CN106299117A - There is sulfonated graphene conductive high molecular dispersion liquid, its preparation method and the application of anisotropy carrier mobility - Google Patents
There is sulfonated graphene conductive high molecular dispersion liquid, its preparation method and the application of anisotropy carrier mobility Download PDFInfo
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Abstract
The invention discloses a kind of sulfonated graphene conductive high molecular dispersion liquid with anisotropy carrier mobility, it comprises sulfonated graphene, to anion, conducting polymer and solvent etc..The invention also discloses method and the application thereof of the sulfonated graphene conductive high molecular dispersion liquid described in a kind of preparation with anisotropy carrier mobility.The sulfonated graphene conductive high molecular dispersion liquid with anisotropy carrier mobility that the present invention provides has the advantages such as stability height and good film-forming property, and the film that formed by it or coating have that light transmission is good and anisotropic carrier mobility (such as, the carrier mobility with film or coated facet parallel direction is 10‑5～10‑2cm2V‑1s‑1, it is 0.1～10cm with the carrier mobility of film or coated facet vertical direction2V‑1s‑1) etc. advantage, its preparation technology is simple simultaneously, it is easy to operation, controllability is good, is suitable to large-scale production, is suitably applied the photoelectric device such as organic solar batteries and Organic Light Emitting Diode.
Description
Technical field
The present invention be more particularly directed to a kind of sulfonated graphene-conducting polymer dispersion liquid, its preparation method and application, belong to material
Material scientific domain.
Background technology
With organic electroluminescence device (OLED), organic photovoltaic devices (OPV) and organic field effect tube (OTFT) it is
Represent organic photoelectric functional device show at novel flat-plate, solid state lighting, Flexible Displays, high density information transmission with store,
The fields such as new forms of energy and photochemistry utilization have manifested wide application prospect, by scientific circles and the common concern of industrial circle.But
It is that organic optoelectronic still has series of problems urgently to be resolved hurrily at the aspect such as material, effect, and these problems are the most considerably made
About organic photoelectric functional material and the technology development in industrialization direction.
As a example by OLED, the effect because of extra electric field is being had by its electronics mainly produced by negative electrode and anode with hole
Machine luminescent layer moves and produces in conjunction with, excite light emitting molecule in organic luminous layer luminous to give off energy.Therefore,
The luminous efficiency of Organic Light Emitting Diode generally depends on whether electronics effectively can be combined with hole in organic luminous layer.So
And, due to have between each film (layer) of OLED can jump, and electronics is different from the transmission speed in hole, it tends to be difficult to electronics and
Effectively controlling in conjunction with providing of hole.
Again as a example by OPV, it does not the most possess directive built in field, and therefore electronics and hole are the most specifically floated
The diffusion that shifting movement direction, electronics and hole are caused at the direction of motion mainly Concentraton gradient of photoactive layer.So at electrode
Hole be the same in concentration with electronics.But owing to the work function of two electrodes is different, hole is tended to be transmitted to merit
Function then tends to be transmitted to work function close to N-shaped close to the electrode of the HOMO highest occupied molecular orbital HOMO energy level of p-type material, electronics
The electrode of material lowest unoccupied molecular orbital lumo energy, thus define the electric current of outwards output.With anodic oxidation indium stannum ITO it is
Example, the work content of ITO between 4.8eV to 5.0eV, is therefore diffused into that the carrier majority of ITO is hole and minority is electronics, expands
The hole being scattered to ITO forms effective current, and the electronics being diffused into ITO then can a part of hole of cancellation.
To this end, industry is it is generally required to arrange hole transmission layer between anode and active layer.It is usually used in hole transport at present
The material of layer is poly-3,4-ethylene dioxythiophene PEDOT: poly styrene sulfonate PSS, but PEDOT:PSS has acidity, right
Having corrosiveness in anode (such as ITO), will have a strong impact on the life-span of organic electro-optic device, significantly this type of hole passes
Defeated layer is on the low side in the carrier mobility being perpendicular to thin film planar direction, it is therefore necessary to has certain thickness and (usually counts
Nm to tens of nm) just can effectively stop electronics, but this can increase the series resistance of device.
Summary of the invention
A kind of sulfonated graphene-conduction with anisotropy carrier mobility of offer is provided
High molecular dispersion liquid and preparation method and application, to overcome deficiency of the prior art.
For realizing aforementioned invention purpose, the technical solution used in the present invention includes:
Embodiments provide a kind of sulfonated graphene-conducting polymer with anisotropy carrier mobility
Dispersion liquid, it comprises sulfonated graphene, to anion, conducting polymer and solvent, and described solvent is at least in order to dispersed
And/or dissolve remaining component in described dispersion liquid and form uniform dispersion.
