CN101694868B - Organic light-emitting device and manufacture method of light extraction structure thereof - Google Patents
Organic light-emitting device and manufacture method of light extraction structure thereof Download PDFInfo
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Abstract
The invention provides an organic light-emitting device which comprises a base plate, a transparent anode positioned on the base plate, an organic cavity transport layer positioned on the transparent anode, a light-emitting layer and an electronic transport layer which are positioned on the organic cavity transport layer, and a cathode, wherein a light extraction structure capable of eliminating total reflection of an interface of the base plate and the air is formed on the surface of the base plate backing on to the transparent anode. The invention also provides a manufacture method of the light extraction structure of the organic light-emitting device. In the invention, the light extraction structure is formed on the base plate and can eliminate the total reflection of the interface of the base plate and the air to further improve the light extraction rate; and the base plate adopts material with high refractive index and high thermal conductivity, and therefore the organic light-emitting device has good heat dissipation performance, and can eliminate the total reflection between the base plate and the transparent anode, and improve the light extraction efficiency and the life of OLED simultaneously.
Description
[technical field]
The present invention relates to photoelectron technology, especially a kind of manufacture method with organic luminescent device and light extraction structure thereof of high light extraction efficiency.
[background technology]
From the initiative work of C.W.Tang, organic luminescent device (OLED) all is greatly improved in brightness, efficient, aspect stable, more than the efficient of green glow can reach 100lm/W, white light efficient has also reached tens lm/W, OLED display based on glass substrate is practical, also is proven based on display and the light source of flexible base, board.Along with the further raising of performance, OLED has possessed to the possibility of power device development.
High strength OLED power device requires OLED to have higher efficient, has higher brightness, can bear higher current density, has the longer life-span.Such as the oled light source, different with application can require at several thousand cd/m
2Under above brightness, reach the life-span more than several ten thousand hours; The Organic Electricity pump laser requires the OLED working current density to reach the even thousands of A/cm of hundreds of
2Because high strength OLED device simultaneously also means high power consumption, and most energy will be converted into heat energy, so high brightness, high current density will cause a series of thermal effect, make the OLED Efficiency Decreasing, and the lost of life is even burnt.Kim studies show that, the thermal conductivity that the self-heating of OLED and glass substrate are low is the main cause that the OLED blackspot forms.Even the OLED display, along with display area increases, resolution improves, and reasonable in design heat management mechanism will improve the life-span of display greatly.
Therefore, realize high strength OLED power device, the luminous efficiency that improves OLED is core, reduces the thermal effect of OLED, and the heat management of strengthening OLED is necessary guarantee.In high strength OLED power device field, due to low conductive coefficient, glass and flexible base, board will face the test of severe thermal effect aspect.
The organic light-emitting device luminous efficiency can represent with quantum efficiency, and quantum efficiency is divided into again internal quantum efficiency and external quantum efficiency.The luminescence mechanism of OLED device is hole and electronics recombination luminescence in luminescent layer, and electric energy directly is converted to luminous energy.The ratio of the sum that internal quantum efficiency refers to all photons of producing in device and injected electrons hole logarithm, external quantum efficiency refer to the ratio of the quantity that device emits on some directions number of photons and injected electrons hole are right.Internal quantum efficiency reflection be that charge carrier forms exciton at device inside, and the efficient of recombination luminescence, elaboration be the internal physical mechanism of device; And external quantum efficiency has reflected the luminous efficiency that device is external.Not all photon can become the outer output light of device, and the luminous flux that can become outer output light is defined as the light extraction efficiency here with the ratio of the inner total light flux of OLED.External quantum efficiency depends on internal quantum efficiency and light extraction efficiency.
Typical case OLED device architecture is: glass substrate/tin indium oxide (ITO) anode/TPD hole transmission layer/Alq
3Luminescent layer/electron transfer layer/metallic cathode, each layer refractive index is respectively n
Alq3=1.7, n
TPD=1.76, n
ITO=1.8, n
Glass=1.5.The light part that electronics and hole-recombination produce becomes emergent light by each interface, and the loss of luminous energy is determined by each interface transmissivity; A part will be led away by waveguiding effect, and then be absorbed, and perhaps pass to substrate side surfaces, and this part light loss is determined by the angle of total reflection at interface.After ignoring the reflection loss of absorption loss water and metal level, the OLED structure of simplification as shown in Figure 1 because n
Alq3≈ n
TPD≈ n
ITOSo need only consider ITO/ glass interface (being the interface between glass substrate 1 and ito anode 2 in Fig. 1), glass/air interface (being the interface between glass substrate 1 and extraneous air in Fig. 1) reflection loss of luminous energy and the loss that the fiber waveguide effect is brought, the interface between glass substrate 1 and extraneous air (being the lower surface of glass substrate 1 in Fig. 1) is be exactly total the light extraction efficiency of the light extraction efficiency OLED that locates.
