transfer layer can not stop the infringement of luminescent layer fully, cause device failure cancellation (G.Parthasarathy easilier than metal level, P.E.Burrows, V.Khalfin, V.G.Kozlov, and S.R.Forrest, Appl.Phys.Lett.72,2138 (1998)).Perhaps, the low work function alkali metal that mixes is again arranged also between micromolecule electron transfer layer and ITO, improve device efficiency (G.Parthasarathy, C.Adachi, P.E.Burrows, and S.R.Forrest, Appl.Phys.Lett.76,2128 (2000)).Aspect sputter, also there is technology not adopt ITO, but the indium oxide (IDIXO) of sputter doping zinc, same damage luminescent layer problem (the Asuka Yamamori easily that exists of this method, Sachiko Hayashi, Toshiki Koyama, and Yoshio Taniguchi, Appl.Phys.Lett.78,3343 (2001); Takashi Hirano, US6774561).In addition, also utilize the plasma technology to form one deck insulating nitride layer at cathode surface, significantly improved device performance, but this manufacture craft relative complex, plasma time requirement strictness (Samil KHO to device substrate, Sunyoung SOHN and Donggeun JUNG, Jpn.J.Appl.Phys.42,552 (2003)).The same with the effect of plasma metal level, also there is method directly to adopt people's methods such as Hung, directly evaporation one heat insulating lamina fluoride is on luminescent material, evaporation metal electrode again on fluoride layer, and such fluoride of forming/metal composite negative electrode also can obtain effective top emission light-emitting device (L.S.Hung, C.W.Tang, M.G.Tang, M.G.Mason, P.Raychaudhuri and J.Madathil, Appl.Phys.Lett.78,544 (2001); Chieh-Wei Chen, Chun-Liang Lin andChung-Chih Wu, Appl.Phys.Lett.85,2469 (2004); S.Han, X.Feng, Z.H.Lu, D.Johnson and R.Wood, Appl.Phys.Lett.82,2715 (2003); HAN Sijin, FENG Xiadong, LU Zhenghong, WOOD, Richard, P., JOHNSON, David, J., WO2004049465); Akio Fukase, US2004/0239239).In addition, the redox polymers (EB-PAni) that is reported in the polyaniline compound that adds one deck conduction between substrate metal layer and the luminescent layer is also arranged, perhaps mix and give body or acceptor material, realize injection (the Satoshi Seo in electronics or hole, Hiroko Yamazaki, US6838836).
Summary of the invention
Purpose of the present invention is exactly in order to solve above-mentioned the deficiencies in the prior art part, and a kind of organic/polymer top emission light-emitting device is provided.These top emission light-emitting device characteristics are to use one to place the high-work-function metal negative electrode on the substrate to form composite cathode with the conjugated polymer of the strong polar compound that contains polar group or ionic group, realize that effective electronics injects, electroluminescence is sent stability and high efficiency by the translucent anode of evaporation on luminescent layer.
The present invention is achieved through the following technical solutions: a kind of organic/polymer top emission light-emitting device, comprise substrate, negative electrode, luminescent layer, anode, it is characterized in that, establish an electron injecting layer between negative electrode and luminescent layer, described electron injecting layer adopts the conjugated polymer of the polarity unit that contains polar group or ionic group.Described substrate, negative electrode, luminescent layer, anode set gradually from the bottom up.
Described electron injecting layer is the conjugated polymer with polarity unit that contains polar group or ionic group of following structure:
N wherein
1=0.5~0.99; n
2=0.1~0.5; n
3=0~0.5; n
1+ n
2+ n
3=1.0;
Wherein A is the polar compound that contains polar group or ionic group, has the combination of following wherein one or more structures:
Poly-fluorenes:
R wherein
1, R
2For having wherein one or more side chain of amido, quaternary ammonium salt base, itrile group, carboxyl, sulfonic group, phosphate; n
1=0.5~0.99;
Poly-to benzene:
R wherein
1, R
2For having amido, quaternary ammonium salt base, itrile group, carboxyl, sulfonic group, wherein one or more side chains of phosphate; n
1=0.5~0.99;
Wherein B has one or more following structures for not containing the component of polarity or ionic group:
Poly-fluorenes:
R wherein
3, R
4Be H, C
1~C
20Alkyl; n
2=0.1~0.5;
Poly-to benzene:
R wherein
3, R
4Be H, C
1~C
20Alkyl, alkoxyl; n
2=0.1~0.5;
Wherein C is any sulphur that contains, nitrogen, and the heterocycle of selenium comprises diazosulfide, selenole; Diazosulfide:
n
3=0~0.5; Selenole:
n
3=0~0.5.
