WO2009110075A1 - Elément à semi-conducteurs organique - Google Patents

Elément à semi-conducteurs organique Download PDF

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Publication number
WO2009110075A1
WO2009110075A1 PCT/JP2008/053978 JP2008053978W WO2009110075A1 WO 2009110075 A1 WO2009110075 A1 WO 2009110075A1 JP 2008053978 W JP2008053978 W JP 2008053978W WO 2009110075 A1 WO2009110075 A1 WO 2009110075A1
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organic semiconductor
organic
layer
electron
semiconductor layer
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PCT/JP2008/053978
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Japanese (ja)
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崇人 小山田
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パイオニア株式会社
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Priority to PCT/JP2008/053978 priority Critical patent/WO2009110075A1/fr
Priority to TW098105975A priority patent/TW200950172A/zh
Publication of WO2009110075A1 publication Critical patent/WO2009110075A1/fr

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/30—Doping active layers, e.g. electron transporting layers
    • 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]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H10K50/165—Electron transporting layers comprising dopants
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/10—Transparent electrodes, e.g. using graphene
    • H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
    • H10K2102/103—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising indium oxides, e.g. ITO

Definitions

  • the present invention relates to an organic semiconductor element, and more particularly to an organic semiconductor element using an organic compound having a charge transporting property (hole or electron mobility) and having an organic semiconductor layer made of such a compound.
  • organic solar cell using an organic material as one of the organic semiconductor elements.
  • Inorganic solar cells using p-type and n-type semiconductors made of inorganic materials such as silicon for the photoelectric conversion layer are mainly used because of high energy conversion efficiency, but p-type organic semiconductors and n-type organic semiconductors are used instead of inorganic semiconductors.
  • Research and development of lightweight, inexpensive, and flexible organic solar cells continues.
  • organic solar cells dye-sensitized solar cells (Gretzel cells), organic thin-film solar cells, and the like are known. Dye-sensitized solar cells are wet, and organic thin-film solar cells are all solid.
  • Solar cells whether organic or inorganic, first absorb solar energy (light collection) and are excited to a high energy state to generate electrons and holes, which are then transferred to the negative electrode (electron transport). Electrical energy is generated by transporting the holes to the positive electrode (hole transport).
  • Organic thin-film solar cells differ greatly from inorganic solar cells in the generation mechanism of electrons and holes.
  • inorganic solar cells represented by silicon electrons and holes are generated at the p-type and n-type semiconductor interfaces simultaneously with light absorption and move to the respective electrodes.
  • Excitons whose holes are strongly bound are generated in the light collection layer and move to the interface with the electron transport layer or the hole transport layer, so that electrons and holes are generated.
  • the organic solar cell uses an organic compound having a charge transporting property. It has a multilayer structure (see Patent Document 1).
  • organic thin film transistor is one of organic semiconductor elements.
  • research and development has been actively conducted, and among these, researches on organic active light emitting devices in which organic electroluminescence devices and organic electroluminescence (EL) devices are driven in an active matrix by organic thin film transistors are being conducted.
  • organic active light emitting devices in which organic electroluminescence devices and organic electroluminescence (EL) devices are driven in an active matrix by organic thin film transistors are being conducted.
  • EL organic electroluminescence
  • a transparent gate electrode is provided on a substrate, a transparent gate insulating film is formed thereon so as to cover the gate electrode, and a source electrode (charge injection) having an opening on the gate insulating film And an organic semiconductor film, an organic EL film is laminated on the organic semiconductor film, and a drain electrode (charge injection) is laminated thereon (see Patent Document 2).
  • the organic EL film has a structure in which a plurality of organic material layers including an organic light emitting layer are stacked.
  • the organic material layer has a layer made of a material having a hole transport ability such as a hole injection layer and a hole transport layer, and an electron transport ability such as an electron transport layer and an electron injection layer. Layers made of materials are included.
  • the electron injection layer includes an inorganic compound.
  • the organic active light emitting device When an electric field is applied to the organic light-emitting layer and the organic EL film of the electron or hole transport layer stack, holes are injected from the source electrode and electrons are injected from the drain electrode. When combined, excitons are formed and emit light when returning to the ground state. In order to improve the light emission efficiency, it is important to efficiently transport carriers such as electrons to the interface, and the organic active light emitting device has a multilayer structure using an organic compound having a charge transporting property.
  • organic EL elements for example, organic EL elements, alkali metals and alkaline earth metals having low work functions, compounds thereof (CsF, Cs 2 CO 3 , Li 2 O, LiF), etc.
