CN101931054B - White organic light emitting device - Google Patents
White organic light emitting device Download PDFInfo
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- CN101931054B CN101931054B CN2009101481879A CN200910148187A CN101931054B CN 101931054 B CN101931054 B CN 101931054B CN 2009101481879 A CN2009101481879 A CN 2009101481879A CN 200910148187 A CN200910148187 A CN 200910148187A CN 101931054 B CN101931054 B CN 101931054B
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Abstract
A white organic light emitting element comprising: the organic electroluminescent device comprises an anode, a hole transport layer, a first luminescent layer, a second luminescent layer, a third luminescent layer, an electron transport layer and a cathode, wherein the second luminescent layer is formed between the first luminescent layer and the third luminescent layer, the luminescent wavelength of the second luminescent layer is longer than that of the first luminescent layer and the third luminescent layer, and main luminescent materials of the first luminescent layer and the third luminescent layer are different materials. The white organic light-emitting element can effectively improve the light-emitting efficiency, reduce the operating voltage and provide color stability.
Description
[technical field]
The present invention system particularly can effectively promote luminous efficiency, reduction operating voltage about a kind of about a kind of organic illuminating element, and the organic white-light emitting element of color stability is provided.
[background technology]
The luminescent layer of phosphorescence organic illuminating element generally is in luminous material of main part (host), to sneak into the luminous element visitor material (guest) with efficient occurred frequently, to reach the luminous efficiency purpose photochromic with adjusting that improves element.Usually, the luminous guest materials of phosphorescence is made up of the organic complex with transition metal.
In the phosphorescence organic illuminating element, the triplet of luminous material of main part can must be back on the lower molecule of triplet to prevent energy greater than luminous guest materials (with reference to Ref.Appl.Ptys.Lett., 83,569 (2003)) on rank, causes efficiency of element to descend.Particularly in blue light phosphorescence organic illuminating element, because the luminous guest materials of phosphorescence of blue light-emitting, its triplet can be about 2.7eV in rank, therefore, need select for use triplet can rank greater than the organic material of 2.7eV as luminous material of main part.Yet big more when the triplet ability rank that organic molecule is required, its singlet state ability rank (or being referred to as band gap (bandgap)) are big more.So, in general, being used for the luminous material of main part of blue light phosphorescence organic illuminating element, its band gap is all greater than 3.0eV.Organic material with large band gap like this is that luminous material of main part is made into luminescent layer, can and adjacent hole transmission layer or electric transmission interlayer, also or with between the two, produce the obstacle of charge transfer.Cause blue light phosphorescence organic illuminating element, the problem of high operation voltage and low luminous efficiency is arranged.
The preparation organic white-light emitting element can see through in single luminous material of main part, the luminous guest materials composition that the two or more differences of mixing are given out light (like indigo plant/Huang, blue/red, or blue/green/red), see through adjustment concentration out of the ordinary and produce white light.Yet the shortcoming of this kind mode is the concentration control difficulty of each luminous guest materials, is unfavorable for processing procedure.
Therefore, industry utilizes the different photochromic luminescent layer of two-layer or multilayer to form organic white-light emitting element usually, and wherein, blue light-emitting is that this composition is indispensable.Yet,, when putting on organic illuminating element, can make charge carrier recombination region territory change and colorific variation makes the generating white light color shift with different operation voltage for the element framework of multilayer luminescent layer.Therefore; No. 2007/0035240 exposure of Taiwan patent I279165 number and United States Patent (USP) US is folded in two-layer red light-emitting interlayer with one deck blue light-emitting; And the luminous material of main part that this two-layer red light luminescent layer comprised, luminous guest materials and layer thickness are all identical, improve color shift by this.Japan Patent is for JP2007/335214 number the organic illuminating element that exposure is folded in a long wavelength luminescent layer two-layer short-wave long light-emitting interlayer; Long wavelength's luminescent layer produces gold-tinted, ruddiness or orange-colored light; And short wavelength's luminescent layer produces blue light or green glow, and the composition of this two-layer blue light-emitting is all identical.Japan Patent discloses the organic illuminating element that one Huang/red light luminescent layer is folded in two-layer blue light emitting interlayer JP2007/189002 number; And the luminous guest materials that this two-layer blue light-emitting comprised is differing from each other, is defined as the material of emission wavelength 430-465nm and 465-485nm respectively.
