CN102074658A - Electric charge production layer, lamination layer organic light-emitting diode and preparation method thereof - Google Patents
Electric charge production layer, lamination layer organic light-emitting diode and preparation method thereof Download PDFInfo
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Abstract
The embodiment of the invention provides an electric charge production layer, a lamination layer organic light-emitting diode and a preparation method thereof, wherein the electric charge production layer is such an electric charge production layer which is obtained by blending a p type organic semiconductor and a n type organic semiconductor; the lamination layer organic light-emitting diode comprises at least two light emitting units and an electric charge production layer connected to adjacent light emitting units, and the electric charge production layer is such an electric charge production layer which is obtained by blending a p type organic semiconductor and a n type organic semiconductor; and the preparation method of lamination layer organic light-emitting diode comprises the following steps of providing a substrate, forming an anode on the substrate, and forming at least two light emitting units and at least one electric charge production layer which is obtained by blending a p type organic semiconductor and a n type organic semiconductor on the anode. The lamination layer organic light-emitting diode provided by the invention has the advantages that the brightness and the current efficiency are improved, the power efficiency is simultaneously improved greatly, and the diode is particularly suitable for illumination and display and the like practical applications.
Description
Technical field
The present invention relates to the Organic Light Emitting Diode technical field, more particularly, relate to a kind of charge generation layer, lamination Organic Light Emitting Diode and preparation method thereof.
Background technology
(Organic Light-Emitting Diode OLED) shows Organic Light Emitting Diode and lighting technology is regarded as emerging demonstration and lighting technology the most popular in flat-panel monitor and the Lighting Industry, has obtained extensive studies at present.Compare with inorganic light-emitting diode, OLED have the material range of choice wide, can realize by blue light region to the full color of red light district show, driving voltage is low, luminosity and current efficiency height, the visual angle is wide, response speed is fast, manufacture craft is simple, cost is low, and easily realize plurality of advantages such as large tracts of land and flexible demonstrations, thereby obtained developing rapidly in the past more than 20 year.At present, the research of organic light emitting display and lighting field is not limited to academia already, nearly all internationally recognizable electronics corporation and chemical company all drop into huge manpower and fund enters this research field, present the situation that research, exploitation and industrialization advance side by side, industrialization that OLED shows and lighting technology is rapidly being marched toward.
Initial OLED has double-deck sandwich structure, and it is made up of hole transmission layer, luminescent layer and electron transfer layer, and (Indium Tin Oxides is ITO) and between the metal electrode to be clipped in indium tin oxide.Produced the OLED of sandwich construction afterwards successively, comprising: hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer, have again, the OLED of dye adulterated type also is designed to create.By organic layer thickness optimization and preparation technology's improvement, the luminescent properties of OLED has obtained improving greatly.
In order to improve the luminescent properties of OLED, lamination OLED arises at the historic moment.Lamination OLED is a kind of OLED that a plurality of luminescence units (OLED) is together in series by charge generation layer and is only controlled by an external power.Compare with traditional OLED, lamination OLED has higher luminosity and current efficiency, and its luminosity and current efficiency are along with the increase of series connection luminescence unit number forms multiplication length; And under same current density, lamination OLED is the same with the ageing property of traditional OLED, but because the original intensity of lamination OLED is bigger, therefore, if be converted into same original intensity, then the life-span of lamination OLED will prolong greatly than traditional OLED.
Why more traditional OLED has luminescent properties preferably to lamination OLED, and key is that there is charge generation layer in its inside.Various studies show that, as long as have charge generation layer among the lamination OLED, no matter this charge generation layer is that what to mix also is non-doping, and the luminosity of lamination OLED and current efficiency are multiplied.
Yet, still there is an important problem in present lamination OLED, that is: when luminosity and current efficiency are multiplied, voltage also has been multiplied, being multiplied of voltage can not reduce power loss effectively, thereby can not improve power efficiency effectively, this is very disadvantageous in illumination is used particularly in actual applications, has also lost the advantage of lamination OLED.
