CN103441219A - Rare earth polymer composite material and film for improving external quantum efficiency of OLED device, preparation method thereof, and OLED device - Google Patents
Rare earth polymer composite material and film for improving external quantum efficiency of OLED device, preparation method thereof, and OLED device Download PDFInfo
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Abstract
The invention relates to a rare earth polymer composite material and a film for improving the external quantum efficiency of an OLED device, the OLED device, and a reparation method of the rare earth polymer composite material and the film. The material and the film aim to improve the light out-coupling efficiency of the OLED device. The OLED device comprises a packaging layer, an organic light-emitting material layer and a substrate in sequence. Moreover, a rare earth polymer composite material layer is arranged between the organic light-emitting material layer and the substrate, and the rare earth polymer composite material layer is the film and composed of rare earth polymer composite materials which are compound Ree-TCPTU generated by TCPTU and rare earth element compound. The rare earth polymer composite material layer with moderate refractive index is arranged between the organic light-emitting material layer and the substrate, and the refractivity difference value of the organic light-emitting material layer and the substrate is large, so that the purposes of increasing the critical angle of total reflection, reducing total reflection and increasing light out-coupling efficiency are achieved.
Description
Technical field
The present invention relates to a kind of rare earth polymer composite material, film and OLED device of the OLED of raising device external quantum efficiency, and the preparation method who improves the rare earth polymer composite material of OLED device external quantum efficiency, the preparation method of film.
Background technology
OLED is Organic Light Emitting Diode, claims again Organic Electricity laser display (Organic Electroluminesence Display, OELD).OLED has self luminous characteristic, adopts very thin coating of organic material and glass substrate, when electric current passes through, organic material will be luminous, and the lighting angle in oled light source is large, and can significantly save electric energy, because this oled light source has but possessed the incomparable advantage of many LCD.
The basic structure of OLED is that the indium tin oxide by a thin and transparent tool characteristic of semiconductor is connected with positive source, adds another metallic cathode, is bundled into the structure as sandwich.The total layer has comprised: hole transmission layer, luminescent layer and electron transfer layer.When power supply is supplied to appropriate voltage, anodal hole and negative electrode electric charge will combinations in luminescent layer, produce light, according to the different red, green and blue RGB three primary colors that produce of its formula, form basic color.The characteristic of OLED is own luminous, do not need backlight, so luminosity and brightness all high, be secondly that voltage requirements is low and to economize electrical efficiency high, add fast, lightweight, the thin thickness of reaction, simple structure, cost is low etc., is regarded as one of product of tool future of 21 century.
The principle of luminosity of organic light emitting diode is similar with the inorganic light-emitting diode.When element is subject to forward bias voltage drop that direct current produces, voltage energy will drive electronics and hole respectively by the negative electrode and positive electrode injection element in addition outward, when both meet in conduction, combination, form so-called electron-hole compound.And, after chemical molecular is subject to external energy excitation, if electron spin and ground state electronics are paired, be singlet state, its light discharged is so-called fluorescence; Otherwise, if the excitation state electronics is not paired and parallel with the ground state electron spin, being called triplet, its light discharged is so-called phosphorescence.
When stable state low energy rank are got back to by excite state high energy rank in the state position of electronics, its energy will be emitted in the mode of photon or heat energy respectively, and wherein the part of photon can be utilized and be used as lighting function; Yet organic fluorescence materials at room temperature and can't observe the phosphorescence of triplet, therefore the theoretical boundary of PM-OLED element luminous efficiency only 25%.
The PM-OLED principle of luminosity is to utilize material energy jump, and the power conversion discharged is become to photon, so we can select suitable material to be used as luminescent layer or dopant dye is to obtain our needed glow color in luminescent layer.In addition, the association reaction in general electronics and hole is all within tens of nanoseconds (ns), therefore the answer speed of PM-OLED is very fast.