Yet; In the organic white-light emitting element of multilayer luminescent layer; When wherein luminescent layer is all formed with identical luminous material of main part, can produce, also or with between the two as between aforementioned and the adjacent hole transmission layer or electron transfer layer; Produce the obstacle of charge transfer, thereby cause this organic illuminating element that the shortcoming of high operation voltage and low luminous efficiency is arranged.
[summary of the invention]
In order to solve aforementioned and other shortcomings, the present invention provides a kind of organic white-light emitting element, comprising: anode; Hole transmission layer is formed on this anode; Be formed at first luminescent layer on this hole transmission layer, comprise the first luminous material of main part, first metal organic complex and carrier transmission material; Be formed at second luminescent layer on this first luminescent layer, make this first luminescent layer be folded between this hole transmission layer and second luminescent layer, this second luminescent layer comprises second metal organic complex; Be formed at the 3rd luminescent layer on this second luminescent layer, make this second luminescent layer be folded between this first luminescent layer and the 3rd luminescent layer, the 3rd luminescent layer comprises the 3rd luminous material of main part, first metal organic complex and carrier transmission material; Electron transfer layer is formed on the 3rd luminescent layer, makes the 3rd luminescent layer be folded between this second luminescent layer and the electron transfer layer; And negative electrode, be formed on the lateral surface of electron transfer layer; Wherein, The emission wavelength of this second luminescent layer is longer than the emission wavelength of first luminescent layer and the 3rd luminescent layer; And this first luminous material of main part and the 3rd luminous material of main part are that different materials is (following sometimes with first luminescent layer abbreviation B1 layer; Second luminescent layer is called for short the Y1 layer, and the 3rd luminescent layer is called for short the B2 layer).
In organic white-light emitting element of the present invention; If only with regard to each layer issued light look or wavelength; Can select the material of metal organic complex to make the jaundice of Y1 layer light, ruddiness or orange-colored light, and also can make B1 layer and B2 layer blue light-emitting or green glow through the selection of metal organic complex.In one embodiment, the emission wavelength of Y1 layer is 520 to 640nm, and the wavelength of B1 layer and/or B2 layer is 400 to 480nm.
In the present invention, the luminous material of main part that B1 layer and B2 layer are comprised is differing from each other, and luminous guest materials (i.e. first metal organic complex) is then identical.The Y1 layer is arranged between B1 layer and the B2 layer, and the Y1 layer also can comprise the second luminous material of main part, and one of the luminous material of main part of the second luminous material of main part that is comprised and B1 layer or B2 layer is identical.
In one embodiment, second luminescent layer also can comprise carrier transmission material.
In one embodiment; Organic white-light emitting element of the present invention also comprises the 4th luminescent layer that is formed between first luminescent layer and the 3rd luminescent layer, and the 4th luminescent layer comprises the 4th luminous material of main part and second metal organic complex (following sometimes with the 4th luminescent layer abbreviation Y2 layer).Wherein, the emission wavelength of Y2 layer is longer than the emission wavelength of B1 layer and B2 layer, Y2 layer can turn to be yellow light, ruddiness or orange-colored light.In one embodiment, the emission wavelength of Y2 layer is 520 to 640nm.
In one embodiment, the 4th luminescent layer also can comprise carrier transmission material.
In the 4th luminescent layer, the 4th luminous material of main part is and the first luminous material of main part or the 3rd main one of the body luminescent material identical materials of sending out, and with the second main light emission material be material different.For example but unrestricted; For example when the luminescent layer of organic white-light emitting element of the present invention is set to B1-Y1-Y2-B2; Then the B1 layer can comprise identical luminous material of main part with the Y1 layer, and the B2 layer can comprise identical luminous material of main part with the Y2 layer, and the luminous material of main part of B1 and B2 differs from one another.
In one embodiment, organic white-light emitting element of the present invention also comprises electronic barrier layer, and it is arranged between the hole transmission layer and first luminescent layer.
In one embodiment, organic white-light emitting element of the present invention also comprises hole blocking layer, and it is arranged between electron transfer layer and the 3rd luminescent layer.
In the present invention, the triplet of carrier transmission material and the first and the 3rd luminous material of main part ability rank all can rank greater than the triplet of first metal organic complex.The triplet ability rank of the carrier transmission material and the second luminous material of main part all can rank greater than the triplet of second metal organic complex.