In some embodiments, in described sulfonated graphene sulfonic content with the mol ratio of carbon Yu element sulphur
It is expressed as 120:1～1:1, preferably 60:1～2:1, preferably 30:1～3:1, preferably 18:1～6:1.
In some embodiments, the radial dimension of described sulfonated graphene is 1 μm～100 μm, preferably 5 μm～80 μ
M, preferably 20 μm～60 μm.
In some embodiments, the thickness of described sulfonated graphene is 0.3nm～50nm, preferably 0.3nm～10nm,
It is preferably 0.3nm～2nm.
In some embodiments, described conducting polymer includes any one in polypyrrole, polythiophene and polyaniline
Or any one derivant, but it is not limited to this.
In some embodiments, described anion at least deriving from polystyrolsulfon acid, camphorsulfonic acid, to methylbenzene
Sulfonic acid, LOMAR PWA EINECS 246-676-2, anthraquinone sulfonic acid, any one in sulphuric acid, but it is not limited to this.Preferably, described to source of anions in poly-
Styrene sulfonic acid.
In some embodiments, described conducting polymer and the mass ratio to anion are 1:1～1:100, are preferably
1:1～1:50, preferably 1:1～1:20, preferably 1:1～1:10.
In some embodiments, the solid content in described dispersion liquid is 0.5wt%～30wt%, preferably 0.8wt%
～10wt%, preferably 1wt%～5wt%.
In some embodiments, described sulfonated graphene and the mass ratio to anion are 1:1000～1000:1, excellent
Elect 1:100～100:1 as, preferably 1:10～10:1, preferably 1:2～2:1.
In some embodiments, the radial dimension of described sulfonated graphene and the particle diameter of conducting polymer than for 5:1～
5000:1, preferably 10:1～500:1, preferably 50:1～100:1.
In some embodiments, described solvent includes water, but is not limited to this.
The embodiment of the present invention additionally provides a kind of sulfonated graphene-conductive polymer with anisotropy carrier mobility
The preparation method of sub-dispersion liquid, comprising:
By sulfonated graphene, being used for providing source material and initiator to anion to be sufficiently mixed in a solvent, formation contains
Initiator and the sulfonated graphene dispersion liquid to anion；
Sulfonated graphene in making described sulfonated graphene dispersion liquid keep scattered in the case of, to described sulfonated graphite
After adding conductive high polymer monomer, fully reaction in alkene dispersion liquid, it is thus achieved that comprise sulfonated graphene, to anion and conductive polymer
There is described in Zi the sulfonated graphene-conducting polymer dispersion liquid of anisotropy carrier mobility.
In some embodiments, described preparation method includes:
By sulfonated graphene and be used for providing the source material of anion is dispersed in solvent after add initiator,
At 1～25 DEG C continuously stirred 5～120 minutes, formed containing initiator and the sulfonated graphene dispersion liquid to anion；
By the described sulfonated graphene dispersion liquid containing initiator ultrasonic disperse 15～120 minutes at 1～10 DEG C, and protecting
In protective atmosphere, in described sulfonated graphene dispersion liquid, it is slowly added to conducting polymer list under conditions of holding ultrasonic disperse
Body, continues ultrasonic disperse 6～72h afterwards, it is thus achieved that described in there is the sulfonated graphene of anisotropy carrier mobility-conduction height
Molecular dispersions.
In some embodiments, described preparation method also includes: have anisotropy carrier described at least removing
Foreign ion in the sulfonated graphene of mobility-conducting polymer dispersion liquid, and there is anisotropy carrier described in making and move
Solid content in the sulfonated graphene of shifting rate-conducting polymer dispersion liquid is 0.5wt%～30wt%, preferably 0.8wt%～
10wt%, preferably 1wt%～5wt%.
In some embodiments, in described sulfonated graphene sulfonic content with the mol ratio of carbon Yu element sulphur
It is expressed as 120:1～1:1, is preferably expressed as 60:1～2:1, be preferably expressed as 30:1～3:1, be preferably expressed as 18:1～6:1.
In some embodiments, the radial dimension of described sulfonated graphene is 1 μm～100 μm, preferably 5 μm～80 μ
M, preferably 20 μm～60 μm.
In some embodiments, the thickness of described sulfonated graphene is 0.3nm～50nm, preferably 0.3nm～10nm,
It is preferably 0.3nm～2nm.
In some embodiments, described conductive high polymer monomer include in pyrroles, thiophene and aniline any one or
Any one derivant, but it is not limited to this.
In some embodiments, described for providing the source material to anion to include polystyrolsulfon acid, Camphora sulphur
Acid, p-methyl benzenesulfonic acid, LOMAR PWA EINECS 246-676-2, anthraquinone sulfonic acid, any one in sulphuric acid, it is preferred that described to source of anions in poly-
Styrene sulfonic acid, but it is not limited to this.
