CN104934545A - Organic light-emitting diode device and preparing method thereof - Google Patents
Organic light-emitting diode device and preparing method thereof Download PDFInfo
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Abstract
The invention provides an organic light-emitting diode device. The organic light-emitting diode device comprises a substrate and a transparent conductive film arranged on the inner side surface of the substrate. The organic light-emitting diode device further comprises a microstructure array and a conductive light extraction grid structure made by a conductive polymer. The microstructure array is printed on the outer side surface of the substrate in an inkjet manner. The conductive light extraction grid structure is printed on the surface, far away from the substrate, of the transparent conductive film in an inkjet manner. According to the invention, the conductive light extraction grid structure and the microstructure array are rapidly prepared by means of aerosol inkjet and piezoelectric inkjet printing, and the light extraction efficiency is effectively increased. The invention further provides a preparing method of the organic light-emitting diode device.
Description
Technical field
The present invention relates to organic light emitting diode device technical field, particularly relate to a kind of utilize that inkjet printing is prepared fast, have conductive light extract lattice structure and micro structure array structure, can effective organic light emitting diode device increasing light extraction efficiency and preparation method thereof.
Background technology
Along with the energy is day by day in short supply, the white-light illuminating technology of exploitation energy-conserving and environment-protective has important economy and social effect, Organic Light Emitting Diode (Organic Light-Emitting Diode, OLED) as a kind of novel solid luminescence technology, having the advantages such as luminous efficiency is high, operating voltage is low, frivolous, is a kind of energy-conservation illuminated by surface light source technology.
Existing OLED internal quantum efficiency is close to 100%, but because OLED inside exists total reflection, external quantum efficiency is also relatively low, and thus destroy OLED inner full-reflection condition, OLED is energy-efficient just seems extremely important to realizing to increase its optical coupling delivery efficiency.
The solution of current increase oled light coupling efficiency is substantially: for organic layer/ITO(nesa coating), ITO/ glass and this interface, three places of glass/air, prepare light extraction micro structures, destroy total reflection, increase OLED optical coupling and export.But, the preparation method of existing micro-structural is as photoetching, electron beam lithography etc., complex process, condition are harsh, cost is higher, and large area when preparing periodic structure homogeneity poor, more difficult and flexible OLED is compatible, can not meet the requirement with tremendous development that widely uses of high efficiency illumination OLED.And do not use micro-structural to increase light extraction, although the solution increasing OLED optical coupling delivery efficiency by effective optical microcavity structure design is effective, but the spherical wave attribute of light can be changed, thus affect the chromatic rendition index of OLED illumination, therefore can not meet the performance requirement of OLED white-light illuminating.
In addition; the light implanted in OLED inside extracts the organic or inorganic periodic structure that micro-nano lattice structure mostly is insulation; the insulating properties of this micro-nano lattice structure can cause the local period of OLED inside to insulate usually; thus affect the injection of charge carrier and the formation of transmission and exciton and luminescence, and then can the electric property of reduction OLED to a certain degree.
Summary of the invention
For the problems referred to above, in order to solve white light OLED device light extraction micro structures complicated process of preparation in prior art, problem that cost is higher, and the local period Insulation Problems that the insulation micro-nano lattice structure of OLED inside is brought, object of the present invention aim to provide a kind of utilize that inkjet printing is prepared fast, have conductive light extract lattice structure and micro structure array structure, can effective organic light emitting diode device increasing light extraction efficiency and preparation method thereof.
A kind of organic light emitting diode device, it nesa coating of inner surface comprising substrate and be arranged at described substrate, the conductive light also comprising micro structure array and be made up of conducting polymer extracts lattice structure, described micro structure array inkjet printing is in the outer surface of described substrate, and described conductive light extracts lattice structure inkjet printing in the surface of described nesa coating away from described substrate.
In a preferred embodiment of the present invention, described micro structure array prints on the outer surface of described substrate by piezoelectric ink jet, and described conductive light is extracted lattice structure and printed on the surface of described nesa coating away from described substrate by aerosol ink-jet.