Organic white-light emitting element of the present invention can provide the white light with color stability, can reduce element operation voltage and significantly improve element efficiency, in addition, forms by the present invention's element, on processing procedure, more can improve convenience.
In addition, organic white-light emitting element of the present invention has planar light source, does not have mercurous metal, the characteristics of no ultraviolet light and high color rendering (color rendering), therefore, can be applicable to lighting apparatus (for example room lighting etc.), also can be applicable to ornamental light source.
Below be execution mode of the present invention to be described, hold within those skilled in the art can be disclosed by this specification and understand other advantages of the present invention and effect by particular specific embodiment.
[description of drawings]
Fig. 1 is the cross-sectional view of the organic white-light emitting element of one embodiment of the invention;
Fig. 2 is used for the organic luminous layer structural representation of organic white-light emitting element for the present invention; And
Fig. 3 is used for the organic luminous layer structural representation of organic white-light emitting element for the present invention.
[main element symbol description]
100 organic white-light emitting elements
102 substrates
104 anodes
106 hole transmission layers
108,208,308 organic luminous layers
110 electron transfer layers
112 negative electrodes
218,318 first luminescent layers
228,328 second luminescent layers
238,338 the 3rd luminescent layers
348 the 4th luminescent layers
[embodiment]
Below will further specify the present invention's characteristics by particular embodiment, but non-category in order to restriction the present invention.
Fig. 1 is the cross-sectional view of organic white-light emitting element of the present invention.In this example, organic white-light emitting element 100 from bottom to top comprises substrate 102, anode 104, hole transmission layer 106, organic luminous layer 108, electron transfer layer 110 and negative electrode 112 in regular turn.In instantiation, substrate 102 is all transparent material with anode 104.The instance of substrate 102 includes, but are not limited to glass substrate or plastic base, and can have flexible advantage with the made organic illuminating element of plastic base.The instance of anode 104 includes, but are not limited to transparent conductive metal oxide film, for example, and indium tin oxide (indium tin oxide is called for short ITO).
The material of hole transmission layer 106 comprises, for example, N, N '-two-(1-naphthyl)-N, N '-diphenyl, 1,1 '-biphenyl-4,4 '-diamines (N, N '-bis-(1-naphthyl)-N, N '-diphenyl, 1,1 '-biphenyl-4,4 '-diamine is called for short NPB).
Fig. 2 is the sketch map of organic luminous layer 208 of the present invention, and this organic luminous layer comprises first luminescent layer (B1 layer) 218, is formed at second luminescent layer (Y1 layer) 228 on first luminescent layer, and is formed at the 3rd luminescent layer (B2 layer) 238 on second luminescent layer.Wherein, this first luminescent layer 218 contacts with hole transmission layer or near hole transmission layer, and the 3rd luminescent layer 238 then contacts with electron transfer layer perhaps near electron transfer layer.More specifically, first luminescent layer 218 and the 3rd luminescent layer 238 are the short-wave long light-emitting layer, are preferably blue light-emitting, and second luminescent layer 228 is the long emission wavelength layer, is preferably gold-tinted or red light luminescent layer.
Fig. 3 is the sketch map of another organic luminous layer 308 of the present invention; This organic luminous layer comprises first luminescent layer (B1 layer) 318, is formed at second luminescent layer (Y1 layer) 328 on first luminescent layer; Be formed at the 4th luminescent layer (Y2 layer) 348 on second luminescent layer, and be formed at the 3rd luminescent layer (B2 layer) 338 on the 4th luminescent layer.Wherein, this first luminescent layer 318 contacts with hole transmission layer or near hole transmission layer, and 338 of the 3rd luminescent layers contact perhaps near electron transfer layer with electron transfer layer.More specifically, first luminescent layer 318 and the 3rd luminescent layer 338 are the short-wave long light-emitting layer, are preferably blue light-emitting, and are provided with second luminescent layer 328 and the 4th luminescent layer 348 of long emission wavelength layer between the two, are preferably gold-tinted or red light luminescent layer.
In one embodiment; First luminescent layer comprises the first luminous material of main part, first metal organic complex and carrier transmission material; Second luminescent layer comprises the second luminous material of main part and second metal organic complex; The 3rd luminescent layer comprises the 3rd luminous material of main part, first metal organic complex and carrier transmission material; Wherein, the triplet of the first luminous material of main part, the 3rd luminous material of main part and carrier transmission material ability rank are all greater than first metal organic complex.In specific embodiment, the triplet of the first luminous material of main part and the 3rd luminous material of main part can rank be greater than 2.7eV.
