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CN108847454B - A kind of stretchable luminescent device of self-healing and preparation method thereof - Google Patents

A kind of stretchable luminescent device of self-healing and preparation method thereof Download PDF

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CN108847454B
CN108847454B CN201810311147.0A CN201810311147A CN108847454B CN 108847454 B CN108847454 B CN 108847454B CN 201810311147 A CN201810311147 A CN 201810311147A CN 108847454 B CN108847454 B CN 108847454B
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healing
self
preparation
carbon nanotube
layer
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CN108847454A (en
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彭慧胜
施翔
周旭峰
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Taihe New Material Group Co ltd
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Fudan University
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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/10OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
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Abstract

The invention belongs to intelligent electronic device technical field, the stretchable luminescent device and preparation method thereof of specially a kind of self-healing.The method of the present invention includes: to prepare the light emitting active layer and transparent electrode with self-healing function using the polyurethane elastomer of transparent self-healing as basis material.Light emitting active layer uses electroluminescent powder, and the unique dispersed structure of luminescent powder realize the healing of luminescent layer can by the healing of self-healing matrix.Electrode material uses aligned carbon nanotube array, make electrode material that there is pleated structure when electrode is in non-stretched state using the method for pre-stretching, the structure can ensure that the stabilization of device resistance during stretching, and the Van der Waals force interaction between carbon nanotube enables the electric conductivity of electrode preferably to restore.Device maximum brightness reaches 121.2 cd/m2, maximum tension amount reaches 400%, stretches circulator part under 200% strain and has good stability, and it is unattenuated to bear 10 cuttings-healing cycle brightness.