In some embodiments, described conducting polymer and the mass ratio to anion are 1:1～1:100, are preferably
1:1～1:50, preferably 1:1～1:20, preferably 1:1～1:10.
In some embodiments, described sulfonated graphene and the mass ratio to anion are 1:1000～1000:1, excellent
Elect 1:100～100:1 as, preferably 1:10～10:1, preferably 1:2～2:1.
In some embodiments, the radial dimension of described sulfonated graphene and the particle diameter of conducting polymer than for 5:1～
5000:1, preferably 10:1～500:1, preferably 50:1～100:1.
In some embodiments, described solvent includes water, but is not limited to this.
In some embodiments, described containing the containing of initiator in initiator and the sulfonated graphene dispersion liquid to anion
Amount is 0.1wt%～5wt%, preferably 0.3wt%～3wt%, preferably 0.5wt%～1wt%.
In some embodiments, described initiator includes Ammonium persulfate., potassium peroxydisulfate, sodium peroxydisulfate, iron chloride, sulphuric acid
Any one or two or more combination in ferrum and hydrogen peroxide, but it is not limited to this.
In some embodiments, described containing in initiator and the sulfonated graphene dispersion liquid to anion to anion
Content is 0.1wt%～5wt%, preferably 0.3wt%～3wt%, preferably 0.5wt%～1wt%.
In some embodiments, described protective atmosphere at least selects inert atmosphere, such as argon gas atmosphere, the most also may be used
To be nitrogen atmosphere etc..
The embodiment of the present invention additionally provides a class film or the preparation method of coating, comprising: each to different to described having
Property carrier mobility sulfonated graphene-conducting polymer dispersion liquid carry out film forming process, prepare described film or coating.
In some embodiments, described preparation method includes: at least select any one in coating, mode of printing to become
The described sulfonated graphene with anisotropy carrier mobility-conducting polymer dispersion liquid is applied to matrix by film mode
Upper also film forming, prepares described film or coating.
Coating method therein include trowelling, spin coating, spray, blade coating etc., mode of printing includes silk screen printing, inkjet printing
Etc., but it is not limited to this.
Wherein, the material of described matrix is selected from inorganic and/or organic material, be for example, at least selected from glass, monometallic,
Any one in metal alloy, ITO, PP, PE, PET and PEN, but it is not limited to this.
The embodiment of the present invention additionally provides class film or a coating, comprises sulfonated graphene, to anion and conducting polymer,
And described film or coating are being 10 with the carrier mobility on film or coated facet parallel direction-5～10-2cm2V-1s-1, excellent
Elect 10 as-4～10-2cm2V-1s-1, preferably 10-3～10-2cm2V-1s-1, and with the load on film or coated facet vertical direction
Stream transport factor is 0.1～10cm2V-1s-1, preferably 1～10cm2V-1s-1, preferably 2～5cm2V-1s-1。
Further, described film or coating by the described sulfonated graphene with anisotropy carrier mobility-
Conducting polymer dispersion liquid is formed or is prepared by the preparation method of any one film aforesaid or coating and formed.
It is high that the embodiment of the present invention additionally provides the described sulfonated graphene with anisotropy carrier mobility-conduction
Molecular dispersions or described film or coating, in the purposes prepared in photoelectric device, are particularly preparing electrode material or electrode modification
Purposes in material, the particularly purposes in preparing hole transmission layer.
Further, described photoelectric device includes organic electro-optic device, it is preferred that described organic electro-optic device includes organic
Solaode or Organic Light Emitting Diode (OLED).
The embodiment of the present invention additionally provides products similar, comprises described film or coating.
Further, described goods include photoelectric device, it is preferred that described photoelectric device includes organic electro-optic device, excellent
Choosing, described organic electro-optic device includes organic solar batteries or Organic Light Emitting Diode.
Further, described goods can be light fixture, electric type equipment, photovoltaic module etc..In merit in these goods
Described film or coating (as hole transmission layer etc.) can be distributed on the anode of element.
Than prior art, the sulfonated graphene with anisotropy carrier mobility that the present invention provides-conduction is high
Molecular dispersions has that stability is high and the advantage such as film property, and the film that formed by it or coating have light transmission good and each to
The advantages such as the carrier mobility of the opposite sex, its preparation technology is simple simultaneously, it is easy to operation, and controllability is good, is suitable to large-scale production,
It is suitably applied the photoelectric device such as organic solar batteries and Organic Light Emitting Diode.
Accompanying drawing explanation
Fig. 1 a and Fig. 1 b be respectively the present invention an exemplary embodiments in one be not added with sulfonated graphene and added sulphur
The dried shape appearance figure of conducting polymer dispersion liquid of functionalized graphene.
Fig. 2 a and Fig. 2 b is the profile that the coating in some exemplary embodiments of the present invention is coated to glass surface respectively.