Typical PM-OLED is comprised of institutes such as glass substrate, ito anode, organic luminous layer and negative electrodes, wherein, thin and transparent ito anode and metallic cathode as sandwich by the organic luminous layer double team wherein, the electronics of hole with negative electrode that injects anode when voltage, when organic luminous layer is combined, excites organic material and luminous.
And luminous efficiency is better, the multilayer PM-OLED structure that generally is used, except glass substrate, anodic-cathodic and organic luminous layer, the structures such as making hole injection layer, hole transmission layer, electron transfer layer and electron injecting layer of still needing, and need to arrange insulating barrier between each transport layer and electrode, therefore hot evaporation difficulty of processing improves relatively, and it is complicated that manufacturing process also becomes.
Due to organic material and metal pair oxygen and aqueous vapor quite responsive, after completing, need to process through packaging protection.Though PM-OLED need be comprised of several layers of organic film, right organic film layer thickness is 1000～1500A ° approximately only, the too late 0.2mm of whole luminous plaque gross thickness after encapsulation adds drier, the advantage that tool is frivolous.
The luminous efficiency of OLED is to be determined by the internal quantum product of device external quantum efficiency and luminescent material.According to the quantum optices theory, the luminous efficiency of wish raising OLED must improve the external quantum efficiency of OLED.
Because the refractive index of organic material luminescent layer material is greater than the refractive index of substrate, the light that some organic material luminescent layer sends is greater than critical angle, has produced total reflection phenomenon.While from the known light sent when the organic material luminescent layer of geometric optics, entering air, total reflection condition is: sin c >=1/n, the general n of organic material luminescent layer>1.8,33 ° of c ≈; If n=2.5,23 ° of light that just mean that the organic material luminescent layer sends of c ≈ only have 1/4 light can enter in air, and 3/4 light turns back to the organic material luminescent layer.
What the light emission rate of OLED referred to is the photon that component internal produces, the photon number that in fact all can measure outside assembly after the absorption through assembly itself, reflection.Therefore the factor that is relevant to light emission rate comprises geometry, the assembly of the absorption of assembly material itself, assembly and closes the refringence of material, the scattering properties of modular construction etc.
Along with continuous research and the optimization of phosphor material now, the internal quantum efficiency of OLED has approached 100%, and external quantum efficiency is subject to the restriction of light emission rate.The refractive index of general OLED organic material is that 2.0-3.5, glass substrate refractive index commonly used are 2.0, the refractive index of air is that 1.0. so just can forming section total reflection in anode and glass-Air Interface, only account for luminous organic material and send 20% of light total amount and really shine outside light, greatly light is distributed to waveguide mode and substrate mode and is limited in organic layer and glass substrate, finally with hot form, consumes.How in the OLED device, to reduce light loss and improve the focus that light emission rate becomes research.
The total reflection that reduces glass and Air Interface can reduce the absorption of substrate mode to light, increases light emission rate.Method commonly used has: glass surface alligatoring, coating framboid, covering scattering medium, high refractive index resins.
The major defect of said method is: " alligatoring ", " framboid ", " scattering medium " have reduced the total reflection of glass and Air Interface, still,
(1) reduce the light transmittance at interface, caused additional light decay, reduced to increase the effect of light emission rate;
(2) the complex manufacturing quality is difficult to guarantee, is not suitable in enormous quantities, large-scale production;
(3) cost is high can't commercialization.
Summary of the invention
The technical problem to be solved in the present invention is to improve the light emission rate of OLED device.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is:
A kind of OLED device comprises successively: encapsulated layer from the encapsulated layer to the substrate; The luminous organic material layer; Substrate;
And, be provided with a rare earth polymer composite layer between luminous organic material layer and substrate.