Description

A kind of stretchable luminescent device of self-healing and preparation method thereof
Technical field
The invention belongs to intelligent electronic device technical fields, and in particular to a kind of stretchable luminescent device of self-healing and its Preparation method.
Background technique
Wearable device has lightweight, flexibility, highly integrated property and multifunctionality etc. as electronic equipment of new generation Advantage.Wearable device usually needs to bear in use complicated deformation in use and such as distorts, collides, scrapes It wipes or tears.In order to avoid irreversible damage generation and extend device lifetime, researcher is developed based on self-healing material A series of self-healing devices.Display device is the unique channel of information transmission and human-computer interaction, is played the part of in wearable devices field Key player, a large amount of research surround flexible, stretchable light-emitting display device and be unfolded.As far as we know, it answers at present With most commonly used Organic Light Emitting Diode, since it is very high to film layer flatness requirement, when device when damaging by shining Layer is difficult to be restored to initial state, and usually used electrode material such as ito glass, since it is inorganic matter, it is difficult to real Now heal.In addition to this, functional layer only has nanometer grade thickness, to realize and almost impossible when healing carry out good accurate boundary Face contact.
For electroluminescent powder as a kind of AC light-emitting material, luminescent layer is compound by luminescent powder and a kind of insulating polymer It forms, there is thicker light emitting layer thickness and has lower requirement to film layer planarization, therefore we can be by exhausted The design of edge polymer, so that device has self-healing and tensility simultaneously.Carbon nanotube is received as a kind of high conductivity Rice material, film layer have the flexibility and transparency of height, are widely used in the exploitation of flexible electronic device.
Summary of the invention
It is an object of that present invention to provide stretchable luminescent devices of a kind of self-healing and preparation method thereof.
The preparation method of the stretchable luminescent device of self-healing provided by the invention, the specific steps are as follows:
(1) transparent self-healing elastomer is prepared;
(2) aligned carbon nanotube array is prepared;
(3) preparation has the self-healing transparent electrode material of fold-like structures;
(4) self-healing luminescence activity layer material is prepared;
(5) by the self-healing light emitting active layer material of the self-healing transparent electrode material of step (3) preparation and step (4) preparation Material with sandwich, i.e. electrode-luminescent layer-electrode mode is overlapped, and is pressurizeed by way of hot-rolling pressure, temperature be 60 DEG C ~ 80 DEG C, pressure is 5 ~ 10N, excludes interlayer bubble, enhances inter-layer bonding force, then heats 12 ~ 18 h at 60 ~ 80 DEG C, Guarantee that interlayer fully achieves molecular level fusion.
In step (1) of the present invention, the detailed process of the preparation self-healing elastomer is as follows:
(1) polyneopentyl glycol adipate (1000 ~ 3000 g/mol of number-average molecular weight) of 10 parts of quality is weighed at three mouthfuls In flask, it is heated to 100 ~ 150 DEG C of 1 ~ 2h of vacuum stirring and carries out water removal operation;
(2) 60 ~ 80 DEG C are cooled to reaction unit, argon inert protection gas are filled with into vacuum, and with syringe to anti- Answer the dibutyl tin laurate of isophorone diisocyanate and 0.05 ~ 1.0 part of quality that 2.0 ~ 3.0 parts of quality are added in system N, N '-dimethyl formamide solution continues to be stirred to react 3 ~ 4h;
(3) 40 ~ 50 DEG C are cooled to reaction unit, the 2- hydroxyethyl disulfide of 0.8 ~ 1.0 part of quality is added thereto N, N '-dimethyl formamide solution is stirred to react after 1.5 ~ 2 h and appropriate N is added, and it is viscous that N '-dimethyl formamide reduces reaction N is added after the reaction was continued 1.5 ~ 2 h in degree again, and N '-dimethyl formamide solution is diluted to ideal concentration, obtains end reaction Product.
In step (2) of the present invention, described prepares orientation carbon nanotube film, is done to aligned carbon nanotube array Method spinning obtains orientation carbon nanotube film;Wherein aligned carbon nanotube array is prepared by chemical vapour deposition technique, and height exists 100-300 μm, be multi wall structure, and caliber is 5-50 nm.
In step (3) of the present invention, the preparation has the specific stream of the self-healing transparent electrode material of fold-like structures Journey is as follows:
(1) a silicone elastomer substrate is taken, pre-stretching 200 ~ 400% is drawn 1 ~ 3 layer of orientation carbon nanotube film on it, released Putting stretching makes silica gel substrate restore long to original, obtains pleated structure;
(2) the self-healing polyurethane solutions that synthesis is poured in film layer, volatilize solvent using heating, vacuum, obtain finished product Electrode.
In step (4) of the present invention, the preparation self-healing light emitting active layer, is by electroluminescent powder and polyurethane by (0.2 ~ 2): 1 mass ratio mixing obtains finished product film layer after solvent volatilizes.The partial size of used electroluminescent powder is 10 ~ 40 μ m。
