JP2003078188A - High polymer structure and functional element having the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the characteristics and/or reliability of a functional element having a conductive high polymer. SOLUTION: The functional element is provided with a pair of electrodes 1 and 4, and a high polymer structure having a hole conductive layer 5 and an electronic conductive layer 2. The high polymer structure is provided with a first super-branch high polymer and a second super-branch high polymer, and at least either the first super-branch high polymer or the second super- branch high polymer is provided with hole conductivity or electronic conductivity. Either the hole conductive layer or the electronic conductive layer is provided with the first super-branch high polymer or the second super-branch high polymer, and a self-organized structure based on non-covalent bonding mutual actions through the first super-branch high polymer or the second super-branch high polymer is provided in at least one of the hole conductive layer, the electronic conductive layer, or between the hole conductive layer and the electronic conductive layer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polymer structure having a hyperbranched polymer having hole conductivity or electron conductivity, and a functional device using the same.

[0002]

2. Description of the Related Art A conductive polymer (including a semiconductor polymer) is excellent in moldability such that it can be easily formed into a thin film, and therefore, a light emitting device, a solar cell, an organic FET device,
Application development to various functional elements such as photoelectric conversion elements is under way. In the above-mentioned functional element, interfaces are present between semiconductors, semiconductors, conductors, etc., and carriers such as holes and electrons pass through these interfaces, thereby exhibiting functions.

It is important that such an interface is in close contact with a large area, but there is a limit to increasing the area of the interface, and many of the interfaces are deteriorated due to a large electric field or stress. Easy to peel off. As a result, the durability is reduced due to the deterioration of the interface, and the response speed is reduced and the output is reduced because the area of the interface is not sufficiently large.

Therefore, US Pat. No. 5,563,424 discloses a technique utilizing a three-dimensional co-continuous phase separation structure of a polymer alloy of a polymer blend type in order to increase the area of the interface. In addition, JP-A-2000-28
Japanese Patent No. 6479 discloses a technique using a polymer alloy of a copolymer type polymer in which the durability of the interface is improved by forming a chemical bond at the interface.

In recent years, hyperbranched polymers such as dendrimers and hyperbranched polymers have attracted attention.
The dendrimer and the hyperbranched polymer are amorphous, soluble in an organic solvent, and have many terminals capable of introducing a functional group. Therefore, L. L. Mi
ller et al .; Am. Chem. Soc. , 199
7,119,1005, a polyamide dendrimer having a quaternary pyridinium salt-bonded 1,4,5,8-naphthalenetetracarboxylic acid diimide residue at the branch end has isotropic electron conductivity, It has been shown that this conductivity is due to π-electron interaction due to the spatial overlap of the branched end structures. Also, Japanese Patent Laid-Open No. 2000-33617
Japanese Unexamined Patent Publication (Kokai) No. 1 discloses a dendrimer using a dendron having a hole-conducting structure at a branched end and not containing a π-electron conjugated system containing a carbonyl group and a benzene ring, and a photoelectric conversion device using the same. Has been done.

Hereinafter, a conductive polymer represented by a conjugated polymer and containing no hyperbranched polymer will be referred to as "conventional conductive polymer".
I will call it.

[0007]

However, in the functional element using the above-mentioned conventional conductive polymer, the high charge conductivity is in the orientation direction of the molecular chain and is influenced by the structure of the polymer.

Further, conventional conductive polymers are generally
Many are rigid and insoluble and infusible. Therefore, a polymer derivative or an oligomer having a side chain introduced therein is used in order to impart or improve the meltability and the solubility (for example, Japanese Patent Application Laid-Open No. Hei 7 (1994) -7).
-126166, JP-A-8-18125, and JP-A-10-92576). However, when a side chain is introduced, the flexibility of the polymer chain becomes high, and the glass transition point is expressed in the operating temperature range. As a result, thermochromism due to micro Brownian motion occurs, the π electron conjugation length becomes short, and There is a problem in that the stability of the characteristics is deteriorated. Further, the use of the oligomer causes problems such as deterioration in reliability.

On the other hand, Japanese Patent Laid-Open No. 2000-336171
In the device disclosed in the publication, only the charge conducting portion is formed by using the dendrimer, and the charge generating portion is formed by using the conventional conductive polymer. Although the characteristics of the conductive part are improved, the characteristics such as energy transfer and carrier transfer between layers are substantially the same as the structure using a conventional conductive polymer, so durability and interface peeling etc. The problem arises.

The present invention has been made in view of the above points, and an object thereof is to improve the characteristics and / or reliability of a functional element using a conductive polymer, and such a functional element. Another object of the present invention is to provide a polymer structure suitable for use in.

[0011]

The polymer structure according to the present invention is a polymer structure having a hole conducting layer and an electron conducting layer, and comprises a first hyperbranched polymer and a second hyperbranched polymer. And at least one of the first hyperbranched polymer and the second hyperbranched polymer has hole conductivity or electron conductivity, and either one of the hole conductive layer and the electron conductive layer Includes at least one of the first hyperbranched polymer and the second hyperbranched polymer, and is provided in at least one of the hole conducting layer, the electron conducting layer, and the hole conducting layer and the electron conducting layer. The present invention is characterized in that it has a self-assembled structure by a non-covalent bond interaction through the first hyperbranched polymer or the second hyperbranched polymer, whereby the above object is achieved.

In a preferred embodiment, the first hyperbranched polymer has hole conductivity and the second hyperbranched polymer has electron conductivity.

The hole conductive layer includes a self-assembled structure formed of a plurality of first hyperbranched polymers, and the electron conductive layer includes a self-assembled structure formed of a plurality of second hyperbranched polymers. It is preferable to include.

The hole conducting layer and the electron conducting layer are laminated on each other, and the first hyperbranched polymer and the second hyperbranched polymer are laminated.
It preferably comprises a self-assembled structure formed by non-covalent interactions with the hyperbranched polymer.

At least one of the hole conductive layer and the electron conductive layer preferably has isotropic characteristics, and more preferably both have isotropic characteristics. An isotropic property means that multiple hyperbranched polymers (of the same kind,
It means that there is no substantial difference in characteristics between the central structure (of any kind) and the branched structure.

