CN1434670A - Electroluminscence multi-color displayed high-molecular film and preparation method thereof - Google Patents
Electroluminscence multi-color displayed high-molecular film and preparation method thereof Download PDFInfo
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Abstract
This invention relates to high polymer thin film of electricity-making multicolor illuminant display and its preparation method in which, the said film is composed of transparent substrate, transparent electrode, hole transmission layer, multilayer polymer film and metal electrode film laminated and the metal electrode layers coat between the first and second, the second and the third, and on the third polymer layers, all metal electrodes are not blocked by each other viewing from the direction vertical to the film. This invention realizes color polymer illuminant display by modulation and control electronics and hole carrier transmission process, utilizing the exciting energy of high-gap polymer illuminant material easy to transit to that of low-gap amont molecules.
Description
Technical field
The present invention relates to realizing the colored electroluminescent material that shows, electricity causes the macromolecule membrane of multicolor luminous demonstration in more detail.
The invention still further relates to this electricity and cause the preparation method of the macromolecule membrane of multicolor luminous demonstration.
Background technology
The luminous phenomenon that the electroluminescent device of constructing with macromolecule membrane can obtain to become clear under low voltage drive is applied to various types of flat-panel monitors gradually, as mobile phone, PDA, computer display terminal, TV, various instrument and meter demonstrations etc.Polymeric light-emitting element as showing usefulness has the incomparable advantage of many similar devices: ultra-thin, in light weight, and active illuminating, wide visual angle, high efficiency, high brightness, technology is simple, low-power consumption, cost are low, flexible screen demonstration etc.The basic structure of this macromolecule display device comprises two-layer electrode, and wherein a lateral electrode is transparent, accompanies the luminous high polymer film between two electrodes, and under electric field action, the light that macromolecule sends transmits from the transparency electrode side.Rotation applies because the technology of preparing of macromolecule membrane mainly adopts, printing, spraying, print geometric ratio and be easier to realize large-area masking technique, realizes the pixel array difficulty relatively of the different glow colors of micron-scale.Up to the present, one of main bottleneck problem of macromolecule display application is how to realize colorize, and this also is that the macromolecular LED display develops the slow slightly one of the main reasons of less mulecular luminescence display development.Realize the major technique that macromolecule colorful light-emitting display adopts at present, and the present subject matter that faces of these technology can be summarized as follows:
(1) variegates the filter method with white light emission.This method is by using colored filter (similar with the colored displaying principle of liquid crystal), the white light that macromolecule is sent filters out the light of three kinds of colors of red, green, blue (three primary colors) by filter, by controlling the brightness of inferior pixel, realize that the colour of band gray scale shows.The subject matter that this method exists is that requirement macromolecule display device can produce high brightness, high efficiency white electroluminescence, so that white light still can provide the sufficiently high red, green, blue transmitted light of brightness by filter through after the energy loss, the brightness of macromolecular LED display does not at present also reach needed level.
(2) thermal shift assay of organic/polymer material.This method be with laser scanning heating or other heating means with graphical luminous organic/polymer film by hot route of metastasis, its distillation is transferred on the substrate of appointment, form and laser scanning dot matrix or the graphical identical figure of pattern, under electric field action, energy transfer process by the substrate fertile material obtains and the identical luminescent spectrum of material luminescent chromaticity that is shifted, by changing the luminescent chromaticity of material for transfer, produce the luminous inferior pixel of red, green, blue.It is higher to carry out large tracts of land transfer techniques difficulty in this way, invests bigger.
(3) ink-jet printing process of luminous high polymer solution.The three kinds of monochromatic Polymer Solutions of red, green, blue that are mixed with certain solution concentration are respectively charged into corresponding position in the print cartridge of printer, adopt with the common similar method of inkjet technology Polymer Solution is printed on the appointment substrate, on substrate, form needed red, green, blue luminous high polymer film dot matrix, the solution that this method requires to print after drying, must form thickness evenly, the pixel dot matrix of regular shape, area unanimity.The subject matter that this method exists is that needed ink-jet printer must be special, the machinery mobile accuracy requires high, substrate surface need through special processing can form after making the Polymer Solution drip-dry dry thickness evenly, the film of regular shape, this method cost of investment height.
