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WO2019066553A2 - Composite électrochromique, élément électrochromique le comprenant, et procédé de fabrication d'élément électrochromique - Google Patents

Composite électrochromique, élément électrochromique le comprenant, et procédé de fabrication d'élément électrochromique Download PDF

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WO2019066553A2
WO2019066553A2 PCT/KR2018/011526 KR2018011526W WO2019066553A2 WO 2019066553 A2 WO2019066553 A2 WO 2019066553A2 KR 2018011526 W KR2018011526 W KR 2018011526W WO 2019066553 A2 WO2019066553 A2 WO 2019066553A2
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unsubstituted
electrochromic
electrode
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WO2019066553A3 (fr
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임보규
이지영
장송림
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LG Chem Ltd
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LG Chem Ltd
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Priority claimed from KR1020180035643A external-priority patent/KR102319360B1/ko
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Priority to CN201880027308.1A priority Critical patent/CN110603309B/zh
Priority to JP2019559109A priority patent/JP6919140B2/ja
Priority to US16/607,760 priority patent/US11891571B2/en
Publication of WO2019066553A2 publication Critical patent/WO2019066553A2/fr
Publication of WO2019066553A3 publication Critical patent/WO2019066553A3/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • C09K9/02—Organic tenebrescent materials
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect

Definitions

  • the present invention relates to an electrochromic composite, an electrochromic device including the electrochromic composite, and a method of manufacturing the electrochromic device.
  • Electrochromism is a technique for changing the color of a material through an electrochemical reaction. Electrochromism is a phenomenon in which the insertion of a cation in the electrode structure by an electrochemical oxidation / reduction reaction, which is caused by a change in applied voltage, It is a characteristic that the color of a substance changes reversibly while electron density changes with desorption.
  • An electrochromic device is a device that changes color by an electrochemical reaction.
  • the electrochromic device when a potential difference is generated by an external electrical stimulus, ions or electrons contained in the electrolyte migrate into the electrochromic layer and an oxidation / reduction reaction occurs.
  • the color of the electrochromic device is changed by the redox reaction of the electrochromic layer.
  • Reduced coloring materials are substances that are colored when a cathodic reaction occurs and are discolored when an anodic reaction occurs.
  • the oxidative discoloring substance means a substance which is colored when it is oxidized and decolorized when it is a reducing reaction.
  • the electrochromic device exhibits a high contrast ratio and can be used for optical shutters, displays, smart windows, or automotive electrochromic mirrors due to its ease of transmission control, low driving voltage, bistability, It has been actively studied in application fields.
  • the present invention is to provide an electrochromic composite, an electrochromic device including the electrochromic composite, and a method of manufacturing the electrochromic device.
  • One embodiment of the present application relates to an organic compound having electrochromic properties; And a carbon nanotube in which at least a part of the surface is covered with a polymer.
  • An embodiment of the present application also includes a first electrode; A second electrode facing the first electrode; An electrolyte layer provided between the first electrode and the second electrode; And an electrochromic layer provided between the electrolyte layer and the second electrode, wherein the electrochromic layer comprises an electrochromic composite according to an embodiment of the present application.
  • one embodiment of the present application is a method comprising: preparing a first electrode; Forming a second electrode facing the first electrode; Forming an electrolyte layer between the first electrode and the second electrode; And forming an electrochromic layer between the electrolyte layer and the second electrode, wherein the electrochromic layer comprises an electrochromic composite according to one embodiment of the present application. to provide.
  • the electrochromic device uses an electrochromic composite comprising an organic compound having excellent electrochromic properties and a carbon nanotube having high charge mobility as an electrochromic layer, Color contrast), and at the same time, provides an electrochromic device improved in electric conductivity and process conditions.
  • the organic compound having an electrochromic property according to one embodiment of the present application is excellent in oxidation stability and has a long life when applied to an electrochromic device.
  • FIG. 1 is a side view of an electrochromic device according to one embodiment of the present application.
  • FIG. 2 is a view showing a form of a carbon nanotube containing a polymer according to an embodiment of the present application.
  • FIG. 8 is a diagram showing the UV spectrum of Compound 3. Fig.
  • FIG. 18 is a graph showing an absorption wavelength according to a voltage change applied to the electrochromic device according to Comparative Example 1.
  • Fig. 19 is a graph showing an absorption wavelength according to a voltage change applied to the electrochromic device according to the first embodiment.
  • FIG. 20 is a graph showing CV results of the electrochromic device according to Example 1 and Comparative Example 1. Fig.
  • FIGS. 21 to 25 are diagrams showing the difference in transmission between the coloration state and the bleaching state of Comparative Example 2 and Examples 2 to 5.
  • FIG. 21 to 25 are diagrams showing the difference in transmission between the coloration state and the bleaching state of Comparative Example 2 and Examples 2 to 5.
  • 26 is a graph showing the change in absorbance of the electrochromic device according to Example 5 according to a voltage change applied thereto.
  • One embodiment of the present application relates to an organic compound having electrochromic properties; And a carbon nanotube in which at least a part of the surface is covered with a polymer.
  • the organic compound having an electrochromic property may include a polymer having an electrochromic property or a compound having an electrochromic property, but the present invention is not limited thereto.