Tsutusi adds the silicon gel of skim low-refraction between ITO (transparent anode) and glass, suppressed the total reflection of ITO/ glass interface, and the light extraction efficiency has improved 80%.But thin silicon gel manufacture difficulty is large, and the OLED performance is affected by it, and practical value is little.Gu etc. form the titanium dioxide mesa structure of high index of refraction between ITO and glass substrate, the light extraction efficiency has improved 1 times, and light strengthens successful, but must fill and lead up mesa structure owing to making negative electrode, and technology difficulty is quite large.
Tradition oled light extraction efficiency is still lower, and lacks the total reflection light that effective method extracts the ITO/ glass interface.According to geometric optical theory and Fig. 1 as can be known: for the isotropic typical oled light source with 100% interior luminous efficiency, 48% light is arranged from the outgoing at the interface between glass substrate 1 and ito anode 2, between glass substrate 1 and extraneous air at the interface, only have 18% light to become outer output light, the internal quantum efficiency of OLED device is more than 5 times of external quantum efficiency.The light loss of OLED is mainly that the total reflection due to ITO/ glass, glass/air two interfaces causes, and is because the refractive index ratio organic layer of glass substrate is low in the total reflection of ITO/ glass interface.
[summary of the invention]
Technical problem to be solved by this invention is to provide a kind of organic luminescent device with high light extraction efficiency.
For solving the problems of the technologies described above, the invention provides a kind of organic luminescent device, comprise substrate, be positioned at transparent anode on substrate, be positioned at organic cavity transmission layer on transparent anode, be positioned at luminescent layer on organic cavity transmission layer and electron transfer layer, negative electrode; Be formed with the light extraction structure of the total reflection that can eliminate substrate-air interface on the surface of the transparent anode dorsad of substrate.
Organic luminescent device of the present invention has changed the light that sends from OLED in the incidence angle of substrate/air interface by the light extraction structure of the total reflection that can eliminate substrate-air interface being set, making on the surface of the transparent anode dorsad of substrate.Make a large amount of original incidence angles can perhaps by the Multi reflection of facet and negative electrode reflecting surface, again become outer emergent light from the facet outgoing greater than the light of the angle of total reflection, thereby make the most of utilizing emitted light of OLED become outer emergent light.Light extraction structure for by substrate surface being carried out the miniature carving face structure that etching processing obtains, can be regular shape (such as cylinder, cone and frustoconical sheets etc.), can be also irregularly shaped, can be random distribution can be also regularly arranged; The cell size scope of these miniature carving face structures is between 1 μ m-20 μ m.
On this basis, further:
Substrate adopts yttrium-aluminium-garnet, crystal class spinelle, polycrystalline spinel-like or aluminium nitride.Adopt the substrate of these materials to have high index of refraction and high heat conductance, substrate can serve as good heat abstractor in the OLED course of work, avoids the impact that OLED is heated and decays, damages; The high index of refraction of substrate can be eliminated the total reflection between substrate and transparent anode, thereby makes total reflection only may occur in interface between substrate and air.
The refractive index of substrate is greater than 1.5, and preferred substrate refractive index is 1.7-2.0.
When light extraction structure was regular shape, the shape of light extraction structure can be selected cylinder, reverse taper or truncation reverse taper.
Another technical problem to be solved by this invention is to provide a kind of manufacture method with organic light-emitting device light extraction structure of high light extraction efficiency.
