CN109935663A - A kind of preparation method of composite material film and QLED device - Google Patents
A kind of preparation method of composite material film and QLED device Download PDFInfo
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Abstract
The present invention discloses the preparation method and QLED device of a kind of composite material film, and method obtains composite material solution comprising steps of amino-acid modified graphene oxide and PEDOT:PSS are dissolved in organic solvent；Film is made in composite material solution, obtains the composite material film.The existing preferable electric property of composite material that the amino-acid modified graphene oxide of the present invention and PEDOT:PSS are formed, and have lower work function, preferable Ohmic contact is formed with the LUMO of quantum dot light emitting material, to improve hole transport performance.Meanwhile effectively electronics can be stopped to be transferred to cathode from luminescent layer and lead to the electrons and holes combined efficiency for reducing luminescent layer, to improve the Integral luminous and display performance of device.
Description
Technical field
The present invention relates to QLED devices fields more particularly to a kind of composite material film and preparation method thereof and QLED device
Part.
Background technique
In many years in past, conducting polymer (PEDOT:PSS (poly- 3,4-rthylene dioxythiophene/polystyrolsulfon acid
Salt)), self assembly organic molecule and broad-band gap vacuum deposition inorganic, metal oxide (such as: MoO3, V2O5, NiO etc.) and it is widely used in
In terms of the hole transport and injection material of QLED.In addition, special metal fluoride, n-type semiconductor (TiO2, ZnO), N-shaped is organic
Semiconductor (BCP) etc. can be used in electron-transport and the injection material aspect of quantum dot LED.Recently, can and solution mutually process
Metal oxide nanoparticles material (MoO3, V2O5, NiO) and become the hot spot that QLED hole transmission layer is studied.Because
The process of these materials gets rid of expensive hot evaporation technology, and with the roll-to-roll processing procedure skill of continous way that can be mass-produced
Art is mutually compatible with.In terms of QLED functional layer, it is some it is new can liquid phase processing material and thinking be developed.Such as it can water phase
The graphene oxide composite material of dissolution, carbon nano dot material etc..These materials can load other with itself or by chemical modification
Nano particle is used as charge injection or transmission material.
Graphene oxide is a kind of common derivative of graphene.Because there is a large amount of oxygen-containing functional group at edge, for example
Carboxyl, hydroxyl, epoxy group etc., so that graphene oxide dispersibility in water, ethyl alcohol equal solvent is preferable.Graphene or oxidation stone
Black alkene is more promising next-generation transparent conductive film on photoelectric device.Good device performance in order to obtain, electrode and work
Property layer will have preferable level-density parameter, can be improved the transmission rate in electronics or hole in this way.However, the function of graphene oxide
Function is about 5.3 eV, and the work function of graphene is about 4.7 eV, they cannot be with the molecule of most of active material
Level-density parameter.So the work function of regulation graphene or graphene oxide is for by its application, application has in the opto-electronic device
There is important meaning.
Summary of the invention
In view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of composite material film and its preparation sides
Method and QLED device, it is intended to solve existing graphene oxide cannot with the molecular entergy level of most of active material is matched asks
Topic.
Technical scheme is as follows:
A kind of preparation method of composite material film, wherein comprising steps of
Amino-acid modified graphene oxide and PEDOT:PSS are dissolved in organic solvent, composite material solution is obtained；
Film is made in composite material solution, obtains the composite material film.
The preparation method of the composite material film, wherein the preparation side of the amino-acid modified graphene oxide
Method makes amino acid in conjunction with graphene oxide, obtains comprising steps of graphene oxide and amino acid are dissolved in organic solvent
Amino-acid modified graphene oxide.
The preparation method of the composite material film, wherein the preparation side of the amino-acid modified graphene oxide
Method comprising steps of
By graphene oxide and sodium chloroacetate dissolved in alkaline aqueous solution, make graphene oxide and sodium chloroacetate that oxidation occur anti-
It should obtain the graphene oxide of carboxylated；
The graphene oxide of carboxylated and chloride reagent are mixed, the graphene oxide of carboxylated and chloride reagent occurs
Substitution reaction obtains the graphene oxide of chloride；
The graphene oxide of chloride and amino acid are dissolved in organic solvent, the graphene oxide of amino acid and chloride is made
In conjunction with amino-acid modified graphene oxide is made.
The preparation method of the composite material film, wherein the amino acid be selected from alanine, lysine, serine,
Glutamic acid, cysteine, phenylalanine, aspartic acid, asparagine, arginine or tyrosine；
And/or the organic solvent is in methanol, acetonitrile, dimethylformamide, dimethyl sulfoxide and N-Methyl pyrrolidone
It is one or more.
The preparation method of the composite material film, wherein organic molten graphene oxide and amino acid to be dissolved in
Be 1:0.02-0.05 by the molar ratio of the graphene oxide and amino acid in step in agent, by the graphene oxide and
The amino acid is dissolved in organic solvent.
The preparation method of the composite material film, wherein the alkaline aqueous solution is dissolved in aqueous solution by alkali and prepares
It obtains, wherein the alkali is selected from sodium hydroxid, potassium hydroxide, lithium hydroxide or ammonium hydroxide；
And/or the chloride reagent is selected from thionyl chloride, oxalyl chloride, sulfonic acid chloride or thionyl chloride.