  • the thin film is uniform, and it is difficult to produce a thick film. Even if the diaphragm can be made thick, the transmittance may be low. As a result, electrochromic contrast using only carbon nanotubes is poor, and carbon nanotubes themselves have poor solubility in organic solvents, so that it is difficult to control the thickness of the thin film.
  • an electrochromic layer when an electrochromic layer is formed using an electrochromic organic compound alone, it has an advantage of excellent electrochromic contrast. However, since it has poor thermal stability and low charge mobility compared to other electrochromic materials such as an oxide semiconductor, Is slow.
  • Carbon nanotubes may have excellent electrical conduction properties, but have limitations in their use in solution processes. Carbon nanotubes can be applied to electrochromic films by other methods than solution processes. However, when the film is formed thick, the degree of bleaching of the carbon nanotubes is unclear due to their low transparency. Therefore, when a polymer-wound carbon nanotube is used, it is possible to form a thin film with good dispersibility, but the electrochromic phenomenon itself is hardly observed.
  • the electrochromic characteristics of the electrochromic organic compound by introducing the electroconductive property, which is an excellent characteristic of the carbon nanotube, by mixing the electrochromic organic compound and the carbon nanotube wound with the polymer .
  • the present application is based on the finding that the use of carbon nanotubes in which at least a part of the surface of the carbon nanotubes is covered with a polymer makes it possible to obtain an electrochromic device having an excellent dispersibility in an organic solvent,
  • the present invention provides an electrochromic device having improved electrochromic characteristics (color contrast) and improved electrical conductivity and process conditions by being used in an electrochromic layer.
  • this includes not only the case where the member is in contact with the other member but also the case where another member exists between the two members.
  • a carbon nanotube having a polymer covered at least a part of the surface thereof has a structure in which the polymer is surrounded by carbon nanotubes.
  • the shape of the carbon nanotubes containing the polymer is such that the polymer has a structure spirally surrounded by the carbon nanotubes.
  • FIG. 2 is a view showing a form of a carbon nanotube in which a polymer is covered at least a part of the surface according to an embodiment of the present application.
  • the carbon nanotube has a structure in which a polymer is spirally surrounded by a carbon nanotube.
  • the polymer comprises at least one selected from the group consisting of a thiophene-based polymer and a fluorene-based polymer.
  • thiophene-based polymer examples include, but are not limited to, P3HT (poly (3-hexylthiophene)) and P3DDT (poly (3-dodecylthiophene-2,5-diyl).
  • the fluorene-based polymer includes, but is not limited to, poly (9,9-di-n-octylfluorenyl-2,7-diyl).
  • the polymer may be P3HT (Poly (3-hexylthiophene)).
  • the weight ratio of the organic compound and the carbon nanotubes covered with the polymer may be 10: 1 to 400: 1, preferably 35: 1 to 150: 1.
  • the weight ratio of the organic compound to the carbon nanotubes covered with the polymer is 10: 1 to 400: 1.
  • the solvent a commonly used solvent may be used, and it is not particularly limited as long as it is capable of dissolving an organic compound having an electrochromic property, specifically, an organic solvent.
  • organic solvent examples include chlorobenzene, toluene, chloroform, 1,2-dichlorobenzene, xylene, and the like, and are not limited as long as they can dissolve an organic compound having an electrochromic property.
  • the polymer is used in an amount of 30 parts by weight to 200 parts by weight, preferably 35 parts by weight to 190 parts by weight, and more preferably 40 parts by weight, based on 100 parts by weight of the carbon nanotubes, Parts by weight to 180 parts by weight.
  • the content of the polymer is in the above range, it is possible to drive the electrochromism even at a low voltage due to an increase in charge mobility and the like, and the coloration and bleaching speed can be accelerated.
  • the electrochromic composite according to one embodiment of the present application can form an electrochromic composite in which an organic compound having excellent electrochromic properties is mixed with the carbon nanotube because the carbon nanotube contains a polymer, Thus, it can be used as an electrochromic layer of an electrochromic device.
  • the weight average molecular weight of the polymer may be from 3,000 g / mol to 1,000,000 g / mol, preferably from 5,000 g / mol to 1,000,000 g / mol.
  • the thermal stability of the polymer itself increases, and when used as an electrochromic layer of the electrochromic device, the thermal stability of the electrochromic device may increase.
  • the organic compound having an electrochromic property may be represented by any one of the following formulas (1) to (7).
  • Ar1 and Ar2 are the same or different and are each a group independently acting as an electron acceptor
  • Ar 3 to Ar 6 are the same or different from each other, and each independently hydrogen; heavy hydrogen; halogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; A substituted or unsubstituted alkoxy group; Or SiRR'R "
  • A is a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
  • T1 and T2 are the same or different and are each independently a direct bond; O; Or S,
  • R1 to R18 are the same or different from each other, and each independently hydrogen; A halogen group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
  • p and q are each an integer of 0 to 5
  • a and b are each an integer of 0 to 3
  • n is an integer of 1 to 1000
  • a1 is a number of 0 ⁇ a1 ⁇ 1
  • a2 is a number of 0 ⁇ a2 ⁇ 1
  • b1 is a number of 0 ⁇ b1 ⁇ 1
  • b2 is a number of 0 ⁇ b2 ⁇
  • a1 + a2 and b1 + b2 are integers of 1,
  • n1, m2, m3, n1 and n2 are integers of 0 to 4, respectively.
