CN1780014A - Production of organic and inorganic light-emitting diodes - Google Patents
Production of organic and inorganic light-emitting diodes Download PDFInfo
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- CN1780014A CN1780014A CNA2004100911720A CN200410091172A CN1780014A CN 1780014 A CN1780014 A CN 1780014A CN A2004100911720 A CNA2004100911720 A CN A2004100911720A CN 200410091172 A CN200410091172 A CN 200410091172A CN 1780014 A CN1780014 A CN 1780014A
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Abstract
A process for preparing organic-inorganic LED includes such steps as providing a substrate, generating the first electrode, generating an organic-inorganic luminescent layer containing multiple organic-inorganic quantum dots consisting of ZnX quantum dot and the organic molecule for covering the quantum dot, and generating the second electrode.
Description
Technical field
The invention relates to a kind of manufacturing method for LED, particularly relevant for the manufacture method of the compound light-emittingdiode of a kind of organic-inorganic.
Background technology
Organic Light Emitting Diode (Organic Light Emitting Diode, OLED) display is a kind of flat-panel monitor (Flat Panel Display) that utilizes organic compound as luminescent material, its luminous mechanism is electroluminescence (electroluminescence, be called for short EL), (the Organic Electroluminescence Device of the display of organic electroluminescence so be otherwise known as, OELD) or dynamo-electric emission display (Organic Electroemissive Device arranged, OED), its structure as shown in Figure 1, comprise base material 10, anode electrode 20, hole transmission layer (Hole Transport Layer, HTL) 30, electroluminescence layer (Electroluminescent Layer, EL) 40, electron transfer layer (ElectronTransport Layer, ETL) 50 and cathode electrode 60.When adding a voltage in this structure outside, electronics 51 and hole 31 can transfer to electroluminescence layer 40 by electron transfer layer 50 and hole transmission layer 30, emit light in conjunction with (recombination) more then in electroluminescence layer 40.Briefly, Organic Light Emitting Diode is a kind of device that is generated light by electricity.
Wherein, base material can be glass baseplate or plastic basis material.Base material is that the Organic Light Emitting Diode of plastic material has pliability.In addition, luminous because electronics only combines in electroluminescence layer with the hole again, and this electroluminescence layer is extremely thin, even can only be the coating of monomolecular layer, thereby very fast in conjunction with speed, make the response time (response time) very short; And panel can be the big panel from 4 microns micro-display (microdisplay) to 100 inches, uses very extensively, does not have the visual angle problem of LCD, and has resolution height, multiple advantages such as light, thin.Therefore, Organic Light Emitting Diode is a kind of quite desirable type of display.
But because the restriction of Organic Light Emitting Diode material itself, characteristics such as its stability, luminous efficiency and emission wavelength remain to be improved always.Because the luminescent layer of Organic Light Emitting Diode all is made up of organic material, and organic material is stable not good enough, thereby makes the useful life of Organic Light Emitting Diode not long.Although present luminous organic material has reached up to ten thousand hours useful life, these useful lifes, there was the problem of colour cast in long luminous organic material, became Chinese red as redness.In addition, because external quantum efficiency (external quantumefficiency) theoretical boundary of the luminescent material that uses itself is very low, be that the luminous energy that sends of element is very low for the electric energy of input element, thereby luminous efficiency is not high, causes the waste of the energy.Emission wavelength is extremely important for display, but because the halfwidth (Full-Width at Half Maximum be called for short FWHM) of luminous organic material in luminescent spectrum is all very wide, thereby do not have the characteristic of high color purity, and the selection of emission wavelength is limited.These problems all can limit the application of light-emitting diode.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of manufacture method of organic and inorganic light-emitting diodes, improve stability, luminous efficiency and the emission wavelength of light-emitting diode by using organic-inorganic compound quantity point.
To achieve these goals, the invention provides a kind of manufacture method of organic and inorganic light-emitting diodes, comprising: a base material is provided; On this base material, form one first electrode; On this first electrode, form an organic and inorganic light-emitting layer, this organic and inorganic light-emitting layer comprises a plurality of sub-points of the organic-inorganic compound quantity in the macromolecule that are scattered in, each organic-inorganic compound quantity point comprises a zinc compound ZnX and an organic molecule that coats this quantum dot surface, wherein, X is one or more in sulphur, selenium, the tellurium; And on this organic and inorganic light-emitting layer, form one second electrode.
Manufacture method according to organic and inorganic light-emitting diodes of the present invention, forming an organic and inorganic light-emitting layer on described first electrode comprises: provide a plurality of organic-inorganic compound quantities sub-point, this organic-inorganic compound quantity point is zinc compound ZnX and an organic molecule that coats this quantum dot surface, wherein, X is one or more in sulphur, selenium, the tellurium; This organic-inorganic compound quantity point is scattered in the macromolecule, forms a solution; And this solution rotating is applied on described first electrode, form described organic and inorganic light-emitting layer.
According to the manufacture method of organic and inorganic light-emitting diodes of the present invention, described base material is a transparent base.
According to the manufacture method of organic and inorganic light-emitting diodes of the present invention, described transparent base is glass baseplate or plastic basis material.
According to the manufacture method of organic and inorganic light-emitting diodes of the present invention, described first electrode is a transparency electrode.
According to the manufacture method of organic and inorganic light-emitting diodes of the present invention, described first electrode is an indium tin oxide.
According to the manufacture method of organic and inorganic light-emitting diodes of the present invention, described second electrode is a metal electrode.
According to the manufacture method of organic and inorganic light-emitting diodes of the present invention, described metal electrode is one or more in lithium, lithium fluoride, magnesium, calcium, aluminium, the silver.
According to the manufacture method of organic and inorganic light-emitting diodes of the present invention, described ZnX is quantum dot-doped other element.
According to the manufacture method of organic and inorganic light-emitting diodes of the present invention, described other element is transition elements, halogen or its combination.
According to the manufacture method of organic and inorganic light-emitting diodes of the present invention, described organic molecule is aliphatic acid or phosphatide.
According to the manufacture method of organic and inorganic light-emitting diodes of the present invention, described macromolecule is a conducting polymer.
