JP2016004073A - Method for forming electrochromic film, electrochromic film, and substrate with coat conductor layer of electrochromic film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for forming an electrochromic film which can be firmly bonded to an ITO substrate, an electrochromic film, and a substrate with a coat conductor layer of an electrochromic film.SOLUTION: A method for forming an electrochromic film comprises the steps of: forming a bonding layer of a conductor layer composed of a first organic molecule on a surface of the conductor layer on a substrate by a wet forming method and manufacturing a working electrode; and forming an electrochromic layer composed of a second organic molecule and a metal ion on the bonding layer of a conductor layer formed on the surface of the conductor layer by an electrolytic polymerization method using the bonding layer of a conductor layer as the working electrode.

Description

The present invention relates to a method for forming an electrochromic film, an electrochromic film, and a substrate with an electrochromic film-coated conductor layer.

With the progress of the information society, various types of information displays have been researched and developed. Compared with light-emitting displays such as liquid crystal displays, plasma displays, and EL displays, non-light-emitting displays are close to paper media in display mode and are promising candidates for display media that can replace paper media.

Up to now, as non-light-emitting displays, the particles composed of the white hemisphere and the black hemisphere are rotated to display black and white, or the white and black particles are moved to the display surface side and displayed in black and white. Types are being developed. However, these display media need to move and rotate particles, and thus have problems such as a slow response speed and difficulty in color display.

On the other hand, electrochromic displays that change the color of the material itself have the potential for high-speed response and color display, and are being researched and developed. For example, it has been suggested that an organic / metal hybrid polymer exhibits an electrochromic phenomenon by an oxidation-reduction reaction, and may solve problems such as response speed and color display (Patent Document 1, Non-Patent Document). 1). However, a method for forming an organic / metal hybrid polymer film is a problem.

As a method for forming a polymer film, there are an alternating layering (Layer abbreviated as LBL) method, an electropolymerization (hereinafter abbreviated as EP) method, and a combination of these methods. It has been reported.

In the LBL method, a positively charged substance and a negatively charged substance are adsorbed alternately and alternately by electrostatic force (Coulomb force), and each layer is laminated alternately to form a thin film. It is a manufacturing method.
A method for producing a polymer thin film using the LBL method has been reported. For example, an LBL structure composed of multi-walled carbon nanotubes modified with terpyridine and ruthenium (III) ions (Non-patent Document 2). There are an LBL hybrid thin film (non-patent document 3) made of carbon nanotubes and Cu ²⁺ functioning in viologenthiol, a metal-organic framework structure by the LBL method (non-patent document 4), and the like.

The EP method is a method of preparing a polymer thin film on an electrode by dissolving a monomer and an electrolyte in a solvent and applying a voltage to the electrode. It's a fast, simple and convenient way. Conductive polymer thin films such as polyester fibers (3,4-ethylenedioxythiophene), polyaniline, polypyrrole, polythiophene are formed (Non-patent Document 5).

As for the EP method, there is a report of a thin film composed of a conjugated polymer such as phosphophore and a thiophene derivative and a metal ion. There is a report of bis [2- (hydroxyphenyl) -2,2 ′: 6,2 ″ -terpyridinyl] (M ²⁺ ) (M: iron and ruthenium) (Non-patent Document 6).
There is a report of a coordination polymer composed of triruthenium clusters and Fe ³⁺ by the LBL method or EP method (Non-patent Document 7).

However, there are almost no reports on methods for producing organic / metal hybrid polymer thin films by the EP method.
The inventor of the present invention recently attempted synthesis of an organic / metal hybrid polymer by EP method and formation of a thin film (Non-patent Document 8). However, only a very thin and non-uniform polymer film could be formed. In addition, since the polymer is only physically adsorbed on the ITO substrate, the adhesiveness is considerably weak, such as being easily separated from the substrate, and the polymer immediately separated in the solution.

Japanese Patent No. 5062712

M.M. Higuchi, G .; Kurth, Chem. Rec. 2007, 7, 203 Y. X. Pan. , Et al. Phys. Chem. C, 2010, 114, 8040-8047 J. et al. Liu, et al. , Langmuir, 2010, 28, 9496-9505. D. Zacher, et al. , Chem. Soc. Rev. , 2009, 38, 1418-1429. J. et al. P. Prince, et al. , Chem. Comm. 2010, 46, 5367-5369 K. Hanabusa, et al. , Polym. Int. 1994, 35, 231-238. H. Houjou, et al. Inorg. Chem. 2011, 50, 5298-5306 Proceedings of the 62nd Polymer Symposium (issued August 28, 2013) C. W. Hu, et al. , J. et al. Mater. Chem. C, 2013, 1, 3408-3413.

It is an object of the present invention to provide a method for forming an electrochromic film that can be firmly bonded to a substrate with a conductor layer such as an ITO substrate, an electrochromic film, and a substrate with an electrochromic film-coated conductor layer.

In view of the above circumstances, by conducting trial and error, the present inventor can increase the adhesion between the substrate and the film by introducing a monomer having an anchor portion that can be firmly connected to the ITO substrate at one end. Depending on the supply number of metal ions and monomers, it is possible to link monomers having the same coordination bond group by introducing a coordinate bond group capable of coordinate bond with metal ion at the other end of the monomer. The length can be extended as much as possible, the film thickness of the polymer can be strictly determined by the number of linked monomers, and the number of linked monomers can be determined by the number of reduced metal ions linked. The number of reduced metal ions can be determined by controlling the size of the electric double layer region formed in the vicinity of the electrode, the electric double layer region The size can be determined by controlling the voltage value, and the first organic molecules having a rigid structure are grown in a direction perpendicular to the substrate surface. It has been found that a porous film can be formed if it can be formed and formed separately.