  • the weight average molecular weight of the organic compound of Formulas 4 to 7 may be 1000 g / mol or more and 100000 g / mol or less, preferably 10000 g / mol or more and 70000 g / mol or less.
  • And Quot means a moiety connected to another substituent.
  • substituted or unsubstituted A halogen group; A nitrile group; A nitro group; A hydroxy group; A carbonyl group; An ester group; Imide; An amino group; Phosphine oxide groups; An alkoxy group; An aryloxy group; An alkyloxy group; Arylthioxy group; An alkylsulfoxy group; Arylsulfoxy group; Silyl group; Boron group; An alkyl group; A cycloalkyl group; An alkenyl group; An aryl group; Aralkyl groups; An aralkenyl group; An alkylaryl group; An alkylamine group; An aralkylamine group; A heteroarylamine group; An arylamine group; Arylphosphine groups; And a heterocyclic group, or a substituted or unsubstituted one in which at least two of the above-exemplified substituents are connected to each other.
  • &quot a substituent to which at least two substituents are connected " may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.
  • examples of the halogen group include fluorine, chlorine, bromine or iodine.
  • the carbon number of the carbonyl group is not particularly limited, but it is preferably 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.
  • the ester group may be substituted with an ester group oxygen by a straight-chain, branched or cyclic alkyl group having 1 to 40 carbon atoms or an aryl group having 6 to 30 carbon atoms.
  • it may be a compound of the following structural formula, but is not limited thereto.
  • the number of carbon atoms of the imide group is not particularly limited, but is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.
  • the silyl group may be represented by the formula of -SiRaRbRc, wherein Ra, Rb and Rc are each hydrogen; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group.
  • Specific examples of the silyl group include, but are not limited to, trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, triphenylsilyl, diphenylsilyl and phenylsilyl groups. Do not.
  • the boron group may be represented by the formula of -BRaRbRc, wherein Ra, Rb and Rc are each hydrogen; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group.
  • the boron group specifically includes, but is not limited to, a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, and a phenylboron group.
  • the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the alkyl group has 1 to 20 carbon atoms. According to another embodiment, the alkyl group has 1 to 10 carbon atoms. According to another embodiment, the alkyl group has 1 to 6 carbon atoms.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, an n-propyl group, an isopropyl group, a butyl group, a n-butyl group, an isobutyl group, Hexyl group, 1-methylpentyl group, 2-methylpentyl group, 4-tert-butylpentyl group, 1-methylbutyl group, Methyl-2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, heptyl group, n-heptyl group, 1-methylhexyl group, cyclopentylmethyl group, cyclohexylmethyl group, octyl group, ethylhexyl group, 1-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, Propyl group,
  • the alkoxy group may be linear, branched or cyclic.
  • the number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 40 carbon atoms. Specific examples include methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, N-hexyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, But is not limited thereto.
  • Substituents comprising the alkyl groups, alkoxy groups and other alkyl moieties described herein include both straight chain and branched forms.
  • the alkenyl group may be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another embodiment, the alkenyl group has 2 to 6 carbon atoms.
  • Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, Butenyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, (Diphenyl-1-yl) vinyl-1-yl, stilbenyl, stilenyl, and the like.
  • the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms. According to one embodiment, the cycloalkyl group has 3 to 40 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 6 carbon atoms.
  • cyclopropyl cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.
  • the number of carbon atoms of the alkylamine group is not particularly limited, but is preferably 1 to 40.
  • Specific examples of the alkylamine group include a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine group, a phenylamine group, a naphthylamine group, a biphenylamine group, an anthracenylamine group, Group, a diphenylamine group, a phenylnaphthylamine group, a ditolylamine group, a phenyltolylamine group, a triphenylamine group, and the like, but are not limited thereto.
  • examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group.
  • the aryl group in the arylamine group may be a monocyclic aryl group or a polycyclic aryl group.
  • the arylamine group containing two or more aryl groups may contain a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group at the same time.
  • arylamine group examples include phenylamine, naphthylamine, biphenylamine, anthracenylamine, 3-methylphenylamine, 4-methyl-naphthylamine, 2-methyl- But are not limited to, cenylamine, diphenylamine, phenylnaphthylamine, ditolylamine, phenyltolylamine, carbazole and triphenylamine groups.
  • examples of the heteroarylamine group include a substituted or unsubstituted monoheteroarylamine group, a substituted or unsubstituted diheteroarylamine group, or a substituted or unsubstituted triheteroarylamine group.
  • the heteroaryl group in the heteroarylamine group may be a monocyclic heterocyclic group or a polycyclic heterocyclic group.
  • the heteroarylamine group containing at least two heterocyclic groups may contain a monocyclic heterocyclic group, a polycyclic heterocyclic group, or a monocyclic heterocyclic group and a polycyclic heterocyclic group at the same time.
  • examples of the arylphosphine group include a substituted or unsubstituted monoarylphosphine group, a substituted or unsubstituted diarylphosphine group, or a substituted or unsubstituted triarylphosphine group.
