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.