In a preferred embodiment of the present invention, described micro structure array is PMMA microprism array, comprises multiple diameter and is 30 ~ 50um, is highly the hemispherical microprism of 50 ~ 500nm; Described conducting polymer is the PEDOT:PSS conducting solution doped with the Au nano particle of diameter between 15 ~ 30nm.
In a preferred embodiment of the present invention, the volume ratio of described PEDOT:PSS conducting solution is PEDOT:PSS conducting solution: alcohol: glycerine=15:1:3, and the mass concentration of described Au nano particle is 10% ~ 20%.
In a preferred embodiment of the present invention, described conductive light extracts the cycle of lattice structure between 50 ~ 250um.
In a preferred embodiment of the present invention, also comprise and extract lattice structure with described conductive light and stack gradually in described nesa coating away from hole transmission layer, electron transfer layer and the luminescent layer on the surface of described substrate, electron injecting layer and negative electrode, the material of making of described hole transmission layer is NPB, and the material of making of described electron transfer layer and luminescent layer is Alq
3, the material of making of described electron injecting layer is LiF, and the material of making of described negative electrode is Al.
The present invention provides a kind of preparation method of organic light emitting diode device in addition, and it comprises the steps:
S101, on the inner surface of substrate, prepare nesa coating, etching OLED required form also cleans;
S103, the conductive light that inkjet printing is made up of conducting polymer on described nesa coating extract lattice structure;
S105, outer surface inkjet printing micro structure array structure at described substrate.
In a preferred embodiment of the present invention, step S103 carries out in ultra-clean chamber, adopt the quick preparation technology of aerosol inkjet printing, and use doped with the PEDOT:PSS conducting solution of metal nano scattering particles as ink, the volume ratio of described ink set is PEDOT:PSS conducting solution: alcohol: glycerine=15:1:3, and in described ink containing mass concentration 10% ~ 20% Au nano particle.
In a preferred embodiment of the present invention, step S105 carries out in ultra-clean chamber, and adopt piezoelectric ink jet to print quick preparation technology, and use PMMA as ink, the mass ratio of described ink set is PMMA: ethyl acetate: terpinol=1:50:10.
In a preferred embodiment of the present invention, after step S105, comprise further:
S107, to extract in lattice structure in described conductive light, prepare deposition of hole transport layer, electron transfer layer and luminescent layer and electron injecting layer successively;
S109, on described electron injecting layer, prepare negative electrode.
In a preferred embodiment of the present invention, step S107 and step S109 all carries out in high vacuum environment, in step S107, the heat sink area method of polynary high vacuum is taked to extract in lattice structure deposition of hole transport layer, electron transfer layer and luminescent layer and electron injecting layer successively in described conductive light, in step S109, take mask method deposition cathode on described electron injecting layer.
Apply technical scheme of the present invention, its beneficial effect is embodied in:
The optical coupling that the present invention is directed to micro-structural increase OLED exports has made improvement, especially have employed the technique that inkjet printing prepares micro-structural fast, extract lattice structure (PEDOT:PSS conductive grid structure) in nesa coating (ito anode) upper preparation conductive light and extract in lattice structure in conductive light and add metal nano scattering particles, and print micro structure array (PMMA microprism array) at substrate outer surface, make OLED when without the need to mask, without the need to photoetching, obtain fast the micro-structural increasing oled light and extract.
In described organic light emitting diode device, conductive light is extracted lattice structure and is avoided in prior art the micro-nano structure that insulate in the inner periodicity minor insulation problem brought of OLED, and facilitate the injection of charge carrier, the maximum current efficiency of OLED can be significantly improved (opposing insulation micro-nano structure).Simultaneously, extract in lattice structure the metal nano scattering particles that mix by scattering total reflection light in conductive light and change its direction of propagation, the light that can strengthen further in OLED optical waveguide mode extracts, and the surface plasma body resonant vibration of metal nano scattering particles self changes the internal electric field distribution of device, greatly facilitates the injection of charge carrier.