At least one of the first hyperbranched polymer and the second hyperbranched polymer is preferably a dendrimer, and more preferably both are dendrimers.

At least one of the first hyperbranched polymer and the second hyperbranched polymer may have two or more different functions. The two functions are, for example, fluorescence and electronic conductivity.

[0018] The polymer structure of one embodiment further comprises a third hyperbranched polymer between the first hyperbranched polymer and the second hyperbranched polymer, and the third hyperbranched polymer is provided. A self-assembled structure is formed by a non-covalent bond interaction between the polymer and the first hyperbranched polymer or the second hyperbranched polymer.

The first hyperbranched polymer has hole conductivity, the second hyperbranched polymer has electron conductivity, and the third hyperbranched polymer has hole conductivity, electron conductivity, and hole conductivity. It may have either ionic conductivity.

The hole conductive layer includes a self-assembled structure formed of a plurality of first hyperbranched polymers, and the electron conductive layer includes a self-assembled structure formed of a plurality of second hyperbranched polymers. And a further functional layer including a self-assembled structure formed by a plurality of third hyperbranched polymers between the hole conductive layer and the electron conductive layer.

The hole conductive layer, the electron conductive layer and the further functional layer are laminated on each other, and
A self-assembled structure formed by a non-covalent bond interaction between the hyperbranched polymer and the third hyperbranched polymer and between the second hyperbranched polymer and the third hyperbranched polymer It is preferable to include at least one of the self-assembled structures formed by non-covalent interactions, and it is more preferable to include both of them.

At least one of the hole conductive layer, the electron conductive layer and the further functional layer preferably has isotropic properties, and more preferably all have isotropic properties.

At least one of the first hyperbranched polymer, the second hyperbranched polymer and the third hyperbranched polymer is
Dendrimers are preferred, and all are more preferred.

At least one of the first hyperbranched polymer, the second hyperbranched polymer and the third hyperbranched polymer is
It may have two or more different functions.

The functional element according to the present invention has any one of the above-mentioned polymer structures and an electrode electrically connected to the polymer structure, thereby achieving the above object.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below. The hyperbranched polymer in the present specification is a polymer having at least one hyperbranched structural unit having a branched structure of any shape. The "hyperbranched structural unit" referred to here is
As schematically shown in FIG. 1, it includes a dendrimer structural unit and a hyperbranched polymer structural unit. As for the dendrimer and the hyperbranched polymer, for example, Masaaki Kakimoto, Kagaku, 50, 608 (1995), High Polymer,
Vol. 47, p. 804 (1998).

The hyperbranched structural unit 12 has one dendritic branch start point 13a. The number of branch points 13 included in the hyperbranched structural unit 12 is not limited, and the start point 13 of the tree-like branch is 13
The structure may be such that only a is the branch point 13. The hyperbranched structural unit 12 may have a regular repeating branched structure like a dendrimer structural unit, or may have an irregular repeating branched structure like a hyperbranched polymer structural unit.

The hyperbranched polymer in the present specification may have at least one hyperbranched structural unit 12 shown in FIG. 1, but like the hyperbranched polymer 10 shown in FIG. ) 14 bound to a plurality of hyperbranched structural units 12 (1
2a-12c). In particular, it is preferable that the hyperbranched polymer 10 and the self-assembled structure of the hyperbranched polymer 10 exhibit isotropic characteristics, and that the molecular structure of the hyperbranched polymer 10 has high symmetry. 12
The number of is preferably 3 or 4. The plurality of hyperbranched structural units 12 may be different from each other, but are preferably the same from the viewpoint of structural symmetry.

The hyperbranched polymer 10 shown in FIG. 2 has a structure in which the tree-like branching starting points 13a of the three hyperbranched structural units 12a, 12b and 12c are bonded to a trifunctional atomic group as the central structure 14. Have The bond between the central structure 14 and the hyperbranched structural unit 12 is typically a covalent bond, but may be a non-covalent bond such as a hydrogen bond or a coordinate bond.

Hyperbranched structural units 12a, 12b and 12
c may be different from each other or may be the same.
It is preferable that the three hyperbranched structural units 12a, 12b and 12c are the same so that the supramolecular polymer 10 has isotropic properties. Hereinafter, the polyfunctional atomic group as the central structure 14 will also be indicated by reference numeral 14.

The hyperbranched polymer 1 used in the present invention
0 may have hole conductivity, electron conductivity, or ionic conductivity on its molecular surface, and may have energy interaction between the molecular surface and the interior, or dendron (in the hyperbranched structural unit). (Repeating unit of) may have carrier conductivity. In the hyperbranched polymer 10 having carrier conductivity on the surface of the molecule, carriers move by hopping between terminal groups having carrier conductivity. When the dendron has carrier conductivity, such as when the dendron has a structure having π electrons such as a π-conjugated chain, the carriers are the central structure 14 and the hyperbranched structural unit 12.
Since it is also possible to move between and, the function of the central structure 14 can be brought out.

The central structure 14 of the hyperbranched polymer 10 refers to the structure of a portion excluding the hyperbranched structural unit 12 after the dendritic branching starting point 13a, which is bonded to any number of dendritic branching starting points 13a. . Hyperbranched polymer 1 preferably used in the present invention
0 has a plurality of hyperbranched structural units 12 around the central structure 14 and has a highly symmetric three-dimensional structure, so that the central structure 14 is at the center of the three-dimensional structure of the hyperbranched polymer 10. To position.

Polyfunctional atomic group 14 constituting the central structure 14
As (1) having 1 to 20 carbon atoms, O, NH,
Unsubstituted or hydroxyl group, carboxyl group, acyl group or halogen-substituted alkylene group such as fluorine atom, chlorine atom, bromine atom or iodine atom, which may have a hetero atom such as N (CH ₃ ), S or SO ₂ interposed; (2) an arylene group having 6 to 20 carbon atoms, (3) a group in which these alkylene groups and an arylene group are bonded, (4) a hydrogen atom bonded to a carbon atom in each of the above groups (1) to (3) A multivalent group eliminated from, (5)
Examples thereof include a polyvalent heterocyclic group, (6) a group in which the polyvalent heterocyclic group is bonded to the hydrocarbon group of (1) to (4), and (7) a porphyrin or a porphyrin complex.