The preparation method of the composite material film, wherein by graphene oxide and sodium chloroacetate dissolved in alkalinity
It is 1:0.04-0.06 by the molar ratio of the graphene oxide and sodium chloroacetate, by the oxidation stone in step in aqueous solution
Black alkene and the sodium chloroacetate dissolved are in alkaline aqueous solution；
And/or occur that graphene oxide and sodium chloroacetate in the step of oxidation reaction obtains the graphene oxide of carboxylated,
The temperature of the oxidation reaction is 20-30 DEG C, and the time of the oxidation reaction is 3-5h.
The preparation method of the composite material film, wherein by the graphene oxide and chloride reagent of carboxylated
In the step of mixing, the concentration that the graphene oxide of the carboxylated accounts for chloride reagent is 2-3mg/mL；
And/or makes the graphene oxide of carboxylated and chloride reagent that substitution reaction occur and obtain the graphene oxide of chloride
In step, the temperature of the substitution reaction is 50-70 DEG C, and the time of the substitution reaction is 20-25h；
And/or be dissolved in the step in organic solvent by the graphene oxide of chloride and amino acid, by the chloride
Graphene oxide and amino acid molar ratio be 1:0.02-0.05, by the graphene oxide of the chloride and the amino
Acid dissolution is in organic solvent；
And/or in making the step of amino acid is in conjunction with the graphene oxide of chloride, the temperature of the combination is 80-100 DEG C,
The time of the combination is 20-25h.
The preparation method of the composite material film, wherein by amino-acid modified graphene oxide and PEDOT:
PSS is dissolved in the step in organic solvent, and the mass ratio by the amino-acid modified graphene oxide and PEDOT:PSS is
The amino-acid modified graphene oxide and the PEDOT:PSS are dissolved in organic solvent by 0.01-0.1:1.
A kind of QLED device, including hole transmission layer, wherein the hole transmission layer is method of the present invention preparation
Obtained composite material film.
The utility model has the advantages that the composite material that is formed of the amino-acid modified graphene oxide of the present invention and PEDOT:PSS it is existing compared with
Good electric property, and have lower work function, preferable Ohmic contact is formed with the LUMO of quantum dot light emitting material, to mention
High hole transport performance.Meanwhile effectively electronics can be stopped to be transferred to cathode from luminescent layer and cause to reduce luminescent layer
Electrons and holes combined efficiency, to improve the Integral luminous and display performance of device.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the QLED device containing electron transfer layer of the positive assembling structure of the present invention.
Fig. 2 is the structural schematic diagram of the QLED device containing electron transfer layer of inverted structure of the present invention.
Specific embodiment
The present invention provides a kind of composite material film and preparation method thereof and QLED device, to make the purpose of the present invention, skill
Art scheme and effect are clearer, clear, and the present invention is described in more detail below.It should be appreciated that tool described herein
Body embodiment is only used to explain the present invention, is not intended to limit the present invention.
The present invention provides a kind of preparation method of composite material film, wherein comprising steps of
Amino-acid modified graphene oxide and PEDOT:PSS are dissolved in organic solvent, composite material solution is obtained；
Film is made in composite material solution, obtains the composite material film.
The existing preferable electrical property of composite material that the amino-acid modified graphene oxide of the present invention and PEDOT:PSS are formed
Can, and have lower work function, preferable Ohmic contact is formed with the LUMO of quantum dot light emitting material, to improve hole biography
Defeated performance.Meanwhile effectively electronics can be stopped to be transferred to cathode from luminescent layer and lead to the electronics for reducing luminescent layer and sky
Cave combined efficiency, to improve the Integral luminous and display performance of device.Wherein the PEDOT:PSS is by PEDOT(3,4-
Ethene dioxythiophene monomer) and PSS(poly styrene sulfonate) a kind of aqueous solution of high molecular polymer that constitutes of two kinds of substances.
In a wherein embodiment, the preparation method of the amino-acid modified graphene oxide is comprising steps of by oxygen
Graphite alkene and amino acid are dissolved in organic solvent, make amino acid in conjunction with graphene oxide, obtain amino-acid modified oxygen
Graphite alkene.Amino acid contains amino, carboxyl, and graphene oxide contains carboxyl, epoxy group, hydroxyl, both substances can be
It is directly chemically reacted under certain condition, amino acid is grafted in graphene oxide layer by covalent bond, to obtain ammonia
The modified graphene oxide of base acid.
In a wherein preferred embodiment, the preparation method of the amino-acid modified graphene oxide includes step
It is rapid:
By graphene oxide and sodium chloroacetate dissolved in alkaline aqueous solution, make graphene oxide and sodium chloroacetate that oxidation occur anti-
It should obtain the graphene oxide of carboxylated；
The graphene oxide of carboxylated and chloride reagent are mixed, the graphene oxide of carboxylated and chloride reagent occurs
Substitution reaction obtains the graphene oxide of chloride；
The graphene oxide of chloride and amino acid are dissolved in organic solvent, the graphene oxide of amino acid and chloride is made
In conjunction with amino-acid modified graphene oxide is made.