The conjugated polymer monomer A also comprises p-phenylene vinylene, poly-spiral shell-to benzene, polyparaphenylene's acetylene or polycarbazole in the described electron injecting layer; The conjugated polymer monomers B also comprises p-phenylene vinylene, poly-spiral shell-to benzene, polyparaphenylene's acetylene or polycarbazole.
Above A, B, three kinds of compositions of C can obtain the target conjugated polymer by the Suzuki coupling reaction.
Synthetic and the chemistry of monomer and polymer, optical physics characteristic and standard back emission (substrate surface emission) preparation of devices reference literature carry out (Huang et al.J.Am.Chem.Soc.2004; 126 (31): 9845-9853; Chem.Mater.2004,16:708-716; PCT application No.PCT/CN2004/001417 (Dec.6,2004)).
Described electron injecting layer is PF-NR
2(poly-[9,9-dioctyl fluorene-9, two (N, the N-dimethyl amine propyl group) fluorenes of 9-]), PF-N
+R
3(poly-[9,9-dioctyl fluorene-9,9-(two (3 '-(N, N-dimethyl)-N-ethyl ammonium) propyl group fluorenes) dibromo]), PFP-NR
2(poly-[1,4-phenylene-9, two (N, the N-dimethyl amine propyl group) fluorenes of 9-]), PFP-N
+R
3(poly-[1,4-phenylene-9,9-(two (3 '-(N, the N-dimethyl)-and the N-ethyl ammonium) the propyl group fluorenes) dibromo]), PFN-BTDZ (poly-[9,9-dioctyl fluorene-9, two (the N of 9-, N-dimethyl amine propyl group) fluorenes-2,1, the 3-diazosulfide]), PFNBr-BTDZ (poly-[9,9-dioctyl fluorene-9,9-(two (3 '-(N, the N-dimethyl)-and the N-ethyl ammonium) propyl group) fluorenes-2,1, the 3-diazosulfide] dibromo), PFN-BseD (poly-[9,9-dioctyl fluorene-9, two (the N of 9-, N-dimethyl amine propyl group) fluorenes-2,1, the 3-selenole]), PFNBr-BseD (poly-[9,9-dioctyl fluorene-9,9-(two (3 '-(N, the N-dimethyl)-and the N-ethyl ammonium) propyl group) fluorenes-2,1, the 3-selenole] dibromo), PFN-DBT (poly-[9,9-dioctyl fluorene-9, the two (N of 9-, N-dimethyl amine propyl group) fluorenes-4,7-two thiophene-2-base-2,1, the 3-diazosulfide]), PFNBr-DBT (poly-[9,9-dioctyl fluorene-9,9-(two (3 '-(N, N-dimethyl)-N-ethyl ammonium) propyl group) fluorenes-4,7-two thiophene-2-base-2,1, the 3-diazosulfide] dibromo), PFN-DBSe (poly-[9,9-dioctyl fluorene-9, the two (N of 9-, N-dimethyl amine propyl group) fluorenes-4,7-two thiophene-2-base-2,1, the 3-selenole]), PFNBr-DBSe (poly-[9,9-dioctyl fluorene-9,9-(two (3 '-(N, N-dimethyl)-N-ethyl ammonium) propyl group) fluorenes-4,7-two thiophene-2-base-2,1, the 3-selenole] dibromo), PFN-TPA-BTDZ (poly-[9,9-dioctyl fluorene-9, the two (N of 9-, N-dimethyl amine propyl group) fluorenes-2,1,3-diazosulfide-N-(4-phenyl)-4,4 '-diphenylamine]), PFNI-TPA-BTDZ (poly-[9,9-dioctyl fluorene-9,9-(two (3 '-(N, N-dimethyl)-N-ethyl ammonium) propyl group) fluorenes-2,1,3-diazosulfide N-(4-phenyl)-4,4 '-diphenylamine] diiodo-), PFN-TH (poly-[9,9-dioctyl fluorene-9, the two (N of 9-, N-dimethyl amine propyl group) fluorenes-2, the 5-thiophene]) or PFNBr-TH (poly-[9,9-dioctyl fluorene-9,9-(two (3 '-(N, the N-dimethyl)-the N-ethyl ammonium) propyl group) fluorenes-2, the 5-thiophene] dibromo) in any one.
Described electron injecting layer thickness is 0.5~30 nanometer; Electron injecting layer by the solution in organic solvent by spin coated, ink-jet, the mode of solution film formings such as printing is coated on the luminescent layer.
Described negative electrode directly adopts work function more than or equal to 3.6 electron-volts high-work-function metal.
Described high-work-function metal is gold, aluminium, copper, silver, indium, nickel, lead, tin, carbon or its alloy.
