WO2016056529A1 - Cellule luminescente électrochimique et composition pour formation de couche luminescente de cellule luminescente électrochimique - Google Patents

Cellule luminescente électrochimique et composition pour formation de couche luminescente de cellule luminescente électrochimique Download PDF

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WO2016056529A1
WO2016056529A1 PCT/JP2015/078277 JP2015078277W WO2016056529A1 WO 2016056529 A1 WO2016056529 A1 WO 2016056529A1 JP 2015078277 W JP2015078277 W JP 2015078277W WO 2016056529 A1 WO2016056529 A1 WO 2016056529A1
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organic
group
salt
combination
light emitting
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PCT/JP2015/078277
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English (en)
Japanese (ja)
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文広 米川
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日本化学工業株式会社
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Priority claimed from JP2015193167A external-priority patent/JP6163185B2/ja
Application filed by 日本化学工業株式会社 filed Critical 日本化学工業株式会社
Priority to US15/516,979 priority Critical patent/US10547019B2/en
Priority to EP15848287.7A priority patent/EP3205924B1/fr
Priority to CN201580053972.XA priority patent/CN106796001B/zh
Priority to KR1020177008860A priority patent/KR20170065522A/ko
Publication of WO2016056529A1 publication Critical patent/WO2016056529A1/fr

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/135—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising mobile ions

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  • the present invention relates to an electrochemiluminescence cell having a light emitting layer containing a light emitting material and two or more organic salts.
  • the present invention also relates to a composition for forming a light emitting layer of an electrochemiluminescence cell.
  • organic electroluminescence (organic EL) elements which are self-luminous elements using electrons and holes as carriers, has been rapidly progressing.
  • Organic EL has features such as being thinner and lighter than a liquid crystal element that does not emit light and requires a backlight, and has excellent visibility.
  • An organic EL element generally includes a pair of substrates on which electrodes are formed on the surfaces facing each other, and a light emitting layer disposed between the pair of substrates.
  • the light emitting layer is made of an organic thin film containing a light emitting substance that emits light when a voltage is applied.
  • a voltage is applied to the organic thin film from the anode and the cathode to inject holes and electrons.
  • holes and electrons are recombined in the organic thin film, and the excitons generated by the recombination return to the ground state, whereby light emission is obtained.
  • the organic EL device in addition to the light emitting layer, a hole injection layer and an electron injection layer for increasing the injection efficiency of holes and electrons between the light emitting layer and the electrode, and recombination of holes and electrons. It is necessary to provide a hole transport layer and an electron transport layer for improving efficiency. As a result, the organic EL element has a multi-layered structure, which complicates the structure and increases the manufacturing process. In organic EL, there are many limitations because it is necessary to consider the work function when selecting the electrode material used for the anode and the cathode.
  • Electrochemiluminescent cells generally have a light emitting layer that includes a salt and an organic light emitting material. When a voltage is applied, cations and anions derived from the salt move toward the cathode and the anode, respectively, in the light emitting layer, which results in a large electric field gradient (electric double layer) at the electrode interface. The formed electric double layer facilitates the injection of electrons and holes in the cathode and the anode, respectively. Therefore, the electrochemiluminescence cell does not require a multilayer structure like an organic EL.
  • the electrochemiluminescence cell is expected as a self-luminous element that can significantly reduce the manufacturing cost as compared with the organic EL.
  • ionic liquids in addition to lithium salts and potassium salts as salts used in electrochemiluminescence cells.
  • This ionic liquid is a non-volatile salt and has a higher reorientation rate due to an electric field than a solid electrolyte, so that ion mobility is ensured and an electric double layer is easily formed, and holes and electrons can be more easily injected. (See Patent Document 1 and Patent Document 2).
  • holes and electrons can be easily moved by adding additives to the layers responsible for the injection and transport of holes and electrons, such as the hole injection layer, hole transport layer, electron injection layer, and electron transport layer. Attempts have been made (see, for example, Patent Documents 3 to 6). In addition, attempts have been made to avoid a reduction in light emission luminance by adjusting the injection balance of holes and electrons into the light emitting layer (see Patent Document 7).
  • an electrochemiluminescence cell particularly an electrochemiluminescence cell having an ionic liquid in a light emitting layer
  • the movement of holes and electrons is already easy, but the thermal stability and electrochemical which affect the operating life Attempts have been made to improve the performance of electrochemiluminescent cells by improving stability or improving the compatibility between ionic liquids and luminescent materials.
  • Patent Document 8 describes that when a plurality of salts are incorporated into a light-emitting polymer layer, the lifetime of the electrochemiluminescent cell is improved.
  • the light emission luminance shown in this document has achieved the maximum luminance of 100 cd / m 2 or less at the maximum even when a voltage of 10 V or more is applied to the electrode, as high as necessary for practical use. Absent.
  • JP 2011-103234 A Special table 2012-516033 gazette JP 2013-171968 A Special table 2012-531737 gazette JP 2011-216893 A International Publication No. 2010/98386 Pamphlet International Publication No. 2013/171872 Pamphlet International Publication No. 2011/032010 Pamphlet
  • the ability to inject holes or electrons from each electrode can be controlled by considering the type of cation or anion of the salt used in the light emitting layer. Specifically, it has been found that the ability to inject holes and electrons into the light emitting layer can be made substantially equal by mixing two or more kinds of salts.