Summary of the invention
In view of this, the invention provides a kind of charge generation layer, lamination Organic Light Emitting Diode and preparation method thereof, this lamination Organic Light Emitting Diode can improve power efficiency effectively.
For achieving the above object, the invention provides following technical scheme:
A kind of charge generation layer, described charge generation layer are to mix the charge generation layer that forms by p type organic semiconductor and n type organic semiconductor.
Preferably, described p type organic semiconductor and n type organic semi-conductor mixed proportion are 4: 1,3: 1,2: 1,3: 2,4: 3,1: 1,3: 4,2: 3,1: 2,1: 3 or 1: 4.
Preferably, described n type organic semi-conductor lowest unoccupied molecular orbital energy level is greater than 4.0eV, described p type organic semi-conductor highest occupied molecular orbital energy level is less than 5.5eV, and the difference of described p type organic semi-conductor highest occupied molecular orbital energy level and n type organic semi-conductor lowest unoccupied molecular orbital energy level is less than 1eV.
The present invention also provides a kind of lamination Organic Light Emitting Diode, and this lamination Organic Light Emitting Diode comprises: at least two luminescence units, connect the charge generation layer of adjacent luminescence unit; Wherein, described charge generation layer is to mix the charge generation layer that forms by p type organic semiconductor and n type organic semiconductor.
Preferably, described p type organic semiconductor and n type organic semi-conductor mixed proportion are 4: 1,3: 1,2: 1,3: 2,4: 3,1: 1,3: 4,2: 3,1: 2,1: 3 or 1: 4.
Preferably, described n type organic semi-conductor lowest unoccupied molecular orbital energy level is greater than 4.0eV, described p type organic semi-conductor highest occupied molecular orbital energy level is less than 5.5eV, and the difference of described p type organic semi-conductor highest occupied molecular orbital energy level and n type organic semi-conductor lowest unoccupied molecular orbital energy level is less than 1eV.
Preferably, described p type organic semiconducting materials is CuPc, Phthalocyanine Zinc, 2,5-is suitable-and (4-2 phenyl)-2 thiophene, pentacene or aphthacene.
Preferably, described n type organic semiconducting materials is C
60, perylene Gan Huo perylene diamides.
The present invention also provides a kind of preparation method of lamination Organic Light Emitting Diode, and described method comprises:
Substrate is provided;
On described substrate, form anode;
On described anode, form at least two luminescence units and at least one charge generation layer that mixes by p type organic semiconductor and n type organic semiconductor.
Preferably, specifically comprise at formation luminescence unit on the described anode: on described anode, form hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer successively.
From technique scheme as can be seen, charge generation layer provided by the present invention is to mix the charge generation layer that forms by p type organic semiconductor and n type organic semiconductor, this kind has the charge generation layer of mixed system, in whole charge layer and all exist p type organic semiconductor and n type organic semi-conductor to interact at the interface, so it is more abundant that electronics is transferred to n type organic semiconductor from p type organic semiconductor, like this, electronics is accumulated in n type organic semiconductor one side, the hole is accumulated in p type organic semiconductor one side, under the certain voltage effect, electronics and hole are respectively to anodal and negative pole transmission, and then form bigger electric current, improve luminosity and current efficiency thereby be beneficial to.Lamination Organic Light Emitting Diode provided by the present invention comprises: at least two luminescence units, connect the charge generation layer of adjacent luminescence unit; Wherein, described charge generation layer is to mix the charge generation layer that forms by p type organic semiconductor and n type organic semiconductor.Owing to comprised the charge generation layer that under the certain voltage effect, can form big electric current in the described lamination Organic Light Emitting Diode, therefore, this lamination Organic Light Emitting Diode can reduce device drive voltage very effectively, when realizing that luminosity and current efficiency increase, can improve power efficiency effectively, reduce power loss, this will help it in illumination and demonstration Application for Field, embody the advantage of lamination Organic Light Emitting Diode.
