CN106489051A - Light-emitting electrochemical element and the light-emitting device with this light-emitting electrochemical element - Google Patents
Light-emitting electrochemical element and the light-emitting device with this light-emitting electrochemical element Download PDFInfo
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- CN106489051A CN106489051A CN201580029272.7A CN201580029272A CN106489051A CN 106489051 A CN106489051 A CN 106489051A CN 201580029272 A CN201580029272 A CN 201580029272A CN 106489051 A CN106489051 A CN 106489051A
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- electrochemical element
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- emitting electrochemical
- emitting
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- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 1
- 125000005497 tetraalkylphosphonium group Chemical group 0.000 description 1
- KBLZDCFTQSIIOH-UHFFFAOYSA-M tetrabutylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC KBLZDCFTQSIIOH-UHFFFAOYSA-M 0.000 description 1
- WGHUNMFFLAMBJD-UHFFFAOYSA-M tetraethylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CC[N+](CC)(CC)CC WGHUNMFFLAMBJD-UHFFFAOYSA-M 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21K—NON-ELECTRIC LIGHT SOURCES USING LUMINESCENCE; LIGHT SOURCES USING ELECTROCHEMILUMINESCENCE; LIGHT SOURCES USING CHARGES OF COMBUSTIBLE MATERIAL; LIGHT SOURCES USING SEMICONDUCTOR DEVICES AS LIGHT-GENERATING ELEMENTS; LIGHT SOURCES NOT OTHERWISE PROVIDED FOR
- F21K2/00—Non-electric light sources using luminescence; Light sources using electrochemiluminescence
- F21K2/06—Non-electric light sources using luminescence; Light sources using electrochemiluminescence using chemiluminescence
- F21K2/08—Non-electric light sources using luminescence; Light sources using electrochemiluminescence using chemiluminescence activated by an electric field, i.e. electrochemiluminescence
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1416—Condensed systems
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- General Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The light-emitting electrochemical element of the present invention is that lamination first electrode, luminescent layer and second electrode form laminate successively, and described luminescent layer contains electric conductive polymer, electrolyte, supports salt and nitrogenous conjugated compound.By applied voltage between described first electrode and described second electrode, described electric conductive polymer carries out blue-light-emitting, form exciplex between described electric conductive polymer and described nitrogenous conjugated compound simultaneously, send exciplex fluorescence, the luminous of white light is carried out by this blue-light-emitting and this exciplex fluorescence.In addition, light-emitting device have this light-emitting electrochemical element and between first electrode and second electrode applied voltage voltage portion.This light-emitting electrochemical element is the component structure being formed by simple structure by each layer, can obtain being infinitely close to white white luminous simultaneously.
Description
Technical field
The present invention relates to a kind of light-emitting electrochemical element and the light-emitting device with this light-emitting electrochemical element.
Background technology
In recent years, organic electroluminescent device (also referred to as OLED) generally can form frivolous and large-area light-emitting area,
Therefore in the various luminaire such as illumination, display using enjoying expectation.
This organic electroluminescent device is generally made up of anode, negative electrode and luminescent layer, by electric by applying between the two poles of the earth
Press and to be lighted in luminescent layer combination from anode injected holes with from negative electrode injected electrons.In order to improve this Organic Electricity
The luminous efficiency of electroluminescent element, in addition to the light-emitting layer, also need to be provided for improve hole and electronics in conjunction with efficiency
Hole injection layer and electron injecting layer etc. form multiple structure.Therefore create structure and manufacturing process becomes numerous and diverse problem.
Produce the problem needing high electric field on driving further.
As the element solving the problems, such as above-mentioned organic electroluminescent device, for example, in patent documentation 1, patent documentation 2 etc.
In propose light-emitting electrochemical element (LEC).
This LEC is made up of first electrode, second electrode and setting luminescent layer in-between the electrodes.Luminescent layer is to make to serve as
The electric conductive polymer of luminescent material is scattered in formation in electrolyte with supporting salt (support salt).It is assumed that
In this LEC, due to being applied with voltage between the two poles of the earth, by come from electrode positive and negative charge injection and support salt just
The mobile formation p-n junction of minus two kinds of ions or p-i-n junction, by hole and electronics in conjunction with and lighted.
For OLED relatively, this LEC generally has following superiority：(1) driving voltage is low；(2) can use in air
In unstable electrode；(3) due to can manufacture element with single luminescent layer, thus component structure is simple etc..Wherein, make
With the LEC of solid electrolyte due to element manufactures when sealing easily and during element rupture the impact to environment little and special
Noticeable.