  • the present invention relates to an electrochemiluminescence cell having a light emitting layer and electrodes disposed on each surface thereof.
  • an electrochemiluminescence cell having a light emitting layer and electrodes arranged on each surface thereof The above-mentioned problem is solved by providing an electrochemiluminescent cell in which the light emitting layer contains a combination of an organic polymer light emitting material and two or more organic salts.
  • this invention solves the said subject by providing the composition for light emitting layer formation of an electrochemiluminescence cell containing the combination of an organic polymer light emitting material, an organic solvent, and 2 or more types of organic salts. is there.
  • an electrochemiluminescence cell having high luminous efficiency and excellent emission luminance is provided.
  • FIG. 1 is a schematic cross-sectional view of an electrochemiluminescence cell according to an embodiment of the present invention.
  • FIG. 2 is a conceptual diagram showing a light emission mechanism of an electrochemiluminescence cell.
  • FIG. 2 (a) shows an electrochemiluminescence cell before voltage application
  • FIG. 2 (b) shows an electrochemiluminescence cell after voltage application.
  • FIG. 3 is a graph showing the measurement results of the emission luminance of the electrochemiluminescence cells obtained in Example 1 and Comparative Example 1.
  • FIG. 4 is a graph showing the measurement results of the light emission luminance of the electrochemiluminescence cells obtained in Example 2 and Comparative Example 2.
  • FIG. 3 is a graph showing the measurement results of the emission luminance of the electrochemiluminescence cells obtained in Example 1 and Comparative Example 1.
  • FIG. 4 is a graph showing the measurement results of the light emission luminance of the electrochemiluminescence cells obtained in Example 2 and Comparative Example 2.
  • FIG. 5 is a graph showing the measurement results of the emission luminance of the electrochemiluminescence cells obtained in Example 3 and Comparative Example 3.
  • FIG. 6 is a graph showing the measurement results of the emission luminance of the electrochemiluminescence cells obtained in Example 4 and Comparative Example 4.
  • FIG. 7 is a graph showing the measurement results of the emission luminance of the electrochemiluminescence cells obtained in Example 5 and Comparative Example 5.
  • FIG. 8 is a graph showing the measurement results of the emission luminance of the electrochemiluminescence cells obtained in Example 6 and Comparative Example 6.
  • FIG. 9 is a graph showing the measurement results of the emission luminance of the electrochemiluminescence cells obtained in Example 7 and Comparative Example 7.
  • FIG. 10 is a graph showing the measurement results of the emission luminance of the electrochemiluminescence cells obtained in Example 8 and Comparative Example 8.
  • FIG. 11 is a graph showing the measurement results of the emission luminance of the electrochemiluminescence cells obtained in Example 9 and Comparative Example 9.
  • FIG. 12 is a graph showing the measurement results of the emission luminance of the electrochemiluminescence cells obtained in Example 10 and Comparative Example 10.
  • FIG. 13 is a graph showing the measurement results of the emission luminance of the electrochemiluminescence cells obtained in Example 11 and Comparative Example 11.
  • FIG. 14 is a graph showing the measurement results of the emission luminance of the electrochemiluminescence cells obtained in Example 12 and Comparative Example 12.
  • the electrochemiluminescence cell 10 of this embodiment includes a light emitting layer 12 and electrodes 13 and 14 disposed on each surface thereof.
  • the electrochemiluminescence cell 10 includes a first electrode 13 and a second electrode 14 that are a pair of electrodes facing each other, and a light emitting layer 12 sandwiched between the pair of electrodes 13 and 14.
  • the light emitting layer emits light when a voltage is applied.
  • the electrochemiluminescence cell 10 is used as various displays. FIG.
  • the first electrode 13 is connected to the anode of the DC power source, and the second electrode 14 is connected to the cathode.
  • the first electrode 13 may be connected to the cathode and the second electrode 14 may be connected to the anode.
  • an AC power source as a power source instead of a DC power source.
  • the first electrode 13 and the second electrode 14 may be transparent electrodes having translucency, or may be translucent or opaque electrodes.
  • Transparent electrodes having translucency include those made of metal oxides such as indium-doped tin oxide (ITO) and fluorine-doped tin oxide (FTO), poly (3,4-ethylenedioxythiophene) with impurities added ( Examples thereof include those made of a polymer having transparency such as PEDOT) and those made of a carbon-based material such as carbon nanotube or graphene.
  • the translucent or opaque electrode include aluminum (Al), silver (Ag), gold (Au), platinum (Pt), tin (Sn), bismuth (Bi), copper (Cu), and chromium (Cr).
  • Metal materials such as zinc (Zn) and magnesium (Mg).
  • the first electrode 13 and the second electrode 14 are used as a transparent electrode because light emitted from the light emitting layer 12 can be easily extracted to the outside. Further, when one is a transparent electrode and the other is an opaque metal electrode, it is preferable because light emitted from the light emitting layer 12 can be taken out while being reflected by the metal electrode. Moreover, it is good also as a see-through light-emitting body by making both the 1st electrode 13 and the 2nd electrode 14 into a transparent electrode.
  • both the first electrode 13 and the second electrode 14 are metal electrodes made of Ag or the like having a high reflectivity, and the thickness of the light emitting layer 12 is controlled, so that the electrochemiluminescence cell 10 is laser-oscillated. It can also be an element.