Amino acid contains amino, carboxyl, and graphene oxide contains carboxyl, epoxy group, hydroxyl, both substances can be one
It is directly chemically reacted under fixed condition, amino acid is grafted in graphene oxide layer by covalent bond.But the present invention is real
Apply the graphene oxide that carboxylated is first made in mode, it is therefore an objective to hydroxyl existing for graphene oxide edge is oxidized to carboxyl, because
It is more active than hydroxyl for carboxyl, it is easier to it is compound with amino acid, to increase the number that amino acid is integrated to surface of graphene oxide
Amount.
Then, by the activated carboxylic in the graphene oxide of carboxylated, particular by chloride reagent and carboxylated
Substitution reaction occurs for graphene oxide, so that-the OH on the graphene oxide edge carboxyl of carboxylated is taken by chloride reagent
In generation, generates the graphene oxide of chloride, and the graphene oxide of the obtained chloride has stronger chemical activity, is easier to
In-the NH with amino acid2Reaction generates amide, to further improve ability of the amino acid in conjunction with graphene oxide.
Amino acid is grafted to the process that graphene oxide is a reduction.When amino acid is grafted on graphene oxide,
The content of O can reduce in amino acid, and the value of C:O can become larger, and amino acid is made to have certain reducing property.Graphene oxide because
To destroy the original perfect sp2 structure of graphene, its electric conductivity being made to be deteriorated containing a large amount of oxygen-containing group, and amino
The reduction of acid has certain contribution to sp2 structure is restored, and has certain help to the recovery of electric conductivity, so, in amino
After acid is grafted to graphene oxide, the more original graphene oxide of amino-acid modified graphene oxide compares, and electric conductivity can become
It is good.
The higher work function (5.3eV) that graphene oxide has, with considering level-density parameter in the opto-electronic device
Problem, high work function are not easy to match with the molecular entergy level of active layer, it is difficult to form Ohmic contact.Amino acid is both sexes dipole
Son ,-COOH is negatively charged ,-NH2Positively charged, which passes through positively charged-NH2Modification is negatively charged in surface of graphene oxide
- COOH deviate from surface of graphene oxide so that foring an interface dipole layer in surface of graphene oxide, direction is by negative electricity
Lotus is directed toward positive charge, i.e. direction graphene oxide, is equivalent to the electric field that added a direction graphene oxide, so that oxidation stone
The interface work function of black alkene reduces.After amino acid modification graphene oxide, so that the work function of graphene oxide has significantly
It reduces, it is minimum to fall below close to 4.0eV, 1.3eV is decreased by, up to 4.5eV is also lower than the work function 4.7eV of graphene
It is some.Therefore the work function of amino-acid modified graphene oxide can be sent out between 4.0~4.5eV in QLED with quantum dot
The LUMO of luminescent material forms preferable Ohmic contact, is easy to electron transfer to electrode, and reduce the compound of electrons and holes, improves
Hole transport efficiency, the performances such as efficiency of device are also improved.
Amino-acid modified graphene oxide can't be used alone on transparent conductive film electrode, on the one hand, because
It is inadequate to the reducing degree of graphene oxide during grafted amino group acid, insufficient, the electric conductivity that sp2 structure is restored
Still it is unsatisfactory for the requirement of membrane electrode；On the other hand, amino-acid modified graphene oxide is the sheet of hundreds of nanometers size
Form, continuous film cannot be formed by being coated in substrate by way of solution, between amino-acid modified graphene oxide not
It can effectively overlap.So the present invention adulterates a certain amount of high-conductivity in amino-acid modified graphene oxide
PEDOT:PSS can improve amino-acid modified graphene oxide on the one hand since the electric conductivity of PEDOT:PSS is very good
Electric conductivity on the other hand PEDOT:PSS is made up of spin coating with amino-acid modified graphene oxide mechanical mixture thin
Film, amino-acid modified graphene oxide and PEDOT are closed by pi-pi bond, since PSS contains electronegative group SO3-, pass through
The composite material that electrostatic repulsion, PEDOT:PSS and amino-acid modified graphene oxide are formed can form stabilization in water
Suspension.
Device of the composite material film that amino-acid modified graphene oxide and PEDOT:PSS is formed as hole transmission layer
Part performance is more preferable than the device performance for individually making hole transmission layer with PEDOT:PSS.Because the energy level band gap of graphene oxide compared with
Width effectively can stop electronics to be transferred to anode from luminescent layer and lead to the compound effect of the electrons and holes for reducing luminescent layer
Rate.The existing preferable electric property of film obtained simultaneously, and can have lower work function, the LUMO with quantum dot light emitting material
Preferable Ohmic contact is formed, hole transport performance is improved, promotes the Integral luminous and display performance of device.
In a wherein embodiment, the amino acid be selected from alanine (Ala), lysine (Lys), serine (Ser),
Glutamic acid (Glu), cysteine (Cys), phenylalanine (Phe), aspartic acid (Asp), asparagine (Asn), arginine
(Arg) or tyrosine (Leu) etc. is without being limited thereto.
