CN102093570A - Electroluminescent molecular self-assembly body and application thereof - Google Patents
Electroluminescent molecular self-assembly body and application thereof Download PDFInfo
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- CN102093570A CN102093570A CN 201010584082 CN201010584082A CN102093570A CN 102093570 A CN102093570 A CN 102093570A CN 201010584082 CN201010584082 CN 201010584082 CN 201010584082 A CN201010584082 A CN 201010584082A CN 102093570 A CN102093570 A CN 102093570A
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- 0 CCCCCCCCC1(c2cc(C(C)(C)c3ccc(CO)cc3)ccc2-c2c1cc(*(C)c1ccc(CO)cc1)cc2)I Chemical compound CCCCCCCCC1(c2cc(C(C)(C)c3ccc(CO)cc3)ccc2-c2c1cc(*(C)c1ccc(CO)cc1)cc2)I 0.000 description 1
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Abstract
The invention discloses an electroluminescent molecular self-assembly body and an application thereof. A and B form a macromolecular complex paired between chain segments in a common solvent through non-covalent bond interaction, such as hydrogen bond interaction or ionic interaction. Nano particles with a nuclear shell structure are produced by adding a precipitator of A or B. After non-covalent bonds are self-assembled in the solution, the spectral character of the self-assembly body, especially the spectral character in a thin solid film, is detected. An electroluminescent device is produced by using a conventional spin coating method.
Description
Technical field
The invention belongs to the photoelectric material technical field, be specifically related to a kind of preparation method of electroluminescent device.
Background technology
In recent years, along with conjugated system begins to be applied in electron device gradually, become a reality gradually based on the dream of the molectronics of conjugated system.Meanwhile, fusion has in logic taken place in nano science and nanotechnology, and academia and industry member also are closely linked for this reason.The result of device physics is that recruit synthetic provides guidance in a kind of uncertain mode, and device performance only just can be improved on novel material synthetic progress basis conversely.Therefore, two key factors of decision conjugated polymers electron device performance are conjugated polymers chemical structure and the nanostructure in solid-state thereof.The physical properties of independent macromolecular chain is mainly by the control of its chemical structure, solid-state in their character will pile up the electron coupling of being brought great change take place owing to interchain between the macromolecular chain.Materials science develops into today, and the character of single-material has had predictability to a certain degree, can solve the problem of conjugated polymers chemical structure to a great extent by rational molecular designing.
By molecular level cut out or assemble realize solid-state in the control of ordered nano-structure be current research focus.The control of conjugated polymers nanostructure in these years has been subjected to the extensive concern of academia and even industry member, and one of them attracting way is exactly to use the self-assembly that the supramolecular chemistry principle realizes conjugated polymers.Utilizing the macromolecular chain self-assembly to construct the nano material with supramolecular structure is to have one of research field of vigor most at present, and the exploitation of carrying out the new function nano material by the self-assembly principle makes first appearance in the application of high-tech sector.The polymer self-assembly can based between polymer molecule or intramolecular special interaction realize.According to the difference of employing polymer concentration, the polymer self-assembly can comprise the lyotropic phase and body self-assembly mutually of dilute solution, high density etc.Wherein the self-assembly behavioral study about the polymer dilute solution gets at most, and macromolecule micelle just is meant the self-assembly behavior of polymer in dilute solution usually.High molecular micella divides by form and can be divided into spherical, vesica shape, cylindric and two-dimentional micella " vermiform " etc.
And the self-assembly of conjugated polymers need be from material and two visual angles of supramolecular chemistry.Having two kinds of important secondary interactions in the design process of supramolecule material promptly is that π-π interacts and interaction of hydrogen bond.Say that in logic π-π interacts and often is present in the pi-conjugated material.But, these interactional intensity and sources change bigger.In the water between the aromatic molecules accumulative facies mutual effect mainly cause by hydrophobic effect.The water molecules energy of aromatic compound surface solventization is higher than pure water, thereby causes the mutual accumulation on aromatic nucleus surface, and then reduces the contact area of they and solvent.Interaction in other solvents except water between the solvent molecule is more weak, and therefore, solvation power role is less.Hydrogen bond is the secondary interaction of ideal of structure supramolecular structure, because they have good selectivity and directivity.
Self-assembly provides very attractive means for the pi-conjugated material that structure has good organization.In the horizontal research material character of supramolecule, and even the macroscopic property regulation and control of carrying out pi-conjugated system all are possible.Super-molecule assembling body is with the macroscopic property that influences material of very big degree.Macromolecularly functionally will not only bring new opportunity aspect the Materials science with combining of supramolecular structure, and will between the wide gap of natural and artificial system, erect a bridge block, help human deep understanding for different levels organisation in the natural system.But, though the supramolecular structure that is formed by organic and macromolecular material tissue is hopeful to be applied to element manufacturing very much, before entering this research level, a lot of problem demanding prompt solutions are arranged still.A plurality of components are self-assembled into the bigger structure of determining through non covalent bond, make wherein different chromophoric grouies show different functions, this remains the work of a very challenging property concerning the chemist.Bibliographical information adopts non-covalent interaction to carry out comprising hydrogen bond to the self-assembly between the receptor body, metal-complexing, and electrostatic interaction etc.These supramolecular systems show short range order, but lack the ability that further is self-assembled into three-dimensional structure, therefore can only be applied to the fundamental research of this molecular level.