  • the aryl group in the arylphosphine group may be a monocyclic aryl group or a polycyclic aryl group.
  • the arylphosphine group having at least two aryl groups may contain a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group at the same time.
  • the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to one embodiment, the aryl group has 6 to 20 carbon atoms.
  • the aryl group may be a phenyl group, a biphenyl group, a terphenyl group or the like as the monocyclic aryl group, but is not limited thereto.
  • polycyclic aryl group examples include, but are not limited to, a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a triphenyl group, a klycenyl group and a fluorenyl group.
  • a fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure.
  • the heterocyclic group is a heterocyclic group and is a heterocyclic group containing at least one of N, O, P, S, Si and Se, and the number of carbon atoms is not particularly limited, but is preferably 1 to 60 carbon atoms. According to one embodiment, the number of carbon atoms of the heterocyclic group is from 1 to 30.
  • heterocyclic group examples include a pyridyl group, a pyrrolyl group, a pyrimidyl group, a pyridazinyl group, a furanyl group, a thiophenyl group, an imidazole group, a pyrazole group, an oxazole group, an isoxazole group, a thiazole group, A thiadiazole group, a thiadiazole group, a tetrazolyl group, a pyranyl group, a thiopyranyl group, a pyrazinyl group, an oxazinyl group, a thiazinyl group, a dioxinyl group, a triazinyl group, a tetrazinyl group, A phenanthridinyl group, a diazanaphthalenyl group, a triazinylidene group, an indole group, a a
  • heterocyclic group in the present specification, the description of the aforementioned heterocyclic group can be applied, except that the heteroaryl group is aromatic.
  • the aryl group in the aryloxy group, the arylthioxy group, the arylsulfoxy group, the arylphosphine group, the aralkyl group, the aralkylamine group, the aralkenyl group, the alkylaryl group, the arylamine group and the arylheteroarylamine group may be applied.
  • the alkyl group in the alkylthio group, the alkylsulfoxy group, the aralkyl group, the aralkylamine group, the alkylaryl group and the alkylamine group can be applied to the alkyl group described above.
  • heteroaryl group in the heteroaryl group, the heteroarylamine group and the arylheteroarylamine group can be applied to the description of the above-mentioned heterocyclic group.
  • alkenyl group in the aralkenyl group can be applied to the description of the alkenyl group described above.
  • aryl group described above can be applied except that arylene is a divalent group.
  • Ar1 and Ar2 are the same or different from each other and each is any one of the following structures.
  • c and d are integers of 1 to 4,
  • R15 to R20 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or
  • R15 to R20 are the same or different and each independently hydrogen; A halogen group; A nitrile group; Amide group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
  • R15 to R20 are the same or different and each independently hydrogen; A halogen group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
  • R15 to R20 are the same or different and each independently hydrogen; Or a substituted or unsubstituted alkyl group.
  • R15 to R20 are the same or different and each independently hydrogen; Or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.
  • R15 to R20 are the same or different and each independently hydrogen; Or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.
  • R15 to R20 are the same or different and each independently hydrogen; Or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.
  • R15 to R20 are the same or different and each independently hydrogen; Or an alkyl group having 1 to 10 carbon atoms.
  • R18 and R20 are hydrogen.
  • Arl and Ar2 are each Lt; 18 > and c are as described above.
  • Arl and Ar2 are each And R18 is hydrogen.
  • Arl and Ar2 are each And R < 15 > is as described above.
  • Arl and Ar2 are each And R15 is an alkyl group having 1 to 10 carbon atoms.
  • Arl and Ar2 are each And R19 is as described above.
  • Arl and Ar2 are each , R < 20 > and d are as described above.
  • Ar3 to Ar6 are the same or different and each independently hydrogen; heavy hydrogen; halogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; A substituted or unsubstituted alkoxy group; Or SiRR'R ".
  • Ar 3 to Ar 6 are the same or different and each independently is a substituted or unsubstituted alkyl group; Or SiRR'R ".
  • Ar 3 to Ar 6 are the same or different and each independently is a substituted or unsubstituted branched alkyl group; Or SiRR'R ".
  • Ar 3 to Ar 6 are the same or different and are each independently a substituted or unsubstituted, branched alkyl group having 3 to 30 carbon atoms; Or SiRR'R ".
  • Ar 3 to Ar 6 are the same or different and are each independently a substituted or unsubstituted, branched alkyl group having 3 to 20 carbon atoms; Or SiRR'R ".
  • Ar6 may be a substituted or unsubstituted, branched alkyl group having 3 to 20 carbon atoms.
  • A is a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group.
  • A provides an electrochromic composite comprising one of the following structures:
  • R21 is hydrogen; A halogen group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; A substituted or unsubstituted heteroaryl group,
  • R22 to R24 are the same or different and each independently represents a substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
  • e is an integer of 1 or 2
  • R 21 are the same or different from each other.
  • R21 is selected from the group consisting of hydrogen; Or a halogen group.
  • R21 is selected from the group consisting of hydrogen; Or fluorine.
  • R22 and R23 may be the same or different and each independently a substituted or unsubstituted alkyl group.
  • R22 and R23 may be the same or different and each independently an alkyl group substituted or unsubstituted with SiRR'R ".