The dendron of the hyperbranched polymer 10 used in the present invention may be aromatic or aliphatic. Specifically, a polymer structure such as an aromatic or aliphatic polyether structure, an aromatic polyester structure, a polysiloxane structure, a polycarbosilane structure, a polyetheramide structure, a polyamidoamine structure, or a polypropyleneimine structure, or polyphenylene or polyphenylene. Examples thereof include conjugated polymer structures such as vinylene and polyphenyleneethynylene, and may include a heterocyclic group such as polythiophene, polythienylenevinylene, polypyrrole, and polysilole.

In order to impart carrier conductivity to the dendron, the dendron may have a π-conjugated structure,
As a hole conduction structure, a structure having a dialkylphenylamine residue, a structure having a triphenylamine residue,
It may have a phenanthroline residue, an imidazole residue or the like. Moreover, you may have a naphthalene tetracarboxylic acid diimide residue etc. as an electronic conduction structure. Further, as the ionic conduction structure, a salt composed of an anion such as a carboxylate or sulfonate functional group and a cation such as an alkali metal or an alkaline earth metal may be provided.

Further, by introducing another functional atomic group (functional group) into the molecule of the hyperbranched polymer, the functions can be compounded. For example, a group having fluorescence or a group having ultraviolet absorption can be introduced into the molecule. Specifically, for example, it is possible to add a rhodamine dye or the like to the central structure of the dendrimer.

As described above, the hyperbranched polymer 10 used in the present invention is not limited in its branched structure as long as it has the hyperbranched structural unit 12, but is a dendrimer from the viewpoint of the symmetry of the molecular structure. preferable. When the hyperbranched polymer 10 is a dendrimer, the number of generations thereof is not particularly limited,
Including those having a large or long central structure 14, the typical number of generations is 1 to 10, and end groups (the end portion of the hyperbranched structural unit 12 and the end portion constituting the surface of the hyperbranched polymer 10). The number of generations is preferably 2 to 8, more preferably 3 to 7, and most preferably 3 to 5 from the viewpoint of the density and the ease of synthesis. In addition, with the generation of dendrimer,
As shown in FIG. 3, it shows the degree of regular branching.

The polymer structure according to the present invention comprises a hole conducting layer and an electron conducting layer, and has a first hyperbranched polymer and a second hyperbranched polymer. First hyperbranched polymer and second
At least one of the hyperbranched polymers has hole conductivity or electron conductivity. One of the hole conducting layer and the electron conducting layer includes one of the first hyperbranched polymer and the second hyperbranched polymer, and the hole conducting layer, the electron conducting layer, and the space between the hole conducting layer and the electron conducting layer. At least one of them has a self-organized structure by a non-covalent bond interaction via the first hyperbranched polymer or the second hyperbranched polymer.

That is, the polymer structure according to the present invention is
It includes a self-assembled structure formed by the non-covalent interaction via the hyperbranched polymer described above. The self-assembled structure may be formed between the same type of hyperbranched polymer or may be formed between different types of hyperbranched polymer.
When the polymer structure contains a conventional chain polymer, it may have a self-assembled structure formed between the hyperbranched polymer and the conventional chain polymer. When using hyperbranched macromolecules, the smallest self-assembled structure can be formed by two hyperbranched macromolecules (two molecules).

One of at least two kinds of hyperbranched polymers contained in the polymer structure according to the present invention has hole conductivity or electron conductivity, and the hole conduction layer and the electron conduction layer contained in the polymer structure. One of the above contains the hyperbranched polymer. For example, when the first hyperbranched polymer has hole conductivity and the second hyperbranched polymer has electron conductivity, the hole conductive layer includes the first hyperbranched polymer and the electron conductive layer has the second hyperbranched polymer. Includes branched polymers. At this time, the self-assembled structure may be formed in the hole conducting layer by the interaction between the first hyperbranched polymers or may be formed in the electron conducting layer by the interaction between the second hyperbranched polymers. Alternatively, it may be formed at the interface between the hole conduction layer and the electron conduction layer by the interaction between the first hyperbranched polymer and the second hyperbranched polymer. Preferably, the hole conductive layer, the electron conductive layer, and between them (interfacial region) all include a self-assembled structure.

The non-covalent bond interaction includes van der Waals force, hydrogen bond, electrostatic interaction, π electron interaction, charge transfer interaction and the like.

The self-assembled structure of the polymer structure of the present invention will be described with reference to FIGS. 4 (a) and 4 (b).

The three-dimensional structure of the hyperbranched polymer used in the present invention has a disk shape (disk shape) as shown in FIG. 4A and a three-dimensional structure as shown in FIG. It is preferably spherical as shown in FIG. The hyperbranched polymer having such a three-dimensional structure can be obtained by appropriately adjusting the central structure, the dendron structure, and the number of generations, as described above.

The disc-shaped hyperbranched polymer 10a is shown in FIG.
As shown in (a), the self-assembled structure 20a is formed by the non-covalent bond interaction between the molecules.
In addition, the spherical hyperbranched polymer 10b forms a self-assembled structure 20b by a non-covalent interaction that acts between its molecules, as shown in FIG. 4 (b). FIG. 4B illustrates a self-assembled structure 20b in which the second-layer hyperbranched polymer 10b is located in the center of the first-layer four hyperbranched polymer 10b. Not limited, first layer and 2
A self-assembled structure may be formed in which the hyperbranched polymer layers 10b in the layer overlap with each other.

In FIGS. 4 (a) and 4 (b), the hyperbranched polymers 10a and 10b laminated on each other may be of the same kind or of different kinds. That is, one functional layer (for example, a hole conduction layer) may be composed of a plurality of layers of the same kind of hyperbranched polymer, or one functional layer may be composed of a monomolecular layer of hyperbranched polymer. Good. Therefore, the self-assembled structures 20a and 20b shown in FIGS. 4A and 4B may form a single functional layer or may form a laminated structure of a plurality of functional layers.

By thus forming the self-organized structure by the non-covalent bond interaction, the energy transfer or carrier transfer generated in each layer is transferred to each layer through the strong non-covalent bond interaction. It occurs smoothly inside and / or between each layer, and the moving speed can be increased.