According to the manufacture method of organic and inorganic light-emitting diodes of the present invention, described conducting polymer is luminous high polymer or conjugated polymer.
According to the manufacture method of organic and inorganic light-emitting diodes of the present invention, described conducting polymer is that formula (1) is to the compound shown in the formula (15).
Manufacture method according to organic and inorganic light-emitting diodes of the present invention also comprises: form a hole transmission layer on described first electrode; And on described organic and inorganic light-emitting layer, form an electron transfer layer.
According to the manufacture method of organic and inorganic light-emitting diodes of the present invention, described hole transmission layer is that formula (16) is to the compound shown in the formula (25).
According to the manufacture method of organic and inorganic light-emitting diodes of the present invention, described electron transfer layer is that formula (26) is to the compound shown in the formula (30).
Manufacture method according to organic and inorganic light-emitting diodes of the present invention also comprises: form a hole transmission layer on described first electrode.
According to the manufacture method of organic and inorganic light-emitting diodes of the present invention, described hole transmission layer is that formula (16) is to the compound shown in the formula (25).
Manufacture method according to organic and inorganic light-emitting diodes of the present invention also comprises: form an electron transfer layer on described organic and inorganic light-emitting layer.
According to the manufacture method of organic and inorganic light-emitting diodes of the present invention, described electron transfer layer is that formula (26) is to the compound shown in the formula (30).
The manufacture method of organic and inorganic light-emitting diodes provided by the invention uses organic-inorganic compound quantity point as luminescent material.Because the existence of inorganic substances ZnX has improved the thermal endurance of light-emitting component, and then has improved its stability, has increased useful life; Simultaneously, its luminous efficiency is higher than general use macromolecule or micromolecular Organic Light Emitting Diode, and than the emitting component height that uses quantum dot separately.Because the luminous crest of inorganic material is narrower than the organic material, promptly the purity of luminous color is higher, adds that the luminous crest of quantum dot is narrower, thereby can obtain the high light-emitting component of color purity.By the doping and/or the size of control ZnX quantum dot, can obtain the light-emitting component of different glow colors, make that the range of choice of glow color is very wide.Structure of organic and inorganic light-emitting diodes provided by the invention uses organic-inorganic compound quantity point as luminescent material.Because the existence of inorganic substances ZnX has improved the thermal endurance of light-emitting component, and then has improved its stability, has increased useful life; Simultaneously, its luminous efficiency is higher than general use macromolecule or micromolecular Organic Light Emitting Diode, and than the emitting component height that uses quantum dot separately.Because the luminous crest of inorganic material is narrower than the organic material, promptly the purity of luminous color is higher, adds that the luminous crest of quantum dot is narrower, thereby can obtain the high light-emitting component of color purity.By the doping and/or the size of control ZnX quantum dot, can obtain the light-emitting component of different glow colors, make that the range of choice of glow color is very wide.
Description of drawings
Fig. 1 is the structure chart of known Organic Light Emitting Diode.
Fig. 2 is the structure chart of embodiment of the present invention 1 and embodiment 1 organic and inorganic light-emitting diodes.
Fig. 3 is voltage, the current relationship figure of the embodiment of the invention 1 and comparing embodiment 1 organic and inorganic light-emitting diodes.
Fig. 4 is voltage, the lumen graph of a relation of the embodiment of the invention 1 and comparing embodiment 1 organic and inorganic light-emitting diodes.
Fig. 5 is the structure chart of embodiment of the present invention 2 and embodiment 2 organic and inorganic light-emitting diodes.
Fig. 6 is voltage, the lumen graph of a relation of the embodiment of the invention 2 and comparing embodiment 2 organic and inorganic light-emitting diodes.
Fig. 7 is the electroluminescent spectrum figure of the embodiment of the invention 2 and comparing embodiment 2 organic and inorganic light-emitting diodes.
Fig. 8 is the structure chart of embodiment of the present invention 3 and embodiment 3 organic and inorganic light-emitting diodes.
Fig. 9 is voltage, the lumen graph of a relation of the embodiment of the invention 3 organic and inorganic light-emitting diodes.
Figure 10 is current density, the lumen graph of a relation of the embodiment of the invention 3 organic and inorganic light-emitting diodes.
Figure 11 is voltage, the lumen graph of a relation of the embodiment of the invention 3 and comparing embodiment 3 organic and inorganic light-emitting diodes.
Figure 12 is current density, the lumen graph of a relation of the embodiment of the invention 3 and comparing embodiment 3 organic and inorganic light-emitting diodes.
Embodiment
[execution mode 1]
Fig. 2 is the structure chart of embodiment of the present invention 1 organic and inorganic light-emitting diodes, is followed successively by base material 110, anode electrode 120, hole transmission layer 130, electroluminescence layer 140 and cathode electrode 160 from bottom to up.Wherein, cathode electrode 160 can comprise one or more electrode, for example, comprises first cathode electrode 161 and second cathode electrode 162 among Fig. 2.A plurality of organic-inorganic compound quantity points 143 are dispersed in the macromolecule 144, form electroluminescence layer 140, and this organic-inorganic compound quantity point 143 comprises (inorganic) quantum dot 141 and organic material 142, and the surface of organic material 142 coated quantum dots 141.