  • R24 may be a substituted or unsubstituted aryl group.
  • R24 may be a substituted or unsubstituted aryl group having 6 to 40 carbon atoms.
  • R24 may be an aryl group having 6 to 40 carbon atoms substituted or unsubstituted with an alkoxy group having 1 to 15 carbon atoms.
  • R24 may be an aryl group having 6 to 40 carbon atoms substituted or unsubstituted with an octyloxy group.
  • R 1 to R 18 are the same or different and each independently hydrogen; A halogen group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group.
  • R 1 to R 18 are the same or different and are each independently selected from the group consisting of hydrogen; A halogen group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; A substituted or unsubstituted C6 to C30 aryl; Or a substituted or unsubstituted C2-C30 heteroaryl group.
  • R 1 to R 18 are the same or different and are each independently selected from the group consisting of hydrogen; A halogen group; An alkoxy group substituted or unsubstituted with an alkyl group having 1 to 30 carbon atoms; Or a linear or branched alkyl group having 3 to 30 carbon atoms.
  • R, R 'and R are the same or different from each other and each independently represents hydrogen, deuterium, halogen, nitrile, nitro, imide, amide, A substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, A substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryloxy group, a substituted or unsub
  • R, R 'and R are the same or different from each other and each independently hydrogen, a substituted or unsubstituted alkyl group, an alkylsilyloxy group, or an alkylthioxy group.
  • R, R 'and R " are the same or different from each other and each independently hydrogen, a linear or branched alkyl group, an alkylsilyloxy group, or an alkylthioxy group.
  • R, R 'and R are the same or different from each other and each independently represents hydrogen, a straight chain alkyl group having 1 to 10 carbon atoms, a branched chain alkyl group having 3 to 20 carbon atoms, an alkylsilyloxy group Or an alkylthio group.
  • a1 is a number of 0 ⁇ a1 ⁇ 1
  • a2 is a number of 0 ⁇ a2 ⁇
  • b1 is a number of 0 ⁇ b1 ⁇ 1
  • b2 is 0 ⁇ a2 ⁇ 1
  • a1 + a2 and b1 + b2 may be integers of 1.
  • a1 may be a number of 0 ⁇ a1 ⁇ 0.8
  • a2 may be a number of 0 ⁇ a2 ⁇
  • a1 may be a number of 0.5 ⁇ a1 ⁇ 0.8
  • a2 may be a number of 0 ⁇ a2 ⁇ 0.29.
  • a1 may be 0.75 and a2 may be 0.25.
  • A1 and a2 mean the molar ratio of the monomers contained in the repeating unit, and a1 may have a number larger than a2.
  • b1 may be a number of 0 ⁇ b1 ⁇ 0.6 and b2 may be a number of 0 ⁇ b2 ⁇ 0.6.
  • b1 may be a number 0.1 ⁇ b1 ⁇ 0.55
  • b2 may be a number 0.1 ⁇ b2 ⁇ 0.55.
  • b1 may be 0.5 and b2 may be 0.5.
  • B1 and b2 mean the molar ratio of the monomers contained in the repeating unit, and b1 and b2 may have the same number.
  • the organic compound having an electrochromic property may be represented by any one of the following compounds.
  • n is an integer of 1 to 1000;
  • One embodiment of the present application includes a first electrode; A second electrode facing the first electrode; An electrolyte layer provided between the first electrode and the second electrode; And an electrochromic layer provided between the electrolyte layer and the second electrode, wherein the electrochromic layer comprises an electrochromic composite according to an embodiment of the present application.
  • the first electrode and the second electrode are not particularly limited as long as they are well known in the art.
  • the first electrode and the second electrode may be formed of indium doped tin oxide (ITO), antimony doped tin oxide (ATO), fluorine doped tin oxide (FTO), indium doped zinc oxide (IZO) , Platinum, and the like, but is not limited thereto.
  • the first electrode and the second electrode may each be a transparent electrode.
  • ITO having a transmittance of 80% or more can be used.
  • the thicknesses of the first electrode and the second electrode are each independently 10 to 500 nm.
  • the first electrode or the second electrode may refer to a substrate coated with an anode active material commonly used in an electrochromic device.
  • the substrate may be a current collector, and a copper, nickel, or SUS current collector may be used depending on a voltage region.
  • a copper current collector may be used.
  • the anode may be coated with a conventional anode active material used in an electrochromic device, and may include lithium, a metal material that can be alloyed with lithium, a transition metal oxide, a material capable of doping and dedoping lithium , A material capable of reversibly inserting and removing lithium ions, and the like can be used.
  • the first electrode and the second electrode are each independently composed of lithium (Li), potassium (K), calcium (Ca), sodium (Na), magnesium (Mg) Aluminum, aluminum, zinc, iron, nickel, tin, lead, copper, indium, titanium, vanadium, And zirconium (Zr), or an alloy thereof.
  • transition metal oxide examples include vanadium oxide and lithium vanadium oxide.
  • material capable of doping and dedoping lithium examples include Si, SiOx (0 ⁇ x ⁇ 2), Si-Y alloy ( (Y is an alkali metal, an alkaline earth metal, a Group 13 element, a Group 14 element, a transition metal, a rare earth element or a combination element thereof and is not Si), Sn, SnO 2 , Sn- Earth metals, Group 13 elements, Group 14 elements, transition metals, rare earth elements, or combinations thereof, but not Sn), and at least one of them may be mixed with SiO 2 .
