CN112968140A - Electroluminescent device with reduced blue light and application thereof - Google Patents
Electroluminescent device with reduced blue light and application thereof Download PDFInfo
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Abstract
The invention provides an electroluminescent device with reduced blue light, which sequentially comprises a substrate (10), a light extraction film (20), an anode (30), a light-emitting layer (40), a cathode (50) and an encapsulation layer (60); the light extraction film (20) contains a light conversion material (21). According to the invention, the fluorescent material is introduced into the inner light extraction layer in the electroluminescent device, so that on one hand, the fluorescent material converts short-wavelength blue light into long-wavelength light for output, the output of blue light components of the device is reduced, the color temperature of the device is reduced, and more healthy light color is obtained. On the other hand, the technology can directly utilize the packaging layer of the existing structure of the electroluminescent device to protect the introduced blue light conversion fluorescent material from water and oxygen erosion. In addition, the introduction of the blue light conversion material is matched with the manufacturing process of the production line electroluminescent device, and the manufacturing process of the existing production line electroluminescent device is not required to be adjusted.
Description
Technical Field
The invention relates to an electroluminescent device with reduced blue light and application thereof, belonging to the field of electroluminescent device application.
Background
The electroluminescent device includes an organic electroluminescent device (OLED), a quantum dot light emitting device (QLED), a perovskite light emitting device, and the like. Because the OLED light-emitting device has the advantages of being light, thin, free of blue harm, low in heat, free of glare, transparent, flexible, bendable and the like, the OLED light-emitting device is widely applied to the lighting market. The most mainstream lighting source in the market at present is an LED light source prepared from an inorganic semiconductor material, compared with the LED light source, the OLED light source has healthier light quality, the OLED spectrum is closer to the sunlight spectrum and is a continuous spectrum, and the blue light component in the OLED light source is much lower than that of the LED. Based on the above advantages, the OLED light source is expected to be in the healthy lighting market.
With the continuous deepening of human cognition on blue light, more and more authoritative medical journals report the potential harm of the blue light, and besides direct damage to retina, yellow spot and the like of eyes, the blue light can increase the probability that human beings suffer from serious diseases such as breast cancer, intestinal cancer and Alzheimer's disease. Therefore, there are many techniques currently focused on addressing the blue light hazards, including illumination and displays. In patents CN201710055171 and CN200810065991, the blue light hazard of a display using an LED chip as a backlight source is successfully reduced by a method of reducing the hazard caused by blue light in a liquid crystal display by adding a blue light adsorption layer. On the other hand, when designing an illumination light source in the current illumination market, the blue light proportion is required to be reduced, the color temperature of the light source is required to be reduced, and the color temperature of the designed illumination light source is required to be compared with the original candle color (1800K). Based on this, candlelight-like OLED lighting sources have also come to the fore, and by virtue of the inherent advantages of OLED device structures, researchers can design OLED light sources completely free of blue light components, such as amber OLED light sources of OLED works in the united states and the first organic photoelectric candlelight-like OLED light source in south beijing.
However, although the direct removal of blue light component in the OLED device can directly obtain a white light source without blue light, the luminance, luminous flux and luminous efficiency of the OLED light source are greatly lost. . Therefore, how to reduce the proportion of blue light without reducing the luminous efficiency of the OLED light source needs to develop new technologies to realize. According to the invention, by adding the light conversion fluorescent material in the internal light extraction film in the OLED device, harmful blue light is converted into healthy candle light color, and finally all emitted photons are effectively utilized, so that a high-efficiency healthy OLED lighting source is realized. Compared with an LED, the patent CN 108134003A provides a method for covering a fluorescent conversion layer on a blue light chip by using fluorescent powder and thermosetting colloid, so that the harm of blue light is reduced, and the original package color point and brightness are maintained. However, the forms and structures of the OLED and the LED are completely different, the LED is a point light source and can be well coated by the colloid, and the method cannot be used when the OLED is a surface light source. Therefore, new techniques are needed to reduce the blue damage of OLED illumination and to reduce the loss of brightness.
Disclosure of Invention
It is an object of the present invention to overcome the disadvantages of the prior art and to provide an electroluminescent device that reduces the blue damage of the OLED illumination and reduces the loss of brightness.