Description of drawings
In order to be illustrated more clearly in the embodiment of the invention or technical scheme of the prior art, to do to introduce simply to the accompanying drawing of required use in embodiment or the description of the Prior Art below, apparently, accompanying drawing in describing below only is some embodiments of the present invention, for those of ordinary skills, under the prerequisite of not paying creative work, can also obtain other accompanying drawing according to these accompanying drawings.
Fig. 1 is the lamination OLED that the embodiment of the invention provided and the structural representation of external devices;
Fig. 2 is the structural representation of charge generation layer among Fig. 1;
Fig. 3 is the structural representation of a kind of luminescence unit that the embodiment of the invention provided;
Fig. 4 is the characteristic curve schematic diagram of brightness-voltage-to-current density of the lamination OLED that the embodiment of the invention provided;
Fig. 5 is the characteristic curve schematic diagram of current efficiency-current density-power efficiency of the lamination OLED that the embodiment of the invention provided;
Fig. 6 is the characteristic curve schematic diagram of the luminescent spectrum of the lamination OLED that the embodiment of the invention provided.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, the specific embodiment of the present invention is described in detail below in conjunction with accompanying drawing.
A lot of details have been set forth in the following description so that fully understand the present invention, but the present invention can also adopt other to be different from alternate manner described here and implement, those skilled in the art can do similar popularization under the situation of intension of the present invention, so the present invention is not subjected to the restriction of following public specific embodiment.
Secondly, the present invention is described in detail in conjunction with schematic diagram, when the embodiment of the invention is described in detail in detail; for ease of explanation; the profile of expression device architecture can be disobeyed general ratio and be done local the amplification, and described schematic diagram is example, and it should not limit the scope of protection of the invention at this.The three dimensions size that in actual fabrication, should comprise in addition, length, width and the degree of depth.
Embodiment one
Just as described in the background section, present lamination OLED is when luminosity and current efficiency are multiplied, and voltage also has been multiplied, thereby can not improve power efficiency effectively.And the charge generation layer among the lamination OLED is the main cause that influences its luminosity and current efficiency, so the inventor discovers: by improving the charge generation layer among the lamination OLED, make it under the certain voltage effect, produce more charge carrier and then the bigger electric current of formation, like this when improving luminosity and current efficiency, voltage is not multiplied, and then can reach the purpose that improves lamination OLED power efficiency.
Based on this, the invention provides a kind of charge generation layer, this charge generation layer is to mix the charge generation layer that forms by p type organic semiconductor and n type organic semiconductor.Because this charge generation layer belongs to a kind of mixed system, therefore, also is called organic semiconductor bulk heterojunction charge generation layer.
Described organic semiconductor bulk heterojunction promptly is p type organic semiconductor and n type organic semiconductor blend by a certain percentage structure together.Because the organic semiconductor bulk heterojunction can be realized the separation of photo-generated carrier effectively, therefore, it has obtained using widely in organic thin film solar cell, especially in the research field of polymer thin-film solar cell.Simultaneously, because it has dipole characteristic preferably, therefore, in the binary channels OTFT, also have broad application prospects.In solar cell device, the organic semiconductor bulk heterojunction produces exciton under illumination, and separates under effect of electric field, transmits and output, finally forms electric current.And the process of the generation of the charge generation layer among lamination OLED charge carrier also similarly, and different is: the charge carrier that produces in the charge generation layer produces under effect of electric field, and transmission and injection under effect of electric field.Based on above-mentioned theory, the inventor has studied a kind of organic semiconductor bulk heterojunction charge generation layer, charge generation layer promptly provided by the present invention.
Charge generation layer provided by the present invention, be to mix the charge generation layer that forms by p type organic semiconductor and n type organic semiconductor, therefore, this charge generation layer constitutes mixed system, whole charge generation layer is interior and all exist p type organic semiconductor and n type organic semi-conductor to interact at the interface, it is more abundant that this will make electronics transfer to n type organic semiconductor from p type organic semiconductor, like this, electronics is accumulated in n type organic semiconductor one side, the hole is accumulated in p type organic semiconductor one side, and under the certain voltage effect, electronics and hole are respectively to anodal and negative pole transmission, and then form bigger electric current, improve luminosity and current efficiency thereby be beneficial to.