  • the element Y include, but are not limited to, Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ti, Ge, Pd, Ru, Os, Hs, Rh, Ir, Pd, P, As, Sb, Bi, S, Se, Te, Po, or a combination thereof.
  • any of carbonaceous anode active materials generally used in electrochromic devices can be used as the carbonaceous material, and typical examples thereof include crystalline carbon, amorphous carbon, Can be used.
  • the crystalline carbon include graphite such as natural graphite or artificial graphite of amorphous, flake, flake, spherical or fiber type.
  • the amorphous carbon include soft carbon (soft carbon) Or hard carbon, mesophase pitch carbide, fired coke, and the like.
  • the method of forming the electrochromic layer may employ any method known in the art, and is not particularly limited. For example, electroplating, sputtering, e-beam evaporation, chemical vapor deposition, or sol-gel coating may be used.
  • the production of the electrolyte layer may utilize materials and methods known in the art. Specifically, pentaerythritol triacrylate (PETA) monomer, 1M or more LiClO 4 , polycarbonate (PC), or the like can be used, but is not limited thereto.
  • PETA pentaerythritol triacrylate
  • 1M or more LiClO 4 polycarbonate
  • PC polycarbonate
  • a solid electrolyte or a liquid electrolyte may be used for the electrolyte layer and is not particularly limited as long as it can act to transfer ions and electrons.
  • the electrolyte layer may include a lithium salt, a plasticizer, an oligomer, a monomer, an additive, a radical initiator, and the like. Oligomers used in the present invention should be compatible with plasticizers.
  • the thickness of the electrochromic layer may be 10 nm or more and 1.5 ⁇ m or less, preferably 20 nm or more and 1 ⁇ m or less.
  • the degree of discoloration and coloring can be controlled by varying the thickness of the electrochromic layer. Thinness can be controlled when transparency is required, and thickness can be adjusted when opacity is required rather than transparency.
  • One embodiment of the present application is a method of manufacturing a semiconductor device, comprising: preparing a first electrode; Forming a second electrode facing the first electrode; Forming an electrolyte layer between the first electrode and the second electrode; And forming an electrochromic layer between the electrolyte layer and the second electrode, wherein the electrochromic layer comprises an electrochromic composite according to one embodiment of the present application. to provide.
  • the method of forming the electrochromic layer may be a solution process.
  • spin coating bar coating, slot die coating, and ink jet coating may be used.
  • FIG. 8 is a diagram showing the UV spectrum of Compound 3. Fig.
  • the compound 3 was dissolved in the chlorobenzene solution, and the film 3 was formed through the spin coating method in the solution state.
  • the precursor and 3-ethylrhodanine were dissolved in CHCl 3 , and three drops of piperidine were added at room temperature and refluxed for 24 hours. After the reaction, the reaction mixture was extracted with DCM, the residue was removed with MgSO 4 (magnesium sulfate), and the solvent was removed under reduced pressure. The residue was purified by silica column (eluent: CHCl 3 to CHCl 3 with EA) to give a dark green solid. The resulting solid (Compound 5) was recrystallized from CHCl 3 and hexane.
  • the precursor and terminal group were dissolved in CHCl 3 , and three drops of piperidine were added at room temperature and refluxed for 24 hours. After the reaction, the reaction mixture was extracted with DCM, the residue was removed with MgSO 4 (magnesium sulfate), and the solvent was removed under reduced pressure. The residue was purified by silica column (eluent: CHCl 3 to CHCl 3 with EA) to give a dark green solid (Compound 6). The resulting solid was recrystallized from CHCl 3 and hexane.
  • the precursor and the terminal group were dissolved in 10 mL of CHCl 3, and 5 mL of pyridine was added thereto at room temperature, followed by refluxing for 24 hours. After the reaction, the reaction mixture was extracted with DCM, the residue was removed with MgSO 4 (magnesium sulfate), and the solvent was removed under reduced pressure. The residual product was purified through silica column (eluent: CH 2 Cl 2 to CHCl 3 ) to give a dark purple solid (Compound 9).
  • the precursor and the terminal group were dissolved in 10 mL of CHCl 3 , 1 mL of piperidine was added at room temperature, and the mixture was refluxed for 24 hours. After the reaction, the reaction mixture was extracted with DCM, the residue was removed with MgSO 4 (magnesium sulfate), and the solvent was removed under reduced pressure. The residue was purified by silica column (eluent: CH 2 Cl 2 to CHCl 3 ) to give a dark purple solid (Compound 10).
  • a microwave reaction vessel was charged with M1 (215 mg, 0.525 mmol), M2 (106 mg, 0.175 mmol), M3 (712 mg, 0.7 mmol), tris (dibenzylideneacetone) dipalladium (0 mol%) (2 mol%) and tri (o-tolyl) phosphine (8 mol%) were dissolved in 6 mL of chlorobenzene. 20 minutes at 170 ° C, 30 minutes at 170 ° C, and 10 minutes at 180 ° C. After the polymerization, 2,5-bis (trimethylstannyl) thiophene and 4-bromobenzotrifluoride were added and further reacted at 150 ° C. for 30 minutes .