The technical scheme of the invention is as follows:
an electroluminescent device with reduced blue light, comprising in order a substrate (10), a light extraction film (20), an anode (30), a light emitting layer (40), a cathode (50), an encapsulation layer (60); the light extraction film (20) contains a light conversion material (21);
the substrate (10) is used for bearing the light extraction film (20), the anode (30), the light emitting layer (40), the cathode (50) and the packaging layer (60);
the light extraction film (20) is used for extracting light to the outside of the device, so that the luminous efficiency of the device is improved;
the light conversion material (21) is used for absorbing blue light and emitting long-wavelength green, yellow or red light; the absorption edge of at least one material in the light conversion material is less than 560 nm; the peak value of the emission spectrum of at least one material in the light conversion materials is more than 550 nm;
the anode (30) is used for introducing positive charges into the light-emitting layer (40);
the light-emitting layer (40) is used for emitting light;
the cathode (50) is used for introducing negative charges into the light-emitting layer (40) and reflecting light to the anode (30);
the encapsulation layer (60) is used for blocking water and oxygen from entering the interior of the electroluminescent device.
In the blue light-reducing electroluminescent device, the material of the substrate (10) is selected from glass or plastic.
In the blue light-reducing electroluminescent device of the present invention, the material of the light extraction film (20) comprises at least a carrier and nanoparticles, the weight ratio of the nanoparticles to the carrier is less than 0.7, and preferably the weight ratio of the nanoparticles to the carrier is 1: 2.
the carrier material is selected from one or a mixture of more of polyester, polyacrylate, polymethacrylate, polyurethane and polyether.
The nano particles are selected from one or a mixture of more of molybdenum oxide, zirconium oxide, aluminum oxide, antimony oxide, titanium oxide, niobium oxide, yttrium oxide, vanadium oxide and scandium oxide.
In the blue light reduced electroluminescent device of the present invention, the light conversion material (21) is selected from the group consisting of organic light emitting small molecules, light emitting polymers or organic light emitting complexes, and the mass ratio of the light conversion material (21) to the light extraction film (20) is between 1/10000 and 1/100. The mass ratio of the light conversion material (21) to the light extraction film (20) is preferably 1/600.
Preferably, the light conversion material may be a green organic fluorescent material selected from (E) -4- ((cyanobenzylidene) amino) benzoic acid, 2, 7-bis (4-pyridyl) -9-fluorenone, 4, 7-bis (3, 5-di-tert-butylphenyl) -2,1, 3-benzothiadiazole, N' -dimethyl-quinacridone and/or 2,3,6, 7-tetrahydro-1, 1,7, 7-tetramethyl-1H, 5H,11H-10- (2-benzothiazolyl) -quinolizino [9,9A,1GH ] coumarin. The light conversion material can be a red organic fluorescent material selected from rubrene, 4-dicyanomethylene-2-tert-butyl-6- (1,1,7, 7-tetramethyljulolidine-4-vinyl) -4H-pyran, [ (2,4, 6-trimethylphenyl) -pyridine-2-methylidene amine ] HgCl2, [ (2-methylphenyl) -pyridine-2-methylidene amine ] HgCl2 and the like.
In the electroluminescent device with reduced blue light, the anode (30) material is selected from ITO, IZO, nano silver or graphene.
In the electroluminescent device with reduced blue light, the luminescent layer (40) comprises at least one of luminescent material, hole injection material, hole transport material, hole blocking material, electron injection material, electron transport material, electron blocking material and valence generation material. Specifically, it may be selected from NPB, Spiro-TPD, β -NPB, Spiro-NPB, TPD, DMFL-TPD, DMFL-NPB, α -NPD, DPFL-TPD, Spiro-TAD, DPFL-NPB, NPAPF, NPBAPF,2,2' -Spiro-DBP, Spiro-2NPB, Spiro-BPA, PAPB, TAPC, Spiro-TTB, α, β -TNB, β -TNB, α -TNB, HMTPD, TTP, TFB, DOFL-NPB, ONPB and the like.
In the electroluminescent device with reduced blue light, the cathode (50) material is selected from one or more than two alloys of magnesium, aluminum, lithium, calcium, cesium and silver.