Another technical scheme that the present invention adopts is:
A kind of rare earth polymer composite material that improves OLED device external quantum efficiency is that TCPTU and rare-earth compound chemical combination form;
Wherein, the poly-thiocarbamate that TCPTU is side chain band siloxanes, structure is as follows:
Wherein, MES is 2,2-disulfide group ethyl sulfide; TDI is 2,4-toluene di-isocyanate(TDI); TMTEA is three ethyl mercaptan ammonia; N is positive integer.
The another technical scheme that the present invention adopts is:
A kind of preparation method who improves the rare earth polymer composite material of OLED device external quantum efficiency comprises the following steps:
S1:TCPTU's is synthetic;
S2:Ree-TCPTU's is synthetic, the compound that wherein Ree-TCPTU is rare earth element and TCPTU.
The another technical scheme that the present invention adopts is:
A kind of film, its composition is the rare earth polymer composite material Ree-TCPTU that improves OLED device external quantum efficiency.
The another technical scheme that the present invention adopts is:
A kind of preparation method of film, is characterized in that, comprises the following steps:
Splash into THF when S31, rapid stirring TBOT, wherein the mol ratio of TBOT and THF is 1:1;
S32, Ree-TCPTU is dissolved in to THF forms Ree-TCPTU-THF solution, the Ree-TCPTU-THF solution of gained is added to the S31 products therefrom;
S33, with spin coater, the S32 products therefrom is coated on glassly, the spin coater rotating speed is 2000-10000 rev/min;
S34, first 100 ℃ solidify 1 hour, then 120 ℃ solidify 2 hours, last 150 ℃ solidify 1 hour.
The invention has the beneficial effects as follows: by adding the rare earth polymer composite material film that a composition of layer is Ree-TCPTU between the organic luminous layer in traditional OLED structure and substrate, and provide the preparation method of described rare earth polymer composite material Ree-TCPTU and the preparation method of film, added the moderate rare earth polymer composite layer of one deck refractive index between organic luminous layer and the larger material of this two-layer refractive index difference of substrate, thereby reach, strengthened the cirtical angle of total reflection, reduce total reflection, increase the effect of light emission rate.
The accompanying drawing explanation
The schematic diagram that the refractive index that Fig. 1 is the rare earth polymer composite material changes with the consumption of reactant rare earth elements;
Fig. 2 is that film refractive index changes schematic diagram;
Fig. 3 is that the film light transmittance changes schematic diagram;
The structural representation that Fig. 4 is a kind of OLED device in an embodiment of the present invention.
Label declaration:
The 1-encapsulated layer; 2-luminous organic material layer; 3-rare earth polymer composite layer; The 4-substrate.
Embodiment
By describing technology contents of the present invention, structural feature in detail, being realized purpose and effect, below in conjunction with execution mode and coordinate accompanying drawing to be explained in detail.
Chinese and the english abbreviation table of comparisons that following table is the material that occurs in the claims in the present invention book or specification:
Material Chinese and the english abbreviation table of comparisons
| Dibutyl tin laurate | DBTL |
| 3-isocyanates triethoxysilane | IPTEOS |
| 2,2-disulfide group ethyl sulfide | MES |
| Butyl titanate | TBOT |
| The poly-Thiocarbamate of side chain band siloxanes | TCPTU |
| 2,4-toluene di-isocyanate(TDI) | TDI |
| Oxolane | THF |
| Three ethyl mercaptan ammonia | TMTEA |
One embodiment of the present invention provide a kind of rare earth polymer composite material of the OLED of raising device external quantum efficiency, are that TCPTU and rare-earth compound chemical combination form;
Wherein, the poly-thiocarbamate that TCPTU is side chain band siloxanes, structure is as follows:
Wherein, MES is 2,2-disulfide group ethyl sulfide; TDI is 2,4-toluene di-isocyanate(TDI); TMTEA is three ethyl mercaptan ammonia; N is positive integer.
