WO2012046715A1 - 発光材料、及びこれを用いた有機発光素子、波長変換発光素子、光変換発光素子、有機レーザーダイオード発光素子、色素レーザー、表示装置並びに照明装置 - Google Patents
発光材料、及びこれを用いた有機発光素子、波長変換発光素子、光変換発光素子、有機レーザーダイオード発光素子、色素レーザー、表示装置並びに照明装置 Download PDFInfo
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Definitions
- the present invention relates to a light emitting material, and an organic light emitting device, a wavelength conversion light emitting device (color conversion light emitting device), a light conversion light emitting device, an organic laser diode light emitting device, a dye laser, a display device, and an illumination device using the same.
- Phosphorescent materials that use light emission from the triplet excited state can achieve higher light emission efficiency than fluorescent light emitting materials that use only fluorescence emission from the singlet excited state. It has been broken.
- a phosphorescent material system that can achieve an internal quantum yield of about 100% at the maximum is introduced into the green pixel and red pixel of the organic EL element.
- Material system is used. This is because blue light emission has higher energy than red or green light emission, and when high energy light emission is obtained from phosphorescence light emission from triplet excitation levels, the weak parts of the molecular structure that are sensitive to high energy deteriorate. This is because it becomes easier.
- an iridium (Ir) complex in which an electron-withdrawing group such as fluorine is introduced as a substituent into a ligand in order to obtain a high-energy triplet excited state is known (for example, non-patent document). See 1-5.)
- the blue phosphorescent material into which an electron withdrawing group is introduced has a relatively good luminous efficiency, it has a problem of poor light resistance and short lifetime.
- light having a short wavelength can be emitted in a complex using a carbene ligand without introducing an electron withdrawing group (see Non-Patent Document 6 and Patent Document 1).
- Non-Patent Document 6 and Patent Document 1 emit blue phosphorescence without introducing an electron-withdrawing group that reduces light resistance, but the light-emitting efficiency is low. Therefore, development of a light emitting material capable of emitting blue light with high light emission efficiency without introducing an electron withdrawing group is desired.
- An aspect of the present invention has been made in view of such conventional circumstances, and is a highly efficient light-emitting material, an organic light-emitting device, a wavelength-converted light-emitting device, a light-converted light-emitting device, and an organic laser diode light-emitting device using the same.
- the present invention provides a dye laser, a display device, and a lighting device.
- the central metal is any one of Ir, Os, and Pt
- the ligand includes a neutral or monoanionic group including a boron atom in the skeleton, and a monodentate, bidentate, or It consists of a transition metal complex having at least one tridentate carbene ligand or neutral or monoanionic group containing a boron atom in the skeleton and a monodentate, bidentate or tridentate silylene ligand .
- the transition metal complex may have a partial structure represented by the following general formula (1) or the following general formula (2).
- the transition metal complex may have a partial structure represented by the following general formula (3) or the following general formula (4).
- the transition metal complex may have a partial structure represented by the following general formula (5) or the following general formula (6).
- the transition metal complex may have a partial structure represented by the following general formula (7) or the following general formula (8).
- the transition metal complex may be an Ir complex having a partial structure represented by the following general formula (9).
- the transition metal complex is a tris body in which three bidentate ligands are coordinated, and the mer body (meridional) is contained in a larger amount than the fac body (facial). It may be.
- An organic light-emitting element which is one embodiment of the present invention includes at least one organic layer including a light-emitting layer and a pair of electrodes sandwiching the organic layer, and the organic layer has a central metal of Ir, Os, or Pt.
- a ligand a neutral or monoanionic carbene ligand containing a boron atom in the skeleton and a monodentate, bidentate or tridentate, or a neutral containing a boron atom in the skeleton
- it contains a transition metal complex having at least one silylene ligand that is monoanionic and monodentate, bidentate or tridentate.
- the light-emitting material may be contained in the light-emitting layer.
- the wavelength conversion light-emitting element which is one embodiment of the present invention is disposed on the organic light-emitting element and a surface side from which the light from the organic light-emitting element is extracted, absorbs light emitted from the organic light-emitting element, and has a wavelength different from absorbed light.
- a phosphor layer configured to emit light
- the organic light emitting element includes at least one organic layer including a light emitting layer and a pair of electrodes sandwiching the organic layer
- the organic layer includes: A carbene ligand in which the central metal is Ir, Os or Pt and the ligand includes a neutral or monoanionic group containing a boron atom in the skeleton and a monodentate, bidentate or tridentate, or It contains a transition metal complex having at least one silylene ligand which is neutral or monoanionic and contains monodentate, bidentate or tridentate containing a boron atom in the skeleton.
- a wavelength conversion light-emitting element which is one embodiment of the present invention is disposed on a light-emitting element and a surface side from which light from the light-emitting element is extracted, absorbs light emitted from the light-emitting element, and emits light having a wavelength different from that of absorbed light.
- the phosphor layer is neutral or monoanionic having a central metal of Ir, Os or Pt and containing a boron atom in the skeleton as a ligand. And at least one monodentate, bidentate or tridentate carbene ligand, or neutral or monoanionic having a boron atom in the skeleton, and monodentate, bidentate or tridentate silylene ligand.
- a transition metal complex is neutral or monoanionic having a central metal of Ir, Os or Pt and containing a boron atom in the skeleton as a ligand.
- the light conversion light-emitting element which is one embodiment of the present invention includes at least one organic layer including a light-emitting layer, a layer that amplifies current, and a pair of electrodes that sandwich the organic layer and the layer that amplifies the current.
- the light-emitting layer includes a host material and a neutral or monoanionic group containing a boron atom in the skeleton as a ligand, and a monodentate, bidentate or A transition metal complex having at least one tridentate carbene ligand or a neutral or monoanionic group containing a boron atom in the skeleton and a monodentate, bidentate or tridentate silylene ligand Have.
- An organic laser diode light-emitting device includes an excitation light source and a resonator structure irradiated with the excitation light source, and the resonator structure includes at least one organic layer including a laser active layer; A pair of electrodes sandwiching an organic layer, wherein the laser active layer includes a host material, a central metal of any one of Ir, Os, and Pt, and includes a boron atom in the skeleton as a ligand.
- a dye laser which is one embodiment of the present invention includes a laser medium including a light-emitting material, and an excitation light source that stimulates and emits phosphorescence from the light-emitting material of the laser medium to cause laser oscillation, and the light-emitting material includes a central metal.
- the ligand is a neutral or monoanionic group containing a boron atom in the skeleton, and a monodentate, bidentate or tridentate carbene ligand, or It is a transition metal complex having at least one silylene ligand which is neutral or monoanionic and contains monodentate, bidentate or tridentate containing a boron atom.
- a display device includes an image signal output unit that generates an image signal, a drive unit that generates a current or voltage based on a signal from the image signal output unit, and a current or voltage from the drive unit.
- the light emitting unit comprises at least one organic layer including a light emitting layer and a pair of electrodes sandwiching the organic layer, and the organic layer has a central metal of Ir, Os or It is either Pt, and a neutral or monoanionic carbene ligand containing a boron atom in the skeleton and a monodentate, bidentate or tridentate as a ligand, or a boron atom in the skeleton
- a display device includes an image signal output unit that generates an image signal, a drive unit that generates a current or voltage based on a signal from the image signal output unit, and a current or voltage from the drive unit.
- a light emitting part that emits light by the organic light emitting element, and the light emitting part is disposed on a surface side from which the light from the organic light emitting element is extracted, absorbs light emitted from the organic light emitting element, and has a wavelength different from that of the absorbed light.
- a phosphor layer configured to emit light
- the organic light emitting element includes at least one organic layer including a light emitting layer and a pair of electrodes sandwiching the organic layer
- the organic layer includes: A carbene ligand in which the central metal is Ir, Os or Pt and the ligand includes a neutral or monoanionic group containing a boron atom in the skeleton and a monodentate, bidentate or tridentate, or In the skeleton Neutral or monoanionic including c atom, and monodentate, a silylene ligand is a bidentate or tridentate, the wavelength conversion light emitting device containing a transition metal complex having at least one.
- a display device includes an image signal output unit that generates an image signal, a drive unit that generates a current or voltage based on a signal from the image signal output unit, and a current or voltage from the drive unit.
- a light emitting portion that emits light, and the light emitting portion includes at least one organic layer including a light emitting layer, a layer that amplifies current, and a pair of electrodes that sandwich the organic layer and the layer that amplifies the current.
- the light-emitting layer includes a host material and a neutral or monoanionic group containing a boron atom in the skeleton as a ligand, and a monodentate, bidentate or Transition metal having at least one tridentate carbene ligand, or neutral or monoanionic structure containing a boron atom in the skeleton, and monodentate, bidentate or tridentate silylene ligand
- An optical conversion element having a body An electronic device which is one embodiment of the present invention may include the above display device.
- the anode and the cathode of the light emitting unit may be arranged in a matrix.
- the light-emitting portion may be driven by a thin film transistor.
- An illumination device includes a driving unit that generates current or voltage, and a light-emitting unit that emits light by current or voltage from the driving unit, and the light-emitting unit includes at least one organic layer including a light-emitting layer.
- the organic layer has a central metal of any one of Ir, Os, and Pt, and contains a neutral or boron atom in the skeleton as a ligand.
- An illumination device includes a driving unit that generates current or voltage, and a light-emitting unit that emits light by current or voltage from the driving unit.
- the light-emitting unit includes an organic light-emitting element and the organic light-emitting element.
- a phosphor layer that is arranged on the surface side from which the light of the element is extracted, is configured to absorb light emitted from the organic light emitting element and emit light having a wavelength different from the absorbed light
- the organic light emitting element comprises: It comprises at least one organic layer including a light emitting layer and a pair of electrodes sandwiching the organic layer.
- the organic layer has a central metal of Ir, Os, or Pt, and serves as a ligand in the skeleton.
- An illumination device includes a driving unit that generates current or voltage, and a light-emitting unit that emits light by current or voltage from the driving unit, and the light-emitting unit includes at least one organic layer including a light-emitting layer. And a pair of electrodes sandwiching the organic layer and the layer for amplifying the current.
- the light emitting layer includes a host material and a central metal of Ir, Os, or Pt.
- a ligand a neutral or monoanionic carbene ligand containing a boron atom in the skeleton and a monodentate, bidentate or tridentate, or neutral or containing a boron atom in the skeleton
- a lighting device which is one embodiment of the present invention may include the above-described lighting device.
- a highly efficient light emitting material and an organic light emitting device a wavelength conversion light emitting device, a light conversion light emitting device, an organic laser diode light emitting device, a dye laser, a display device, and a lighting device using the same are provided. Can do.
- 1 is a schematic diagram showing a first embodiment of an organic light-emitting device of the present invention. It is a schematic sectional drawing which shows 2nd Embodiment of the organic light emitting element of this invention. It is a schematic sectional drawing which shows 1st Embodiment of the wavelength conversion light emitting element of this invention. It is a top view of the wavelength conversion light emitting element shown in FIG. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows 1st Embodiment of the light conversion light emitting element of this invention.
- 1 is a schematic diagram illustrating a first embodiment of an organic laser diode light-emitting element of the present invention. It is a schematic diagram showing a first embodiment of the dye laser of the present invention.
- the central metal is Ir, Os or Pt
- the ligand is neutral or monoanionic having a boron atom in the skeleton, and monodentate, bidentate or tridentate. It consists of a transition metal complex having at least one carbene ligand, or neutral or monoanionic containing a boron atom in the skeleton, and a monodentate, bidentate or tridentate silylene ligand.
- the central metal when the central metal is Ir or Os, a hexacoordinate octahedral structure is formed.
- the central metal is Pt, a tetracoordinate planar tetragonal structure is formed. It becomes.
- the transition metal complex that is the light-emitting material of the present embodiment preferably has a partial structure represented by the following general formula (1) or the following general formula (2).
- M represents Ir, Os or Pt
- X represents C or Si
- R 11 , R 12 and R 13 each independently represents a monovalent organic group.
- Y represents a divalent hydrocarbon group
- Z represents a divalent organic group
- V represents a divalent organic group having a ring structure.
- Examples of the monovalent organic group represented by R 11 , R 12 and R 13 include an aliphatic hydrocarbon group having 1 to 8 carbon atoms or an aromatic group having 1 to 10 carbon atoms.
- the aliphatic hydrocarbon group and aromatic group which are R 11 , R 12 and R 13 may have a substituent.
- Examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms which is R 11 , R 12 and R 13 include a linear, branched or cyclic aliphatic hydrocarbon group, specifically, a methyl group Ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, cyclohexyl group and the like.
- R 11 and R 12 may be bonded together to form a ring structure.
- Examples of the aromatic group having 1 to 10 carbon atoms as R 11 , R 12 and R 13 include a phenyl group and a naphthyl group, and these aromatic groups may have a substituent.
- Examples of the divalent hydrocarbon group that is Y include divalent hydrocarbon groups having 1 to 3 carbon atoms, and specifically include —CH 2 —, —CH 2 —CH 2 —, —C (CH 3 ) 2- and the like, among which -CH 2 -is preferable.
- Examples of the divalent organic group having a ring structure as V include a cyclic divalent organic group having aromaticity, and an aromatic hydrocarbon group or an aromatic group containing nitrogen and carbon is preferable.
- Specific examples of the divalent organic group having a ring structure as V are preferably those represented by the following general formulas (V-1) to (V-5).
- R 15 , R 16 , R 17 and R 18 each independently represent a monovalent organic group, and are a hydrogen atom, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, or Examples thereof include aromatic groups having 1 to 10 carbon atoms.
- the aliphatic hydrocarbon group and aromatic group which are R 15 , R 16 , R 17 and R 18 may have a substituent.
- Examples of the aliphatic hydrocarbon group or aromatic group as R 15 , R 16 , R 17 and R 18 include those similar to R 11 , R 12 and R 13 in the general formula (1) or (2). It is done.
- R 15 and R 16 , R 16 and R 17 , and R 17 and R 18 may be bonded together to form a ring structure. Specifically, a structure in which a part of R 15 and R 16 are bonded and linked by a cyclic group such as adamantane can be given.
- R 19 and R 20 each independently represent a monovalent organic group, and are a hydrogen atom, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, or a group having 1 to 10 carbon atoms.
- An aromatic group is mentioned.
- the aliphatic hydrocarbon group and aromatic group which are R 19 and R 20 may have a substituent.
- Examples of the aliphatic hydrocarbon group or aromatic group as R 19 and R 20 include the same groups as R 11 , R 12 and R 13 in the general formula (1) or (2).
- R 19 and R 20 may be bonded together to form a ring structure. Specific examples include a structure in which a part of R 19 and R 20 are bonded and linked by a cyclic group such as adamantane.
- R 21 represents a monovalent organic group, and examples thereof include a hydrogen atom, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, and an aromatic group having 1 to 10 carbon atoms.
- the aliphatic hydrocarbon group and aromatic group which are R 21 may have a substituent.
- Examples of the aliphatic hydrocarbon group or aromatic group as R 21 include the same groups as those of R 11 , R 12 and R 13 in the general formula (1) or (2).
- R 22 , R 23 and R 24 each independently represent a monovalent organic group, and are a hydrogen atom, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, or 1 carbon atom. Up to 10 aromatic groups.
- the aliphatic hydrocarbon group and aromatic group which are R 22 , R 23 and R 24 may have a substituent. Examples of the aliphatic hydrocarbon group or aromatic group as R 22 , R 23 and R 24 include the same groups as those of R 11 , R 12 and R 13 in the general formula (1) or (2).
- R 22 and R 23 , and R 23 and R 24 may be partly combined to form a ring structure. Specific examples include a structure in which a part of R 22 and R 23 are bonded and linked by a cyclic group such as adamantane.
- the divalent organic group that is Z preferably includes an atom having an electron donating property. That is, the luminescent material of the present embodiment has the following general formula (3). Alternatively, a transition metal complex having a partial structure represented by the following general formula (4) is preferable.
- M represents Ir, Os or Pt
- X represents C or Si
- R 11 , R 12 , R 13 and R 14 each independently represents a monovalent organic compound.
- Y represents a divalent hydrocarbon group
- D represents an electron donating atom
- V represents a divalent organic group having a ring structure.
- R 11 , R 12 , R 13 , X, M, V, and Y are the same as described above.
- Examples of the monovalent organic group represented by R 14 include an aliphatic hydrocarbon group having 1 to 8 carbon atoms and an aromatic group having 1 to 10 carbon atoms.
- the aliphatic hydrocarbon group and aromatic group as R 14 may have a substituent.
- Examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms as R 14 include a linear, branched or cyclic aliphatic hydrocarbon group, and specifically include a methyl group, an ethyl group, an n- Examples include propyl group, isopropyl group, n-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, cyclohexyl group and the like.
- R 11 and R 12 may be bonded together to form a ring structure.