Prior art literature
Patent documentation
Patent documentation 1：JP 2008-291230 publication
Patent documentation 2：Te Biao 2012-516033 publication
Content of the invention
The technical problem to be solved in the present invention
However, in the case that such LEC is applied to illumination or the purposes such as display, need to carry out white luminous.With
Toward LEC exploitation as shown in above-mentioned patent documentation 1 and 2, be intended for that blue (B), green (G), red (R) etc. are monochromatic to be sent out
The performance boost of optical element, by LEC produce white luminous be not yet developing region.For forming white luminous LEC it is considered to
Formed by three-decker red, that green and blue constitutes luminescent layer, or arrange light filter to change color, but not yet obtain so far
Satisfactorily white luminous LEC in performance, one-tenth present aspect, preparation method.
Therefore, the problem of the present invention is to provide a kind of light-emitting electrochemical element and has sending out of this light-emitting electrochemical element
Electro-optical device, described light-emitting electrochemical element is the component structure being formed by the simple structure of monolayer, is infinitely connect simultaneously
It is bordering on white white luminous.
Solve the technological means of technical problem
After the present inventor conducts in-depth research to above-mentioned problem, develop following LEC, thus completing this
Invention, described LEC is in the LEC of lamination first electrode, luminescent layer and second electrode successively, and luminescent layer contains conductive
Polymer, electrolyte, support salt and nitrogenous conjugated compound.Specifically, find by first electrode and second electrode it
Between applied voltage, send the blue-light-emitting coming from electric conductive polymer, and by electric conductive polymer and nitrogenous conjugation chemical combination
The exciplex fluorescence that the exciplex being formed between thing produces, is lighted based on both and sends under the driving voltage of bottom
The excellent white light of high brightness, and then complete the present invention.
That is, according to the present invention, provide a kind of light-emitting electrochemical element, in lamination first electrode, luminescent layer and second successively
In the light-emitting electrochemical element of electrode, described luminescent layer contains electric conductive polymer, electrolyte, supports salt and nitrogenous conjugation
Compound, by applied voltage between described first electrode and described second electrode, described electric conductive polymer carries out blueness
Luminous, form exciplex between described electric conductive polymer and described nitrogenous conjugated compound and to send exciplex glimmering
Light.
Additionally, it is provided a kind of light-emitting device in the voltage portion with this light-emitting electrochemical element and applied voltage.Preferably should
Light-emitting device carries out white luminous.
Further according to the present invention, provide a kind of polymer with fluorene skeleton and the compound with triphenylamine skeleton
Group is combined in the purposes in the manufacture of light-emitting electrochemical element,
The described polymer with fluorene skeleton is compound shown in formula (1)
[chemical formula 1]
In formula (1), R is the alkyl of carbon number 1～20, and m represents the degree of polymerization, represents more than 5 integer,
Lamination first electrode, luminescent layer and second electrode form described light-emitting electrochemical element successively, and described luminescent layer contains
There is polymer, electrolyte, support salt and the described compound with triphenylamine skeleton of fluorene skeleton, by described described in having
Applied voltage between first electrode and described second electrode, the described polymer with fluorene skeleton carries out blue-light-emitting, described tool
Have and form exciplex between the polymer of fluorene skeleton and the described compound with triphenylamine skeleton, send exciplex
Fluorescence.
Invention effect
The light-emitting electrochemical element of the present invention can make luminescent layer be formed as monolayer, is by simply constructing the element being formed
Structure, obtains high brightness simultaneously under low driving voltage and is infinitely close to white white luminous.In the present invention, infinite approach
Refer in white white, in CIExy chromaticity diagram, x and y falls into 0.33 ± 0.09 scope.The light-emitting electrochemical unit of the present invention
The glow color of the luminophor that part and this element are related to is, by " instantaneous Multichannel photometric system (wide dynamic range type)
The result that MCPD9800 " (big Electronics Co., Ltd system) measures corresponds to color during cie color coordinate.In addition, hereafter
Sometimes this good whiteness is referred to as high whiteness.
In addition, the light-emitting device employing the light-emitting electrochemical element of the present invention can be to obtain high brightness and high whiteness
White light light-emitting device.
Brief description
Fig. 1 is the summary sectional view of the light-emitting electrochemical element of the present invention.
Fig. 2 is luminance-voltage (L-V) characteristic pattern of each element of embodiment and comparative example.
Fig. 3 is EL (electroluminescent) spectrogram of each element of embodiment and comparative example.
Fig. 4 is PL (luminescence generated by light) spectrogram of each element of embodiment and comparative example.
Fig. 5 is the CIExy chromaticity diagram of each element of embodiment and comparative example.
Description of reference numerals
1. first electrode；2. luminescent layer；3. second electrode.
Specific embodiment
Below the present invention is described in detail.