The addition polymers of ethylenic unsaturation hydrogen class or bunching optical resin, can calculate refractive index by following formula:
Lorentz–Lorenz
Gladstone–Dale
Vogel
In above formula, R is molar refraction, and M is molecular weight, and V is molal volume.Visible, refractive index is inversely proportional to molal volume, is directly proportional to molar refraction, ratio R
lL/ V, R
gD/ V, R
v/ V has characterized the refracting power of material; Also can rationally infer, introduce the higher material of this ratio of R/V and contribute to improve refractive index polymer in polymer; Described rare-earth compound can be cerium sesquioxide, ceria, lanthana, praseodymium oxide, rubidium oxide, samarium oxide, thulium oxide, neodymia, yittrium oxide, holimium oxide, terbium oxide, luteium oxide, ytterbium oxide, dysprosia, scandium oxide, erbium oxide, gadolinium oxide or europium oxide.And lanthanide rare material element and compound thereof all have higher ratio.
Preferably, the rare earth polymer composite material of described raising OLED device external quantum efficiency is formed by TCPTU and lanthana chemical combination, and its structure is as follows:
Preferably, in the rare earth polymer composite material of described raising OLED device external quantum efficiency, between TCPTU and rare-earth compound, with covalent bond, be connected.
Preferably, the rare earth polymer composite material of described raising OLED device external quantum efficiency is to using TCPTU and rare-earth compound as reactant, by sol-gal process, reacts and obtains.
Sol-gel process is to make presoma with the compound containing high chemism component, under liquid phase, these raw materials are evenly mixed, and be hydrolyzed, the condensation chemical reaction, form stable vitreosol system in solution, colloidal sol is slowly polymerization through between the ageing micelle, form the gel of three-dimensional space network structure, be full of the solvent lost flowability between gel network, form gel.Gel is prepared the material of molecule and even nanometer substructure through super-dry, sintering curing.
Preferably, the ranges of indices of refraction of the rare earth polymer composite material of described raising OLED device external quantum efficiency is between 2.5-3.0.Refractive index changes with the consumption of reactant rare earth elements, thus can reach the purpose of regulating refractive index by regulating rare earth element dosage, or select corresponding rare earth element dosage after determining the refractive index needed.The schematic diagram changed with the consumption of reactant rare earth elements as Fig. 1 refractive index that is the rare earth polymer composite material.
Another embodiment of the invention provides a kind of preparation method of rare earth polymer composite material of the OLED of raising device external quantum efficiency, comprise the following steps:
S11,4.85 gram TMTEA, 140 milliliters of THF, 0.07 gram DBTL are mixed, under inert gas shielding, be warming up to 35-55 ℃;
S12,5.82 gram IPTEOS are dissolved in to 14 milliliters of THF, evenly splashed in one hour in step S11 gained mixture, then react 0.9-1.2 hour;
S13, add 6.09 gram TDI and 3.5 milliliters of THF in the S12 products therefrom, reaction 3.9-4.1 hour under 40 ℃;
S14, add 2.73 gram MES in the S13 products therefrom, under 50 ℃, reaction is 3.9 hours;
S15, in the S14 products therefrom, add n-hexane, be precipitated thing and be TCPTU.
S2:Ree-TCPTU's is synthetic, the compound that wherein Ree-TCPTU is rare earth element and TCPTU.
A kind of preparation method who improves the rare earth polymer composite material of OLED device external quantum efficiency of the present invention comprises the following steps:
S11,5.13 gram TMTEA, 260 milliliters of THF, 0.13 gram DBTL are mixed, be warming up to 35 ℃ under inert gas shielding;
S12,6.18 gram IPTEOS are dissolved in to 26 milliliters of THF, evenly splashed in one hour in step S11 gained mixture, then react 1.2 hours;
S13, add 11.3 gram TDI and 6.5 milliliters of THF in the S12 products therefrom, under 60 ℃, reaction is 4.1 hours;
S14, add 5.07 gram MES in the S13 products therefrom, under 70 ℃, reaction is 4.1 hours;
S15, in the S14 products therefrom, add n-hexane, be precipitated thing and be TCPTU.