Above-mentioned explanation is only the general introduction of technical solution of the present invention, in order to technological means of the present invention can be better understood, and can be implemented according to the content of specification, and can become apparent to allow above and other objects of the present invention, feature and advantage, below especially exemplified by embodiment, and coordinate accompanying drawing, be described in detail as follows.
Accompanying drawing explanation
The schematic diagram of the organic light emitting diode device that Fig. 1 provides for first embodiment of the invention;
The flow chart of the preparation method of the organic light emitting diode device that Fig. 2 provides for second embodiment of the invention;
Fig. 3 is the schematic diagram of micro structure array in organic light emitting diode device shown in Fig. 1;
Fig. 4 is the schematic diagram of conductive light extraction lattice structure in organic light emitting diode device shown in Fig. 1;
Fig. 5 is that the conductive light of different cycles extracts lattice structure to the influence curve figure of organic light emitting diode device luminous efficiency;
Fig. 6 is that the conductive light of different cycles extracts lattice structure to the influence curve figure of organic light emitting diode device current efficiency;
Fig. 7 is the influence curve figure of different grid to organic light emitting diode device current efficiency;
Fig. 8 is the influence curve figure of different grid to organic light emitting diode device luminous efficiency.
Embodiment
Below in conjunction with drawings and the specific embodiments, the present invention is further detailed explanation.
Refer to Fig. 1, the invention provides a kind of organic light emitting diode device 10, it comprises substrate 100, nesa coating 200, micro structure array 300 and conductive light extract lattice structure 400, described substrate 100 has relative inner surface 101 and outer surface 103, described nesa coating 200 is arranged at the inner surface 101 of described substrate 100, described micro structure array 300 inkjet printing is in the outer surface 103 of described substrate 100, described conductive light is extracted lattice structure 400 and is made up of conducting polymer, described conductive light extracts lattice structure 400 inkjet printing in the surface of described nesa coating 200 away from described substrate.
In the present embodiment, described substrate 100 is preferably clear glass, is understandable that, described substrate 100 is not limited to the present embodiment, also can adopt other backing materials.
In the present embodiment, described nesa coating 200 is ito film, and its sheet resistance is 10 Europe/.Be understandable that, namely described nesa coating 200 forms the anode of described light-emitting diode tube device 10.
In the present embodiment, described micro structure array 300 is PMMA(polymethyl methacrylate) microprism array, comprise multiple diameter and be 30 ~ 50um, be highly the hemispherical microprism 301 of 50 ~ 500nm; Described micro structure array 300 prints on the outer surface 103 of described substrate 100 by piezoelectric ink jet.
In the present embodiment, the material of making that described conductive light extracts lattice structure 400 is containing metal nano scattering particles 401PEDOT:PSS.Preferably, described conductive light extracts the material of making of lattice structure 400 is PEDOT:PSS conducting solution doped with the Au nano particle of diameter between 15 ~ 30nm; Described conductive light is extracted lattice structure 400 and is printed on the surface of described nesa coating 200 away from described substrate 100 by aerosol ink-jet.Particularly, the volume ratio of described PEDOT:PSS conducting solution is PEDOT:PSS conducting solution: alcohol: glycerine=15:1:3, and the mass concentration of described Au nano particle is 10% ~ 20%.In the present embodiment, PEDOT:PSS model is 4083, certainly, is not limited thereto, and other models are also passable.
Preferably, described conductive light extracts the cycle of lattice structure 400 between 50 ~ 250um.