  • CsF, Cs 2 CO 3 , Li 2 O, LiF compounds thereof
  • these materials are difficult to handle because they are easily oxidized, decomposed (Cs 2 CO 3 ) depending on the material, and have deliquescence.
  • Cs 2 CO 3 since these have high reactivity, there also exists a problem which reacts with a vapor deposition boat and corrodes.
  • Cs simple substance is a conductive metal, but because of its high reactivity, it becomes Cs 2 O cesium oxide during film formation by vacuum deposition. ing.
  • the problem to be solved by the invention is, for example, to provide an organic semiconductor element such as an organic EL element capable of extending the life.
  • An organic semiconductor device is an organic semiconductor device including a plurality of organic semiconductor layers stacked between a pair of opposed first and second electrodes, wherein the second electrode is a negative electrode,
  • An electron transporting organic semiconductor layer made of an organic semiconductor that is in contact with the interface of the organic semiconductor layer and doped with a metal acid salt compound having an electron donating metal as a counter cation between the second electrode and the organic semiconductor layer. It is characterized by having. Since the electron-transporting organic semiconductor layer is provided, the device life can be improved.
  • the electron-transporting organic semiconductor layer can efficiently inject electrons even in a cathode having a high work function of 4.5 eV or more. Since the electron transporting organic semiconductor layer is used, there is an effect that the electron injection layer is unnecessary. That is, since the electron transporting organic semiconductor layer is in contact with the cathode, electrons can be injected.
  • the electron transporting organic semiconductor layer has an effect that the metal salt compound does not diffuse under high temperature storage.
  • the electron donating metal is one or more metals selected from metals having a work function of 3.5 eV or less among transition metals including alkali metals, alkaline earth metals, and rare earth metals.
  • the concentration of the metal salt compound in the electron transporting organic semiconductor layer can be 0.1 to 40% by weight.
  • the electron transporting organic semiconductor layer has a specific concentration or a certain concentration or more, it has an effect of reducing the driving voltage of the element.
  • the electron transporting organic semiconductor layer may have a thickness of 1 nm to 300 nm.
  • the electron transporting organic semiconductor layer can be formed by single vapor deposition or multiple vapor deposition. Since the metal salt compound only needs to be vapor-deposited, the process is simplified.
  • the electron transporting organic semiconductor layer film may have a transmittance of 50% or more.
  • the metal acid salt compound may include a conductive oxide semiconductor.
  • the conductive oxide semiconductor has a carrier mobility of 1 ⁇ 10 ⁇ 10 to 1 ⁇ 10 10 cm 2 / Vs or a conductivity of 10 10 to 10 ⁇ 10 ⁇ ⁇ cm. Can have.
  • the organic semiconductor may have a carrier mobility of 1 ⁇ 10 ⁇ 10 to 1 ⁇ 10 10 cm 2 / Vs.
  • the plurality of organic semiconductor layers include a light emitting layer, and one of the first and second electrodes is translucent or transparent, or the first and second electrodes are It can be an organic electroluminescent device that is transparent.
  • the driving voltage of the organic electroluminescent element is lowered, and the consumption voltage of the organic electroluminescent element panel is reduced.
  • the calorific value of a panel can be suppressed by reducing the power consumption of a panel.
  • the plurality of organic semiconductor layers may be organic solar cells including a light collection layer and at least one of an electron transport layer and a hole transport layer.
  • an example of the organic EL element of the present embodiment includes, in order, a transparent first electrode (anode) 2, a hole transport layer 4 made of an organic compound, on a transparent substrate 1 such as glass, An organic light emitting layer 5 made of an organic compound, an electron transporting organic semiconductor layer 7 made of an organic compound, and a second electrode (cathode that is a negative electrode) 8 made of a metal are laminated. That is, in the organic EL element, a pair of first and second electrodes facing each other correspond to an anode and a cathode, and a plurality of organic semiconductor layers stacked between them are a hole injection layer, a hole transport layer, Includes a light emitting layer.
  • An electron-transporting organic semiconductor layer is disposed between the cathode of the second electrode and the organic semiconductor layer (light-emitting layer) in contact with the interface of the light-emitting layer, which is doped with a metal salt compound having an electron-donating metal as a counter cation.
  • a metal salt compound having an electron-donating metal as a counter cation Made of organic semiconductor.
  • anode 2 / hole injection layer 3 / hole transport layer 4 / light emitting layer 5 / electron transporting organic semiconductor layer 7 / cathode 8 / in addition to the structure of anode 2 / hole injection layer 3 / hole transport layer 4 / light emitting layer 5 / electron transporting organic semiconductor layer 7 / cathode 8 /, as shown in FIG.