In a wherein embodiment, the organic solvent is selected from methanol, acetonitrile, dimethylformamide (DMF), dimethyl
One of sulfoxide (DMSO) and N-Methyl pyrrolidone (NMP) etc. are a variety of.
In a wherein embodiment, the alkaline aqueous solution is dissolved in aqueous solution by alkali and prepares to obtain, wherein the alkali
It is without being limited thereto selected from sodium hydroxid, potassium hydroxide, lithium hydroxide or ammonium hydroxide etc..
In a wherein embodiment, the chloride reagent is selected from thionyl chloride, oxalyl chloride, sulfonic acid chloride or thionyl chloride
Etc. without being limited thereto.
In a wherein embodiment, in the step by graphene oxide and sodium chloroacetate dissolved in alkaline aqueous solution
In, it is 1:0.04-0.06 by the molar ratio of the graphene oxide and sodium chloroacetate, by the graphene oxide and the chloroethene
Sour sodium is dissolved in alkaline aqueous solution.The reaction of graphene oxide and sodium chloroacetate need to carry out under alkaline condition, work as monoxone
When sodium is less, carboxylation reaction is not enough, and when sodium chloroacetate is more, subsequent wash operates more difficult removing.To solution colour
Black is gradually become by the khaki of graphene oxide, illustrates that the hydroxyl of graphene oxide has been converted into carboxyl.
In a wherein embodiment, the oxygen of carboxylated is obtained making graphene oxide and sodium chloroacetate that oxidation reaction occur
In the step of graphite alkene, the temperature of the oxidation reaction is 20-30 DEG C, and the time of the oxidation reaction is 3-5h, at this
Carboxylation reaction is abundant under part.
In a wherein embodiment, in the step of mixing the graphene oxide of carboxylated and chloride reagent, institute
It is 2-3mg/mL that the graphene oxide for stating carboxylated, which accounts for the concentration of chloride reagent, when chloride reagent is less, substitution reaction
It is not enough, when chloride reagent is more, chloride reagent is difficult to remove by evaporation.
In a wherein embodiment, makes the graphene oxide of carboxylated and chloride reagent that substitution reaction occur and obtain acyl
In the step of graphene oxide of chlorination, the temperature of the substitution reaction is 50-70 DEG C, and the time of the substitution reaction is 20-
25h, substitution reaction is abundant under this condition.
In a wherein embodiment, it has been dissolved in by the graphene oxide of graphene oxide or chloride and amino acid
In step in solvent, the molar ratio by the graphene oxide and amino acid of the graphene oxide or chloride is 1:
The graphene oxide and the amino acid of the graphene oxide or chloride are dissolved in organic solvent by 0.02-0.05.When
When amino acid is less, graphene oxide work function reducing effect is unobvious, when amino acid modification is more, surface of graphene oxide
Modified layer is too thick, influences hole transport efficiency.
In a wherein embodiment, in making the step of amino acid is in conjunction with the graphene oxide of chloride, the knot
The temperature of conjunction is 80-100 DEG C, and the time of the combination is 20-25h, under this condition the graphite oxide of amino acid and chloride
Alkene combines abundant.
It is organic molten amino-acid modified graphene oxide and PEDOT:PSS to be dissolved in a wherein embodiment
It is 0.01-0.1:1 by the mass ratio of the amino-acid modified graphene oxide and PEDOT:PSS, by institute in step in agent
It states amino-acid modified graphene oxide and the PEDOT:PSS is dissolved in organic solvent.When amino-acid modified oxidation stone
When black alkene is more, dispersion effect of the amino-acid modified graphene oxide in PEDOT:PSS matrix is bad, Film roughness compared with
Height influences device performance.
It is described in detail below by preparation method of the embodiment to composite material film.
Embodiment one: below to utilize graphene oxide, sodium hydroxide, sodium chloroacetate, thionyl chloride, alanine, diformazan
Base formamide (DMF) describes in detail for preparing composite material film.
(1) 1g graphite powder, 0 .5g sodium nitrate and 3g potassium permanganate the preparation of graphene oxide: are added sequentially to 23mL
In the concentrated sulfuric acid, (temperature is maintained at 10 DEG C or less) stirs 2h in ice-water bath；Then, 35 DEG C are warming up to, continues to stir 30min,
It is slowly added to 150mL deionized water；95 DEG C are heated to, 30min is kept stirring, adds 30% hydrogen peroxide (15mL), while hot mistake
Filter；And washed until sulfate radical-free is detected in filtrate with 5%HCl solution and deionized water, finally by filtration cakes torrefaction；
(2) preparation of the graphene oxide of carboxylated: by 200mg graphene oxide, 10mg sodium hydroxide and 10mg sodium chloroacetate
It is dissolved in 400mL deionized water, room temperature ultrasound 4h, centrifugation 5 times is then washed with deionized, then use salt acid elution 2 times,
Solution is modulated into neutrality, is then washed with deionized again 3 times, finally for 24 hours by 50 DEG C of sample vacuum drying, obtains carboxylated
Graphene oxide；
(3) preparation of the graphene oxide of chloride: the graphene oxide of 50mg carboxylated and 20mL thionyl chloride are mixed,
Reflow treatment is kept the temperature for 24 hours at 60 DEG C.Then by thionyl chloride evaporative removal at 100 DEG C, solid mixture ethanol washing is obtained
To the graphene oxide of chloride；
(4) preparation of amino-acid modified graphene oxide: by the graphene oxide of obtained 30mg chloride and 10 mmol third
Propylhomoserin is dissolved in 30mLDMF, 90 DEG C of insulated and stirreds for 24 hours, then successively with 5 wt% sodium hydroxide solutions, deionized water, ethyl alcohol
Washing for 24 hours by 50 DEG C of sample vacuum drying obtains amino-acid modified graphene oxide；
(5) by 30mg amino-acid modified graphene oxide and appropriate PEDOT:PSS mixing wiring solution-forming (amino-acid modified oxygen
The mass ratio of graphite alkene and PEDOT:PSS are as follows: 1:0.05), form composite material solution；
(6) by composite material sol drop to substrate, 120 DEG C of annealing film forming of spin coating.