- the aromatic group having 1 to 10 carbon atoms as R 14 include a phenyl group and a naphthyl group, and these aromatic groups may have a substituent.
- Specific examples of the electron donating atom as D include C, N, P, O, and S. Among them, C or N is preferable, and N is particularly preferable.
- the light emitting material of the present embodiment is preferably a transition metal complex having a partial structure represented by the following general formula (5) or the following general formula (6).
- M represents Ir, Os or Pt
- X represents C or Si
- R 11 , R 12 , R 13 and R 14 each independently represents a monovalent organic compound.
- Y represents a divalent hydrocarbon group
- V represents a divalent organic group having a ring structure.
- the light emitting material of the present embodiment is preferably a transition metal complex having a partial structure represented by the following general formula (7) or the following general formula (8).
- M represents Ir, Os or Pt
- X represents C or Si
- R 18 each independently represents a monovalent organic group
- Y represents a divalent hydrocarbon group.
- the light emitting material of the present embodiment is particularly preferably an Ir complex having a partial structure represented by the following general formula (9).
- R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , and R 18 each independently represents a monovalent organic group.
- the luminescent material of this embodiment is preferably a tris body in which three bidentate ligands are coordinated.
- the luminescent material of this embodiment may be either mer or fac, and mer and fac are mixed. May be.
- the mer body is contained more than the fac body because the PL quantum yield is improved.
- transition metal complex which is the light-emitting material of the present embodiment
- present embodiment is not limited to these examples.
- geometric isomers are not particularly distinguished and not illustrated, and any geometric isomer is included as the light emitting material of the present embodiment.
- Ph represents a phenyl group.
- the following compounds are particularly preferable as the light emitting material of the present embodiment.
- the light emitting material of the present embodiment is a transition metal complex whose central metal is Ir, Os, or Pt.
- Ir, Os, and Pt have a relatively short atomic radius due to lanthanoid contraction, but have a large atomic weight. The effect can be caused effectively. Therefore, the luminescent material of the present embodiment can increase the PL quantum yield due to the heavy atom effect, and can exhibit high luminous efficiency.
- the light-emitting material of this embodiment is a transition metal complex having at least one carbene ligand or silylene ligand containing a boron atom in the skeleton.
- a ligand containing a carbene skeleton containing a boron atom was used for the metal complex, a result of efficient light emission was obtained as shown in the examples described later.
- Boron has a high Lewis acidity, an empty p-orbital, and a strong electron accepting property. Further, it is known that N and B are bonded to each other so that they have a property close to a C ⁇ C bond.
- a material capable of donating electrons to the metal center a material containing a structure that does not satisfy the octet rule as a carbene as a metal complex is preferable as the light emitting material of the present embodiment.
- the electron donating property is strong
- the electron donating property to the metal center is increased, and the electron donating property of the original metal part in MLCT can be increased.
- the MLCT property can be increased. Therefore, as the light emitting material of the present embodiment, in addition to the carbene complex, a silylene (Si) complex is also preferable from the viewpoint that ⁇ donor property is particularly strong.
- the light emitting material of this embodiment can realize blue light emission and high efficiency even when it does not have an electron withdrawing group that is normally required.
- the transition metal complexes having the partial structures represented by the general formulas (1) to (9) can be synthesized by combining conventionally known methods.
- the ligand is J. Am. Chem. Soc. ., 2005, 127, 10182, Eur. J. Inorg. Chem., 1999, 1765, J. Am. Chem. Soc. , 125, 389, J. Organanometal. Chem., 11 (1968), 399, etc.
- transition metal complexes are Dalton Trans., 2008, 916, Angew. Chem. Int. Ed. , 2008, 47, 4542, etc.
- the Ir complex (compound (a-5)) having a partial structure of the carbene ligand (X ⁇ C) represented by the general formula (8) can be synthesized by the following synthesis route.
- the compound (a-4) as a ligand is synthesized with reference to, for example, J. Am. Chem. Soc., 2005, 127, 10182 and Eur. J. Inorg. Chem., 1999, 1765. be able to.
- compound (a-3) can be synthesized by reacting compound (a-1) and compound (a-2) in a toluene solution at ⁇ 78 ° C. and then raising the temperature to room temperature.
- an n-butyllithium solution is added dropwise to the compound (a-3) at 0 ° C. and then cooled to ⁇ 100 ° C., and a dibromoborane compound having the desired ligand R 13 is added, and then slowly raised to room temperature.
- Compound (a-4) can be synthesized by heating.
- the synthesis of the compound (a-5) which is a transition metal complex can be performed with reference to, for example, Dalton Trans., 2008, 916.
- To 1 equivalent of [IrCl (COD)] 2 (COD 1,5-cyclooctadiene), 6 equivalents of compound (a-4) are added, and silver oxide is further added to the mixture. 5) can be synthesized.
- a tris isomer such as compound (a-5)
- a transition metal complex is synthesized with reference to Angew. Chem. Int. Ed., 2008, 47, 4542, etc. Can do.
- an Ir complex [Ir (La) 2 (Lb)] having two bidentate ligands La and one bidentate ligand Lb, 1 equivalent of [IrCl (COD)] 2 By heating and refluxing 4 equivalents of the ligand La in an alcohol solution in the presence of sodium methoxy by the method described in Dalton Trans., 2008, 916 etc., a chlorine-bridged binuclear iridium complex [Ir ( ⁇ -Cl) By synthesizing (La) 2 ] 2 and reacting this chlorine-bridged binuclear iridium complex with the ligand Lb, an Ir complex [Ir (La) 2 (Lb)] can be synthesized.
- the transition metal complex which is a synthesized light-emitting material, can be identified from MS spectrum (FAB-MS), 1 H-NMR spectrum, LC-MS spectrum, and the like.
- FIG. 1 is a schematic configuration diagram illustrating a first embodiment of an organic light-emitting device according to this embodiment.
- the organic EL layer 17 sandwiched between the first electrode 12 and the second electrode 16 is configured by laminating a hole transport layer 13, an organic light emitting layer 14, and an electron transport layer 15 in this order. Has been.
- the first electrode 12 and the second electrode 16 function as a pair as an anode or a cathode of the organic light emitting device 10. That is, when the first electrode 12 is an anode, the second electrode 16 is a cathode, and when the first electrode 12 is a cathode, the second electrode 16 is an anode.
- FIG. 1 and the following description a case where the first electrode 12 is an anode and the second electrode 16 is a cathode will be described as an example.
- the hole injection layer and the hole transport layer are arranged on the second electrode side 16 in a laminated structure of an organic EL layer (organic layer) 17 described later.
- the electron injection layer and the electron transport layer may be on the first electrode 12 side.
- the organic EL layer (organic layer) 17 may have a single layer structure of the organic light emitting layer 14 or a multilayer structure such as a stacked structure of the hole transport layer 13, the organic light emitting layer 14, and the electron transport layer 15 as shown in FIG. Structure may be sufficient.
- Specific examples of the organic EL layer (organic layer) 17 include the following configurations, but the present embodiment is not limited thereto. In the following configuration, the hole injection layer and the hole transport layer 13 are disposed on the first electrode 12 side that is an anode, and the electron injection layer and the electron transport layer 15 are disposed on the second electrode 16 side that is a cathode.
- Organic light emitting layer 14 (2) Hole transport layer 13 / organic light emitting layer 14 (3) Organic light emitting layer 14 / electron transport layer 15 (4) Hole injection layer / organic light emitting layer 14 (5) Hole transport layer 13 / organic light emitting layer 14 / electron transport layer 15 (6) Hole injection layer / hole transport layer 13 / organic light emitting layer 14 / electron transport layer 15 (7) Hole injection layer / hole transport layer 13 / organic light emitting layer 14 / electron transport layer 15 / electron injection layer (8) Hole injection layer / hole transport layer 13 / organic light emitting layer 14 / hole prevention layer / Electron transport layer 15 (9) Hole injection layer / hole transport layer 13 / organic light emitting layer 14 / hole prevention layer / electron transport layer 15 / electron injection layer (10) hole injection layer / hole transport layer 13 / electron prevention layer / Organic Light-Emitting Layer 14 / Hole Prevention Layer / Electron Transport Layer 15 / Electron Injection Layer
- the organic light emitting layer 14 may be composed only of the light emitting material of the present embodiment described above.
- the organic light emitting layer 14 may be configured in combination with a host material using the light emitting material of this embodiment as a dopant, and optionally includes a hole transport material, an electron transport material, an additive (donor, acceptor, etc.) and the like.
- distributed in the polymeric material (binding resin) or the inorganic material may be sufficient. From the viewpoint of luminous efficiency and lifetime, a material in which the light emitting material of the present embodiment, which is a light emitting dopant, is dispersed in a host material is preferable.
- the organic light emitting layer 14 recombines holes injected from the first electrode 12 and electrons injected from the second electrode 16, and phosphorescence emission of the light emitting material of the present embodiment included in the organic light emitting layer 14 is performed. , Emit light (emit light).
- a conventionally known organic EL host material can be used as the host material.
- host materials include 4,4′-bis (carbazole) biphenyl, 9,9-di (4-dicarbazole-benzyl) fluorene (CPF), 3,6-bis (triphenylsilyl) carbazole (mCP).
- Carbazole derivatives such as poly (N-octyl-2,7-carbazole-O-9,9-dioctyl-2,7-fluorene) (PCF), 4- (diphenylphosphoyl) -N, N-diphenylaniline Aniline derivatives such as (HM-A1), 1,3-bis (9-phenyl-9H-fluoren-9-yl) benzene (mDPFB), 1,4-bis (9-phenyl-9H-fluoren-9-yl) ) Fluorene derivatives such as benzene (pDPFB), 1,3,5-tris [4- (diphenylamino) phenyl] benzene (TDAPB), 1 , 4-bistriphenylsilylbenzene (UGH-2) and the like.
- PCF poly (N-octyl-2,7-carbazole-O-9,9-dioctyl-2,7-fluorene)
- the hole injection layer and the hole transport layer 13 are formed of the first electrode 12 and the organic layer for the purpose of more efficiently injecting holes from the first electrode 12 that is an anode and transporting (injecting) the organic light emitting layer 14. It is provided between the light emitting layer 14.
- the electron injection layer and the electron transport layer 15 are used for the purpose of more efficiently injecting electrons from the second electrode 16 serving as a cathode and transporting (injecting) them to the organic light emitting layer 14. Between.
- the hole injection layer, the hole transport layer 13, the electron injection layer, and the electron transport layer 15 may each be composed of only the materials exemplified below.
- the hole injection layer, the hole transport layer 13, the electron injection layer, and the electron transport layer 15 may each optionally contain an additive (donor, acceptor, etc.) and the like in the materials exemplified below.
- the hole injection layer, the hole transport layer 13, the electron injection layer, and the electron transport layer 15 may have a configuration in which the following materials are dispersed in a polymer material (binding resin) or an inorganic material. .
- Examples of the material constituting the hole transport layer 13 include oxides such as vanadium oxide (V 2 O 5 ) and molybdenum oxide (MoO 2 ), inorganic p-type semiconductor materials, porphyrin compounds, N, N′-bis ( Aromatics such as 3-methylphenyl) -N, N′-bis (phenyl) -benzidine (TPD), N, N′-di (naphthalen-1-yl) -N, N′-diphenyl-benzidine (NPD)
- Low molecular weight materials such as tertiary amine compounds, hydrazone compounds, quinacridone compounds, styrylamine compounds, polyaniline (PANI), polyaniline-camphor sulfonic acid (polyaniline-camphorsulfonic acid; PANI-CSA), 3,4-polyethylenedioxy Thiophene / polystyrene sulfonate (PEDOT / PSS), poly (triphenylamine) derivative (Poly
- the material used as the hole injection layer is the highest occupied molecular orbital (HOMO) than the material used for the hole transport layer 13. It is preferable to use a material having a low energy level. As the hole transport layer 13, it is preferable to use a material having a higher hole mobility than the material used for the hole injection layer.
- the material for forming the hole injection layer include phthalocyanine derivatives such as copper phthalocyanine, 4,4 ′, 4 ′′ -tris (3-methylphenylphenylamino) triphenylamine, and 4,4 ′, 4 ′′ -tris.
- acceptor a conventionally well-known material can be used as an acceptor material for organic EL.
- Acceptor materials include Au, Pt, W, Ir, POCl 3 , AsF 6 , Cl, Br, I, vanadium oxide (V 2 O 5 ), molybdenum oxide (MoO 2 ), and other inorganic materials, TCNQ (7, 7 , 8,8, -tetracyanoquinodimethane), TCNQF4 (tetrafluorotetracyanoquinodimethane), TCNE (tetracyanoethylene), HCNB (hexacyanobutadiene), DDQ (dicyclodicyanobenzoquinone), etc.
- Examples thereof include compounds, compounds having a nitro group such as TNF (trinitrofluorenone) and DNF (dinitrofluorenone), and organic materials such as fluoranyl, chloranil and bromanyl.
- compounds having a cyano group such as TCNQ, TCNQF4, TCNE, HCNB, and DDQ are more preferable because they can increase the carrier concentration effectively.
- the electron blocking layer the same materials as those described above can be used as the hole transport layer 13 and the hole injection layer.
- Examples of the material constituting the electron transport layer 15 include an inorganic material that is an n-type semiconductor, an oxadiazole derivative, a triazole derivative, a thiopyrazine dioxide derivative, a benzoquinone derivative, a naphthoquinone derivative, an anthraquinone derivative, a diphenoquinone derivative, a fluorenone derivative, Low molecular materials such as benzodifuran derivatives; polymer materials such as poly (oxadiazole) (Poly-OXZ) and polystyrene derivatives (PSS).
- the material constituting the electron injection layer examples include fluorides such as lithium fluoride (LiF) and barium fluoride (BaF 2 ), and oxides such as lithium oxide (Li 2 O).
- fluorides such as lithium fluoride (LiF) and barium fluoride (BaF 2 )
- oxides such as lithium oxide (Li 2 O).
- the energy level of the lowest unoccupied molecular orbital (LUMO) is higher than that of the material used for the electron transport layer 15 in that electrons are injected and transported more efficiently from the second electrode 16 serving as the cathode.
- the material used for the electron transport layer 15 is preferably a material having higher electron mobility than the material used for the electron injection layer.
- the electron injection layer and the electron transport layer 15 are preferably doped with a donor.
- a donor a conventionally well-known material can be used as a donor material for organic EL.
- donor materials inorganic materials such as alkali metals, alkaline earth metals, rare earth elements, Al, Ag, Cu, and In, anilines, phenylenediamines, N, N, N ′, N′-tetraphenylbenzidine, N , N′-bis- (3-methylphenyl) -N, N′-bis- (phenyl) -benzidine, N, N′-di (naphthalen-1-yl) -N, N′-diphenyl-benzidine, etc.
- Benzidines triphenylamine, 4,4′4 ′′ -tris (N, N-diphenyl-amino) -triphenylamine, 4,4′4 ′′ -tris (N-3-methylphenyl-N-phenyl) -Amino) -triphenylamine, triphenylamines such as 4,4′4 ′′ -tris (N- (1-naphthyl) -N-phenyl-amino) -triphenylamine, N, N′-di- (4-methyl-phenyl)
- compounds having an aromatic tertiary amine skeleton of triphenyldiamines such as —N, N′-diphenyl-1,4-phenylenediamine, and condensed polycyclic compounds such as phenanthrene, pyrene, perylene, anthracene, tetracene and pentacene ( However, the condensed polycyclic compound may have
- a compound having an aromatic tertiary amine as a skeleton, a condensed polycyclic compound, and an alkali metal are more preferable because the carrier concentration can be increased more effectively.
- the hole blocking layer the same materials as those described above can be used as the electron transport layer 15 and the electron injection layer.
- the above materials are used.
- a coating solution for forming an organic EL layer dissolved and dispersed in a solvent a coating method such as a spin coating method, a dipping method, a doctor blade method, a discharge coating method, a spray coating method, an ink jet method, a relief printing method, an intaglio printing method
- a coating method such as a spin coating method, a dipping method, a doctor blade method, a discharge coating method, a spray coating method, an ink jet method, a relief printing method, an intaglio printing method
- a known wet process such as a printing method such as a printing method, a screen printing method, and a micro gravure coating method.
- a method of forming the above-described material by a known dry process such as a resistance heating vapor deposition method, an electron beam (EB) vapor deposition method, a molecular beam epitaxy (MBE) method, a sputtering method, or an organic vapor deposition (OVPD) method can be given. It is done.
- a method of forming by a laser transfer method or the like can be given.
- the organic EL layer 17 is formed by a wet process
- the organic EL layer forming coating solution may contain additives for adjusting the physical properties of the coating solution, such as a leveling agent and a viscosity modifier. .
