CN100521847C - Color organic electroluminescence device with emission structure at top, and preparation method - Google Patents
Color organic electroluminescence device with emission structure at top, and preparation method Download PDFInfo
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- CN100521847C CN100521847C CNB200710055879XA CN200710055879A CN100521847C CN 100521847 C CN100521847 C CN 100521847C CN B200710055879X A CNB200710055879X A CN B200710055879XA CN 200710055879 A CN200710055879 A CN 200710055879A CN 100521847 C CN100521847 C CN 100521847C
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Abstract
The invention uses the metal Ag with high reflection rate as anode; above the anode are a hole-injection layer (such as V205), hole-transport layer (such as NPB) and luminescence layer (such as Alq3); above the luminescence layer, is a semi transparent metal cathode (such as metal Sm); a forward bias is applied on a portion between metal anode and metal cathode to realize the organic light emitting (OLE) function.
Description
Technical field
The present invention relates to a kind of Organic Light Emitting Diode (OLED) display device, particularly color organic electroluminescence device with emission structure at top and preparation method thereof.
Background technology
Organic Light Emitting Diode (OLED) device has very wide application prospect in the demonstration field, can be used for fields such as mobile phone, digital camera, computer, TV.Therefore the colorize of realizing OLED shows it is the most important target of OLED development, and it is directly determining the competitiveness of following OLED in the flat panel display field.The method that realizes the colorize demonstration of OLED has following several:
(1) red, green, blue three primary colors pixel is independent luminous
Utilize three kinds of different luminescent materials to prepare independently ruddiness, green glow and blue light emitting device respectively, realize colored the demonstration.This method complicated process of preparation.
(2) photochromic conversion
Photochromic conversion is to realize that in conjunction with the optical color conversion film array ruddiness, green glow and blue light three primary colors show with blue light OLED.At first prepare blue light OLED luminescent device, utilize blue-light excited photochromic transition material to obtain ruddiness and green glow then, thereby obtain to comprise that the colour of red, green, blue three primary colors shows.Its shortcoming is the blue light in the easy absorbing environmental of photochromic transition material, causes picture contrast to descend, and luminous efficiency is not high yet simultaneously.
(3) utilize colored filter to realize colored the demonstration
This kind technology is to utilize white light OLED to realize ruddiness, green glow and blue light three-color light-emitting in conjunction with colored filter, thereby realizes colored the demonstration.Can utilize the colored filter manufacturing technology of ripe LCD (LCD).This method can increase cost of manufacture to a certain extent, and colorized optical filtering sector-meeting simultaneously causes the light loss up to 2/3rds.
(4) utilize micro-cavity structure to realize three-color light-emitting
In microcavity type OLED device, organic luminous layer is placed between two high reflecting metal electrodes, and one of them metal electrode is translucent.Two high reflecting metal electrodes form Fabry-Perot micro chamber, and microcavity effect can change the luminescent properties of device, make the light near microcavity resonance wavelength obtain the resonance reinforcement, and the light that departs from microcavity resonance wavelength then is suppressed.So only need between two high reflection mirrors, to put into monochromatic light material, just can access ruddiness, green glow and blue light three primary colors emission light by regulating and design microcavity resonance wavelength with broad spectrum.Simultaneously microcavity effect can also reduce the width (raising colorimetric purity) of emission spectrum and improve the luminous efficiency of device, and these characteristics make the more bright-coloured exquisiteness of the color of display device, and the while luminosity is higher.
The emission structure at top organic electroluminescence device is meant that the light that luminescent device produces sends from the opposite side of substrate.To the ORGANIC ELECTROLUMINESCENCE DISPLAYS of active driving, the emission structure at top luminescent device can be integrated on the substrate and needn't consider the problem of percent opening driving with thin-film transistor, thereby can effectively improve display quality.
Summary of the invention
The invention provides color organic electroluminescence device with emission structure at top, it is a luminescent device of realizing that ruddiness, green glow and blue light three primary colors show.This device architecture is made up of emission structure at top organic electroluminescence device and the adjusted and controlled two parts of optics: it is luminous to utilize the emission structure at top organic electroluminescence device to realize, utilizes the adjusted and controlled generation ruddiness of optics, green glow and blue light three-color light-emitting.