Further, since the hyperbranched polymer having a three-dimensional spread and / or its self-assembled structure has a function such as conductivity, the one-dimensional conjugated chain has a high conductivity. The occurrence of the problem that the characteristics tend to depend on the temperature like the molecule is suppressed.

As a method of forming a functional layer such as a hole conductive layer or an electron conductive layer using a hyperbranched polymer, known film forming methods can be widely applied. Since the hyperbranched polymer has a higher solubility in a solvent than a conventional conjugated conductive polymer or the like, a solution can be prepared using various solvents. This solution is applied or printed on the substrate (support) 21 by a method such as a spin coating method, a dip coating method, a casting method, a printing method and an inkjet method, dried and then heat-treated if necessary A branched polymer film can be formed.

For example, a monomolecular film of hyperbranched polymer can be formed by immersing the substrate 21 in a solution having a predetermined concentration for a predetermined time. If a layer showing a non-covalent bond interaction with the hyperbranched polymer is previously formed on the surface of the substrate, a monomolecular layer is formed while forming a self-assembled structure.

As described above, the polymer structure of the present invention can be formed by sequentially forming the hyperbranched polymer film on the substrate 21.

Further, since the hyperbranched polymer melts at a lower temperature than conventional conjugated conductive polymers and the like, it can be molded into various shapes by hot pressing, injection molding, transfer molding, or the like. You can also The polymer structure of the present invention can be obtained by stacking the obtained hyperbranched polymer films.

In FIGS. 4 (a) and 4 (b), the self-assembled structure due to the non-covalent interaction between hyperbranched polymers was explained. Self-assembled structures can also be formed by non-covalent interactions of. For example, the hole conducting layer is formed of the first hyperbranched polymer, the electron conducting layer is formed of the conventional conductive polymer (chain conjugated polymer), and self-coupling is performed by the non-covalent interaction between them. It is also possible to form an organized structure.

As the polymer other than the hyperbranched polymer, for example, a phthalocyanine derivative, an azo compound derivative, or perylene is added to the main chain such as polystyrene chain, polysiloxane chain, polyether chain, polyester chain, polyamide chain or polyimide chain. Derivatives, quinacridone derivatives, polycyclic quinone derivatives, cyanine derivatives, fullerene derivatives,
Examples thereof include nitrogen-containing cyclic compound derivatives such as indole and carbazole, hydrazone derivatives, triphenylamine derivatives, and polycyclic aromatic compound derivatives into which side chains are introduced. Furthermore, a conjugated polymer chain, an aromatic conjugated polymer such as polyparaphenylene, an aliphatic conjugated polymer such as polyacetylene, a heterocyclic conjugated polymer such as polypyrrole or polythiophene, polyaniline or Heteroatom-containing conjugated polymers such as polyphenylene sulfide, poly (phenylene vinylene), poly (arylene vinylene), and composites having a structure in which the constituent units of the above conjugated polymers such as poly (thienylene vinylene) are alternately bonded. Examples thereof include carbon-type conjugated polymers such as type-conjugated polymers, polysilanes, disilanylene polymers, and disiranylene-carbon-based conjugated polymer structures.

The polymer structure according to the present invention typically has a laminated structure as described above, but it does not necessarily have to have a laminated structure. For example, a mixture of a first hyperbranched polymer and a second hyperbranched polymer and a self-assembled structure formed by a non-covalent bond interaction between them is mixed in a polymer matrix. It may be dispersed. Furthermore, when the concentration of the hyperbranched polymer in the polymer matrix is sufficiently high, for example, the composition in which the hole-conducting hyperbranched polymer is dispersed in the insulating polymer matrix is used to conduct hole conduction. Layers can be formed. At this time, not only the self-assembled structure is formed by the non-covalent bond interaction between the hyperbranched polymers dispersed in the polymer matrix, but also the electron conduction layer formed adjacent to the hole conduction layer. In some cases, a self-organized structure is formed between and. The electron conducting layer may also be formed from a composition in which a hyperbranched polymer is dispersed in a polymer matrix.

The material of the polymer matrix is not particularly limited as long as it does not inhibit the formation of the self-assembled structure, and for example, 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A) is used. Polycarbonate as a raw material, 2,2-bis (3-methyl-4-hydroxyphenyl) propane (commonly called bisphenol C)
Polycarbonate made from bis (4-hydroxyphenyl) phenylmethane (commonly called bisphenol P)
, A polycarbonate made from 1,1-bis (4-hydroxyphenyl) cyclohexane (commonly called bisphenol Z) as a raw material, an aromatic polycarbonate resin, a polyarylate resin, an acrylic resin, a styrene resin, polyvinyl chloride, Examples thereof include thermoplastic or thermosetting resins such as vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyvinylidene chloride, phenoxy resin, epoxy resin and phenol resin.

When the hyperbranched polymer is used by dispersing it in the polymer matrix, the content of the hyperbranched polymer is 40% by weight or more and less than 100% by weight, preferably 60% by weight or more and less than 100% by weight. Is.

The method for preparing such a hyperbranched polymer dispersion composition is not particularly limited, and for example, it can be prepared by using various solvents. Solvents that are suitably used include tetrahydrofuran (THF), 1,4-
Dioxane, cyclohexanone, toluene, chlorobenzene, methyl ethyl ketone (MEK), acetone, N,
Examples thereof include N-dimethylformaldehyde (DMF) and methylene chloride. The resulting solution is applied or printed by a method such as a spin coating method, a dip coating method, a casting method, a printing method and an inkjet method, dried and then heat-treated as necessary to obtain a hyperbranched polymer dispersion composition. A film of material can be formed.

Additives such as dopants may be added to the solution of the hyperbranched polymer or the solution of the composition containing the hyperbranched polymer. Examples of the additive include styryl dye (DCM)
Etc. and n-type and p-type dopants and the like. Various additives can be used depending on the type and function of the hyperbranched polymer. In particular, the hyperbranched polymer may have a plurality of functions by introducing a group having fluorescence or a group having ultraviolet absorptivity into the molecule, and thus by using the additive, The characteristics can be improved and further functions can be combined.