Actually, 4 ′-(4- (2- (triethoxysilyl) vinyl) phenyl) -2,2 ′: 6 ′, 2 ″ -terpyridine is used as the first organic molecule, and 4 ′ is used as the second organic molecule. 4 ′ ″ ″-(1,4-phenylene) -bis (2,2 ′: 6 ′, 2 ″ -terpyridine) is synthesized, and the electrochemical redox reaction of Fe ions is used on the ITO substrate. An attempt was made to form a film by the EP method. As a result, an Fe-based organic / metal hybrid polymer thin film having a substantially constant film thickness and very high adhesion to an ITO substrate could be formed. This film had an optical switching time of 2 s and a transmittance. The study was completed by finding an electrochromic property of 54% change and color efficiency of 142.6 cm ² C ⁻¹ .
The present invention has the following configuration.

(1) A step of forming a conductor layer bonding layer made of a first organic molecule on the surface of a conductor layer formed on a substrate by a wet film forming method, and an electropolymerization method on the conductor layer bonding layer. And a step of forming an electrochromic layer comprising second organic molecules and metal ions.

(2) The method for forming an electrochromic film according to (1), wherein the first organic molecule is a molecule obtained by connecting a conductor layer bonding group, a spacer portion, and a coordination bond group in this order. .
(3) The method for forming an electrochromic film according to (1), wherein the second organic molecule is a molecule in which a coordination bond group, a spacer portion, and a coordination bond group are connected in this order.
(4) The method for forming an electrochromic film as described in (2), wherein the conductor layer bonding group is -Si- (O-R) ₃ group.

(5) The method for forming an electrochromic film according to (2) or (3), wherein the coordination bond group is a terpyridine group.
(6) The method for forming an electrochromic film according to (2) or (3), wherein the spacer portion has a benzene skeleton.
(7) The electrochromic film forming method according to (1), wherein the wet film forming method is any one of a spin coating method, a spray coating method, a casting method, a dip method, and an ink jet method.

(8) A solution obtained by dispersing the second organic molecules and metal ions in a solvent by using the substrate on which the conductor layer bonding layer made of the first organic molecules is formed on the surface of the conductor layer by the electrolytic polymerization method. The method for forming an electrochromic film according to (1), wherein the electrode is immersed together with a counter electrode and a reference electrode, and a voltage is applied between the electrodes.
(9) The method for forming an electrochromic film according to (8), wherein a constant voltage is applied.
(10) The method for forming an electrochromic film according to (8), wherein a cyclic voltage is applied.

(11) An electrochromic film comprising a conductor layer bonding layer and an electrochromic layer.
(12) The conductor layer bonding layer is a layer made of a first organic molecule in which a conductor layer bonding group, a spacer portion, and a coordination bond group are connected in this order, and the conductor layer bonding group is on the same surface. The electrochromic film according to (11), wherein the first organic molecules are arranged so as to form
(13) The electrochromic layer is a layer composed of a second organic molecule and a metal ion in which a coordination bond group, a spacer part, and a coordination bond group are connected in this order, and the arrangement of different second organic molecules. The electrochromic film according to (11), wherein the coordinate bonding group is coordinated by sharing one metal ion and the second organic molecule is linked.

(14) The electrochromic film according to (12), wherein the conductor layer bonding group is -Si- (O-R) ₃ group.
(15) The electrochromic film according to (12) or (13), wherein the coordination bond group is a terpyridine group.
(16) The electrochromic film according to (12) or (13), wherein the spacer portion has a benzene skeleton.

(17) The first organic molecule is 4 ′-(4- (2- (triethoxysilyl) vinyl) phenyl) -2,2 ′: 6 ′, 2 ″ -terpyridine ( The electrochromic film as described in 12).
(18) The second organic molecule is 4′4 ′ ″ ″-(1,4-phenylene) -bis (2,2 ′: 6 ′, 2 ″ -terpyridine) ( The electrochromic film as described in 13).

(19) A substrate, a conductor layer formed on the substrate, and the electrochromic film according to any one of (11) to (18) coated on the surface of the conductor layer. A substrate with an electrochromic film coated conductor layer.
(20) The substrate with an electrochromic film-coated conductor layer according to (19), wherein the conductor layer is an ITO layer or a ZnO layer.

The electrochromic film forming method of the present invention includes a step of forming a conductor layer bonding layer made of a first organic molecule on the surface of a conductor layer formed on a substrate by a wet film forming method, and an electrolytic polymerization method. And a step of forming an electrochromic layer composed of second organic molecules and metal ions on the conductive layer bonding layer, so that an electro that can be firmly bonded to a substrate with a conductive layer, for example, an ITO substrate. A chromic film can be easily formed.

Since the electrochromic film of the present invention comprises a conductor layer bonding layer and an electrochromic layer, it can be firmly bonded to a substrate with a conductor layer, for example, an ITO substrate.

Since the substrate with an electrochromic film coated conductor layer of the present invention has a substrate, a conductor layer formed on the substrate, and the electrochromic film described above coated on the surface of the conductor layer, A substrate with a conductor layer coated with an electrochromic film firmly bonded to the conductor layer, for example, an ITO substrate can be provided.