Above-mentioned organic and inorganic light-emitting diodes, because it is that the below is luminous, thereby employed base material 110 need be a transparent material with anode electrode 120.In the present embodiment, base material 110 is glass baseplate or plastic basis material, and the Organic Light Emitting Diode that uses plastic basis material to make has flexual advantage, anode electrode 120 be indium tin oxide (indium tin oxide, ITO).Indium tin oxide is a kind of electric conducting material, is usually used in the Organic Light Emitting Diode.Cathode electrode 160 is a metal electrode, as calcium (Ca), silver (Ag), lithium (Li), lithium fluoride (LiF), magnesium (Mg), aluminium (Al) and composition thereof.The hole transmission layer 130 that is positioned on the anode electrode 120 is NPB (referring to formula 16), DMFL-NPB (referring to formula 17), Spiro-NPB (referring to formula 18), TPD (referring to formula 19), Spiro-TPD (referring to formula 20), DMFL-TPD (referring to formula 21), PVK (referring to formula 22), MCP (referring to formula 23), TCP (referring to formula 24), TNB (referring to formula 25).Electroluminescence layer 140 is the most important one decks of the present invention, and quantum dot 141 wherein is zinc compound ZnX, and wherein, X is one or more in sulphur (S), selenium (Se), the tellurium (Te).This ZnX quantum dot other element that can also mix is as transition elements, halogen or its combination, with characteristics such as the luminous efficiency that changes this quantum dot and emission wavelengths.Different quantum dot sizes also can influence its luminous efficiency and emission wavelength.In addition, the organic material 142 on coated quantum dots 141 surfaces is aliphatic acid or phosphatide.Quantum dot 141 constitutes organic inorganic compounding quantum dot 143 with organic material 142, and this organic-inorganic compound quantity point 143 can be dispersed in the macromolecule 144 by intermolecular force, and this macromolecule 144 is a conducting polymer.This conducting polymer is luminous high polymer or conjugated polymer, as: MEH-PPV (referring to formula 1), MEH-BP-PPV (referring to formula 2), PF-BV-MEH (referring to formula 3), PF-DMOP (referring to formula 4), PFH (referring to formula 5), PFH-EC (referring to formula 6), PFH-MEH (referring to formula 7), PFO (referring to formula 8), PF-PPV (referring to formula 9), PF-PH (referring to formula 10), PF-SP (referring to formula 11), poly-TPD (referring to formula 12), poly-TPD-POSS (referring to formula 13), TAB-PFH (referring to formula 14), PPB (referring to formula 15).
Organic and inorganic light-emitting diodes shown in Figure 2, its manufacture method is as follows: base material 110 is provided; On base material 110, form anode electrode 120; On anode electrode 120, form hole transmission layer 130; On above-mentioned hole transmission layer 130, form electroluminescence layer 140; And on electroluminescence layer 140, form first cathode electrode 161 and second cathode electrode 162 successively, constitute cathode electrode 160.
In above-mentioned organic and inorganic light-emitting diodes manufacture method, wherein anode electrode 120, hole transmission layer 130, first cathode electrode 161 and second cathode electrode 162 all use the known method manufacturing.The detailed method for making of emphasis electroluminescence layer 140 of the present invention is as follows: with the ZnSe quantum dot and the MEH-PPV of coated fat acid or phosphatide, MEH-BP-PPV, PF, PF-BV-MEH, PF-DMOP, PFH, PFH-EC, PFH-MEH, PFO, PFOB, PF-PPV, PF-PH, PF-SP, poly-TPD, poly-TPD-POSS, TAB-PFH, PPB mixes, hybrid mode is that (mg represents milligram with 10mg/ml with macromolecule earlier, ml represents milliliter) be dissolved in the toluene solvant, and then with the quantum dot blending in aforementioned Polymer Solution, form a mixed solution, wherein, macromolecule can be 1: 0 with the ratio of the weight of quanta point material, 1: 0.025,1: 0.05 one of them; Again with this mixed solution rotary coating on hole transmission layer 130, this rotary coating mode is in being full of the glove box of nitrogen, with aforementioned mixing drop on the indium tin oxide transparent conducting glass, and use rotary coating machine, with the spin coating rotating speed spin coating of 4000rpm (rpm represents revolutions per minute) 20 seconds, polymeric membrane is prepared on the indium tin oxide transparent conducting glass.The polymeric membrane that plating is good places vacuum drying oven to dry, and the vacuum degree of this vacuum drying oven is 10
-3Torr (1torr equals 133.322 Pascals) after 5 hours, promptly forms electroluminescence layer 140 through 70 to 80 ℃ of heat treatments again.
[execution mode 2]
Fig. 5 is the structure chart of embodiment of the present invention 2 organic and inorganic light-emitting diodes, is followed successively by base material 210, anode electrode 220, hole transmission layer 230, electroluminescence layer 240, electron transfer layer 250 and cathode electrode 260 from down to up.Wherein, cathode electrode 260 can comprise one or more electrode, for example, comprises first cathode electrode 261 and second cathode electrode 262 among Fig. 5.A plurality of organic-inorganic compound quantity points 243 are dispersed in the macromolecule 244, form electroluminescence layer 240, and this organic-inorganic compound quantity point 243 comprises (inorganic) quantum dot 241 and organic material 242, and the surface of organic material 242 coated quantum dots 241.
Above-mentioned organic and inorganic light-emitting diodes, because it is that the below is luminous, thereby employed base material 210 need be a transparent material with anode electrode 220.In the present embodiment, base material 210 is glass baseplate or plastic basis material, and the Organic Light Emitting Diode that uses plastic basis material to make has flexual advantage, anode electrode 220 be indium tin oxide (indium tin oxide, ITO).Indium tin oxide is a kind of electric conducting material, is usually used in the Organic Light Emitting Diode.Cathode electrode 260 is a metal electrode, as calcium (Ca), silver (Ag), lithium (Li), lithium fluoride (LiF), magnesium (Mg), aluminium (Al) and composition thereof.The hole transmission layer 230 that is positioned on the anode electrode 220 is NPB (referring to formula 16), DMFL-NPB (referring to formula 17), Spiro-NPB (referring to formula 18), TPD (referring to formula 19), Spiro-TPD (referring to formula 20), DMFL-TPD (referring to formula 21), PVK (referring to formula 22), MCP (referring to formula 23), TCP (referring to formula 24), TNB (referring to formula 25).Electroluminescence layer 240 is the most important one deck of the present invention, and quantum dot 241 wherein is zinc compound ZnX, and wherein, X is one or more in sulphur (S), selenium (Se), the tellurium (Te).This ZnX quantum dot other element that can also mix is as transition elements, halogen or its combination, with characteristics such as the luminous efficiency that changes this quantum dot and emission wavelengths.Different quantum dot sizes also can influence its luminous efficiency and emission wavelength.In addition, the organic material 242 on coated quantum dots 241 surfaces is aliphatic acid or phosphatide; Quantum dot 241 constitutes organic inorganic compounding quantum dot 243 with organic material 242, this organic-inorganic compound quantity point 243 can be dispersed in the macromolecule 244 by intermolecular force, this macromolecule 244 is a conducting polymer, this conducting polymer is luminous high polymer or conjugated polymer, as: MEH-PPV (referring to formula 1), MEH-BP-PPV (referring to formula 2), PF-BV-MEH (referring to formula 3), PF-DMOP (referring to formula 4), PFH (referring to formula 5), PFH-EC (referring to formula 6), PFH-MEH (referring to formula 7), PFO (referring to formula 8), PF-PPV (referring to formula 9), PF-PH (referring to formula 10), PF-SP (referring to formula 11), poly-TPD (referring to formula 12), poly-TPD-POSS (referring to formula 13), TAB-PFH (referring to formula 14), PPB (referring to formula 15).The electron transfer layer 250 that is positioned on the electroluminescence layer 240 is Alq
3(referring to formula 26), BAlq
3(referring to formula 27), BCP (referring to formula 28), CBP (referring to formula 29), TAZ (referring to formula 30).