The device architecture that the present invention adopts as shown in Figure 1, device architecture is:
1) glass substrate 1; 2) the high reflecting metal anode 2, are aluminium or silver; 3) organic layer comprises hole injection layer 3/ hole transmission layer, 4/ electric transmission and luminescent layer 5; 4) low reflection semitransparent cathode 6 is samarium, calcium, barium, ytterbium or indium tin oxide; 5) optical adjustment layer 7; 6) translucent high reflecting metal mirror 8; 7) protective layer 9;
Described high reflecting metal anode 2 and semi-transparent metals negative electrode 6 and each organic layer are between the two formed the emission structure at top organic luminescent device, add forward bias and can realize top emission electroluminescence between two electrodes; It is adjusted and controlled to be stamped the optics of being made up of optical adjustment layer 7 and translucent high reflecting metal mirror 8 and protective layer 9 on the ballistic device structure of top; can change the glow color of top emission light-emitting device by the thickness that changes optical adjustment layer 7; can realize blue light respectively; green glow and red emission, thus realize colored the demonstration.
Realization emission structure at top ruddiness of the present invention, the concrete preparation process of green glow and blue light three primary colors electroluminescent device is: the ITO that will have the square area of fine strip shape ITO electro-conductive glass middle etches away, remaining all around ITO will contact with metal electrode, to be convenient for measuring electrology characteristic and to reduce contact resistance.The sheet glass that etching is good carries out ultrasonic cleaning with chloroform and acetone solvent successively and cleaning agent cleans, and uses deionized water rinsing then, and the drying in oven of the sheet glass that cleans up being put into 120 ℃ is standby.
Preparation of devices is carried out in multi-source organic molecule depositing system.The substrate of glass 1 that etching is good is put into vacuum chamber, simultaneously with Ag, and V
2O
5, NPB, Alq
3, metal such as Sm and organic material are put in the evaporation boat in the vacuum chamber, and sealing multi-source organic molecule depositing system is when vacuum degree is 3 x 10
-4Pa. the time, according to device architecture in the accompanying drawing 1, order each organic layer of evaporation or metal level are: 2 layers is the Ag electrode, and 3 layers is V
2O
5, 4 layers is NPB, 5 layers is Alq
3, 6 layers is the Sm electrode, 7 layers is Alq
3, the 8th, Ag, 9 layers is Alq
3The thickness of each layer is monitored by film-thickness monitoring.The electricity of device and the characteristics of luminescence are respectively with Keithley2400 source table and PR650 spectrometer measurement.
Characteristics of the present invention are that introducing optics is adjusted and controlled on top radiation organic EL part, realize the electrical properties of device and the purpose that the characteristics of luminescence is regulated and control respectively, under the situation that does not influence the device electrology characteristic, by regulating the glow color that the optical adjustment layer thickness of optics in adjusted and controlled can change device, as realizing ruddiness respectively, green glow and blue light three-color light-emitting, thus realize colored the demonstration.This invention device preparation technology is simple, can not influence electric properties of devices during the glow color of trim, is a kind of colored effective way that shows of emission structure at top that realizes.
The present invention will be further described below in conjunction with drawings and Examples.
Description of drawings
Fig. 1 is a device architecture schematic diagram of the present invention.Wherein: the 1st, the substrate of glass that etching is good, the 2nd, Ag electrode, the 3rd, V
2O
5, the 4th, NPB, the 5th, Alq
3, the 6th, Sm electrode, the 7th, Alq
3, the 8th, Ag, the 9th, Alq
3This figure also is the accompanying drawing of specification digest.
Fig. 2 is the electroluminescent spectrum figure of three top emission electroluminescent devices among the embodiment 1-3.
Fig. 3 is the current density～voltage～light characteristic figure of device 1,2,3 among the embodiment 1-3.
Embodiment:
To have fine strip shape ITO electro-conductive glass middle area earlier is 400mm
2The ITO of square area etch away, remaining all around ITO is as contacting with negative electrode with anode, to be convenient for measuring electrology characteristic.Again that etching is good sheet glass carries out ultrasonic cleaning with chloroform and acetone solvent, uses cleaning agent (ZD4) to clean repeatedly again 3 times, uses washed with de-ionized water then.The drying in oven of the sheet glass that cleans up being put into 120 ℃ is standby.