  • Compound 5 according to Preparation Example 5 was dissolved in chlorobenzene solvent in a concentration of 7 wt% and carbon nanotubes surrounded by P3HT (poly (3-hexylthiophene) were mixed with a chlorobenzene solution (concentration -100 ⁇ g / mL) And then the mixture was mixed in a volume ratio of 1: 1. Then, the mixture was spin-coated on an ITO (indium tin oxide) substrate as a working electrode and dried, and LiClO 4 was dissolved in propylene carbonate as an electrolyte layer. And a silver electrode were used to fabricate an electrochromic device.
  • P3HT poly (3-hexylthiophene
  • Example 1 an electrochromic device was fabricated in the same manner as in Example 1 except that P3HT (poly (3-hexylthiophene) -containing carbon nanotubes were not used.
  • P3HT poly (3-hexylthiophene) -containing carbon nanotubes
  • the electrochromic device manufactured according to Example 1 and Comparative Example 1 was subjected to measurement of change in absorption wavelength according to a voltage change. The results are shown in FIGS. 18 and 19.
  • FIG. 20 is a graph showing CV results of Example 1 and Comparative Example 1. Fig. As can be seen from FIG. 20, it was confirmed that the electrochromic device of Example 1 decreased the oxidation potential by about 0.2 V as compared with the electrochromic device of Comparative Example 1 on CV, which means that the electrochemical reaction activity was increased .
  • P3HT was dissolved in chlorobenzene solvent to a concentration of 7 wt%, and carbon nanotubes surrounded by P3HT (poly (3-hexylthiophene) were mixed with chlorobenzene solution (concentration -100 ⁇ g / mL) at a volume ratio of 0.5: 1.
  • ITO indium tin oxide
  • LiClO 4 was dissolved in propylene carbonate as an electrolyte layer, which was used as an electrolyte, and a counter electrode and a reference electrode were electroplated A coloring element was prepared.
  • P3HT was dissolved in chlorobenzene solvent to a concentration of 7 wt%, and carbon nanotubes surrounded by P3HT (poly (3-hexylthiophene) were mixed in a 1: 1 volume ratio with chlorobenzene solution (concentration -100 ⁇ g / mL)
  • ITO indium tin oxide
  • LiClO 4 was dissolved in propylene carbonate as an electrolyte layer, which was used as an electrolyte, and a counter electrode and a reference electrode were electroplated A coloring element was prepared.
  • P3HT was dissolved in a chlorobenzene solvent to a concentration of 7 wt%, and then carbon nanotubes surrounded by poly (3-hexylthiophene) were mixed with a chlorobenzene solution (concentration: -100 ⁇ g / mL) in a volume ratio of 2: 1.
  • ITO indium tin oxide
  • LiClO 4 was dissolved in propylene carbonate as an electrolyte layer, which was used as an electrolyte, and a counter electrode and a reference electrode were electroplated A coloring element was prepared.
  • the electrochromic device was fabricated in the same manner as in Example 2 except that P3HT (poly (3-hexylthiophene) -containing carbon nanotubes were not used in Example 2.
  • Compound 13 according to Preparation Example 13 was dissolved in chlorobenzene solvent in a concentration of 7 wt%, and carbon nanotubes surrounded by P3HT (poly (3-hexylthiophene) were mixed with chlorobenzene solution (concentration -100 ⁇ g / mL) And then the mixture was mixed in a volume ratio of 1: 1. Then, the mixture was spin-coated on an ITO (indium tin oxide) substrate as a working electrode and dried, and LiClO 4 was dissolved in propylene carbonate as an electrolyte layer. And a silver electrode were used to fabricate an electrochromic device.
  • P3HT poly (3-hexylthiophene
  • the electrochromic devices prepared according to Example 5 were subjected to measurement of spectroelectrochemical graphs according to the voltage change. The results are shown in FIG. 26.
  • FIGS. 21 to 25 are diagrams showing the difference in transmittance between the coloration state and the bleaching state of Comparative Example 2 and Examples 2 to 5.
  • FIG. 21 to 25 are diagrams showing the difference in transmittance between the coloration state and the bleaching state of Comparative Example 2 and Examples 2 to 5.
  • FIG. 21 is a graph showing the difference in transmittance between the coloration state and the bleaching state of Comparative Example 2.
  • FIG. 21 the difference in transmission between the coloration state and the bleaching state is 42.3%, the coloration speed is 1.1 seconds, and the bleaching speed is 1.5 seconds.
  • FIG. 22 is a graph showing the difference in transmission between the coloration state and the bleaching state of Example 2.
  • FIG. The difference in transmittance between the coloration state and the bleaching state was 42.8%, which is not much different from that of Comparative Example 2 in which carbon nanotubes were not mixed.
  • the change in transmittance was not significant, the coloring speed was 0.4 seconds and the bleaching speed was 0.4 seconds.
  • the rate of electrochromatography was improved as compared with Comparative Example 2.
  • FIG. 23 is a graph showing the difference in transmittance between the coloration state and the bleaching state of Example 3.