In the blue light-reducing electroluminescent device of the present invention, the encapsulation layer (60) is used to achieve a water vapor transmission rate of less than 10-5g/m2Day, oxygen transmission rate less than 10-4cm3/m2The effect of/day, the packaging layer (60) is a single inorganic layer such as glass or a composite structure of multiple inorganic layers and organic layers;
the inorganic layer material is selected from one or a mixture of more of aluminum oxide, titanium oxide, silicon oxide, tin oxide, nickel oxide and molybdenum oxide;
the organic layer material is at least one selected from polyethylene glycol acrylate and derivatives thereof, triethylene glycol diacrylate and derivatives thereof, triethylene glycol acrylate and derivatives thereof, diethylene glycol diacrylate and derivatives thereof, diethylene glycol acrylate and derivatives thereof, and alkyl methacrylate and derivatives thereof.
In the present invention, the method for producing a light extraction film containing a light conversion material comprises the following steps:
the first step is as follows: selecting proper carriers, nano particles, light conversion materials, solvents and proper additives to prepare a solution for later use; the additive can be a surfactant for adjusting the surface tension of the solution on the substrate so as to better form a film, a leveling agent for better leveling, an antioxidant for improving the weather resistance of the light extraction film, an adhesion promoter for improving the adhesion of the film and the substrate, and a dispersant for providing the dispersibility of the solution so as to better form a film;
the second step is that: cleaning the selected substrate, wherein the cleaning operation can be performed by at least one or a combination of water cleaning, cleaning liquid cleaning, rolling brush scrubbing, ultrasonic cleaning, two-fluid cleaning, plasma cleaning and UVO cleaning;
and thirdly, uniformly coating the solution on the substrate by using a coating device, wherein the coating device can be a spin coating device, a screen printing device, an ink jet printing device, a slit coating device, a blade coating device and the like, and is preferably used for large-area production, and coating is performed by using the slit coating device. And after coating is finished, taking out the solvent in the film by baking. The baking can be ordinary baking, flat heating baking, and also can be optimized vacuum baking or nitrogen auxiliary baking.
And fourthly, curing the coated film, further, selecting UV curing equipment for UV curing if the selected carrier is a UV curing type material, and performing thermal curing by using a hot plate or an oven and the like if the carrier is a thermal curing type material to obtain the substrate with the light extraction film.
In the present invention, the method for manufacturing an electroluminescent device with reduced blue light can be divided into the following steps:
the method comprises the following steps: cleaning the prepared light extraction substrate, wherein the cleaning is at least one selected from water washing, cleaning liquid cleaning, ultrasonic cleaning, two-fluid cleaning or plasma cleaning;
step two: preparing an anode on the light-extraction substrate by using magnetron sputtering equipment, wherein the thickness of the plated film is preferably 80-400 nm;
step three: and (4) carrying out thermal evaporation coating of luminescent materials, cathodes and the like on the film obtained in the step four. The process is a standard evaporation process and is not described herein in detail. Preferably, in order to reduce the leakage or short circuit phenomenon of the electroluminescent device, a layer of short circuit release layer can be coated by a wet process before evaporation. Preferably, the short-circuit layer may be a hole injection layer, such as PEDOT: PSS or HAT-CN ink, etc.;
step four: and packaging the prepared device, wherein the packaging is selected from UV adhesive packaging, film packaging, glass powder laser packaging and the like. And completing the preparation of the electroluminescent device with high light extraction efficiency after the packaging is completed.
The invention also provides an electroluminescent panel or lighting device having an electroluminescent device with reduced blue light as described above.