Embodiment two
The present invention also provides a kind of lamination OLED, and described lamination OLED comprises: the charge generation layer of at least two luminescence units (being OLED), the adjacent luminescence unit of connection; Wherein, described charge generation layer is to mix the charge generation layer that forms by p type organic semiconductor and n type organic semiconductor.
Charge generation layer among the initial lamination OLED is by ITO or vanadic oxide (V
2O
5) mix 2 with caesium (Cs), 9-dimethyl-4,7-diphenyl-1, the double-decker that 10-o-phenanthroline (BCP) is formed.Though this charge generation layer can improve luminosity and the current efficiency of lamination OLED, also improved voltage simultaneously, thereby be unfavorable for reducing power loss, raising power efficiency.Secondly, this charge generation layer adopts doped structure, and this makes device become complicated on the one hand in preparation process, on the other hand, the guest molecule that mixes very easily is diffused in the luminescent layer of luminescence unit, forms the cancellation center, and then the luminescent properties of device is had a significant impact.Have again, adopt inorganic, metal oxide in this charge generation layer, the higher evaporating temperature of described inorganic, metal oxide will be destroyed organic layer and at the light transmittance of visible region, can make the photon that produces not emit effectively, has reduced the transmitance of light.
Lamination OLED provided by the present invention, charge generation layer among this lamination OLED is to mix the charge generation layer that forms by p type organic semiconductor and n type organic semiconductor, this charge generation layer is interior and all exist p type organic semiconductor and n type organic semi-conductor to interact at the interface, it is more abundant that this just makes electronics transfer to n type organic semiconductor from p type organic semiconductor, like this, electronics is accumulated in n type organic semiconductor one side, the hole is accumulated in p type organic semiconductor one side, under the certain voltage effect, electronics and hole are respectively to anodal and negative pole transmission, and then form bigger electric current, improve luminosity and current efficiency thereby be beneficial to.Promptly under the situation of voltage undouble, realize being doubled and redoubled of luminosity and current efficiency, thereby reduced power loss, improved power efficiency.
The OLED of lamination described in the present embodiment owing to do not mix impurity in the charge generation layer in it, therefore makes preparation process comparatively simple, and the molecular diffusion of not worrying mixing forms the cancellation center in luminescent layer.Have, the charge generation layer of described lamination OLED is that p type organic semiconductor and n type organic semiconductor mix the charge generation layer that forms, and does not exist metal ion or organic molecule to mix in the promptly whole charge generation layer, therefore, can improve the transmitance of light greatly again.
Embodiment three
Describe charge generation layer provided by the present invention and lamination OLED in detail below in conjunction with accompanying drawing.
With reference to figure 1, Fig. 1 is the lamination OLED that the embodiment of the invention provided and the structural representation of external devices.Described lamination OLED1 comprises: at least two luminescence units, connect the charge generation layer of adjacent luminescence unit; Wherein, described charge generation layer is to mix the charge generation layer that forms by p type organic semiconductor and n type organic semiconductor.
With reference to figure 2, Fig. 2 is the structural representation of charge generation layer among Fig. 1.Described charge generation layer is to mix the charge generation layer that forms by a certain percentage by p type organic semiconductor and n type organic semiconductor.N type organic semiconductor is meant with the electronics to be the organic semiconductor of majority carrier, and p type organic semiconductor is meant with the hole to be the organic semiconductor of majority carrier; N type organic semiconductor will have lower lowest unoccupied molecular orbital energy level and suitable electron affinity, be beneficial to the injection and the transmission of electronics, p type organic semiconductor will have higher highest occupied molecular orbital energy level and suitable ionization gesture, is beneficial to the injection and the transmission in hole.Find that after deliberation described p type organic semiconductor and n type organic semi-conductor mixed proportion can be 4: 1,3: 1,2: 1,3: 2,4: 3,1: 1,3: 4,2: 3,1: 2,1: 3 or 1: 4 etc.Described n type organic semi-conductor lowest unoccupied molecular orbital energy level is greater than 4.0eV, described p type organic semi-conductor highest occupied molecular orbital energy level is less than 5.5eV, and the difference of described p type organic semi-conductor highest occupied molecular orbital energy level and n type organic semi-conductor lowest unoccupied molecular orbital energy level is less than 1eV.