Described luminescent layer adopts any organic molecule luminescent material or high-molecular luminous material; Described high-molecular luminous material comprises poly-fluorenes, poly-to benzene, p-phenylene vinylene, poly-spiral shell (SPIRO)-to benzene, trapezoidal poly-one or more co-mixing system in benzene (ladder-PPP) or the polyparaphenylene's acetylene.
Another object of the present invention is exactly the application of this organic/polymer top emission light-emitting device in the panchromatic planar top emission display of high-resolution.
Table 1 is that this tests used polarity electronics injection material.Three component copolymers (the monomer diazosulfide of narrow band gap) that comprise Ionized poly-[9,9-dioctyl fluorene-9, two (N, the N-dimethyl amine propyl group) fluorenes of 9-] copolymerization narrow band gap (PFNBr-BTDZ05) and its neutral persursor material (PFN-BTDZ05).
Table 1 polarity electronics used in the present invention injection material
* the mole ratio of numeral heterocyclic monomer in copolymer after being called for short, as PFNBr-BTDZ10, the mole ratio of the BTDZ content in the expression copolymer is 10%.
The good metal of employing environmental stability of the present invention is such as aluminium during directly as the substrate negative electrode, employing by the conjugated polymer of the strong polar compound that contains ionic group or polar group as electron transfer layer, manufacture craft is very simple, and obtains the top emission light-emitting device of stability and high efficiency.In preparation top emission light-emitting device of the present invention, for overcome low workfunction metal in the device preparation process, be easy to solvent in residual water, the oxygen reaction, cause device efficiency to lower, the rapid difficulty in ageing failure and the processing that causes thus, and the low electron injection efficiency of employed high-work-function metal among the present invention, the solution of above-mentioned ionic polymers and neutral presoma thereof is passed through rotation, modes such as printing apply skim on the high-work-function metal cathode layer, swaying hair photosphere thereon plates translucent high-work-function metal again as anode then, and it is good to obtain environmental stability, efficiently, the top emission light-emitting device of the electronics of balance injection.
The present invention compared with prior art has following advantage and beneficial effect:
(1) no matter the used electric transmission co-polymer of the present invention can realize that to the red, green, blue three-colour light-emitting material of which kind of band gap width excellent electronics injects;
(2) with red, green, electronics can not be subjected to the influence of cathodic metal work function in the multilayer top emission light-emitting device that blue three-colour light-emitting polymer is formed, even use work function as gold is done negative electrode and anode simultaneously up to the high stable metal of 5.2eV, also can obtain and low work function injecting electrode high-quantum efficiency equally or more, the luminescent device that long-time stability are good is applicable to the panchromatic top of high-resolution plane of departure display;
(3) this class material of having a polar group is dissolvable in water in water or the methyl alcohol isopolarity solvent, and the luminous high polymer material generally is insoluble to this kind solvent, therefore between electron transfer layer and the luminescent layer mixing phenomena can not take place when constructing multilayer device;
(4) because high-work-function metals such as aluminium have excellent air and steam stability, the stability that the combination electrode tool that uses the metal of polymer provided by the present invention and high work function to form is processed in atmosphere, the stability of device itself also improves greatly, huge potential using value in organic and macromolecule top emission light emitting display technology;
(5) the top emission light-emitting device negative electrode in the invention is attached on the substrate, and general top emission light-emitting device is that anode is attached on the substrate, has great superiority when using on active driving display screen.
Description of drawings
Fig. 1 (a) is common end ballistic device structure chart.1a is a substrate glass, and 2a is transparent ito anode, and 3a is a hole transmission layer, and 4a is a luminescent layer, and 5a is an electron transfer layer, and 6a is a metallic cathode.
Fig. 1 (b) for transparent cathode make progress anode under the top emission light-emitting device structure chart.1b is a substrate, and 2b is an anode, and 3b is a hole transmission layer, and 4b is a luminescent layer, and 5b is an electron transfer layer, and 6b is a transparent cathode.
Fig. 1 (c) for transparent anode make progress negative electrode under the top emission light-emitting device structure chart.1c is a substrate, and 2c is a negative electrode, and 3c is an electron transfer layer, and 4c is a luminescent layer, and 5c is a hole transmission layer, and 6c is a transparent anode.The black representative is light tight among the figure.
Fig. 2 is the structural representation of top emission light-emitting device of the present invention.1 is substrate, and 2 is negative electrode, and 3 is electron injecting layer, and 4 is luminescent layer, and 5 is transparent anode.