The invention has the following technical effects:
according to the invention, the fluorescent material is introduced into the inner light extraction layer in the electroluminescent device, so that on one hand, the fluorescent material converts short-wavelength blue light into long-wavelength light for output, the output of blue light components of the device is reduced, the color temperature of the device is reduced, and more healthy light color is obtained. On the other hand, the technology can directly utilize the packaging layer of the existing structure of the electroluminescent device to protect the introduced blue light conversion fluorescent material from water and oxygen erosion. In addition, the introduction of the blue light conversion material is matched with the manufacturing process of the production line electroluminescent device, and the manufacturing process of the existing production line electroluminescent device is not required to be adjusted. The technology can convert harmful light in the electroluminescent device into healthy light, and also fully utilizes the structure of the existing device to protect the fluorescent material, and has obvious advantages. In addition, the addition of a fluorescent material to the light extraction film does not cause light loss. For individual fluorescent materials, especially organic fluorescent materials, large concentrations cause concentration quenching and thus only light absorption, not light emission, occurs. It is therefore essential to disperse the material with the carrier. If the fluorescent material is added to the support alone, the loss of light is directly caused due to the matching problem of refractive index, whereas if the fluorescent material is added to the light extraction film, the synergistic effect of light extraction and light conversion can be obtained by the action of the nanoparticles. Furthermore, the addition of the light conversion material can increase the effect of the light extraction film, and the nanoparticles in the light extraction film generally have better extraction effect on yellow green light than blue light, so that when a part of light converted by the light conversion material is reflected back through the cathode and then reflected back, the light can be extracted more easily, that is to say, the addition of the light conversion material further improves the light extraction capability of the light extraction film.
Drawings
Fig. 1 is a schematic diagram of a blue light-reducing electroluminescent device of the present invention.
Fig. 2 and 3 show an absorption spectrum and an emission spectrum of the light extraction film, respectively.
Fig. 4 is a schematic structural diagram of devices a and B.
Fig. 5 is a graph comparing the spectra of devices a and B.
In which 10 is a substrate, 20 is a light extraction film, 21 is a light conversion material, 30 is an anode, 40 is a light emitting layer, 50 is a cathode, and 60 is an encapsulation layer.
Detailed Description
Example 1
In the following examples, the preparation of an internal light extraction film (20) containing a light conversion function is described.
1) A light extraction layer solution was prepared, wherein THF 33g, zirconia 2g, polyacrylic resin 4g, and Y4080.01g were contained therein. The polyacrylic resin is purchased from a self-excitation intelligent technology, and the model is UV 7200. The zirconia was purchased from Henan Detai chemical products, Inc., CAS: 1314-23-4. Y408 is an organic fluorescent material purchased from Ningbo Lu Milan New Material Co., Ltd.
2) Cleaning a substrate, wherein the substrate is selected from glass, and the glass is brushed by a brush, cleaned by ultrasonic waves by cleaning liquid and baked for 2 hours at 200 ℃ for later use;
3) coating a light extraction film, uniformly dispersing the prepared light extraction solution on a substrate by using spin coating equipment, wherein the rotating speed of a coating machine is 2000rpm, and the time is 40 s;
4) carrying out UV curing treatment on the coated light extraction film; a substrate with a light extraction film was obtained.
Testing the light conversion performance of the film:
the thickness of the film was about 3 μm, and the refractive index of the film was 1.6. FIGS. 2 and 3 show the absorption spectrum and emission spectrum of the light extraction film, respectively, and it can be seen that the film has an absorption range of 200nm to 553nm and emits yellow light upon photoexcitation (excitation wavelength: 460nm), the wavelength range: the half-peak width of the emission spectrum of 540 nm-650 nm is 77nm, the emission peak is 559nm, and the internal light extraction film can be preliminarily judged to have the light conversion function.
Example 2
This example compares the spectrum, color temperature, efficiency of the device A, B. Wherein device a was provided with the internal light extraction film of example 1 and device B was provided with the internal light extraction film without introducing a light conversion material. The schematic structure of devices a and B is shown in fig. 4.
A device A including, in order, a substrate (10), a light extraction film (20), an anode (30), a light-emitting layer (40), a cathode (50), and an encapsulation layer (60); the light extraction film (20) contains a light conversion material (21);
a device B including, in order, a substrate (10), a light extraction film (20), an anode (30), a light emitting layer (40), a cathode (50), and an encapsulation layer (60); the light extraction film (20) does not contain a light conversion material (21).