  • the first electrode 13 is a transparent electrode and the second electrode 14 is an opaque or translucent metal electrode
  • the first electrode 13 is, for example, 10 nm or more and 500 nm or less from the viewpoint of realizing appropriate resistivity and light transmittance. It is preferable to have a thickness of
  • the second electrode 14 preferably has a thickness of, for example, 10 nm or more and 500 nm or less from the viewpoint of realizing an appropriate resistivity and light transmittance in the same manner as the first electrode 13.
  • the light emitting layer 12 is formed by mixing an organic polymer light emitting material and an organic salt.
  • the light emitting layer 12 may be in a solid state or a liquid state. When the light emitting layer 12 is solid, it can maintain a certain shape and can resist the force applied from the outside.
  • the organic salt contained in the light emitting layer 12 is a substance for ensuring ion mobility, forming an electric double layer easily, and facilitating injection of holes and electrons.
  • phosphonium salts, ammonium salts, pyridinium salts, imidazolium salts, pyrrolidinium salts, and the like can be used as organic salts.
  • these organic salts as the phosphonium salt and ammonium salt, for example, those represented by the following formula (1) can be used.
  • pyridinium salt, imidazolium salt, and pyrrolidinium salt include anions such as halide ions such as fluorine, bromine, iodine and chlorine, tetrafluoroborate (BF 4 ), benzotriazolate (N 3 (C 6 H 4 ) ), Tetraphenylborate (B (C 6 H 5 ) 4 ), hexafluorophosphate (PF 6 ), bis (trifluoromethylsulfonyl) imide (N (SO 2 CF 3 ) 2 ), bis (fluorosulfonyl) imide ( N (SO 2 F) 2 ), trifluoromethanesulfonate (SO 3 CF 3 ), methanesulfonate (SO 3 CH 3 ), tris (pentafluoroethyl) trifluorophosphate ((C 2 H 5 ) 3 PF 3 ), tri trifluoroacetic acid (CF 3 COO), amino acids, Bisuok
  • the molecular weight of the cation in the organic salt is 270 or more and 900 or less, particularly 300 or more and 850 or less, particularly 330 or more and 800 or less, and the luminous efficiency of the electrochemiluminescence cell is further improved and the emission luminance is further improved. To preferred.
  • the organic salt may be solid or liquid at normal temperature (25 ° C.).
  • organic salts for example, those represented by the following formula (1) can be used as the solid organic salt.
  • R 1 , R 2 , R 3 and R 4 are each an alkyl group, an alkoxyalkyl group, a trialkylsilylalkyl group, an alkenyl group, an alkynyl group, an aryl group, which may be substituted with a functional group, or Represents a heterocyclic group, R 1 , R 2 , R 3 and R 4 may be the same or different from each other, M represents N or P, and X ⁇ represents an anion.
  • liquid organic salts examples include ionic liquids that maintain a liquid state at room temperature (25 ° C.) while being ionic species.
  • a substance represented by the above formula (1) can be used as the liquid organic salt.
  • the organic salt represented by the formula (1) is in a solid or liquid state depending on the combination of the selected cation and anion and the structure of R 1 to R 4 which are side chains of the cation.
  • all of them may be solid at room temperature, or all of them may be liquid at room temperature. Further, at least one of them may be liquid at normal temperature, and at least one of them may be solid at normal temperature.
  • R 1 to R 4 may be an alkyl group, an alkoxyalkyl group, a trialkylsilylalkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group.
  • R 1 to R 4 may be the same as or different from each other.
  • the alkyl group used as any one of R 1 to R 4 is a linear or branched saturated aliphatic group having 1 to 20 carbon atoms, 3 to 20 saturated alicyclic groups are mentioned. Specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, s-butyl group, t-butyl group, isobutyl group, amyl group, isoamyl group, t-amyl group, hexyl group, heptyl group, Isoheptyl, t-heptyl, n-octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, isotridecyl, Examples include tetradecyl group,
  • examples of the alkoxy group in the alkoxyalkyl group used as any one of R 1 to R 4 include the alkoxides of the alkyl groups described above.
  • examples of the alkyl group in the alkoxyalkyl group include the same alkyl groups as described above.
  • alkenyl group used as any one of R 1 to R 4 those having 2 to 20 carbon atoms are preferably used.
  • examples of the alkynyl group used as any one of R 1 to R 4 include an ethynyl group and a prop-2-yn-1-yl group.
  • examples of the aryl group used as any one of R 1 to R 4 include a phenyl group, a naphthyl group, and an anthracenyl group.
  • examples of the heterocyclic group include monovalent groups derived from pyridine, pyrrole, furan, imidazole, pyrazole, oxazole, imidazoline, pyrazine and the like.
  • one or two or more of the hydrogen atoms contained therein may be substituted with a functional group.
  • the functional group include an amino group, a nitrile group, a phenyl group, a benzyl group, a carboxyl group, and an alkoxy group having 1 to 12 carbon atoms.
  • a group in which the above-described alkyl group is substituted with a phenyl group as a functional group, that is, an aromatic alkyl group can be used.
  • a benzyl group that is a group in which a methyl group as an alkyl group is substituted with a phenyl group as a functional group can be used.
  • anion represented by X ⁇ in the formula (1) examples include halogen ions such as fluorine, bromine, iodine and chlorine, tetrafluoroborate (BF 4 ), benzotriazolate (N 3 (C 6 H 4 )).