(4) blue-light excited transformation approach down.This method need realize the blue coloured electroluminous of high efficiency, high brightness, by blue-light excited green or the red illuminating material that emits, obtain corresponding green glow and ruddiness with this, such device architecture is that electroluminescence combines with the luminescence generated by light physical process, thereby obtain the red, green, blue three-color light-emitting, realize that coloured image shows.The subject matter of this method is to be prerequisite with acquisition high brightness, high efficiency, long-life blue light electroluminescence, the bottleneck problem that this present just Polymerr Electroluminescent Display faces.
(5) adopt the laminated device structure of transparency electrode at micromolecule light-emitting film interlayer.By driving the red, green, blue luminescent device respectively, obtain the luminous of corresponding red, green, blue look, the luminous of generation radiates from the transparency electrode side.The defective of this method is in preparation colorful light-emitting display device technology, need prepare the organic layer more than nine layers simultaneously, two-layer above transparent electrode layer, three-layer metal layer, technology are very numerous and diverse, in the device preparation process, the time that needs is long, causes cost height, rate of finished products low.
Summary of the invention
The objective of the invention is to problem at the prior art existence, provide a kind of electricity to cause the macromolecule membrane of multicolor luminous demonstration, by regulation and control electronics and holoe carrier transmission course, utilize the excitation energy of broad stopband high-molecular luminous material to carry out the luminous demonstration of intermolecular energy metastasis realization coloured polymer to the low energy gap high-molecular luminous material easily; That this film has is ultra-thin, stable, the effect and the advantage of scalable glow color.
The present invention also aims to provide this electricity to cause the preparation method of the macromolecule membrane of multicolor luminous demonstration, adopt simply, technology path cheaply, realize the making of macromolecule colorful display screen.
The macromolecule membrane device that electricity of the present invention causes multicolor luminous demonstration is stacked gradually by transparent substrates 1, transparency electrode 2, hole transmission layer 3, layer high molecule film and metal electrode film and constitutes; Between first macromolecule layer 4 and second macromolecule layer 5, between second macromolecule layer 5 and the 3rd macromolecule layer 6, and on the 3rd macromolecule layer 6, respectively be coated with metal electrode layer 7, from observing perpendicular to the film direction, all metal electrode layers do not block each other, purpose is that all light of emission are not blocked by the metal electrode layer near transparent substrates, film is by enclosure 8 sealings, as Fig. 1.
The macromolecule membrane preparation of devices method that described electricity causes multicolor luminous demonstration is to apply successively on the transparency conductive electrode substrate or macromolecule layer, first polymeric luminescence layer, the first metal layer, second polymeric luminescence layer, second metal level, the 3rd polymeric luminescence layer, the 3rd metal level are injected in the modification of plating transparency electrode or hole transport or hole; From observing perpendicular to the film direction, do not block each other between the metal electrode layer, the light that second layer macromolecule is sent is not blocked by the ground floor metal electrode layer, and the light that the 3rd floor height molecule sends is not blocked by ground floor and second layer metal electrode layer.
Described macromolecule layer material therefor composition is common volume or a non-volume system altogether of doing main chain with carbon and silicon, comprises elements such as phenyl ring and heterocycle structure and sulphur, tin, aluminium, zinc, rare earth, transition metal, heavy metal; Metal electrode layer material therefor composition is lithium metal, boron, sodium, calcium, magnesium, beryllium, barium, potassium, aluminium, gold, silver and oxide thereof or alloy.Prior art is adopted in film preparation, for macromolecule membrane, adopt as vacuum thermal evaporation, rotation diagram cover, gown film, printing, inkjet printing, spraying, plasma polymerization etc.; For metal, adopt as vacuum thermal evaporation, magnetron sputtering, electron beam evaporation etc.
The macromolecule membrane device that described electricity causes multicolor luminous demonstration preparation method more specifically comprises the steps:
(1) on the transparency conductive electrode substrate, prepares transparency electrode modification or hole transport or hole with rotation coating, printing or spraying method and inject macromolecule layer;
(2) prepare first polymeric luminescence layer with rotation coating, printing or spraying method;
(3) prepare the first metal layer with vacuum evaporation or sputtering method;
(4) prepare second polymeric luminescence layer with rotation coating, printing or spraying method;
(5) prepare second metal level with vacuum evaporation or sputtering method;
(6) prepare the 3rd polymeric luminescence layer with rotation coating, printing or spraying method;
(7) prepare the 3rd metal level with vacuum evaporation or sputtering method.
Cover macromolecule membrane and metal electrode with airtight enclosure, and obturage with airtight glue, making in the enclosure and between the external world does not have Gas Exchange.