Organic and inorganic light-emitting diodes shown in Figure 5, its manufacture method is as follows: base material 210 is provided; On base material 210, form anode electrode 220; On anode electrode 220, form hole transmission layer 230; On above-mentioned hole transmission layer 230, form electroluminescence layer 240; On electroluminescence layer 240, form electron transfer layer 250; And on electron transfer layer 250, form first cathode electrode 261 and second cathode electrode 262 successively, constitute cathode electrode 260.
In above-mentioned organic and inorganic light-emitting diodes manufacture method, wherein anode electrode 220, hole transmission layer 230, electron transfer layer 250, first cathode electrode 261 and second cathode electrode 262 all use the known method manufacturing.The detailed method for making of emphasis electroluminescence layer 240 of the present invention is as follows: with the ZnSe quantum dot and the MEH-PPV of coated fat acid or phosphatide, MEH-BP-PPV, PF, PF-BV-MEH, PF-DMOP, PFH, PFH-EC, PFH-MEH, PFO, PFOB, PF-PPV, PF-PH, PF-SP, poly-TPD, poly-TPD-POSS, TAB-PFH, PPB mixes, hybrid mode is for being dissolved in macromolecule in the toluene solvant with 10mg/ml earlier, and then with the quantum dot blending in aforementioned Polymer Solution, form a mixed solution, wherein, macromolecule can be 1: 0 with the ratio of the weight of quanta point material, 1: 0.025,1: 0.05 one of them; Again with this mixed solution rotary coating on hole transmission layer 230, this rotary coating mode is in being full of the glove box of nitrogen, with aforementioned mixing drop on hole transmission layer 230, and use rotary coating machine, with the spin coating rotating speed spin coating of 4000rpm 20 seconds, polymeric membrane is prepared on the hole transmission layer 230.The polymeric membrane that plating is good places vacuum drying oven to dry, and the vacuum degree of this vacuum drying oven is 10
-3Torr after 5 hours, promptly forms electroluminescence layer 240 through 70～80 ℃ of heat treatments again.
[execution mode 3]
Fig. 8 is the structure chart of embodiment of the present invention 3 organic and inorganic light-emitting diodes, is followed successively by base material 310, anode electrode 320, electroluminescence layer 340, electron transfer layer 350 and cathode electrode 360 from down to up.Wherein, cathode electrode 360 can comprise one or more electrode, for example, comprises first cathode electrode 361 and second cathode electrode 362 among Fig. 8.A plurality of organic-inorganic compound quantity points 343 are dispersed in the macromolecule 344, form electroluminescence layer 340, and this organic-inorganic compound quantity point 343 comprises (inorganic) quantum dot 341 and organic material 342, and the surface of organic material 342 coated quantum dots 341.
Above-mentioned organic and inorganic light-emitting diodes, because it is that the below is luminous, thereby employed base material 310 need be a transparent material with anode electrode 320.In the present embodiment, base material 310 is glass baseplate or plastic basis material, and the Organic Light Emitting Diode that uses plastic basis material to make has flexual advantage, anode electrode 320 be indium tin oxide (indium tin oxide, ITO).Indium tin oxide is a kind of electric conducting material, is usually used in the Organic Light Emitting Diode.Cathode electrode 360 is a metal electrode, as lithium fluoride (LiF), aluminium (Al), lithium (Li), calcium (Ca), magnesium (Mg), aluminium (Ag) and composition thereof.Electroluminescence layer 340 is the most important one decks of the present invention, and quantum dot 341 wherein is zinc compound ZnX, and wherein, X is one or more in sulphur (S), selenium (Se), the tellurium (Te).This ZnX quantum dot other element that can also mix is as transition elements, halogen or its combination, with characteristics such as the luminous efficiency that changes this quantum dot and emission wavelengths.Different quantum dot sizes also can influence its luminous efficiency and emission wavelength.In addition, the organic material 342 on coated quantum dots 341 surfaces is aliphatic acid or phosphatide.Quantum dot 341 constitutes organic inorganic compounding quantum dot 343 with organic material 342, this organic-inorganic compound quantity point 343 can be dispersed in the macromolecule 344 by intermolecular force, this macromolecule 344 is a conducting polymer, this conducting polymer is luminous high polymer or conjugated polymer, as: MEH-PPV (referring to formula 1), MEH-BP-PPV (referring to formula 2), PF-BV-MEH (referring to formula 3), PF-DMOP (referring to formula 4), PFH (referring to formula 5), PFH-EC (referring to formula 6), PFH-MEH (referring to formula 7), PFO (referring to formula 8), PF-PPV (referring to formula 9), PF-PH (referring to formula 10), PF-SP (referring to formula 11), poly-TPD (referring to formula 12), poly-TPD-POSS (referring to formula 13), TAB-PFH (referring to formula 14), PPB (referring to formula 15).The electron transfer layer 350 that is positioned on the electroluminescence layer 240 is Alq
3(referring to formula 26), BAlq
3(referring to formula 27), BCP (referring to formula 28), CBP (referring to formula 29), TAZ (referring to formula 30).
Organic and inorganic light-emitting diodes shown in Figure 8, its manufacture method is as follows: base material 310 is provided; On base material 310, form anode electrode 320; On above-mentioned anode electrode 320, form electroluminescence layer 340; On electroluminescence layer 340, form electron transfer layer 350; And on electron transfer layer 350, form first cathode electrode 361 and second cathode electrode 362 successively, constitute cathode electrode 360.