Embodiment two: below to utilize graphene oxide, sodium hydroxide, sodium chloroacetate, oxalyl chloride, lysine, dimethyl
Sulfoxide (DMSO) describes in detail for preparing composite material film.
(1) preparation of graphene oxide: with embodiment one；
(2) preparation of the graphene oxide of carboxylated: by 200mg graphene oxide, 10mg sodium hydroxide and 10mg sodium chloroacetate
It is dissolved in 400mL deionized water, room temperature ultrasound 4h, centrifugation 5 times is then washed with deionized, then use salt acid elution 2 times,
Solution is modulated into neutrality, is then washed with deionized again 3 times, finally for 24 hours by 50 DEG C of sample vacuum drying, obtains carboxylated
Graphene oxide；
(3) preparation of the graphene oxide of chloride: the graphene oxide of 50mg carboxylated and 20mL oxalyl chloride are mixed, 60
Reflow treatment is kept the temperature for 24 hours at DEG C.Then by oxalyl chloride evaporative removal at 100 DEG C, acyl is made in solid mixture ethanol washing
The graphene oxide of chlorination；
(4) preparation of amino-acid modified graphene oxide: the graphene oxide of obtained 30mg chloride and 10mmol are relied
Propylhomoserin is dissolved in 30mL DMSO, 90 DEG C of insulated and stirreds for 24 hours, then successively with 5 wt% sodium hydroxide solutions, deionized water, second
For 24 hours by 50 DEG C of sample vacuum drying amino-acid modified graphene oxide is made in alcohol washing；
(5) by 30mg amino-acid modified graphene oxide and appropriate PEDOT:PSS mixing wiring solution-forming (amino-acid modified oxygen
The mass ratio of graphite alkene and PEDOT:PSS are as follows: 1:0.01), form composite material solution；
(6) by composite material sol drop to substrate, 120 DEG C of annealing film forming of spin coating.
Embodiment three: below to utilize graphene oxide, sodium hydroxide, sodium chloroacetate, sulfonic acid chloride, glutamic acid, N- methyl
Pyrrolidones (NMP) describes in detail for preparing composite material film.
(1) preparation of graphene oxide: with embodiment one；
(2) preparation of the graphene oxide of carboxylated: by 200mg graphene oxide, 10mg sodium hydroxide and 10mg sodium chloroacetate
It is dissolved in 400mL deionized water, room temperature ultrasound 4h, centrifugation 5 times is then washed with deionized, then use salt acid elution 2 times,
Solution is modulated into neutrality, is then washed with deionized again 3 times, finally for 24 hours by 50 DEG C of sample vacuum drying, obtains carboxylated
Graphene oxide；
(3) preparation of the graphene oxide of chloride: the graphene oxide of 50mg carboxylated and 20mL sulfonic acid chloride are mixed, 60
Reflow treatment is kept the temperature for 24 hours at DEG C.Then by sulfonic acid chloride evaporative removal at 100 DEG C, solid mixture ethanol washing obtains acyl
The graphene oxide of chlorination；
(4) preparation of amino-acid modified graphene oxide: by the graphene oxide of obtained 30mg chloride and 10mmol paddy
Propylhomoserin be added in 30mLNMP, 90 DEG C of insulated and stirreds for 24 hours, then successively with 5 wt% sodium hydroxide solutions, deionized water, ethyl alcohol
Washing for 24 hours by 50 DEG C of sample vacuum drying obtains amino-acid modified graphene oxide；
(5) by 30mg amino-acid modified graphene oxide and appropriate PEDOT:PSS mixing wiring solution-forming (PEDOT:PSS and ammonia
The mass ratio of the modified graphene oxide of base acid are as follows: 1:0.1), form composite material solution；
(6) by composite material sol drop to substrate, 120 DEG C of annealing film forming of spin coating.
The present invention also provides a kind of composite material films, wherein is prepared using preparation method of the present invention.
The present invention also provides a kind of QLED devices, including hole transmission layer, wherein the hole transmission layer is institute of the present invention
The composite material film stated.