- the film thickness of each layer constituting the organic EL layer 17 is usually about 1 nm to 1000 nm, and more preferably 10 nm to 200 nm. If the film thickness of each layer constituting the organic EL layer 17 is less than 10 nm, it may not be possible to obtain originally required physical properties (charge (electron, hole) injection characteristics, transport characteristics, confinement characteristics); There is a risk of pixel defects due to foreign matter such as dust. Moreover, when the film thickness of each layer constituting the organic EL layer 17 exceeds 200 nm, the driving voltage increases, which may lead to an increase in power consumption.
- the first electrode 12 is formed on a substrate (not shown), and the second electrode 16 is formed on an organic EL layer (organic layer) 17.
- an electrode material for forming the first electrode 12 and the second electrode 16 a known electrode material can be used.
- a material for forming the first electrode 12 that is an anode from the viewpoint of efficiently injecting holes into the organic EL layer 17, gold (Au), platinum (Pt), a work function of 4.5 eV or more, Metals such as nickel (Ni) and oxides (ITO) made of indium (In) and tin (Sn), oxides made of tin (Sn) (SnO 2 ), oxides made of indium (In) and zinc (Zn) (IZO) etc. are mentioned.
- an electrode material which forms the 2nd electrode 16 which is a cathode from a viewpoint of performing injection
- the first electrode 12 and the second electrode 16 can be formed on the substrate using the above materials by a known method such as an EB (electron beam) vapor deposition method, a sputtering method, an ion plating method, or a resistance heating vapor deposition method.
- a known method such as an EB (electron beam) vapor deposition method, a sputtering method, an ion plating method, or a resistance heating vapor deposition method.
- the present embodiment is not limited to these forming methods.
- the formed electrode can be patterned by a photolithographic fee method or a laser peeling method, or a patterned electrode can be directly formed by combining with a shadow mask.
- the film thickness of the first electrode 12 and the second electrode 16 is preferably 50 nm or more. When the film thicknesses of the first electrode 12 and the second electrode 16 are less than 50 nm, the wiring resistance increases, so that the drive voltage may increase.
- the organic light emitting device 10 shown in FIG. 1 is configured to contain the light emitting material of the present embodiment in the organic EL layer (organic layer) 17 including the organic light emitting layer 14, and is injected from the first electrode 12. By recombining the injected holes and the electrons injected from the second electrode 16 and phosphorescent emission of the light emitting material of the present embodiment contained in the organic layer 17 (organic light emitting layer 14), blue light can be efficiently emitted. Can emit (emit) light.
- the organic light emitting device of the present embodiment may be composed of a bottom emission type device that emits emitted light through a substrate, or a top emission type that emits to the opposite side of the substrate instead. You may be comprised with the device of.
- the driving method of the organic light emitting element of the present embodiment is not particularly limited and may be an active driving method or a passive driving method, but it is preferable to drive the organic light emitting element by the active driving method.
- Employing the active driving method is preferable because the light emission time of the organic light-emitting element can be extended compared to the passive driving method, the driving voltage for obtaining a desired luminance can be reduced, and the power consumption can be reduced.
- FIG. 2 is a schematic cross-sectional view showing a second embodiment of the organic light-emitting device according to this embodiment.
- An organic light emitting device 20 shown in FIG. 2 includes a substrate 1, a TFT (thin film transistor) circuit 2 provided on the substrate 1, and an organic light emitting device 10 (hereinafter sometimes referred to as “organic EL device 10”).
- the organic light emitting device 10 includes a pair of electrodes 12 and 16 provided on the substrate 1 and an organic EL layer (organic layer) 17 sandwiched between the pair of electrodes 12 and 16.
- the organic light emitting element 20 is a top emission type organic light emitting element driven by an active driving method.
- FIG. 2 the same components as those of the organic light emitting device 10 shown in FIG.
- the 2 includes a substrate 1, a TFT (thin film transistor) circuit 2, an interlayer insulating film 3, a planarizing film 4, an organic EL element 10, an inorganic sealing film 5, and a sealing substrate. 9 and the sealing material 6.
- a TFT (Thin Film Transistor) circuit 2 is provided on the substrate 1.
- the interlayer insulating film 3 and the planarizing film 4 are provided on the substrate.
- the organic EL element 10 is formed on the substrate with the interlayer insulating film 3 and the planarizing film 4 interposed therebetween.
- the inorganic sealing film 5 covers the organic EL element 10.
- the sealing substrate 9 is provided on the inorganic sealing film 5.
- the sealing material 6 is filled between the substrate 1 and the sealing substrate 9.
- the organic EL element 10 includes an organic EL layer (organic layer) 17, a first electrode 12 and a second electrode 16 that sandwich the organic EL layer (organic layer) 17, and a reflective electrode 11.
- the organic EL layer (organic layer) 17 is formed by laminating a hole transport layer 13, a light emitting layer 14, and an electron transport layer 15.
- a reflective electrode 11 is formed on the lower surface of the first electrode 12.
- the reflective electrode 11 and the first electrode 12 are connected to one of the TFT circuits 2 by a wiring 2 b provided through the interlayer insulating film 3 and the planarizing film 4.
- the second electrode 16 is connected to one of the TFT circuits 2 by a wiring 2 a provided through the interlayer insulating film 3, the planarizing film 4 and the edge cover 19.
- a TFT circuit 2 and various wirings (not shown) are formed on the substrate 1, and an interlayer insulating film 3 and a planarizing film 4 are sequentially stacked so as to cover the upper surface of the substrate 1 and the TFT circuit 2.
- the substrate for example, an inorganic material substrate made of glass, quartz or the like, a plastic substrate made of polyethylene terephthalate, polycarbazole, polyimide or the like, an insulating substrate such as a ceramic substrate made of alumina or the like, aluminum (Al), iron (Fe ), Etc., a substrate on which an insulating material such as silicon oxide (SiO 2 ) is coated on the surface, or a method of anodizing the surface of a metal substrate made of Al or the like
- the present embodiment is not limited to these.
- the TFT circuit 2 is formed on the substrate 1 in advance before the organic light emitting element 20 is formed, and functions as a switching device and a driving device.
- a conventionally known TFT circuit 2 can be used.
- a metal-insulator-metal (MIM) diode can be used instead of the TFT for switching and driving.
- the TFT circuit 2 can be formed using a known material, structure, and formation method.
- amorphous silicon amorphous silicon
- polycrystalline silicon polysilicon
- microcrystalline silicon inorganic semiconductor materials such as cadmium selenide, zinc oxide, indium oxide-oxide
- oxide semiconductor materials such as gallium-zinc oxide
- organic semiconductor materials such as polythiophene derivatives, thiophene oligomers, poly (p-ferylene vinylene) derivatives, naphthacene, and pentacene.
- examples of the structure of the TFT circuit 2 include a stagger type, an inverted stagger type, a top gate type, and a coplanar type.
- the gate insulating film of the TFT circuit 2 used in this embodiment can be formed using a known material. Examples thereof include SiO 2 formed by thermally oxidizing a SiO 2 film or a polysilicon film formed by a plasma induced chemical vapor deposition (PECVD) method, a low pressure chemical vapor deposition (LPCVD) method, or the like. Further, the signal electrode line, the scanning electrode line, the common electrode line, the first drive electrode, and the second drive electrode of the TFT circuit 2 used in the present embodiment can be formed using a known material, for example, tantalum. (Ta), aluminum (Al), copper (Cu), and the like.
- PECVD plasma induced chemical vapor deposition
- LPCVD low pressure chemical vapor deposition
- the interlayer insulating film 3 can be formed using a known material, for example, silicon oxide (SiO 2 ), silicon nitride (SiN or Si 2 N 4 ), tantalum oxide (TaO or Ta 2 O). 5 )) or an organic material such as an acrylic resin or a resist material.
- a known material for example, silicon oxide (SiO 2 ), silicon nitride (SiN or Si 2 N 4 ), tantalum oxide (TaO or Ta 2 O). 5 )
- an organic material such as an acrylic resin or a resist material.
- Examples of the method for forming the interlayer insulating film 3 include a dry process such as a chemical vapor deposition (CVD) method and a vacuum deposition method, and a wet process such as a spin coating method. Moreover, it can also pattern by the photolithographic method etc. as needed.
- the organic light emitting device 20 of the present embodiment since the light emitted from the organic EL device 10 is extracted from the sealing substrate 9 side, external light enters the TFT circuit 2 formed on the substrate 1 and changes to TFT characteristics. In order to prevent the occurrence of this, it is preferable to use the interlayer insulating film 3 (light-shielding insulating film) having light-shielding properties. In the present embodiment, the interlayer insulating film 3 and the light-shielding insulating film can be used in combination.
- Examples of the light-shielding insulating film include those obtained by dispersing pigments or dyes such as phthalocyanine and quinaclone in polymer resins such as polyimide, color resists, black matrix materials, inorganic insulating materials such as Ni x Zn y Fe 2 O 4, and the like. It is done.
- the flattening film 4 has defects in the organic EL element 10 due to irregularities on the surface of the TFT circuit 2 (for example, pixel electrode defects, organic EL layer defects, counter electrode disconnection, pixel electrode-counter electrode short circuit, reduction in breakdown voltage). Etc.) etc. are provided in order to prevent the occurrence.
- the planarization film 4 can be omitted.
- the planarization film 4 can be formed using a known material, and examples thereof include inorganic materials such as silicon oxide, silicon nitride, and tantalum oxide, and organic materials such as polyimide, acrylic resin, and resist material.
- planarizing film 4 examples include a dry process such as a CVD method and a vacuum deposition method, and a wet process such as a spin coating method, but the present embodiment is not limited to these materials and the forming method. . Further, the planarizing film 4 may have a single layer structure or a multilayer structure.
- the second electrode 16 is half-finished. It is preferable to use a transparent electrode.
- a transparent electrode As the material of the translucent electrode, it is possible to use a metal translucent electrode alone or a combination of a metal translucent electrode and a transparent electrode material. From the viewpoint of reflectance and transmittance, silver or a silver alloy Is preferred.
- the first electrode 12 positioned on the side opposite to the side from which the light emission from the organic light emitting layer 14 is extracted in order to increase the extraction efficiency of light emission from the organic light emitting layer 14, light is used. It is preferable to use an electrode with high reflectivity (reflecting electrode).
- electrode materials used in this case include reflective metal electrodes such as aluminum, silver, gold, aluminum-lithium alloys, aluminum-neodymium alloys, and aluminum-silicon alloys, transparent electrodes, and reflective metal electrodes (reflective electrodes). The electrode etc. which combined these are mentioned.
- FIG. 2 shows an example in which the first electrode 12 that is a transparent electrode is formed on the planarizing film 4 with the reflective electrode 11 interposed therebetween.
- a plurality of first electrodes 12 positioned on the substrate 1 side are arranged in parallel corresponding to each pixel.
- An edge cover 19 made of an insulating material is formed so as to cover each edge portion (end portion) of the adjacent first electrodes 12 and 12. The edge cover 19 is provided for the purpose of preventing leakage between the first electrode 12 and the second electrode 16.
- the edge cover 19 can be formed using an insulating material by a known method such as an EB vapor deposition method, a sputtering method, an ion plating method, a resistance heating vapor deposition method, or the like, and a pattern can be formed by a known dry or wet photolithography method.
- a known method such as an EB vapor deposition method, a sputtering method, an ion plating method, a resistance heating vapor deposition method, or the like
- a pattern can be formed by a known dry or wet photolithography method.
- the present embodiment is not limited to these formation methods.
- an insulating material layer which comprises the edge cover 19 a conventionally well-known material can be used, although it does not specifically limit in this embodiment, It is necessary to permeate
- the film thickness of the edge cover 19 is preferably 100 nm to 2000 nm. By setting the film thickness of the edge cover 19 to 100 nm or more, it is possible to maintain sufficient insulation, and increase in power consumption or non-light emission caused by leakage between the first electrode 12 and the second electrode 16. Can be prevented from happening. Further, by setting the film thickness of the edge cover 19 to 2000 nm or less, it is possible to prevent the productivity of the film forming process from being lowered and the disconnection of the second electrode 16 in the edge cover 19 from occurring. Further, the reflective electrode 11 and the first electrode 12 are connected to one of the TFT circuits 2 by a wiring 2 b provided through the interlayer insulating film 3 and the planarizing film 4.
- the second electrode 16 is connected to one of the TFT circuits 2 by a wiring 2 a provided through the interlayer insulating film 3, the planarizing film 4 and the edge cover 19.
- Wiring 2a, 2b should just be comprised from the electroconductive material, although it does not specifically limit, For example, it is comprised from materials, such as Cr, Mo, Ti, Ta, Al, Al alloy, Cu, Cu alloy. .
- the wirings 2a and 2b are formed by a conventionally known method such as a sputtering or CVD method and a mask process.
- An inorganic sealing film 5 made of SiO, SiON, SiN or the like is formed so as to cover the upper surface and side surfaces of the organic EL element 10 formed on the planarizing film 4.
- the inorganic sealing film 5 can be formed by depositing an inorganic film such as SiO, SiON, SiN or the like by plasma CVD, ion plating, ion beam, sputtering, or the like.
- the inorganic sealing film 5 needs to be light transmissive in order to extract light from the organic EL element 10.
- a sealing substrate 9 is provided on the inorganic sealing film 5, and the organic light emitting element 10 formed between the substrate 1 and the sealing substrate 9 is enclosed in a sealing region surrounded by the sealing material 6. Has been.
- substrate 9 In the organic light emitting element 20 of this embodiment, light emission is taken out from the sealing board
- a conventionally known sealing material can be used for the sealing material 6, and a conventionally known sealing method can also be used as a method for forming the sealing material 6.
- a resin (curable resin) can be used as the sealing material 6, for example.
- a curable resin (photo-curing property) is formed on the upper surface and / or the side surface of the inorganic sealing film 5 of the substrate 1 on which the organic EL element 10 and the inorganic sealing film 5 are formed, or on the sealing substrate 9.
- Resin, thermosetting resin is applied by using a spin coating method or a laminating method, and the substrate 1 and the sealing substrate 9 are bonded together via a resin layer, and are light-cured or heat-cured to thereby seal the sealing material 6.
- the sealing material 6 needs to have a light transmittance.
- an inert gas such as nitrogen gas or argon gas may be injected between the inorganic sealing film 5 and the sealing material 6, and an inert gas such as nitrogen gas or argon gas is sealed in a sealing substrate such as glass. 9 is used.
- a hygroscopic agent such as barium oxide in the enclosed inert gas.
- the organic light emitting device 20 of the present embodiment is configured to contain the light emitting material of the present embodiment in the organic EL layer (organic layer) 17.
- the holes injected from the first electrode 12 and the electrons injected from the second electrode 16 are recombined to emit blue light by phosphorescence emission of the light emitting material of the present embodiment contained in the organic layer 17 (organic light emitting layer 14). Can be emitted (emitted) with good efficiency.
- the wavelength conversion light-emitting device of this embodiment is a phosphor that is disposed on the light-emitting device and the light-emitting surface side of the light-emitting device, absorbs light emitted from the light-emitting device, and emits light having a wavelength different from the absorbed light. Constructed with layers.
- FIG. 3 is a schematic cross-sectional view showing a first embodiment of the wavelength conversion light-emitting device according to this embodiment
- FIG. 4 is a top view of the organic light-emitting device shown in FIG.
- a green phosphor layer 18G is provided.
- the red phosphor layer 18R and the green phosphor layer 18G may be collectively referred to as “phosphor layers”.
- the same components as those of the organic light-emitting devices 10 and 20 of the present embodiment described above are denoted by the same reference numerals and description thereof is omitted.
- the 3 includes a substrate 1, a TFT (thin film transistor) circuit 2, an interlayer insulating film 3, a planarizing film 4, an organic light emitting element (light source) 10, a sealing substrate 9,
- the red color filter 8R, the green color filter 8G, the blue color filter 8B, the red phosphor layer 18R, the green phosphor layer 18G, the sealing substrate 9, the black matrix 7, and the scattering layer 31 are schematically configured.
- a TFT (Thin Film Transistor) circuit 2 is provided on the substrate 1.
- the organic light emitting element (light source) 10 is provided on the substrate 1 via the interlayer insulating film 3 and the planarizing film 4.
- the red color filter 8R, the green color filter 8G, and the blue color filter 8B are partitioned by the black matrix 7 on one surface of the sealing substrate 9 and arranged in parallel.
- the red phosphor layer 18R is formed in alignment with the red color filter 8R on one surface of the sealing substrate 9.
- the green phosphor layer 18G is formed in alignment with the green color filter 8G on one surface on the sealing substrate 9.
- the scattering layer 31 is formed on the blue color filter 8B on the sealing substrate 9 so as to be aligned.
- the substrate 1 and the sealing substrate 9 are arranged so that the organic light emitting element 10 and the phosphor layers 18R and 18G and the scattering layer 31 face each other with a sealing material interposed therebetween.