Summary of the invention
The object of the present invention is to provide a kind of electroluminescent molecule self-assembly and the using method on electroluminescent device thereof.
Concrete technical scheme is as follows:
A kind of electroluminescent molecule self-assembly, obtain by following approach: compd A and B pass through non-covalent interaction, in cosolvent (being the equal simultaneously energy dissolved of A and B solvent), form the intersegmental paired macromole of chain complex compound as tetrahydrofuran (THF) and water etc.; The nanoparticle of (promptly be that nuclear is the package structure of shell with B with A, vice versa) is the molecule self-assembly to have nucleocapsid structure by adding the precipitation agent (as water and tetrahydrofuran (THF) etc.) of A wherein or B, generating;
Synthesize a series of structures, form the lower molecular weight high-molecular material A and the B that contain active end group on the clear and definite side chain by molecular designing, have following general formula: A:X
1-(R
1)
n-X
1B:X
2-R
2-X
2
The mol ratio of described compd A and compd B is (0.05～10): 1;
Wherein, R
1Refer to the conjugated structure unit that its oligopolymer or polymkeric substance can be luminous; Preferably, R
1Be acetylene and derivative, benzene and derivative thereof (other aromatic rings, fragrant heterocycle, condensed ring, volution and derivative thereof), phenylacetylene support and derivative, vinylbenzene support and derivative, fluorenes and derivative thereof, fluorenes penylene and derivative thereof, fluorenes ethynylene and derivative thereof, fluorene ethylene support and derivative, dipyridyl and derivative thereof, thiophene and derivative, oxadiazole class thereof etc.; Best R
1Be benzene, phenylacetylene support, vinylbenzene support, fluorenes, fluorenes penylene, fluorenes ethynylene, fluorene ethylene support, dipyridyl, thiophene Huo oxadiazole etc.
R
2Be the alkyl of any chain length, or contain the assorted alkyl of N, O atom and amido linkage; Preferably, R
2Be hexylidene or inferior hexyloxy
X
1For-CONH
2,-COOH ,-OH ,-CONHCHOHCHO;
X
2For-CONH
2,-COOH ,-OH, the energy and the X of correspondence among the-CONHCHOHCHO
1Form the group of hydrogen bond or other non covalent bond.
Above-mentioned described polymer A and B, its molecular weight is between 5000～200000, and molecular weight distribution is 0～2.
Further, described non-covalent interaction is hydrogen bond, metal-complexing or electrostatic interaction.
The spectrum property of realizing detecting after the non covalent bond self-assembly in the solution gained self-assembly is its spectral quality in solid film particularly, adopts conventional spin-coating method to carry out the preparation of electroluminescent device and investigate its performance again.
The preparation method of above electroluminescent device at first is the first layer conductive layer, vacuum evaporation hole mobile material on conductive layer then, the luminescent layer be made up of above-mentioned self-assembly of spin coating again, electron transfer layer on the evaporation then, last evaporation second layer conductive layer.
The first layer conductive layer preferably is produced on the substrate, and substrate is generally glass or plastics.
The first layer conductive layer is an anode, and second layer conductive layer is a negative electrode.Negative electrode is made of the metal or the semi-transparent conductor that can produce reflection, is generally calcium, magnesium, aluminium, silver or alloy.Anode (as polyaniline, PANI) is made of tin indium oxide (ITO) or transparent conductive polymer.
Device anode in the technology of the present invention is an ito glass, and the film thickness of luminescent layer is 10～100nm.Negative electrode can be made of calcium, magnesium, aluminium, silver or alloy, and thickness is 10～150nm.
The present invention carries out the device preparation in conjunction with the non covalent bond self-assembly means in the present comparatively sophisticated solution of research and conventional membrane sepn means (as spin-coating etc.), in the intermediate level of molecule to device---done some good tries aspect the constructing of nanostructure.Utilize two kinds of secondary interactions mentioned above can in selectivity solution, realize the non covalent bond self-assembly of polycomponent conjugated polymers very easily, the present invention and then propose a possible approach and effectively control polymer nanocomposite structure in solid-state, after promptly in selectivity solution, realizing the non covalent bond self-assembly of the polycomponent conjugated polymers that molecular weight is lower, means such as spin-coating by routine are assembled into controlled architecture, thereby reach the self-organization purpose, improve the performance of final electron device.
Description of drawings
Fig. 1. the photoluminescence spectrum of the device of embodiment 1;
Fig. 2. the voltage-to-current curve of the device of embodiment 1;
Fig. 3. the electroluminescent brightness-voltage curve of the device of embodiment 1.
Embodiment
Further specify technical scheme of the present invention below by embodiment, so that understand content of the present invention better.