  • the electrochemiluminescence cell 10 of this embodiment is characterized in that two or more different organic salts contained in the light emitting layer 12 are used in combination.
  • two or more kinds of organic salts in combination the ability of injecting holes and electrons into the light-emitting layer 12 becomes substantially equal, thereby increasing the luminous efficiency.
  • the electrochemiluminescence cell 10 of the present embodiment is excellent in emission luminance.
  • organic salts for example, in the case of two kinds of combinations, (a) a combination of organic salts having the same cation and different anions, and (b) anion having different cations and anions And (c) combinations of organic salts in which cations are different and anions are different.
  • a pyridinium ion that is a cation is common, and a combination of organic salts having different types of anions among the above-mentioned anions such as tetrafluoroborate ion and bis (trifluoromethanesulfonyl) imide ion is used.
  • anions such as tetrafluoroborate ion and bis (trifluoromethanesulfonyl) imide ion is used.
  • the aforementioned anions such as tetrafluoroborate ions and bis (trifluoromethanesulfonyl) imide ions are common, and a combination of organic salts in which the cations are imidazolium ions and pyrrolidinium ions can be mentioned.
  • a combination of a bis (trifluoromethanesulfonyl) imide salt of a pyridinium ion and a tetrafluoroborate ion salt of a pyrrolidinium ion may be mentioned.
  • the combination of organic salts includes (i) a combination of organic salts in which the cation is the same and the anion is different (the above (i) and (ii) or (iii) and (iv) Or (b) a combination of organic salts having different cations and the same anion (a combination of (i) and (iii) or (ii) and (iv)). preferable.
  • two or more organic salts are a combination of liquid organic salts.
  • two or more organic salts are a combination of solid organic salts.
  • the combination of two or more organic salts may be a combination of a liquid organic salt and a solid organic salt.
  • Preferred organic salt combinations include those represented by the formula (1).
  • the first organic salt and the second organic salt are: It has been found that it is preferable to have the same kind of cation and different anions. It was also found that (b) it is preferable that they have the same type of anion and the cation is different.
  • the first organic salt and the second organic salt have the same kind of cation, for example, the same kind of ammonium ion or the same kind of phosphonium ion.
  • the first organic salt and the second organic salt have different anions.
  • the first organic salt and the second organic salt are the same type of anion, for example, ions of halogen such as bistrifluoromethanesulfonylimide, fluorine, bromine, tetrafluoroborate (BF 4 ), hexa It has ions of halogen-containing compounds such as fluorophosphate (PF 6 ).
  • the first organic salt and the second organic salt have different cations.
  • any of the different cations can be an ammonium ion.
  • any heterogeneous cation can be a phosphonium ion.
  • one of the different cations can be an ammonium ion and the other can be a phosphonium ion.
  • R 1 , R 2 , R 3 and R 4 in the formula (1) are the same alkyl group, and the rest One is preferably an alkyl group different from the alkyl group, or an aromatic alkyl group. This is because one of R 1 , R 2 , R 3, and R 4 is a heterogeneous group, which is structurally asymmetrical, and the fluidity of the organic salt is easily obtained even when the number of carbons increases. is there. Since the molecular weight of the cation can be increased by increasing the number of carbon atoms, the charge density is structurally reduced, so the polar component required to stabilize the charge can be reduced. Leads to increased compatibility with non-polar organic light emitting materials.
  • the cation is the same kind of tetraalkylammonium ion, the same kind of trialkylbenzylammonium ion, the same kind of tetraalkylphosphonium ion, or It is the same kind of trialkylbenzylphosphonium ion, and different anions are ions of bistrifluoromethanesulfonylimide, halogen ions such as fluorine and bromine, or halogens such as tetrafluoroborate (BF 4 ) and hexafluorophosphate (PF 6 ).
  • BF 4 tetrafluoroborate
  • PF 6 hexafluorophosphate
  • the same type of anion is bistrifluoromethanesulfonylimide, halogen ions such as fluorine and bromine, or halogen-containing compounds such as tetrafluoroborate (BF 4 ) and hexafluorophosphate (PF 6 ).
  • a different cation is a combination of different tetraalkylammonium ions, a combination of different trialkylbenzylammonium ions, a combination of different tetraalkylphosphonium ions, a combination of different trialkylbenzylphosphonium ions, tetraalkylammonium Ion and trialkylbenzylammonium ion combination, tetraalkylphosphonium ion and trialkylbenzylphosphonium ion combination, tetraalkylammonium ion
  • the ratio between the first organic salt and the second organic salt can be selected from a wide range according to the type of these organic salts. For example, as illustrated in the examples described later, there may be a combination that exhibits the maximum light emission luminance at substantially equal mass ratios, or the first organic salt and the second organic salt are 20:80 or 80. In some cases, the combination shows the maximum luminance when the mass ratio is 20.
  • the combination of the first organic salt and the second organic salt is merely an example, and achieves the object of the present invention to make the injection ability of holes and electrons into the light emitting layer 12 substantially equal. Therefore, a combination of a plurality of types of ionic liquids such as three or more types can also be employed.
  • the organic salt represented by the formula (1) can be produced, for example, as follows.