For solving this technical problem, the invention provides the manufacture method of the light extraction structure in a kind of organic luminescent device, comprise the steps:
A. adopt magnetron sputtering or plasma chemical vapor deposition (PECVD) to make silicon dioxide or silicon nitride masking layer on substrate surface, adopt the method for photoetching to form pattern on the masking layer of substrate one side surface, surperficial crested, the remainder that masking layer is retained the below of part that be positioned at of substrate exposes;
B. 85% phosphoric acid is heated to 150-170 ℃ of dehydration 10 minutes, then mixes in the ratio of 3: 1 with 98% sulfuric acid, slowly be warmed up to 190-300 ℃, obtain etching liquid;
C. substrate is put into the etching liquid that step b obtains and carried out etching, take out substrate after etching and lower the temperature in cold sulfuric acid, then use the deionized water rinsing substrate, remove masking layer with hydrofluoric acid.
In the inventive method, step a and step b both can carry out simultaneously, also can divide and successively carry out.
As preferably, step c is: basal plate preheating to 100-150 ℃, is then put into etching liquid and carried out etching, take out substrate after etching and lower the temperature in cold sulfuric acid, then use the deionized water rinsing substrate, remove masking layer with hydrofluoric acid.First basal plate preheating can be improved etching effect before etching.
The invention has the beneficial effects as follows: the present invention forms light extraction structure on substrate, can eliminate the total reflection of substrate-air interface, improves the light extraction efficiency; Substrate adopts high index of refraction and high heat conductance material, and heat radiation is good, can eliminate the total reflection between substrate and transparent anode, the life-span of improving the light extraction efficiency and improving simultaneously OLED.
[description of drawings]
Below by embodiment also by reference to the accompanying drawings, the present invention is described in further detail:
Fig. 1 is the simplified structure schematic diagram of OLED of the prior art;
Fig. 2 is the structural representation of a kind of embodiment of organic light-emitting device of the present invention;
Fig. 3 is the elevational schematic view of Fig. 2;
Fig. 4 is the structural representation of the another kind of embodiment of organic light-emitting device of the present invention;
Fig. 5 is the elevational schematic view of Fig. 4;
Fig. 6 is Fig. 2 and organic light-emitting device light path principle figure shown in Figure 3.
[embodiment]
Embodiment one (organic luminescent device)
Fig. 2, Fig. 3 and Fig. 6 show a kind of embodiment of organic light-emitting device of the present invention.
As shown in Figures 2 and 3, this organic luminescent device comprises substrate 1, transparent anode 2, organic cavity transmission layer 3, luminescent layer and electron transfer layer 4 and negative electrode 5.Transparent anode 2 is positioned on substrate 1, and organic cavity transmission layer 3 is positioned on transparent anode 2, and luminescent layer and electron transfer layer 4 are positioned on organic cavity transmission layer 3, and negative electrode 5 is positioned on luminescent layer and electron transfer layer 4.
In conjunction with Fig. 2 and Fig. 3, substrate 1 is formed with light extraction structure on the surface of transparent anode dorsad, and each facet of light extraction structure surrounds the reverse taper of rule.Fig. 6 shows the light path principle that this organic light-emitting device light extraction structure improves the light extraction efficiency.When light during from the inside directive extraneous air of substrate 1, a part of light (as light 50) reflexes to this light extraction structure from a facet of a light extraction structure in the inside of substrate 1 another facet is transmitted to air by this another facet; Part light (as light 60) goes out from the direct transmission of the facet of light extraction structure; Another part light (as light 70) reflexes to air by this facet from the facet that a facet of a light extraction structure is transmitted to the adjacent light drawing-out structure; Some light (as light 20) reflexes to the reflective cathode 10 of OLED in the inside of substrate 1 from a facet of a light extraction structure, then by negative electrode 10 reflections, then the mode with light 50, light 60 or light 70 penetrates.Adopt this light extraction structure on substrate 1, can eliminate the total reflection between substrate 1 and air, effectively improve the light extraction efficiency.
Embodiment two (organic luminescent device)
Fig. 4 and Fig. 5 show the another kind of embodiment of organic light-emitting device of the present invention.
This organic luminescent device is from the difference of embodiment one: substrate 1 shape of the lip-deep light extraction structure of transparent anode dorsad is different, and in the present embodiment, each facet of light extraction structure surrounds the truncation reverse taper of rule; Substrate 1 adopts aluminium nitride, and its refractive index is 1.87-2.20, and thermal conductivity is 1.4-2W/cmK (300k).
The principle that this organic luminescent device improves the light extraction efficiency is identical with embodiment one.
