CN1960024B - Method for manufacturing true color display of electroluminescence polymer - Google Patents
Method for manufacturing true color display of electroluminescence polymer Download PDFInfo
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- CN1960024B CN1960024B CN2006100947416A CN200610094741A CN1960024B CN 1960024 B CN1960024 B CN 1960024B CN 2006100947416 A CN2006100947416 A CN 2006100947416A CN 200610094741 A CN200610094741 A CN 200610094741A CN 1960024 B CN1960024 B CN 1960024B
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Abstract
The disclosed display device of polymer is capable of realizing luminescence in red, green, and blue colors from a single substrate. The structure includes two layers of luminescence layers. According to fabricating sequence, the first layer is single red luminescence polymer, and the second layer is co-fixing object of green and red luminescence polymers. Luminescence in red, green, and blue colors can be realized dependent on combination of whether two pieces of luminescence are irradiated. After whole structure of device is completed, under power is on, it emits red light from the portion with no layer being irradiated in fabricating process; it emits green light from the portion with only first layer being irradiated; it emits blue light from the portion with both layers being irradiated. Thus, fine optical positioning technique is applicable to locating tricolor so as to obtain true color display of polymer in low cost, large area and high resolution etc.
Description
Technical field
The invention belongs to organic polymer thin film electronics and application thereof (as polymer electroluminescence) field.Concretely, the present invention is in the device preparation process, by photoluminescence layer optionally, makes and realize the luminous polymer full color Display Technique of red, green, blue three looks (RGB) on single substrate.
Background technology
At present, be that the electroluminescent device of luminescent material is realized with the organic substance.Because organic processed technology is simple, and its device is from main light emission, compare with traditional display, with the organic luminescent device be the display of display unit have response speed fast, no visual angle variation, in light weight, can obtain advantages such as large tracts of land and high-resolution and production cost are low.Therefore, the organic light emission flat-panel monitor is considered to be hopeful most to replace main flow flat-panel monitor LCD (LCD) in the market and becomes the main product of flat-panel monitor industry of future generation.Organic luminescent device is divided into two kinds by luminous organic material, a kind of be with the organic molecule be luminescent layer be called micromolecule luminescent device (SMOLED) [S.A.VanSlyke and C.W.Tang, US patent #4539507], and with the polymer be luminescent layer be called polymer light-emitting device (PLED) [R.H.Friend, J.H.Burroughes and D.D.Bradley, US patent #5247190, H.Burroughes et al., Nature 347,539 (1990), G.Gustafsson et al, Nature 357,477 (1992)].No matter be micromolecule luminescent device or polymer light-emitting device, all reached the commercial needed basic standard of using at present in the efficient of monochrome devices with on the life-span.But, want to make these luminescent devices really to be used for commercial display and on market, have competitiveness, with a kind of method of simple possible make on single substrate, be easy to realize red,
Green, blue three-color light-emitting, thus and realize that full color display is vital can for the accurate precision positioning in corresponding position on substrate of these three primary colors.For the micromolecule luminescent device, owing to be deposited on the substrate and film forming by the thermal evaporation micromolecule, in evaporation during film forming crosses, can whether block by mask plate and control micromolecule having or not on substrate, thereby can control three look small molecule materials on substrate the position and realize that full color shows.Polymeric material is used in luminous demonstration aspect and has more superiority than small molecule material on processing technology, because the film forming procedure of polymer is the solution course of processing, and can be by spin coating, get rid of very simple method such as film and realize film forming.Yet, thereby be difficult in spin coating, get rid of film etc. and directly just directly realize multicolor luminous in the film forming procedure to three primary colors dot matrix location.