The specific fabrication steps of device A, B are as follows:
the method comprises the following steps: cleaning of the substrate with light extraction film prepared in example 1
The cleaning mode adopts rotary cleaning, the cleaning solution is general alkaline cleaning solution, after cleaning, the cleaning solution is respectively cleaned by ultrapure water and two fluids, then the cleaning solution is dried by vacuum drying equipment,wherein the vacuum degree of the vacuum drying equipment is 1x10-4Pa, at 100 deg.C for 30 min. It is worth mentioning that the front of the film is kept downward in the vacuum baking process, so that the falling particles in the baking process are prevented from polluting the surface.
Step two: preparation of anodes, luminescent layers and cathodes
The preparation of the anode ITO film is carried out by adopting a magnetron sputtering method, the thickness of the film is 100nm, and the sheet resistance is 20 omega/□. And preparing the luminous layer and the cathode in sequence by adopting an evaporation process. The device structure and materials are as follows:
ITO(100nm)/HATCN(50nm)/TAPC(40nm)/TCTA(10nm)/mCBP:BCz-TRz:RD54(10nm,18wt％,0.15wt％)/T2T(10nm)/ET64(50nm)/ET64:Li(10nm,2.5wt％)/TAPC:HI09(10nm,6wt％)/TAPC(50nm)/GH025:GD594:RD54(20nm,1:2wt％:0.2wt％)/ET64(50nm)/Liq(2nm)/Ag(150nm)。
among them, RD54, GH025, GD594, RD54 and ET64 were purchased from nipur new materials, inc; other materials are all common materials.
Step three: preparation of encapsulation layer
In the embodiment, a traditional UV glue packaging process is adopted, and glass is used as a packaging cover plate to package the device for blocking water and oxygen.
And (3) detecting the performance of the device:
the devices A, B were tested for their respective optoelectronic properties using IVL testing equipment, and the results are shown in table 1. It can be seen that the same voltage is applied to the device a as compared to the device B, which results from the structural uniformity of the OLED device itself, and the EQE drop results from the partial conversion after the blue light is absorbed by the internal light extraction film of the device a. The color temperature of the device A is reduced due to the absorption of blue light by the internal light extraction film, and the color coordinate is shifted to the red and yellow directions due to the large reduction of the proportion of the blue light.
Watch 1
| voltage/V | EQE/％ | CCT/K | CIEx | CIEy | |
| Device A | 6.1 | 28 | 2400 | 0.4306 | 0.4204 |
| Device B | 6.1 | 36 | 4500 | 0.3508 | 0.3121 |
Fig. 5 is a comparison graph of spectra of the device a and the device B, and it can be seen that successful absorption of blue light by the internal light extraction film greatly reduces the spectral intensity of the blue light band, and a newly added spectrum appears near 560nm, which proves successful conversion of blue light components by the light conversion material in the internal light extraction film, and confirms the feasibility of the technology of the present invention.
Example 3
This example compares the color temperature and efficiency of devices B and C. The device B is the same as the device B in embodiment 2, the device C is obtained by adding the light conversion material Y3096 into the device B, the addition method refers to embodiment 1, the light conversion efficiency of Y3096 is 98%, and the Y3096 is purchased from osford optical and electrical technology ltd, shenzhen. The structure and fabrication of the two devices are referred to in example 2.
The EQE and color temperature for device B and device C are shown in table 2. The EQE of device C is increased by nearly 10% compared to device B, while the color temperature drops below 2000K. Although the light conversion efficiency of the light conversion material reaches 98%, 100% conversion is performed, the EQE of device C exceeds that of device B because a portion of the blue light is converted into yellow-green light, and the enhancement of the yellow-green light by the nanoparticles is more efficient, so that it can be seen that the addition of the light conversion material improves the extraction efficiency of the light extraction film.