- the phosphor layers 18R and 18G and the scattering layer 31 are partitioned by the black matrix 7.
- the organic EL light emitting unit 10 is covered with the inorganic sealing film 5.
- a hole transport layer 13, and an organic EL layer (organic layer) 17 in which a light emitting layer 14 and an electron transport layer 15 are stacked are sandwiched between a first electrode 12 and a second electrode 16.
- a reflective electrode 11 is formed on the lower surface of the first electrode 12.
- the reflective electrode 11 and the first electrode 12 are connected to one of the TFT circuits 2 by a wiring 2 b provided through the interlayer insulating film 3 and the planarizing film 4.
- the second electrode 16 is connected to one of the TFT circuits 2 by a wiring 2 a provided through the interlayer insulating film 3, the planarizing film 4 and the edge cover 19.
- the wavelength conversion light-emitting element 30 of the present embodiment light emitted from the organic light-emitting element 10 that is a light source is incident on the phosphor layers 18R and 18G and the scattering layer 31, and the incident light remains as it is in the scattering layer 31.
- the light is transmitted, converted in each of the phosphor layers 18R and 18G, and emitted to the sealing substrate 9 side (observer side) as light of three colors of red, green, and blue.
- the wavelength conversion light-emitting element 30 of the present embodiment has a red phosphor layer 18 ⁇ / b> R and a red color filter 8 ⁇ / b> R, a green phosphor layer 18 ⁇ / b> G and a green color filter 8 ⁇ / b> G, and a scattering layer 31 and a blue color.
- An example in which the color filters 8B are juxtaposed one by one is shown.
- each color filter 8R, 8G, 8B surrounded by a broken line extends in a stripe shape along the y-axis, and each color filter 8R, 8G, 8B along the x-axis.
- each RGB pixel (each color filter 8R, 8G, 8B) is arranged in stripes, but this embodiment is not limited to this, and the arrangement of each RGB pixel is a mosaic.
- a conventionally known RGB pixel array such as an array or a delta array may be used.
- the red phosphor layer 18 ⁇ / b> R absorbs blue region light emitted from the organic light emitting element 10 that is a light source, converts the light into red region light, and emits red region light to the sealing substrate 9 side.
- the green phosphor layer 18G absorbs light in the blue region emitted from the organic light emitting element 10 that is a light source, converts it into light in the green region, and emits light in the green region to the sealing substrate 9 side.
- the scattering layer 31 is provided for the purpose of improving the viewing angle characteristics and extraction efficiency of light in the blue region emitted from the organic light emitting element 10 that is a light source, and emits light in the blue region to the sealing substrate 9 side. To do.
- the scattering layer 31 can be omitted.
- the red phosphor layer 18R and the green phosphor layer 18G are converted, and three colors of red, green, and blue are obtained. By emitting this light from the sealing substrate 9 side, full color display can be performed.
- the color filters 8R, 8G, and 8B arranged between the sealing substrate 9 on the light extraction side (observer side), the phosphor layers 18R and 18G, and the scattering layer 31 are wavelength conversion light emitting elements (color conversion light emitting elements). ) Is provided for the purpose of increasing the color purity of red, green, and blue emitted from 30 and expanding the color reproduction range of the wavelength conversion light-emitting element 30. Further, the red color filter 8R formed on the red phosphor layer 18R and the green color filter 8G formed on the green phosphor layer 18G absorb the blue component and the ultraviolet component of external light. Therefore, it is possible to reduce / prevent emission of the phosphor layers 8R, 8G due to external light, and to reduce / prevent a decrease in contrast.
- the color filters 8R, 8G, and 8B are not particularly limited, and conventionally known color filters can be used. Further, the color filters 8R, 8G, and 8B can be formed by a conventionally known method, and the film thickness can be adjusted as appropriate.
- the scattering layer 31 is configured by dispersing transparent particles in a binder resin.
- the thickness of the scattering layer 31 is usually 10 ⁇ m to 100 ⁇ m, preferably 20 ⁇ m to 50 ⁇ m.
- the binder resin used for the scattering layer 31 conventionally known binder resins can be used and are not particularly limited, but those having optical transparency are preferable.
- the transparent particles are not particularly limited as long as they can scatter and transmit light from the organic light emitting device 10, and for example, polystyrene particles having an average particle size of 25 ⁇ m and a standard deviation of the particle size distribution of 1 ⁇ m are used. Can do. Further, the content of the transparent particles in the scattering layer 31 can be appropriately changed and is not particularly limited.
- the scattering layer 31 can be formed by a conventionally known method and is not particularly limited.
- a spin coating method using a coating solution in which a binder resin and transparent particles are dissolved and dispersed in a solvent for example, a spin coating method using a coating solution in which a binder resin and transparent particles are dissolved and dispersed in a solvent.
- Known wet processes such as coating methods such as dipping method, doctor blade method, discharge coating method, spray coating method, ink jet method, relief printing method, intaglio printing method, screen printing method, micro gravure coating method, etc. Can be formed.
- the red phosphor layer 18 ⁇ / b> R includes a phosphor material that can absorb and excite the light in the blue region emitted from the organic light emitting element 10 and emit the fluorescence in the red region.
- the green phosphor layer 18G includes a phosphor material that can absorb and excite light in the blue region emitted from the organic light emitting element 10 to emit fluorescence in the green region.
- the red phosphor layer 18R and the green phosphor layer 18G may be composed of only the phosphor materials exemplified below, and may optionally be composed of additives, and these materials are polymeric materials. (Binding resin) or dispersed in an inorganic material.
- the phosphor material for forming the red phosphor layer 18R and the green phosphor layer 18G a conventionally known phosphor material can be used. Such phosphor materials are classified into organic phosphor materials and inorganic phosphor materials. Specific examples of these phosphor materials are shown below, but the present embodiment is not limited to these materials.
- organic phosphor materials will be exemplified.
- the phosphor material used for the red phosphor layer 18R include cyanine dyes such as 4-dicyanomethylene-2-methyl-6- (p-dimethylaminostyryl) -4H-pyran, 1-ethyl-2- [4 Pyridine dyes such as-(p-dimethylaminophenyl) -1,3-butadienyl] -pyridinium-perchlorate, and rhodamine B, rhodamine 6G, rhodamine 3B, rhodamine 101, rhodamine 110, basic violet 11, sulforhodamine 101, etc. And rhodamine dyes.
- the phosphor material used for the green phosphor layer 18G includes 2,3,5,6-1H, 4H-tetrahydro-8-trifluoromethylquinolidine (9,9a, 1-gh) coumarin (coumarin 153). , 3- (2′-benzothiazolyl) -7-diethylaminocoumarin (coumarin 6), 3- (2′-benzoimidazolyl) -7-N, N-diethylaminocoumarin (coumarin 7), and the like, and basic yellow 51, naphthalimide dyes such as Solvent Yellow 11 and Solvent Yellow 116. It is also possible to use the light-emitting material described in this embodiment.
- an inorganic phosphor material is illustrated.
- Y 2 O 2 S Eu 3+ , YAlO 3 : Eu 3+ , Ca 2 Y 2 (SiO 4 ) 6 : Eu 3+ , LiY 9 (SiO 4 ) 6 O 2 : Eu 3+ , YVO 4 : Eu 3+ , CaS: Eu 3+ , Gd 2 O 3 : Eu 3+ , Gd 2 O 2 S: Eu 3+ , Y (P, V) O 4 : Eu 3+ , Mg 4 GeO 5.5 F: Mn 4+ , Mg 4 GeO 6 : Mn 4+ , K 5 Eu 2.5 (WO 4 ) 6.25 , Na 5 Eu 2.5 (WO 4 ) 6.25 , K 5 Eu 2.5 (MoO 4 ) 6.25, and, Na 5 Eu 2.5 (MoO 4 ) 6.25 , and the like.
- the phosphor materials used for the green phosphor layer 18G include (BaMg) Al 16 O 27 : Eu 2+ , Mn 2+ , Sr 4 Al 14 O 25 : Eu 2+ , (SrBa) Al 12 Si 2 O 8 : Eu.
- the inorganic phosphor material it is preferable to subject the inorganic phosphor material to a surface modification treatment as necessary.
- chemical treatment such as a silane coupling agent or addition of fine particles of submicron order, etc.
- the thing by physical processing, the thing by those combined use, etc. are mentioned.
- an inorganic phosphor material for its stability.
- the average particle size (d50) of the material is preferably 0.5 ⁇ m to 50 ⁇ m.
- the photosensitive resin includes a photosensitive resin having a reactive vinyl group such as an acrylic resin, a methacrylic resin, a polyvinyl cinnamate resin, and a hard rubber resin (a photocurable resist material). ), One kind or a plurality of kinds of mixtures can be used.
- the red phosphor layer 18R and the green phosphor layer 18G are formed by using a phosphor layer forming coating solution in which the phosphor material (pigment) and the resin material are dissolved and dispersed in a solvent, and a known wet process, It can be formed by a process or a laser transfer method.
- known wet processes include spin coating methods, dipping methods, doctor blade methods, discharge coating methods, spray coating methods and other coating methods, ink jet methods, letterpress printing methods, intaglio printing methods, screen printing methods, and micro printing methods. Examples of the printing method include a gravure coating method.
- Known dry processes include resistance heating vapor deposition, electron beam (EB) vapor deposition, molecular beam epitaxy (MBE), sputtering, and organic vapor deposition (OVPD).
- the film thickness of the red phosphor layer 18R and the green phosphor layer 18G is usually about 100 nm to 100 ⁇ m, and preferably 1 ⁇ m to 100 ⁇ m. If the film thickness of each of the red phosphor layer 18R and the green phosphor layer 18G is less than 100 nm, it is difficult to sufficiently absorb the blue light emitted from the organic light emitting device 10, and thus light emission in the wavelength conversion light emitting device 30 is performed. There may be a case where efficiency is deteriorated and color purity is deteriorated due to mixing of blue transmitted light with the converted light converted by the phosphor layers 18R and 18G.
- the thickness of each phosphor layer 18R, 18G is 1 ⁇ m or more. Preferably there is. Even if the film thickness of each of the red phosphor layer 18R and the green phosphor layer 18G exceeds 100 ⁇ m, the blue light emitted from the organic light emitting element 10 is already sufficiently absorbed, and thus the light emitted from the wavelength conversion light emitting element 30 is emitted. It does not lead to an increase in efficiency. For this reason, since the raise of material cost can be suppressed, the film thickness of the red fluorescent substance layer 18R and the green fluorescent substance layer 18G has preferable 100 micrometers or less.
- An inorganic sealing film 5 is formed so as to cover the upper surface and side surfaces of the organic light emitting element 10. Furthermore, on the inorganic sealing film 5, the red fluorescence conversion layer 8R, the green fluorescence conversion layer 8G, the scattering layer 31, and the color filters 8R, 8G, which are partitioned in parallel by the black matrix 7 on one surface. , 8B are disposed so that the phosphor layers 18R and 18G and the scattering layer 31 and the organic light emitting element face each other.
- a sealing material 6 is sealed between the inorganic sealing film 5 and the sealing substrate 9. That is, each of the phosphor layers 18R and 18G and the scattering layer 31 disposed so as to face the organic light emitting element 10 are each surrounded by the black matrix 7 and surrounded by the sealing material 6. It is enclosed in a sealing area.
- (Curable resin) is applied by spin coating or laminating. Then, the sealing material 6 can be formed by bonding the board
- the surfaces of the fluorescence conversion layers 18R and 18G and the scattering layer 31 opposite to the sealing substrate 9 are preferably flattened by a flattening film or the like (not shown).
- a flattening film or the like not shown.
- the organic light emitting element 10 and the phosphor layers 18R and 18G and the scattering layer 31 are opposed to each other through the sealing material 6, the organic light emitting element 10 and the phosphor layers 18R, 18G, and Depletion between the functional layer 31 and the functional layer 31 can be prevented.
- the adhesion between the substrate 1 on which the organic light emitting element 10 is formed and the sealing substrate 9 on which the phosphor layers 18R and 18G, the scattering layer 31, and the color filters 8R, 8G, and 8B are formed can be improved.
- the planarizing film the same one as the planarizing film 4 described above can be used.
- the black matrix 7 conventionally known materials and forming methods can be used and are not particularly limited. Among them, it is preferable that the light scattered and incident on the phosphor layers 18R and 18G is further reflected by the phosphor layers 18R and 18G, such as a metal having light reflectivity. .
- the organic light emitting device 10 desirably has a top emission structure so that a large amount of light reaches each of the phosphor layers 18R and 18G and the scattering layer 31.
- the first electrode 12 and the second electrode 16 are reflective electrodes, and the optical distance L between these electrodes 12 and 16 is adjusted to constitute a microresonator structure (microcavity structure). Is preferred.
- a reflective electrode as the first electrode 12 and a translucent electrode as the second electrode 16.
- a metal translucent electrode can be used alone, or a combination of a metal translucent electrode and a transparent electrode material can be used.
- the translucent electrode material it is preferable to use silver or a silver alloy from the viewpoint of reflectance and transmittance.
- the film thickness of the second electrode 16 which is a translucent electrode is preferably 5 nm to 30 nm. If the film thickness of the semi-transparent electrode is less than 5 nm, there is a possibility that light cannot be sufficiently reflected and the interference effect cannot be obtained sufficiently. Moreover, when the film thickness of a semi-transparent electrode exceeds 30 nm, since the light transmittance falls rapidly, there exists a possibility that a brightness
- the first electrode 12 that is a reflective electrode it is preferable to use an electrode with high reflectivity that reflects light.
- the reflective electrode include reflective metal electrodes such as aluminum, silver, gold, aluminum-lithium alloy, aluminum-neodymium alloy, and aluminum-silicon alloy.
- FIG. 3 shows an example in which the first electrode 12 that is a transparent electrode is formed on the planarizing film 4 via the reflective electrode 11.
- the microresonator structure (microcavity structure) is configured by the first electrode 12 and the second electrode 16
- the light emission of the organic EL layer 17 is caused to occur in the front direction (by the interference effect between the first electrode 12 and the second electrode 16).
- Light can be condensed in the light extraction direction (sealing substrate 9 side). That is, since the directivity can be given to the light emission of the organic EL layer 17, the light emission loss escaping to the surroundings can be reduced, and the light emission efficiency can be increased. Thereby, the luminescence energy generated in the organic light emitting element 10 can be more efficiently propagated to the phosphor layers 18R and 18G, and the front luminance of the wavelength conversion light emitting element 30 can be increased.
- the emission spectrum of the organic EL layer 17 can be adjusted, and the desired emission peak wavelength and half width can be adjusted. Therefore, the emission spectrum of the organic EL layer 17 can be controlled to a spectrum that can effectively excite the phosphors in the phosphor layers 18R and 18B.
- a translucent electrode as the second electrode 16
- light emitted in the direction opposite to the light extraction direction of the phosphor layers 18R and 18G and the scattering layer 31 can be reused.
- each phosphor layer 18R, 18G the optical distance from the light emission position of the converted light to the light extraction surface is set to be different for each color of the light emitting element.
- the “light emitting position” is a surface facing the organic light emitting device 10 side in each of the phosphor layers 18R and 18G.
- the optical distance from the emission position of the converted light to the light extraction surface in each phosphor layer 18R and 18G is adjusted by the film thickness of each phosphor layer 18R and 18G.
- each phosphor layer 18R, 18G depends on the printing conditions of the screen printing method (squeegee printing pressure, squeegee attack angle, squeegee speed, or clearance width), screen plate specifications (screen selection, emulsion thickness, tension Or the strength of the frame) or the specification of the phosphor-forming coating liquid (viscosity, fluidity, or blending ratio of resin, pigment, and solvent).
- the wavelength conversion light emitting device 30 of the present embodiment enhances the light emitted from the organic light emitting device 10 by a microresonator structure (microcavity structure), and increases the light extraction efficiency of the light converted by each phosphor layer 18R, 18G. It can be improved by adjusting the optical distance (adjusting the thickness of each phosphor layer 18R, 18G). Thereby, the luminous efficiency of the wavelength conversion light emitting element 30 can be further improved.
- a microresonator structure microcavity structure
- the wavelength conversion light emitting device 30 of the present embodiment is configured to convert the light from the organic light emitting device 10 using the light emitting material of the present embodiment described above by the phosphor layers 18R and 18G, and thus emits light with good efficiency. be able to.
- the wavelength conversion light emitting device of this embodiment is not limited to the above embodiment.
- the wavelength conversion light emitting device 30 of the above embodiment it is also preferable to provide a polarizing plate on the light extraction side (on the sealing substrate 9).
- the polarizing plate a combination of a conventionally known linearly polarizing plate and a ⁇ / 4 plate can be used.