At present, several ways are attempted being used to realize the polychrome light polymer emitting display device.These ways comprise, unite with the white luminous light as a setting of polymer and to use have good positioning red, green, blue three-colour filter [J.Kido, M.Kimura, K.Nagai, Science 267,1332 (1995)] or energy shift with material [S.Tasch etal, Adv.Mater.9,33 (1997)], and wide emission light is the good micro-cavity structure of bias light alignment by union [A.Dodabalapur, L J.Rothberg, T.M.Miller, Elect.Lett.30,1000 (1994)], however requirement will have the white light or the broad-band illumination of high brightness like this, up till now for the white light of stability and high efficiency rate or broadband polymer light-emitting device academia still in making great efforts research, and device is lower common useful life of working under high brightness; Do base material with the light emitting polymer film besides, respectively the dyestuff of glow color in three is located by thermal diffusion or way such as contact diffusion etc. and to be diffused into [F.Pschenitzka in the polymeric substrate film, J.C.Sturm, Appl.Phys.Lett.74,1913 (1999)], and this way implementation procedure complexity also is difficult to accurately location.In addition, in recent years, industry is hankered after locating the polymer three primary colors to realize the full color polymer light-emitting device by the mode of printing always, as screen printing [J.Bimstock et al, Appl.Phys.Lett.78,3905 (2001), D.A.Pardo, G E.Jabbour, N.Peyghambarian, Adv.Mater.12,1249 (2000) .] and inkjet printing art [J.Bharathan, Y.Yang, Appl.Phys.Lett.72,2660 (1998)].Wherein, screen printing is a kind of simple and both economical method, yet this printing process can not precision positioning, thereby can not obtain high-resolution.And another kind can realize that high-resolution mode of printing is exactly an inkjet printing, yet, because polymer luminescent material is not branding fluid after all, between the various light emitting polymers and between light emitting polymer and electronics or the hole transmission layer because viscosity and affine degree varies such as cause at influence, it is very complicated to cause printing technology, the machinery equipment etc. that is used for inkjet printing like this is also very expensive, causes the production cost of device very high.
Along with photoetching technique more and more accurate and ripe in the extensive use in fields such as micromachined and photoetching technique, by illumination spin coating, to locate three-color light-emitting be the most simple and can obtain high-resolution method to get rid of the good light emitting polymer film of film forming such as film.In recent years, by the blend of photooxidation individual layer RGB luminescent dye [S.Shirai is arranged, J.Kido, J.Photopolym.Sci.Technol.14,317 (2001)] or the thin polymer film of light emitting polymer [A.Pogantsch etal, Adv.Mater.14,1722 (2002)] obtained multiple colour light emitting, but in these methods, the glow color that is obtained from single thin film is very responsive to light application time and photoenvironment, is difficult to accurately obtain to be used for full color necessary for displaying luminescent spectrum color.Recently, a kind of ratio is easier to by light-seeking and determines that more accurately the method for glow color is, but on light emitting polymer, introduce the active group of some glue connection, the place of being arrived by illumination like this, polymer is difficult to be removed by solvent etc. because of producing the glue connection, otherwise the polymer that is joined by glue just can not removed, like this, the light emitting polymer of three kinds of colors can be regardless of the illumination of passing through of order in the same way and remove unwanted part then and be positioned in [C.D.M ü lleretal on the same substrate, Nature 421,829 (2003)].In this method, must remove unwanted part in the thin polymer film with solvent very clean (stay a bit hardly, otherwise influence glow color purity).Like this, just cause that the light-seeking process is actual to become very complicated, and unavoidable in the process of a kind of polymeric material of solvent clean simultaneously the influence another kind need stay polymeric material on the substrate.
Summary of the invention
In the present invention, we have adopted a kind of method of new light-seeking to obtain polymer device rubescent, green, blue three color light, can in the course of processing, not be removed or destroy by the good polymer light-emitting film of formation such as spin coating with this way, and, for any colour light emitting all is what to determine very much, is not subjected to the environmental condition in the course of processing and the time effects of illumination substantially.
In the present invention, we have adopted double-deck polymer emitting structural.By the processing sequence in the device preparation process, wherein ground floor is as red emission layer (not by the illumination oxidation) or as hole transmission layer (after the illumination oxidation); The second layer is as green light emitting layer (not by the illumination oxidation) or as blue light-emitting layer (by the illumination oxidation).Therefore, by at the first tunic Cheng Haohou, need be with mask plate illumination and shelter from and do not allow illumination on substrate, need the part that glows in the part of green light on the substrate and blue light, again at the second tunic Cheng Haohou, on substrate, need the part of blue light-emitting and shelter from not allow the part of illumination green light with mask plate illumination.Like this, after finishing, device fabrication just can on the substrate that color has been had good positioning, obtain the red, green, blue three-colour light-emitting.Because, in this device architecture, need illumination by oxidized more favourable to illumination effect more fully of the material of photooxidation, under can be by the situation of fully photooxidation, the device effect be subjected to environmental condition and the light application time in the course of processing to influence very little.