Embodiment three (manufacture method of organic light-emitting device light extraction structure)
Light extraction structure in embodiment one and embodiment two on substrate 1 adopts following steps to make:
1. adopt magnetron sputtering or plasma chemical vapor deposition to make silicon dioxide or silicon nitride masking layer on substrate 1 surface, substrate 1 one side surfaces (should the surface on organic luminescent device dorsad optical clear layer 2, towards air) masking layer on adopt the method for photoetching to form pattern, surperficial crested, the remainder that masking layer is retained the below of part that be positioned at of substrate exposes;
2. 85% phosphoric acid is heated to 150-170 ℃ of dehydration 10 minutes, then mixes in the ratio of 3: 1 with 98% sulfuric acid, slowly be warmed up to 190-300 ℃, obtain etching liquid;
3. substrate 1 is preheated to 100-150 ℃;
4. the substrate 1 after preheating is put into the etching liquid that step 2 obtains and carried out etching, take out substrate after etching and lower the temperature in cold sulfuric acid, then use the deionized water rinsing substrate, remove masking layer with hydrofluoric acid.
During concrete enforcement, the light extraction structure in embodiment one and embodiment two also can adopt cylinder.
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that concrete enforcement of the present invention is confined to these explanations.For the general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, can also make some simple deduction or replace, all should be considered as belonging to protection scope of the present invention.
Claims (1)
1. organic luminescent device comprises substrate, is positioned at transparent anode on described substrate, is positioned at organic cavity transmission layer on described transparent anode, is positioned at luminescent layer on described organic cavity transmission layer and electron transfer layer, negative electrode, it is characterized in that: described substrate adopts the monocrystalline yttrium-aluminium-garnet, its refractive index is 1.83-1.87, thermal conductivity is 0.11W/cmK, be formed with the light extraction structure of the total reflection that can eliminate substrate-air interface on the surface of the described transparent anode dorsad of described substrate, light extraction structure adopts magnetron sputtering or plasma chemical vapor deposition to make silicon dioxide or silicon nitride masking layer on substrate surface for by following steps, substrate surface being carried out the miniature carving face structure that etching processing obtains: a., adopt the method for photoetching to form pattern on the masking layer of substrate one side surface, substrate be positioned at the surperficial crested of below that masking layer is retained part, remainder exposes, b. 85% phosphoric acid is heated to 150-170 ℃ of dehydration 10 minutes, then mixes in the ratio of 3: 1 with 98% sulfuric acid, slowly be warmed up to 190-300 ℃, obtain etching liquid, c. substrate is put into the etching liquid that step b obtains and carried out etching, take out substrate after etching and lower the temperature in cold sulfuric acid, then use the deionized water rinsing substrate, remove masking layer with hydrofluoric acid, the cell size scope of these miniature carving face structures is between 1 μ m-20 μ m, and each facet surrounds the reverse taper of rule.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102386340A (en) * | 2010-09-02 | 2012-03-21 | 奇美电子股份有限公司 | Image display system |
| JP6025367B2 (en) * | 2011-05-12 | 2016-11-16 | キヤノン株式会社 | Organic EL device |
| CN104167431B (en) * | 2014-08-12 | 2018-05-25 | 京东方科技集团股份有限公司 | OLED display device and apply its OLED display |
| CN104362260A (en) * | 2014-11-18 | 2015-02-18 | 上海交通大学 | OLED device for utilizing microstructure to improve light extraction efficiency |
| CN104882567A (en) | 2015-05-26 | 2015-09-02 | 京东方科技集团股份有限公司 | Electroluminescent device, manufacturing method, display substrate and display device |
| TWI635639B (en) * | 2017-01-05 | 2018-09-11 | 機光科技股份有限公司 | High refraction and high thermal conductivity OLED element |
| CN112799158B (en) * | 2021-01-27 | 2022-04-08 | 福州大学 | Quasi-resonant cavity light extraction structure based on optical waveguide |
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Patent Citations (6)
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| US4106975A (en) * | 1977-06-30 | 1978-08-15 | International Business Machines Corporation | Process for etching holes |
| CN1141720C (en) * | 1997-05-15 | 2004-03-10 | Tdk株式会社 | Magnetostatic wave device and method for manufacturing the same |
| CN100483777C (en) * | 2003-05-02 | 2009-04-29 | 三星移动显示器株式会社 | Display device with light-shielding substrate |
| CN1294649C (en) * | 2004-05-18 | 2007-01-10 | 中国科学院物理研究所 | A method for corroding sapphire graphic substrate by wet-process |
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