Various functional elements can be constructed by providing electrodes for applying a voltage to the polymer structure according to the present invention. For example, the polymer structure according to the present invention can be used for a solar cell, a photoelectric conversion element, an organic FET element, a capacitor, a light emitting element, an electrochromic element, a polymer secondary battery and the like. The details of the device structure suitable for each application will be described below.

In the photoelectric conversion element or the solar cell,
Generally, the polymer structure is arranged so as to be sandwiched between a pair of parallel plate electrodes, but it may be formed on a comb-shaped electrode and is not limited to this. The electrode material is not particularly limited, but in the case of a parallel plate electrode, at least one electrode is preferably an ITO electrode or a transparent electrode such as tin oxide doped with fluorine. The polymer structure may include a p-type semiconducting or hole-conducting hyperbranched polymer,
It is formed of a semiconducting or electron-conducting hyperbranched polymer. In addition, a photosensitizing dye group is introduced into either one of the above-mentioned two layers of hyperbranched polymer, or HOMO is provided between the above two layers.
(Highest occupied electron band) Level is lower than HOMO of hole-conducting hyperbranched polymer, LUMO (Lowest unoccupied electron band)
When a polymer having a photosensitizing dye molecular structure having a higher level than the LUMO of an electron-conducting hyperbranched polymer or a hyperbranched polymer is introduced, the level is further improved, and when used as a solar cell, highly efficient power generation is achieved. Can be done.

Furthermore, between the p-type semiconducting or hole-conducting hyperbranched polymer and the n-type semiconducting or electron-conducting hyperbranched polymer, an oxidatively reducible ion-conducting hyperbranched polymer or An electrochemical photoelectric conversion element can be formed by providing the ion conductive polymer.
At this time, the oxidation-reduction order of the ion-conducting hyperbranched polymer or the ion-conducting polymer is such that when the p-type semiconducting or hole-conducting hyperbranched polymer is photoexcited, Higher than LUMO of polymer, LU of n-type semiconducting or electron-conducting hyperbranched polymer
It is preferably set lower than MO. On the other hand, when the n-type semiconducting or electron-conducting hyperbranched polymer is photoexcited, the n-type semiconducting or electron-conducting hyperbranched polymer is higher than the HOMO of the p-type semiconducting or hole-conducting hyperbranched polymer. It is preferable to be set lower than the HOMO of. When both the p-type semiconducting or hole-conducting hyperbranched polymer and the n-type semiconducting or electron-conducting hyperbranched polymer are photoexcited, the LUMO of the p-type semiconducting or hole-conducting hyperbranched polymer is used. It is preferably higher than the HOMO of the n-type semiconducting or electron-conducting hyperbranched polymer. Further, if necessary, a photosensitizing dye group may be introduced into any of the layers.

In the polymer structure having a three-layer structure, at least two layers are hyperbranched polymers, preferably adjacent layers are hyperbranched polymers, and more preferably all three layers are composed of hyperbranched polymers. It is preferably formed. By forming a self-assembled structure within and between each layer, the characteristics and reliability can be improved.

Also in a light emitting element, in many cases, the polymer structure of the present invention is disposed between parallel plate electrodes.
The structures of typical functional elements are shown below in FIGS.
1, reference numerals 1 and 4 represent a pair of electrodes, reference numeral 2 is an electron conductive layer, reference numeral 3 is an electron conductive layer (or a light emitting layer), reference numeral 5 is a hole conductive layer, and reference numeral 6 is a hole conductive layer. (Or a light emitting layer), reference numeral 7 is a light emitting layer,
Reference numeral 8 indicates a charge generation layer.

In the structure 1 shown in FIG. 5A, the structure 2 shown in FIG. 5B, and the structure 3 shown in FIG. 5C,
It is possible to improve the recombination efficiency of the positive and negative carriers injected from the pair of both electrodes 1 and 4. In the structure 4 shown in FIG. 5D, the electrodes 1 and 4 and the light emitting layer 7 and the carrier conduction layer (the electron conduction layer 2 and the hole conduction layer 5) are more reliably contacted with each other, and The carrier injection efficiency of can be increased. Further, as described in the section of the photoelectric conversion element, a group related to light emission, a group of a dye, a group related to light emission in the central structure may be introduced into the hyperbranched polymer. Further, hyperbranched polymers having different functions may be mixed to form a self-assembled structure of the hyperbranched polymer, thereby having a structure having both a carrier conducting function and a light emitting function.

As described above, in the functional device according to the present invention, it is possible to combine the functions of the hyperbranched polymer in the molecule and the functions of the self-assembled structure due to the non-covalent interaction between the molecules. Is. In addition, in a known coating method such as a dipping method, an inkjet method, or a spin coating method, a self-assembled structure is formed by non-covalent interaction by overcoating, ink of the inkjet method, a dipping method, a spin coating method, or the like. It is possible to form a self-assembled structure by non-covalent interactions during film formation at the same time as mixing in a solution and removing the solvent or the solvent. The polymer structure may be directly formed on the substrate for the functional element, or the polymer structure separately formed as described above may be transferred to the substrate for the functional element.

The self-assembled structure by the non-covalent interaction is controlled at the molecular level by the nano structure, and it is possible to easily control the film thickness and the molecular orientation of the laminated structure having a layer of several to several tens nm. In addition, due to the electric field concentration effect, there is an effect such that the injection efficiency between the layers of carriers is increased, so that the performance can be greatly improved.

The organic transistor element uses a polymer structure in which one of the hole conductive layer and the electron conductive layer is a conductive layer, the other is a semiconductor layer, and an insulating layer is provided between the conductive layer and the semiconductor layer. , A gate electrode on this polymer structure,
It can be realized by forming a source electrode and a drain electrode.

A capacitor (capacitor) also has a polymer structure in which one of the hole conductive layer and the electron conductive layer is a conductive layer, the other is a semiconductor layer, and an insulating layer is provided between the conductive layer and the semiconductor layer. Is formed using. Further, the hole conductive layer and the electron conductive layer are conductive layers, an ion conductive layer is inserted between the conductive layers, the hole conductive layer is a p-type semiconductor layer, and the electron conductive layer is an n-type semiconductor layer. You may form the continuous layer of.