The light-emitting electrochemical element of the present invention has the laminate knot of lamination first electrode, luminescent layer and second electrode successively
Structure.And, luminescent layer is characterised by, containing electric conductive polymer, electrolyte, supports salt and nitrogenous conjugated compound, passes through
Applied voltage between described first electrode and described second electrode, described electric conductive polymer carries out blue-light-emitting, simultaneously institute
State formation exciplex between electric conductive polymer and described nitrogenous conjugated compound and send exciplex fluorescence, by this
Multiple light to carry out white luminous.
Herein, exciplex refers to the dimer being formed by diverse two kinds of atoms or molecule, by excited state
Atom or molecule be combined into the atom of other kinds of ground state or molecule.In addition, exciplex fluorescence refers to by swashing
Send out the fluorescence that the exciplex of state sends.
As the electrolyte containing in luminescent layer, polymer dielectric, inorganic electrolyte etc. can be enumerated.Wherein, preferably
For polymer.As this polymer, polyalkylene oxide (polyalkylene oxide), polyalkyleneimine, poly- Asia can be enumerated
Hydrocarbonylation sulfur etc..Skeleton unit for example can be enumerated respectively with-(C-C-O)n-、-(C-C(CH3)-O)n-、-(C-C-N)n- or-(C-C-
S)nThe poly(ethylene oxide) of-expression, polypropylene oxide, polyethyleneimine, poly- cured ethylene, or as on main chain or side chain
There are these polymer architectures and there is the resin of apparatus derivatoriuses.In addition, the skeleton of these polymer such as such as poly(ethylene oxide)
The hydrogen atom that unit is bonded can also be replaced by aryl such as the alkyl such as methyl, ethyl or phenyl etc..Additionally, poly- methyl-prop
The resins such as e pioic acid methyl ester, Kynoar, Vingon, Merlon, polyacrylonitrile are also suitable for present embodiment
The polymer of electrolyte.
Wherein, from processability, ionic conductivity, mechanical performance, transparent angle, preferable polyalkylene oxide, enter one
Walk more preferred poly(ethylene oxide).
Contain support salt in luminescent layer further, as this support salt, LiCl, LiBr, LiI, LiBF can be enumerated4、
LiClO4、LiPF6、LiCF3SO3Deng lithium salts, KCl, KI, KBr, KCF3SO3Deng potassium salt, the sodium salt such as NaCl, NaI, NaBr, or four
Ethyl ammonium tetrafluoroborate, tetraethyl ammonium perchlorate, tetrabutyl ammonium tetrafluoroborate, tetrabutylammonium perchlorate, tetrabutyl ammonium halide etc.
Tetraalkylammonium salt.The alkyl chain length of above-mentioned quaternary ammonium salt can identical it is also possible to different, can also may be used only using a kind as needed
It is applied in combination with two or more.Wherein, from ionic conductivity, intersolubility, stability angle, preferably KCF3SO3.
In addition, as the support salt containing in luminescent layer, it is possible to use ionic liquid.The ionic liquid of the present invention is
Refer to the salt existing under room temperature (25 DEG C) with liquid.As the cation of ionic liquid, for example, can enumerate glyoxaline cation, pyrrole
Pyridine cation, pyrrolidine cation, piperidines cation, tetraalkylammonium cation, pyrazoles cation or tetraalkyl
Cation etc..
As above-mentioned glyoxaline cation, can enumerate 1- ethyl-3-methylimidazole, 1- butyl -3- Methylimidazole.,
1- ethyl -2,3- methylimidazole, 1- pi-allyl -3- Methylimidazole., 1- pi-allyl -3- ethyl imidazol(e), 1- pi-allyl -
3- 1-Butyl-1H-imidazole, 1,3- diallyl imidazoles etc..
As above-mentioned pyridylium, for example, can enumerate 1- propyIpyridine, 1- butyl-pyridinium, 1- ethyl -3- (hydroxyl
Methyl) pyridine, 1- ethyl -3- picoline etc..
As above-mentioned pyrrolidine cation, for example, can enumerate N- Methyl-N-propyl pyrrolidine, N- methyl-N- butyl
Pyrrolidine, N- methyl-N-methoxy crassitude etc..
As above-mentioned piperidines cation, for example, can enumerate N- Methyl-N-propyl piperidines etc..
As above-mentioned tetraalkylammonium cation, for example, can enumerate N, N, N- trimethyl-N- propyl ammonium, methyl trioctylammonium
Deng.
As above-mentioned pyrazoles cation, for example, can enumerate 1- ethyl -2,3,5- trimethylpyrazol, 1- propyl group -2,3,
5- trimethylpyrazol, 1- butyl -2,3,5- trimethylpyrazol etc..