  • a quaternary phosphonium halide obtained by reacting a tertiary phosphine compound corresponding to the target phosphonium cation and a halogenated hydrocarbon compound is used, and an ionic liquid in which the anion is halogen is prepared.
  • An anion component other than halogen can be obtained by reacting the quaternary phosphonium halide with a metal salt of the anion component to exchange anions.
  • an ionic liquid having a phosphonium cation in which three of R 1 , R 2 , R 3 and R 4 in formula (1) are alkyl groups, and the other is an aromatic alkyl group, and the anion component is halogen can be obtained by using a trialkylphosphine as the tertiary phosphine compound and a compound in which an aromatic alkyl group is bonded to halogen as the halogenated hydrocarbon compound. Further, among R 1 , R 2 , R 3 and R 4 in the formula (1), three have an alkyl group and the other one has a phosphonium cation which is an aromatic alkyl group, and the anion component is other than halogen.
  • the organic salt is a bis (trifluoromethylsulfonyl) imide, tetrafluoroborate (BF 4 ), hexafluorophosphate (PF 6 ), or bisoxalato borate (B (C 2). It can be obtained by anion exchange with O 4 ) 2 ), thiocyanate (SCN) or the like.
  • the ratio of the organic salt in the light emitting layer 12 is preferably 1% by mass or more and 30% by mass or less from the viewpoint of securing ion mobility and improving the film forming property of the light emitting layer 12. % Or less is more preferable.
  • the content of the organic salt in the light emitting layer 12 is preferably 10 parts by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the organic polymer light emitting material.
  • the organic polymer light emitting material contained in the light emitting layer 12 functions as a carrier body of electrons and holes by being doped with anions and cations, and emits light when excited by the combination of electrons and holes.
  • organic polymer light emitting materials include various ⁇ -conjugated polymers. Specific examples include poly (paraphenylene vinylene), poly (fluorene), poly (1,4-phenylene), polythiophene, polypyrrole, poly (paraphenylene sulfide), polybenzothiadiazole, polybiothiophine and the like. it can.
  • derivatives obtained by introducing substituents into these and copolymers thereof can also be used as the organic polymer light-emitting material.
  • Examples of such a substituent include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 18 carbon atoms, and [(—CH 2 CH 2 O—) n CH 3 ]. And a group represented by the formula (where n is an integer of 1 to 10).
  • Examples of the copolymer include those obtained by bonding each repeating unit of two or more kinds of the above-mentioned ⁇ -conjugated polymers.
  • Examples of the arrangement of each repeating unit in the copolymer include a random arrangement, an alternating arrangement, a block arrangement, or a combination thereof.
  • a commercial item can also be used as an organic polymer light-emitting material.
  • PFO-DMP Poly (9,9-dioctylfluorenyl-2,7-diyl) end capped with dimethylphenyl
  • LT-S934 Luminescence Technology under the name LT-S934
  • Aldrich Poly [(9,9-di-n-octylfluorenyl-2,7-diyl) -alt- (benzo [2,1,3] thiadiazol-4,8-diyl)]
  • Aldrich Poly [(9,9-di-n-octylfluorenyl-2,7-diyl) -alt- (benzo [2,1,3] thiadiazol-4,8-diyl)]
  • the ratio in the light emitting layer 12 is preferably 10% by mass or more and 95% by mass or less, and 20% by mass or more and 90% by mass or less. It is more preferable.
  • the light emitting layer 12 may contain substances other than organic polymer light emitting materials and organic salts.
  • substances other than organic polymer light emitting materials and organic salts include surfactants, polymer components for improving conductivity (polyethylene oxide, etc.), polymer components for improving film forming properties (polystyrene, polymethyl methacrylate (PMMA), etc.), organic salts, and the like. Other salts may be mentioned.
  • the amount of components other than the organic polymer light-emitting material and organic salt (excluding the solvent) in the light-emitting layer 12 is preferably 90 parts by mass or less when the entire light-emitting layer 12 is 100 parts by mass, and 60 parts by mass. More preferably, it is more preferably 30 parts by mass or less.
  • the film thickness of the light emitting layer 12 thus configured is preferably 10 nm or more and 200 nm or less, and more preferably 50 nm or more and 150 nm or less.
  • the film thickness of the light emitting layer 12 is within this range, it is preferable from the viewpoints that light emission can be sufficiently and efficiently obtained from the light emitting layer 12, defects in a light emission scheduled portion can be suppressed, and short circuit prevention can be achieved.
  • the electrochemiluminescence cell 10 of this embodiment can be manufactured by the following manufacturing method, for example.
  • a substrate provided with the first electrode 13 is prepared.
  • the first electrode 13 is formed from, for example, ITO, by forming a deposited ITO film in a pattern on the surface of a glass substrate or the like by using a photolithography method or a combination of the photolithography method and the lift-off method, A first electrode 13 made of ITO can be formed on the surface.
  • an organic salt and an organic polymer light-emitting material are dissolved in an organic solvent to prepare a composition for forming a light-emitting layer of an electrochemiluminescence cell.
  • an organic solvent from the viewpoint of efficiently mixing the organic salt and the organic polymer light-emitting material, it is preferable to use toluene, benzene, tetrahydrofuran, dimethyl chloride, chlorobenzene, chloroform, or the like as the organic solvent.
  • These organic solvents can be used individually by 1 type or in combination of 2 or more types.