- a polarizing plate it is possible to prevent external light reflection from the first electrode 12 and the second electrode 16 and external light reflection on the surface of the substrate 1 or the sealing substrate 9, and wavelength conversion.
- the contrast of the light emitting element 30 can be improved.
- the organic light emitting element 10 using the luminescent material of this embodiment was used as a light source (light emitting element), this embodiment is not limited to this.
- the wavelength conversion light-emitting element may be a single-color light-emitting element having only one type of phosphor layer, and includes multi-primary color elements such as white, yellow, magenta, and cyan in addition to red, green, and blue light-emitting elements. You can also.
- a phosphor layer corresponding to each color may be used. As a result, it is possible to reduce power consumption and expand the color reproduction range.
- the multi-primary color phosphor layer can be easily formed by using a resist photo, a printing method, or a wet forming method, rather than using a mask coating or the like.
- the light conversion light-emitting device of this embodiment includes at least one organic layer including a light-emitting layer containing the light-emitting material of the present embodiment, a current amplifying layer, an organic layer, and a current amplifying layer. It has a pair of electrodes to hold.
- FIG. 5 is a schematic diagram showing one embodiment of the light conversion light-emitting device according to this embodiment.
- the light conversion light emitting element 40 shown in FIG. 5 uses photoelectric conversion by a photocurrent multiplication effect, and converts the obtained electrons into light again using the principle of EL light emission.
- the 5 includes an element substrate 41, a lower electrode 42, an organic EL layer 17, an organic photoelectric material layer 43, and an Au electrode 44.
- the element substrate 41 is made of a transparent glass substrate.
- the lower electrode 42 is formed on one surface of the element substrate 41 and is made of an ITO electrode or the like. On the lower electrode 42, the organic EL layer 17, the organic photoelectric material layer 43, and the Au electrode 44 are sequentially stacked.
- the lower electrode 42 is connected to the positive pole of the driving power source, and the Au electrode 44 is connected to the negative pole of the driving power source.
- the organic EL layer 17 can use the same configuration as the organic EL layer 17 described above in the organic light emitting device of the first embodiment.
- the organic photoelectric material layer 43 exhibits a photoelectric effect for amplifying current, and may be configured by only one NTCDA (naphthalene tetracarboxylic acid) layer, or may be configured by a multilayer having selectable sensitivity wavelength regions. For example, it can be composed of two layers, a Me-PTC (perylene pigment) layer and an NTCDA layer.
- the thickness of the organic photoelectric material layer 43 is not particularly limited and is, for example, about 10 nm to 100 nm, and is formed by a vacuum deposition method or the like.
- the light conversion light emitting element 40 of the present embodiment is generated by irradiation of light when a predetermined voltage is applied between the lower electrode 42 and the Au electrode 44 and light is irradiated from the outside of the Au electrode 44 (incident light 48).
- the holes are trapped and accumulated in the vicinity of the Au electrode 44 that is the negative electrode.
- the electric field concentrates on the interface between the organic photoelectric material layer 43 and the Au electrode 44, and electrons are injected from the Au electrode 44, thereby causing a current doubling phenomenon. Since the amplified current is emitted from the organic EL layer 17, good light emission characteristics can be exhibited.
- Light generated in the organic EL layer 17 is emitted to the outside as outgoing light 49 through the element substrate 41. Since the light conversion light emitting element 40 of the present embodiment includes the organic EL layer 17 including the light emitting material of the first embodiment described above, the light emission efficiency can be further improved.
- the organic laser diode light emitting device of this embodiment includes an excitation light source (including a continuous wave excitation light source) and a resonator structure irradiated with the excitation light source.
- the resonator structure is formed by sandwiching at least one organic layer including a laser active layer between a pair of electrodes.
- FIG. 6 is a schematic diagram showing one embodiment of the organic laser diode light emitting device according to this embodiment.
- the organic laser diode light emitting element 50 shown in FIG. 6 includes an excitation light source 50a that emits laser light and a resonator structure 50b.
- the resonator structure 50 b includes an ITO substrate 51, a hole transport layer 52, a laser active layer 53, a hole block layer 54, an electron transport layer 55, an electron injection layer 56, and an electrode 57.
- a hole transport layer 52, a laser active layer 53, a hole block layer 54, an electron transport layer 55, an electron injection layer 56, and an electrode 57 are sequentially stacked.
- the ITO electrode formed on the ITO substrate 51 is connected to the positive electrode of the driving power source, and the electrode 57 is connected to the negative electrode of the driving power source.
- the hole transport layer 52, the hole blocking layer, the electron transport layer 55, and the electron injection layer 56 are the hole transport layer 13, the hole prevention layer, and the electron transport layer described above in the organic light emitting device of the first embodiment, respectively. 15 and the electron injection layer.
- the laser active layer 53 can have the same configuration as that of the organic light emitting layer 14 described above in the organic light emitting device of the first embodiment, and a host material doped with the light emitting material of the first embodiment is preferable.
- 6 illustrates an organic EL layer 58 in which a hole transport layer 52, a laser active layer 53, a hole block layer 54, an electron transport layer 55, and an electron injection layer 56 are sequentially stacked.
- the organic laser diode light emitting device 50 according to the first embodiment is not limited to this example, and may be configured in the same manner as the organic light emitting layer 14 described above in the organic light emitting device according to the first embodiment.
- the organic laser diode light emitting device 50 of the present embodiment irradiates laser light 59a from the excitation light source 50a from the ITO substrate 51 side which is an anode, and according to the excitation intensity of the laser light from the side surface side of the resonator structure 50b.
- ASE oscillation light emission edge light emission 59b in which the peak luminance increases can be performed.
- FIG. 7 is a schematic diagram showing one embodiment of a dye laser according to this embodiment.
- a dye laser 60 illustrated in FIG. 7 includes an excitation light source 61, a dye cell 62, a lens 66, a partial reflection mirror 65, a diffraction grating 63, and a beam expander 64.
- the excitation light source 61 emits pump light 67.
- the lens 66 condenses the pump light 67 on the dye cell 62.
- the partial reflecting mirror 65 is disposed opposite to the beam expander 64 with the dye cell 62 interposed therebetween.
- the beam expander 64 is disposed between the diffraction grating 63 and the dye cell 62.
- the beam expander 64 collects the light from the diffraction grating 63.
- the dye cell 62 is made of quartz glass or the like.
- the dye cell 62 is filled with a laser medium that is a solution containing the light emitting material of the present embodiment.
- the pump light 67 is emitted from the excitation light source 61
- the pump light 67 is condensed on the dye cell 62 by the lens 66, and the light emission of the present embodiment in the laser medium of the dye cell 62 is performed.
- the material is excited and emits light.
- Light emitted from the luminescent material is emitted to the outside of the dye cell 62 and is reflected and amplified between the partial reflection mirror 62 and the diffraction grating 63.
- the amplified light passes through the partial reflection mirror 65 and is emitted to the outside.
- the light emitting material of this embodiment can also be applied to a dye laser.
- the organic light-emitting element, wavelength-converted light-emitting element, and light-converted light-emitting element of the present embodiment described above can be applied to display devices, lighting devices, and the like.
- the display device of the present embodiment includes an image signal output unit, a drive unit, and a light emitting unit.
- the image signal output unit generates an image signal.
- the drive unit generates a current or a voltage based on a signal from the image signal output unit.
- the light emitting unit emits light by current or voltage from the driving unit.
- the light emitting unit is configured by any one of the organic light emitting element, the wavelength conversion light emitting element, and the light conversion light emitting element according to the present embodiment described above.
- the case where the light emitting unit is the organic light emitting device of the present embodiment will be described as an example. It can also be comprised from a light emitting element or a light conversion light emitting element.
- FIG. 8 is a configuration diagram illustrating an example of a connection configuration of a wiring structure and a driving circuit of a display device including the organic light emitting element 20 and the driving unit according to the second embodiment.
- FIG. 9 is a pixel circuit diagram showing a circuit constituting one pixel arranged in the display device using the organic light emitting element of the present embodiment.
- scanning lines 101 and signal lines 102 are wired in a matrix in a plan view with respect to the substrate 1 of the organic light emitting element 20.
- Each scanning line 101 is connected to a scanning circuit 103 provided on one side edge of the substrate 1.
- Each signal line 102 is connected to a video signal driving circuit 104 provided at the other side edge of the substrate 1.
- a driving element such as a thin film transistor of the organic light emitting element 20 shown in FIG.
- a pixel electrode is connected to each drive element.
- These pixel electrodes correspond to the reflective electrodes 11 of the organic light emitting element 20 having the structure shown in FIG. 2, and these reflective electrodes 11 correspond to the first electrodes 12.
- the scanning circuit 103 and the video signal driving circuit 104 are electrically connected to the controller 105 via control lines 106, 107, and 108.
- the operation of the controller 105 is controlled by the central processing unit 109.
- a power supply circuit 112 is connected to the scanning circuit 103 and the video signal driving circuit 104 via power supply wirings 110 and 111 separately.
- the image signal output unit includes a CPU 109 and a controller 105.
- the drive unit that drives the organic EL light emitting unit 10 of the organic light emitting element 20 includes a scanning circuit 103, a video signal drive circuit 104, and an organic EL power supply circuit 112.
- a TFT circuit 2 of the organic light emitting element 20 shown in FIG. 2 is formed in each region partitioned by the scanning line 101 and the signal line 102.
- FIG. 9 shows a pixel circuit diagram constituting one pixel of the organic light emitting element 20 disposed in each region partitioned by the scanning line 101 and the signal line 102.
- a scanning signal is applied to the scanning line 101
- this signal is applied to the gate electrode of the switching TFT 124 formed of a thin film transistor to turn on the switching TFT 124.
- a pixel signal is applied to the signal line 102
- this signal is applied to the source electrode of the switching TFT 124, and the storage capacitor 125 connected to the drain electrode via the switching TFT 124 that is turned on is charged.
- the storage capacitor 125 is connected between the source electrode and the gate electrode of the driving TFT 126.
- the gate voltage of the driving TFT 126 is held at a value determined by the voltage of the storage capacitor 125 until the switching TFT 124 is next selected for scanning.
- the power line 123 is connected to a power circuit (FIG. 8). The current supplied from the power supply line 123 flows to the organic light emitting element (organic EL element) 127 through the driving TFT 126 and causes the element 127 to emit light continuously.
- the organic light emitting element 20 corresponding to the pixel can emit light, and visible region light can be emitted from the corresponding pixel, so that a desired color or image can be displayed.
- the display device includes a display device with good luminous efficiency by including any one of an organic light emitting element, a wavelength conversion light emitting element, and a light conversion light emitting element using the light emitting material of the present embodiment as a light emitting unit. Become.
- the display device according to this embodiment described above can be incorporated into various electronic devices.
- an electronic apparatus including the display device according to the present embodiment will be described with reference to FIGS.
- the display device according to the present embodiment described above can be applied to, for example, the mobile phone shown in FIG.
- a cellular phone 210 illustrated in FIG. 13 includes a voice input unit 211, a voice output unit 212, an antenna 213, an operation switch 214, a display unit 215, a housing 216, and the like.
- the display apparatus of this embodiment can be suitably applied as the display unit 215.
- the display device according to this embodiment described above can be applied to the flat-screen television shown in FIG.
- a thin television 220 illustrated in FIG. 14 includes a display portion 221, speakers 222, a cabinet 223, a stand 224, and the like.
- the display device of this embodiment can be suitably applied as the display unit 221.
- a portable game machine 230 illustrated in FIG. 15 includes operation buttons 231 and 232, an external connection terminal 233, a display unit 234, a housing 235, and the like.
- the display device of this embodiment can be suitably applied as the display unit 234.
- a notebook computer 240 illustrated in FIG. 13 includes a display portion 241, a keyboard 242, a touch pad 243, a main switch 244, a camera 245, a recording medium slot 246, a housing 247, and the like.
- the display apparatus of the above-mentioned embodiment can be applied suitably as the display part 241 of this notebook personal computer 240.
- FIG. By applying the display device according to the embodiment of the present invention to the display unit 241 of the notebook computer 240, it is possible to display an image with good issue efficiency.
- FIG. 10 is a schematic perspective view showing an embodiment of a lighting device according to the present embodiment.
- the illuminating device 70 shown in FIG. 10 includes a drive unit 71 that generates a current or voltage, and a light emitting unit 72 that emits light by the current or voltage from the drive unit 71.
- the light emitting unit 72 includes any one of the organic light emitting element, the wavelength conversion light emitting element, and the light conversion light emitting element of the above-described embodiment.
- the light emitting unit is the organic light emitting element 10 of the embodiment will be described as an example. It can also be comprised from a light emitting element or a light conversion light emitting element.
- the illuminating device 70 shown in FIG. 10 applies an electric voltage to the organic EL layer (organic layer) 17 sandwiched between the first electrode 12 and the second electrode 16 from the drive unit, and thereby an organic light emitting element corresponding to the pixel. 10 can be emitted to emit blue light.
- the organic light emitting element 10 corresponds to a pixel selected by the driving unit.
- the organic light emitting layer 14 of the organic light emitting element 10 is conventionally well-known organic.
- An EL light emitting material may be contained.
- the illuminating device 70 of this embodiment although illustrated about the case where the organic light emitting element 10 of 1st Embodiment was provided as a light emission part, this embodiment is not limited to this, 1st this embodiment mentioned above as a light emission part. Any of the organic light emitting device, the wavelength conversion light emitting device, and the light conversion light emitting device according to the present invention can be suitably provided.
- the illuminating device 70 according to the present embodiment includes any one of an organic light emitting element, a wavelength conversion light emitting element, and a light conversion light emitting element using the light emitting material according to the present embodiment as a light emitting unit, so that an illuminating apparatus having good luminous efficiency. 70.
- the lighting device according to this embodiment described above can be incorporated into various lighting devices.
- the organic light-emitting element, wavelength-converted light-emitting element, and light-converted light-emitting element of the present embodiment can also be applied to, for example, a ceiling light (illumination device) shown in FIG.
- a ceiling light 250 shown in FIG. 11 includes a light emitting unit 251, a hanging line 252, a power cord 253, and the like.
- the organic light emitting element of this embodiment a wavelength conversion light emitting element, and a light conversion light emitting element are applicable suitably.
- the ceiling light 250 includes the organic light emitting device, the wavelength conversion light emitting device, and the light conversion light emitting device that use the transition metal complex according to the present embodiment as the light emitting unit 251, thereby achieving good luminous efficiency. Lighting equipment.
- the organic light emitting device, the wavelength conversion light emitting device, and the light conversion light emitting device of the present embodiment can be applied to, for example, a lighting stand (lighting device) shown in FIG.
- the illumination stand 260 shown in FIG. 12 includes a light emitting unit 261, a stand 262, a main switch 263, a power cord 264, and the like.
- the organic light emitting element of this embodiment a wavelength conversion light emitting element, and a light conversion light emitting element can be applied suitably.
- the illumination stand 260 includes any one of an organic light emitting element, a wavelength conversion light emitting element, and a light conversion light emitting element using the transition metal complex according to the present embodiment as the light emitting unit 261, so that the light emission efficiency is improved. Lighting equipment.
- the display device described in the above embodiment preferably includes a polarizing plate on the light extraction side.
- a polarizing plate a combination of a conventional linear polarizing plate and a ⁇ / 4 plate can be used.
- a polarizing plate By providing such a polarizing plate, external light reflection from the electrodes of the display device or external light reflection from the surface of the substrate or the sealing substrate can be prevented, and the contrast of the display device can be improved.
- specific descriptions regarding the shape, number, arrangement, material, formation method, and the like of each component of the phosphor substrate, the display device, and the lighting device are not limited to the above-described embodiment, and can be changed as appropriate.
- Synthesis of Compound B Compound A (0.1 mol) was added dropwise to an aqueous solution of methylamine (0.5 mol). After stirring for several minutes, a solid precipitated. Water was added to the reaction solution, and the solid was filtered by liquid separation treatment and dried to obtain Compound B. Yield: 82%.
- Synthesis of Compound C To a solution of compound B (10.2 mmol) dissolved in THF (tetrahydrofuran), a hexane solution of n-BuLi (10.2 mmol) was slowly added at room temperature. After 30 minutes, trimethylsilyl chloride (10.2 mmol) was added. Thereafter, the solvent was removed under reduced pressure, and extraction with ether yielded Compound C. Yield: 93%.
- Synthesis of Compound D Sn (CH 3 ) 4 (5 mol) was added to BBr 3 (10 mol) at ⁇ 50 ° C. with stirring, and the mixture was stirred for 1 hour. Thereafter, the solvent was removed under reduced pressure, and extraction with ether yielded Compound D. Yield: 80%.
- Synthesis of Compound E N-BuLi (9 mmol) was added dropwise at ⁇ 10 ° C. to a hexane solution in which methylamine (10 mmol) was dissolved, and a hexane solution (50 mL) of dibromomethylborane (Compound D: 9 mmol) was added to ⁇ 20 ° C. Was slowly added dropwise.