In one embodiment, the QLED device includes the anode of lamination setting, hole transmission layer, quantum dot light emitting
Layer and cathode, wherein the hole transmission layer is composite material film of the present invention.
In a preferred embodiment, the QLED device includes the anode of lamination setting, hole transmission layer, quantum
Point luminescent layer, electron transfer layer and cathode, wherein the hole transmission layer is composite material film of the present invention.
It should be noted that the present invention is not limited to the QLED devices of above structure, can also further comprise interfactial work ergosphere or
One of interface-modifying layer, including but not limited to electronic barrier layer, hole blocking layer, electrode modification layer, isolated protective layer or
It is a variety of.QLED device of the present invention with partial encapsulation, full encapsulation or can not encapsulate.
It elaborates below to the QLED device architecture and preparation method thereof containing electron transfer layer:
According to the difference of the QLED device emission type, the QLED device can be divided into the QLED device of positive assembling structure and fall
The QLED device of assembling structure.
As a wherein embodiment, when the QLED device is positive the QLED device of assembling structure, as shown in Figure 1, institute
State QLED device include from the bottom up lamination setting anode 2(described in 2 lamination of anode be set on substrate 1), hole transmission layer
3, quantum dot light emitting layer 4, electron transfer layer 5 and cathode 6, wherein the hole transmission layer 3 is composite material of the present invention
Film.
As wherein another embodiment, when the QLED device is the QLED device of inverted structure, as shown in Fig. 2,
The QLED device include from the bottom up lamination setting cathode 6(described in 6 lamination of cathode be set on substrate 1), electron-transport
Layer 5, quantum dot light emitting layer 4, hole transmission layer 3 and anode 2, wherein the hole transmission layer 3 is composite wood of the present invention
Expect film.
Preferably, the material of the anode is selected from blended metal oxide；Wherein, the blended metal oxide include but
It is not limited to indium doping tin oxide (ITO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), aluminium-doped zinc oxide
(AZO), Ga-doped zinc oxide (GZO), indium doping zinc oxide (IZO), magnesium doping zinc-oxide (MZO), aluminium doping magnesia (AMO)
One of or it is a variety of.
Preferably, the material of the quantum dot light emitting layer be selected from one of red quantum dot, green quantum dot, blue quantum dot or
It is a variety of, also selected from gold-tinted quantum dot.Specifically, the material of the quantum dot light emitting layer be selected from CdS, CdSe, CdTe, ZnO,
ZnS、ZnSe、ZnTe、GaAs、GaP、GaSb、HgS、HgSe、HgTe、InAs、InP、InSb、AlAs、AlP、CuInS、
CuInSe and one of various nuclear shell structure quantum points or alloy structure quantum dot or a variety of.Quantum dot of the present invention
It can be selected from containing cadmium or without cadmium quantum dot.The quantum dot light emitting layer of the material has exciting light spectrum width and continuously distributed,
The features such as emission spectrum stability is high.
Preferably, the material of the electron transfer layer is selected from the material with good electron transport ability, such as can be
But it is not limited to ZnO, Ca, Ba, CsF, LiF, CsCO3And Alq3One of or it is a variety of.
Preferably, the material of the cathode is in conductive carbon material, conductive metal oxide material and metal material
It is one or more；Wherein conductive carbon material include but is not limited to doped or non-doped carbon nanotube, doped or non-doped graphene,
One of doped or non-doped graphene oxide, C60, graphite, carbon fiber and porous carbon are a variety of；Conductive metal oxide material
Material includes but is not limited to one of ITO, FTO, ATO and AZO or a variety of；Metal material include but is not limited to Al, Ag, Cu, Mo,
Au or their alloy；Wherein in the metal material, form include but is not limited to dense film, nano wire, nanosphere,
One of nanometer rods, nanocone and nano-hollow ball are a variety of.
The present invention also provides a kind of preparation methods of the QLED device containing electron transfer layer of positive assembling structure, including walk as follows
It is rapid:
Substrate containing anode is provided, hole transmission layer is prepared on anode, wherein the hole transmission layer is of the present invention
Composite material film；
Quantum dot light emitting layer is prepared on the hole transport layer；
Electron transfer layer is prepared on quantum dot light emitting layer；
Cathode is prepared on the electron transport layer, obtains QLED device.
The preparation method of above layers can be chemical method or physical method, and wherein chemical method includes but is not limited to chemical gaseous phase
One of sedimentation, successive ionic layer adsorption and reaction method, anodizing, strike, coprecipitation are a variety of；Object
Logos includes but is not limited to physical coating method or solwution method, and wherein solwution method includes but is not limited to spin-coating method, print process, blade coating
Method, dip-coating method, infusion method, spray coating method, roll coating process, casting method, slit coating method, strip rubbing method；Physical coating method
Including but not limited to thermal evaporation coating method, electron beam evaporation deposition method, magnetron sputtering method, multi-arc ion coating embrane method, physical vapor
One of sedimentation, atomic layer deposition method, pulsed laser deposition are a variety of.