S2:Ree-TCPTU's is synthetic, the compound that wherein Ree-TCPTU is rare earth element and TCPTU.
A kind of preparation method who improves the rare earth polymer composite material of OLED device external quantum efficiency of the present invention comprises the following steps:
S11,5 gram TMTEA, 200 milliliters of THF, 0.1 gram DBTL are mixed, be warming up to 45 ℃ under inert gas shielding;
S12,6 gram IPTEOS are dissolved in to 20 milliliters of THF, evenly splashed in one hour in step S11 gained mixture, then react 2 hours;
S13, add 8.7 gram TDI and 5 milliliters of THF in the S12 products therefrom, under 50 ℃, reaction is 4 hours;
S14, add 3.9 gram MES in the S13 products therefrom, under 60 ℃, reaction is 4 hours;
S15, in the S14 products therefrom, add n-hexane, be precipitated thing and be TCPTU.
S2: TCPTU is dissolved in organic solvent and forms uniform solution, add lanthana, reaction forms gel, and drying and sintering curing prepare La-TCPTU; The compound that wherein La-TCPTU is lanthana and TCPTU.
Preferably, in the preparation method of the rare earth polymer composite material of described raising OLED device external quantum efficiency, the refractive index of product La-TCPTU is 2.5-3.0, the refractive index of La-TCPTU is directly proportional to the consumption of reactant lanthana, and in reactant, the consumption of the lanthana refractive index required according to product determined.
Another embodiment of the invention provides a kind of film, the composition of described film is the rare earth polymer composite material, is specially Ree-TCPTU.The optical property of gained film is as follows:
1) variations in refractive index changes as shown in schematic diagram as Fig. 2 film refractive index;
2) light transmittance changes as shown in Fig. 3 film light transmittance variation schematic diagram;
Another embodiment of the invention provides a kind of preparation method of rare earth polymer composite material film, comprise the following steps:
Splash into THF when S31, rapid stirring TBOT, wherein the mol ratio of TBOT and THF is 1:1;
S32, Ree-TCPTU is dissolved in to THF forms Ree-TCPTU-THF solution, the Ree-TCPTU-THF solution of gained is added to the S31 products therefrom;
S33, with spin coater, the S32 products therefrom is coated on glassly, the spin coater rotating speed is 2000-10000 rev/min;
S34, first 100 ℃ solidify 1 hour, then 120 ℃ solidify 2 hours, last 150 ℃ solidify 1 hour.
Preferably, in described method for manufacturing thin film, the mass percent of the described lanthana of the step S32 refractive index required according to product determined;
When lanthana accounts for described Ree-TCPTU-THF solution gross mass mark and is 7 ‰, refractive index is about 4.0;
When lanthana accounts for described Ree-TCPTU-THF solution gross mass mark and is 5 ‰, refractive index is about 3.2;
When lanthana accounts for described Ree-TCPTU-THF solution gross mass mark and is 3 ‰, refractive index is about 2.4.
Preferably, in the step S33 in described method for manufacturing thin film, the spin coater rotating speed film thickness required according to product determined.
As the structural representation that Fig. 4 is a kind of OLED device in an embodiment of the present invention, another embodiment of the invention provides a kind of OLED device, from the encapsulated layer to the substrate, comprise successively:
Encapsulated layer 1;
Luminous organic material layer 2;
Be provided with a rare earth polymer composite layer 3 at luminous organic material layer 2 and 4 of substrates.
When light enters optically thinner medium by optically denser medium, when incidence angle θ is increased to a certain degree, total reflection can occur.Refraction angle is that the corresponding incidence angle of 90 degree is critical angle, also claims the angle of total reflection, is denoted as i
c.Formula is arranged:
Sin i
c=n/n ', wherein n is the optically thinner medium refractive index; N' is optically denser medium refractive index (n<n').