In preferred embodiment, first luminescent layer is between the anode and second luminescent layer, and the 3rd luminescent layer is between second luminescent layer and negative electrode.
In practical implementation of the present invention, this first luminous material of main part and the 3rd luminous material of main part are material different, and the second luminous material of main part then is and the first luminous material of main part or the 3rd any one identical materials of luminous material of main part.
In specific embodiment, this first luminous material of main part is selected from carbazoles (carbazole-based) compound or contains the aromatic series compounds of tertiary amine.Preferably, can select one or more main light emission material for use, particularly; The first luminous material of main part is selected from 9-(4-tert-butyl benzene)-3, two (triphenyl the is silica-based)-9H-carbazoles (CzSi), 2,2 ' of 6--two (4-carbazyl phenyl)-1; 1 '-biphenyl (4CzPBP), 4,4 '-two (9-carbazyl)-2,2 '-dimethyl-biphenyl (CDBP), N; N '-two carbazyl-2,5-benzene (mCP), 3, two (9-carbazyl) tetraphenyl silane (SimCP), three [4-(the 9-phenyl fluorenes-9-yl) phenyl] amine (TFTPA), 4 of 5-; 4 ', 4 '-three (N-carbazyl) triphenylamines (TCTA), two [4-(p, p '-dimethyl hexichol amido)-phenyl] diphenyl silane (DTASi), 1; Two [4-[N, N-two (p-tolyl) amido] phenyl] cyclohexane (TAPC) or their combinations of 1-.
In the specific embodiment of the invention, the 3rd luminous material of main part can be selected from phosphine oxide class (phosphineoxide-based), compound in triazine class or glyoxaline compound.Preferably, in the 3rd luminescent layer, also can select one or more the 3rd luminous material of main part for use, particularly; The 3rd luminous material of main part is selected from phosphine oxide 2, two (diphenylphosphino) dibenzofurans (DPDBF), 2 of 8-, two (diphenylphosphino) dibenzothiophenes (PPT), 2 of 8-; 4, the 6-carbazole also-1,3; 5-triazine (TRZ), 1,3,5-three (phenyl benzimidazolyl-2 radicals-yl) benzene (TPBI) or their combination.
In organic illuminating element of the present invention, first luminescent layer is identical metal organic complex with the first contained metal organic complex of the 3rd luminescent layer.
In specific embodiment, first metal organic complex is the person that can produce the blue light, and independently is selected from couple (4, the 6-difluorophenyl)-pyridine-N, C
2') pyridine carboxylic acid iridium (III) (FIrpic), two (4 '; 6 '-difluorophenyl pyridine) wantonly (1-pyrazolyl) boric acid iridium (III) (FIr6), two (4; 6-difluorophenyl pyridine) (3-(trifluoromethyl)-5-(pyridine-2-yl)-1; 2,4-triazine ester iridium (III) (FIrtaz) or two (4,6-difluorophenyl pyridine) (5-(pyridine-2-yl)-1H-tetrazine ester iridium (III) (FIrN4) etc.
In organic illuminating element of the present invention, contained second metal organic complex of second luminescent layer and the 4th optional luminescent layer is for can produce ruddiness or gold-tinted person.In specific embodiment, second metal organic complex can be selected from two, and (2-phenylchinoline base-N, C2) (acetylacetone,2,4-pentanedione) iridium (III) is (PQIr) or as shown in the formula PO-01 of structure etc.
In specific embodiment, carrier transmission material can be and contains the tertiary amine aromatic compound, is selected from following structural (I) or (II):
Wherein, Ar1, Ar2 and Ar3 independently are selected from C
6-X
10Aryl or 1 to 3 substituted C of substituting group of warp
6-C
10Aryl, wherein, this substituting group is selected from C
1-C
6Alkyl, C
1-C
6Alkoxyl, C
1-C
6Alkyl amine group, N-carbazyl or 9-phenyl fluorenes-9-base; And L independently is selected from single covalent bond, C
3-C
10Cycloalkyl, silicon, list-or two-phenyl silane base.
Preferably; Carrier transmission material can be selected from three [4-(9-phenyl fluorenes-9-yl) phenyl] amine (TFTPA), 4; 4 ', 4 '-three (N-carbazyl) triphenylamines (TCTA), two [4-(p, p '-dimethyl hexichol amido)-phenyl] diphenyl silane (DTASi), 1; Two [4-[N, N-two (p-tolyl) amido] phenyl] cyclohexane (TAPC) or their combinations of 1-.