- Synthesis of Compound F A solution in which compound E (10.2 mmol) was dissolved in 20 mL of toluene was added dropwise to a solution in which compound C (10.2 mmol) was dissolved in 10 mL of toluene at ⁇ 78 ° C. with stirring. The mixture was returned to room temperature and stirred for 1 hour, and the solvent was removed under reduced pressure. Thereafter, extraction with hexane gave Compound F. Yield: 80%.
- Synthesis of Compound G Dibromophenylborane (Compound D) and Compound F were dissolved in 20 mL of chloroform and refluxed for 1.5 days.
- the PL quantum yield was measured according to the following procedure. First, the emission spectrum of each compound was measured with a PL measuring device FluoroMax-4 (manufactured by HORIBA, excitation wavelength 380 nm), and the absorbance was measured with an absorbance measuring device UV-2450 (manufactured by Shimadzu Corporation).
- Example 2 [Production of organic light-emitting element and evaluation of organic EL characteristics] (Example 2) A silicon semiconductor film was formed on a glass substrate by a plasma chemical vapor deposition (plasma CVD) method, subjected to crystallization treatment, and then a polycrystalline semiconductor film (polycrystalline silicon thin film) was formed. Subsequently, the polycrystalline silicon thin film was etched to form a plurality of island patterns. Next, silicon nitride (SiN) was formed as a gate insulating film on each island of the polycrystalline silicon thin film.
- plasma CVD plasma chemical vapor deposition
- SiN silicon nitride
- a laminated film of titanium (Ti) -aluminum (Al) -titanium (Ti) was sequentially formed as a gate electrode, and patterned by an etching process.
- a source electrode and a drain electrode were formed using Ti—Al—Ti to manufacture a plurality of thin film transistors (thin film TFTs).
- an interlayer insulating film having a through hole was formed on the formed thin film transistor and planarized.
- an indium tin oxide (ITO) electrode was formed as an anode through the through hole. After patterning so as to surround the periphery of the ITO electrode with a single layer of polyimide resin, the substrate on which the ITO electrode was formed was ultrasonically cleaned and baked at 200 ° C. under reduced pressure for 3 hours.
- UGH2 (1,4-bistriphenylsilylbenzene) and Compound 1 (mer form) were co-evaporated on the hole transport layer by a vacuum deposition method to form an organic light emitting layer.
- doping was performed so that about 7.5% of the compound 1 was contained in the host material UGH2.
- UGH2 having a thickness of 5 nm is formed as a hole blocking layer on the organic light emitting layer, and 1,3,5-tris (N-phenylbenzimidazol-2-yl) is further formed on the hole blocking layer.
- Benzene (TPBI) was deposited by a vacuum deposition method to form an electron transport layer having a thickness of 30 nm on the hole blocking layer.
- LiF lithium fluoride
- Al aluminum
- a laminated film of LiF and Al was formed as a cathode, and an organic EL element (organic light emitting element) was produced.
- the current efficiency (luminous efficiency) at 1000 cd / m 2 of the obtained organic EL element was measured. As a result, the current efficiency was 12.2 cd / A, the emission wavelength was 2.8 eV (440 nm), and blue light emission with good efficiency was exhibited.
- Examples 3 to 8 and Comparative Examples 1 and 2 An organic EL device (organic light-emitting device) was prepared in the same manner as in Example 2 except that the dopant (luminescent material) doped in the organic light-emitting layer was changed to the compounds shown in Table 2, and the resulting organic EL device was obtained.
- the current efficiency (luminescence efficiency) and emission wavelength at 1000 cd / m 2 of the device were measured. The results are shown in Table 2. In Examples 3 to 8, mer bodies were used, and in Comparative Examples 1 and 2, mer bodies were used.
- the organic EL device using the compounds 1 to 7 which are the light emitting materials of the present example has higher light emission efficiency (current efficiency) than the organic EL device using the conventional compounds 1 and 2 as the light emitting material.
- )Met In addition to compound 6, the emission wavelength was 460 nm or less (2.69 eV or more), and good blue emission was exhibited.
- Example 9 a wavelength-converting light-emitting element that converts the light from the organic light-emitting element to red using the blue organic light-emitting element (organic EL element) including the light-emitting material of one embodiment of the present invention, A wavelength conversion light-emitting element that converts the light from the organic light-emitting element into green is produced.
- organic EL substrate A reflective electrode is formed by depositing silver with a thickness of 100 nm on a 0.7 mm-thick glass substrate by sputtering, and indium-tin oxide (ITO) is formed thereon with a thickness of 20 nm.
- ITO indium-tin oxide
- a reflective electrode anode
- the first electrode was patterned into 90 stripes having an electrode width of 2 mm by a conventional photolithography method.
- 200 nm of SiO 2 is laminated on the first electrode (reflecting electrode) by sputtering, and patterned to cover the edge portion of the first electrode (reflecting electrode) by a conventional photolithography method.
- a cover was formed.
- the edge cover has a structure in which the short side of the reflective electrode is covered with SiO 2 by 10 ⁇ m from the end. After washing with water, pure water ultrasonic cleaning was performed for 10 minutes, acetone ultrasonic cleaning for 10 minutes, and isopropyl alcohol vapor cleaning for 5 minutes, followed by drying at 100 ° C. for 1 hour.
- the dried substrate was fixed to a substrate holder in an inline type resistance heating vapor deposition apparatus, and the pressure was reduced to a vacuum of 1 ⁇ 10 ⁇ 4 Pa or less to form each organic layer of the organic EL layer.
- TAPC 1,1-bis-di-4-tolylamino-phenyl-cyclohexane
- N, N′-di-1-naphthyl-N, N′-diphenyl-1,1′-biphenyl-1,1′-biphenyl-4,4′-diamine is used as the hole transport material.
- a hole transport layer having a film thickness of 40 nm was formed on the hole injection layer by resistance heating vapor deposition.
- a blue organic light emitting layer was formed at a desired pixel position on the hole transport layer.
- This blue organic light-emitting layer is composed of 1,4-bis-triphenylsilyl-benzene (UGH-2) (host material) and compound 1 with a deposition rate of 1.5 ⁇ / sec and 0.2 ⁇ / sec, respectively. It was prepared by co-evaporation with. Subsequently, a hole blocking layer (thickness: 10 nm) was formed on the organic light emitting layer by using 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP). Next, an electron transport layer (thickness: 30 nm) was formed on the hole blocking layer using tris (8-hydroxyquinoline) aluminum (Alq3). Next, an electron injection layer (thickness: 0.5 nm) was formed on the electron transport layer using lithium fluoride (LiF). Through the above treatment, each organic layer of the organic EL layer was formed.
- a semitransparent electrode was formed as a second electrode on the electron injection layer.
- the substrate on which the electron injection layer was formed as described above was fixed in a metal vapor deposition chamber, and the shadow mask for forming the translucent electrode (second electrode) was aligned with the substrate.
- the shadow mask a mask having an opening so that a translucent electrode (second electrode) can be formed in a stripe shape having a width of 2 mm in a direction opposite to the stripe of the reflective electrode (first electrode) is used. .
- magnesium and silver are co-deposited on the surface of the electron injection layer of the organic EL layer by a vacuum deposition method at a deposition rate of 0.1 ⁇ / sec and 0.9 ⁇ ⁇ / sec, respectively, so that the magnesium silver has a desired pattern. Formation (thickness: 1 nm). Furthermore, silver is formed in a desired pattern at a deposition rate of 1 mm / sec (thickness: 19 nm) for the purpose of emphasizing the interference effect and preventing voltage drop due to wiring resistance at the second electrode. )did. A semitransparent electrode (second electrode) was formed by the above treatment.
- a microcavity effect appears between the reflective electrode (first electrode) and the semi-transmissive electrode (second electrode), and the front luminance can be increased.
- a red phosphor layer was separately formed on a 0.7 mm glass substrate with a red color filter, and a green phosphor layer was separately formed on a 0.7 mm glass substrate with a green color filter.
- the red phosphor layer was formed according to the following procedure. First, 15 g of ethanol and 0.22 g of ⁇ -glycidoxypropyltriethoxysilane were added to 0.16 g of aerosol having an average particle diameter of 5 nm, and the mixture was stirred for 1 hour at room temperature in an open system.
- the prepared red phosphor layer forming coating solution was applied to the red pixel position on the glass substrate with CF with a width of 3 mm by screen printing. Then, it heat-dried for 4 hours in the vacuum oven (200 degreeC, 10 mmHg conditions), and formed the 90-micrometer-thick red fluorescent substance layer.
- the green phosphor layer was formed by the following procedure. First, 15 g of ethanol and 0.22 g of ⁇ -glycidoxypropyltriethoxysilane were added to 0.16 g of an aerosol having an average particle diameter of 5 nm, and the mixture was stirred at room temperature for 1 hour. Transfer this mixture and green phosphor (pigment) Ba 2 SiO 4 : Eu 2+ 20 g to a mortar, mix well, then heat in an oven at 70 ° C. for 2 hours, and further heat in an oven at 120 ° C. for 2 hours. Thus, surface-modified Ba 2 SiO 4 : Eu 2+ was obtained.
- the green phosphor layer-forming coating solution was prepared by stirring the above.
- the produced green phosphor layer forming coating solution was applied to the green pixel position on the glass substrate 16 with CF with a width of 3 mm by screen printing. Then, it heat-dried for 4 hours in the vacuum oven (200 degreeC, 10 mmHg conditions), and formed the 60-micrometer-thick green fluorescent substance layer.
- the phosphor substrate on which the red phosphor layer was formed and the phosphor substrate on which the green phosphor layer was formed were prepared by the above processing.
- the organic EL substrate and the phosphor substrate manufactured as described above are aligned by the alignment marker formed outside the pixel arrangement position. Went.
- a thermosetting resin was applied to the phosphor substrate before alignment. After alignment, both substrates were brought into close contact with each other through a thermosetting resin, and cured by heating at 90 ° C. for 2 hours. The bonding process of both substrates was performed in a dry air environment (water content: ⁇ 80 ° C.) in order to prevent the organic EL layer from being deteriorated by water.
- the terminal formed in the periphery was connected to the external power supply. As a result, good green light emission and red light emission were obtained.
- Example 10 A display device in which the organic light emitting elements (organic EL elements) prepared in Examples 2 to 8 were arranged in a matrix of 100 ⁇ 100 was prepared, and a moving image was displayed.
- the display device is arranged in a matrix of 100 ⁇ 100, an image signal output unit that generates an image signal, a scan electrode drive circuit that generates an image signal from the image signal output unit, and a drive unit that has a signal drive circuit.
- a light emitting unit having an organic light emitting element (organic EL element) All the display devices obtained good images with high color purity. Moreover, even when the display device was repeatedly produced, there was no variation between devices, and a display device having excellent in-plane uniformity was obtained.
- Example 11 An illumination device including a drive unit that generates current and a light-emitting unit that emits light based on the current generated from the drive unit was manufactured.
- an organic light emitting element organic EL element
- an organic light emitting element organic EL element
- a voltage was applied to the organic light-emitting device and it was turned on, a uniform surface-emitting illuminating device having a curved surface shape was obtained without using indirect illumination leading to loss of luminance.
- the manufactured lighting device could also be used as a backlight for a liquid crystal display panel.
- Example 12 The light conversion light emitting element shown in FIG. 5 was produced.
- the light conversion light emitting element was produced in the following procedure. First, the steps up to the formation of the electron transport layer of Example 1 were performed in the same manner, and then NTCDA (naphthalene tetracarboxylic acid) as a photoelectric material layer was formed to 500 nm on the electron transport layer. Next, an Au electrode formed of an Au thin film having a thickness of 20 nm was formed on the NTCDA layer. Here, a part of the Au electrode was drawn out to the end of the element substrate through a predetermined pattern of wiring integrally formed of the same material, and connected to the negative electrode of the drive power supply.
- NTCDA naphthalene tetracarboxylic acid
- a part of the ITO electrode is drawn out to the end of the element substrate through a predetermined pattern of wiring integrally formed of the same material, and is connected to the positive electrode of the drive power supply.
- a predetermined voltage is applied between the pair of electrodes (ITO electrode, Au electrode).
- a positive voltage was applied to the ITO electrode side, and a monochromatic light having a wavelength of 335 nm was irradiated to the Au electrode side, and the photocurrent at room temperature was emitted from the compound 1 at that time.
- Luminous illuminance (wavelength 442 nm) was measured for each applied voltage and measured for the applied voltage, and a photomultiplier effect was observed when driven at 20 V.
- Example 13 A dye laser shown in FIG. 7 was produced.
- a dye laser was prepared in the XeCl excimer (excitation wavelength: 308 nm) using Compound 1 (in degassed acetonitrile solution: concentration 1 ⁇ 10 ⁇ 4 M) as a laser dye, the oscillation wavelength was 430 to 450 nm.
- a phenomenon was observed in which the intensity increased around 440 nm.
- a hole injection layer having a thickness of 20 nm was formed on the substrate. Thereafter, N, N-dicarbazoyl-3,5-benzene (mCP) and compound 1 (mer form) were co-evaporated by a vacuum deposition method to form an organic light emitting layer. At this time, the doping was performed so that about 5.0% of the compound 1 was contained in the host material mCP.
- 1,4-bis-triphenylsilyl-benzene having a thickness of 5 nm is formed as a hole blocking layer on the organic light emitting layer
- 1,3,5-tris N— Phenylbenzimidazol-2-yl) benzene (TPBI) was deposited by a vacuum deposition method to form an electron transport layer having a thickness of 30 nm on the hole blocking layer.
- MgAg 9: 1, film thickness: 2.5 nm
- an ITO film was formed by sputtering to form a 20 nm organic laser diode light emitting device.
- the laser Nd: YAG laser SHG, 532 nm, 10 Hz, 0.5 ns
- the ASE oscillation characteristic was investigated.
- oscillation started at 1.0 ⁇ J / cm 2
- an ASE oscillation in which the peak luminance increased in proportion to the excitation intensity was observed.
- the light emitting material of the aspect of the present invention can be used for, for example, an organic electroluminescence element (organic EL element), a wavelength conversion light emitting element, a light conversion light emitting element, a photoelectric conversion element, a laser dye, an organic laser diode element, and the like. Also, it can be used for a display device and a lighting device using each light emitting element.
- organic EL layer (organic layer), 18R ... red Phosphor layer, 18G ... green phosphor layer, 19 ... edge cover, 30 ... wavelength conversion light emitting element, 31 ... scattering layer, 40 ... light conversion light emitting element, 50 ... organic laser diode element, 60 ... dye laser, 70 ... illumination apparatus.