The whole preparation flow and device architecture of step of the present invention are as shown in Figure 1.Device is electrode-luminescent layer-electrode Sandwich structure.Light emitting active layer uses electroluminescent powder, and the unique dispersed structure of luminescent powder makes the healing of luminescent layer can be with It is realized by the healing of self-healing matrix.Electrode material uses aligned carbon nanotube array, makes electricity using the method for pre-stretching Pole material has pleated structure when electrode is in non-stretched state, which can ensure that device resistance during stretching Stablize, the Van der Waals force interaction between carbon nanotube enables the electric conductivity of electrode preferably to restore.Device is most highlighted Degree reaches 121.2 cd/m2, maximum tension amount reaches 400%, and circulator part, which is stretched, under 200% strain has good stability, and After device undergoes cutting-agglutination, brightness does not obviously decay under pulled out condition.It, can be in repeatedly cutting Healing Experiments It is unattenuated to bear 10 cuttings-healing cycle brightness.
Detailed description of the invention
Fig. 1 is whole preparation flow and device architecture schematic diagram in embodiment.
Fig. 2 is the brightness-voltage curve of device healing front and back in embodiment.
Fig. 3 is device healing front and back brightness in embodiment with the variation of amount of tension.
Fig. 4 is the stretching circulating luminance test of device healing front and back in embodiment.
Fig. 5 is device repeatedly influence of the cutting-healing to light emission luminance.
Fig. 6 is photo of the device healing front and back under 0% and 400% amount of tension.
Specific embodiment
Below in conjunction with specific implementation case, illustrative explanation and help further understand the present invention, but case study on implementation has Body details does not represent technical solution whole under present inventive concept merely to illustrate the present invention, therefore should not be construed as pair The restriction of the total technical solution of the present invention, it is some for the technician, without departing from present inventive concept unsubstantiality increase and Change, such as simply change or replace with the technical characteristic with same or similar technical effect, belong to present invention protection model It encloses.
1, the preparation of self-healing polyurethane elastomer: polyneopentyl glycol adipate (the equal molecule of number of 10 parts of quality is weighed Measure 2000 g/mol) in three-necked flask, it is heated to 120 DEG C of 1 h of vacuum stirring and carries out water removal operation;It is cooled to reaction unit 70 DEG C, it is filled with argon inert protection gas into vacuum, and the isophorone of 2.8 parts of quality is added into reaction system with syringe The N of diisocyanate and the dibutyl tin laurate of 0.07 part of quality, N '-dimethyl formamide solution continue to be stirred to react 3 h;40 DEG C are cooled to reaction unit, the N of the 2- hydroxyethyl disulfide of 0.96 part of quality, N '-dimethyl first are added thereto Amide solution is stirred to react after 1.5 h and appropriate N is added, and N '-dimethyl formamide reduces reaction viscosity, after the reaction was continued 1.5 h N is added again, N '-dimethyl formamide solution is diluted to ideal concentration, obtains final reacting product.
2, orientation can spin the preparation of carbon nano pipe array: carbon nano pipe array can be spun using chemical vapour deposition technique preparation: By electron beam evaporation deposition method in the successive deposition of aluminium oxide (Al of Si on piece2O3) and iron (Fe), Al2O3As buffer layer, Fe makees For catalyst.Wherein, SiO2Layer is with a thickness of 400 μm, Al2O3Layer is with a thickness of 3 nm, and Fe layers with a thickness of 1.2 nm.Catalysis will be coated with The silicon wafer of agent is put into tube furnace, adjusts ventilation pipe flow are as follows: argon gas: 400sccm;Hydrogen: 30sccm;Ethylene gas: 90sccm.First only to remove the air in pipeline, then opening hydrogen and ethylene, control 15 min of tube furnace within logical argon gas 10 minutes 740 DEG C are risen to from room temperature, then stable 10 min at 740 DEG C, turn off ethylene and hydrogen when program starts voluntarily to cool down, drop It obtains that carbon nano pipe array can be spun after temperature.
3, the preparation of the self-healing transparent electrode of fold-like structures: taking silicone elastomer substrate, and pre-stretching 400% is drawn on it 3 layers of orientation carbon nanotube film, release, which stretches, makes silica gel substrate restore long to original, obtains pleated structure;It is poured in film layer The self-healing polyurethane solutions of synthesis, volatilize solvent using heating, vacuum, obtain finished electrode.
4, the preparation of self-healing light emitting active layer: being 0.2 ~ 2: 1 by electroluminescent powder and polyurethane mixing mass ratio, warp It crosses after solvent volatilizes and obtains finished product film layer.
5, the assembling and preparation of device: self-healing prepared by self-healing transparent electrode and step 4 prepared by step 3 shines Active layer is overlapped with sandwich, i.e. electrode-luminescent layer-electrode mode, and by way of hot-rolling pressure, and 80 DEG C of temperature, pressure Power 10N excludes interlayer bubble, enhances inter-layer bonding force, uses 60 DEG C of heat treatment 12h later, guarantees that interlayer fully achieves point Sub- grade fusion.