Described first macromolecule layer can be the blue light-emitting material, second macromolecule layer can be a green luminescent material, the 3rd macromolecule layer can be the material that glows, and metal electrode all is the metals with low work function, and enclosure can be materials such as air-locked glass, metal, pottery.When first, second and third phase add negative voltage to the reference transparency electrode, can observe the blueness, green and the emitting red light that send from first, second and the 3rd macromolecule layer respectively.
We achieve success in following experiment.With poly-fluorene derivative (polyflurene) as blue light emitting material, with p-phenylene vinylene (P-PPV) as green light luminescent material, with poly (p phenylene vinylene) derivatives (MEH-PPV) as red illuminating material, all the method that adopts rotation to apply prepares macromolecule membrane, the emission spectrum that obtains is as Fig. 2.Fig. 2 illustrates that the technology path that the present invention proposes can realize polychrome or colorful light-emitting.Peak is that the luminescent spectrum of 445nm is typical blue-light-emitting, and is luminous from the feature of PF material; Peak is that the luminescent spectrum of 550nm is typical green emitting, and is luminous from the feature of P-PPV material; Peak is that the luminescent spectrum of 600nm is typical emitting red light, and is luminous from the feature of MEH-PPV material.Like this, PF, P-PPV, three kinds of materials of MEH-PPV can excite down at electric field in the laminar film structure, provide blueness, green and emitting red light respectively.Be characterized on same substrate, can realizing simultaneously that the red, green, blue look luminous.Further,, can realize various photochromicly, reach the purpose that realizes colorful light-emitting by the luminous intensity or the emittance (as changing excitation voltage or electric current or light-emitting area) of control red, green, blue each color.
Advantage of the invention and effect: with the technology and the method for large-area preparation macromolecule membranes such as rotation coating, printing, spraying, approach and the corresponding multiple layer metal electrode of introducing by preparation multilayer functional polymer film, control the different metal electrode at the same time or separately with voltage, can obtain the electroluminescence of different colours.This electroluminescent device advantage is the easy processing characteristics that makes full use of macromolecular material, realizes the characteristics of large area film easily, by the device architecture design, realizes macromolecule color electroluminescent device with simple process.This is a kind of new way that can realize red, green, blue polychrome, coloured polymer light-emitting display device.Three kinds of color high molecule electroluminescents of the red, green, blue model machine that on identical transparent substrates, obtains.
Description of drawings
Fig. 1 electricity of the present invention causes the macromolecule membrane structural representation of multicolor luminous demonstration;
Fig. 2 electricity of the present invention causes the macromolecule membrane electroluminescent spectrum of multicolor luminous demonstration.
Embodiment
The best execution mode of the present invention is to adopt the ITO transparent conducting glass as substrate, prepares PEDOT (polyaniline derivative) hole transmission layer (thickness 70nm) with the rotation painting method, and heating is 70 ℃ in vacuum drying oven, 2 hours.Select high-luminous-efficiency, and have the macromolecular material of red (poly-to this acetylene-derivative MEHPPV) of hole transport ability, green (poly-to this acetylene-derivative P-PPV) and blue (poly-fluorenes PF) glow color, molecular structural formula is as follows:
MEHPPV, P-PPV and PF are dissolved in the toluene solvant, make 0.5mol/ml respectively, the toluene solution of 1mol/ml and 2mol/ml prepares this three kinds of macromolecule homogeneous films respectively with the rotation painting method.On the PEDOT macromolecule membrane, make blueness (PF) light-emitting film (thickness 60nm), green (P-PPV) light-emitting film (thickness 50nm) and red (MEH-PPV) light-emitting film (thickness 50nm) successively, at the metal electrode (two kinds of metals of Ca-4nm/Al-200nm) of these three layers of luminous high polymer film back vacuum evaporation low work functions, this three-layer metal electrode does not block on perpendicular to the film direction each other.Finish on the film preparation basis, the enclosure made from the glass plate corrosion film of obturaging, purpose is an air-isolation, makes macromolecule not contact oxygen with metallic film material in air, and is not oxidized, prolongs the useful life of device.Under nitrogen or argon gas atmosphere, between metal electrode and ITO electrode (positive pole), apply voltage, can observe blueness, green and emitting red light simultaneously from ITO electrode side.