It is the schematic which shows an example of the electrochromic film | membrane which is embodiment of this invention, Comprising: It is a top view (a), a side view (b), and A part enlarged view (c). It is a figure which shows an example of a 1st organic molecule. It is a figure which shows an example of a 2nd organic molecule. It is a flowchart figure which shows an example of the film-forming method of the electrochromic film | membrane which is embodiment of this invention. It is process drawing which shows an example of a conductor operation joining layer formation process. It is process drawing which shows an example of the apparatus before a voltage application. It is the B section enlarged view before voltage application. It is the B section enlarged view at the moment of applying a voltage. It is the B section enlarged view at the moment of applying a voltage. It is the B section enlarged view immediately after that. Furthermore, it is the B section enlarged view immediately after that. Furthermore, it is the B section enlarged view immediately after that. Furthermore, it is the B section enlarged view immediately after that. It is another schematic diagram explaining the voltage application process. It is process drawing which shows an example of the apparatus after a voltage application. It is the schematic of a production substrate. It is an electropolymerization process figure before electropolymerization. It is an electrolytic-polymerization process figure after electrolytic polymerization (20 cycles). It is a graph which shows the CV measurement result of an EP-MSP thin film creation process. It is an absorbance measurement process figure at 2500 s. It is a graph which shows an absorbance measurement result. It is a CV graph of an organic / metal hybrid polymer film. It is a graph which shows the voltage value dependence measurement result of a light absorbency. It is explanatory drawing of the electrochromic phenomenon of an organic / metal hybrid polymer film. It is a graph which shows the scanning speed dependence of CV of an organic / metal hybrid polymer film. It is an AFM image of the surface of an organic / metal hybrid polymer film. It is a graph which shows the reproduction test result of an electrochromic characteristic. It is a graph which shows the CV measurement result at the time of using the ITO board | substrate which does not coat with L1.

(Electrochromic film)
First, an electrochromic film that is an embodiment of the present invention will be described.
FIG. 1 is a schematic view showing an example of an electrochromic film according to an embodiment of the present invention, and is a plan view (a), a side view (b), and an enlarged view of part A (c).
As shown in FIG. 1A, an electrochromic film 10 according to an embodiment of the present invention has a substantially rectangular shape in plan view. However, the present invention is not limited to this, and may be a polygonal shape in plan view, a circular shape in plan view, or the like.
The electrochromic layer 14 is exposed on the surface.

As shown in FIG. 1B, an electrochromic film 10 according to an embodiment of the present invention is formed on a substrate 15 with a conductor layer.
The substrate 15 with a conductor layer is configured by forming a conductor layer 12 on a substrate 11.
Examples of the conductor layer 12 include an ITO (indium tin oxide) layer or a ZnO (zinc oxide) layer. The conductor layer bonding layer 13 can be firmly bonded to these conductor layers 12.
As the substrate 11, a glass substrate, a quartz substrate, a plastic substrate, or the like can be used. A transparent substrate is preferred as a display element application.

A conductor layer bonding layer 13 is formed on the surface of the conductor layer 12 on the substrate 11, an electrochromic layer 14 is formed on the conductor layer bonding layer 13, and the electrochromic film 10 is formed.
As shown in FIG. 1C, the first organic molecules L <b> 1 are densely arranged on the conductor layer 12 to form the conductor layer bonding layer 13. The conductor layer bonding layer 13 is formed of a single molecular layer of the first organic molecules L1.

The second organic molecules L2 are densely arranged on the conductor layer bonding layer 13 to form the electrochromic layer 14.
The electrochromic layer 14 is formed of a bimolecular layer of a first layer 21 and a second layer 22. However, it is not limited to this. The electrochromic layer 14 is preferably a single molecular layer to a 1000 molecular layer of the second organic molecule L2, more preferably a 10 molecular layer to a 500 molecular layer, and a 50 molecular layer to a 400 molecular layer. Is more preferable. Thereby, the response speed of the electrochromic characteristics can be increased.

The second organic molecule L2 is upright and joined to each of the first organic molecules L1, and the second organic molecule L2 is upright and joined, and the electrochromic layer 14 is formed of the second organic molecule L2. It is formed of a bimolecular layer of a first layer 21 and a second layer 22 of second organic molecules L2.
Note that the electrochromic film 10 is not limited to such a dense aspect, and the first organic molecules L1 may be arranged apart from each other. In this case, the extended polymer chain is rounded and a hole is formed between adjacent polymer chains. Thereby, a porous film can be formed.

FIG. 2 is a diagram illustrating an example of the first organic molecule.
The first organic molecule L1 shown in FIG. 2 (a) is 4 '-(4- (2- (triethoxysilyl) vinyl) phenyl) -2,2': 6 ', 2 "-terpyridine. The diagram indicated by L1 is an explanatory model structure diagram.
As shown in FIG. 2B, the first organic molecule L1 is formed by connecting the conductor layer bonding group 41, the spacer portion 42, and the coordination bond group 43 in this order.
As shown in FIGS. 2A and 2B, examples of the conductor layer bonding group include —Si— (O—R) ₃ groups. By providing this bonding group, this bonding group can be bonded to the conductor layer as an anchor, and a film having high adhesive strength can be formed.

FIG. 3 is a diagram illustrating an example of the second organic molecule.
The second organic molecule L2 shown in FIG. 3 (a) is 4′4 ′ ″ ″-(1,4-phenylene) -bis (2,2 ′: 6 ′, 2 ″ -terpyridine). The diagram indicated by L2 is an explanatory model structure diagram.
As shown in FIG. 3B, the second organic molecule L2 is formed by connecting a coordination bond group 43, a spacer portion 42, and a coordination bond group 43 in this order.