Main light emission material, carrier transmission material and phosphor material that chemical formula and table 1 are given an example and adopted in the embodiment of the invention.
The luminous material of main part of the luminous material of main part B2 layer of B1 layer
The luminous guest materials carrier transmission material of the phosphorescence of B1 layer and B2 layer
The phosphor material Y1 layer of Y1 layer and Y2 layer and the phosphor material of Y2 layer
Table 1
| Compound | HOMO(eV) | LUMO(eV) | Triplet can rank |
| 4CzPBP | 6.1 | 2.6 | 2.8 |
| PPT | 6.6 | 2.9 | 3.1 |
| DTASi | 5.6 | 2.3 | 3.0 |
| Bphen | 6.4 | 3.0 | 2.5 |
| FIrpic | 5.8 | 2.9 | 2.7 |
| TCTA | 5.9 | 2.7 | 2.9 |
Therefore; With reference to figure 1, when at organic white-light emitting element applied voltage of the present invention, electronics and hole can transfer to organic luminous layer 108 with hole transmission layer 106 by electron transfer layer 110; Subsequently, electronics can be to combine in the organic luminous layer 108 with the hole and emit light.At this moment, because the triplet ability rank of the triplet of luminous material of main part ability rank and carrier transmission material so needed element operation voltage is lower, can be improved the luminous efficiency of element respectively greater than the triplet ability rank of metal organic complex simultaneously.
Below be the explanation of each embodiment of organic white-light emitting element of the present invention, but the material that each layer used, thickness and concentration are not the scope in order to restriction the present invention.
Embodiment 1
In embodiment 1, the composition that B1, B2, Y1, Y2 comprised is following:
B1: main light emission material 4CzPBP, the first metal organic complex FIrpic and carrier transmission material TCTA, each weight ratio of constituents is 75: 15: 10.
Y1: main light emission material 4CzPBP, the second metal organic complex PO-01 and carrier transmission material TCTA, each weight ratio of constituents is 85: 5: 10.
Y2: main light emission material PPT, the second metal organic complex PO-01 and carrier transmission material TCTA, each weight ratio of constituents is 85: 5: 10.
B2: main light emission material PPT, the first metal organic complex FIrpic and carrier transmission material TCTA, each weight ratio of constituents is 75: 15: 10.
And according to following flow preparation organic white-light emitting element of the present invention.
On the glass substrate of thickness 0.7 millimeter (mm), form 150 nanometers (nm) indium tin oxides (ITO) as anode; Afterwards on this anode with hot vapor deposition mode; The NPB that plates thickness 10nm is as hole transmission layer, then with the DTASi of hot vapor deposition mode plated thickness 20nm on hole transmission layer as electronic barrier layer.4CzPBP, FIrpic and TCTA are total to vapor deposition on electronic barrier layer, form first luminescent layer (B1 layer) of thickness 8nm.Then, 4CzPBP, PO-01 and TCTA are total to vapor deposition on first luminescent layer, form second luminescent layer (Y1 layer) of thickness 0.2nm.Then, PPT, PO-01 and TCTA are total to vapor deposition on second luminescent layer, form the 4th luminescent layer (Y2 layer) of thickness 0.2nm.Then, PPT, FIrpic and TCTA are total to vapor deposition on the 4th luminescent layer, form the 3rd luminescent layer (B2 layer) of thickness 0.2nm.
Afterwards, on the 3rd luminescent layer, plating thickness with hot vapor deposition mode is 4 of 25nm, 7-diphenyl-1, the 10-phenanthroline (4,7-diphenyl-1,10-phenanthroline is hereinafter to be referred as Bphen) as electron transfer layer.Then, weight ratio is respectively 20: 80 cesium carbonate (Cs
2CO
3) and the common vapor deposition of Bphen on electron transfer layer, forming thickness is the electron injecting layer of 20nm.With hot vapor deposition mode, forming thickness is the aluminium negative electrode of 100nm at last.
In the present embodiment, luminescent layer B1-Y1-Y2-B2 with four layers of blue-yellow-Huang-blue light formed, and each layer all comprises carrier transmission material.In element brightness is 1000cd/m
2Current efficiency and the test result of operating voltage, and element white light chromaticity coordinate is as shown in table 2.