As above-mentioned tetra alkyl phosphonium cation, for example, can enumerate tetramethyl, tetrabutyl etc..
In addition, constituting the anion of ionic liquid as with above-mentioned cation combination, for example, can enumerate BF4-、NO3-、
PF6-、SbF6-、CH3CH2OSO3-、CH3CO2- or CF3CO2-、CF3SO3-、(CF3SO2)2[double (trifluoromethyl sulfonyl) is sub- for N-
Amine], (CF3SO2)3The fluorine-containing alkyl anion such as C-.
In addition, luminescent layer contains the electric conductive polymer as luminophor.Electric conductive polymer lights at itself
Meanwhile, form exciplex and nitrogenous conjugated compound between, send exciplex fluorescence.In addition, the conduction of the present invention
Property polymer be have electronics and/or hole transport function, can be with the polymer of good efficiency transmission electronics and/or hole.
Wherein, from the good angle sending exciplex fluorescence in the combining of nitrogenous conjugated compound, preferably have
The polymer of fluorene skeleton or copolymer.There is the polymer of fluorene skeleton or copolymer can carry out the same of blue-light-emitting at itself
When, form exciplex and send exciplex fluorescence.
As the above-mentioned polymer with fluorene skeleton, the preferably polymer shown in following formula (1).Reason is that it can obtain height
The white light of whiteness.
[chemical formula 2]
In formula (1), R is the alkyl of carbon number 1～20, and m represents the degree of polymerization, represents more than 5, is preferably more than 10, enters
One step is preferably more than 20 integer.
As polymer or the copolymer with fluorene skeleton of above-mentioned formula (1), following Examples can be enumerated.
Poly- (the 9,9- di-n-hexyl fluorenyl -2,7- diyl) of following formula (2).
[chemical formula 3]
In formula (2), n represents the degree of polymerization, represents more than 5, is preferably more than 10, more preferably more than 20 integer.
Poly- [9,9- pair-(2- ethylhexyl) -9H- fluorenes -2,7- diyl] of following formula (3).
[chemical formula 4]
In formula (3), n represents the degree of polymerization, represents more than 5, is preferably more than 10, more preferably more than 20 integer.
Poly- (the 9,9- di-n-octyl fluorenyl -2,7- diyl) of following formula (4).
[chemical formula 5]
In formula (4), n represents the degree of polymerization, represents more than 5, is preferably more than 10, more preferably more than 20 integer.
Poly- (the 9,9- bis- dodecyl fluorenyl -2,7- diyl) of following formula (5).
[chemical formula 6]
In formula (5), n represents the degree of polymerization, represents more than 5, is preferably more than 10, more preferably more than 20 integer.
In addition, poly- [(9,9- dioctyl fluorenyl -2,7- the diyl)-co- Dithiophene] of the following formula (6) as copolymer.
[chemical formula 7]
In formula (6), m, n represent the degree of polymerization, represent more than 5 respectively, be preferably more than 10, more preferably more than 20
Integer.M and n can identical it is also possible to different.
Poly- [(9,9- di-n-octyl fluorenyl -2,7- diyl)-alt- (benzo [2,1,3] thiadiazoles -4,8- two of following formula (7)
Base)].
[chemical formula 8]
In formula (7), n represents the degree of polymerization, represents more than 5, is preferably more than 10, more preferably more than 20 integer.
Poly- (the 9,9- positive dihexyl -2,7- fluorenes-alt-9- phenyl -3,6- carbazole) of following formula (8).
[chemical formula 9]
In formula (8), n represents the degree of polymerization, represents more than 5, is preferably more than 10, more preferably more than 20 integer.
Poly- [(9,9- dihexyl fluorenes -2,7- the diyl)-co- (anthracene -9,10- diyl)] of following formula (9).
[chemical formula 10]
In formula (9), m, n represent the degree of polymerization, represent more than 5 respectively, be preferably more than 10, more preferably more than 20
Integer.M and n can identical it is also possible to different.
Poly- [(9,9- dihexyl fluorenes -2,7- the diyl)-co- (9- ethyl carbazole -2,7- diyl)] of following formula (10).
[chemical formula 11]
In formula (10), m, n represent the degree of polymerization, represent more than 5 respectively, be preferably more than 10, more preferably more than 20
Integer.M and n can identical it is also possible to different.
Poly- [(9,9- dihexyl fluorenes -2,7- the diyl)-alt- (2,5- dimethyl -1,4- phenylene)] of following formula (11).
[chemical formula 12]
In formula (11), n represents the degree of polymerization, represents more than 5, is preferably more than 10, more preferably more than 20 integer.
The copolymerization with 2,7-9,9- di-n-octyl fluorenes diyl, 2,7-9,9- diisoamyl fluorenes diyl can be enumerated further
Compound etc..