In above-mentioned organic and inorganic light-emitting diodes manufacture method, wherein anode electrode 320, electron transfer layer 350, first cathode electrode 361 and second cathode electrode 362 all use the known method manufacturing.The detailed method for making of emphasis electroluminescence layer 340 of the present invention is as follows: the ZnSe quantum dot that will coat organic material mixes with MEH-PPV, MEH-BP-PPV, PF, PF-BV-MEH, PF-DMOP, PFH, PFH-EC, PFH-MEH, PFO, PFOB, PF-PPV, PF-PH, PF-SP, poly-TPD, poly-TPD-POSS, TAB-PFH, PPB, and the concentration of this organic and inorganic light-emitting diodes in this macromolecule is respectively 0,0.25,0.5mg/ml.Hybrid mode is for being dissolved in macromolecule in the toluene solvant with 10mg/ml earlier, and then with the quantum dot blending in aforementioned Polymer Solution, form a mixed solution, wherein, the ratio of macromolecule and the weight of quanta point material can for 1: 0,1: 0.025,1: 0.05 one of them; Again with this mixed solution rotary coating on anode electrode 320, this rotary coating mode is in being full of the glove box of nitrogen, with aforementioned mixing drop on anode electrode 320, and use rotary coating machine, with the spin coating rotating speed spin coating of 4000rpm 20 seconds, polymeric membrane is prepared on the anode electrode 320.The polymeric membrane that plating is good places vacuum drying oven to dry, and the vacuum degree of this vacuum drying oven is 10
-3Torr after 5 hours, promptly forms electroluminescence layer 340 through 70～80 ℃ of heat treatments again.
For making above-mentioned and other purposes of the present invention, feature and advantage clear understandable, hereinafter provide preferred embodiment, and be elaborated in conjunction with the accompanying drawings.
[embodiment 1]
As shown in Figure 2, at first carry out the cleaning of indium tin oxide transparent conducting glass 120, earlier indium tin oxide transparent conducting glass 120 is carefully washed by rubbing with the hands with cleaner special, in 50 ℃, the cleaner special, deionized water, isopropyl alcohol, deionized water, acetone, isopropyl alcohol of dilution, respectively carry out 15 minutes supersonic oscillations more successively, dry up standby again with nitrogen.Again indium tin oxide transparent conducting glass 120 is immersed 80 ℃, the volume ratio of deionized water, hydrogen peroxide, ammoniacal liquor is in 5: 1: 1 the solution 40 minutes.
Next, hole mobile material is mixed with toluene, form the hole transport solution of 10mg/ml; Again the organic light emission macromolecular material is mixed with toluene, form the organic light emission Polymer Solution of 5mg/ml; And then quanta point material sneaked in the luminous high polymer solution, form luminous high polymer and quantum dot mixed solution, wherein, the weight ratio of luminous high polymer and quanta point material can for 1: 0,1: 0.025,1: 0.05 one of them.Then, with the hole transport solution for preparing and luminous high polymer and quantum dot mixed solution syringe filter purifying with 0.45 μ m aperture, up to solution do not have obvious particle suspending wherein till.
In being full of the glove box of nitrogen with the hole transport drips of solution on indium tin oxide transparent conducting glass 120, and utilize the rotary coating machine with the spin coating rotating speed spin coating of 4000rpm 20 seconds, promptly on indium tin oxide transparent conducting glass 120, form hole transmission layer 130.The hole transmission layer 130 that plating is good places and carried out annealing in process in the vacuum drying oven 12 hours, and its vacuum degree is 10
-3Torr, temperature is 70 ℃.
Then, utilize above-mentioned spin coating step that luminous high polymer and quantum dot mixed solution are coated with on the hole transmission layer, form luminous high polymer layer 140, and utilize above-mentioned baking step to carry out annealing in process.
Next, respectively with 0.5 and the evaporation speed of 1nm/sec (nm represents nanometer, sec represent second) make calcium metallic cathode 161 and silver-colored protective layer 162.
[comparing embodiment 1]
This embodiment organic LED structure and manufacture method thereof, except not having organic inorganic compounding quantum dot 143, remaining structure is identical with embodiment 1 with manufacture method.
Next will measure the efficient of embodiment 1 and comparing embodiment 1 organic and inorganic light-emitting diodes.
Fig. 3 has the organic and inorganic light-emitting diodes of organic-inorganic compound quantity point and voltage, the current relationship figure of the Organic Light Emitting Diode that does not have organic-inorganic compound quantity point.Being presented at same electrical among the figure depresses, organic and inorganic light-emitting diodes with organic-inorganic compound quantity point, its electric current is greater than the electric current of the Organic Light Emitting Diode that does not have organic-inorganic compound quantity point, this is because when quantum dot surface during at low current density, form the charge carrier trap (carrier trap) in electronics and hole, and cause local electric field effect on the quantum dot surface, this field effect can increase the electric charge carrier charge velocity, cause preferable electron/hole-recombination (recombination) ratio, and make Organic Light Emitting Diode have preferable luminous efficiency with organic-inorganic compound quantity point.
Fig. 4 has the organic and inorganic light-emitting diodes of organic-inorganic compound quantity point and voltage, the lumen graph of a relation of the Organic Light Emitting Diode that does not have organic-inorganic compound quantity point.Be presented at same electrical among the figure and depress, have the organic and inorganic light-emitting diodes of organic-inorganic compound quantity point, its lumen value is greater than the lumen value of the Organic Light Emitting Diode that does not have organic-inorganic compound quantity point.Therefore, when these two light-emitting diodes were in identical voltage, the luminous efficiency of organic and inorganic light-emitting diodes of the present invention was greater than the luminous efficiency of existing Organic Light Emitting Diode.In addition, the maximum lumen value of embodiment 1 organic and inorganic light-emitting diodes is 2200cd/m
2About, and the maximum lumen value of comparing embodiment 1 Organic Light Emitting Diode only is about 1200cd/m
2About, differ 1000cd/m
2About, this luminous efficiency that shows light-emitting diode of the present invention is better than the efficient of existing light-emitting diode.