The THICKNESS CONTROL of each charge generation layer is between 25nm～35nm in the embodiment of the invention.The material of each charge generation layer is the avirulence material, and described n type organic semiconductor can be C
60Or derivatives thereof; Also Ke Yi is derivative You Xuan perylene acid anhydride (the PTCDA) Huo perylene diamides (PTCDI) of derivative ， perylene of perylene.Described p type organic semiconductor can be metallo phthalocyanine, thiophenes or biphenyl class, preferred CuPc of phthalocyanine-like compound (CuPc) or Phthalocyanine Zinc (ZnPc); Thiophenes is preferred 2, and 5-is suitable-(4-2 phenyl)-2 thiophene (BP2T); Preferred pentacene of biphenyl class (pentacene) or aphthacene (Tetracene).
Lamination OLED1 has been shown among Fig. 1 has been clipped between anode 3 and the negative electrode 6, anode 3 is positioned on the substrate 2, and anode 3 links to each other by positive pole, the negative pole of lead 7 and power supply 8 respectively with negative electrode 6.Have at least one to be transparency electrode in described anode 3 and the negative electrode 6.The OLED1 of lamination described in the present embodiment comprises N luminescence unit (N is a positive integer, and N 〉=2, below identical, all no longer dated) and N-1 charge generation layer.A described N luminescence unit 6 piles up one by one from anode 3 to negative electrode, they be followed successively by the first luminescence unit 4-1, the second luminescence unit 4-2 ..., N-1 luminescence unit 4-(N-1), N luminescence unit 4-N.A described N-1 charge generation layer be respectively the first charge generation layer 5-1, the second charge generation layer 5-2 ..., N-1 charge generation layer 5-(N-1), a described N-1 charge generation layer lays respectively between per two luminescence units, promptly the first charge generation layer 5-1 is between the first luminescence unit 4-1 and the second luminescence unit 4-2, the second charge generation layer 5-2 is between the second luminescence unit 4-2 and the 3rd luminescence unit 4-3, and the like, N-1 charge generation layer 5-(N-1) is positioned between N-1 luminescence unit 4-(N-1) and the N luminescence unit 4-N.
When power supply 8 provided voltage for lamination OLED1, the hole was injected into the first luminescence unit 4-1 by anode 3, and electronics is injected into N luminescence unit 4-N by negative electrode 6; Meanwhile, (j is a positive integer to j charge generation layer 5-j, and 1≤j≤N-1, produce electronics and hole down together), the electronics that is produced injects the j luminescence unit 4-j towards anode 3 directions that is adjacent under effect of electric field, the j+1 luminescence unit 4-(j+1) towards negative electrode 6 directions that is adjacent is injected in the hole that is produced under effect of electric field.For example, the electronics that N-1 charge generation layer 5-(N-1) produces is injected into N-1 luminescence unit 4-(N-1) towards anode 3 directions, the hole that N-1 charge generation layer 5-(N-1) produces is injected into N luminescence unit 4-N towards negative electrode 6 directions, the hole that N-2 charge generation layer 5-(N-2) produces is injected into N-1 luminescence unit 4-(N-1) towards negative electrode 6 directions, then, N luminescence unit 4-N receives respectively from the electronics of negative electrode 6 with from the hole of N-1 charge generation layer 5-(N-1), N-1 luminescence unit 4-(N-1) receives respectively from the electronics of N-1 charge generation layer 5-(N-1) with from the hole of N-2 charge generation layer 5-(N-2), and recombination luminescence is all passed through in electronics and hole in N luminescence unit 4-N and the N-1 luminescence unit 4-(N-1).