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Abstract
Description
本願は、2010年10月6日に、日本に出願された特願2010-226740号に基づき優先権を主張し、その内容をここに援用する。
また、電子吸引基を導入せずとも、カルベン配位子を用いた錯体において、短波長の発光が可能であることが報告されている(非特許文献6および特許文献1参照)。
そのため、電子吸引基を導入せずとも高い発光効率で青色を発光しうる発光材料の開発が望まれる。
本発明の態様は、このような従来の実情に鑑みてなされたものであり、高効率な発光材料及びこれを用いた有機発光素子、波長変換発光素子、光変換発光素子、有機レーザーダイオード発光素子、色素レーザー、表示装置並びに照明装置を提供するものである。
本発明の一態様である発光材料は、前記遷移金属錯体が、下記一般式(1)又は下記一般式(2)で表される部分構造を有していてもよい。
(一般式(1)および(2)中、MはIr、OsまたはPtを表し、XはCまたはSiを表し、R11、R12およびR13はそれぞれ独立に、1価の有機基を表し、Yは2価の炭化水素基を表し、Zは2価の有機基を表し、Vは環構造を有する2価の有機基を表す。)
本発明の一態様である発光材料は、前記遷移金属錯体が、下記一般式(3)または下記一般式(4)で表される部分構造を有していてもよい。
(一般式(3)および(4)中、MはIr、OsまたはPtを表し、XはCまたはSiを表し、R11、R12、R13およびR14はそれぞれ独立に、1価の有機基を表し、Yは2価の炭化水素基を表し、Dは電子供与性原子を表し、Vは環構造を有する2価の有機基を表す。)
本発明の一態様である発光材料は、前記遷移金属錯体が、下記一般式(5)または下記一般式(6)で表される部分構造を有していてもよい。
(一般式(5)および(6)中、MはIr、OsまたはPtを表し、XはCまたはSiを表し、R11、R12、R13およびR14はそれぞれ独立に、1価の有機基を表し、Yは2価の炭化水素基を表し、Vは環構造を有する2価の有機基を表す。)
本発明の一態様である発光材料は、前記遷移金属錯体が、下記一般式(7)または下記一般式(8)で表される部分構造を有していてもよい。
(一般式(7)および(8)中、MはIr、OsまたはPtを表し、XはCまたはSiを表し、R11、R12、R13、R14、R15、R16、R17、およびR18はそれぞれ独立に、1価の有機基を表し、Yは2価の炭化水素基を表す。)
本発明の一態様である発光材料は、前記遷移金属錯体が、下記一般式(9)で表される部分構造を有するIr錯体であってもよい。
(一般式(9)中、R11、R12、R13、R14、R15、R16、R17、およびR18はそれぞれ独立に、1価の有機基を表す。)
本発明の一態様である発光材料は、前記遷移金属錯体が、3つの2座配位子が配位したトリス体であり、mer体(meridional)がfac体(facial)よりも多く含有されてなってもよい。
本発明の一態様である有機発光素子において、前記発光材料が前記発光層に含有されていてもよい。
本発明の一態様である波長変換発光素子は、有機発光素子と、前記有機発光素子の光を取り出す面側に配され、前記有機発光素子からの発光を吸収して、吸収光とは異なる波長の発光を行うよう構成された蛍光体層とを備え、前記有機発光素子は、発光層を含む少なくとも一層の有機層と、前記有機層を狭持する一対の電極からなり、前記有機層は、中心金属がIr、OsまたはPtのいずれかであり、配位子として、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるカルベン配位子、または、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるシリレン配位子を、少なくとも1つ有する遷移金属錯体を含有する。
本発明の一態様である波長変換発光素子は、発光素子と、この発光素子の光を取り出す面側に配され、前記発光素子からの発光を吸収して、吸収光とは異なる波長の発光を行うよう構成された蛍光体層とを備え、前記蛍光体層は、中心金属がIr、OsまたはPtのいずれかであり、配位子として、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるカルベン配位子、または、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるシリレン配位子を、少なくとも1つ有する遷移金属錯体を含有する。
本発明の一態様である光変換発光素子は、発光層を含む少なくとも一層の有機層と、電流を増幅させる層と、前記有機層と前記電流を増幅させる層を狭持する一対の電極とを備え、前記発光層は、ホスト材料と、中心金属がIr、OsまたはPtのいずれかであり、配位子として、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるカルベン配位子、または、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるシリレン配位子を、少なくとも1つ有する遷移金属錯体とを有する。
本発明の一態様である色素レーザーは、発光材料を含むレーザー媒質と、前記レーザー媒質の前記発光材料からの燐光を誘導放出させてレーザー発振させる励起用光源を備え、前記発光材料は、中心金属がIr、OsまたはPtのいずれかであり、配位子として、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるカルベン配位子、または、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるシリレン配位子を、少なくとも1つ有する遷移金属錯体である。
本発明の一態様である表示装置は、画像信号を発生する画像信号出力部と、前記画像信号出力部からの信号に基づき電流もしくは電圧を発生する駆動部と、前記駆動部からの電流もしくは電圧により発光する発光部とを備え、前記発光部が有機発光素子と、前記有機発光素子の光を取り出す面側に配され、前記有機発光素子からの発光を吸収して、吸収光とは異なる波長の発光を行うよう構成された蛍光体層とを備え、前記有機発光素子は、発光層を含む少なくとも一層の有機層と、前記有機層を狭持する一対の電極からなり、前記有機層は、中心金属がIr、OsまたはPtのいずれかであり、配位子として、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるカルベン配位子、または、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるシリレン配位子を、少なくとも1つ有する遷移金属錯体を含有する波長変換発光素子である。
本発明の一態様である表示装置は、画像信号を発生する画像信号出力部と、前記画像信号出力部からの信号に基づき電流もしくは電圧を発生する駆動部と、前記駆動部からの電流もしくは電圧により発光する発光部とを備え、前記発光部が発光層を含む少なくとも一層の有機層と、電流を増幅させる層と、前記有機層と前記電流を増幅させる層を狭持する一対の電極とを備え、前記発光層は、ホスト材料と、中心金属がIr、OsまたはPtのいずれかであり、配位子として、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるカルベン配位子、または、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるシリレン配位子を、少なくとも1つ有する遷移金属錯体とを有する光変換発光素子である。
本発明の一態様である電子機器は、上述の表示装置を有していてもよい。
本発明の一態様である表示装置において、前記発光部の陽極と陰極がマトリックス状に配置されていてもよい。
本発明の一態様である表示装置において、前記発光部が、薄膜トランジスタによって駆動されてもよい。
本発明の一態様である照明装置は、電流もしくは電圧を発生する駆動部と、前記駆動部からの電流もしくは電圧により発光する発光部とを備え、前記発光部が有機発光素子と、前記有機発光素子の光を取り出す面側に配され、前記有機発光素子からの発光を吸収して、吸収光とは異なる波長の発光を行うよう構成された蛍光体層とを備え、前記有機発光素子は、発光層を含む少なくとも一層の有機層と、前記有機層を狭持する一対の電極からなり、前記有機層は、中心金属がIr、OsまたはPtのいずれかであり、配位子として、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるカルベン配位子、または、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるシリレン配位子を、少なくとも1つ有する遷移金属錯体を含有する波長変換発光素子である。
本発明の一態様である照明装置は、電流もしくは電圧を発生する駆動部と、前記駆動部からの電流もしくは電圧により発光する発光部とを備え、前記発光部が発光層を含む少なくとも一層の有機層と、電流を増幅させる層と、前記有機層と前記電流を増幅させる層を狭持する一対の電極とを備え、前記発光層は、ホスト材料と、中心金属がIr、OsまたはPtのいずれかであり、配位子として、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるカルベン配位子、または、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるシリレン配位子を、少なくとも1つ有する遷移金属錯体とを有する光変換発光素子である。
本発明の一態様である照明機器は、上述の照明装置を有していてもよい。
<発光材料>
本実施形態の発光材料は、中心金属がIr、OsまたはPtのいずれかであり、配位子として、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるカルベン配位子、または、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるシリレン配位子を、少なくとも1つ有する遷移金属錯体からなる。本実施形態の発光材料である遷移金属錯体において、中心金属がIrまたはOsである場合は、6配位の正八面体型構造となり、中心金属がPtである場合は4配位の平面四角形型構造となる。
(一般式(1)および(2)中、MはIr、OsまたはPtを表し、XはCまたはSiを表し、R11、R12およびR13はそれぞれ独立に、1価の有機基を表し、Yは2価の炭化水素基を表し、Zは2価の有機基を表し、Vは環構造を有する2価の有機基を表す。)
R11、R12およびR13である炭素数1~8の脂肪族炭化水素基としては、直鎖状、分岐鎖状または環状の脂肪族炭化水素基が挙げられ、具体的には、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、tert-ブチル基、n-ペンチル基、n-ヘキシル基、n-ヘプチル基、n-オクチル基、シクロヘキシル基等が挙げられる。R11およびR12は、それらの一部が結合して一体化し、環構造を形成していてもよい。
R11、R12およびR13である炭素数1~10の芳香族基としては、フェニル基、ナフチル基などが挙げられ、これらの芳香族基は置換基を有していてもよい。
Vである環構造を有する2価の有機基としては、芳香族性を有する環状の2価の有機基が挙げられ、芳香族炭化水素基、または窒素および炭素を含む芳香族基が好ましい。Vである環構造を有する2価の有機基としては、具体的には下記一般式(V-1)~(V-5)で表されるものが好ましい。
(一般式(3)および(4)中、MはIr、OsまたはPtを表し、XはCまたはSiを表し、R11、R12、R13およびR14はそれぞれ独立に、1価の有機基を表し、Yは2価の炭化水素基を表し、Dは電子供与性原子を表し、Vは環構造を有する2価の有機基を表す。)
R14である1価の有機基としては、炭素数1~8の脂肪族炭化水素基、または炭素数1~10の芳香族基が挙げられる。R14である脂肪族炭化水素基および芳香族基は、置換基を有していてもよい。
R14である炭素数1~8の脂肪族炭化水素基としては、直鎖状、分岐鎖状または環状の脂肪族炭化水素基が挙げられ、具体的には、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、tert-ブチル基、n-ペンチル基、n-ヘキシル基、n-ヘプチル基、n-オクチル基、シクロヘキシル基等が挙げられる。R11およびR12は、それらの一部が結合して一体化し、環構造を形成していてもよい。
R14である炭素数1~10の芳香族基としては、フェニル基、ナフチル基などが挙げられ、これらの芳香族基は置換基を有していてもよい。
Dである電子供与性原子としては、具体的には、C、N、P、O、Sが挙げられ、中でもCまたはNが好ましく、Nが特に好ましい。
本実施形態の発光材料は、一例として、下記一般式(5)または下記一般式(6)で表される部分構造を有する遷移金属錯体であることが好ましい。
(一般式(5)および(6)中、MはIr、OsまたはPtを表し、XはCまたはSiを表し、R11、R12、R13およびR14はそれぞれ独立に、1価の有機基を表し、Yは2価の炭化水素基を表し、Vは環構造を有する2価の有機基を表す。)
さらに、本実施形態の発光材料は、一例として、下記一般式(7)または下記一般式(8)で表される部分構造を有する遷移金属錯体であることが好ましい。
(一般式(7)および(8)中、MはIr、OsまたはPtを表し、XはCまたはSiを表し、R11、R12、R13、R14、R15、R16、R17、およびR18はそれぞれ独立に、1価の有機基を表し、Yは2価の炭化水素基を表す。)
また、本実施形態の発光材料は、一例として、下記一般式(9)で表される部分構造を有するIr錯体であることが特に好ましい。
また、本実施形態の発光材料は、中心金属がIrまたはOsである場合、3つの2座配位子が配位したトリス体であることが好ましい。この場合、mer体(meridional)とfac体(facial)の幾何異性体が存在するが、本実施形態の発光材料は、mer体およびfac体のいずれでもよく、mer体とfac体が混在していてもよい。中でも、後述の実施例に示す如く、mer体がfac体よりも多く含有されてなることが、PL量子収率が良好となるため好ましい。
特にホウ素原子を含むカルベン骨格を含む配位子を金属錯体に用いると、後述の実施例に示す如く、効率良く発光する結果が得られた。ホウ素は高いルイス酸性を有し、空のp軌道があり、しかも電子受容性が強い性質を有する。また、NとBが結合することでC=C結合に近い性質を有することが知られている。今回、C=C結合よりも電荷の局在化が大きく、電子余剰状態を作り出し、かつ少なくとも1つ以上の芳香環(環電流効果により、電子が動きやすくなる)をカルベン部位に形成させることにより、MLCTでの発光機構が優勢になり、発光効率がよくなったと考えられる。
また、金属中心に電子を供与できるものとして、カルベン同様にオクテット則を満たさない構造を金属錯体として含むものが本実施形態の発光材料として好ましい。オクテット則を満たさないことにより、電子供与性が強く、金属中心への電子供与性が大きくなり、MLCTでの元々の金属部位の電子供与性を大きくすることができたと考えられる。結果としてMLCT性を増大させることができる。従って、本実施形態の発光材料としては、カルベン錯体以外に、特にσドナー性が強いという観点で、シリレン(Si)錯体も好ましい。
遷移金属錯体である化合物(a-5)の合成は、例えば、Dalton Trans., 2008, 916等を参照しながら行うことができる。[IrCl(COD)]2(COD=1,5-シクロオクタジエン)1当量に対して、化合物(a-4)6当量を加え、さらに酸化銀を加えて加熱還流することにより化合物(a-5)を合成することができる。なお、化合物(a-5)のようなトリス体の場合、幾何異性体であるmer体とfac体が存在するが、これら幾何異性体は再結晶などの方法により分離可能である。
なお、合成した発光材料である遷移金属錯体の同定は、MSスペクトル(FAB-MS)、1H-NMRスペクトル、LC-MSスペクトル等より行うことができる。
<有機発光素子>
本実施形態の有機発光素子(有機EL素子)は、発光層を含む少なくとも一層の有機層が、一対の電極間に狭持されて構成されている。
図1は、本実施形態に係る有機発光素子の第1実施形態を示す概略構成図である。図1に示す有機発光素子10は、基板(図示略)上に、第1電極12、有機EL層(有機層)17、第2電極16がこの順に積層されて構成されている。図1に示す例では、第1電極12と第2電極16により狭持された有機EL層17は、正孔輸送層13と有機発光層14と電子輸送層15とがこの順に積層されて構成されている。
(1)有機発光層14
(2)正孔輸送層13/有機発光層14
(3)有機発光層14/電子輸送層15
(4)正孔注入層/有機発光層14
(5)正孔輸送層13/有機発光層14/電子輸送層15
(6)正孔注入層/正孔輸送層13/有機発光層14/電子輸送層15
(7)正孔注入層/正孔輸送層13/有機発光層14/電子輸送層15/電子注入層
(8)正孔注入層/正孔輸送層13/有機発光層14/正孔防止層/電子輸送層15
(9)正孔注入層/正孔輸送層13/有機発光層14/正孔防止層/電子輸送層15/電子注入層
(10)正孔注入層/正孔輸送層13/電子防止層/有機発光層14/正孔防止層/電子輸送層15/電子注入層
ここで、有機発光層14、正孔注入層、正孔輸送層13、正孔防止層、電子防止層、電子輸送層15及び電子注入層の各層は、単層構造でも多層構造でもよい。
これらの正孔注入層、正孔輸送層13、電子注入層、及び電子輸送層15は、それぞれ、従来公知の材料を用いることができる。正孔注入層、正孔輸送層13、電子注入層、及び電子輸送層15は、それぞれ以下に例示する材料のみから構成されていてもよい。正孔注入層、正孔輸送層13、電子注入層、及び電子輸送層15は、それぞれ、以下に例示する材料に任意に添加剤(ドナー、アクセプター等)等を含んでいてもよい。正孔注入層、正孔輸送層13、電子注入層、及び電子輸送層15は、以下に例示する材料が高分子材料(結着用樹脂)又は無機材料中に分散された構成であってもよい。