  • the structure of anode 2 / hole injection layer 3 / light emitting layer 5 / electron transporting organic semiconductor layer 7 / cathode 8 / as shown in FIG. 3, anode 2 / hole transport layer 4 / light emitting layer 5 / electron transport The structure of the conductive organic semiconductor layer 7 / cathode 8 / and the structure of the anode 2 / light emitting layer 5 / electron transporting organic semiconductor layer 7 / cathode 8 / as shown in FIG.
  • the organic EL element by this invention should just have the electron transport organic-semiconductor layer 7 in the interface with the cathode 8.
  • the electron transporting organic semiconductor layer 7 adjacent layer is not limited to the light emitting layer, and a block layer and / or a buffer layer between the light emitting layer and the electron transporting organic semiconductor layer, for example, as shown in FIG.
  • the electron transporting organic semiconductor layer 7 adjacent layer is not limited to the light emitting layer, and a block layer and / or a buffer layer between the light emitting layer and the electron transporting organic semiconductor layer, for example, as shown in FIG.
  • FIG. 1 In addition to the structure of anode 2 / hole injection layer 3 / hole transport layer 4 / light emitting layer 5 / hole blocking layer 6 / electron transporting organic semiconductor layer 7 / cathode 8 /, as shown in FIG.
  • anode 2 / hole injection layer 3 / light emitting layer 5 / hole blocking layer 6 / electron transporting organic semiconductor layer 7 / cathode 8 / as shown in FIG. 7, anode 2 / hole transport layer 4 /
  • the configuration of layer 7 / cathode 8 / is also included in the present invention.
  • first and second electrodes-- In addition to the glass transparent material of the substrate 1, in addition to a translucent material such as a plastic material such as polystyrene, an opaque material such as silicon or Al, a thermosetting resin such as a phenol resin, a thermoplastic resin such as a polycarbonate, etc. Can be used.
  • a translucent material such as a plastic material such as polystyrene
  • an opaque material such as silicon or Al
  • a thermosetting resin such as a phenol resin
  • thermoplastic resin such as a polycarbonate
  • Electrode materials of the first electrode (anode) 2 and the second electrode (cathode) 8 Ti, Al, Al, Cu, Ni, Ag, Mg: Ag, Au, Pt, Pd, Ir, Cr, Mo, W And metals such as Ta and alloys thereof.
  • a conductive polymer such as polyaniline or PEDT: PSS can be used.
  • an oxide transparent conductive thin film for example, one containing indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide, tin oxide or the like as a main composition can be used.
  • the thickness of each electrode is preferably about 10 to 500 nm.
  • These electrode materials are preferably produced by vacuum deposition or sputtering.
  • a conductive material having a work function larger than that of the second electrode (cathode) 8 is selected for the first electrode (anode) 2 as the positive electrode. Further, the materials of the first and second electrodes are selected so that the light emission side is transparent or translucent. In particular, it is preferable to select a material in which one or both of the first and second electrodes have a transmittance of at least 10% at the emission wavelength obtained from the organic light emitting material.
  • Organic semiconductor layer-- The organic semiconductor layer constituting the main components of the hole injection layer 3, the hole transport layer 4, the light emitting layer 5, and the electron transport organic semiconductor layer 7 has a charge transport property (hole and / or electron mobility). Utilizes organic compounds.
  • Examples of the organic compound having an electron transporting property as a main component of the light emitting layer and the electron transporting organic semiconductor layer include polycyclic compounds such as p-terphenyl and quaterphenyl and derivatives thereof, naphthalene, tetracene, pyrene, coronene, chrysene Condensed polycyclic hydrocarbon compounds such as anthracene, diphenylanthracene, naphthacene, phenanthrene and their derivatives, condensed heterocyclic compounds such as phenanthroline, bathophenanthroline, phenanthridine, acridine, quinoline, quinoxaline, phenazine and their derivatives, Fluorescein, perylene, phthaloperylene, naphthaloperylene, perinone, phthaloperinone, naphthaloperinone, diphenylbutadiene, tetraphenylbutadiene, oxadiazol
  • a metal chelate complex compound particularly a metal chelated oxanoid compound, tris (8-quinolinolato) aluminum, bis (8-quinolinolato) magnesium, bis [benzo (f) -8-quinolinolato Zinc, bis (2-methyl-8-quinolinolato) aluminum, tris (8-quinolinolato) indium, tris (5-methyl-8-quinolinolato) aluminum, 8-quinolinolatolithium, tris (5-chloro-8- There may also be mentioned metal complexes having at least one 8-quinolinolato or a derivative thereof such as quinolinolato) gallium and bis (5-chloro-8-quinolinolato) calcium as a ligand.