Each luminescence unit is all supported electronics and hole transport among the lamination OLED1 that the embodiment of the invention provided.With reference to figure 3, Fig. 3 is the structural representation of a kind of luminescence unit that the embodiment of the invention provided.Described luminescence unit comprises: the hole injection layer 41 that sets gradually, hole transmission layer 42, luminescent layer 43, electron transfer layer 44 and electron injecting layer 45.
In addition, described luminescence unit can also be set to other structure that is arranged in order, and is as follows respectively: hole transmission layer, electric transmission luminescent layer; Hole transmission layer, luminescent layer, electron transfer layer; Hole injection layer, hole transmission layer, luminescent layer, electron transfer layer; Hole injection layer, hole transmission layer, electronic barrier layer, luminescent layer, electron transfer layer, electron injecting layer; Hole injection layer, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, electron injecting layer etc.
Luminescence unit among the lamination OLED1 provided by the present invention can be set to identical structure, also can be set to different structures, and to this, there is no particular restriction in the present invention.
The substrate 2 that the embodiment of the invention provided can be glass or Merlon flexible material, and anode 3 and negative electrode 6 can be made by ITO and aluminium respectively.
The THICKNESS CONTROL of each luminescence unit among the lamination OLED1 provided by the present invention is between 140nm～150nm, and the THICKNESS CONTROL of each organic layer in each luminescence unit is between 10nm～90nm.
Fig. 3 has provided the structural representation of a kind of luminescence unit that the embodiment of the invention provided, and this luminescence unit is made of the hole injection layer 41, hole transmission layer 42, luminescent layer 43, electron transfer layer 44 and the electron injecting layer 45 that connect successively.
Wherein, hole injection layer 41 materials can be V
2O
5, molybdenum trioxide (MoO
3) or tungstic acid (WO
3), perhaps be V
2O
5, MoO
3And WO
3In a kind of doping N, N '-two (1-naphthyl)-N, N '-diphenyl-1,1 '-diphenyl-4,4 '-diamines (NPB); Hole injection layer 41 THICKNESS CONTROL are between 3nm～20nm.Hole transmission layer 42 materials are NPB; Hole transmission layer 42 THICKNESS CONTROL are between 50nm～90nm.Electron transfer layer 44 materials can be oxine aluminium (Alq
3); Electron transfer layer 44 THICKNESS CONTROL are between 10nm～30nm.Electron injecting layer 45 materials can be LiF, perhaps are: active metal Li or Cs doped with Al q
3If LiF, then controlling its thickness is about 1nm, if Li or Cs doped with Al q
3, then controlling its thickness is about 20nm.
Embodiment four
The present invention also provides the preparation method of a kind of lamination OLED, and this method comprises:
Step S1: substrate is provided.
Substrate in this step is glass or Merlon flexible material.
Step S2: on described substrate, form anode.
Adopt the method for chemical vapour deposition (CVD), physical vapour deposition (PVD) or sputter on described substrate, to prepare ito thin film, and adopt photoetching, etching technics described ITO rete to be made into the electrode of required fine strip shape, clean then, nitrogen dries up, and uses oxygen plasma treatment again 2 minutes.
Step S3: on described anode, form at least two luminescence units and at least one charge generation layer that mixes by p type organic semiconductor and n type organic semiconductor.
Be that example describes at first with two luminescence units of formation and a charge generation layer on anode.
The substrate that will comprise anode is put into vacuum coating system, and described vacuum coating system is vacuumized, and treats that the air pressure of vacuum chamber reaches 5 * 10
-4During handkerchief, evaporation first luminescence unit, first charge generation layer, second luminescence unit and negative electrode on described anode successively.On described anode, form luminescence unit, can comprise again: on described anode, form hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer successively.