Embodiment 2
In embodiment 2, the composition that B1, B2, Y1, Y2 comprised is following:
B1: main light emission material 4CzPBP, the first metal organic complex FIrpic and carrier transmission material TCTA, each weight ratio of constituents is 75: 15: 10.
Y1: the main light emission material 4CzPBP and the second metal organic complex PO-01, each weight ratio of constituents is 95: 5.
Y2: the main light emission material PPT and the second metal organic complex PO-01, each weight ratio of constituents is 95: 5.
B2: main light emission material PPT, the first metal organic complex FIrpic and carrier transmission material TCTA, each weight ratio of constituents is 75: 15: 10.
In addition, according to the organic white-light emitting element of embodiment 1 said flow preparation embodiment 2.
In the present embodiment, luminescent layer B1-Y1-Y2-B2 with four layers of blue-yellow-Huang-blue light formed, and Y1 and Y2 do not contain carrier transmission material.In element brightness is 1000cd/m
2Current efficiency and the test result of operating voltage, and the white light chromaticity coordinate of element is as shown in table 2.
Embodiment 3
In embodiment 3, the composition that B1, B2, Y1 comprised is following:
B1: main light emission material 4CzPBP, the first metal organic complex FIrpic and carrier transmission material TCTA, each weight ratio of constituents is 75: 15: 10.
Y1: the second metal organic complex PO-01.
B2: main light emission material PPT, the first metal organic complex FIrpic and carrier transmission material TCTA, each weight ratio of constituents is 75: 15: 10.
In addition, then according to the organic white-light emitting element of embodiment 1 said flow preparation embodiment 3, wherein the thickness of Y1 layer is 0.1nm.In the present embodiment, luminescent layer B1-Y1-B2 with three layers of blue-yellow-blue light formed.In element brightness is 1000cd/m
2Current efficiency and the test result of operating voltage, and the white light system of chromatic coordinates of element is as shown in table 2.
Comparative example 1
The composition that B1, B2, Y1, Y2 comprised is following:
B1: the main light emission material 4CzPBP and the first metal organic complex FIrpic, each weight ratio of constituents is 85: 15.
Y1: the main light emission material 4CzPBP and the second metal organic complex PO-01, each weight ratio of constituents is 95: 5.
Y2: the main light emission material PPT and the second metal organic complex PO-01, each weight ratio of constituents is 95: 5.
B2: the main light emission material PPT and the first metal organic complex FIrpic, each weight ratio of constituents is 85: 15.
In addition, then according to the organic white-light emitting element of embodiment 1 said flow preparation comparative example 1.
In the present embodiment, luminescent layer B1-Y1-Y2-B2 with four layers of blue-yellow-Huang-blue light formed, and B1, B2, Y1, Y2 all do not add carrier transmission material.In element brightness is 1000cd/m
2Current efficiency and the test result of operating voltage, and the white light chromaticity coordinate of element is as shown in table 2.
Comparative example 2
The composition that B1, B2, Y1 comprised is following:
B1: the main light emission material 4CzPBP and the first metal organic complex FIrpic, each weight ratio of constituents is 85: 15.
Y1: the main light emission material 4CzPBP and the second metal organic complex PO-01, each weight ratio of constituents is 95: 5.
B2: the main light emission material 4CzPBP and the first metal organic complex FIrpic, each weight ratio of constituents is 85: 15.
And according to following flow preparation organic white-light emitting element of the present invention.
On 0.7 millimeter (mm) glass substrate of thickness, form 150 nanometers (nm) indium tin oxides (ITO) as anode; Afterwards on this anode with hot vapor deposition mode; The NPB that plates thickness 10nm is as hole transmission layer, and the DTASi that then on hole transmission layer, plates thickness 20nm with hot vapor deposition mode is as electronic barrier layer.4CzPBP and FIrpic are total to vapor deposition on electronic barrier layer, form first luminescent layer (B1 layer) of thickness 8nm.Then, 4CzPBP and PO-01 are total to vapor deposition on first luminescent layer, form second luminescent layer (Y1 layer) of thickness 0.2nm.Then, 4CzPBP and FIrpic are total to vapor deposition on second luminescent layer, form the 3rd luminescent layer (B2 layer) of thickness 8nm.