  • organic compounds having electron transport properties oxadiazoles, triazines, stilbene derivatives, distyrylarylene derivatives, styryl derivatives, and diolefin derivatives can be suitably used.
  • organic compound that can be used as an organic compound having an electron transporting property 2,5-bis (5,7-di-t-benzyl-2-benzoxazolyl) -1,3,4-thiazole, 4, 4'-bis (5,7-t-pentyl-2-benzoxazolyl) stilbene, 4,4'-bis [5,7-di- (2-methyl-2-butyl) -2-benzoxazoly Ru] stilbene, 2,5-bis (5.7-di-t-pentyl-2-benzoxazolyl) thiophene, 2,5-bis [5- ( ⁇ , ⁇ -dimethylbenzyl) -2-benzoxa Zolyl] thiophene, 2,5-bis [5,7-di- (2-methyl-2-butyl) -2-benzoxazolyl] -3,4-diphenylthiophene, 2,5-bis (5- Methyl-2-benzoxazolyl) thiophene, 4,
  • 1,4-bis (2-methylstyryl) benzene 1,4-bis (3-methylstyryl) benzene, 1,4-bis (4-methylstyryl) benzene, Distyrylbenzene, 1,4-bis (2-ethylstyryl) benzene, 1,4-bis (3-ethylstyryl) benzene, 1,4-bis (2-methylstyryl) -2-methylbenzene, 1,4 Examples thereof include -bis (2-methylstyryl) -2-ethylbenzene.
  • organic compound having an electron transporting property 2,5-bis (4-methylstyryl) pyrazine, 2,5-bis (4-ethylstyryl) pyrazine, 2,5-bis [2- (1- Naphthyl) vinyl] pyrazine, 2,5-bis (4-methoxystyryl) pyrazine, 2,5-bis [2- (4-biphenyl) vinyl] pyrazine, 2,5-bis [2- (1-pyrenyl) vinyl ] Pyrazine etc. are mentioned.
  • organic compounds having electron transport properties include 1,4-phenylene dimethylidin, 4,4'-phenylene dimethylidin, 2,5-xylylene dimethylidin, and 2,6-naphthylene dimethylidene. Din, 1,4-biphenylenedimethylidin, 1,4-p-terephenylenedimethylidin, 9,10-anthracenediyldimethylidin, 4,4 '-(2,2-di-t-butylphenylvinyl
  • Known materials conventionally used for the production of organic EL devices such as biphenyl and 4,4 ′-(2,2-diphenylvinyl) biphenyl can be appropriately used.
  • organic compounds having hole transporting properties include N, N, N ′, N′-tetraphenyl-4,4′-diaminophenyl, N, N′-diphenyl-N, N′-di (3-methyl Phenyl) -4,4′-diaminobiphenyl, 2,2-bis (4-di-p-tolylaminophenyl) propane, N, N, N ′, N′-tetra-p-tolyl-4,4′- Diaminobiphenyl, bis (4-di-p-tolylaminophenyl) phenylmethane, N, N′-diphenyl-N, N′-di (4-methoxyphenyl) -4,4′-diaminobiphenyl, N, N, N ′, N′-tetraphenyl-4,4′-diaminodiphenyl ether, 4,4′-bis (diphenylamino) quadriphenyl
  • the hole injection layer, the hole transport layer, and the hole transporting light emitting layer those obtained by dispersing the above organic compound in a polymer or those polymerized can be used.
  • So-called ⁇ -conjugated polymers such as polyparaphenylene vinylene and derivatives thereof, hole-transporting non-conjugated polymers typified by poly (N-vinylcarbazole), and sigma-conjugated polymers of polysilanes can also be used.
  • the hole injection layer is not particularly limited, but conductive polymers such as metal phthalocyanines such as copper phthalocyanine and metal-free phthalocyanines, carbon films, and polyaniline can be preferably used.
  • the compound is disposed, while the organic compound layer (electron injection layer) on the cathode side is doped with an electron-donating metal having a reducing action, but the doping form is fixed in the stoichiometric form of the metal salt compound.
  • the electron-donating metal is not particularly limited as long as it is an alkali metal such as Li, an alkaline earth metal such as Mg, or a transition metal containing a rare earth metal.
  • a metal having a work function of 4.0 eV or less can be suitably used. Specific examples include Cs, Li, Na, K, Be, Mg, Ca, Sr, Ba, Y, La, Mg, Sm, Gd, Yb, Etc.