In addition, the degree of polymerization no maximum of electric conductive polymer, as long as luminous layer composition can be prepared, by making this combination
Thing melts or is dissolved in solvent and is coated etc. and can form the polymerization scope of luminescent layer.
As the above-mentioned polymer with fluorene skeleton, poly- (9,9- bis- dodecyls particularly more preferably shown in formula (5)
Fluorenyl -2,7- diyl).Reason is it to be obtained in that more to increase the white light of whiteness.
In addition, as the nitrogenous conjugated compound containing in the luminescent layer of the present invention, as long as light with as above-mentioned
Form exciplex between the electric conductive polymer of compound, have no particular limits, in applied voltage, it rises
Effect to high efficiency of transmission hole.Wherein, from the good angle sending exciplex fluorescence it may be preferred to use tool
There are low molecular compound and the macromolecular compound of triphenylamine skeleton.
As the above-mentioned low molecular compound with triphenylamine skeleton, the compound shown in following formula (12) can be enumerated.
[chemical formula 13]
In formula (12), n1～n3Can all identical it is also possible to different, represent 1～3 integer, Ar respectively1～Ar3Permissible
All identical it is also possible to different, represent the group selected from hydrogen atom, the alkyl of carbon number 1～22 and aryl respectively.
As compound shown in formula (12), for example, can enumerate triphenylamine, N- (4- butyl phenyl)-N, N- diphenylamines, N, N'-
Diphenyl-N, N'- double (3- aminomethyl phenyl)-[1,1'- xenyl] -4,4'- diamidogen, N, N'- is double, and (3- aminomethyl phenyl-N, N'- are double
(2- naphthyl)-[1,1'- biphenyl] -4,4'- diamidogen etc..In addition, as can be enterprising in the aromatic rings of these triphenylamine compounds
The group that row replaces, can enumerate the alkyl that carbon number is 1～22, alkoxyl etc..
In addition, as have triphenylamine skeleton other low molecular compounds, can also use 4,4', 4 "-three (N, N- bis-
Phenyl-amino) triphenylamine (TDATA), 4,4', 4 "-three [N- (3- aminomethyl phenyl)-N- phenyl-amino] triphenylamine (m-
MTDATA double (3- the aminomethyl phenyl)-N of), N, N'-, the double [N- of N'- diphenyl -1,1'- biphenyl -4,4'- diamidogen (TPD), 4,4'-
(1- naphthyl)-N- phenyl-amino] biphenyl (α-NTPD), double [N- (4- (bis- tolyls of N, the N-) amino) phenyl-N- benzene of 4,4'-
Base amino] biphenyl (DNTPD), 4,4', 4 "-three [biphenyl -2- base (phenyl) amino] triphenylamine, 4,4', 4 "-three [biphenyl -4- bases
(3- aminomethyl phenyl) amino] triphenylamine, 4,4', 4 "-three [9,9- dimethyl -2- fluorenyl (phenyl) amino] triphenylamine, 4,4',
4 "-three [2- naphthyl (phenyl) amino] triphenylamine (2-TNATA), 4,4', the 4 " fragrance such as-three (N- carbazyl) triphenylamine (TCTA)
Aminated compoundss.
Wherein, the m-MTDATA of preferred following formula (13), it is multiple that formation that can be good between electric conductive polymer swashs base
Compound and send exciplex fluorescence.
[chemical formula 14]
In addition, as the above-mentioned macromolecular compound with triphenylamine skeleton, it is possible to use shown in following formula (14) or (15)
Macromolecular compound.Hole mobility is high, efficiency can form exciton well, thus obtaining the white light of high whiteness.
[chemical formula 15]
In formula (14), L is alkylidene, and n represents the degree of polymerization, represents more than 5, is preferably more than 10, more preferably 20
Above integer.
[chemical formula 16]
In formula (15), Ar can identical it is also possible to different, represent to phenylene or metaphenylene respectively.N represents polymerization
Degree, represents more than 5, is preferably more than 10, more preferably more than 20 integer.
As the specific example of the above-mentioned macromolecular compound with triphenylamine skeleton, the Asia of above-mentioned formula (14) can be enumerated
Alkyl (L) is-CH (CH3)-(following formula (16)) ,-CH (C2H5)-wait macromolecular compound etc..Following formula particularly can be enumerated
(16).Reason is it to be obtained in that more to increase the white light of whiteness.
[chemical formula 17]
In formula (16), n represents the degree of polymerization, represents more than 5, is preferably more than 10, more preferably more than 20 integer.