As shown in FIGS. 2A and 3A, examples of the coordination bond group include a terpyridine group. Coordination bonds with metal ions can be made efficiently and with high bonding strength. Other examples include pyridine, bipyridine, and phenanthroline.
As shown in FIGS. 2A and 3A, examples of the spacer portion include a structure having a benzene skeleton. 2 or more and 5 or less benzene may be conjugated or non-conjugated, and C6 or less alkyl substituent may be bonded to benzene. When more than 5 benzenes are connected, it is difficult to arrange the molecules in a forest, which is not preferable. In addition, when an alkyl substituent of C7 or more is introduced, it is difficult to arrange them closely due to steric hindrance. In addition to the benzene skeleton, the spacer portion may be a rigid conjugated skeleton such as thiophene, carbazole, alkene, and alkyne.

In addition, as shown in FIG.1 (c), a 1st organic molecule is arrange | positioned so that the conductor layer joining base 41 may form the same surface, and the monomolecular layer 21 is formed. The conductor layer bonding group 41 is bonded to the conductor layer 12. Further, on the conductor layer bonding layer 13, the first organic molecule L1 and the second organic molecule L2 are coordinated and bonded by the metal ions 52, and the conductor layer bonding layer 13 and the electrochromic layer 14 are firmly connected. Is done. In addition, the coordination bond group of the second organic molecule L2 is coordinated by sharing one metal ion, and the second organic molecules L2 are connected to each other, so that the electrochromic layer 14 is firmly formed.

(Electrochromic film deposition method)
Next, a method for forming an electrochromic film according to an embodiment of the present invention will be described.
FIG. 4 is a flowchart showing an example of a method for forming an electrochromic film according to an embodiment of the present invention.
As shown in FIG. 4, the method for forming an electrochromic film according to an embodiment of the present invention includes a conductor manipulation bonding layer forming step S <b> 1 and an electrochromic layer forming step S <b> 2.

(Electric conductor operation joining layer formation process S1)
FIG. 5 is a process diagram showing an example of a conductor handling bonding layer forming process.
First, as shown in FIG. 5A, the conductor layer 12 is prepared. Usually, a substrate 15 with a conductor layer in which a conductor layer 12 is formed on a substrate 11 is prepared in response to a request for handling.
Next, the conductor layer bonding layer 13 made of the first organic molecules L1 is formed on the surface of the conductor layer 12 on the substrate 11 by a wet film forming method.

As the first organic molecule L1, a molecule in which the conductor layer bonding group 41, the spacer portion 42, and the coordination bond group 43 are connected in this order can be used.
Examples of the wet film forming method include any of a spin coating method, a spray coating method, a casting method, a dip method, and an ink jet method.

(Electrochromic layer forming step S2)
The electrochromic layer is formed by a method of applying a constant voltage between the electrodes or an electrolytic polymerization method of applying a cyclic voltage.

FIG. 6 is a process diagram showing an example of an apparatus before voltage application.
First, as shown in FIG. 6, a conductive layer bonding layer 13 formed on a conductive layer 12 of a substrate 15 with a conductive layer is used as a working electrode 49, and together with a counter electrode 48 and a reference electrode 47, a container 45. Is immersed in a solution in which the second organic molecules L2 and the metal ions 51 filled in the solvent are dispersed in the solvent 50. For example, an electrolyte such as LiClO ₄ is preferably added to the solvent. For example, a mixed solvent composed of acetonitrile (ACN) and DMSO or an ACN solvent is used.

The working electrode 49, the counter electrode 48, and the reference electrode 47 are connected to a power source (not shown) by wirings 46, 45, and 44, respectively, and a predetermined voltage can be applied between the electrodes.
As the 2nd organic molecule L2, the molecule | numerator which connected the coordination bond group 43, the spacer part 42, and the coordination bond group 43 in this order can be used.
The metal ion 51 is a metal ion that can be easily reduced, and is, for example, Fe ³⁺ . Fe ³⁺ is easily reduced to Fe ²⁺ .

FIG. 7 is an enlarged view of part B before voltage application. Before the voltage application, the coordination bond group such as terpyridine of the conductor layer bonding layer 13 made of the first organic molecule L1 on the conductor layer 12 is stable with the metal ion 51 such as Fe ^{3+ in} the solvent 50. Since no coordination bond can be formed, the second organic molecule L2 cannot be connected, and no film is formed on the conductor layer bonding layer 13.

After immersion, a predetermined voltage is applied between the electrodes.
8 and 9 are enlarged views of the B part at the moment when a voltage is applied. As shown in FIG. 8, electrons are emitted from the ITO surface. Thereby, the electric double layer region 60 is formed in the vicinity of the working electrode. As a result, the metal ions 51 in the electric double layer region 60 are reduced to become reduced metal ions 52. For example, Fe ³⁺ is defined as Fe ²⁺ .

FIG. 10 is an enlarged view of part B immediately after that. In the vicinity of the working electrode, metal ions 52 reduced in the electric double layer region 60, for example, Fe ^2+, are coordinated with a coordination bond group of the layer 13 composed of the first organic molecules 31 on the conductor layer 12.

FIG. 11 is an enlarged view of part B immediately after that. The coordination bond group of the second organic molecule L2 is coordinated to the reduced metal ion 52, for example, Fe ²⁺ coordinated with the coordination bond group of the layer 13 composed of the first organic molecule L1. The first layer 21 of the second organic molecule L2 is formed.

FIG. 12 is an enlarged view of part B immediately after that. The reduced metal ions 52 and Fe ²⁺ in the electric double layer region 60 are bonded to the coordination bond group of the first layer 21.