In the electrochromic device, the hole conductive layer is a polymer layer capable of p-type doping, and the color is changed by a redox reaction, and the electron conductive layer is a polymer layer capable of n-type doping, and a color is changed by a redox reaction. , A polymer structure having a layer containing a supporting electrolyte salt between the layers. Further, this element structure can be used also as a polymer secondary battery, and a secondary battery having high capacity and low internal resistance can be provided.

As described above, the functional device of the present invention contains a hyperbranched polymer having isotropic characteristics, and further has a self-organized structure through noncovalent interaction of the hyperbranched polymer. Since the polymer structure is provided, it is possible to provide a functional element which is isotropic and has extremely high carrier conductivity, and moreover, the layers are surely brought into contact with each other to have high reliability and high durability. Further, the functional element of the present invention is formed by simply coating a polymer solution (or polymer), and it is possible to control the film thickness and the molecular orientation at the nanoscale molecular level.

Further, it has a complex function by introducing various functional groups into the molecule of the hyperbranched polymer, a complex function by a self-organized structure by a non-covalent interaction, and a new function expression. It is possible to provide a functional element and an element structure which have not existed in the past. This is a structure that cannot be formed by a conventional polymer material or polymer alloy system.

An example of synthesizing a hyperbranched polymer is shown below.

As a polypropyleneimine type compound, first, a primary amine compound of the chemical formula 1 is subjected to a cyanoethylation reaction with acrylonitrile in water-toluene with an acetic acid catalyst to produce a compound of the chemical formula 2.

[0074]

[Chemical 1]

[0075]

[Chemical 2]

Next, the compound of formula 3 is produced by subjecting the compound of formula 2 to hydrogenation reaction with a cobalt catalyst (Raney catalyst).

[0077]

[Chemical 3]

That is, two branched amino groups (Chemical formula 2) are obtained from one amino group (Chemical formula 1), and by repeating the above reaction, Chemical formula 4 to Chemical formula 6
The compound of is easily obtained.

[0079]

[Chemical 4]

[0080]

[Chemical 5]

[0081]

[Chemical 6]

Further, the dendrimer represented by the chemical formula 7 can be synthesized by the divergent method of synthesizing the hyperbranched polymer from the outside toward the center or the convergent method of synthesizing from the outside to the center.

[0083]

[Chemical 7]

Further, a commercially available polypropylene imine dendrimer (catalog DAB-Am-4, manufactured by Aldrich,
8, 16, 32, 64) may be used. There, 4-
Ethyl (N, N-diethylamino) benzoate, or 4
-(1,8-Naphthaldiimidylbenzoic acid) methyl and the like were dissolved in N, N-dimethylformaldehyde, and the solution was concentrated under reduced pressure.
The ethanol produced was distilled off with heating and stirring at 0 ° C.
After concentration, the product is purified by silica gel chromatography to convert the amino group at the branched end of the dendrimer or hyperbranched polymer into an amide of 4-diethylaminobenzoic acid or an amide of 4- (1,8-naphthalimidyl) benzoic acid. A substance is obtained.

As a polybenzyl ether type 4-
1,3,5 with methyl bromomethylenebenzoate
-Using trihydroxybenzene (Chem. 9), Hawk
er, C.I. J. et al. J .; Am. Chem. S
oc. , 112. p. Hyperbranched polymer compound (Chemical formula 1) by etherification reaction using anhydrous potassium carbonate and 18-crown-6 ether as in 7638 (1990).
It is possible to obtain polybenzyl ether-based dendrimers and hyperbranched polymers such as
In the case of methyl bromomethylenebenzoate, it is possible to convert the terminal methyl ester group into a carboxyl group, potassium salt or the like.

[0086]

[Chemical 8]

[0087]

[Chemical 9]

[0088]

[Chemical 10]

As the polyphenylene vinylene type,
Shirshend K. Debet al. J .;
Am. Chem. Soc, 119, p. 9079 (19
97), 3,5-di-tert-butylbenzaldehyde (Chemical formula 11) and the product of the Arbuzov reaction (Chemical formula 12) from 5-bromo-m-xylene were treated with sodium hydride and N-methyl-2. -Reacting in pyrrolidone (NMP) to synthesize the product. One more
Two bromines of 3,5-tribromobenzene are added to Still
It is converted to vinyl by the coupling reaction and the product (Chemical Formula 1
4) is generated. By repeating these, a polyphenylene vinylene dendron such as the product (Formula 15) is produced. Benzotriphosphate (Chemical formula 1)
By reacting with 6) or the like which can be a central structure, a polyphenylene vinylene-based dendrimer or hyperbranched polymer such as a hyperbranched polymer compound (Chemical formula 17) can be produced.

[0090]

[Chemical 11]

[0091]

[Chemical 12]

[0092]

[Chemical 13]

[0093]

[Chemical 14]

[0094]

[Chemical 15]

[0095]

[Chemical 16]

[0096]

[Chemical 17]

In the above example, the hyperbranched polymer in which the central structure and the hyperbranched structure are bonded via a covalent bond is exemplified, but the hyperbranched polymer used in the present invention is not limited to this, and the central structure is not limited thereto. And the hyperbranched structure may be bonded via a non-covalent bond.

For example, in the molecule A represented by the following (Chemical formula 18), six molecules are bonded to each other by hydrogen bonds,
Form a dendrimer as shown in 9).

[0099]

[Chemical 18]

[0100]

[Chemical 19]

As described above in detail, according to the present invention, it is possible to improve the performance of a functional device by a device structure which does not exist in the prior art and which uses a hyperbranched polymer. It can be easily manufactured, and has a great industrial value.

[0102]

EXAMPLES Examples of the functional element according to the embodiment of the present invention will be described below together with comparative examples. However, the present invention is not limited to these examples.

Example 1 ITO was formed on a glass substrate of an organic light emitting device as an anode, and a randomly conductive ionized hyperbranched polymer compound 1 (Chemical Formula 20) in tetrahydrofuran was used as a hole conduction layer.
The hyperbranched polymer compound 1 was formed into a film by a spin coating method at room temperature. The film thickness was 100 nm. Further, a hyperbranched polymer compound 2 (Chemical Formula 21), which also serves as a light emitting layer and an electron conductive layer, is spin-coated at room temperature by a spin coating method using a tetrahydrofuran solution.
To obtain a polymer structure in which a thin film of the hyperbranched polymer compound 1 and a thin film of the hyperbranched polymer compound 2 formed a self-assembled structure by electrostatic interaction. The film thickness of the hyperbranched polymer compound 2 was 50 nm. Then, a MgAg alloy (weight ratio 10: 1) was vapor-deposited to form a cathode, and a light emitting device having a structure shown in FIG.