Fig. 3 (a) makes electron injecting layer to PFNBr-BTDZ05, with poly-[2-methoxyl group (5-(2 '-ethyl)-hexyl oxygen-1,4-phenylacetylene)] (MEH-PPV) do luminescent material, with aluminium make negative electrode, with the golden voltage-to-current-luminosity figure that makes the top emission light-emitting device of transparent anode.
Fig. 3 (b) is the electroluminescent spectrum of this top emission light-emitting device.
Fig. 4 (a) makes electron injecting layer to PFN-BTDZ05, with poly-[2-methoxyl group (5-(2 '-ethyl)-hexyl oxygen-1,4-phenylacetylene)] (MEH-PPV) do luminescent material, with aluminium make negative electrode, with the golden voltage-to-current-luminosity figure that makes the top emission light-emitting device of transparent anode.
Fig. 4 (b) is voltage-to-current-luminosity comparison diagram of making negative electrode, make the top emission light-emitting device of transparent anode with gold with golden.
Fig. 4 (c) makes negative electrode, makes the top emission light-emitting device electroluminescent spectrum of transparent anode with gold with aluminium.
Fig. 5 (a) is to PF-N
+R
3Make electron injecting layer, with poly-[2-methoxyl group (5-(2 '-ethyl)-hexyl oxygen-1,4-phenylacetylene)] (MEH-PPV) do luminescent material, with aluminium make negative electrode, with the golden voltage-to-current-luminosity figure that makes the top emission light-emitting device of transparent anode.
Fig. 5 (b) is the electroluminescent spectrum of this top emission light-emitting device.
Fig. 6 (a) is to PF-NR
2Make electron injecting layer, with poly-[2-methoxyl group (5-(2 '-ethyl)-hexyl oxygen-1,4-phenylacetylene)] (MEH-PPV) do luminescent material, with aluminium make negative electrode, with the golden voltage-to-current-luminosity figure that makes the top emission light-emitting device of transparent anode.
Fig. 6 (b) is the electroluminescent spectrum of this top emission light-emitting device.
Fig. 7 (a) be to PFNBr-BTDZ05 as electron injecting layer, to the phenyl of green light replace p-phenylene vinylene (P-PPV), with aluminium make negative electrode, with the golden voltage-to-current-luminosity figure that makes the top emission light-emitting device of transparent anode.
Fig. 7 (b) is the electroluminescent spectrum of this top emission light-emitting device.
Among Fig. 8 (a) be to PFN-BTDZ05 as electron injecting layer, to the phenyl of green light replace p-phenylene vinylene (P-PPV), with aluminium make negative electrode, with the golden voltage-to-current-luminosity figure that makes the top emission light-emitting device of transparent anode.
Fig. 8 (b) is the electroluminescent spectrum of this top emission light-emitting device.
Fig. 9 (a) be with PFN-BTDZ05 as electron injecting layer, to the poly-fluorenes (PFO) of blue light-emitting, with aluminium make negative electrode, with the golden voltage-to-current-luminosity figure that makes the top emission light-emitting device of transparent anode.
Fig. 9 (b) is the electroluminescent spectrum of this top emission light-emitting device.
Be to make negative electrode, make the voltage-to-current-luminosity figure of the individual layer top emission light-emitting device of transparent anode among Figure 10 (a) with gold with aluminium.
Figure 10 (b) is the electroluminescent spectrum of this top emission light-emitting device.
Embodiment
The present invention is described in further detail below in conjunction with drawings and Examples, but embodiments of the present invention are not limited thereto.
Being existing common end ballistic device structure chart as shown in Figure 1a, is end emission (the electroluminescence screen sends by substrate) device.As Fig. 1 b be depicted as existing transparent cathode make progress anode under top ballistic device structure chart, its structure of this top emission light-emitting device be anode on the substrate, the transparent cathode evaporation is on luminescent layer.The transparent anode that is depicted as existing report as Fig. 1 c make progress negative electrode under top ballistic device structure chart, this top emission light-emitting device adopts the structure of transparent anode on luminescent layer.The black representative is light tight among the figure.
As shown in Figure 2, be top emission light-emitting device of the present invention, stack gradually and constitute by glass substrate 1, high-work-function metal negative electrode 2, electron injecting layer 3, macromolecule/organic luminous layer 4, translucent high-work-function metal anode 5.