When optically denser medium is air or vacuum, refractive index n=1, sini
c=1/n'.
When the incidence angle of light is greater than the angle of total reflection, incident light will be reflected back toward the incident aspect.As previously mentioned, the angle of total reflection is relevant with the ratio of the refractive index of adjacent media.Two refraction rate variances Yu be not greatly, i.e. more large than n of n ', and the angle of total reflection is less.The angular range of exportable light and narrow, export light fewer.So, between larger material, add the refraction materials of one deck compromise at two-layer refractive index difference, can strengthen the angle of total reflection and light emission rate.
Preferably, the composition of the rare earth polymer composite layer 3 in described OLED device is the rare earth polymer composite material, is specially Ree-TCPTU.
Preferably, the method that in described OLED device, described rare earth polymer composite layer 3 is incorporated into to substrate 4 is the method for manufacturing thin film of one of embodiment of the present invention.
By set up one deck rare earth polymer composite layer 3 between luminous organic material layer 2 and substrate 4, reduced the total reflection of light, improved light emission rate.Experiment shows:
1) rare earth polymer composite material refractive index brings up to 3.0 from 1.8; The light emission rate of OLED device is brought up to more than 60% from 42%.
2) OLED device light efficiency is brought up to 150lm/W from 100lm/W.
The foregoing is only embodiments of the invention; not thereby limit the scope of the claims of the present invention; every equivalent structure or conversion of equivalent flow process that utilizes specification of the present invention and accompanying drawing content to do; or directly or indirectly be used in other relevant technical fields, all in like manner be included in scope of patent protection of the present invention.
Claims (19)
1. a rare earth polymer composite material that improves OLED device external quantum efficiency, is characterized in that, is that TCPTU and rare-earth compound chemical combination form;
Wherein, the poly-thiocarbamate that TCPTU is side chain band siloxanes, structure is as follows:
Wherein, MES is 2,2-disulfide group ethyl sulfide; TDI is 2,4-toluene di-isocyanate(TDI); TMTEA is three ethyl mercaptan ammonia; N is positive integer.
2. the rare earth polymer composite material of raising OLED device external quantum efficiency as claimed in claim 1, is characterized in that, described rare-earth compound is cerium sesquioxide, ceria.
3. the rare earth polymer composite material of raising as claimed in claim 1 OLED device external quantum efficiency, it is characterized in that, described rare-earth compound is lanthana, praseodymium oxide, rubidium oxide, samarium oxide, thulium oxide, neodymia, yittrium oxide, holimium oxide, terbium oxide, luteium oxide, ytterbium oxide, dysprosia, scandium oxide, erbium oxide, gadolinium oxide or europium oxide.
4. the rare earth polymer composite material of raising OLED device external quantum efficiency as claimed in claim 3, is characterized in that, by TCPTU and lanthana chemical combination, formed, its structure is as follows:
5. the rare earth polymer composite material of as described as claims 1 to 3 any one raising OLED device external quantum efficiency, is characterized in that, between TCPTU and rare-earth compound, with covalent bond, is connected.
6. the rare earth polymer composite material of raising as claimed in claim 5 OLED device external quantum efficiency, is characterized in that, is to using TCPTU and rare-earth compound as reactant, by sol-gal process, reacts and obtain.
7. the rare earth polymer composite material of raising as claimed in claim 1 OLED device external quantum efficiency, it is characterized in that: its ranges of indices of refraction is between 2.5-3.0.
8. a preparation method who improves the rare earth polymer composite material of OLED device external quantum efficiency, is characterized in that, comprises the following steps:
S1:TCPTU's is synthetic;
S2:Ree-TCPTU's is synthetic, the compound that wherein Ree-TCPTU is rare earth element and TCPTU.