[0104]

[Chemical 20]

[0105]

[Chemical 21]

A predetermined voltage was applied to this light emitting element to drive it to emit light, and the initial luminance was measured to be 1500.
It showed a luminance of cd / m ² . Furthermore, it took 3000 hours or more to reduce the initial luminance by half.

Comparative Example 1 A light emitting device having the same structure as in Example 1 was prepared except that a mixture of polyethylenedioxythiophene and sodium polystyrene sulfonate was used for the hole conductive layer. Applying a predetermined voltage to this light emitting element,
When it was driven to emit light and the initial luminance was measured, it was 80
It showed a luminance of 0 cd / m ² . Furthermore, it took 800 hours for the initial luminance to be reduced by half.

Example 2 ITO was formed as an anode on a glass substrate of an organic light emitting device, and a tetrahydrofuran solution of a hyperbranched polymer compound 3 (Chemical Formula 22) was used as a hole conduction layer. The branched polymer compound 3 was formed into a film. Film thickness is 5
It was set to 0 nm. Further, a hyperhydrogenated polymer compound 4 (Chemical formula 23) solution of tetrahydrofuran was used as a light emitting layer, and the hyperbranched polymer compound 4 was formed at room temperature by spin coating. The film thickness was 30 nm. Further, a film of the hyperbranched polymer compound 5 was formed at room temperature by a spin coating method using a tetrahydrofuran solution of the hyperbranched polymer compound 5 (Chemical Formula 24) as an electron conductive layer. A polymer structure was obtained in which the thin film and the thin film of the hyperbranched polymer compound 5 formed a self-assembled structure by electrostatic interaction. The film thickness of the hyperbranched polymer compound 5 was 50 nm. Then, a MgAg alloy (weight ratio 10: 1) was vapor-deposited to form a cathode, and a light emitting device having a structure shown in FIG. 5D was manufactured.

A predetermined voltage was applied to this light emitting device to drive it to emit light, and the initial luminance was measured to be 1500.
It showed a luminance of cd / m ² . Furthermore, it took 3000 hours or more to reduce the initial luminance by half.

[0110]

[Chemical formula 22]

[0111]

[Chemical formula 23]

[0112]

[Chemical formula 24]

Comparative Example 2 A light emitting device having the same structure as in Example 2 was prepared except that a mixture of polyethylenedioxythiophene and sodium polystyrenesulfonate was used for the hole conducting layer and polyhexylthiophene was used for the light emitting layer. . A predetermined voltage was applied to this light emitting element to drive it to emit light, and the initial luminance was measured to be 800 cd /
It showed a brightness of m ² . Furthermore, it took 800 hours for the initial luminance to be reduced by half.

Example 3 A MgAg alloy (weight ratio 10: 1) vapor deposition electrode was formed on a glass substrate of an organic rectifying element, and a hyperbranched polymer compound 1 was used as a hole conduction layer.
Using the tetrahydrofuran solution of (Chemical Formula 20), the hyperbranched polymer compound 1 was formed into a film by a spin coating method at room temperature. The film thickness was 50 nm. Further, a film of the hyperbranched polymer compound 1 is formed at room temperature by a spin coating method using a tetrahydrofuran solution of the hyperbranched polymer compound 5 (Chemical Formula 24) as an electron conductive layer to form a thin film of the hyperbranched polymer compound 1. A polymer structure in which a thin film of the hyperbranched polymer compound 5 formed a self-assembled structure by electrostatic interaction was obtained. The film thickness of the hyperbranched polymer compound 5 was 50 nm. Then, an MgAg alloy (weight ratio 10: 1) was vapor-deposited to form an upper electrode, and an organic rectifying device was produced.

The current-voltage characteristic of this rectifying device was measured by blocking light. The rectification characteristic is shown that the current flows only when the upper electrode is made negative. Furthermore, when this rectifying device was left at room temperature for 3 months and then subjected to the same measurement, deterioration of the characteristics and peeling of the film interface did not occur.

Comparative Example 3 An organic rectifying device having the same structure as in Example 3 was prepared, except that a mixture of polyethylenedioxythiophene and sodium polystyrene sulfonate was used for the hole conducting layer.

The current-voltage characteristic of this rectifying device was measured by blocking light. When the upper electrode was made negative, a rectifying characteristic in which a current flows was shown, but when this rectifying element was left at room temperature for 3 months and the same measurement was performed, deterioration of the characteristic and peeling of the film interface occurred.

Example 4 ITO was formed as an electrode on a glass substrate of an organic solar cell element, and a tetrahydrofuran solution of a hyperbranched polymer compound 3 (Chem. 22) was used as a hole conductive layer at room temperature by spin coating. Then, the hyperbranched polymer compound 5 was formed into a film. The film thickness was 50 nm. Further, a film of the hyperbranched polymer compound 6 was formed at room temperature by a spin coating method using a tetrahydrofuran solution of the hyperbranched polymer compound 6 (Chemical Formula 25) as the charge generation layer. The film thickness was 30 nm. Furthermore, as the electron conducting layer, the hyperbranched polymer compound 5 (Chemical Formula 2
4) The film of the hyperbranched polymer compound 5 is formed at room temperature by spin coating using the tetrahydrofuran solution of 4), and the thin film of the hyperbranched polymer compound 6 and the thin film of the hyperbranched polymer compound 5 cause electrostatic interaction. A polymer structure having a self-assembled structure was obtained. The film thickness of the hyperbranched polymer compound 5 was 50 nm. And MgAg alloy (weight ratio 10:
1) was vapor-deposited to form an electrode, and an organic solar cell element was produced.

[0119]

[Chemical 25]

This solar cell element was irradiated with a tungsten lamp light having a wavelength of 400 nm or less, and the initial energy conversion efficiency was measured, and a good value of 1.8 to 2.2% was obtained.