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearer, below in conjunction with some embodiments, to this
Invention is further elaborated.Should be appreciated that specific embodiment described herein, and need not only in order to explain the present invention
In limiting the present invention.As long as additionally, technical characteristic involved in each embodiment of invention described below is each other
Between do not constitute conflict and just can be mutually combined, thus constitute new or preferred technical scheme.As space is limited, the most another at this
One tired states.
The various raw materials addressed in the various embodiments of the invention all can be obtained by market approach, and some of them are former
Material, example sulfonated graphene as mentioned (i.e. having sulfonic Graphene) also can be according to the conjunction known known to those skilled in the art
Suitable mode is prepared and (such as Graphene and oleum, chlorosulfonic acid etc. is reacted formation jointly, refering to literary compositions such as CN103539105A
Offer), and each class testing equipment related to, all can select known in the art knowing and usual model.
Postscript, the composition of the various products employed in below embodiment and/or structural parameters, various reaction participation
Thing and process conditions are all more typical examples, but verify through inventor's lot of experiments, in those listed above its
Its Different structural parameters, other type of reaction partner and other process conditions are the most all applicable, and also equal attainable cost
The technique effect that invention is claimed.
One aspect of the embodiment of the present invention provide a class have the sulfonated graphene of anisotropy carrier mobility-
Conducting polymer dispersion liquid, it is mainly by sulfonated graphene, uniformly dividing anion, conducting polymer and solvent formation
Dissipate liquid.
The radial dimension of aforementioned sulfonated graphene is 1 μm～100 μm, preferably 5 μm～80 μm, preferably 20 μm～60 μ
M, thickness is 0.3nm～50nm, preferably 0.3nm～10nm, preferably 0.3nm～2nm.
Further, in described sulfonated graphene, sulfonic content is expressed as 120:1 with the mol ratio of carbon Yu element sulphur
～1:1, it is preferably expressed as 60:1～2:1, is preferably expressed as 30:1～3:1, be preferably expressed as 18:1～6:1.
Aforesaid conductive macromolecule is selected from the derivant of polypyrrole, polythiophene, polyaniline and this three, accordingly, and these
The monomer of the conducting polymer at least preferably (ginseng of any one or any one the derivant in pyrroles, thiophene and aniline
Read " preparation of polyaniline derivative and performance study ", Zhang Lin, Heilongjiang University's master thesis, in June, 2010；" poly-pyrrole
Cough up and the progress of copolymer ", " polymer material science and engineering ", in July, 2011, the 7th phase of volume 27；" conduction height
Molecule polythiophene and the progress of derivant thereof ", " material Leader ", the 1st phase of volume 20 in January, 2006), but it is not limited to this.
The radial dimension of aforementioned sulfonated graphene can be 5:1～5000:1 with the particle diameter ratio of conducting polymer, is preferably
10:1～500:1, preferably 50:1～100:1.
Aforementioned anion at least can be derived from polystyrolsulfon acid, camphorsulfonic acid, p-methyl benzenesulfonic acid, LOMAR PWA EINECS 246-676-2, anthracene
Quinone sulfonic acid, any one in sulphuric acid, but it is not limited to this.
Aforementioned sulfonated graphene with to the mass ratio of anion can be 1:1000～1000:1, preferably 1:100～
100:1, preferably 1:10～10:1, preferably 1:2～2:1.
Solid content in aforementioned dispersion liquid is 0.5wt%～30wt%, preferably 0.8wt%～10wt%, is preferably
1wt%～5wt%.
Aforementioned solvents preferably uses water, and it has the advantage such as low cost, environmental protection.Certainly for the need of some actual application
Ask, it is possible to mix or substitute with alcohols, ethers, hydro carbons, ketones solvent etc..
Sulfonated graphene-the conduction to this type of related in the embodiment of the present invention with anisotropy carrier mobility is high
Molecular dispersions is observed, it is found that it is all for uniform and stable dispersion liquid, and color is light blue, at room temperature condition
Under can stand up to six months and substantially to occur without sedimentation phenomenon.It addition, this type of is had anisotropy carrier mobility
The viscosity etc. of sulfonated graphene-conducting polymer dispersion liquid is observed, it appeared that its viscosity generally 10-5000cp it
Between, therefore there is the best mobility, be beneficial to be transmitted by pump, pipeline etc., and be beneficial to film forming device, printing device, spray
Automatic doubler surface glouers etc. carry out film forming process, therefore adapt to the demand of large-scale production.