In order to form exciplex, for electric conductive polymer with the content ratio of nitrogenous conjugated compound, relatively
In 100 weight portion electric conductive polymers, nitrogenous conjugated compound is preferably 1～200 weight portion, more preferably 10～120 weights
Amount part.In the case that the content of nitrogenous conjugated compound is than not up to above-mentioned lower limit, exciplex fluorescence may become
Few, thus there being the possibility that cannot obtain white light.In the case that the content ratio of nitrogenous conjugated compound exceedes above-mentioned higher limit,
Glow color and luminous efficiency have the possibility of variation.
As the thickness of the luminescent layer of the present invention, because luminescent properties are not rely on thickness in principle, therefore permissible
It is arbitrary thickness, but generally from the point of view of practicality, apply desired thickness in the range of 5nm～10mm.?
It is possible to be short-circuited in the case that the above-mentioned lower limit of Thickness ratio is little, in the case that thickness exceedes above-mentioned higher limit, sharp base is multiple
The formation efficiency of compound may step-down.
Constituting at least one of the first electrode of light-emitting electrochemical element and the second electrode of present invention electrode is printing opacity
Property electrode, i.e. transparency electrode.This is to extract sent light.As the material of transparency electrode, stannum oxide, oxygen can be enumerated
Change zinc, Indium sesquioxide., tin indium oxide, Indium sesquioxide. zinc oxide composites, tin-antiomony oxide complex, gallium oxide zinc oxide are combined
Thing etc..
In addition, as another electrode it is not necessary to be transparency electrode, for example can using aluminum, indium, magnesium, tungsten, titanium, molybdenum,
The metals such as calcium, sodium, potassium, yttrium, lithium, manganese, gold, silver, copper, palladium, platinum, stannum, lead, nickel, alloy of these metals etc..
That is, as one of first electrode and second electrode electrode, preferably there is the ITO (tin indium oxide) of the transparency,
As its relative electrode, from the point of view of electric conductivity, economy, preferably aluminum.
First electrode, second electrode can by the direct lamination of the electrode layer constituting these metals etc. on luminescent layer shape
Become, or can also be formed by structures such as these metals on the transparency carriers such as the glass substrate being commonly used for light-emitting component
The electrode layer becoming is making.Formation for electrode layer, it is possible to use sputtering method, vacuum vapour deposition etc..
Light-emitting electrochemical element as the present invention of said structure passes through to apply between first electrode and second electrode
Voltage, makes the electric conductive polymer contained by luminescent layer carry out blue-light-emitting.In addition, electric conductive polymer and nitrogenous conjugation chemical combination
Form exciplex between thing, send exciplex fluorescence.This blue-light-emitting is mixed with exciplex fluorescence, in outside
Lighted as white light.
The structure of the light-emitting device of the present invention is to have the light-emitting electrochemical element of the invention described above and at this
The voltage portion of applied voltage on Optical Electro-Chemistry element.As this voltage portion, appointing in DC voltage or alternating voltage can be applied
A kind of.
Next, the example of the manufacture method for the light-emitting electrochemical element of the present invention, illustrate with reference to Fig. 1.
As light-emitting electrochemical element shown in Fig. 1 10, on the substrate of glass etc., setting ITO electrode etc. is as first electrode
1 (anode), in its surface using the coating of such as spin-coating film method by electric conductive polymer, electrolyte, support salt and nitrogenous common
Compound conjugate dissolving is scattered in the dispersion soln formed in solvent, and being dried and removing solvent lamination is luminescent layer 2.Herein, it is used for
As long as the solvent of dispersion soln dissolves the solvent of each constituent, have no particular limits, for example can use chloroform,
Ketohexamethylene, toluene and mixed solvent equal solvent.
Then, on luminescent layer 2, carry out being deposited with by using such as vacuum vapour deposition, masking and lamination be as second electrode 3
The aluminum of (negative electrode).
Light-emitting electrochemical element 10 can be made in the above described manner.
In addition, though hereinbefore indicate first electrode be anode, second electrode be negative electrode, but in light-emitting electrochemical element
In, electrode does not need so to fix, for example, it is possible to use same material to first electrode and second electrode, arbitrary decision is cloudy
Pole and anode carry out applied voltage.
The element characteristic of the light-emitting electrochemical element 10 of the present invention can use luminance-voltage (L-V) characteristic, EL spectrogram, PL
Spectrogram and chromaticity diagram (chromaticity coordinate) are being evaluated.
In L-V evaluating characteristics, the relation between driving voltage and the brightness of the light sending can be evaluated.In EL spectrogram
In, the concrete condition of glow color can be held by the luminous intensity of each wavelength during applied voltage.In PL spectrogram,
The concrete condition of glow color can be held by absorbing the luminous intensity of each wavelength during exciting light.Further, it is possible to
It is used CIExy chromaticity diagram to represent glow color by the numerical value of xy coordinate it is possible to the numerical value of xy coordinate to being used as this
The white content of the bright white light of a purpose is evaluated.