Afterwards, on the 3rd luminescent layer, plating thickness with hot vapor deposition mode is that the Bphen of 25nm is as electron transfer layer.Then, weight ratio is respectively 20: 80 cesium carbonate and the common vapor deposition of Bphen on electron transfer layer, forming thickness is the electron injecting layer of 20nm.With hot vapor deposition mode, forming thickness is the aluminium negative electrode of 100nm at last.
In this comparative example, luminescent layer B1-Y1-B2 with three layers of blue-yellow-blue light formed, B1 is identical with the main light emission material of B2, and each layer all do not comprise carrier transmission material.In element brightness is 1000cd/m
2Current efficiency and the test result of operating voltage, and the white light chromaticity coordinate of element is as shown in table 2.
Comparative example 3
The composition that B1, Y1 comprised is following:
B1: main light emission material 4CzPBP, the first metal organic complex FIrpic and carrier transmission material TCTA, each weight ratio of constituents is 75: 15: 10.
Y1: the main light emission material 4CzPBP and the second metal organic complex PO-01, each weight ratio of constituents is 95: 5.
And according to following flow preparation organic white-light emitting element of the present invention.
The indium tin oxide (ITO) that on the glass substrate of thickness 0.7mm, forms 150nm is as anode; Afterwards on this anode with hot vapor deposition mode; The NPB that plates thickness 10nm is as hole transmission layer, and the DTASi that then on hole transmission layer, plates thickness 20nm with hot vapor deposition mode is as electronic barrier layer.4CzPBP and PO-01 are total to vapor deposition on electronic barrier layer, form second luminescent layer (Y1 layer) of thickness 12nm.Then, 4CzPBP, FIrpic and TCTA are total to vapor deposition on second luminescent layer, form first luminescent layer (B1 layer) of thickness 8nm.Afterwards, on first luminescent layer, plating thickness with hot vapor deposition mode is that the Bphen of 25nm is as electron transfer layer.Then, weight ratio is respectively 20: 80 cesium carbonate and the common vapor deposition of Bphen on electron transfer layer, forming thickness is the electron injecting layer of 20nm.With hot vapor deposition mode, forming thickness is the aluminium negative electrode of 100nm at last.
In this comparative example, luminescent layer Y1-B1 is formed with the two-layer of Huang-blue light.In element brightness is 1000cd/m
2Current efficiency and the test result of operating voltage, and the white light chromaticity coordinate of element is as shown in table 2.
Table 2
For chromaticity coordinate; (the Commission International del ' Eclairage of Commission Internationale De L'Eclairage; The chromaticity coordinate of the standard white of CIE) working out (x, y) value is (0.33,0.33); But white light also comprise different colour temperatures (as cold white, daylight white, warm white etc.), so the cie color value of white light has big relatively excursion.
According to the result shown in the table 2; Compare with comparative example 1; The embodiment of the invention 1 and 2 element (B1 layer and B2 layer have carrier transmission material) because of carrier transmission material being arranged in blue light-emitting, effectively reduce operating voltage and reach 16% and the about 36-43% of lift elements efficient.Compare with comparative example 2, the embodiment of the invention 1 and 2 element (B1 layer and B2 layer have carrier transmission material) when two blue light-emittings are formed by the luminous material of main part of difference, effectively reduce operating voltage and lift elements efficient.In addition, the element of the embodiment of the invention 3, when the Yellow light emitting layer was formed by single metal organic complex, element still can be kept high luminous efficiency and low operating voltage.
In sum, the luminous efficiency that organic white-light emitting element of the present invention can reduce the operating voltage of organic white-light emitting element simultaneously and significantly improve element, and the white light with stable colourity can be provided.
The foregoing description is illustrative constituent of the present invention and preparation method only, but not is used to limit the present invention.Any those skilled in the art all can be under spirit of the present invention and category, and the foregoing description is modified and changed.Therefore, rights protection scope of the present invention is as the criterion with accompanying claims.