  • the concentration of the metal salt compound in the electron transporting organic semiconductor layer is preferably 0.1 to 40% by weight. If it is less than 0.1% by weight, the concentration of the molecule reduced by the electron donating metal of the metal salt compound is too low, and the effect of doping is small. If it exceeds 40% by weight, the metal salt compound concentration in the film is organic. The concentration of semiconductor molecules is exceeded and the effect of doping is also reduced.
  • the thickness of the electron transporting organic semiconductor layer is not particularly limited, but is preferably 1 nm to 300 nm. If the thickness is less than 1 nm, the amount of reducing molecules present in the vicinity of the electrode interface is small, so that the effect of doping is small. If the thickness exceeds 300 nm, the entire organic layer is too thick, leading to an increase in driving voltage.
  • At least the film of the electron transporting organic semiconductor layer is set to have a transmittance of 50% or more at the emission wavelength obtained from the organic light emitting material.
  • the film forming method of the electron transporting organic semiconductor layer 7 may be any thin film forming method.
  • a vapor deposition method or a sputtering method can be used.
  • the electron transporting organic semiconductor layer is preferably formed by single vapor deposition or multiple vapor deposition.
  • a coating method from a solution such as a spin coating method or a dip coating method can be used.
  • the organic compound to be doped and the dopant may be dispersed in an inert polymer.
  • the metal salt compound (Cs 2 MoO 4 etc.) in the present invention is a transition metal containing alkali metal, alkaline earth metal and rare earth metal having a work function of 4.0 eV or less (particularly preferably 3.5 eV or less) as the first component. And the like, and using a conductive metal oxide (MoOx, WOx, TiOx, SnOx, VxOy, ZnOx, ZrOx (x represents an atomic ratio), etc.) as the second component, the thermal stability is increased, and Since it is an oxide, its adhesion to the cathode (for example, Al, etc.) is increased and it becomes difficult to peel off.
  • a conductive metal oxide MoOx, WOx, TiOx, SnOx, VxOy, ZnOx, ZrOx (x represents an atomic ratio), etc.
  • the main component of such an organic semiconductor layer has a mobility (10 ⁇ 8 to 10 1 cm 2 / Vs) or conductivity (10 8 to 10 ⁇ 1 ⁇ ⁇ cm) lower than that of an inorganic compound. Since the conductivity of the conductive metal oxide corresponding to the second component supplements the conductivity of the organic semiconductor layer, both the electron injection property and the electron transport property can be improved. Further, as mentioned above, since an electron injection layer of an inorganic compound is not required, the thickness can be reduced.
  • the conductive metal oxide as the second component preferably has a specific resistance of 10 8 ⁇ ⁇ cm or less (MoO 3 : 2.5 ⁇ ⁇ cm).
  • the second component The conductive metal oxide is supplemented by carrier concentration or mobility.
  • the organic semiconductor material has a very low or no carrier concentration (10 5 to 10 10 cm ⁇ 3 ), the presence of the carrier concentration inside the thin film is very effective for improving electron transport properties. is there.
  • An electron transporting organic semiconductor layer (for example, Alq3) of a conventional element has an increased driving voltage as the film thickness increases.
  • An electron transporting organic semiconductor layer doped with this metal salt compound in an electron transporting organic semiconductor layer By using (a metal-inorganic-organic composite (composite) layer), an increase in driving voltage with respect to an increase in film thickness can be suppressed.
  • a plurality of organic EL devices each including a metal-inorganic-organic composite electron-transporting organic semiconductor layer comprising a metal acid salt compound having an electron-donating metal as a counter cation and an electron-transporting organic semiconductor were produced.
  • the driving voltage and luminance with respect to the salt compound concentration, lifetime characteristics, and film thickness dependence characteristics of the electron transporting organic semiconductor layer were measured and evaluated.
  • cesium molybdate Cs 2 MoO 4 and cesium tungstate Cs 2 WO 4 were used.
  • the electron transporting organic semiconductor EIL shown in Table 1 below was used as the electron transporting organic semiconductor.
  • Example 1 On the glass substrate on which the transparent electrode ITO was formed as an anode, copper phthalocyanine CuPc was formed in a thickness of 25 nm as a hole injection layer in order by vacuum deposition, and NPB: N, N ′ as a hole transport layer was formed thereon. -Bis (naphthalene-2-yl) -N, N'-diphenyl-benzidine was formed to a thickness of 45 nm.
  • Alq3 is formed as an organic light emitting layer on the hole transport layer with a thickness of 30 nm, and further, Cs 2 MoO 4
  • An electron transporting organic semiconductor layer made of Alq3 doped with a concentration of 0.85 wt%, 1.7 wt%, 3.3 wt%, 3.3 wt%, 5 wt%, 10 wt%, 20 wt%, and 40 wt% at a thickness of 30 nm by co-evaporation.