Wherein, in the evaporation first luminescence unit process, the hole injection layer material adopts MoO
3, V
2O
5And WO
3In a kind of, or adopt MoO
3, V
2O
5And WO
3In a kind of doping NPB; Hole transport layer material adopts NPB; The luminescent layer material adopts C545T doped with Al q
3, DCJTB doped with Al q
3, DCJTB and C545T codope Alq
3, DSA-ph doping MADN or DCJTB and DSA-ph codope MADN; The electric transmission layer material adopts Alq
3The electron injecting layer material adopts LiF, perhaps adopts active metal Li or Cs doped with Al q
3The hole injection layer material adopts MoO
3, hole transport layer material adopts NPB, electric transmission layer material to adopt Alq
3The time, all controlling its evaporation rate is 0.2nm/s; The evaporation rate of organic dyestuff is that the evaporation rate of 0.002nm/s, organic main body material is 0.2nm/s in the control luminescent layer; The evaporation rate of LiF is 0.02nm/s in the control electron injecting layer.When hole injection layer and electron injecting layer mix, metal oxide or active metal and organic main body material while evaporation in different evaporation sources, the metal oxide that mixes and the weight ratio of organic main body material are controlled between 10%～50%, and the weight ratio of the active metal of doping and organic main body material is controlled at 1%～10%; When luminescent layer mixes, organic dyestuff and organic main body material while evaporation in different evaporation sources, the weight ratio of the organic dyestuff of doping and organic main body material is controlled between 0.5%～1%.The gross thickness of first luminescence unit is controlled between 140nm～150nm.
In the evaporation first charge generation layer process, the mixed by a certain percentage organizator heterojunction of p type organic semiconducting materials and n type organic semiconducting materials, the mixed proportion that specifically can control p type organic semiconducting materials and n type organic semiconducting materials is: 4: 1,3: 1,2: 1,3: 2,4: 3,1: 1,3: 4,2: 3,1: 2,1: 3 or 1: 4 etc.Described p type organic semiconducting materials and n type organic semiconducting materials be according to the mixed proportion requirement, in different evaporation sources with different evaporation rates evaporation simultaneously.The THICKNESS CONTROL of first charge generation layer is between 25nm～35nm.
The process and evaporation first luminescence unit of evaporation second luminescence unit are similar, do not do too much explanation at this.The gross thickness of described second luminescence unit also is controlled between 140nm～150nm.
Adopt metal A l during the evaporation negative electrode, the evaporation rate of control Al is 1nm/s, and the thickness of evaporating Al is about 120nm.The mutual cross section of anode and negative electrode forms the luminous zone of device, and the area of luminous zone described in the embodiment of the invention is 16 square millimeters.
The embodiment of the invention is prepared a kind of lamination OLED according to the method described above, and described lamination OLED comprises: first luminescence unit, first charge generation layer and second luminescence unit.Wherein, described first luminescence unit comprises: the MoO of 5nm
3The C545T doped with Al q of the NPB hole transmission layer of hole injection layer, 80nm, 35nm
3The Alq of luminescent layer, 20nm
3The LiF electron injecting layer of electron transfer layer, 1nm.Described first charge generation layer comprises: the pentacene of 30nm and C
60Mixed proportion be 1: 1 bulk heterojunction structure.The second luminescence unit structure is identical with described first luminescence unit, also comprises: the MoO of 5nm
3The C545T doped with Al q of the NPB hole transmission layer of hole injection layer, 80nm, 35nm
3The Alq of luminescent layer, 20nm
3The LiF electron injecting layer of electron transfer layer, 1nm.
With reference to figure 4, Fig. 4 is the characteristic curve schematic diagram of brightness-voltage-to-current density of above-mentioned lamination OLED.As can be seen from Figure, the brightness of this lamination OLED raises with the rising of current density and voltage, and the bright voltage of lamination OLED is 4.9V, is 20.7V at voltage, and current density is 122.9mA/cm
2The time lamination OLED brightness be 44000cd/m
2With reference to figure 5, Fig. 5 is the characteristic curve schematic diagram of current efficiency-current density-power efficiency of above-mentioned lamination OLED.The maximum current efficient of described lamination OLED is 36cd/A, and maximum power efficiency is 21lm/W.With reference to figure 6, Fig. 6 is the characteristic curve schematic diagram of the luminescent spectrum of above-mentioned lamination OLED.Curve is the luminescent spectrum of described lamination OLED under the 10V driving voltage among the figure, and this lamination OLED shows the green glow feature emission of C545T, and the device chromaticity coordinates is (0.32,0.61), is good green emission.