[embodiment 2]
As shown in Figure 5, at first carry out the cleaning of indium tin oxide transparent conducting glass 220, earlier indium tin oxide transparent conducting glass 220 is carefully washed by rubbing with the hands with cleaner special, in 50 ℃, the cleaner special, deionized water, isopropyl alcohol, deionized water, acetone, isopropyl alcohol of dilution, respectively carry out 15 minutes supersonic oscillations more successively, dry up standby again with nitrogen.Again indium tin oxide transparent conducting glass 220 is immersed 80 ℃, the volume ratio of deionized water, hydrogen peroxide, ammoniacal liquor is in 5: 1: 1 the solution 40 minutes.
Next, hole mobile material is mixed with toluene, form the hole transport solution of 10mg/ml; Again the organic light emission macromolecular material is mixed with toluene, form the organic light emission Polymer Solution of 5mg/ml; And then quanta point material sneaked in the luminous high polymer solution, form luminous high polymer and quantum dot mixed solution, wherein, the weight ratio of luminous high polymer and quanta point material can for 1: 0,1: 0.025,1: 0.05 one of them.Then, with the hole transport solution for preparing and luminous high polymer and quantum dot mixed solution syringe filter purifying with 0.45 μ m aperture, up to solution do not have obvious particle suspending wherein till.
In being full of the glove box of nitrogen with the hole transport drips of solution on indium tin oxide transparent conducting glass 220, and utilize the rotary coating machine with the spin coating rotating speed spin coating of 4000rpm 20 seconds, promptly on indium tin oxide transparent conducting glass 220, form hole transmission layer 230.The hole transport stratification 230 that plating is good carried out annealing in process 12 hours in vacuum drying oven, its vacuum degree is 10
-3Torr, temperature is 70 ℃.
Then, utilize above-mentioned spin coating step that luminous high polymer and quantum dot mixed solution are coated with on the hole transmission layer, form luminous high polymer layer 240, and utilize above-mentioned baking step to carry out annealing in process.
Next, utilize the vacuum thermal evaporation device that the evaporation speed of electron transport material with 0.1nm/sec is coated with on the luminous high polymer layer, form electron transfer layer 250; At last, respectively with 0.5 and the evaporation speed of 1nm/sec make calcium metallic cathode 261 and silver-colored protective layer 262.
[comparing embodiment 2]
This embodiment organic LED structure and manufacture method thereof, except not having organic inorganic compounding quantum dot 243, remaining structure is identical with embodiment 2 with manufacture method.
Next will measure the efficient of embodiment 2 and comparing embodiment 2 organic and inorganic light-emitting diodes.
Fig. 6 has the organic and inorganic light-emitting diodes of organic-inorganic compound quantity point and voltage, the lumen graph of a relation of the Organic Light Emitting Diode that does not have organic-inorganic compound quantity point.Be presented at same electrical among the figure and depress, have the organic and inorganic light-emitting diodes of organic-inorganic compound quantity point, its lumen value is greater than the lumen value of the Organic Light Emitting Diode that does not have organic-inorganic compound quantity point.Therefore, when these two light-emitting diodes were in identical voltage, the luminous efficiency of organic and inorganic light-emitting diodes of the present invention was greater than the luminous efficiency of existing Organic Light Emitting Diode.In addition, the maximum lumen value of embodiment 2 organic and inorganic light-emitting diodes is 4000cd/m
2About, and the maximum lumen value of comparing embodiment 2 Organic Light Emitting Diodes only is about 1000cd/m
2About, differ 3000cd/m
2About, this luminous efficiency that shows light-emitting diode of the present invention is better than the efficient of existing light-emitting diode.
Fig. 7 has the organic and inorganic light-emitting diodes of organic-inorganic compound quantity point and the exciting light spectrogram of the Organic Light Emitting Diode that does not have organic-inorganic compound quantity point, and this figure shows the addition of MEH-PPV and quantum dot spectrum.
[embodiment 3]
As shown in Figure 8, at first carry out the cleaning of indium tin oxide transparent conducting glass 320, earlier indium tin oxide transparent conducting glass 320 is carefully washed by rubbing with the hands with cleaner special, in 50 ℃, the cleaner special, deionized water, isopropyl alcohol, deionized water, acetone, isopropyl alcohol of dilution, respectively carry out 15 minutes supersonic oscillations more successively, dry up standby again with nitrogen.Again indium tin oxide transparent conducting glass 320 is immersed 80 ℃, deionized water, hydrogen peroxide, ammoniacal liquor volume ratio are in 5: 1: 1 the solution 40 minutes.
Next, the organic light emission macromolecular material is mixed with toluene, form the organic light emission Polymer Solution of 5mg/ml; And then quanta point material sneaked in the luminous high polymer solution, to form luminous high polymer and quantum dot mixed solution, wherein, the weight ratio of luminous high polymer and quanta point material can for 1: 0,1: 0.025,1: 0.05 one of them.Then, with the luminous high polymer for preparing and quantum dot mixed solution syringe filter purifying with 0.45 μ m aperture, up to solution do not have obvious particle suspending wherein till.
In being full of the glove box of nitrogen, luminous high polymer and quantum dot mixed solution are dripped on indium tin oxide transparent conducting glass 320, and utilize the rotary coating machine with the spin coating rotating speed spin coating of 4000rpm 20 seconds, promptly on indium tin oxide transparent conducting glass 320, form luminous high polymer layer 340.The luminous high polymer layer 340 that plating is good places and carried out annealing in process in the vacuum drying oven 12 hours, and its vacuum degree is 10
-3Torr, temperature is 70 ℃.
Next, utilize the vacuum thermal evaporation device that the evaporation speed of electron transport material with 0.1nm/sec is coated with on the luminous high polymer layer 350, form electron transfer layer 360; At last, respectively with 0.5 and the evaporation speed of 1nm/sec make calcium metallic cathode 361 and silver-colored protective layer 362.
Fig. 9 is voltage, the lumen graph of a relation of the organic and inorganic light-emitting diodes of different proportion organic-inorganic compound quantity point.This organic-inorganic compound quantity point shared ratio in Polymer Solution is respectively 5mg/ml, 10mg/ml, 15mg/ml and 20mg/ml.Be presented at same electrical among the figure and depress, the concentration of organic-inorganic compound quantity point is high more, and its lumen value is high more, and promptly luminous efficiency is good more.But when concentration by behind the 15mg/ml to 20mg/ml, the lumen value reduces on the contrary, this phenomenon can utilize the concentration quenching (concentration quenching) in the nanometer theory to explain.