The concrete device architecture and the course of processing are as shown in Figure 1 among the present invention, wherein to be used as the polymer of emission be the poly-to styrene support [English name poly (2-methoxy of the red polymer luminescent material band alkyl side chain used always to ground floor, 5-(2-ethylhexyloxy)-1,4-phenylene vinylene) (MEH-PPV)], the polymer that the second layer is used as emission is the poly-fluorenes [English name poly (9,9-dioctyl-fluorene) (PFO)] of band alkyl chain and the poly-blend to styrene support [English name phenyl-substituted poly (p-phenylene vinylene) derivative (P-PPV)] of band phenyl chain for blue emitting material commonly used.Complete device architecture is ITO/PEDOT:PSS/MEH-PPV/PFo:P-PPV/Ca/Ag.Carry out illumination by the needed glow color of substrate desired location with mask plate after each layer luminescent layer spin-coating film, the length of light application time is insensitive substantially to the device property influence, and 1-2 minute light application time just can usually.
Obtain red among the present invention, green, the basic principle of Lan Sanse emission is: in device architecture, when first and second layer light emitting polymer during all not by illumination, because polymer MEH-PPV and the polymer P-PPV of the second layer and the energy level difference of PFO of ground floor, make under the energising situation, electronics that is injected into and hole are difficult to cross over the interface of the ground floor and the second layer, thereby make electronics and hole accumulate in this interface and form exciton, because MEH-PPV has than P-PPV and the low exciton energy of PFO, so the compound back emission for MEH-PPV of formed exciton glows at the interface; When an illumination ground floor and during the not illumination second layer, photooxidation reaction make the two keys of C=C in its molecular structure become singly-bound owing to can take place under ultraviolet lighting MEH-PPV, thereby make the conjugated degree of polymer molecule reduce and can be with and broaden (greater than P-PPV and PFO), just can not be launched by the MEH-PPV of photooxidation like this and only as hole transmission layer, and emission layer only is the second layer, and in the second layer, owing to there is exciton
Energy shifts, and the PFO exciton energy is transferred to the lower P-PPV of exciton energy substantially, so the light of only sending out P-PPV is green glow; When ground floor and the second layer during all by illumination, the same with MEH-PPV, the two keys of the C=C of P-PPV equally can ultraviolet lighting be oxidized to singly-bound makes its molecular conjugation degree reduce, and can be with broaden (greater than PFO's), and the PFO exciton energy can't shift and the light of only sending out PFO is blue light.Like this, make electroluminescent device on the same substrate, in manufacturing process, by locating the two-layer film that includes polymer of illumination successively, make that wherein ground floor is luminescent layer or is transport layer, on whole base plate, can obtain the luminous array of three kinds of colors (containing two kinds or a kind of color).
Therefore, one aspect of the present invention can be located the position of determining on same substrate as luminescent material with polymer by the mode of light-seeking and be obtained corresponding red, green, blue three-color light-emitting.On the other hand, the polymer film forming in the course of processing of the present invention adopts simple spin coating to get rid of film method.Again on the other hand, three kinds of color effects of red, green, blue are subjected to factor affecting such as processing conditions, time little among the present invention, are easy to control.
Description of drawings
Fig. 1: the preparation process schematic diagram of the chemical constitution of polymer luminescent material and red, green, blue three look ballistic devices, numeral and symbol description among the figure:
The molecular structure of I-emitting red light polymer MEH-PPV;
The molecular structure of I I-green emitting polymer P-PPV;
The molecular structure of III-blue luminescent polymer PFO.
Numeral " one " arrives " five "-technology step successively;
The 1-glass substrate;
The 2-ITO transparent positive electrode;
3-hole mobile material PEDOT:PSS layer;
4-emitting red light polymer MEH-PPV layer;
MEH-PPV layer behind the 5-ultraviolet lighting;
The mixture PFO:P-PPV layer of 6-green and blue luminescent polymer;
PFO:P-PPV layer behind the 7-ultraviolet lighting;
8-metal negative electrode;
The 9-shading mask plate;
The 10-ultraviolet light;
The A-emitting red light;
The B-green emitting;
The C-blue-light-emitting.
Fig. 2: the light emitting polymer of the spectrum (black triangle solid line) of red, green, blue three looks emission and three kinds of colors of red, green, blue is respectively applied for and manufactures the contrast of the spectrum of monochromatic emission (hollow circular dashed line) separately, numeral and symbol description among the figure among the present invention:
A-emitting red light spectrum;
B-green emitting spectrum;
C-blue-light-emitting spectrum.