Below with Ionized poly-[9,9-dioctyl fluorene-9, two (the N of 9-, N-dimethyl amine propyl group) fluorenes] the copolymerization narrow band gap three component copolymers (the monomer diazosulfide of narrow band gap) (PFNBr-BTDZ05)) or its neutral presoma copolymer (PFN-BTDZ05), and Ionized replacing (2,5-pair (3-[N, N-diethyl amido]-1-oxygen propyl group-1,4-benzene-be total to-9,9-dioctyl fluorene copolymer (PF-N
+R
3) or its neutral presoma copolymer (PF-NR
2) illustrate.Top emission light-emitting device is taked sandwich construction or single layer structure.When between traditional luminescent conjugated polymers and work function metal higher, that environmental stability, adaptability are good such as aluminium, gold, inserting the polyelectrolytes film of skim, the injection barrier of minority carrier electronics will be reduced greatly, thereby strengthen the injection efficiency of electronics, the balanced bipolar charge carrier, make hole-electron recombination, and then the efficient of radioluminescence (electroluminescent internal quantum efficiency) is improved.
Embodiment 1
The ITO electro-conductive glass, square resistance~20 Ω/ does not perhaps have the simple glass of ITO, precuts into 15 millimeters * 15 millimeters square sheets.Use acetone, micron order semiconductor special purpose detergent, deionized water, isopropyl alcohol ultrasonic cleaning successively, it is standby that the nitrogen purging is placed on constant temperature oven, is for further processing in the oxygen plasma washer before use.
Fluorescent conjugated polymer after the weighing, changes nitrogen protection film forming special gloves case (VAC company) in clean bottle, dissolve in toluene, with 0.45 micron membrane filtration.Polymer light-emitting layer optimum thickness is 70~90 nanometers.Thickness is measured with the TENCORALFA-STEP-500 surface profiler.With PFNBr-BTDZ05, PFN-BTDZ05, PF-N
+R
3, PF-NR
2In methyl alcohol, dissolve respectively, be mixed with 0.02%, 0.1%, the solution of 0.2% 3 kind of concentration.Utilize sol evenning machine spin coated on the metallic cathode layer of evaporation in advance to generate their skim polymer, its thickness is respectively about 5,10,20 nanometers when getting rid of film when rotating with 2000rpm with 0.02%, 0.1%, 0.2% concentration.Aluminium or gold electrode evaporation vacuum degree in vacuum coating equipment reach 3 * 10
-4Finish when Pa is following.The thickness of plated film speed and each layer electrode is by quartz vibrator film thickness monitor (STM-100 type, Sycon company) monitoring in real time.The light-emitting zone of device is defined as 0.15 square centimeter by mask and the mutual zone that covers of ITO.All preparation process are all carried out the I-E characteristic of device in the glove box of nitrogen inert atmosphere is provided, luminous intensity and external quantum efficiency are recorded by Keithley236 current/voltage source-measuring system and a calibrated silicon photo diode.
Evaporation high work function aluminium (4.4 electron-volts) is on substrate, with Ionized poly-[9 of variable concentrations, 9-dioctyl fluorene-9, two (N, the N-dimethyl amine propyl group) fluorenes of 9-] the copolymerization narrow band gap three component copolymers (the monomer diazosulfide of narrow band gap) (PFNBr-BTDZ05)) or its neutral presoma copolymer (PFN-BTDZ05), and Ionized alternately (2, two (the 3-[N of 5-, N-diethyl amido]-1-oxygen propyl group-1,4-benzene-be total to-9,9-dioctyl fluorene copolymer (PF-N
+R
3) or its neutral presoma copolymer (PF-NR
2) methanol solution under the thin layer of spin coating on the Al cathode layer as electron injecting layer, adopt the poly-[2-methoxyl group (5-(2 '-ethyl)-hexyl oxygen-1 of 90 nanometer thickness, the 4-phenylacetylene)] (MEH-PPV) conjugated polymer thin films is a luminescent layer, vacuum evaporation covers gold (Au on the luminescent layer, 5.3 electron-volt) the 20nm laminate structure is made the polymer top emission light-emitting diode that sends tangerine color of light as transparent anode.As luminescent layer, to different electronics injection materials, measurement result is listed in table 2 (PFNBr-BTDZ05 makes electron injecting layer) respectively, table 3 (PFN-BTDZ05 makes electron injecting layer), table 4 (PF-N with MEH-PPV
+R
3Make electron injecting layer), table 5 (PF-NR
2Make electron injecting layer).
Table 2 is made negative electrode, is made transparent anode, uses the electroluminescent properties of PFNBr-BTDZ05 as the top emission light-emitting device of electron injecting layer with gold with aluminium based on red light material MEH-PPV
Top emission light-emitting device structure in the table 2 is ITO/Al/PFNBr-BTDZ05/MEH-PPV/Au.
Fig. 3 (a) makes electron injecting layer to PFNBr-BTDZ05, with poly-[2-methoxyl group (5-(2 '-ethyl)-hexyl oxygen-1,4-phenylacetylene)] (MEH-PPV) do luminescent material, with aluminium make negative electrode, with the golden voltage-to-current-luminosity figure that makes the top emission light-emitting device of transparent anode.Fig. 3 (b) is the electroluminescent spectrum of this top emission light-emitting device.