  • the difference in transmittance between the coloration state and the bleaching state is 43.5%, which means that the carbon nanotubes are not mixed
  • the coloring speed was 0.5 seconds and the bleaching speed was 1.1 seconds as compared with Comparative Example 2, although there was no significant difference from Comparative Example 2 in which the carbon nanotubes were introduced , It was confirmed that the rate of electrochromatography was improved.
  • FIG. 24 is a graph showing the difference in transmittance between the coloration state and the bleaching state of the fourth embodiment.
  • the difference in transmittance between the coloration state and the bleaching state was 33.6%, the coloration speed was 0.4 seconds, and the bleaching speed was 0.5 seconds.
  • Comparative Example 2 Of the total population.
  • FIG. 25 is a graph showing the difference in transmittance between the coloration state and the bleaching state of the fifth embodiment.
  • the difference in transmittance between the coloration state and the bleaching state was 19.5%, the coloration speed was 0.19 seconds, and the bleaching speed was 0.47 seconds.
  • Comparative Example 2 Of the total population.
  • the carbon nanotube-based electrochromic coloring has a disadvantage in that the transmittance is poor in a coloration state, but the carbon nanotube-based carbon nanotube (P3HT) It can be seen that there is no great difference in the transmittance of the coloration state of the second to fourth embodiments relative to the second comparative example.
  • the coloration rate refers to the time taken to have the color in the discolored state-the time taken to less than 5% of the final color (transmittance). For example, if the transmittance of a colored state is 0% and the transmittance of a decolored state is 100%, the time it takes to change from 100% to 5% is the coloration speed.
  • the bleaching speed means the time taken to decolorize in the state of having color - the time taken up to less than 5% of the final decoloring. For example, assuming that the transmittance of a colored state is 0% and the transmittance of a decolored state is 100%, the time it takes to change from 0% to 95% is the bleaching speed.

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Abstract

La présente invention concerne un composite électrochromique, un élément électrochromique le comprenant, et un procédé de fabrication d'un élément électrochromique.
PCT/KR2018/011526 2017-09-28 2018-09-28 Composite électrochromique, élément électrochromique le comprenant, et procédé de fabrication d'élément électrochromique Ceased WO2019066553A2 (fr)

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CN201880027308.1A CN110603309B (zh) 2017-09-28 2018-09-28 电致变色复合材料、包含其的电致变色元件和电致变色元件的制造方法
JP2019559109A JP6919140B2 (ja) 2017-09-28 2018-09-28 エレクトロクロミック複合体、これを含むエレクトロクロミック素子およびエレクトロクロミック素子の製造方法
US16/607,760 US11891571B2 (en) 2017-09-28 2018-09-28 Electrochromic composite, electrochromic element comprising same, and manufacturing method for electrochromic element

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CN110003245A (zh) * 2019-04-09 2019-07-12 常州大学 一类烷基/硫烷基氮杂芳环末端的D(A-Ar)2型共轭化合物及其制备方法与应用
US11094890B2 (en) 2017-09-18 2021-08-17 Lg Chem, Ltd. Organic transistor
US11158818B2 (en) * 2017-03-21 2021-10-26 Lg Chem, Ltd. Compound and organic solar cell comprising same
CN114874169A (zh) * 2022-03-18 2022-08-09 上海钥熠电子科技有限公司 有机化合物、包含该有机化合物的材料和有机发光器件
US11422425B2 (en) 2017-07-10 2022-08-23 Lg Chem, Ltd. Electrochromic device comprising electrochromic compound and manufacturing method therefor

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KR100880523B1 (ko) * 2005-12-30 2009-01-28 주식회사 엘지화학 공융혼합물을 포함하는 전해질을 구비한 전기변색소자
MX2012011075A (es) * 2010-03-25 2013-02-21 Univ Connecticut Formacion de polimeros conjugados para dispositivos de estado solido.
CN103777424A (zh) * 2012-10-17 2014-05-07 珠海兴业绿色建筑科技有限公司 一种光电致变色器件
CN104774432B (zh) * 2015-04-15 2018-01-26 华中科技大学 一种聚3‑己基噻吩/碳纳米管复合材料及制备方法

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US11158818B2 (en) * 2017-03-21 2021-10-26 Lg Chem, Ltd. Compound and organic solar cell comprising same
US11422425B2 (en) 2017-07-10 2022-08-23 Lg Chem, Ltd. Electrochromic device comprising electrochromic compound and manufacturing method therefor
US11094890B2 (en) 2017-09-18 2021-08-17 Lg Chem, Ltd. Organic transistor
CN110003245A (zh) * 2019-04-09 2019-07-12 常州大学 一类烷基/硫烷基氮杂芳环末端的D(A-Ar)2型共轭化合物及其制备方法与应用
CN110003245B (zh) * 2019-04-09 2021-06-22 常州大学 一类烷基/硫烷基氮杂芳环末端的D(A-Ar)2型共轭化合物及其制备方法与应用
CN114874169A (zh) * 2022-03-18 2022-08-09 上海钥熠电子科技有限公司 有机化合物、包含该有机化合物的材料和有机发光器件
CN114874169B (zh) * 2022-03-18 2024-06-04 上海钥熠电子科技有限公司 有机化合物、包含该有机化合物的材料和有机发光器件

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