FIG. 13 is an enlarged view of part B immediately after that. A coordinate bond group of another second organic molecule L2 is coordinated to the reduced metal ion 52 coordinated with the first layer 21, for example, Fe ²⁺ , and the second organic molecule L2 Form two layers 22

8 to 13 are performed instantaneously when a voltage is applied.
FIG. 14 is another schematic diagram illustrating the voltage application process. When a voltage is applied, Fe ³⁺ in the solution is reduced to Fe ²⁺ by the electric double layer region, which connects the first organic molecule and the second organic molecule, and also connects the second organic molecule to each other. An electrochromic layer is formed instantaneously.

FIG. 15 is a process diagram showing an example of the apparatus after voltage application.
Through the above steps, the electrochromic layer 10 made of the second organic molecules L2 and the metal ions 52 is formed on the conductor layer bonding layer 13 made of the first organic molecules L1, and the electrochromic film 10 is formed. . As a result, a substrate 70 with an electrochromic film coating conductor layer having the substrate 11, the conductor layer 12 formed on the substrate 11, and the electrochromic film 10 coated on the surface of the conductor layer 12 is formed. .

In the electrochromic film forming method according to the embodiment of the present invention, the conductive layer bonding layer 13 made of the first organic molecules L1 is formed on the surface of the conductive layer 12 formed on the substrate 11 by a wet film forming method. And a step of forming the electrochromic layer 14 composed of the second organic molecules L2 and the metal ions 52 on the conductor layer bonding layer 13 by an electropolymerization method. For example, an electrochromic film that can be firmly bonded to an ITO substrate can be easily formed.

In the method for forming the electrochromic film 10 according to the embodiment of the present invention, the first organic molecule L1 is a molecule in which the conductor layer bonding group 41, the spacer part 42, and the coordination bond group 43 are connected in this order. Therefore, the conductor layer bonding layer 13 composed of the first organic molecules L1 firmly bonded to the substrate with the conductor layer, for example, the ITO substrate can be easily formed.

In the film formation method of the electrochromic film 10 according to the embodiment of the present invention, the second organic molecule L2 is a molecule in which the coordination bond group 43, the spacer part 42, and the coordination bond group 43 are connected in this order. The electrochromic layer 14 made of a connected organic / metal hybrid polymer can be easily formed by coordinating and bonding the second organic molecules L2 to each other with the metal ion 52 through the coordination bond group.

Since the method for forming the electrochromic film 10 according to the embodiment of the present invention is a structure in which the conductor layer bonding group 41 is —Si— (O—R) _3, it is strong on a substrate with a conductor layer, for example, an ITO substrate. Can be joined.

Since the method for forming the electrochromic film 10 according to the embodiment of the present invention is a configuration in which the coordination bond group 43 is a terpyridine group, it can be coordinated with a metal ion to form an organic / metal hybrid polymer.

In the film forming method of the electrochromic film 10 according to the embodiment of the present invention, since the spacer portion 42 has a benzene skeleton, a rigid film can be formed.

The electrochromic film 10 according to an embodiment of the present invention has a structure in which the wet film forming method is any one of a spin coating method, a spray coating method, a casting method, a dip method, and an ink jet method. The conductor layer bonding layer 13 made of the first organic molecules L1 firmly bonded to the attached substrate, for example, the ITO substrate can be easily formed.

The method of forming the electrochromic film 10 according to the embodiment of the present invention uses the substrate 11 in which the conductor layer bonding layer 13 made of the first organic molecule L1 is formed on the surface of the conductor layer 12 by the electrolytic polymerization method. Since the electrode 49 is configured to be immersed in a solution in which the second organic molecule L2 and the metal ion 51 are dispersed in the solvent 50 together with the counter electrode 48 and the reference electrode 47 and to apply a voltage between the electrodes, the second organic The electrochromic layer 14 composed of a connected organic / metal hybrid polymer can be easily formed by coordination bonding of the molecules L2 to the metal ion 52 through the coordination bond group.

Since the film forming method of the electrochromic film 10 according to the embodiment of the present invention is configured to apply a constant voltage, the electrochromic layer 14 made of an organic / metal hybrid polymer can be easily formed.

Since the film forming method of the electrochromic film 10 according to the embodiment of the present invention is configured to apply a cyclic voltage, the electrochromic layer 14 made of an organic / metal hybrid polymer can be easily formed.

Since the electrochromic film 10 according to the embodiment of the present invention is composed of the conductor layer bonding layer 13 and the electrochromic layer 14, it can be firmly bonded to a substrate with a conductor layer, for example, an ITO substrate. Electrochromic display can be performed.

The electrochromic film 10 according to the embodiment of the present invention includes a conductive layer bonding layer 13 from a first organic molecule L1 in which a conductive layer bonding group 41, a spacer portion 42, and a coordination bond group 43 are connected in this order. Since the first organic molecule L1 is arranged so that the conductor layer bonding base 41 forms the same surface, it can be firmly bonded to a substrate with a conductor layer, for example, an ITO substrate. it can.

In the electrochromic film 10 according to the embodiment of the present invention, the electrochromic layer 14 includes a second organic molecule L2 and a metal ion 52 in which the coordination bond group 43, the spacer portion 42, and the coordination bond group 43 are connected in this order. In which the coordination bond group 43 of the different second organic molecule L2 is coordinated and shared by sharing one metal ion 52, and the second organic molecule L2 is linked. The chromic display can be performed and the film thickness can be controlled.