  • the blending ratio (mass ratio) of the organic salt and the organic polymer light-emitting material in the composition for forming a light-emitting layer is preferably 1: 1 to 20 in the former: latter.
  • This composition for forming a light emitting layer is applied onto the first electrode 13 of the substrate by a spin coating method or the like. Thereafter, the coating film formed by this coating is dried to evaporate the organic solvent, thereby forming the light emitting layer 12.
  • the preparation of the light emitting layer forming composition and the formation of the light emitting layer 12 are preferably performed in an inert gas atmosphere having a moisture content of 100 ppm or less.
  • the inert gas include argon, nitrogen, helium and the like.
  • the second electrode 14 is formed on the formed light emitting layer 12.
  • an electrode having a predetermined pattern is formed on the light emitting layer 12 by evaporating aluminum (Al) into a film shape by, for example, a vacuum evaporation method through a mask.
  • Al aluminum
  • the second electrode 14 is formed on the light emitting layer 12.
  • the obtained electrochemiluminescence cell 10 may be vacuum-dried from the viewpoint of improving the film quality of the light emitting layer 12. This vacuum drying may be performed at room temperature or may be performed under heating.
  • the electrochemiluminescence cell 10 of the present embodiment emits light by the following light emission mechanism.
  • a voltage is applied to the light emitting layer 12 so that the first electrode 13 serves as an anode and the second electrode 14 serves as a cathode.
  • ions in the light emitting layer 12 move along the electric field, and a layer in which anion species are collected in the vicinity of the interface between the light emitting layer 12 and the first electrode 13 is formed.
  • a layer in which cationic species are collected in the vicinity of the interface with the second electrode 14 in the light emitting layer 12 is formed. In this way, an electric double layer is formed at the interface of each electrode.
  • the p-doped region 16 is spontaneously formed in the vicinity of the first electrode 13 that is the anode
  • the n-doped region 17 is spontaneously formed in the vicinity of the second electrode 14 that is the cathode.
  • These doped regions constitute a pin junction with a high carrier density.
  • the energy difference (band gap) between the highest occupied orbital (Highest Occupied Molecular Orbital) and the lowest unoccupied orbital (Lowest Unoccupied Molecular Orbital) corresponds to the desired wavelength. What is necessary is just to select a material.
  • the present invention further discloses the following electrochemiluminescence cell.
  • the electrochemiluminescence cell in an electrochemiluminescence cell having a light emitting layer and electrodes arranged on each surface thereof, The electrochemiluminescence cell in which the light emitting layer includes a combination of an organic polymer light emitting material and two or more organic salts.
  • the organic salt is an organic salt selected from a phosphonium salt, an ammonium salt, a pyridinium salt, an imidazolium salt, and a pyrrolidinium salt.
  • R 1 , R 2 , R 3 and R 4 are each an alkyl group, an alkoxyalkyl group, a trialkylsilylalkyl group, an alkenyl group, an alkynyl group, an aryl group, which may be substituted with a functional group, or Represents a heterocyclic group, R 1 , R 2 , R 3 and R 4 may be the same or different from each other, M represents N or P, and X ⁇ represents an anion.
  • the organic salt is a plurality of organic salts represented by the formula (1), and all of them are liquid at room temperature.
  • a plurality of organic salts represented by the formula (1) is used as the organic salt, at least one of them is liquid at normal temperature, and at least one of them is solid at normal temperature
  • the electrochemiluminescence cell of description [8] The light emitting layer includes a combination of two organic salts represented by the formula (1), The two organic salts have the same kind of cation, and the anion is different, [4] to [7]. [9] The electrochemiluminescence cell according to [8], wherein one of the different anions is bistrifluoromethanesulfonylimide and the other is halogen.
  • the light emitting layer includes a combination of two organic salts represented by the formula (1),
  • the two types of organic salts are the electrochemiluminescence cells according to any one of [4] to [7], wherein the two kinds of organic salts have the same kind of anion and the cation is different.
  • the electrochemiluminescence cell according to [10] wherein the different cations are all ammonium ions or phosphonium ions.
  • the electrochemiluminescence cell according to [10] wherein one of the different cations is an ammonium ion and the other is a phosphonium ion.
  • a composition for forming a light emitting layer of an electrochemiluminescent cell comprising a combination of an organic polymer light emitting material, an organic solvent, and two or more organic salts.
  • Example 1 and Comparative Example 1 A commercially available glass substrate with an ITO film (manufactured by Geomatic Co., Ltd., ITO film thickness 200 nm) was used as the first electrode.
  • Mn average molecular weight
  • the composition for forming a light-emitting layer prepared above is applied by spin coating on the first electrode of the glass substrate at room temperature in a glove box in an argon atmosphere, and further, 30% on a hot plate at 50 ° C.
  • the organic solvent was evaporated by heating for minutes.
  • a solid light emitting layer having a thickness of 100 nm was formed.
  • a second electrode made of aluminum (Al) having a thickness of 30 nm was formed on the formed light emitting layer by the method described above. In this way, an electrochemiluminescence cell having an area of a 2 mm ⁇ 2 mm square of a planned emission portion was produced.
  • the first electrode was connected to the direct current anode
  • the second electrode was connected to the cathode
  • a voltage was applied up to 20 V
  • the maximum luminance during this period was defined as the emission luminance.
  • the luminance was measured using CS-2000 (manufactured by Konica Minolta). The results are shown in FIG.