Preparation of devices is carried out in multi-source organic molecule depositing system.First with Ag, V
2O
5, NPB, Alq
3, metal such as Sm and organic material are put in the evaporation boat in the vacuum chamber, bullion electrode mask plate and organic layer square mask plate are put well again, then the glass of oven dry being sunk to the bottom 1 is put on the support, send in the vaporization chamber, seal multi-source organic molecule depositing system at last, vacuumize.When vacuum degree is 3 x 10
-4Pa. the time; according to device architecture: glass substrate 1/ high reflecting metal anode, 2/ hole injection layer 3/ hole transmission layer, 4/ electric transmission and luminescent layer 5/ semi-transparent metals negative electrode 6/ optical adjustment layer 7/ translucent high reflecting metal mirror 8/ protective layer 9, order each metal of evaporation and organic layer.Each layer thickness is as follows: glass sinks to the bottom/Ag60 nanometer/V
2O
51.7 nanometer/NPB 40 nanometers/Alq
360 nanometers/Sm 40 nanometers/Alq
360 nanometers/Ag 40 nanometers/Alq
340 nanometers.Every layer thickness is monitored by film-thickness monitoring.The evaporation rate of metal anode Ag is 3～4 nm/sec, and the evaporation rate of metallic cathode Sm is 1.5～2 nm/sec, and the evaporation rate of organic layer is 0.2～0.4 nm/sec, as the Alq of optical adjustment layer and protective layer use
3Evaporation rate be 0.4～0.6 nm/sec.This device is an emission structure at top blue light emitting device.
Described optical adjustment layer 7 bed thickness are 100 nanometers.Remaining is with embodiment 1.This device is an emission structure at top green luminescence device.
Described optical adjustment layer 7 bed thickness are 140 nanometers.Remaining is with embodiment 1.This device is an emission structure at top red light-emitting device.
Fig. 2 is the spectrogram of embodiment 1-3.Device among the corresponding embodiment 1～3 of curve 1～3 difference among the figure, curve 4 is Alq
3Photic spectrum, be used for the contrast.As can be seen from the figure along with the increase of the thickness of optical adjustment layer 7, the red shift gradually of the spectrum of device, peak wavelength changes in 476 nanometers～630 nanometer range, presents blue light respectively, green glow and red emission.Device 1～3 halfwidth is respectively 52 nanometers, 41 nanometers, and 79 nanometers, except the halfwidth broad of device 3, the bandwidth of other emission spectrum obviously narrows down, and is about Alq
3Half of PL spectrum halfwidth (84 nanometer).The peak wavelength of device 1～3 is respectively 476 nanometers, 552 nanometers and 636 nanometers, good corresponding blue light, green glow and ruddiness three-color light-emitting.
Fig. 3 is the current density～voltage～light characteristic figure of luminescent device among the embodiment 1-3.As can be seen from the figure their current density～voltage characteristic is consistent substantially.This explanation does not have influence on electric properties of devices when regulating optical characteristics, that is to say can first optimised devices electrology characteristic, and then the characteristics of luminescence of optimised devices, realized the purpose of electricity and characteristics of luminescence separate regulation, thereby for realizing that OLED colorize Display Technique provides a valid approach.
Claims (6)
1. color organic electroluminescence device with emission structure at top is characterized in that, device is composed as follows: 1) glass substrate (1); 2) high reflecting metal anode (2) is aluminium or silver; 3) organic layer comprises hole injection layer (3)/hole transmission layer (4)/electric transmission and luminescent layer (5); 4) low reflection semitransparent cathode (6) is samarium, calcium, barium, ytterbium or indium tin oxide; 5) optical adjustment layer (7); 6) translucent high reflecting metal mirror (8); 7) protective layer (9); Glass substrate (1), high reflecting metal anode (2), hole injection layer (3), hole transmission layer (4), electric transmission and luminescent layer (5), semi-transparent metals negative electrode (6), optical adjustment layer (7), translucent high reflecting metal mirror (8) and protective layer (9) are connected in turn; Described high reflecting metal anode (2) and semi-transparent metals negative electrode (6) and each organic layer are between the two formed the emission structure at top organic luminescent device, add forward bias and can realize top emission electroluminescence between two electrodes; It is adjusted and controlled to be stamped the optics of being made up of optical adjustment layer (7) and translucent high reflecting metal mirror (8) and protective layer (9) on the ballistic device structure of top; can change the glow color of top ballistic device by the thickness that changes optical adjustment layer (7); thereby realization blue light; green glow and red emission constitute colored the demonstration.