Be understandable that, the optical coupling of described organic light emitting diode device 10 extract depend on micro structure array 300 and containing metal nano scattering particles 401, by conductive PEDOT: the conductive light that PSS is prepared from extracts lattice structure 400.In the present embodiment, described micro structure array 300 adopts piezoelectric ink jet to print quick preparation technology and obtains, its diameter is 30-50 μm, highly be 50 ~ 150nm, refractive index is 1 ~ 1.6, described micro structure array 300 can increase light extraction effectively.Described conductive light is extracted lattice structure 400 and is adopted the quick preparation technology of aerosol inkjet printing to obtain, its live width 30 μm, the high 50 ~ 150nm of line, refractive index is 1 ~ 1.6, described conductive light is extracted in lattice structure 400, the conductivity of PEDOT:PSS conducting solution make described micro structure array can structure well with described organic light emitting diode device 10 inside compatible, and the described conductive light grid cycle of extracting lattice structure 400 greatly can increase the coupling output of the light of waveguiding effect in described organic light emitting diode device 10.
Further, described organic light emitting diode device 10 also comprises and extracts lattice structure 400 with described conductive light and stack gradually in described nesa coating 200 away from hole transmission layer 500, electron transfer layer and luminescent layer 600, electron injecting layer 700 and the negative electrode 800 on the surface of described substrate 100.In the present embodiment, the material of making of described hole transmission layer 500 is NPB(N, N '-diphenyl-N, N '-bis (1-naphthyl)-(1,1 '-biphenyl)-4,4 '-diamine), its thickness is 60nm; The material of making of described electron transfer layer and luminescent layer 600 is Alq
3, thickness is 60nm; The material of making of described electron injecting layer 700 is LiF, and thickness is 1nm; The material of making of described negative electrode 800 is Al, and thickness is 200nm.
Be understandable that, in described organic light emitting diode device 10, described micro structure array 300, described substrate 100, described nesa coating 200, described conductive light extract lattice structure 400, described hole transmission layer 500, described electron transfer layer and luminescent layer 600, described electron injecting layer 700 and described negative electrode 800 stacked formation layer structure successively from top to bottom.
Refer to Fig. 2, second embodiment of the invention provides the preparation method of described organic light emitting diode device 10, and it comprises the steps:
S101, on the inner surface of substrate 100, prepare nesa coating 200, etching OLED required form also cleans.
S103, the conductive light that inkjet printing is made up of conducting polymer on described nesa coating 200 extract lattice structure 400.
In the present embodiment, described conductive light is extracted being prepared in ultra-clean chamber of lattice structure 400 and is carried out, and adopts the quick preparation technology of aerosol inkjet printing, and uses PEDOT:PSS conducting solution doped with metal nano scattering particles 401 as ink.
Preferably, the volume ratio of described ink set is 4083PEDOT:PSS conducting solution: alcohol: glycerine=15:1:3, and in described ink containing mass concentration 10% ~ 20% Au nano particle.
S105, outer surface inkjet printing micro structure array structure 300 at described substrate 100.
In the present embodiment, being prepared in ultra-clean chamber of described micro structure array 300 is carried out, and adopt piezoelectric ink jet to print quick preparation technology, and use PMMA as ink, the mass ratio of described ink set is PMMA: ethyl acetate: terpinol=1:50:10.
Be understandable that, the order of step S103 and step S105 can be changed, and is not limited to the present embodiment.
S107, to extract in lattice structure 400 in described conductive light, prepare deposition of hole transport layer 500, electron transfer layer and luminescent layer 600 and electron injecting layer 700 successively.
In the present embodiment, this step is carried out in high vacuum (about 5 × 10-4 handkerchief) environment, and, take the heat sink area method of polynary high vacuum to extract in lattice structure 400 in described conductive light, deposition of hole transport layer 500, electron transfer layer and luminescent layer 600 and electron injecting layer 700 successively.
S109, on described electron injecting layer 700, prepare negative electrode 800.
In the present embodiment, this step is carried out in high vacuum (about 5 × 10-4 handkerchief) environment, and, take mask method deposition cathode 800 on described electron injecting layer 700.
In the present embodiment, in the preparation process of described organic light emitting diode device 10, prepare vacuum chamber used and be in air-tight state always, thickness, the deposition rate of all functions layer material of described organic light emitting diode device 10 are monitored by film thickness gauge, and by regulating hot-fluid power supply to realize.