  • Example 2 and Comparative Example 2 A combination of an ionic liquid tributyloctylammonium bistrifluoromethanesulfonylimide (N4448TFSI) and an ionic liquid trioctylmethylammonium bistrifluoromethanesulfonylimide (N8881TFSI) was used as an organic salt.
  • the mass ratio between the two was as shown in FIG. 4 (in FIG. 4, x on the horizontal axis represents the mass fraction). Except this, an electrochemiluminescence cell was produced in the same manner as in Example 1. About the obtained electrochemiluminescence cell, the same measurement as Example 1 was performed. The result is shown in FIG.
  • Example 3 and Comparative Example 3 A combination of ionic liquid trioctylbenzylphosphonium bistrifluoromethanesulfonylimide (P888BzTFSI) and ionic liquid trioctylbenzylphosphonium bromide (P888BzBr) was used as an organic salt. The mass ratio between the two was as shown in FIG. Except this, an electrochemiluminescence cell was produced in the same manner as in Example 1. About the obtained electrochemiluminescence cell, the same measurement as Example 1 was performed. The result is shown in FIG.
  • P888BzTFSI ionic liquid trioctylbenzylphosphonium bistrifluoromethanesulfonylimide
  • P888BzBr ionic liquid trioctylbenzylphosphonium bromide
  • Example 4 and Comparative Example 4 A combination of ionic liquid trioctylbenzylphosphonium bistrifluoromethanesulfonylimide (P888BzTFSI) and ionic liquid triethylpentylphosphonium bistrifluoromethanesulfonylimide (P2225TFSI) was used as an organic salt. The mass ratio between the two was as shown in FIG. Except this, an electrochemiluminescence cell was produced in the same manner as in Example 1. About the obtained electrochemiluminescence cell, the same measurement as Example 1 was performed. The result is shown in FIG.
  • P888BzTFSI ionic liquid trioctylbenzylphosphonium bistrifluoromethanesulfonylimide
  • P2225TFSI ionic liquid triethylpentylphosphonium bistrifluoromethanesulfonylimide
  • Example 5 and Comparative Example 5 A commercially available glass substrate with an ITO film (manufactured by Geomatic Co., Ltd., ITO film thickness 200 nm) was used as the first electrode.
  • F8BT Poly [(9,9-di-n-octylfluorenyl-2,7-diyl) -alt- (benzo [2,1,3] thiadiazol-4,8-diyl)]
  • Aldrich's average molecular weight (Mn) 10000 to 20000) was used.
  • Example 1 As an organic salt, a combination of ionic liquid tributyloctylammonium bistrifluoromethanesulfonylimide (N4448TFSI) and ionic liquid tributyloctylammonium bromide (N4448Br) was used. The mass ratio between the two was as shown in FIG. Except this, an electrochemiluminescence cell was produced in the same manner as in Example 1. About the obtained electrochemiluminescence cell, the same measurement as Example 1 was performed. The result is shown in FIG.
  • N4448TFSI ionic liquid tributyloctylammonium bistrifluoromethanesulfonylimide
  • N4448Br ionic liquid tributyloctylammonium bromide
  • Example 6 and Comparative Example 6 A combination of ionic liquid trioctylmethylammonium bistrifluoromethanesulfonylimide (N8881TFSI) and ionic liquid trioctylhexadecammonium bistrifluoromethanesulfonylimide (N888 (16) TFSI) was used as an organic salt. The mass ratio between the two was as shown in FIG. Other than this, an electrochemiluminescence cell was produced in the same manner as in Example 5. About the obtained electrochemiluminescence cell, the same measurement as Example 5 was performed. The result is shown in FIG.
  • Example 7 and Comparative Example 7 A combination of ionic liquid trioctylbenzylphosphonium bistrifluoromethanesulfonylimide (P888BzTFSI) and ionic liquid triethylpentylphosphonium bistrifluoromethanesulfonylimide (P2225TFSI) was used as an organic salt. The mass ratio between the two was as shown in FIG. Other than this, an electrochemiluminescence cell was produced in the same manner as in Example 5. About the obtained electrochemiluminescence cell, the same measurement as Example 5 was performed. The result is shown in FIG.
  • P888BzTFSI ionic liquid trioctylbenzylphosphonium bistrifluoromethanesulfonylimide
  • P2225TFSI ionic liquid triethylpentylphosphonium bistrifluoromethanesulfonylimide
  • Example 8 and Comparative Example 8 A combination of an ionic liquid trioctylmethylammonium bistrifluoromethanesulfonylimide (N8881TFSI) and an ionic liquid trioctylbenzylphosphonium bistrifluoromethanesulfonylimide (P888BzTFSI) was used as an organic salt. The mass ratio between the two was as shown in FIG. Other than this, an electrochemiluminescence cell was produced in the same manner as in Example 5. About the obtained electrochemiluminescence cell, the same measurement as Example 5 was performed. The result is shown in FIG.
  • N8881TFSI ionic liquid trioctylmethylammonium bistrifluoromethanesulfonylimide
  • P888BzTFSI ionic liquid trioctylbenzylphosphonium bistrifluoromethanesulfonylimide
  • Example 9 and Comparative Example 9 A combination of ionic liquid tributyloctylammonium bistrifluoromethanesulfonylimide (N4448TFSI) and solid tributyloctylammonium tetrafluoroborate (N4448BF 4 ) was used as an organic salt. The mass ratio between the two was as shown in FIG. Except this, an electrochemiluminescence cell was produced in the same manner as in Example 1. About the obtained electrochemiluminescence cell, the same measurement as Example 1 was performed. The result is shown in FIG.