As a wherein embodiment, the hole transmission layer of high quality in order to obtain, (such as ITO is conductive for the substrate containing anode
Glass) it needs by pre-treatment step.Specific pre-treatment step includes: to clean full wafer ITO electro-conductive glass with detergent, just
Spot existing for step removal surface, is then successively cleaned by ultrasonic in deionized water, acetone, dehydrated alcohol, deionized water respectively
20 min are finally dried up with high pure nitrogen with removing impurity existing for surface, and ITO electro-conductive glass can be obtained.
It as a wherein embodiment, is specifically included in the step of preparing hole transmission layer on anode: will be prepared
Composite material solution is spun on anode, film forming of then annealing at 100-120 DEG C.It wherein can be by adjusting composite material sol
Concentration, spin speed and the spin-coating time of liquid controls film thickness, it is preferred that the hole transmission layer with a thickness of 20-60nm.
As a wherein embodiment, the step of preparing quantum dot light emitting layer on the hole transport layer, is specifically included: will
The substrate for preparing hole transmission layer is placed on sol evenning machine, will prepare certain density quantum dot light emitting substance solution spin coating at
Film is dried at moderate temperatures.Quantum dot light emitting layer is controlled by adjusting concentration, spin speed and the spin-coating time of solution
Thickness, it is preferred that the quantum dot light emitting layer with a thickness of 20-60 nm.
It as a wherein embodiment, is specifically included in the step of preparing electron transfer layer on quantum dot light emitting layer: will
The substrate for preparing quantum dot light emitting layer is placed in vapor deposition storehouse the electron-transport for passing through one layer of about 70-90nm thickness of mask plate hot evaporation
Layer, evaporation rate is about 0.01 ~ 0.5nm/s.
As a wherein embodiment, the step of preparing cathode on the electron transport layer, is specifically included: will deposit each function
The substrate of ergosphere is placed in vapor deposition storehouse through the metallic silver of one layer of 15-30nm of mask plate hot evaporation or aluminium etc. as cathode, or
Person uses nanometer Ag line or Cu line etc., and there is above-mentioned material lesser resistance carrier is smoothly injected.
The present invention also provides a kind of preparation methods of the QLED device containing electron transfer layer of inverted structure, including walk as follows
It is rapid:
Substrate containing cathode is provided, prepares electron transfer layer on the cathode；
Quantum dot light emitting layer is prepared on the electron transport layer；
Hole transmission layer is prepared on quantum dot light emitting layer, wherein the hole transmission layer is composite material of the present invention
Film；
Anode is prepared on the hole transport layer, obtains QLED device.
The preparation method of above layers can be chemical method or physical method, and wherein chemical method includes but is not limited to chemical gaseous phase
One of sedimentation, successive ionic layer adsorption and reaction method, anodizing, strike, coprecipitation are a variety of；Object
Logos includes but is not limited to physical coating method or solwution method, and wherein solwution method includes but is not limited to spin-coating method, print process, blade coating
Method, dip-coating method, infusion method, spray coating method, roll coating process, casting method, slit coating method, strip rubbing method；Physical coating method
Including but not limited to thermal evaporation coating method, electron beam evaporation deposition method, magnetron sputtering method, multi-arc ion coating embrane method, physical vapor
One of sedimentation, atomic layer deposition method, pulsed laser deposition are a variety of.
It as a wherein embodiment, is specifically included in the step of preparing electron transfer layer on the substrate containing cathode: will
Substrate containing cathode is placed in vapor deposition storehouse the electron transfer layer for passing through one layer of about 70-90nm thickness of mask plate hot evaporation, vapor deposition speed
Degree is about 0.01 ~ 0.5nm/s.
As a wherein embodiment, the step of preparing quantum dot light emitting layer on the electron transport layer, is specifically included: will
The substrate for preparing electron transfer layer is placed on sol evenning machine, will prepare certain density quantum dot light emitting substance solution spin coating at
Film is dried at moderate temperatures.Quantum dot light emitting layer is controlled by adjusting concentration, spin speed and the spin-coating time of solution
Thickness, it is preferred that the quantum dot light emitting layer with a thickness of 20-60 nm.
It as a wherein embodiment, is specifically included in the step of preparing hole transmission layer on quantum dot light emitting layer: will
Prepared composite material solution is spun on quantum dot light emitting layer, film forming of then annealing at 100-120 DEG C.Can wherein it lead to
The concentration, spin speed and spin-coating time of composite material solution are overregulated to control film thickness, it is preferred that the hole transmission layer
With a thickness of 20-60nm.
As a wherein embodiment, the step of preparing anode on the hole transport layer, is specifically included: will deposit each function
The substrate of ergosphere is placed in vapor deposition storehouse through the metallic silver of one layer of 15-30nm of mask plate hot evaporation or aluminium etc. as anode, or
Person uses nanometer Ag line or Cu line etc..
The invention also includes steps: being packaged processing to the obtained QLED device, the encapsulation process can be used
Common machine encapsulation, can also be using encapsulation manually.Preferably, in the environment of the encapsulation process, oxygen content and water content
It is below 0 .1ppm, to guarantee the stability of QLED device.