(Comparative Example 4) A light emitting device having the same structure as in Example 2 was prepared, except that a mixture of polyethylenedioxythiophene and sodium polystyrenesulfonate was used for the hole conductive layer and copper phthalocyanine was used for the charge generation layer. .

This solar cell element was irradiated with a tungsten lamp light having a wavelength of 400 nm or less to measure the initial energy conversion efficiency, and a value of 1.0 to 1.2% was obtained.

From the above results, in the functional devices of Examples 1 to 4, since the functional layers composed of two or more hyperbranched polymers formed the self-organized structure by the noncovalent interaction, the device structure (particularly It has been found that the interface structure) is stabilized and the characteristics can be dramatically improved.

[0124]

The polymer structure according to the present invention contains a hyperbranched polymer and has a self-assembled structure by a non-covalent interaction through the polymer, so that it has a function using a conventional conductive polymer. The characteristics and reliability of the device can be improved.

The functional element according to the present invention can be suitably applied to a light emitting element, a display, a solar cell, a photoelectric conversion element, a light modulation element, an organic FET element, a capacitor, a rectifying element or various sensor elements.

[Brief description of drawings]

FIG. 1 is a conceptual diagram schematically showing the structure and classification of hyperbranched polymers.

FIG. 2 is a diagram schematically showing the structure of a hyperbranched polymer used in the present invention.

FIG. 3 is a schematic diagram showing the concept of the number of generations of dendrimers.

4 (a) and (b) are schematic views showing an example of a self-assembled structure formed by a hyperbranched polymer according to the present invention.

5A to 5E are schematic cross-sectional views showing an example of a functional element according to an embodiment of the present invention.

[Explanation of symbols]

1,4 electrodes 2 Electron conductive layer 3 electron conduction, light emitting layer 5 hole conductive layer 6 hole conduction, light emitting layer 7 Light-emitting layer 8 Charge generation layer

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H01L 33/00 H05B 33/22 B 5H032 H05B 33/14 H01M 14/00 P 33/22 H01L 29/28 / / H01M 14/00 31/04 DF Term (reference) 3K007 AB03 AB11 AB14 AB15 DB03 4F100 AA28 AA33 AG00 AK01A AK01B AK31 AK46 AK54 BA02 BA03 BA04 BA05 BA07 EH46 GB41 JG01 JG01A JG01B JG10B 4J11 BA09 BA10 BA07 BA07 BA18 BA07 BB02 BB03 BB06 BD21 5F041 CA45 CA86 CA88 5F051 AA11 CB13 FA04 FA06 5H032 AA06 AS09 AS16

Claims (15)

[Claims] 1. A polymer structure comprising a hole conduction layer and an electron conduction layer, comprising a first hyperbranched polymer and a second hyperbranched polymer, wherein the first hyperbranched polymer and the At least one of the second hyperbranched polymers has hole conductivity or electron conductivity, and one of the hole conductive layer and the electron conductive layer has the first hyperbranched polymer and the second hyperbranched polymer. At least one of the hole conducting layer, the electron conducting layer, and the hole conducting layer and the electron conducting layer, the first hyperbranched polymer or the second superconducting polymer. It has a self-organized structure by non-covalent interactions through branched polymers.
Polymer structure. 2. The polymer structure according to claim 1, wherein the first hyperbranched polymer has hole conductivity and the second hyperbranched polymer has electron conductivity. 3. The hole conductive layer includes a self-assembled structure formed of a plurality of first hyperbranched polymers, and the electron conductive layer includes a self-organized structure formed of a plurality of second hyperbranched polymers. The polymer structure according to claim 2, wherein the polymer structure comprises an activated structure. 4. The hole conducting layer and the electron conducting layer are stacked on each other and are formed by a non-covalent interaction between the first hyperbranched polymer and the second hyperbranched polymer. The polymer structure according to claim 3, comprising a self-assembled structure. 5. The at least one of the hole conductive layer and the electron conductive layer has isotropic characteristics.
Alternatively, the polymer structure according to item 4. 6. At least one of the first hyperbranched polymer and the second hyperbranched polymer is a dendrimer,
The polymer structure according to claim 1. 7. The polymer structure according to claim 1, wherein at least one of the first hyperbranched polymer and the second hyperbranched polymer has two or more different functions. 8. The third hyperbranched polymer is further provided between the first hyperbranched polymer and the second hyperbranched polymer, and the third hyperbranched polymer and the first hyperbranched polymer are provided. The polymer structure according to claim 1, wherein a self-assembled structure is formed by a non-covalent bond interaction between the polymer and the second hyperbranched polymer. 9. The first hyperbranched polymer has hole conductivity, the second hyperbranched polymer has electron conductivity, and the third hyperbranched polymer has hole conductivity, electron conductivity. 9. The polymer structure according to claim 8, which has either conductivity or ionic conductivity. 10. The hole conductive layer includes a self-assembled structure formed of a plurality of first hyperbranched polymers, and the electron conductive layer includes a self-organized structure formed of a plurality of second hyperbranched polymers. The high functional layer according to claim 9, further comprising a self-assembled structure including a self-assembled structure formed by a plurality of third hyperbranched polymers between the hole conductive layer and the electron conductive layer. Molecular structure. 11. The hole-conducting layer, the electron-conducting layer and the further functional layer are laminated on each other, and a non-covalent bond between the first hyperbranched polymer and the third hyperbranched polymer is provided. At least one of a self-assembled structure formed by an action and a self-assembled structure formed by a non-covalent bond interaction between the second hyperbranched polymer and the third hyperbranched polymer The polymer structure according to claim 10. 12. The polymer structure according to claim 10, wherein at least one of the hole conductive layer, the electron conductive layer and the further functional layer has an isotropic property. 13. The high polymer according to claim 8, wherein at least one of the first hyperbranched polymer, the second hyperbranched polymer and the third hyperbranched polymer is a dendrimer. Molecular structure. 14. The method according to claim 8, wherein at least one of the first hyperbranched polymer, the second hyperbranched polymer and the third hyperbranched polymer has two or more different functions.
The polymer structure according to any one of 1. 15. A functional element comprising the polymer structure according to claim 1 and an electrode electrically connected to the polymer structure.