Table 3 based on red light material poly-[2-methoxyl group (5-(2 '-ethyl)-hexyl oxygen-1,4-phenylacetylene)] (MEH-PPV) is used the electroluminescent properties of PFN-BTDZ05 as the top emission light-emitting device of electron transfer layer
Top emission light-emitting device structure in the table 3 is ITO/Al/PFN-BTDZ05/MEH-PPV/Au, and structure I TO/Au/PFN-BTDZ05/MEH-PPV/Au is a comparative device.
Fig. 4 (a) makes electron injecting layer to PFN-BTDZ05, with poly-[2-methoxyl group (5-(2 '-ethyl)-hexyl oxygen-1,4-phenylacetylene)] (MEH-PPV) do luminescent material, with aluminium make negative electrode, with the golden voltage-to-current-luminosity figure that makes the top emission light-emitting device of transparent anode.Fig. 4 (b) be with gold do negative electrode, with golden do the top emission light-emitting device of transparent anode voltage-to-current-luminosity figure as a comparison.Fig. 4 (c) makes negative electrode, makes the top emission light-emitting device electroluminescent spectrum of transparent anode with gold with aluminium.
Table 4 is made negative electrode, is made transparent anode, uses PF-N with gold with aluminium based on red light material MEH-PPV
+R
3Electroluminescent properties as the top emission light-emitting device of electron injecting layer
Top emission light-emitting device structure in the table 4 is ITO/Al/PF-N
+R
3/ MEH-PPV/Au.
Fig. 5 (a) is to PF-N
+R
3Make electron injecting layer, with poly-[2-methoxyl group (5-(2 '-ethyl)-hexyl oxygen-1,4-phenylacetylene)] (MEH-PPV) do luminescent material, with aluminium make negative electrode, with the golden voltage-to-current-luminosity figure that makes the top emission light-emitting device of transparent anode.Fig. 5 (b) is the electroluminescent spectrum of this top emission light-emitting device.
Table 5 is made negative electrode, is made transparent anode, uses PF-NR with gold with aluminium based on red light material MEH-PPV
2Electroluminescent properties as the top emission light-emitting device of electron injecting layer
Top emission light-emitting device structure in the table 5 is ITO/Al/PF-NR
2/ MEH-PPV/Au.
Fig. 6 (a) is to PF-NR
2Make electron injecting layer, with poly-[2-methoxyl group (5-(2 '-ethyl)-hexyl oxygen-1,4-phenylacetylene)] (MEH-PPV) do luminescent material, with aluminium make negative electrode, with the golden voltage-to-current-luminosity figure that makes the top emission light-emitting device of transparent anode.Fig. 6 (b) is the electroluminescent spectrum of this top emission light-emitting device.
The result of example can prove absolutely the MEH-PPV to glowing thus, directly with placing the high work functions such as aluminium on the substrate to make negative electrode, make anode with transparent high-work-function metal Au, with Ionized poly-[9,9-dioctyl fluorene-9, two (the N of 9-, N-dimethyl amine propyl group) fluorenes] the copolymerization narrow band gap three component copolymers (the monomer diazosulfide of narrow band gap) (PFNBr-BTDZ05)) or its neutral presoma copolymer (PFN-BTDZ05), and Ionized alternately (2, two (the 3-[N of 5-, N-diethyl amido]-1-oxygen propyl group-1,4-benzene-be total to-9,9-dioctyl fluorene copolymer (PF-N
+R
3) or its neutral presoma copolymer (PF-NR
2) make electron transport material respectively, realized red top emission light-emitting device.
Embodiment 2
Repeat example 1, replace p-phenylene vinylene (P-PPV) but the polymer light-emitting stratification is changed to the phenyl of green light, electron injecting layer adopts PFNBr-BTDZ05 or neutral presoma PFN-BTDZ05 respectively.Experimental result is summarized in table 6 and table 7 respectively.
Table 6 is made negative electrode, is made transparent anode, uses the electroluminescent properties of PFNBr-BTDZ05 as the top emission light-emitting device of electron injecting layer with gold with aluminium based on green light material P-PPV
Top emission light-emitting device structure in the table 6 is ITO/Al/PFNBr-BTDZ05/P-PPV/Au.
Fig. 7 (a) be to PFNBr-BTDZ05 as electron injecting layer, to the phenyl of green light replace p-phenylene vinylene (P-PPV), with aluminium make negative electrode, with the golden voltage-to-current-luminosity figure that makes the top emission light-emitting device of transparent anode.Fig. 7 (b) is the electroluminescent spectrum of this top emission light-emitting device.