  • Al having a predetermined film thickness was formed thereon as a cathode by vacuum deposition.
  • the organic EL element of Example 1 was produced.
  • Alq3 is formed as an organic light emitting layer with a thickness of 60 nm by vapor deposition
  • Cs 2 MoO 4 is formed as an inorganic electron injection layer with a thickness of 1 nm thereon
  • Al having a predetermined thickness was formed as a cathode by vacuum deposition.
  • the organic EL element of the comparative example was produced.
  • a comparative organic EL device using Li 2 O instead of the inorganic electron injection layer Cs 2 MoO 4 was also produced.
  • Example and the comparative example each was driven on the conditions of current density 7.5mA / cm ⁇ 2 >, and the drive voltage V and the brightness
  • the electron transporting organic semiconductor layer film of Cs 2 MoO 4 : Alq3 has a driving voltage lower than that of the comparative element at 10% concentration or more. If the light-emitting layer and the electron-transporting organic semiconductor layer are considered to be electron-transporting light-emitting layers, if the metal salt compound of the electron-donating metal counter cation is doped at a predetermined concentration from the contacting cathode side to the predetermined film thickness, It can be understood that the drive voltage can be reduced.
  • Example 2 In the same manner as in Example 1, a plurality of precursors formed up to the hole transport layer were prepared, and Alq3 was formed as an organic light emitting layer with a thickness of 30 nm on the hole transport layer. 2 An electron transporting organic semiconductor layer made of TPBI doped with MoO 4 at a concentration of 5 wt%, 10 wt%, and 20 wt% is formed by co-evaporation to a thickness of 30 nm. It was formed by vapor deposition. Thus, the organic EL element of Example 2 was produced.
  • Alq3 is formed as an organic light emitting layer by vapor deposition by a thickness of 30 nm
  • TPBI is formed as an electron transport layer by a thickness of 30 nm
  • Li 2 O was formed by vapor deposition as an inorganic electron injection layer with a thickness of 1 nm
  • Al having a predetermined thickness was formed thereon as a cathode by vacuum vapor deposition.
  • Example and the comparative example each was driven on the conditions of current density 7.5mA / cm ⁇ 2 >, and the drive voltage V and the brightness
  • the electron transporting organic semiconductor layer film of Cs 2 MoO 4 : TPBI has a driving voltage lower than that of the comparative element at 5% concentration or more. If the light-emitting layer and the electron-transporting organic semiconductor layer are considered to be electron-transporting light-emitting layers, if the metal salt compound of the electron-donating metal counter cation is doped at a predetermined concentration from the contacting cathode side to the predetermined film thickness, It can be understood that the drive voltage can be reduced.
  • Example 3 In the same manner as in Example 1, a plurality of precursors formed up to the hole transport layer were prepared, and Alq3 was formed as an organic light emitting layer with a thickness of 30 nm on the hole transport layer. 2 An electron transporting organic semiconductor layer composed of NBphen doped with MoO 4 at a concentration of 1.7 wt%, 3.3 wt%, 5 wt%, 10 wt%, and 20 wt% is formed by co-evaporation to a thickness of 30 nm. As a cathode, Al having a predetermined thickness was formed by vacuum deposition. Thus, the organic EL element of Example 3 was produced.
  • the driving voltage V and the luminance L were measured by driving each of the examples under the condition of a current density of 7.5 mA / cm 2 .
  • the electron transporting organic semiconductor layer film of Cs 2 MoO 4 : NBphen has a concentration of 1.7% or more and a driving voltage lower than that of the comparative element. If the light-emitting layer and the electron-transporting organic semiconductor layer are considered to be electron-transporting light-emitting layers, if the metal salt compound of the electron-donating metal counter cation is doped at a predetermined concentration from the contacting cathode side to the predetermined film thickness, It can be understood that the drive voltage can be reduced.
  • Example 4 In the same manner as in Example 1, a plurality of precursors formed up to the hole transport layer were prepared, and Alq3 was formed as an organic light emitting layer with a thickness of 30 nm on the hole transport layer. 2 An electron transporting organic semiconductor layer made of DBzA doped with MoO 4 at a concentration of 0.85 wt%, 1.7 wt%, 3.3 wt%, 5 wt%, 10 wt%, and 20 wt% is formed by co-evaporation to a thickness of 30 nm. On top of that, Al having a predetermined film thickness was formed as a cathode by vacuum deposition. Thus, the organic EL element of Example 4 was produced.
  • the driving voltage V and the luminance L were measured by driving each of the examples under the condition of a current density of 7.5 mA / cm 2 .