Preparation method according to above-mentioned lamination OLED, if want to prepare the lamination OLED that comprises more than two luminescence units, luminescence unit of every increase in above-mentioned steps then, will correspondingly increase a charge generation layer, the luminescence unit of described increase and corresponding charge produce layer can be between first charge generation layer and second luminescence unit, described luminescence unit can carry out evaporation according to the formation method of first luminescence unit or second luminescence unit, and described charge generation layer can carry out evaporation according to the formation method of first charge generation layer.
Need to prove, in this article, relational terms such as first and second grades only is used for an entity or operation are made a distinction with another entity or operation, and not necessarily requires or hint and have the relation of any this reality or in proper order between these entities or the operation.And, term " comprises ", " comprising " or its any other variant are intended to contain comprising of nonexcludability, thereby make and comprise that process, method, article or the equipment of a series of key elements not only comprise those key elements, but also comprise other key elements of clearly not listing, or also be included as this process, method, article or equipment intrinsic key element.Do not having under the situation of more restrictions, the key element that limits by statement " comprising ... ", and be not precluded within process, method, article or the equipment that comprises described key element and also have other identical element.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be conspicuous concerning those skilled in the art, and defined herein General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.
Claims (10)
1. a charge generation layer is characterized in that, described charge generation layer is to mix the charge generation layer that forms by p type organic semiconductor and n type organic semiconductor.
2. charge generation layer according to claim 1 is characterized in that, described p type organic semiconductor and n type organic semi-conductor mixed proportion are 4: 1,3: 1,2: 1,3: 2,4: 3,1: 1,3: 4,2: 3,1: 2,1: 3 or 1: 4.
3. charge generation layer according to claim 1, it is characterized in that, described n type organic semi-conductor lowest unoccupied molecular orbital energy level is greater than 4.0eV, described p type organic semi-conductor highest occupied molecular orbital energy level is less than 5.5eV, and the difference of described p type organic semi-conductor highest occupied molecular orbital energy level and n type organic semi-conductor lowest unoccupied molecular orbital energy level is less than 1eV.
4. a lamination Organic Light Emitting Diode is characterized in that, comprising: at least two luminescence units, connect the charge generation layer of adjacent luminescence unit;
Wherein, described charge generation layer is to mix the charge generation layer that forms by p type organic semiconductor and n type organic semiconductor.
5. lamination Organic Light Emitting Diode according to claim 4, it is characterized in that described p type organic semiconductor and n type organic semi-conductor mixed proportion are 4: 1,3: 1,2: 1,3: 2,4: 3,1: 1,3: 4,2: 3,1: 2,1: 3 or 1: 4.
6. lamination Organic Light Emitting Diode according to claim 4, it is characterized in that, described n type organic semi-conductor lowest unoccupied molecular orbital energy level is greater than 4.0eV, described p type organic semi-conductor highest occupied molecular orbital energy level is less than 5.5eV, and the difference of described p type organic semi-conductor highest occupied molecular orbital energy level and n type organic semi-conductor lowest unoccupied molecular orbital energy level is less than 1eV.
7. lamination Organic Light Emitting Diode according to claim 4 is characterized in that, described p type organic semiconducting materials is CuPc, Phthalocyanine Zinc, 2,5-is suitable-and (4-2 phenyl)-2 thiophene, pentacene or aphthacene.
8. lamination Organic Light Emitting Diode according to claim 4 is characterized in that, described n type organic semiconducting materials is C
60, perylene Gan Huo perylene diamides.
9. the preparation method of a lamination Organic Light Emitting Diode is characterized in that, comprising:
Substrate is provided;
On described substrate, form anode;
On described anode, form at least two luminescence units and at least one charge generation layer that mixes by p type organic semiconductor and n type organic semiconductor.
10. method according to claim 9 is characterized in that, forms luminescence unit on described anode, comprising: form hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer on described anode successively.
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