Table 7 is made negative electrode, is made transparent anode, uses the electroluminescent properties of PFN-BTDZ05 as the top emission light-emitting device of electron injecting layer with gold with aluminium based on green light material P-PPV
Top emission light-emitting device structure in the table 7 is ITO/Al/PFN-BTDZ05/P-PPV/Au.
Among Fig. 8 (a) be to PFN-BTDZ05 as electron injecting layer, to the phenyl of green light replace p-phenylene vinylene (P-PPV), with aluminium make negative electrode, with the golden voltage-to-current-luminosity figure that makes the top emission light-emitting device of transparent anode.Fig. 8 (b) is the electroluminescent spectrum of this top emission light-emitting device.
Make anode with transparent high-work-function metal Au, make the electronics injection material, realized green top emission light-emitting device with ionization PFNBr-BTDZ05 or neutral presoma PFN-BTDZ05.
Embodiment 3
Repeat the poly-fluorenes (PFO) that example 2 is changed to the polymer light-emitting stratification blue light-emitting, with poly-[9,9-dioctyl fluorene-9, two (N, N-dimethyl amine propyl group) fluorenes of 9-] three component copolymers (the monomer diazosulfide of narrow band gap) of copolymerization narrow band gap (PFN-BTDZ05) make electron injecting layer.Experimental result is summarized in table 8.Fig. 9 (a) be with PFN-BTDZ05 as electron injecting layer, to the poly-fluorenes (PFO) of blue light-emitting, with aluminium make negative electrode, with the golden voltage-to-current-luminosity figure that makes the top emission light-emitting device of transparent anode.Fig. 9 (b) is the electroluminescent spectrum of this top emission light-emitting device.
Table 8 is made negative electrode, is made transparent anode, uses the electroluminescent properties of PFN-BTDZ05 as the top emission light-emitting device of electron injecting layer with gold with aluminium based on blue light material PFO
Top emission light-emitting device structure in the table 8 is ITO/Al/PFN-BTDZ05/PFO/Au.
The result of example can prove absolutely the PFO to blue light-emitting thus, directly makes negative electrode, makes anode with transparent high-work-function metal Au with high work functions such as aluminium, makes electron transport material with PFN-BTDZ05, has realized blue top emission light-emitting device.
Embodiment 4
Directly with polar polymer PFN-BTDZ05 as luminescent layer, other condition is constant.Experimental result is summarized in table 9.Be to make negative electrode, make the voltage-to-current-luminosity figure of the individual layer top emission light-emitting device of transparent anode among Figure 10 (a) with gold with aluminium.Figure 10 (b) is the electroluminescent spectrum of this top emission light-emitting device.
Table 9 is based on material PFN-BTDZ05, makes negative electrode, makes the electroluminescent properties of the individual layer top emission light-emitting device of transparent anode with gold with aluminium
Top emission light-emitting device structure in the table 9 is ITO/Al/PFN-BTDZ05/Au.
The result of example can prove absolutely the polar material PFN-BTDZ05 for individual layer thus, directly makes negative electrode, makes anode with transparent high-work-function metal Au with high work functions such as aluminium, has realized the individual layer top emission light-emitting device.
Embodiment 5
Top emission light-emitting device of the present invention is stacked gradually and is constituted by glass substrate, high-work-function metal negative electrode, electron injecting layer, macromolecule/organic luminous layer, translucent high-work-function metal anode.
Be luminescent layer wherein, make the high-work-function metal negative electrode, make transparent anode, use PFP-NR with gold with gold with red light material MEH-PPV
2As the top emission light-emitting device of electron injecting layer, electron injecting layer thickness is 0.5 nanometer.
Embodiment 6
Top emission light-emitting device of the present invention is stacked gradually and is constituted by glass substrate, high-work-function metal negative electrode, electron injecting layer, macromolecule/organic luminous layer, translucent high-work-function metal anode.
With red light material MEH-PPV is luminescent layer, makes the high-work-function metal negative electrode, makes transparent anode with gold with copper, uses PFP-N
+R
3As the top emission light-emitting device of electron injecting layer, electron injecting layer thickness is 1 nanometer.
Embodiment 7
Top emission light-emitting device of the present invention is stacked gradually and is constituted by glass substrate, high-work-function metal negative electrode, electron injecting layer, macromolecule/organic luminous layer, translucent high-work-function metal anode.
With red light material MEH-PPV is luminescent layer, makes the high-work-function metal negative electrode, makes transparent anode with gold with silver, and with the top emission light-emitting device of PFN-BseD as electron injecting layer, electron injecting layer thickness is 5 nanometers.