Since the electrochromic film 10 according to the embodiment of the present invention has a structure in which the conductor layer bonding group 41 is -Si- (O-R) ₃ group, it is strongly bonded to a substrate with a conductor layer, for example, an ITO substrate. Can do.

Since the electrochromic film 10 according to the embodiment of the present invention has a configuration in which the coordination bond group 43 is a terpyridine group, a metal ion and a coordination bond group are coordinated to link organic molecules to form an organic / metal. An electrochromic layer made of a hybrid polymer can be formed.

The electrochromic film 10 according to the embodiment of the present invention can form a stable film because the spacer portion 42 has a benzene skeleton.

In the electrochromic film 10 according to the embodiment of the present invention, the first organic molecule L1 is 4 ′-(4- (2- (triethoxysilyl) vinyl) phenyl) -2,2 ′: 6 ′, 2 ″. -Since it is a structure which is terpyridine, it can be firmly joined to the board | substrate with a conductor layer, for example, an ITO board | substrate.

In the electrochromic film according to the embodiment of the present invention, the second organic molecule L2 is 4′4 ″ ″ ″-(1,4-phenylene) -bis (2,2 ′: 6 ′, 2 ″ -terpyridine. ), An electrochromic layer made of an organic / metal hybrid polymer can be formed.

The substrate 70 with an electrochromic film coated conductor layer according to an embodiment of the present invention includes a substrate 11, a conductor layer 12 formed on the substrate 11, an electrochromic film 10 coated on the surface of the conductor layer 12, Therefore, a substrate with a conductor layer coated with an electrochromic film firmly bonded to the conductor layer can be provided.

The substrate 70 with an electrochromic film coated conductor layer according to an embodiment of the present invention has a configuration in which the conductor layer 12 is an ITO layer or a ZnO layer, and thus an ITO substrate coated with an electrochromic film firmly bonded to the conductor layer. Alternatively, a ZnO layer can be provided.

The method for forming an electrochromic film, the electrochromic film, and the substrate with an electrochromic film-coated conductor layer, which are embodiments of the present invention, are not limited to the above-described embodiments, and are within the scope of the technical idea of the present invention. Thus, various modifications can be made. Specific examples of this embodiment are shown in the following examples. However, the present invention is not limited to these examples.

(Example 1)
(Creation of organic / metal hybrid polymer film by electrolytic polymerization of CV method)
First, a substrate with an ITO layer in which an ITO layer was formed on a glass substrate was prepared.
Next, a solution in which 4 ′-(4- (2- (triethoxysilyl) vinyl) phenyl) -2,2 ′: 6 ′, 2 ″ -terpyridine (L1) is dispersed is applied to the ITO surface. Then, the substrate was dried to produce a substrate having an L1 layer formed on the ITO surface.
FIG. 16 is a schematic view of a manufacturing substrate. As shown in FIG. 16, the ITO surface was not completely covered with L1, leaving a portion where the ITO surface was exposed.
L1 was synthesized by a known synthesis process.

Next, 4′4 ″ ″ ′-(1,4-phenylene) -bis (2,2 ′: 6 ′, 2 ″ -terpyridine) (L2) in a solvent to which LiClO ₄ was added (ACN + DMSO) Was dispersed in an equimolar amount with FeCl ₃ (Fe ³⁺ ) (purity:> 99.9%) to prepare an electroplating solution.
L2 had no binding affinity with FeCl ₃ (Fe ³⁺ ) at all, did not aggregate and precipitate, and could be a uniform dispersion solution.

FIG. 17 is an electrolytic polymerization process diagram before electrolytic polymerization.
Next, as shown in FIG. 17, a three-electrode system was used, and the previous substrate was used as a working electrode, and was immersed in an electroplating solution together with a counter electrode and a reference electrode.

Next, a voltage (CV) was periodically applied to the working electrode at a scan speed of 100 mVs ⁻¹ and 20 cycles.
FIG. 18 is an electrolytic polymerization process diagram after electrolytic polymerization (20 cycles).
As shown in FIG. 18, an organic / metal hybrid polymer (Electropolymerized metallo-supermolecular polymer: hereinafter abbreviated as EP-MSP) thin film was formed on an ITO substrate by electrolytic polymerization.

FIG. 19 is a graph showing a CV measurement result in the EP-MSP thin film forming step.
In the 1st cycle, two redox pairs appeared at the positions of −0.67 V / 0.31 V and 0.73 V / 1.00 V.

The reduction wave of −0.67 V is not due to the reduction of Fe ³⁺ ions bonded to L1 to Fe ²⁺ ions, and is not liganded to L2, and on the exposed ITO surface. This is because Fe ³⁺ ions are reduced to Fe ²⁺ ions.
On the other hand, the reduction wave of 0.73 V is due to reduction of Fe ³⁺ ions coordinated by L1 or L2 to Fe ²⁺ ions in the EP-MSP thin film. In the 1st cycle, the peak separation width was as narrow as 0.27V.

From the 1st cycle to the 20th cycle, as the number of cycles increased, the oxidation-reduction potential shifted at a constant rate. This time applies a negative potential, Fe ³⁺ in the solution is electrochemically reduced to Fe ^2+, organic / metal hybrid polymer film acts strong binding affinity between the L1 and Fe ²⁺ is in uniform thickness formed I guessed that it was.

When the number of cycles is increased from the 1st cycle to the 20th cycle, the redox pair at the positive potential (0.73V / 1.00V) increases and the redox pair at the negative potential (−0.67V / 0.31V) decreases. did. This was considered because the EP-MSP thin film was formed on the ITO surface, and the exposed ITO surface area decreased.