Figure 10 is current density, the lumen graph of a relation of the organic and inorganic light-emitting diodes of different proportion organic-inorganic compound quantity point.This organic-inorganic compound quantity point shared ratio in macromolecule is respectively 5mg/ml, 10mg/ml, 15mg/ml and 20mg/ml.Be presented among the figure under the same current density, the concentration of organic-inorganic compound quantity point is high more, and its lumen value is high more, and promptly luminous efficiency is good more.But when concentration by behind the 10mg/ml to 15mg/ml, the lumen value reduces on the contrary, this phenomenon can utilize the concentration quenching (concentration quenching) in the nanometer theory to explain.
[comparing embodiment 3]
This embodiment organic LED structure and manufacture method thereof, except not having organic inorganic compounding quantum dot 343, remaining structure is identical with embodiment 3 with manufacture method.
Next will measure the efficient of embodiment 3 and comparing embodiment 3 organic and inorganic light-emitting diodes.
Figure 11 is the organic and inorganic light-emitting diodes and the voltage, the lumen graph of a relation that do not have the Organic Light Emitting Diode of quantum dot with organic-inorganic compound quantity point.Be presented at same electrical among the figure and depress, have the organic and inorganic light-emitting diodes of organic-inorganic compound quantity point, its lumen value is greater than the lumen value of the Organic Light Emitting Diode that does not have organic-inorganic compound quantity point.Therefore, when these two light-emitting diodes were in identical voltage, the luminous efficiency of organic and inorganic light-emitting diodes of the present invention was greater than the luminous efficiency of existing Organic Light Emitting Diode.
In addition, for the organic and inorganic light-emitting diodes of embodiment 3, be the sub-point of organic-inorganic compound quantity of 0.25mg/ml as long as in macromolecule, add concentration, its lumen value (is about 6500cd/m
2) will be higher than the Organic Light Emitting Diode that does not add organic inorganic compounding quantum dot of comparing embodiment 3, therefore, only need to add the sub-point of low concentration organic-inorganic compound quantity and can produce better effect.When the interpolation concentration of organic inorganic compounding quantum dot reaches 15mg/ml (as shown in Figure 9), its lumen value can reach 8500cd/m
2More than, with the lumen value of the existing Organic Light Emitting Diode that does not add organic inorganic compounding quantum dot at a distance of 2000cd/m
2More than.
Figure 12 is the organic and inorganic light-emitting diodes and the current density, the lumen graph of a relation that do not have the Organic Light Emitting Diode of quantum dot with organic-inorganic compound quantity point.Be presented among the figure under the same current density, have the organic and inorganic light-emitting diodes of organic-inorganic compound quantity point, its lumen value is greater than the lumen value of the Organic Light Emitting Diode that does not have organic-inorganic compound quantity point.Therefore, when these two light-emitting diodes were in same current density, the luminous efficiency of organic and inorganic light-emitting diodes of the present invention was greater than the luminous efficiency of existing Organic Light Emitting Diode.
In addition, for the organic and inorganic light-emitting diodes of embodiment 3, be organic-inorganic compound quantity of 0.25mg/ml as long as in macromolecule, add concentration, its lumen value (is about 6500cd/m
2) will be higher than the Organic Light Emitting Diode that does not add organic inorganic compounding quantum dot of comparing embodiment 3, therefore, only need to add the sub-point of low concentration organic-inorganic compound quantity and can produce better effect.When the interpolation concentration of organic inorganic compounding quantum dot reaches 15mg/ml (as shown in figure 10), its lumen value can reach 8500cd/m
2More than, with the lumen value of the existing Organic Light Emitting Diode that does not add organic inorganic compounding quantum dot at a distance of 2000cd/m
2More than.
Though the present invention by the preferred embodiment explanation as above, this preferred embodiment is not in order to limit the present invention.Those skilled in the art without departing from the spirit and scope of the present invention, should have the ability this preferred embodiment is made various changes and replenished, so protection scope of the present invention is as the criterion with the scope of claims.
Being simply described as follows of symbol in the accompanying drawing:
10,110,210,310: base material
20,120,220,320: anode electrode
30,130,230: hole transmission layer
31: the hole
40,140,240,340: electroluminescence layer
50,250,350: electron transfer layer
51: electronics
60,160,260,360: cathode electrode
141,241,341: quantum dot
142,242,342: organic material
143,243,343: the sub-point of The quantity of complexed organic Carbon
144,244,344: macromolecule
161,261,361: the first cathode electrodes
162,262,362: the second cathode electrodes
Claims (21)
1, a kind of manufacture method of organic and inorganic light-emitting diodes is characterized in that, the manufacture method of this organic and inorganic light-emitting diodes comprises:
A base material is provided;
On this base material, form one first electrode;
On this first electrode, form an organic and inorganic light-emitting layer, this organic and inorganic light-emitting layer comprises a plurality of sub-points of the organic-inorganic compound quantity in the macromolecule that are scattered in, each organic-inorganic compound quantity point comprises a zinc compound ZnX and an organic molecule that coats this quantum dot surface, wherein, X is one or more in sulphur, selenium, the tellurium; And
On this organic and inorganic light-emitting layer, form one second electrode.
2, the manufacture method of organic and inorganic light-emitting diodes according to claim 1 is characterized in that forming an organic and inorganic light-emitting layer and comprises on described first electrode:
Provide a plurality of organic-inorganic compound quantities sub-point, this organic-inorganic compound quantity point is zinc compound ZnX and an organic molecule that coats this quantum dot surface, and wherein, X is one or more in sulphur, selenium, the tellurium;
This organic-inorganic compound quantity point is scattered in the macromolecule, forms a solution; And
This solution rotating is applied on described first electrode, forms described organic and inorganic light-emitting layer.
3, the manufacture method of organic and inorganic light-emitting diodes according to claim 1 is characterized in that described base material is a transparent base.