Embodiment 8
Top emission light-emitting device of the present invention is stacked gradually and is constituted by glass substrate, high-work-function metal negative electrode, electron injecting layer, macromolecule/organic luminous layer, translucent high-work-function metal anode.
With red light material MEH-PPV is luminescent layer, makes the high-work-function metal negative electrode, makes transparent anode with gold with indium, and with the top emission light-emitting device of PFNBr-BseD as electron injecting layer, electron injecting layer thickness is 10 nanometers.
Embodiment 9
Top emission light-emitting device of the present invention is stacked gradually and is constituted by glass substrate, high-work-function metal negative electrode, electron injecting layer, macromolecule/organic luminous layer, translucent high-work-function metal anode.
Co-mixing system with MEH-PPV and P-PPV is a luminescent layer, makes the high-work-function metal negative electrode, makes transparent anode with gold with nickel, and with the top emission light-emitting device of PFN-DBT as electron injecting layer, electron injecting layer thickness is 15 nanometers.
Embodiment 10
Top emission light-emitting device of the present invention is stacked gradually and is constituted by glass substrate, high-work-function metal negative electrode, electron injecting layer, macromolecule/organic luminous layer, translucent high-work-function metal anode.
With p-phenylene vinylene is luminescent layer, makes the high-work-function metal negative electrode, makes transparent anode with gold with lead, and with the top emission light-emitting device of PFNBr-DBT as electron injecting layer, electron injecting layer thickness is 20 nanometers.
Embodiment 11
Top emission light-emitting device of the present invention is stacked gradually and is constituted by glass substrate, high-work-function metal negative electrode, electron injecting layer, macromolecule/organic luminous layer, translucent high-work-function metal anode.
To gather benzene is luminescent layer, makes the high-work-function metal negative electrode, makes transparent anode with gold with tin, and with the top emission light-emitting device of PFN-DBSe as electron injecting layer, electron injecting layer thickness is 25 nanometers.
Embodiment 12
Top emission light-emitting device of the present invention is stacked gradually and is constituted by glass substrate, high-work-function metal negative electrode, electron injecting layer, macromolecule/organic luminous layer, translucent high-work-function metal anode.
With poly-spiral shell (SPIRO)-to benzene is luminescent layer, makes negative electrode, makes transparent anode with gold with carbon, and with the top emission light-emitting device of PFNBr-DBSe as electron injecting layer, electron injecting layer thickness is 30 nanometers.
Embodiment 13
Top emission light-emitting device of the present invention is stacked gradually and is constituted by glass substrate, high-work-function metal negative electrode, electron injecting layer, macromolecule/organic luminous layer, translucent high-work-function metal anode.
With trapezoidal poly-be luminescent layer to benzene (ladder-PPP), make negative electrode, make transparent anode with graphite with gold, usefulness PFN-TPA-BTDZ is as the top emission light-emitting device of electron injecting layer, electron injecting layer thickness is 12 nanometers.
Embodiment 14
Top emission light-emitting device of the present invention is stacked gradually and is constituted by glass substrate, high-work-function metal negative electrode, electron injecting layer, macromolecule/organic luminous layer, translucent high-work-function metal anode.
With polyparaphenylene's acetylene is luminescent layer, makes the high-work-function metal negative electrode, makes transparent anode with gold with terne metal, and with the top emission light-emitting device of PFNI-TPA-BTDZ as electron injecting layer, electron injecting layer thickness is 8 nanometers.
Embodiment 15
Top emission light-emitting device of the present invention is stacked gradually and is constituted by glass substrate, high-work-function metal negative electrode, electron injecting layer, macromolecule/organic luminous layer, translucent high-work-function metal anode.
With micromolecule luminescent material tris-(8-hydroxyquinoline) aluminum (AlQ3) is luminescent layer, makes negative electrode, makes transparent anode with gold with aluminium, and with the top emission light-emitting device of PFN-TH as electron injecting layer, electron injecting layer thickness is 12 nanometers.
Embodiment 16
Top emission light-emitting device of the present invention is stacked gradually and is constituted by glass substrate, high-work-function metal negative electrode, electron injecting layer, macromolecule/organic luminous layer, translucent high-work-function metal anode.
With the metal complex phosphor material Bis (1-phenylisoquinoline) of triplet state phosphor material such as iridium (acetylacetonate) iridium (III) be luminescent layer (PhqIr), make the high-work-function metal negative electrode, make transparent anode with aluminium with gold, with the top emission light-emitting device of PFNBr-TH as electron injecting layer, electron injecting layer thickness is 9 nanometers.