(Creation of organic / metal hybrid polymer film by electropolymerization method of Chronoamperometry)
Next, a thin film of an organic / metal hybrid polymer film was formed using a constant potential electrolysis method in which a constant negative voltage (−1.5 V) was applied to the working electrode, and the absorbance of the thin film was measured in situ.
In-situ measurement was performed when the voltage application time was 0, 100, 300, 500, 750, 1000, 1500, 2000, 2500 s.

FIG. 20 is an absorbance measurement process diagram at 2500 s.
After applying a constant negative voltage (-1.5 V) for 2500 s, the voltage application is stopped, the irradiated light is applied to the organic / metal hybrid polymer film on the spot, the transmitted light is measured, and the absorbance is measured. did.
Absorbance was measured in the same manner at each voltage application time.

FIG. 21 is a graph showing the absorbance measurement results.
As shown in FIG. 21, the peak wavelength λ _max was 578 nm. The absorbance at 578 nm is due to a metal-to-ligand charge transfer (abbreviated as MLCT) effect between L2 and Fe ²⁺ ions.
The absorbance at 0 s was weak. In the electroplating solution, Fe ²⁺ originates from impurities of FeCl ₃ or originates only from Fe ^3+, and it is presumed that L2 could hardly be bound because there was almost no Fe ²⁺ . On the other hand, the absorbance increased at a constant rate as the voltage application time was increased. As the voltage application time was increased, L2 was linked with Fe ²⁺ and became longer and linear, and the absorbance due to MLCT absorption from Fe ²⁺ bound to L 2 increased.

(CV of organic / metal hybrid polymer film)
Next, the CV of the organic / metal hybrid polymer film was measured in a positive potential range in a 0.1 M LiClO ₄ / ACN solution under the condition of a scan rate of 20 mVs ⁻¹ .
FIG. 22 is a CV graph of the organic / metal hybrid polymer film.
As shown in FIG. 22, redox waves appeared at 830 and 690 mV (vs. Ag / Ag ⁺ ). That is, at 0.6 V or more, the Fe ²⁺ ions in the polymer chain were oxidized to Fe ³⁺ ions. The potential difference (ΔEp) between the oxidation potential and the reduction potential in this oxidation-reduction wave was 140 mV. This value was significantly larger than that of the conventional organic / metal hybrid polymer film formed by spin coating or the like (27 mV: Non-Patent Document 9). This is thought to be because the polymer chain is oriented perpendicular to the electrode, so that the electron transfer between the polymer chains hardly occurs and the intra-polymer electron transfer between the metals via the long and rigid ligand L2 becomes rate-limiting. It is done.

(Electrochromic properties of organic / metal hybrid polymer film)
Next, the voltage value dependency of the absorbance when the voltage value applied to the working electrode was changed was observed in situ. The voltage values were 0, 0.6, 0.7, 0.75, 0.8, 0.9, and 1.0V.
FIG. 23 is a graph showing a measurement result of voltage dependence of absorbance.
As the voltage value was increased at 0.6 V or higher, the absorbance at the peak wavelength of 578 nm gradually decreased and almost disappeared at 1.0 V.

FIG. 24 is an explanatory diagram of the electrochromic phenomenon of the organic / metal hybrid polymer film.
Before voltage application, all metal ions of the EP-MSP film are Fe ²⁺ ions. When a voltage of 0.6 V is applied, some Fe ²⁺ ions are oxidized to Fe ³⁺ ions. When a voltage of 1.0 V is applied, all Fe ²⁺ ions are oxidized to Fe ³⁺ ions. The disappearance of the absorbance at 578 nm is due to the fact that the Fe ²⁺ ions in the polymer chain are oxidized to Fe ³⁺ ions and the MLCT effect of L1 and Fe ²⁺ ions disappears.
Note that once the Fe ²⁺ ions form an organic / metal hybrid polymer film, even if they are oxidized to Fe ³⁺ ions, the coordination bond is released and the connection is not released.

(Dependence of CV scan rate on organic / metal hybrid polymer film)
Next, CV of the organic / metal hybrid polymer film was measured in a 0.1 M LiClO ₄ / ACN solution under conditions of scan speeds of 10, 25, 50, 75, 100, 150, 200, 250, and 300 mVs ⁻¹ .
FIG. 25 is a graph showing the CV scan rate dependence of the organic / metal hybrid polymer film.
The peak current value increased as the scanning speed increased.

(AFM image of the surface of the organic / metal hybrid polymer film)
Next, an AFM image of the surface of the organic / metal hybrid polymer film was observed.
FIG. 26 is an AFM image of the surface of the organic / metal hybrid polymer film.
FIGS. 26A and 26B are AFM images of the surface of the organic / metal hybrid polymer film formed under the condition of applying a constant voltage of −1.5 V and 300 s, and FIGS. It is an AFM image of the surface of the organic / metal hybrid polymer film | membrane formed on the conditions of the constant voltage application of -1.5V and 2000s. The length of the bar in the image is 500 nm.
It was a fiber-like structure with a spherical polymer. The spherical polymer had an average diameter size of about 100 nm. The black shadow portion was a hole where no polymer was present, and minute irregularities were formed on the surface.