Fig. 3: the light emitting polymer of red among the present invention (circle), green (triangle), the emission of blue (prismatic) three looks (solid solid line) and red (circle), green (triangle), blue (prismatic) three kinds of colors is respectively applied for manufactures the current-voltage-brightness curve (a) of monochromatic emission (hollow dotted line) and the contrast of electric current-luminous efficiency (b) separately.
Embodiment
A: luminescent material formulations prepared from solutions: MEH-PPV and P-PPV are dissolved in the mixed solution of dimethylbenzene and oxolane by the mass volume ratio of 4/1000 (g/L); PFO is dissolved in the toluene solution by the mass volume ratio of 1/1000 (g/L).Then, P-PPV and PFO are dissolved each other by a certain percentage.
B: element manufacturing: the ito glass of conduction is earlier with drying after organic solvent and the washed with de-ionized water, spin coating last layer PEDOT:PSS after the plasma ozone treatment then, ground floor luminescent layer film forming in the spin coating again, then block the part that need glow with mask, carry out ultraviolet lighting in air, second layer luminescent layer film forming in the spin coating again after the illumination is then blocked the part that need glow and need green light with mask, in air, carry out ultraviolet lighting, metal electrode on the evaporation in the last vacuum.
Claims (3)
1. the manufacture method of electroluminescent polymer full color display device is characterized in that making electroluminescent device on same substrate, includes the electroluminescent thin polymer film of energy of two-layer spin-coating film successively in the structure of device; Processing sequencing according to film in manufacturing process is defined as the ground floor and the second layer respectively with this two-layer light emitting polymer film, wherein ground floor is that the poly-of red polymer luminescent material band alkyl side chain supportted styrene, be specially poly (2-methoxy, 5-(2-ethylhexyloxy)-1,4-phenylene vinylene) (MEH-PPV), the second layer is the poly-fluorenes of blue polymer luminescent material band alkyl chain and the poly-blend to the styrene support of green polymer luminescent material band phenyl chain, be specially poly (9, the 9-dioctyl-fluorene) blend of (PFO) and phenyl-substituted poly (p-phenylene vinylene) derivative (P-PPV); After first tunic forms, by with mask plate optionally illumination need and shelter from the part that need on substrate, glow simultaneously in the part of green light on the substrate and blue light-emitting, again after second tunic forms, by mask plate optionally illumination need be in the part of blue light-emitting on the substrate and shelter from simultaneously and need on substrate, glow and the part of green light; Then, becoming structure by the evaporated metal electrode preparation is the device of ITO/PEDOT:PSS/MEH-PPV/PFO:P-PPV/Ca/Ag, obtains the electroluminescent device of red, green, blue three-colour light-emitting on same substrate.
2. method according to claim 1 is characterized in that the used light source of illumination is a ultraviolet light.
3. method according to claim 1 is characterized in that photoenvironment is in the air.
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| CN2006100947416A CN1960024B (en) | 2006-01-23 | 2006-07-13 | Method for manufacturing true color display of electroluminescence polymer |
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| CN2006100947416A CN1960024B (en) | 2006-01-23 | 2006-07-13 | Method for manufacturing true color display of electroluminescence polymer |
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| CN105449111B (en) * | 2016-01-08 | 2018-03-20 | 京东方科技集团股份有限公司 | Light emitting diode with quantum dots substrate with binder course and preparation method thereof |
| TWI677979B (en) * | 2019-03-21 | 2019-11-21 | 友達光電股份有限公司 | Display panel and method for manufacturing the same |
| CN110571339A (en) * | 2019-08-19 | 2019-12-13 | 深圳市华星光电半导体显示技术有限公司 | Organic light emitting display device and method of fabricating the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6127693A (en) * | 1998-07-02 | 2000-10-03 | National Science Council Of Republic Of China | Light emitting diode with blue light and red light emitting polymers |
| CN1622721A (en) * | 2003-11-25 | 2005-06-01 | 三星Sdi株式会社 | Full color organic electroluminescent device |
| CN1643992A (en) * | 2002-03-15 | 2005-07-20 | 出光兴产株式会社 | Color light emitting device |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6127693A (en) * | 1998-07-02 | 2000-10-03 | National Science Council Of Republic Of China | Light emitting diode with blue light and red light emitting polymers |
| CN1643992A (en) * | 2002-03-15 | 2005-07-20 | 出光兴产株式会社 | Color light emitting device |
| CN1622721A (en) * | 2003-11-25 | 2005-06-01 | 三星Sdi株式会社 | Full color organic electroluminescent device |
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