4, the manufacture method of organic and inorganic light-emitting diodes according to claim 3 is characterized in that described transparent base is glass baseplate or plastic basis material.
5, the manufacture method of organic and inorganic light-emitting diodes according to claim 4 is characterized in that described first electrode is a transparency electrode.
6, the manufacture method of organic and inorganic light-emitting diodes according to claim 5 is characterized in that described first electrode is an indium tin oxide.
7, the manufacture method of organic and inorganic light-emitting diodes according to claim 1 is characterized in that described second electrode is a metal electrode.
8, the manufacture method of organic and inorganic light-emitting diodes according to claim 7 is characterized in that described metal electrode is one or more in lithium, lithium fluoride, magnesium, calcium, aluminium, the silver.
9, the manufacture method of organic and inorganic light-emitting diodes according to claim 1, it is characterized in that described ZnX is quantum dot-doped has other element.
10, the manufacture method of organic and inorganic light-emitting diodes according to claim 9 is characterized in that described other element is transition elements, halogen or its combination.
11, the manufacture method of organic and inorganic light-emitting diodes according to claim 1 is characterized in that described organic molecule is aliphatic acid or phosphatide.
12, the manufacture method of organic and inorganic light-emitting diodes according to claim 1 is characterized in that described macromolecule is a conducting polymer.
13, the manufacture method of organic and inorganic light-emitting diodes according to claim 12 is characterized in that described conducting polymer is luminous high polymer or conjugated polymer.
14, the manufacture method of organic and inorganic light-emitting diodes according to claim 12 is characterized in that described conducting polymer is that formula (1) is to the compound shown in the formula (15)
15, the manufacture method of organic and inorganic light-emitting diodes according to claim 1 is characterized in that the manufacture method of this organic and inorganic light-emitting diodes also comprises:
On described first electrode, form a hole transmission layer; And
On described organic and inorganic light-emitting layer, form an electron transfer layer.
16, the manufacture method of organic and inorganic light-emitting diodes according to claim 15 is characterized in that described hole transmission layer is that formula (16) is to the compound shown in the formula (25)
17, the manufacture method of organic and inorganic light-emitting diodes according to claim 15 is characterized in that described electron transfer layer is that formula (26) is to the compound shown in the formula (30)
18, the manufacture method of organic and inorganic light-emitting diodes according to claim 1 is characterized in that the manufacture method of this organic and inorganic light-emitting diodes also comprises:
On described first electrode, form a hole transmission layer.
19, the manufacture method of organic and inorganic light-emitting diodes according to claim 18 is characterized in that described hole transmission layer is that formula (31) is to the compound shown in the formula (40)
20, the manufacture method of organic and inorganic light-emitting diodes according to claim 1 is characterized in that the manufacture method of this organic and inorganic light-emitting diodes also comprises:
On described organic and inorganic light-emitting layer, form an electron transfer layer.
21, the manufacture method of organic and inorganic light-emitting diodes according to claim 20 is characterized in that described electron transfer layer is that formula (41) is to the compound shown in the formula (45)
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| CN101937975A (en) * | 2010-08-20 | 2011-01-05 | 电子科技大学 | Organic/inorganic composite light-emitting diode and preparation method thereof |
| WO2014201712A1 (en) * | 2013-06-21 | 2014-12-24 | 深圳市华星光电技术有限公司 | Light emitting device, display panel and manufacturing method thereof |
| CN104882554A (en) * | 2015-04-30 | 2015-09-02 | 中国科学院半导体研究所 | Inorganic and organic hybrid electroluminescent element and manufacturing method thereof |
| CN108447998A (en) * | 2018-03-19 | 2018-08-24 | 京东方科技集团股份有限公司 | Quantum dot light emitting device and preparation method, quantum dot light emitting display device |
| CN109119541A (en) * | 2017-06-26 | 2019-01-01 | 东丽先端材料研究开发（中国）有限公司 | Quantum dot light emitting element |
| CN109148702A (en) * | 2017-06-19 | 2019-01-04 | Tcl集团股份有限公司 | The mixed film and preparation method and QLED device of quantum dot and carrier crosslinking |
| CN109148701A (en) * | 2017-06-19 | 2019-01-04 | Tcl集团股份有限公司 | The mixed film and preparation method and QLED device of quantum dot and carrier crosslinking |
| CN110212119A (en) * | 2019-05-21 | 2019-09-06 | 南昌航空大学 | Electron pole light emitting diode with quantum dots |
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| CN1130956C (en) * | 1996-07-29 | 2003-12-10 | 剑桥显示技术有限公司 | Electroluminescent devices with electrode protection |
| KR100373203B1 (en) * | 1999-03-31 | 2003-02-25 | 주식회사 엘지화학 | New organometallic complexes for use in light emitting devices |
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2004
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| CN101937975A (en) * | 2010-08-20 | 2011-01-05 | 电子科技大学 | Organic/inorganic composite light-emitting diode and preparation method thereof |
| WO2014201712A1 (en) * | 2013-06-21 | 2014-12-24 | 深圳市华星光电技术有限公司 | Light emitting device, display panel and manufacturing method thereof |
| CN104882554A (en) * | 2015-04-30 | 2015-09-02 | 中国科学院半导体研究所 | Inorganic and organic hybrid electroluminescent element and manufacturing method thereof |
| CN109148702A (en) * | 2017-06-19 | 2019-01-04 | Tcl集团股份有限公司 | The mixed film and preparation method and QLED device of quantum dot and carrier crosslinking |
| CN109148701A (en) * | 2017-06-19 | 2019-01-04 | Tcl集团股份有限公司 | The mixed film and preparation method and QLED device of quantum dot and carrier crosslinking |
| CN109119541A (en) * | 2017-06-26 | 2019-01-01 | 东丽先端材料研究开发（中国）有限公司 | Quantum dot light emitting element |
| CN108447998A (en) * | 2018-03-19 | 2018-08-24 | 京东方科技集团股份有限公司 | Quantum dot light emitting device and preparation method, quantum dot light emitting display device |
| CN110212119A (en) * | 2019-05-21 | 2019-09-06 | 南昌航空大学 | Electron pole light emitting diode with quantum dots |
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| CN100474651C (en) | 2009-04-01 |
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