  • the electron transporting organic semiconductor layer film of Cs 2 MoO 4 : DBzA has a concentration of 3.3% or more and a driving voltage lower than that of the comparative element.
  • the comparative element driving voltage is equivalent and effective even at a low concentration of 1.7%. If the light-emitting layer and the electron-transporting organic semiconductor layer are considered to be electron-transporting light-emitting layers, if the metal salt compound of the electron-donating metal counter cation is doped at a predetermined concentration from the contacting cathode side to the predetermined film thickness, It can be understood that the drive voltage can be reduced.
  • Example 5 For the electron transport materials Alq3, TPBI, NBphen, and DBzA devices of Examples 1 to 4, changes in driving voltage against the metal salt compound Cs 2 MoO 4 doping concentration were plotted. All the luminances were about 300 cd / m 2 .
  • FIG. 9 a comparative example at the time of Example 1 is also shown.
  • the energy gap becomes narrower.
  • MoO 2 is less permeable than MoO 3 .
  • optical transmission loss is low because it exists as a single compound with the same number of oxygen atoms to exist in the state of a metal salt compound composed of this electron-donating metal pair cation. I can expect that.
  • the effect of doping the metal semiconductor compound into the organic semiconductor layer is also selective in the doped organic semiconductor layer.
  • An impurity level is formed locally or mostly in the thin film, and the level is filled with the charge (carrier) of the metal salt, so that it can be expected that the electron transport property is improved.
  • it can be expected to improve conductivity by forming and synthesizing a new compound by co-evaporation in a vacuum with a material having an unpaired electron such as a bathophenanthroline derivative such as NBphen.
  • Example 6 In the same manner as in Example 1, a plurality of precursors formed up to the hole transport layer were prepared, and Alq3 was formed as an organic light-emitting layer with a thickness of 30 nm on each of the hole transport layers.
  • a predetermined thickness of Al was formed by vacuum deposition. Thus, the organic EL element of Example 6 was produced.
  • Alq3 is formed as an organic light emitting layer with a thickness of 60 nm by vapor deposition on the hole transport layer of the precursor, and CsF is formed with a thickness of 1 nm as an inorganic electron injection layer thereon, and As a cathode, Al having a predetermined thickness was formed by vacuum deposition.
  • an organic EL element of ITO / CuPc (25 nm) / NPB (45 nm) / Alq3 (60 nm) / CsF (1 nm) / Al as a comparative example was produced.
  • Example 6 and Comparative Example CsF were each driven at a current density of 7.5 mA / cm 2 to measure drive voltage V and luminance L.
  • metal salt compounds Cs 2 WO 4 and Cs 2 MoO The drive voltage change versus 4 doping concentration was plotted. The results are shown in FIG. 10 (the plot of Example 3 is also shown).
  • the concentration is lower than that of the conventional electron injection material (CsF). It can be seen that the doping has the effect of suppressing the luminance deterioration and greatly suppressing the increase of the driving voltage.
  • Example 7 The element of Example 3 (Cs 2 MoO 4 concentration 1.7 wt%) was driven for 100 hours or more under the condition of a current density of 21 mA / cm 2 . The changes over time in the light emission intensity and the driving voltage in this case were plotted. The results are shown in FIGS. 11 and 12 (also driven in the same manner as using the electron injection layer Li 2 O in the comparative example when the example 1, the results also are shown together).
  • Example 8 In the same manner as in Example 1, a plurality of precursors formed up to the hole transport layer were prepared, and Alq3 was formed as an organic light emitting layer with a thickness of 30 nm on the hole transport layer. 2 An electron transporting organic semiconductor layer made of NBphen doped with MoO 4 at a concentration of 1.7 wt% is formed by co-evaporation to a thickness of 30 nm and 90 nm, and a predetermined thickness of Al is formed thereon as a cathode by vacuum evaporation. Formed. Thus, the organic EL element of Example 8 was produced.
  • the driving voltage V and the luminance L were measured by driving each of the examples under the condition of a current density of 7.5 mA / cm 2 .
  • Example 7 The device of Example 3 (Cs 2 MoO 4 concentration 1.7 wt%) and the device using the electron injection layer Li 2 O of the comparative example in Example 1 were exposed to the atmosphere without using a desiccant. For more than 655 hours. Each result is shown in FIG.
  • metal salt compounds include potassium molybdate K 2 MoO 4 , calcium molybdate CaMoO 4 , and molybdic acid.