Claims (13)
1. organic white-light emitting element comprises:
Anode;
Hole transmission layer, it is formed on this anode;
Be formed at first luminescent layer on this hole transmission layer, it comprises the first luminous material of main part, first metal organic complex and carrier transmission material;
Be formed at second luminescent layer on this first luminescent layer, make this first luminescent layer be folded between this hole transmission layer and second luminescent layer, this second luminescent layer comprises second metal organic complex;
Be formed at the 3rd luminescent layer on this second luminescent layer, make this second luminescent layer be folded between this first luminescent layer and the 3rd luminescent layer, the 3rd luminescent layer comprises the 3rd luminous material of main part, first metal organic complex and carrier transmission material;
Electron transfer layer, it is formed on the 3rd luminescent layer, makes the 3rd luminescent layer be folded between this second luminescent layer and the electron transfer layer; And
Negative electrode, it is formed on the lateral surface of electron transfer layer;
Wherein, the emission wavelength of this second luminescent layer is longer than the emission wavelength of first luminescent layer and the 3rd luminescent layer, and this first luminous material of main part and the 3rd luminous material of main part are different materials;
Also comprise the 4th luminescent layer that is formed between first luminescent layer and the 3rd luminescent layer; The 4th luminescent layer comprises the 4th luminous material of main part and second metal organic complex, and the emission wavelength of the 4th luminescent layer is longer than the emission wavelength of first luminescent layer and the 3rd luminescent layer.
2. organic white-light emitting element as claimed in claim 1, wherein, this second luminescent layer also comprises second luminous material of main part and the carrier transmission material.
3. organic white-light emitting element as claimed in claim 2, wherein, this second luminous material of main part is and one of the first luminous material of main part or the 3rd luminous material of main part identical materials.
4. organic white-light emitting element as claimed in claim 1, wherein, the emission wavelength of this first luminescent layer and the 3rd luminescent layer is 400 to 480nm, the emission wavelength of this second luminescent layer is 520 to 640nm.
5. organic white-light emitting element as claimed in claim 1, wherein, the 4th luminescent layer also comprises carrier transmission material.
6. organic white-light emitting element as claimed in claim 2, wherein, the 4th luminous material of main part is and one of the first luminous material of main part or the 3rd luminous material of main part identical materials, and with the second luminous material of main part be material different.
7. organic white-light emitting element as claimed in claim 2; Wherein, the triplet of this carrier transmission material and the first and the 3rd luminous material of main part can rank all can rank greater than the triplet of this first metal organic complex and the triplet of this carrier transmission material and the second luminous material of main part can rank all can rank greater than the triplet of this second metal organic complex.
8. organic white-light emitting element as claimed in claim 1, wherein, this carrier transmission material is selected from following structural (I) or (II):
Wherein, Ar1, Ar2 and Ar3 independently are selected from C
6-C
10Aryl or 1 to 3 substituted C of substituting group of warp
6-C
10Aryl, wherein, this substituting group is selected from C
1-C
6Alkyl, C
1-C
6Alkoxyl, C
1-C
6Alkyl amine group, N-carbazyl or 9-phenyl fluorenes-9-base; And
L independently is selected from single covalent bond, C
3-C
10Cycloalkyl, silicon, list-or two-phenyl silane base.
9. organic white-light emitting element as claimed in claim 8; Wherein, this carrier transmission material is selected from three [4-(9-phenyl fluorenes-9-yl) phenyl] amine, 4,4 '; 4 '-three (N-carbazyl) triphenylamine, two [4-(p; P '-dimethyl hexichol amido)-and phenyl] diphenyl silane, and 1, at least a in two [4-[N, N-two (p-tolyl) amido] phenyl] cyclohexanes of 1-.
10. organic white-light emitting element as claimed in claim 1, wherein, the aromatic series compounds that this first luminous material of main part is selected from carbazole compound or contains tertiary amine.
11. organic white-light emitting element as claimed in claim 1, wherein, the 3rd luminous material of main part is selected from phosphine oxide compounds, compound in triazine class or glyoxaline compound.
12. organic white-light emitting element as claimed in claim 1, wherein, this first metal organic complex independently is selected from two (4, the 6-difluorophenyl)-pyridine-N, C
2') pyridine carboxylic acid iridium (III), two (4 '; 6 '-difluorophenyl pyridine) four (1-pyrazolyl) boric acid iridium (III), two (4; 6-difluorophenyl pyridine) (3-(trifluoromethyl)-5-(pyridine-2-yl)-1; 2,4-triazine ester iridium (III) or two (4,6-difluorophenyl pyridine) (5-(pyridine-2-yl)-1H-tetrazine ester iridium (III).
13. organic white-light emitting element as claimed in claim 1, wherein, this second metal organic complex is selected from two (2-phenylchinoline base-N, C2) (acetylacetone,2,4-pentanedione) iridium (III) or have the PO-01 of following formula
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