  • N4448TFSI ionic liquid tributyloctylammonium bistrifluoromethanesulfonylimide
  • N4448BF 4 solid tributyloctylammonium tetrafluoroborate
  • Example 10 and Comparative Example 10 A combination of ionic liquid tributyloctylammonium bistrifluoromethanesulfonylimide (N4448TFSI) and solid tributyloctylammonium hexafluorophosphate (N4448PF 6 ) was used as an organic salt. The mass ratio between the two was as shown in FIG. Except this, an electrochemiluminescence cell was produced in the same manner as in Example 1. About the obtained electrochemiluminescence cell, the same measurement as Example 1 was performed. The result is shown in FIG.
  • N4448TFSI ionic liquid tributyloctylammonium bistrifluoromethanesulfonylimide
  • N4448PF 6 solid tributyloctylammonium hexafluorophosphate
  • Example 11 and Comparative Example 11 A commercially available glass substrate with an ITO film (manufactured by Geomatic Co., Ltd., ITO film thickness 200 nm) was used as the first electrode.
  • PFO-Spiro Poly [(9,9-dioctylfluorenyl-2,7-diyl) -alt-co- (9,9'-spirobifluorene-2,7-diyl)]]
  • Solaris Chem Manufactured by SOL2412
  • Example 12 and Comparative Example 12 A commercially available glass substrate with an ITO film (manufactured by Geomatic Co., Ltd., ITO film thickness 200 nm) was used as the first electrode.
  • PFO-Spiro Poly [(9,9-dioctylfluorenyl-2,7-diyl) -alt-co- (9,9'-spirobifluorene-2,7-diyl)]]
  • Solaris Chem Manufactured by SOL2412 As an organic salt, a combination of solid tetrabutylphosphonium dibutyl phosphate (P4P4) and liquid tetrabutylphosphonium dimethyl phosphate (P4P1) was used. The mass ratio between the two was as shown in FIG. Except this, an electrochemiluminescence cell was produced in the same manner as in Example 1. About the obtained electrochemiluminescence cell, the same measurement as Example 1 was performed. The result is shown in FIG.
  • Electrochemiluminescence cell 12 Light emitting layer 13 1st electrode 14 2nd electrode 16 p doped area

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  • Electroluminescent Light Sources (AREA)

Abstract

L'invention concerne une cellule luminescente électrochimique (10) qui comporte une couche luminescente (12) et des électrodes (13, 14) disposées sur chaque surface de la couche luminescente (12). La couche luminescente (12) comprend un matériau luminescent polymère organique et une combinaison d'au moins deux types de sels organiques. En particulier, la couche luminescente comprend de préférence une combinaison d'au moins deux types de liquides ioniques représentés par la formule (1) (dans laquelle R1, R2, R3 et R4 représentent chacun un groupe alkyle, un groupe alcoxyalkyle, un groupe trialkylsilylalkyle, un groupe alcényle, un groupe alcynyle, un groupe aryle ou un groupe hétérocyclique, qui peut être substitué par un groupe fonctionnel ; R1, R2, R3 et R4 peuvent être identiques ou différents l'un de l'autre ; M représente N ou P ; et X- représente un anion).
PCT/JP2015/078277 2014-10-09 2015-10-06 Cellule luminescente électrochimique et composition pour formation de couche luminescente de cellule luminescente électrochimique WO2016056529A1 (fr)

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EP15848287.7A EP3205924B1 (fr) 2014-10-09 2015-10-06 Cellule luminescente électrochimique et composition pour formation de couche luminescente de cellule luminescente électrochimique
CN201580053972.XA CN106796001B (zh) 2014-10-09 2015-10-06 电化学发光电池和电化学发光电池的发光层形成用组合物
KR1020177008860A KR20170065522A (ko) 2014-10-09 2015-10-06 전기 화학 발광 셀 및 전기 화학 발광 셀의 발광층 형성용 조성물

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018124102A1 (fr) * 2016-12-27 2018-07-05 国立大学法人北陸先端科学技術大学院大学 Cellule électroluminescente électrochimique
WO2018151086A1 (fr) * 2017-02-17 2018-08-23 日本化学工業株式会社 Cellule électroluminescente électrochimique et composition de formation de couche électroluminescente de cellule électroluminescente électrochimique

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JP2000067601A (ja) * 1998-08-17 2000-03-03 Fuji Photo Film Co Ltd 電気化学発光素子の製造方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000067601A (ja) * 1998-08-17 2000-03-03 Fuji Photo Film Co Ltd 電気化学発光素子の製造方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018124102A1 (fr) * 2016-12-27 2018-07-05 国立大学法人北陸先端科学技術大学院大学 Cellule électroluminescente électrochimique
CN110121795A (zh) * 2016-12-27 2019-08-13 国立大学法人北陆先端科学技术大学院大学 电化学发光电池
WO2018151086A1 (fr) * 2017-02-17 2018-08-23 日本化学工業株式会社 Cellule électroluminescente électrochimique et composition de formation de couche électroluminescente de cellule électroluminescente électrochimique

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