Claims (5)

1. a kind of preparation method of the stretchable luminescent device of self-healing, which is characterized in that specific step is as follows:
(1) transparent self-healing elastomer is prepared;
(2) orientation carbon nanotube film is prepared;
(3) preparation has the self-healing transparent electrode material of fold-like structures, and detailed process is as follows:
(a) healing elastomer is derived from as substrate, 1 ~ 3 layer of orientation carbon nanotube film is drawn in pre-stretching 200 ~ 400% on it, Release, which stretches, makes silica gel substrate restore long to original, obtains pleated structure;
(b) the self-healing polyurethane solutions that synthesis is poured in film layer, volatilize solvent using heating, vacuum, obtain finished product electricity Pole;
(4) self-healing luminescence activity layer material is prepared;
(5) by step (3) preparation self-healing transparent electrode material and step (4) preparation self-healing luminescence activity layer material with Sandwich, i.e. electrode-luminescent layer-electrode mode are overlapped, and are pressurizeed by way of hot-rolling pressure, and temperature is 60 DEG C ~ 80 DEG C, Pressure is 5 ~ 10N, excludes interlayer bubble, then heats 12 ~ 18 h at 60 ~ 80 DEG C, guarantees that interlayer fully achieves molecule Grade fusion.
2. preparation method according to claim 1, which is characterized in that preparation self-healing elastomer described in step (1) Detailed process is as follows:
(1) polyneopentyl glycol adipate for weighing 10 parts of quality is placed in three-necked flask, is heated to 100 ~ 150 DEG C, vacuum 1 ~ 2h is stirred, water removal operation is carried out;1000 ~ 3000 g/mol of number-average molecular weight of polyneopentyl glycol adipate;
(2) 60 ~ 80 DEG C are cooled to reaction unit, argon inert protection gas are filled with into vacuum, and with syringe to reactant The N of the isophorone diisocyanate of 2.0 ~ 3.0 parts of quality and the dibutyl tin laurate of 0.05 ~ 1.0 part of quality is added in system, N '-dimethyl formamide solution continues to be stirred to react 3 ~ 4h;
(3) 40 ~ 50 DEG C are cooled to reaction unit, the N of the 2- hydroxyethyl disulfide of 0.8 ~ 1.0 part of quality are added thereto, Appropriate N is added after being stirred to react 1.5 ~ 2 h in N '-dimethyl formamide solution, and N '-dimethyl formamide reduces reaction viscosity, after N is added again after 1.5 ~ 2 h of continuous reaction, N '-dimethyl formamide solution is diluted to ideal concentration, obtains final reacting product.
3. preparation method according to claim 2, which is characterized in that step prepares aligned carbon nanotube described in (2) Film is to carry out dry spinning to aligned carbon nanotube array to obtain orientation carbon nanotube film;Wherein aligned carbon nanotube battle array Column are prepared by chemical vapour deposition technique, and height is multi wall structure at 100-300 μm, and caliber is 5-50 nm.
4. preparation method according to claim 3, which is characterized in that prepare self-healing luminescence activity described in step (4) Layer, be with polyurethane by electroluminescent powder by (0.2 ~ 2): 1 mass ratio mixes, and finished product film layer is obtained after solvent volatilizes; The partial size of used electroluminescent powder is 10 ~ 40 μm.
5. a kind of stretchable luminescent device for the self-healing that the preparation method as described according to claim 1 one of -4 obtains.
CN201810311147.0A 2018-04-09 2018-04-09 A kind of stretchable luminescent device of self-healing and preparation method thereof Active CN108847454B (en)

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CN110105532A (en) * 2019-05-05 2019-08-09 湖北三江航天江河化工科技有限公司 Thermoplasticity selfreparing polyurethane resin and preparation method thereof for 3D printing composite material
CN110246886A (en) * 2019-06-28 2019-09-17 京东方科技集团股份有限公司 A kind of flexible display panels, display device and display methods
CN110591035A (en) * 2019-07-09 2019-12-20 武汉大学 Rapid self-healing polyurethane elastomer with up-conversion fluorescent response and preparation method thereof
WO2021142121A1 (en) * 2020-01-07 2021-07-15 The Regents Of The University Of California High-surface area electrodes for wearable electrochemical biosensing
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