Watch two
| voltage/V | EQE/％ | CCT/K | |
| Device B | 6.1 | 36 | 4500 |
| Device C | 6.1 | 39 | 1900 |
。
Claims (10)
1. An electroluminescent device with reduced blue light, characterized by comprising, in order, a substrate (10), a light extraction film (20), an anode (30), a light emitting layer (40), a cathode (50), and an encapsulation layer (60); the light extraction film (20) contains a light conversion material (21);
the substrate (10) is used for bearing the light extraction film (20), the anode (30), the light emitting layer (40), the cathode (50) and the packaging layer (60);
the light extraction film (20) is used for extracting light to the outside of the device, so that the luminous efficiency of the device is improved;
the light conversion material (21) is used for absorbing blue light and emitting long-wavelength green, yellow or red light; the absorption edge of at least one material in the light conversion material is less than 560 nm; the peak value of the emission spectrum of at least one material in the light conversion materials is more than 550 nm;
the anode (30) is used for introducing positive charges into the light-emitting layer (40);
the light-emitting layer (40) is used for emitting light;
the cathode (50) is used for introducing negative charges into the light-emitting layer (40) and reflecting light to the anode (30);
the encapsulation layer (60) is used for blocking water and oxygen from entering the interior of the electroluminescent device.
2. A blue-light-reduced electroluminescent device as claimed in claim 1, characterized in that the material of the substrate (10) is selected from glass or plastic.
3. A blue-light-reduced electroluminescent device according to claim 1, characterized in that the material of the light extraction film (20) comprises at least a carrier and nanoparticles;
the carrier material is selected from one or a mixture of more of polyester, polyacrylate, polymethacrylate, polyurethane and polyether;
the nano particles are selected from one or a mixture of more of molybdenum oxide, zirconium oxide, aluminum oxide, antimony oxide, titanium oxide, niobium oxide, yttrium oxide, vanadium oxide and scandium oxide.
4. A blue-light-reduced electroluminescent device as claimed in claim 1, characterized in that the light-converting material (21) is selected from the group consisting of small organic light-emitting molecules, light-emitting polymers or organic light-emitting complexes, and the mass specific gravity of the light-converting material (21) to the light extraction film (20) is between 1/10000 and 1/100.
5. A blue light-reduced electroluminescent device as claimed in claim 4, characterized in that the light-converting material (21) is a green organic fluorescent material or a red organic fluorescent material,
the green organic fluorescent material is selected from (E) -4- ((cyanobenzylidene) amino) benzoic acid, 2, 7-bis (4-pyridyl) -9-fluorenone, 4, 7-bis (3, 5-di-tert-butylphenyl) -2,1, 3-benzothiadiazole, N' -dimethyl-quinacridone and/or 2,3,6, 7-tetrahydro-1, 1,7, 7-tetramethyl-1H, 5H,11H-10- (2-benzothiazolyl) -quinolizino [9,9A,1GH ] coumarin;
the red light organic fluorescent material is selected from rubrene, 4-dicyanomethylene-2-tert-butyl-6- (1,1,7, 7-tetramethyl julolidine-4-vinyl) -4H-pyran or [ (2,4, 6-trimethylphenyl) -pyridine-2-methylene amine ] HgCl2, [ (2-methylphenyl) -pyridine-2-methylene amine ] HgCl 2.
6. A blue-light-reduced electroluminescent device according to claim 1, characterized in that the anode (30) material is selected from ITO, IZO, nanosilver or graphene.
7. A blue light-reducing electroluminescent device according to claim 1, characterized in that the light-emitting layer (40) comprises at least one of a light-emitting material, a hole-injecting material, a hole-transporting material, a hole-blocking material, an electron-injecting material, an electron-transporting material, an electron-blocking material, a valence-generating material.
8. A blue-light-reduced electroluminescent device according to claim 1, characterized in that the cathode (50) material is selected from one or an alloy of two or more of magnesium, aluminum, lithium, calcium, cesium and silver.
9. The blue-light-reduced electroluminescent device as claimed in claim 1, wherein the material of the encapsulation layer (60) is a single inorganic layer or a composite structure of multiple inorganic layers and organic layers;
the inorganic layer material is selected from one or a mixture of more of aluminum oxide, titanium oxide, silicon oxide, tin oxide, nickel oxide and molybdenum oxide;
the organic layer material is at least one selected from polyethylene glycol acrylate and derivatives thereof, triethylene glycol diacrylate and derivatives thereof, triethylene glycol acrylate and derivatives thereof, diethylene glycol diacrylate and derivatives thereof, diethylene glycol acrylate and derivatives thereof, and alkyl methacrylate and derivatives thereof.
10. An electroluminescent panel or lighting device having a blue light reducing electroluminescent device as claimed in any one of claims 1 to 9.
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