The aforementioned sulfonation with anisotropy carrier mobility is prepared in another aspect provides of the embodiment of the present invention
The method of Graphene-conducting polymer dispersion liquid, comprising:
By sulfonated graphene, being used for providing source material and initiator to anion to be sufficiently mixed in a solvent, formation contains
Initiator and the sulfonated graphene dispersion liquid to anion；
Sulfonated graphene in making described sulfonated graphene dispersion liquid keep scattered in the case of, to described sulfonated graphite
After adding conductive high polymer monomer, fully reaction in alkene dispersion liquid, it is thus achieved that comprise sulfonated graphene, to anion and conductive polymer
There is described in Zi the sulfonated graphene-conducting polymer dispersion liquid of anisotropy carrier mobility.
In some more specific embodiment, described preparation method may include that
Initiator is added, at suitable temperature (such as 1 after sulfonated graphene and aforesaid source material being dispersed in water
～25 DEG C) under continuously stirred certain time (such as 5～120 minutes), formed containing initiator and the sulfonated graphene to anion
Dispersion liquid；
By certain for the described sulfonated graphene dispersion liquid containing initiator ultrasonic disperse under suitable temperature (such as 1～10 DEG C)
Time (such as 15～120min), and keeping under conditions of ultrasonic disperse in protective atmosphere to described containing initiator with right
It is slowly added to (such as drip or be slowly injected into) conductive high polymer monomer in the sulfonated graphene dispersion liquid of anion, continues afterwards
Ultrasonic disperse certain time (such as 6～72h), it is thus achieved that the sulfonated graphene-conduction with anisotropy carrier mobility is high
The thick liquid of molecular dispersions；
And, the sulfonated graphene-conducting polymer dispersion liquid described in removing with anisotropy carrier mobility is thick
Foreign ion in liquid, and form the uniform dispersion with suitable solid content (such as 0.5wt%～30wt%), it is described
There is the sulfonated graphene-conducting polymer dispersion liquid of anisotropy carrier mobility.
Aforesaid conductive high polymer monomer can as it was noted above, selected from pyrroles, in thiophene and aniline any one or arbitrarily
A kind of derivant etc., but it is not limited to this.
It is previously used for providing the source material to anion to include polystyrolsulfon acid, camphorsulfonic acid, p-methyl benzenesulfonic acid, naphthalene
Sulfonic acid, anthraquinone sulfonic acid, any one in sulphuric acid, it is preferred that described to source of anions in polystyrolsulfon acid, but be not limited to
This.
Aforementioned containing the content of initiator in initiator and the sulfonated graphene dispersion liquid to anion be 0.1wt%～
5wt%, preferably 0.3wt%～3wt%, preferably 0.5wt%～1wt%.
Foregoing initiators is selected from Ammonium persulfate., potassium peroxydisulfate, sodium peroxydisulfate, iron chloride, iron sulfate and hydrogen peroxide
Any one or two or more combination, but it is not limited to this.
Aforementioned containing content to anion in initiator and the sulfonated graphene dispersion liquid to anion be 0.1wt%～
5wt%, preferably 0.3wt%～3wt%, preferably 0.5wt%～1wt%.
Aforementioned protective atmosphere at least selects inert atmosphere, such as argon gas atmosphere, naturally it is also possible to be nitrogen atmosphere etc..
In aforementioned preparation process, can with select the mode such as dialysis remove described in there is the sulphur of anisotropy carrier mobility
Foreign ion etc. in functionalized graphene-thick liquid of conducting polymer dispersion liquid.
In aforementioned preparation process, can by the modes such as evaporation, dialysis remove described in there is anisotropy carrier mobility
Partial solvent in the sulfonated graphene of rate-conducting polymer dispersion liquid so that it is solid content reaches required scope.
Another aspect of the embodiment of the present invention additionally provides the aforementioned sulfonation stone with anisotropy carrier mobility
The purposes of ink alkene-conducting polymer dispersion liquid, includes but not limited to the purposes in preparing film, coating or photoelectric device.
Such as, the preparation method of a class film or coating may include that have anisotropy carrier mobility to aforesaid
Sulfonated graphene-conducting polymer dispersion liquid carry out film forming process, prepare described film or coating.
Wherein, available thin film-forming method includes coating (trowelling, spin coating, spray, blade coating etc.), mode of printing (screen printing
Brush, inkjet printing etc.) etc., but it is not limited to this, can also be such as the modes such as casting film-forming.
For example, it is possible to by the aforesaid sulfonated graphene-conducting polymer dispersion with anisotropy carrier mobility
Liquid is uniformly applied to matrix surface, is dried 5～30min afterwards, is allowed to solidify to form film or painting between 100～150 DEG C
Layer.
The material of aforementioned substrates is selected from inorganic and/or organic material, is for example, at least selected from glass, monometallic, metal
Any one in alloy, ITO, PP, PE, PET and PEN, but it is not limited to this.