9. the preparation method of the rare earth polymer composite material of raising OLED device external quantum efficiency as claimed in claim 8, is characterized in that, step S1 specifically comprises:
S11,4.85 – 5.13 gram TMTEA, 140-260 milliliter THF, 0.07-0.13 gram DBTL are mixed, under inert gas shielding, be warming up to 35-55 ℃;
S12,5.82-6.18 gram IPTEOS is dissolved in to 14-26 milliliter THF, evenly splashed in one hour in step S11 gained mixture, then react 0.9-1.2 hour;
S13, add 6.09-11.3 gram TDI and 3.5-6.5 milliliter THF in the S12 products therefrom, reaction 3.9-4.1 hour under 40-60 ℃;
S14, add 2.73-5.07 gram MES in the S13 products therefrom, reaction 3.9-4.1 hour under 50-70 ℃;
S15, in the S14 products therefrom, add n-hexane, be precipitated thing and be TCPTU.
10. the preparation method of the rare earth polymer composite material of raising OLED device external quantum efficiency as claimed in claim 8, is characterized in that, step S1 specifically comprises:
S11,5 gram TMTEA, 200 milliliters of THF, 0.1 gram DBTL are mixed, be warming up to 45 ℃ under inert gas shielding;
S12,6 gram IPTEOS are dissolved in to 20 milliliters of THF, evenly splashed in one hour in step S11 gained mixture, then react 2 hours;
S13, add 8.7 gram TDI and 5 milliliters of THF in the S12 products therefrom, under 50 ℃, reaction is 4 hours;
S14, add 3.9 gram MES in the S13 products therefrom, under 60 ℃, reaction is 4 hours;
S15, in the S14 products therefrom, add n-hexane, be precipitated thing and be TCPTU.
11. the preparation method of the rare earth polymer composite material of raising OLED device external quantum efficiency as claimed in claim 8, is characterized in that, step S2 is specially:
TCPTU is dissolved in organic solvent and forms uniform solution, add lanthana, reaction forms gel, and drying and sintering curing prepare La-TCPTU; The compound that wherein La-TCPTU is lanthana and TCPTU.
12. the preparation method of the rare earth polymer composite material of raising OLED device external quantum efficiency as claimed in claim 11, it is characterized in that: the refractive index of product La-TCPTU is 2.5-3.0, the refractive index of La-TCPTU is directly proportional to the consumption of reactant lanthana, and in reactant, the consumption of the lanthana refractive index required according to product determined.
13. a film is characterized in that: its composition is the rare earth polymer composite material of raising OLED device external quantum efficiency as described as any one in claim 1-4.
14. the preparation method of film as claimed in claim 13, is characterized in that, comprises the following steps:
Splash into THF when S31, rapid stirring TBOT, wherein the mol ratio of TBOT and THF is 1:1;
S32, Ree-TCPTU is dissolved in to THF forms Ree-TCPTU-THF solution, the Ree-TCPTU-THF solution of gained is added to the S31 products therefrom;
S33, with spin coater, the S32 products therefrom is coated on glassly, the spin coater rotating speed is 2000-10000 rev/min;
S34, curing.
15. method for manufacturing thin film as claimed in claim 14 is characterized in that:
The mass percent of the described lanthana of the step S32 refractive index required according to product determined.
16. method for manufacturing thin film as claimed in claim 14 is characterized in that:
In step S33, the spin coater rotating speed film thickness required according to product determined.
17. an OLED device comprises successively from the encapsulated layer to the substrate:
Encapsulated layer;
The luminous organic material layer;
Substrate;
It is characterized in that, be provided with a rare earth polymer composite layer between luminous organic material layer and substrate.
18. OLED device as claimed in claim 17 is characterized in that:
The rare earth polymer composite material that the composition of described rare earth polymer composite layer is the described raising of any one OLED device external quantum efficiency in claim 1-4.
19. OLED device as claimed in claim 17 is characterized in that:
The method that described rare earth polymer composite layer is incorporated into to substrate is the described method for manufacturing thin film of any one in claim 14-16.
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