Embodiment
Embodiment is set forth below the present invention is specifically explained, but the invention is not limited in these embodiments.
Embodiment 1
<Luminescent layer：Compositionss 1>
As compositionss 1, with the interpolation of table 1 than mixing following ingredients (A1)～(A4).
(A1) electric conductive polymer：Poly- (9,9- bis- dodecyl fluorenyl -2,7- diyl) using above-mentioned formula (5)
(PFD) (Aldrich society system).
(A2) nitrogenous conjugated compound：4,4', 4 "-three [N- (3- aminomethyl phenyl)-N- phenyl-amino] triphenylamine (m-
MTDATA)
(A3) electrolyte：Poly(ethylene oxide)
(A4) support salt：KCF3SO3
<Light-emitting electrochemical element：The making of element A>
Carry out UV ozone cleaning as first electrode 1 (anode) setting ITO electrode on the glass substrate.Then, pass through
Spin-coating film method, coats in this first electrode 1 and for above-mentioned composition 1 to be dissolved in chloroform/Ketohexamethylene (1.08:1.0) mixed solvent
In solution 14.6 (mg/mL solvent), then be dried remove this mixed solvent, the luminescent layer 2 of lamination 150nm.Further,
The vacuum evaporation of aluminum is carried out on this luminescent layer 2, lamination thickness is the second electrode 3 (negative electrode) of 100nm.
Make element A in the above described manner.Obtained element A is implemented with luminance-voltage (L-V) characteristic, EL spectrogram, PL spectrum
Glow color evaluation in figure and CIExy chromaticity diagram.L-V characteristic is shown in Fig. 2, EL spectrogram is shown in Fig. 3, PL spectrogram is shown in figure
Chromaticity coordinate xy that 4, CIExy colourities are illustrated on Fig. 5, and CIExy chromaticity diagram is shown in Table 2.
Embodiment 2 and 3
<Luminescent layer：Compositionss 2,3>
As compositionss 2,3, with the interpolation of table 1 than mixing mentioned component (A1)～(A4).
<Light-emitting electrochemical element：The making of element B, C>
Be changed to compositionss 2,3 respectively to carry out the compositionss 1 of alternate embodiment 1 and make luminescent layer, in addition, with reality
Apply example 1 identical mode and make element B, C, and same being evaluated.Result is shown in Fig. 2～5 and table 2.
Comparative example 1
<Luminescent layer：Compositionss 4>
As compositionss 4, with the interpolation of table 1 than mixing mentioned component (A1), (A2) and (A4).
<Light-emitting electrochemical element：The making of element D>
Be changed to compositionss 4 to carry out the compositionss 1 of alternate embodiment 1 and make luminescent layer, in addition, with embodiment 1
Identical mode makes element D, and same being evaluated.Result is shown in Fig. 2～5 and table 2.
[table 1]
[table 2]
As shown in Figure 2, the beginning voltage that lights is 3.5～4.5V, starts at lower voltages to light.In addition, the EL by Fig. 3
Spectrogram is compared with the PL spectrogram of Fig. 4, represents the wavelength of emitting red light in EL spectrogram：Shoulder is confirmed at 600nm～700nm
Peak, but in PL spectrogram medium wavelength：Do not find fluorescence at 600nm～700nm, thus learn electric conductive polymer PFD with contain
Define exciplex between nitrogen conjugated compound m-MTDATA, lighted.Learnt by the chromaticity diagram of Fig. 5, light electricity
Chemical component A～C all carries out white luminous under driving voltage 7.5V～8.5V.In addition learn, element A～C all obtains no
Limit is close to white white luminous.
In addition, so-called pure white light refers to that its chromaticity coordinate is (x, y)=(0.33,0.33).
Claims (9)
1. a kind of light-emitting electrochemical element,
In the light-emitting electrochemical element of lamination first electrode, luminescent layer and second electrode successively,
Described luminescent layer contains electric conductive polymer, electrolyte, supports salt and nitrogenous conjugated compound,
By applied voltage between described first electrode and described second electrode, described electric conductive polymer carries out blue sending out
Light, forms exciplex between described electric conductive polymer and described nitrogenous conjugated compound, sends exciplex fluorescence.
2. light-emitting electrochemical element as claimed in claim 1, wherein, described electric conductive polymer is having shown in formula (1)
The polymer of fluorene skeleton,
[chemical formula 1]
In formula (1), R is the alkyl of carbon number 1～20, and m represents the degree of polymerization, represents more than 5 integer.