Claims (4)
1, a kind of electricity causes the macromolecule membrane of multicolor luminous demonstration, it is characterized in that being stacked gradually by transparent substrates, transparency electrode, hole transmission layer, layer high molecule film and metal electrode film constituting; Between first macromolecule layer and second macromolecule layer, between second macromolecule layer and the 3rd macromolecule layer, and on the 3rd macromolecule layer, respectively be coated with metal electrode layer, from observing perpendicular to the film direction, all metal electrode layers do not block each other, described macromolecule layer material therefor composition is common volume or a non-volume system altogether of doing main chain with carbon and silicon, comprises elements such as phenyl ring and heterocycle structure and sulphur, tin, aluminium, zinc, rare earth, transition metal, heavy metal; Metal electrode layer material therefor composition is lithium metal, boron, sodium, calcium, magnesium, beryllium, barium, potassium, aluminium, gold, silver and oxide thereof or alloy.
2, electricity according to claim 1 causes the macromolecule membrane of multicolor luminous demonstration, it is characterized in that described first macromolecule layer is the blue light-emitting material, second macromolecule layer is a green luminescent material, the 3rd macromolecule layer is the material that glows, metal electrode all is the metals with low work function, enclosure can be materials such as air-locked glass, metal, pottery, when first, second and third phase add negative voltage to the reference transparency electrode, can observe the blueness, green and the emitting red light that send from first, second and the 3rd macromolecule layer respectively.
3, the described electricity of claim 1 causes the preparation method of the macromolecule membrane of multicolor luminous demonstration, it is characterized in that on the transparency conductive electrode substrate applying successively or macromolecule layer, first polymeric luminescence layer, the first metal layer, second polymeric luminescence layer, second metal level, the 3rd polymeric luminescence layer, the 3rd metal level are injected in the modification of plating transparency electrode or hole transport or hole; From observing perpendicular to the film direction, do not block each other between the metal electrode layer, the light that second layer macromolecule is sent is not blocked by the ground floor metal electrode layer, and the light that the 3rd floor height molecule sends is not blocked by ground floor and second layer metal electrode layer.
4, electricity according to claim 3 causes the preparation method of the macromolecule membrane of multicolor luminous demonstration, it is characterized in that comprising the steps:
(1) on the transparency conductive electrode substrate, prepares transparency electrode modification or hole transport or hole with rotation coating, printing or spraying method and inject macromolecule layer;
(2) prepare first polymeric luminescence layer with rotation coating, printing or spraying method;
(3) prepare the first metal layer with vacuum evaporation or sputtering method;
(4) prepare second polymeric luminescence layer with rotation coating, printing or spraying method;
(5) prepare second metal level with vacuum evaporation or sputtering method;
(6) prepare the 3rd polymeric luminescence layer with rotation coating, printing or spraying method;
(7) prepare the 3rd metal level with vacuum evaporation or sputtering method;
Cover macromolecule membrane and metal electrode with airtight enclosure, and obturage with airtight glue.
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| CN 03113885 CN1210996C (en) | 2003-03-10 | 2003-03-10 | Electroluminscence multi-color displayed high-molecular film and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100466330C (en) * | 2003-09-27 | 2009-03-04 | 华南理工大学 | High-colour-purity electroluminescent device and preparing method thereof |
| CN103681484A (en) * | 2012-08-31 | 2014-03-26 | 三星显示有限公司 | Flexible display device manufacturing method and carrier substrate for manufacturing same |
| CN103956374A (en) * | 2014-04-22 | 2014-07-30 | 华南理工大学 | Maskless organic color electroluminescence displayer and manufacturing method thereof |
| CN111716843A (en) * | 2020-06-28 | 2020-09-29 | 广州市兴联达塑料制品有限公司 | 3D developing polymer film and preparation method thereof |
-
2003
- 2003-03-10 CN CN 03113885 patent/CN1210996C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100466330C (en) * | 2003-09-27 | 2009-03-04 | 华南理工大学 | High-colour-purity electroluminescent device and preparing method thereof |
| CN103681484A (en) * | 2012-08-31 | 2014-03-26 | 三星显示有限公司 | Flexible display device manufacturing method and carrier substrate for manufacturing same |
| CN103956374A (en) * | 2014-04-22 | 2014-07-30 | 华南理工大学 | Maskless organic color electroluminescence displayer and manufacturing method thereof |
| CN103956374B (en) * | 2014-04-22 | 2017-01-18 | 华南理工大学 | Maskless organic color electroluminescence displayer and manufacturing method thereof |
| CN111716843A (en) * | 2020-06-28 | 2020-09-29 | 广州市兴联达塑料制品有限公司 | 3D developing polymer film and preparation method thereof |
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| CN1210996C (en) | 2005-07-13 |
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