Refer to Fig. 3 and Fig. 4, be respectively the micro structure array 300 and conductive light extraction lattice structure 400 that are obtained by the preparation method of described organic light emitting diode device 10.Wherein, the diameter of micro structure array 300 shown in Fig. 3 is 50 μm, is highly 120nm.Conductive light shown in Fig. 4 extracts that the line thickness of lattice structure 400 is 30 μm, the cycle is 100 μm, highly be 120nm.
Experiment shows, adopts micro structure array 300 shown in Fig. 3, and the current efficiency of described organic light emitting diode device 10 improves 1.27 times, power efficiency improves 1.23 times; Adopt conductive light shown in Fig. 4 to extract lattice structure 400, the current efficiency of described organic light emitting diode device 10 improves 1.93 times, power efficiency improves 1.27 times; Extract the acting in conjunction of lattice structure 400 in conductive light shown in micro structure array 300 shown in Fig. 3 and Fig. 4 under, the current efficiency of described organic light emitting diode device 10 improves 2.3 times, power efficiency improves 1.5 times, and do not affect luminescent spectrum, known, there is consequence in organic light emitting diode device 10 provided by the invention and preparation method thereof office in OLED white-light illuminating and large area preparation.
Below, the present invention will further illustrate principle and the effect of described organic light emitting diode device 10 and preparation method thereof by experiment.
Experiment 1:
Substrate 100 is glass, nesa coating 200 is the anode ito film of 10 Europe/, after cleaning substrate 100 and nesa coating 200, under the operating condition of clean room, aerosol inkjet printing is adopted to prepare microstructure technology fast, nesa coating 200 is prepared conductive light and extracts lattice structure 400, afterwards in atmosphere with the temperature of 120 DEG C baking 10min; Then send in high vacuum (5 × 10-4 handkerchief) environment, adopt polynary high vacuum heat deposition system, extract in lattice structure 400 in conductive light, deposition of hole transport layer 500(NPB thickness is 60nm successively), electron transfer layer and luminescent layer 600(Alq
3thickness is 60nm), then deposit electron injecting layer 700(thin layer LiF, thickness is 1nm); Last mask deposition negative electrode 800(metallic cathode Al, thickness is 200nm).
The cycle of lattice structure 400 is extracted in order to find optimum conductive light, this experiment have employed PEDOT:PSS layer, 50 μm, 100 μm, 150 μm, 200 μm and 250 μm of six kinds of structures respectively, and contrast with the OLED not having conductive light to extract lattice structure 400, as shown in Figure 5 and Figure 6.
Result shows: conductive light is extracted lattice structure 400 pairs of OLED and really be there is effective light extraction effect, wherein, the cycle conductive light of 50 μm extracts the best results of lattice structure 400, and the current efficiency of its corresponding OLED improves 1.56 times, power efficiency improves 1.61 times.The cycle conductive light of 100 μm extracts the performance that lattice structure 400 also can significantly improve OLED, and its current efficiency and power efficiency improve 1.38 times and 1.55 times respectively.
Experiment 2:
On the basis of experiment 1, the design of this experiment amendment part Experiment, relatively conductive light extraction lattice structure, the conductive light extraction lattice structure of mixing nano Au particle and PMMA grid are to the performance impact of OLED, and other preparation conditions are all identical with experiment 1, as shown in Figure 7 and Figure 8.
Result shows: add the conductive light after nano Au particle and extract lattice structure to the performance raising of OLED at most, and the performance of nonconducting PMMA grid to OLED does not have beneficial effect.
The above, only embodiments of the invention, not any pro forma restriction is done to the present invention, although the present invention discloses as above with embodiment, but and be not used to limit the present invention, any those skilled in the art, do not departing within the scope of technical solution of the present invention, make a little change when the technology contents of above-mentioned announcement can be utilized or be modified to the Equivalent embodiments of equivalent variations, in every case be do not depart from technical solution of the present invention content, according to any simple modification that technical spirit of the present invention is done above embodiment, equivalent variations and modification, all still belong in the scope of technical solution of the present invention.