  • Strontium SrMoO 4 sodium molybdate (anhydrous) Na 2 MoO 4 , barium molybdate BaMoO 4 , lithium molybdate Li 2 MoO 4 , rubidium molybdate Rb 2 MoO 4 , calcium metastannate CaSnO 3 , strontium metastannate SrO ⁇ SnO 2, meta tin barium BaSnO 3, metatitanic acid magnesium MgTiO 3, metatitanic acid lithium Li 2 TiO 3, dichromate potassium K 2 Cr 2 O 7, calcium chromate (n-hydrate) CaCrO 4 ⁇ nH 2 O, The Strontium romate SrCrO 4 , cesium dichromate Cs 2 Cr 2 O 7
  • the organic EL element has been described as the organic semiconductor element in the above embodiment, in the organic solar cell in which the plurality of organic semiconductor layers include a light collection layer, and at least one of an electron transport layer and a hole transport layer, An electron composed of an organic semiconductor that is in contact with the interface of the organic semiconductor layer between the second electrode of the negative electrode and the adjacent organic semiconductor layer and is doped with the above metal salt compound having an electron donating metal as a counter cation.
  • the electron-donating metal is in contact with the interface of the organic semiconductor layer between the second electrode of the negative electrode and the adjacent organic semiconductor layer in the organic active light-emitting device or the organic thin film transistor.
  • the structure having an electron-transporting organic semiconductor layer made of an organic semiconductor doped with a metal acid salt compound as described above having a counter cation as well as prolonging the life similar to the above examples Achieve the results and moisture effect.

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  • Engineering & Computer Science (AREA)
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  • Electroluminescent Light Sources (AREA)

Abstract

La présente invention a trait à un élément à semi-conducteurs organique comprenant une paire de première et seconde électrodes opposées et une pluralité de couches semi-conductrices organiques disposées de façon empilée entre les première et seconde électrodes. La seconde électrode est une électrode négative. Une couche semi-conductrice organique de transport d'électrons, qui est en contact avec l'interface de la couche semi-conductrice organique et qui est constituée d'un semi-conducteur organique dopé avec un composé de sel acide métallique dans lequel un métal donneur d'électrons est un contre-cation, est disposée entre la seconde électrode et la couche semi-conductrice organique.
PCT/JP2008/053978 2008-03-05 2008-03-05 Elément à semi-conducteurs organique WO2009110075A1 (fr)

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TW098105975A TW200950172A (en) 2008-03-05 2009-02-25 Organic semiconductor device

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JP2009246126A (ja) * 2008-03-31 2009-10-22 Sumitomo Chemical Co Ltd 有機エレクトロルミネッセンス素子及びその製造方法
JP2009246124A (ja) * 2008-03-31 2009-10-22 Sumitomo Chemical Co Ltd 中間層形成塗布液、および有機エレクトロルミネッセンス素子の製造方法、並びに有機エレクトロルミネッセンス素子
JP2009246127A (ja) * 2008-03-31 2009-10-22 Sumitomo Chemical Co Ltd 有機エレクトロルミネッセンス素子及びその製造方法
WO2012169069A1 (fr) * 2011-06-10 2012-12-13 パイオニア株式会社 Panneau à électroluminescence organique
WO2013171872A1 (fr) * 2012-05-17 2013-11-21 パイオニア株式会社 Panneau électroluminescent (el) organique et dispositif électroluminescent
JP2015144233A (ja) * 2013-08-09 2015-08-06 株式会社半導体エネルギー研究所 発光素子、ディスプレイモジュール、照明モジュール、発光装置、表示装置、電子機器及び照明装置

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CN105580153B (zh) 2013-09-17 2018-01-02 九州有机光材股份有限公司 有机电致发光元件

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009246126A (ja) * 2008-03-31 2009-10-22 Sumitomo Chemical Co Ltd 有機エレクトロルミネッセンス素子及びその製造方法
JP2009246124A (ja) * 2008-03-31 2009-10-22 Sumitomo Chemical Co Ltd 中間層形成塗布液、および有機エレクトロルミネッセンス素子の製造方法、並びに有機エレクトロルミネッセンス素子
JP2009246127A (ja) * 2008-03-31 2009-10-22 Sumitomo Chemical Co Ltd 有機エレクトロルミネッセンス素子及びその製造方法
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WO2012169069A1 (fr) * 2011-06-10 2012-12-13 パイオニア株式会社 Panneau à électroluminescence organique
WO2013171872A1 (fr) * 2012-05-17 2013-11-21 パイオニア株式会社 Panneau électroluminescent (el) organique et dispositif électroluminescent
JP2015144233A (ja) * 2013-08-09 2015-08-06 株式会社半導体エネルギー研究所 発光素子、ディスプレイモジュール、照明モジュール、発光装置、表示装置、電子機器及び照明装置

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