Refer to one in the exemplary embodiments that Fig. 1 a and Fig. 1 b is the present invention be not added with sulfonated graphene and added
The dried shape appearance figure of conducting polymer dispersion liquid of sulfonated graphene.It is not added with the conductive polymer solution master of sulfonated graphene
Want composition and index as follows: poly-(3,4-rthylene dioxythiophene): polyphenyl ethyl sulfonic acid aqueous solution, solid content be about 1% (if not following
Special instruction, then be wt%), the content of polystyrolsulfon acid is about 0.75%.Add the conductive polymer of sulfonated graphene
Sub-main component in solution and index are as follows: poly-(3,4-rthylene dioxythiophene): polyphenyl ethyl sulfonic acid/sulfonated graphite aqueous solution, Gu
Content is about 1%, and the content of polystyrolsulfon acid is about 0.4%, and the content of sulfonated graphene is about 0.35%, sulfonated graphene
Thickness be about 1nm, radial dimension is about 40 μm, and in sulfonated graphene, the mol ratio of carbon and element sulphur is about 12:1, sulphur
Functionalized graphene and poly-(3,4-ethene dioxythiophene): the particle diameter of polyphenyl ethyl sulfonic acid is than about 500:1.
To this type of film related in the embodiment of the present invention or coating (the embodiment film in such as Fig. 2 a-Fig. 2 b) at such as glass
The section pattern of the matrix surfaces such as glass is observed, it is found that its section is smooth bright and clean, basic flawless, and thickness is homogeneous, sulphur
Functionalized graphene is uniformly distributed at film or coat inside, and is tightly combined with matrix, without obvious combination interface.Wherein in Fig. 1 b film or
The cross sectional photograph of coating see Fig. 2 a-Fig. 2 b.
Again the carrier mobility etc. of this type of film or coating is tested, it appeared that it is being put down with film or coated facet
Carrier mobility on line direction is 10-5～10-2cm2V-1s-1, preferably 10-4～10-2cm2V-1s-1, preferably 10-3~
10-2cm2V-1s-1, and be 0.1～10cm with the carrier mobility on film or coated facet vertical direction2V-1s-1, it is preferably
1～10cm2V-1s-1, preferably 2～5cm2V-1s-1。
It is for instance possible to use aforesaid film or coating production, with aforesaid, there is anisotropy carrier mobility
Sulfonated graphene-conducting polymer dispersion liquid electrode in photoelectric device, particularly organic electro-optic device (particularly sun
Pole) and functional layer (active layer etc.) between form the film as hole transmission layer or coating, or, directly with described film or painting
Layer is as the electrode in photoelectric device.
Aforementioned organic electro-optic device includes organic solar batteries or Organic Light Emitting Diode (OLED).
Such as, a kind of typical OLED sample can include anode, the hole transmission layer being formed on this anode, be located at this
Organic luminous layer, the electron transfer layer being located on this organic luminous layer on hole transmission layer, it is located on this electron transfer layer
Electron injecting layer, is located at the negative electrode etc. on this electron injecting layer.
Wherein, the material of luminescent layer can be little molecule luminous organic material or macromolecule/polymer luminescent material,
Dissimilar to form little molecule Organic Light Emitting Diode (SM-OLED) or macromolecule Organic Light Emitting Diode (PLED) etc. respectively
Organic luminescent assembly.The material of electron transfer layer can be trimerization benzimidazole (TPBi).The material of electron injecting layer can be fluorine
Change lithium (LiF).Anode, the material of negative electrode can be metal or alloy, lead including aluminum, calcium, magnesium, indium, stannum, manganese, chromium, copper, silver, gold etc.
The most preferably metal or its alloy.
Wherein, foregoing hole transport layer selects aforesaid film or coating.
As a comparison, PEDOT:PSS thin film is used to substitute aforesaid film or the coating hole biography as aforementioned OLED sample
Defeated layer.
By the performance of the two class OLED samples being consequently formed is tested, it appeared that use hole transport of the present invention
The current efficiency of layer reaches as high as 0.9cd/A, and uses the hole transmission layer current efficiency of PEDOT:PSS thin film to be only 0.2cd/
A。
The most such as, a kind of typical organic solar batteries can be made up of llowing group of materials layer successively: anode, hole transport
Layer, carrier produces layer, electron transfer layer, electronic barrier layer, negative electrode.
Aforesaid anode can be ITO, or is made up of gold evaporation, nickel or nickel oxide layer on ITO.Aforementioned carrier produces layer can be by
CuPc and C60 of coevaporation or CuPc and the PTCBI composition of coevaporation.Aforementioned electronic transport layer can be C60 or PTCBI.Aforementioned
Electronic barrier layer can be BCP or AlQ3.Said cathode can be Al, Ag or magnesium silver alloy.
Wherein, foregoing hole transport layer selects aforesaid film or coating.
As a comparison, PEDOT:PSS thin film is used to substitute aforesaid film or coating as aforementioned organic solar batteries
Hole transmission layer.