(Change of 578 nm transmittance of organic / metal hybrid polymer film)
Next, changes in the transmittance and current value of 578 nm of the organic / metal hybrid polymer film were observed when the applied voltage was switched between 0 V and 1.2 V every 10 s.
FIG. 27 is a graph showing the results of an electrochromic characteristics reproduction test.
FIG. 27A is a graph showing a change in transmittance at 578 nm of the organic / metal hybrid polymer film, and FIG. 27B is a graph showing a change in current in the field.
As shown in FIG. 27, both the current value and the transmittance according to the voltage were almost the same, indicating high reproducibility.
This film exhibited electrochromic properties with a switching time of 2 s, a transmittance change of 54%, and a color efficiency of 142.6 cm ² C ⁻¹ .

(Comparative Example 1)
CV measurement was performed in the same manner as in Example 1 except that an ITO substrate not coated with L2 was used instead of the substrate on which L2 was formed on the ITO surface.

FIG. 28 is a graph showing CV measurement results when an ITO substrate not coated with L1 is used.
Even if the number of cycles was increased from the 1st cycle to the 20th cycle, it increased in the positive potential range, but the redox pair of Fe ³⁺ / Fe ²⁺ ions in the negative potential range hardly changed. As a result, a slight EP-MSP thin film was formed on the ITO surface. However, due to the weak adhesive force, the thin film was easily peeled off in the electroplating solution after electrolytic polymerization, and no film was formed.

The method for forming an electrochromic film, the electrochromic film, and the substrate with an electrochromic film coating conductor layer of the present invention can easily form an electrochromic film firmly bonded to an ITO substrate. In addition, since the electrochromic film can be held stably and can exhibit good electrochromic characteristics, it is possible to produce a non-light emitting display device with high reproducibility and long element life, such as the information display device manufacturing industry, etc. May be available in

DESCRIPTION OF SYMBOLS 10 ... Electrochromic film | membrane, 11 ... Board | substrate, 12 ... ITO layer, 13 ... Conductor layer joining layer, 14 ... Electrochromic layer, 15 ... Substrate with ITO layer, 21 ... 1st layer of 2nd organic molecule, 22 ... Second layer of second organic molecule, 41 ... Conductor layer bonding group, 42 ... Spacer portion, 43 ... Coordination bonding group, 49 ... Working electrode, 44, 45, 46 ... Wiring, 47 ... Reference electrode, 48 ... Counter electrode 50 ... Solvent (including electrolyte), 51 ... Metal ion, 52 ... (Reduced) metal ion, 60 ... Electric double layer region, 70 ... Substrate with electrochromic film coating conductor layer, L1 ... First Organic molecule, L2 ... second organic molecule.

Claims (20)

Forming a conductive layer bonding layer made of a first organic molecule on the surface of the conductive layer formed on the substrate by a wet film formation method;
Forming an electrochromic layer composed of second organic molecules and metal ions on the conductor layer bonding layer by electrolytic polymerization. 2. The method of forming an electrochromic film according to claim 1, wherein the first organic molecule is a molecule in which a conductor layer bonding group, a spacer portion, and a coordination bond group are connected in this order. 2. The method of forming an electrochromic film according to claim 1, wherein the second organic molecule is a molecule in which a coordination bond group, a spacer portion, and a coordination bond group are connected in this order. The method for forming an electrochromic film according to claim 2, wherein the conductor layer bonding group is a —Si— (O—R) ₃ group. 4. The method for forming an electrochromic film according to claim 2, wherein the coordination bond group is a terpyridine group. The method for forming an electrochromic film according to claim 2, wherein the spacer portion has a benzene skeleton. 2. The electrochromic film forming method according to claim 1, wherein the wet film forming method is any one of a spin coating method, a spray coating method, a casting method, a dip method, and an ink jet method. In the electrolytic polymerization method, a substrate in which a conductive layer bonding layer made of first organic molecules is formed on the surface of the conductive layer is used as a working electrode, and a solution in which second organic molecules and metal ions are dispersed in a solvent 2. The method of forming an electrochromic film according to claim 1, wherein a voltage is applied between the electrodes by immersing together with the electrode and the reference electrode. The method of forming an electrochromic film according to claim 8, wherein a constant voltage is applied. The method for forming an electrochromic film according to claim 8, wherein a cyclic voltage is applied. An electrochromic film comprising a conductor layer bonding layer and an electrochromic layer. The conductor layer bonding layer is a layer made of a first organic molecule in which a conductor layer bonding group, a spacer part, and a coordination bond group are connected in this order;
12. The electrochromic film according to claim 11, wherein the first organic molecules are arranged so that the conductor layer bonding groups form the same surface. The electrochromic layer is a layer composed of a second organic molecule and a metal ion in which a coordination bond group, a spacer portion, and a coordination bond group are linked in this order;
The electrochromic film according to claim 11, wherein the coordination bond groups of different second organic molecules are coordinated by sharing one metal ion, and the second organic molecules are linked. The electrochromic film according to claim 12, wherein the conductor layer bonding group is —Si— (O—R) ₃ group. The electrochromic film according to claim 12 or 13, wherein the coordination bond group is a terpyridine group. The electrochromic film according to claim 12 or 13, wherein the spacer portion has a benzene skeleton. 13. The first organic molecule is 4 '-(4- (2- (triethoxysilyl) vinyl) phenyl) -2,2': 6 ', 2 "-terpyridine. The electrochromic film as described. 14. The second organic molecule is 4'4 "" "-(1,4-phenylene) -bis (2,2 ': 6', 2" -terpyridine). The electrochromic film as described. An electrochromic film comprising: a substrate; a conductor layer formed on the substrate; and the electrochromic film according to claim 11 coated on a surface of the conductor layer. A substrate with a coated conductor layer. The substrate with an electrochromic film-coated conductor layer according to claim 19, wherein the conductor layer is an ITO layer or a ZnO layer.