Claims (11)
1. an organic light emitting diode device, it nesa coating of inner surface comprising substrate and be arranged at described substrate, it is characterized in that, the conductive light also comprising micro structure array and be made up of conducting polymer extracts lattice structure, described micro structure array inkjet printing is in the outer surface of described substrate, and described conductive light extracts lattice structure inkjet printing in the surface of described nesa coating away from described substrate.
2. LED device as claimed in claim 1, it is characterized in that, described micro structure array prints on the outer surface of described substrate by piezoelectric ink jet, and described conductive light is extracted lattice structure and printed on the surface of described nesa coating away from described substrate by aerosol ink-jet.
3. LED device as claimed in claim 1, it is characterized in that, described micro structure array is PMMA microprism array, comprises multiple diameter and is 30 ~ 50um, is highly the hemispherical microprism of 50 ~ 500nm; Described conducting polymer is the PEDOT:PSS conducting solution doped with the Au nano particle of diameter between 15 ~ 30nm.
4. LED device as claimed in claim 3, it is characterized in that, the volume ratio of described PEDOT:PSS conducting solution is PEDOT:PSS conducting solution: alcohol: glycerine=15:1:3, and the mass concentration of described Au nano particle is 10% ~ 20%.
5. LED device as claimed in claim 1, is characterized in that, described conductive light extracts the cycle of lattice structure between 50 ~ 250um.
6. the LED device as described in any one of Claims 1 to 5, it is characterized in that, also comprise and extract lattice structure with described conductive light and stack gradually in described nesa coating away from hole transmission layer, electron transfer layer and the luminescent layer on the surface of described substrate, electron injecting layer and negative electrode, the material of making of described hole transmission layer is NPB, and the material of making of described electron transfer layer and luminescent layer is Alq
3, the material of making of described electron injecting layer is LiF, and the material of making of described negative electrode is Al.
7. a preparation method for organic light emitting diode device, is characterized in that, comprises the steps:
S101, on the inner surface of substrate, prepare nesa coating, etching OLED required form also cleans;
S103, the conductive light that inkjet printing is made up of conducting polymer on described nesa coating extract lattice structure;
S105, outer surface inkjet printing micro structure array structure at described substrate.
8. the preparation method of organic light emitting diode device as claimed in claim 7, it is characterized in that, step S103 carries out in ultra-clean chamber, adopt the quick preparation technology of aerosol inkjet printing, and use doped with the PEDOT:PSS conducting solution of metal nano scattering particles as ink, the volume ratio of described ink set is PEDOT:PSS conducting solution: alcohol: glycerine=15:1:3, and in described ink containing mass concentration 10% ~ 20% Au nano particle.
9. the preparation method of organic light emitting diode device as claimed in claim 7, it is characterized in that, step S105 carries out in ultra-clean chamber, piezoelectric ink jet is adopted to print quick preparation technology, and using PMMA as ink, the mass ratio of described ink set is PMMA: ethyl acetate: terpinol=1:50:10.
10. the preparation method of the organic light emitting diode device as described in any one of claim 7 ~ 9, is characterized in that, after step S105, comprises further:
S107, to extract in lattice structure in described conductive light, prepare deposition of hole transport layer, electron transfer layer and luminescent layer and electron injecting layer successively;
S109, on described electron injecting layer, prepare negative electrode.
The preparation method of 11. organic light emitting diode devices as claimed in claim 10, it is characterized in that, step S107 and step S109 all carries out in high vacuum environment, in step S107, the heat sink area method of polynary high vacuum is taked to extract in lattice structure deposition of hole transport layer, electron transfer layer and luminescent layer and electron injecting layer successively in described conductive light, in step S109, take mask method deposition cathode on described electron injecting layer.
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Application publication date: 20150923 |
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