By the performance of the two class organic solar batteries being consequently formed is tested, it appeared that use the present invention empty
The conversion efficiency of cave transport layer is averagely up to 5%, and uses PEDOT:PSS thin film the highest as the conversion efficiency of hole transmission layer
It is only 3%.
It should be noted last that, above example is only in order to illustrate technical scheme and unrestricted.Although ginseng
According to embodiment, the present invention is described in detail, it will be understood by those within the art that, the technical side to the present invention
Case is modified or equivalent, and without departure from the spirit and scope of technical solution of the present invention, it all should be contained in the present invention
Right in the middle of.
Claims (23)
1. sulfonated graphene-conducting polymer dispersion liquid with anisotropy carrier mobility, it is characterised in that bag
Containing sulfonated graphene, to anion, conducting polymer and solvent, described solvent is at least in order to dispersed and/or dissolving institute
State remaining component in dispersion liquid and form uniform dispersion.
Dispersion liquid the most according to claim 1, it is characterised in that: in described sulfonated graphene, sulfonic content is with carbon unit
Element is expressed as 120:1～1:1 with the mol ratio of element sulphur, is preferably expressed as 60:1～2:1, is preferably expressed as 30:1～3:1, excellent
Choosing is expressed as 18:1～6:1.
Dispersion liquid the most according to claim 1, it is characterised in that: the radial dimension of described sulfonated graphene is 1 μm～100
μm, preferably 5 μm～80 μm, preferably 20 μm～60 μm.And/or, the thickness of described sulfonated graphene is 0.3nm～50nm,
It is preferably 0.3nm～10nm, preferably 0.3nm～2nm.
Dispersion liquid the most according to claim 1, it is characterised in that: described conducting polymer includes polypyrrole, polythiophene and
Any one or any one derivant in polyaniline.
Dispersion liquid the most according to claim 1, it is characterised in that: described anion is at least derived from polystyrene sulphur
Acid, camphorsulfonic acid, p-methyl benzenesulfonic acid, LOMAR PWA EINECS 246-676-2, anthraquinone sulfonic acid, any one in sulphuric acid, it is preferred that described to anion
Derive from polystyrolsulfon acid.
Dispersion liquid the most according to claim 1, it is characterised in that: described solvent includes water.
Dispersion liquid the most according to claim 1, it is characterised in that: described conducting polymer with to the mass ratio of anion is
1:1～1:100, preferably 1:1～1:50, preferably 1:1～1:20, preferably 1:1～1:10.
Dispersion liquid the most according to claim 1, it is characterised in that: the solid content in described dispersion liquid be 0.5wt%～
30wt%, preferably 0.8wt%～10wt%, preferably 1wt%～5wt%.
Dispersion liquid the most according to claim 1, it is characterised in that: described sulfonated graphene with to the mass ratio of anion is
1:1000～1000:1, preferably 1:100～100:1, preferably 1:10～10:1, preferably 1:2～2:1.
Dispersion liquid the most according to claim 1, it is characterised in that: the radial dimension of described sulfonated graphene and conduction height
The particle diameter of molecule is than for 5:1～5000:1, preferably 10:1～500:1, preferably 50:1～100:1.
The preparation method of 11. 1 kinds of sulfonated graphene-conducting polymer dispersion liquids with anisotropy carrier mobility, its
It is characterised by including:
By sulfonated graphene, it is used for providing source material and initiator to anion to be sufficiently mixed in a solvent, is formed containing causing
Agent and the sulfonated graphene dispersion liquid to anion；
Sulfonated graphene in making described sulfonated graphene dispersion liquid keep scattered in the case of, divide to described sulfonated graphene
Dissipate and add conductive high polymer monomer in liquid, fully after reaction, it is thus achieved that comprise sulfonated graphene, to anion and conducting polymer
Described sulfonated graphene-conducting polymer the dispersion liquid with anisotropy carrier mobility.
12. preparation methoies according to claim 11, it is characterised in that including:
By sulfonated graphene and be used for providing the source material of anion is dispersed in solvent after add initiator, 1～
At 25 DEG C continuously stirred 5～120 minutes, formed containing initiator and the sulfonated graphene dispersion liquid to anion；
By the described sulfonated graphene dispersion liquid containing initiator ultrasonic disperse 15～120 minutes at 1～10 DEG C, and keeping super
In protective atmosphere, in described sulfonated graphene dispersion liquid, it is slowly added to conductive high polymer monomer under the conditions of sound is scattered, it
Rear continuation ultrasonic disperse 6～72h, it is thus achieved that described in there is the sulfonated graphene-conducting polymer of anisotropy carrier mobility
Dispersion liquid.
13. according to the preparation method described in claim 11 or 12, it is characterised in that also include: at least remove described in have each to
Foreign ion in the sulfonated graphene-conducting polymer dispersion liquid of opposite sex carrier mobility, and have described in making each to different
Property carrier mobility sulfonated graphene-conducting polymer dispersion liquid in solid content be 0.5wt%～30wt%, be preferably
0.8wt%～10wt%, preferably 1wt%～5wt%.