2, color organic electroluminescence device with emission structure at top as claimed in claim 1; it is characterized in that described high reflecting metal anode (2) is that 60 nanometers, hole injection layer (3) are that 1.7 nanometers, hole transmission layer (4) are that 40 nanometers, electric transmission and luminescent layer (5) are that 60 nanometers, semi-transparent metals negative electrode (6) are that 40 nanometers, optical adjustment layer (7) are that 40 nanometers and protective layer (9) are 40 nanometers for 60-140 nanometer, translucent high reflecting metal mirror (8).
3, the preparation method of color organic electroluminescence device with emission structure at top as claimed in claim 2 is characterized in that, described optical adjustment layer (7) thickness is 60 nanometers, device emission blue light.
4, the preparation method of color organic electroluminescence device with emission structure at top as claimed in claim 2 is characterized in that, described optical adjustment layer (7) thickness is 100 nanometers, the device transmitting green light.
5, the preparation method of color organic electroluminescence device with emission structure at top as claimed in claim 2 is characterized in that, described optical adjustment layer (7) thickness is 140 nanometers, the device red-emitting.
6. the preparation method of color organic electroluminescence device with emission structure at top as claimed in claim 1 is characterized in that,
The ITO that will have the square area of fine strip shape ITO electro-conductive glass middle etches away, remaining all around ITO will contact with electrode, to be convenient for measuring electrology characteristic, the sheet glass that etching is good cleans with chloroform and acetone solvent excusing from death successively, carry out again cleaning with cleaning agent, use deionized water rinsing then, the drying in oven of the sheet glass that cleans up being put into 120 ℃ is standby;
Preparation of devices is carried out in multi-source organic molecule depositing system; the substrate of glass that etching is good (1) is put into vacuum chamber; with Ag; V2O5; NPB; Alq3 and Sm put in the evaporation boat in the vacuum chamber, and sealing multi-source organic molecule depositing system vacuumizes; when vacuum degree is 3x10-4 Pascal; evaporation in order: high reflecting metal anode (2) layer Ag, hole injection layer (3) V2O5, hole transmission layer (4) NPB; electric transmission and luminescent layer (5) Alq3; semitransparent cathode (6) Sm, transparent optical regulating course (7) Alq3, translucent high reflecting metal mirror (8) Ag and protective layer (9) Alq3.
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| CN100521847C true CN100521847C (en) | 2009-07-29 |
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| KR101647134B1 (en) * | 2010-03-29 | 2016-08-10 | 삼성디스플레이 주식회사 | Organic Light Emitting Device |
| KR101829890B1 (en) | 2011-12-23 | 2018-02-20 | 삼성디스플레이 주식회사 | Organic light emitting display apparatus and method of manufacturing the same |
| CN102969454A (en) * | 2012-12-06 | 2013-03-13 | 吉林大学 | High-contrast organic light-emitting device (OLED) with band-pass filter film and top-emitted green ray |
| CN103646957B (en) * | 2013-11-18 | 2015-08-19 | 上海和辉光电有限公司 | A kind of OLED display panel and the blue light filtering method for this OLED display panel |
| CN103824969B (en) * | 2014-03-10 | 2016-03-23 | 太原理工大学 | There is the organic electroluminescence device of multilayer metal compound electrode |
| CN105070845B (en) * | 2015-07-17 | 2017-12-26 | 京东方科技集团股份有限公司 | A kind of organic electroluminescence device and preparation method thereof, display device |
| CN104993064B (en) * | 2015-07-29 | 2017-08-29 | 苏州大学 | A kind of anti-short-circuit transparent OLED device and preparation method thereof |
| CN107958963A (en) * | 2017-12-14 | 2018-04-24 | 安徽熙泰智能科技有限公司 | True color OLED micro-display devices and preparation method thereof |
| JP6939727B2 (en) * | 2018-07-18 | 2021-09-22 | セイコーエプソン株式会社 | Image display module and image display device |
| CN109148505B (en) | 2018-08-23 | 2022-04-29 | 京东方科技集团股份有限公司 | Top-emitting Mircro LED display panel and manufacturing method thereof |
| CN111682051A (en) * | 2020-06-23 | 2020-09-18 | 昆明京东方显示技术有限公司 | Silicon-based organic electroluminescent display substrate, manufacturing method thereof and display panel |
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| JP2004127588A (en) * | 2002-09-30 | 2004-04-22 | Toyota Industries Corp | Light-emitting device, display, and luminaire |
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