Embodiment 1
The preparation of electroluminescent device A
A is the poly-fluorenes PFOH of terminal hydroxy group:
B is a polymethyl acrylic acid;
A and B are dissolved in (weight ratio of A and B is 1: 11) in the tetrahydrofuran (THF) together, make solution, A and B form the intersegmental paired macromole of chain complex compound by interaction of hydrogen bond in tetrahydrofuran (THF).In ultrasonic oscillation, add the precipitation agent water of A, generate nanoparticle with nucleocapsid structure.Adopt the laser radiation sample should find tangible diffuse-reflectance, i.e. Tyndall phenomenon this moment.
This AB assembly spin coating is made film, measure its photoluminescence spectrum.Preparation method according to previously described electroluminescent device, the employing ito glass is a conductive layer, vacuum evaporation hole mobile material on this conductive layer, the luminescent layer be made up of above-mentioned self-assembly AB of spin coating again, electron transfer layer on the evaporation then, last evaporation second layer conductive layer.
Obtained device architecture is as follows: the film thickness of electric transmission/hole blocking layer is 30nm.Luminescent layer is an AB non covalent bond self-assembly, and thickness is 30nm.It is the hole transmission layer (NPB) of 80nm that one layer thickness is arranged between luminescent layer and anode (ITO).Electron transfer layer is between electric transmission/hole blocking layer and negative electrode, and material therefor is AlQ, and film thickness is 60nm.Except that luminescent layer adopted the spin coating preparation, other all materials all adopted the vacuum thermal evaporation technology to film.The structure of device is: ITO/NPB/AB/ electric transmission/hole blocking layer/Alq
3/ Al.
Test result is as shown in Figure 1-Figure 3:
Fig. 1 is the photoluminescence spectrum after sample P 1 spin-coating film, and this figure shows main peak at 425nm, and secondary peak may exist a plurality of, and the most significantly the luminous position of secondary peak is at the 460nm place;
Fig. 2 for its in clean room (dust granule density be approximately several thousand/square) atmosphere, the scanning peak voltage is the voltage-to-current curve of 18V; This curve display trigger voltage is about 10V;
The electroluminescent brightness of Fig. 3-voltage curve shows that the above luminosity of 12V becomes positive correlation with voltage.
Claims (5)
1. electroluminescent molecule self-assembly is characterized in that:
Obtain by following approach: compd A and B form the intersegmental paired macromole of chain complex compound by non-covalent interaction in cosolvent; By adding the precipitation agent of A wherein or B, generating the nanoparticle with nucleocapsid structure is the molecule self-assembly;
The mol ratio of described compd A and compd B is (0.05～10): 1, and its structure is respectively:
A：X
1-(R
1)
n-X
1B：X
2-R
2-X
2；
Wherein, R
1Refer to the conjugated structure unit that its oligopolymer or polymkeric substance can be luminous;
R
2Be the alkyl of any chain length, or contain the assorted alkyl of N, O atom and amido linkage;
X
1For-CONH
2,-COOH ,-OH ,-CONHCHOHCHO;
X
2For-CONH
2,-COOH ,-OH, the energy and the X of correspondence among the-CONHCHOHCHO
1Form the group of hydrogen bond or other non covalent bond.
Above-mentioned described polymer A and B, its molecular weight is between 5000～200000, and molecular weight distribution is 0～2.
2. electroluminescent molecule self-assembly according to claim 1 is characterized in that: described non-covalent interaction is hydrogen bond, metal-complexing or electrostatic interaction.
3. electroluminescent molecule self-assembly according to claim 1 and 2 is characterized in that: described R
1Be benzene, phenylacetylene support, vinylbenzene support, fluorenes, fluorenes penylene, fluorenes ethynylene, fluorene ethylene support, dipyridyl, thiophene Huo oxadiazole.
4. electroluminescent molecule self-assembly according to claim 1 and 2 is characterized in that: described R
2Be hexylidene or inferior hexyloxy.
5. the preparation method of an electroluminescent device, it is characterized in that: by spin-coating method the described molecule self-assembly of claim 1 is deposited on the substrate, this substrate is an anode.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106242938A (en) * | 2016-07-30 | 2016-12-21 | 沈阳大学 | Fluorenes ethene derivatives and synthetic method thereof |
-
2010
- 2010-12-10 CN CN 201010584082 patent/CN102093570A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| 《Chemistry Letters》 20050723 Liang-Liang Qiang et al. Novel Water-soluble Light-emitting Materials Prepared by Noncovalently Bonded Self-assembly 第1164-1165页 1-5 第34卷, 第8期 * |
| 《Macromolecular Symposia》 20030731 Ming Jiang et al， Macromolecular Assembly:From Irregular Aggregates to Regular Nanostructures 第167-170页 1-5 第195卷, * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106242938A (en) * | 2016-07-30 | 2016-12-21 | 沈阳大学 | Fluorenes ethene derivatives and synthetic method thereof |
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Application publication date: 20110615 |