14. according to the preparation method described in claim 11 or 12, it is characterised in that: sulfonic in described sulfonated graphene contain
Amount is expressed as 120:1～1:1 with the mol ratio of carbon Yu element sulphur, is preferably expressed as 60:1～2:1, is preferably expressed as 30:1
～3:1, it is preferably expressed as 18:1～6:1.And/or, the radial dimension of described sulfonated graphene is 1 μm～100 μm, preferably 5 μ
M～80 μm, preferably 20 μm～60 μm.And/or, the thickness of described sulfonated graphene is 0.3nm～50nm, preferably 0.3nm
～10nm, preferably 0.3nm～2nm.And/or, it is any one that described conductive high polymer monomer includes in pyrroles, thiophene and aniline
Kind or any one derivant.And/or, described for providing the source material to anion to include polystyrolsulfon acid, Camphora
Sulfonic acid, p-methyl benzenesulfonic acid, LOMAR PWA EINECS 246-676-2, anthraquinone sulfonic acid, any one in sulphuric acid, it is preferred that described to source of anions in
Polystyrolsulfon acid.And/or, described conducting polymer and the mass ratio to anion are 1:1～1:100, preferably 1:1～1:
50, preferably 1:1～1:20, preferably 1:1～1:10.And/or, described sulfonated graphene and the mass ratio to anion are 1:
1000～1000:1, preferably 1:100～100:1, preferably 1:10～10:1, preferably 1:2～2:1.And/or, described sulphur
The radial dimension of functionalized graphene and the particle diameter of conducting polymer ratio for 5:1～5000:1, preferably 10:1～500:1, is preferably
50:1～100:1.And/or, described solvent includes water.And/or, described disperse containing initiator with to the sulfonated graphene of anion
In liquid, the content of initiator is 0.1wt%～50wt%, preferably 0.5wt%～10wt%, preferably 1wt%～5wt%.
And/or, it is any that described initiator includes in Ammonium persulfate., potassium peroxydisulfate, sodium peroxydisulfate, iron chloride, iron sulfate and hydrogen peroxide
One or more combination.And/or, described containing in initiator and the sulfonated graphene dispersion liquid to anion to anion
Content be 0.1wt%～5wt%, preferably 0.3wt%～3wt%, preferably 0.5wt%～1wt%.And/or, described guarantor
Protecting property atmosphere at least selects inert atmosphere.
15. films or the preparation method of coating, it is characterised in that including: to having according to any one of claim 1-10 each to
Sulfonated graphene-conducting polymer the dispersion liquid of opposite sex carrier mobility carries out film forming process, prepares described film or coating.
16. preparation methoies according to claim 15, it is characterised in that including: at least select in coating, mode of printing
Any one thin film-forming method is by the described sulfonated graphene with anisotropy carrier mobility-conducting polymer dispersion liquid application
It is added on matrix and film forming, prepares described film or coating.
17. preparation methoies according to claim 16, it is characterised in that: the material of described matrix is at least selected from glass, list
Any one in metal, metal alloy, ITO, PP, PE, PET and PEN.
18. films or coating, comprise sulfonated graphene, to anion and conducting polymer, and described film or coating with film or
Carrier mobility in coated facet parallel direction is 10-5～10-2cm2V-1s-1, preferably 10-4～10-2cm2V-1s-1, excellent
Elect 10 as-3～10-2cm2V-1s-1, and be 0.1～10cm with the carrier mobility on film or coated facet vertical direction2V- 1s-1, preferably 1～10cm2V-1s-1, preferably 2～5cm2V-1s-1。
19. films or coating, it is by the sulfonation with anisotropy carrier mobility according to any one of claim 1-10
Graphene-conducting polymer dispersion liquid is formed or is formed by method preparation according to any one of claim 15-17.
The sulfonated graphene with anisotropy carrier mobility according to any one of 20. claim 1-10-conduction is high
Film according to any one of molecular dispersions or claim 18-19 or coating, in the purposes prepared in photoelectric device, particularly exist
Prepare the purposes in electrode material or electrode modified material, the particularly purposes in preparing hole transmission layer.
21. purposes according to claim 21, it is characterised in that: described photoelectric device includes organic electro-optic device, preferably
, described organic electro-optic device includes organic solar batteries or Organic Light Emitting Diode.
22. goods, comprise the film described in claim 18 or 19 or coating.
23. goods according to claim 22, it is characterised in that: described goods include photoelectric device, it is preferred that described light
Electrical part includes organic electro-optic device, it is preferred that described organic electro-optic device includes organic solar batteries or organic light emission two
Pole is managed.
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