3. light-emitting electrochemical element as claimed in claim 1 or 2, wherein, described electrolyte contains polyalkylene oxide.
4. the light-emitting electrochemical element as any one of claim 1-3, wherein, described nitrogenous conjugated compound is to have
The compound of triphenylamine skeleton.
5. the light-emitting electrochemical element as any one of claim 1-4, wherein, described electric conductive polymer contains poly-
(9,9- bis- dodecyl fluorenyl -2,7- diyl).
6. the light-emitting electrochemical element as any one of claim 1-5, wherein, described electrolyte contains polycyclic oxygen second
Alkane.
7. the light-emitting electrochemical element as any one of claim 1-6, wherein, described nitrogenous conjugated compound contains 4,
4', 4 "-three [N- (3- aminomethyl phenyl)-N- phenyl-amino] triphenylamine (m-MTDATA).
8. the light-emitting electrochemical element as any one of claim 1-7, wherein, conductive with respect to described in 100 weight portions
Property polymer, the content of described nitrogenous conjugated compound is 1～200 weight portion.
9. a kind of light-emitting device, it has the light-emitting electrochemical element any one of claim 1-8 and lights at this
The voltage portion of applied voltage between the first voltage of electrochemical element and second voltage.
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| JP2014116176A JP6296239B2 (en) | 2014-06-04 | 2014-06-04 | Light emitting electrochemical element and light emitting device having the light emitting electrochemical element |
| JP2014-116176 | 2014-06-04 | ||
| PCT/JP2015/064863 WO2015186547A1 (en) | 2014-06-04 | 2015-05-25 | Light emitting electrochemical element and light emitting device comprising light emitting electrochemical element |
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| KR (1) | KR101954688B1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112750958A (en) * | 2021-01-05 | 2021-05-04 | 吉林大学 | White organic electroluminescent device realized by blue dye and exciplex |
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| JP6675611B2 (en) * | 2015-02-06 | 2020-04-01 | Ｊｘｔｇエネルギー株式会社 | Light-emitting composition, light-emitting electrochemical element, and light-emitting device |
| JP6661113B2 (en) * | 2016-01-12 | 2020-03-11 | Ｊｘｔｇエネルギー株式会社 | Light emitting electrochemical element and light emitting device having the light emitting electrochemical element |
| JP2017155125A (en) * | 2016-03-01 | 2017-09-07 | Ｊｘｔｇエネルギー株式会社 | Light-emitting composition, light-emitting electrochemical element, and light-emitting device |
| KR102141633B1 (en) * | 2016-11-25 | 2020-08-05 | 주식회사 엘지화학 | An Electrochemical Light Emitting Element |
| WO2020148935A1 (en) * | 2019-01-18 | 2020-07-23 | 株式会社ジャパンディスプレイ | Illumination device and display device |
| JP2021032913A (en) * | 2019-08-14 | 2021-03-01 | 株式会社ジャパンディスプレイ | Display and display |
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| JP2005294066A (en) * | 2004-03-31 | 2005-10-20 | Toshiba Corp | Light emitting display device and its driving method |
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| JP5095476B2 (en) | 2008-04-18 | 2012-12-12 | 独立行政法人科学技術振興機構 | Poly (diene-arylene) and process for producing the same |
| US9123908B2 (en) | 2009-01-21 | 2015-09-01 | Lunalec Ab | Light-emitting electrochemical cell and system, use thereof and method for their operation |
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2014
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004281204A (en) * | 2003-03-14 | 2004-10-07 | Sharp Corp | Organic electrochemical luminescent element |
| JP2005294066A (en) * | 2004-03-31 | 2005-10-20 | Toshiba Corp | Light emitting display device and its driving method |
| CN101040175A (en) * | 2004-10-15 | 2007-09-19 | 皇家飞利浦电子股份有限公司 | Temperature indicator |
| JP2009054952A (en) * | 2007-08-29 | 2009-03-12 | Toshiba Corp | Light-emitting device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112750958A (en) * | 2021-01-05 | 2021-05-04 | 吉林大学 | White organic electroluminescent device realized by blue dye and exciplex |
| CN112750958B (en) * | 2021-01-05 | 2022-06-14 | 吉林大学 | White organic electroluminescent device realized by blue dye and exciplex |
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| Publication number | Publication date |
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| TW201546240A (en) | 2015-12-16 |
| CN106489051B (en) | 2019-07-02 |
| TWI660027B (en) | 2019-05-21 |
| KR20170013328A (en) | 2017-02-06 |
| WO2015186547A1 (en) | 2015-12-10 |
| KR101954688B1 (en) | 2019-03-07 |
| JP2015230955A (en) | 2015-12-21 |
| JP6296239B2 (en) | 2018-03-20 |
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