In conclusion a kind of composite material film provided by the invention and preparation method thereof and QLED device, ammonia of the present invention
The existing preferable electric property of composite material that the modified graphene oxide of base acid and PEDOT:PSS are formed, and have lower function
Function forms preferable Ohmic contact with the LUMO of quantum dot light emitting material, to improve hole transport performance.In addition, ammonia
The composite material that the modified graphene oxide of base acid and PEDOT:PSS are formed effectively can stop electronics from quantum dot light emitting layer
It is transferred to anode and leads to the electrons and holes combined efficiency for reducing quantum dot light emitting layer, to promote the Integral luminous of device
With display performance.
It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can
With improvement or transformation based on the above description, all these modifications and variations all should belong to the guarantor of appended claims of the present invention
Protect range.
Claims (10)
1. a kind of preparation method of composite material film, which is characterized in that comprising steps of
Amino-acid modified graphene oxide and PEDOT:PSS are dissolved in organic solvent, composite material solution is obtained；
Film is made in composite material solution, obtains the composite material film.
2. the preparation method of composite material film according to claim 1, which is characterized in that the amino-acid modified oxygen
The preparation method of graphite alkene makes amino acid and oxygen comprising steps of graphene oxide and amino acid are dissolved in organic solvent
Graphite alkene combines, and obtains amino-acid modified graphene oxide.
3. the preparation method of composite material film according to claim 1, which is characterized in that the amino-acid modified oxygen
The preparation method of graphite alkene comprising steps of
By graphene oxide and sodium chloroacetate dissolved in alkaline aqueous solution, make graphene oxide and sodium chloroacetate that oxidation occur anti-
It should obtain the graphene oxide of carboxylated；
The graphene oxide of carboxylated and chloride reagent are mixed, the graphene oxide of carboxylated and chloride reagent occurs
Substitution reaction obtains the graphene oxide of chloride；
The graphene oxide of chloride and amino acid are dissolved in organic solvent, the graphene oxide of amino acid and chloride is made
In conjunction with amino-acid modified graphene oxide is made.
4. the preparation method of composite material film according to claim 1-3, which is characterized in that the amino acid
Selected from alanine, lysine, serine, glutamic acid, cysteine, phenylalanine, aspartic acid, asparagine, arginine or
Tyrosine；
And/or the organic solvent is in methanol, acetonitrile, dimethylformamide, dimethyl sulfoxide and N-Methyl pyrrolidone
It is one or more.
5. the preparation method of composite material film according to claim 2, which is characterized in that by graphene oxide and ammonia
Base acid dissolution is 1:0.02-0.05 by the molar ratio of the graphene oxide and amino acid in the step in organic solvent, will
The graphene oxide and the amino acid are dissolved in organic solvent.
6. the preparation method of composite material film according to claim 3, which is characterized in that the alkaline aqueous solution is by alkali
It is dissolved in aqueous solution to prepare to obtain, wherein the alkali is selected from sodium hydroxid, potassium hydroxide, lithium hydroxide or ammonium hydroxide；
And/or the chloride reagent is selected from thionyl chloride, oxalyl chloride, sulfonic acid chloride or thionyl chloride.
7. the preparation method of composite material film according to claim 3, which is characterized in that by graphene oxide and chlorine
Sodium acetate is dissolved in the step in alkaline aqueous solution, is 1:0.04- by the molar ratio of the graphene oxide and sodium chloroacetate
0.06, by the graphene oxide and the sodium chloroacetate dissolved in alkaline aqueous solution；
And/or occur that graphene oxide and sodium chloroacetate in the step of oxidation reaction obtains the graphene oxide of carboxylated,
The temperature of the oxidation reaction is 20-30 DEG C, and the time of the oxidation reaction is 3-5h.
8. the preparation method of composite material film according to claim 3, which is characterized in that by the oxidation stone of carboxylated
In the step of black alkene and chloride reagent mix, the concentration that the graphene oxide of the carboxylated accounts for chloride reagent is 2-3mg/
mL；
And/or makes the graphene oxide of carboxylated and chloride reagent that substitution reaction occur and obtain the graphene oxide of chloride
In step, the temperature of the substitution reaction is 50-70 DEG C, and the time of the substitution reaction is 20-25h；
And/or be dissolved in the step in organic solvent by the graphene oxide of chloride and amino acid, by the chloride
Graphene oxide and amino acid molar ratio be 1:0.02-0.05, by the graphene oxide of the chloride and the amino
Acid dissolution is in organic solvent；
And/or in making the step of amino acid is in conjunction with the graphene oxide of chloride, the temperature of the combination is 80-100 DEG C,
The time of the combination is 20-25h.
9. the preparation method of composite material film according to claim 1-3, which is characterized in that by amino acid
Modified graphene oxide and PEDOT:PSS is dissolved in the step in organic solvent, by the amino-acid modified oxidation stone
The mass ratio of black alkene and PEDOT:PSS are 0.01-0.1:1, by the amino-acid modified graphene oxide and the PEDOT:
PSS is dissolved in organic solvent.
10. a kind of QLED device, including hole transmission layer, which is characterized in that the hole transmission layer is that claim 1-9 is any
The composite material film that method described in is prepared.
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