正孔注入層を形成する材料としては、例えば、銅フタロシアニン等のフタロシアニン誘導体、4,4’,4”-トリス(3-メチルフェニルフェニルアミノ)トリフェニルアミン、4,4’,4”-トリス(1-ナフチルフェニルアミノ)トリフェニルアミン、4,4’,4”-トリス(2-ナフチルフェニルアミノ)トリフェニルアミン、4,4’,4”-トリス[ビフェニル-2-イル(フェニル)アミノ]トリフェニルアミン、4,4’,4”-トリス[ビフェニル-3-イル(フェニル)アミノ]トリフェニルアミン、4,4’,4”-トリス[ビフェニル-4-イル(3-メチルフェニル)アミノ]トリフェニルアミン、4,4’、4”-トリス[9,9-ジメチル-2-フルオレニル(フェニル)アミノ]トリフェニルアミン等のアミン化合物、酸化バナジウム(V2O5)、酸化モリブデン(MoO2)等の酸化物等が挙げられるが、これらに限定されるものではない。
アクセプター材料としては、Au、Pt、W、Ir、POCl3、AsF6、Cl、Br、I、酸化バナジウム(V2O5)、酸化モリブデン(MoO2)等の無機材料、TCNQ(7,7,8,8,-テトラシアノキノジメタン)、TCNQF4(テトラフルオロテトラシアノキノジメタン)、TCNE(テトラシアノエチレン)、HCNB(ヘキサシアノブタジエン)、DDQ(ジシクロジシアノベンゾキノン)等のシアノ基を有する化合物、TNF(トリニトロフルオレノン)、DNF(ジニトロフルオレノン)等のニトロ基を有する化合物、フルオラニル、クロラニル、ブロマニル等の有機材料が挙げられる。これらの中でも、TCNQ、TCNQF4、TCNE、HCNB、DDQ等のシアノ基を有する化合物が、キャリア濃度を効果的に増加させることが可能であるためより好ましい。
電子防止層としては、正孔輸送層13及び正孔注入層として前記したものと同じものを使用することができる。
電子注入層を構成する材料としては、特に、フッ化リチウム(LiF)、フッ化バリウム(BaF2)等のフッ化物、酸化リチウム(Li2O)等の酸化物等が挙げられる。
陰極である第2電極16から電子の注入および輸送をより効率よく行う点で、電子注入層として用いる材料としては、電子輸送層15に使用する材料より最低空分子軌道(LUMO)のエネルギー準位が高い材料を用いることが好ましく、電子輸送層15として用いる材料としては、電子注入層に使用する材料より電子の移動度が高い材料を用いることが好ましい。
ドナー材料としては、アルカリ金属、アルカリ土類金属、希土類元素、Al、Ag、Cu、In等の無機材料、アニリン類、フェニレンジアミン類、N,N,N’,N’-テトラフェニルベンジジン、N,N’-ビス-(3-メチルフェニル)-N,N’-ビス-(フェニル)-ベンジジン、N,N’-ジ(ナフタレン-1-イル)-N,N’-ジフェニル-ベンジジン等のベンジジン類、トリフェニルアミン、4,4’4''-トリス(N,N-ジフェニル-アミノ)-トリフェニルアミン、4,4’4''-トリス(N-3-メチルフェニル-N-フェニル-アミノ)-トリフェニルアミン、4,4’4''-トリス(N-(1-ナフチル)-N-フェニル-アミノ)-トリフェニルアミン等のトリフェニルアミン類、N,N’-ジ-(4-メチル-フェニル)-N,N’-ジフェニル-1,4-フェニレンジアミン等のトリフェニルジアミン類の芳香族3級アミンを骨格にもつ化合物、フェナントレン、ピレン、ペリレン、アントラセン、テトラセン、ペンタセン等の縮合多環化合物(ただし、縮合多環化合物は置換基を有してもよい)、TTF(テトラチアフルバレン)類、ジベンゾフラン、フェノチアジン、カルバゾール等の有機材料がある。これらの中でも、芳香族3級アミンを骨格にもつ化合物、縮合多環化合物、アルカリ金属がよりキャリア濃度を効果的に増加させることが可能であるためより好ましい。
正孔防止層としては、電子輸送層15及び電子注入層として前記したものと同じものを使用することができる。
第1電極12及び第2電極16を形成する電極材料としては公知の電極材料を用いることができる。陽極である第1電極12を形成する材料としては、有機EL層17への正孔の注入をより効率よく行う観点から、仕事関数が4.5eV以上の金(Au)、白金(Pt)、ニッケル(Ni)等の金属、及び、インジウム(In)と錫(Sn)からなる酸化物(ITO)、錫(Sn)の酸化物(SnO2)インジウム(In)と亜鉛(Zn)からなる酸化物(IZO)等が挙げられる。また、陰極である第2電極16を形成する電極材料としては、有機EL層17への電子の注入をより効率よく行う観点から、仕事関数が4.5eV以下のリチウム(Li)、カルシウム(Ca)、セリウム(Ce)、バリウム(Ba)、アルミニウム(Al)等の金属、又は、これらの金属を含有するMg:Ag合金、Li:Al合金等の合金が挙げられる。
第1電極12及び第2電極16の膜厚は、50nm以上が好ましい。第1電極12及び第2電極16の膜厚が50nm未満の場合には、配線抵抗が高くなることから、駆動電圧の上昇が生じるおそれがある。
[第2実施形態]
基板1としては、例えば、ガラス、石英等からなる無機材料基板、ポリエチレンテレフタレート、ポリカルバゾール、ポリイミド等からなるプラスティック基板、アルミナ等からなるセラミックス基板等の絶縁性基板、アルミニウム(Al)、鉄(Fe)等からなる金属基板、前記基板上に酸化シリコン(SiO2)などの有機絶縁材料等からなる絶縁物を表面にコーティングした基板、又は、Al等からなる金属基板の表面を陽極酸化等の方法で絶縁化処理を施した基板等が挙げられるが、本実施形態はこれらに限定されるものではない。
TFT回路2は、公知の材料、構造及び形成方法を用いて形成することができる。TFT回路2の活性層の材料としては、例えば、非晶質シリコン(アモルファスシリコン)、多結晶シリコン(ポリシリコン)、微結晶シリコン、セレン化カドミウム等の無機半導体材料、酸化亜鉛、酸化インジウム-酸化ガリウム-酸化亜鉛等の酸化物半導体材料又は、ポリチオフェン誘導体、チオフエンオリゴマー、ポリ(p-フェリレンビニレン)誘導体、ナフタセン、ペンタセン等の有機半導体材料が挙げられる。また、TFT回路2の構造としては、例えば、スタガ型、逆スタガ型、トップゲート型、コプレーナ型が挙げられる。
層間絶縁膜3の形成方法としては、化学気相成長(CVD)法、真空蒸着法等のドライプロセス、スピンコート法等のウエットプロセスが挙げられる。また、必要に応じてフォトリソグラフィー法等によりパターニングすることもできる。
本実施形態の有機発光素子20においては、有機EL素子10からの発光を封止基板9側から取り出すため、外光が基板1上に形成されたTFT回路2に入射して、TFT特性に変化が生じることを防ぐ目的で、遮光性を兼ね備えた層間絶縁膜3(遮光性絶縁膜)を用いることが好ましい。また、本実施形態においては、層間絶縁膜3と遮光性絶縁膜とを組み合わせて用いることもできる。遮光性絶縁膜としては、フタロシアニン、キナクロドン等の顔料又は染料をポリイミド等の高分子樹脂に分散したもの、カラーレジスト、ブラックマトリクス材料、NixZnyFe2O4等の無機絶縁材料等が挙げられる。
平坦化膜4は、公知の材料を用いて形成することができ、例えば、酸化シリコン、窒化シリコン、酸化タンタル等の無機材料、ポリイミド、アクリル樹脂、レジスト材料等の有機材料等が挙げられる。平坦化膜4の形成方法としては、CVD法、真空蒸着法等のドライプロセス、スピンコート法等のウエットプロセスが挙げられるが、本実施形態はこれらの材料及び形成方法に限定されるものではない。また、平坦化膜4は、単層構造でも多層構造でもよい。
また、反射電極11及び第1電極12は、層間絶縁膜3及び平坦化膜4を貫通して設けられた配線2bにより、TFT回路2の1つに接続されている。第2電極16は、層間絶縁膜3、平坦化膜4及びエッジカバー19を貫通して設けられた配線2aによりTFT回路2の1つに接続されている。配線2a、2bは、導電性の材料より構成されていればよく、特に限定されないが、例えば、Cr、Mo、Ti、Ta、Al、Al合金、Cu、Cu合金等の材料より構成されている。配線2a、2bは、スパッタリングまたはCVD法、及びマスク工程等の従来公知の方法により形成される。
無機封止膜5上には、封止基板9が設けられており、基板1と封止基板9間に形成された有機発光素子10は、封止材6に囲まれた封止領域に封入されている。
無機封止膜5および封止材6を設けることにより、外部から有機EL層17内へ酸素や水分や混入することを防止することができ、有機発光素子20の寿命を向上させることができる。
封止材6は、従来公知の封止材料を用いることができ、封止材6の形成方法も従来公知の封止方法を用いることができる。
封止材6としては、例えば、樹脂(硬化性樹脂)を用いることができる。この場合は、有機EL素子10及び無機封止膜5が形成された基材1の無機封止膜5の上面および/または側面、或いは、封止基板9上に、硬化性樹脂(光硬化性樹脂、熱硬化性樹脂)をスピンコート法、ラミネート法を用いて塗布し、基板1と封止基板9とを樹脂層を介して貼り合わせて、光硬化または熱硬化することにより封止材6を形成することができる。なお、封止材6は光透過性を有する必要がある。
また、無機封止膜5と封止材6との間に窒素ガス、アルゴンガス等の不活性ガスを注入してもよく、窒素ガス、アルゴンガス等の不活性ガスをガラス等の封止基板9で封止する方法が挙げられる。
この場合、水分による有機EL部の劣化を効果的に低減するためには、封入する不活性ガス中に、酸化バリウム等の吸湿剤等を混入することが好ましい。
本実施形態の波長変換発光素子は、発光素子と、この発光素子の光を取り出す面側に配され、当該発光素子からの発光を吸収して、吸収光とは異なる波長の発光を行う蛍光体層を備えて構成される。
図3は、本実施形態に係る波長変換発光素子の第1実施形態を示す概略断面図であり、図4は図3に示す有機発光素子の上面図である。図3に示す波長変換発光素子30は、前記した本実施形態の有機発光素子からの青色発光を吸収して、赤色に変換する赤色蛍光体層18Rと、青色発光を吸収して緑色に変換する緑色蛍光体層18Gを備えている。以下、これらの赤色蛍光体層18R、緑色蛍光体層18Gを総称して「蛍光体層」と称することがある。図3に示す波長変換発光素子30において、前記した本実施形態の有機発光素子10、20と同一の構成要素には同一の符号を付し、説明を省略する。
なお、図4に示す例では各RGB画素(各カラーフィルター8R、8G、8B)がストライプ配列された例を示しているが、本実施形態はこれに限定されず、各RGB画素の配列はモザイク配列、デルタ配列など、従来公知のRGB画素配列とすることもできる。
緑色蛍光体層18Gは、光源である有機発光素子10から発光された青色領域の光を吸収して、緑色領域の光に変換して封止基材9側に緑色領域の光を放出する。
散乱層31は、光源である有機発光素子10から発光された青色領域の光の視野角特性、取り出し効率を高める目的で設けられるものであり、封止基材9側に青色領域の光を放出する。なお、散乱層31は省略することが可能である。
このように赤色蛍光体層18R、緑色蛍光体層18G(および散乱層31)を設ける構成とすることにより、有機発光素子10から放出された光を変換して、赤色、緑色、青色の三色の光を封止基板9側から射出することにより、フルカラー表示することができる。
カラーフィルター8R、8G、8Bとしては、特に限定されず、従来公知のカラーフィルターを用いることが可能である。また、カラーフィルター8R、8G、8Bの形成方法も従来公知の方法を用いることができ、その膜厚も適宜調整可能である。
散乱層31に使用されるバインダー樹脂としては、従来公知のものを使用することができ、特に限定されるものではないが、光透過性を有するものが好ましい。透明粒子としては、有機発光素子10からの光を散乱、透過させることができるものであれば特に限定されず、例えば、平均粒径25μm、粒度分布の標準偏差1μmのポリスチレン粒子等を使用することができる。また、散乱層31中の透明粒子の含有量は、適宜変更可能であり、特に限定されない。
散乱層31は、従来公知の方法で形成することができ、特に限定されるものではないが、例えば、バインダー樹脂と透明粒子とを溶剤に溶解、分散させた塗液を用いて、スピンコーティング法、ディッピング法、ドクターブレード法、吐出コート法、スプレーコート法等の塗布法、インクジェット法、凸版印刷法、凹版印刷法、スクリーン印刷法、マイクログラビアコート法等の印刷法等による公知のウエットプロセス等により形成することができる。
緑色蛍光体層18Gは、有機発光素子10から発光された青色領域の光を吸収して励起し、緑色領域の蛍光を発光することのできる蛍光体材料を含んでなる。
赤色蛍光体層18R及び緑色蛍光体層18Gは、以下に例示する蛍光体材料のみから構成されていてもよく、任意に添加剤等を含んで構成されてもよく、これらの材料が高分子材料(結着用樹脂)または無機材料中に分散して構成されてもよい。
赤色蛍光体層18R及び緑色蛍光体層18Gを形成する蛍光体材料としては、従来公知の蛍光体材料を用いることができる。このような蛍光体材料は、有機系蛍光体材料と無機系蛍光体材料とに分類される。これらの蛍光体材料について、具体的な化合物を以下に例示するが、本実施形態はこれらの材料に限定されるものではない。
また、赤色蛍光体層18R及び緑色蛍光体層18Gが、前記蛍光体材料が高分子材料(結着用樹脂)に分散して構成されている場合、高分子材料として、感光性の樹脂を用いることで、フォトリソグラフィー法により、パターン化が可能となる。ここで、上記感光性樹脂としては、アクリル酸系樹脂、メタクリル酸系樹脂、ポリ桂皮酸ビニル系樹脂、及び、硬ゴム系樹脂等の反応性ビニル基を有する感光性樹脂(光硬化型レジスト材料)のうち、一種類または複数種類の混合物を用いる事が可能である。
半透明電極の材料としては、金属の半透明電極を単体で用いたり、金属の半透明電極と透明電極材料の組み合わせを用いたりすることができる。特に、半透明電極材料としては、反射率及び透過率の観点から、銀又は銀合金を用いることが好ましい。
半透明電極である第2電極16の膜厚は、5nm~30nmが好ましい。仮に半透明電極の膜厚が5nm未満の場合には、光の反射が十分行えず、干渉の効果を十分得るとこができない可能性がある。また、半透明電極の膜厚が30nmを超える場合には、光の透過率が急激に低下することから、輝度及び効率が低下するおそれがある。
なお、第2電極16として半透明電極を用いることによって、各蛍光体層18R、18G及び散乱層31の光取り出し方向とは反対方向に放出される光を再利用することもできる。
ここで、各蛍光体層18R及び18Gにおける変換光の発光位置から光取り出し面までの光学距離は、各蛍光体層18R及び18Gの膜厚により調整される。各蛍光体層18R、18Gの膜厚は、スクリーン印刷法の印刷条件(スキージ印圧、スキージアタック角度、スキージ速度、もしくはクリアランス巾)、スクリーン版の仕様(スクリーン紗の選定、乳剤の厚み、テンション、もしくは枠の強度)、または、蛍光体形成用塗液の仕様(粘度、流動性、もしくは樹脂、顔料、及び溶剤の配合比率)を変えることによって調節することができる。
また、上記実施形態では、本実施形態の発光材料を用いてなる有機発光素子10を光源(発光素子)として用いたが、本実施形態はこれに限定されない。発光素子として、他の発光材料を用いた有機EL、無機EL、LED(発光ダイオード)等の光源を用い、この発光素子(光源)からの光を吸収して青色の光を放出する蛍光体層として、本実施形態の発光材料を含有してなる層を設けることも可能である。この際、光源である発光素子は、青色よりも短波長の光(紫外光)を発光することが望ましい。
本実施形態の光変換発光素子は、前記本実施形態の発光材料が含有されてなる発光層を含む少なくとも一層の有機層と、電流を増幅させる層と、有機層と電流を増幅させる層を狭持する一対の電極を有する。
図5は、本実施形態に係る光変換発光素子の一実施形態を示す概略模式図である。図5に示す光変換発光素子40は、光電流増倍効果による光電変換を利用し、得た電子をEL発光の原理を用いて再び光に変換するである。
図5に示す光変換発光素子40は、素子基板41と、下部電極42と、有機EL層17と、有機光電材料層43と、Au電極44とを有する。素子基板41は、透明なガラス基板からなる。下部電極42は、素子基板41の一方の面上に形成され、ITO電極等からなる。下部電極42上に、有機EL層17と、有機光電材料層43と、Au電極44が順次積層形成されている。下部電極42には駆動電源の+極が接続され、Au電極44には駆動電源の-極が接続されている。
有機光電材料層43は、電流を増幅させる光電効果を示し、NTCDA(ナフタレンテトラカルボン酸)層1層のみの構成としてもよいし、感度波長域が選択可能な複層で構成することもできる。例えば、Me-PTC(ペリレン顔料)層とNTCDA層の2層で構成することもできる。有機光電材料層43の厚さは特に限定されず、例えば、10nm程度~100nm程度とされ、真空蒸着法などにより形成される。
本実施形態の光変換発光素子40は、前記した第1実施形態の発光材料を含む有機EL層17を備えるため、発光効率をより良好なものとすることができる。
本実施形態の有機レーザーダイオード発光素子は、励起光源(連続波励起光源を含む)と、この励起光源が照射される共振器構造とを含む。該共振器構造は、レーザー活性層を含む少なくとも一層の有機層を一対の電極間に狭持させてなる。
図6は、本実施形態に係る有機レーザーダイオード発光素子の一実施形態を示す概略模式図である。図6に示す有機レーザーダイオード発光素子50は、レーザー光を発光する励起光源50aと、共振器構造50bよりなる。共振器構造50bは、ITO基板51と、正孔輸送層52と、レーザー活性層53と、正孔ブロック層54と、電子輸送層55と、電子注入層56と、電極57を有する。ITO基板51上に、正孔輸送層52、レーザー活性層53、正孔ブロック層54、電子輸送層55、電子注入層56、電極57が順次積層形成されている。ITO基板51に形成されたITO電極は駆動電源の+極に接続され、電極57は駆動電源の-極に接続されている。
図7は、本実施形態に係る色素レーザーの一実施形態を示す概略模式図である。図7に示す色素レーザー60は、励起用光源61と、色素セル62と、レンズ66と、部分反射鏡65と、回折格子63と、ビームエキスパンダー64を有する。励起用光源61は、ポンプ光67を発光する。レンズ66は、ポンプ光67を色素セル62に集光する。部分反射鏡65は、色素セル62を挟んでビームエキスパンダー64と対向配置されている。ビームエキスパンダー64は、回折格子63と色素セル62の間に配されている。ビームエキスパンダー64は、回折格子63からの光を集光する。色素セル62は、石英ガラス等で形成されている。色素セル62内には、本実施形態の発光材料を含む溶液であるレーザー媒質が満たされている。
本実施形態の色素レーザー60において、励起用光源61よりポンプ光67を発光すると、このポンプ光67はレンズ66により色素セル62に集光され、色素セル62のレーザー媒質中の本実施形態の発光材料を励起し、発光させる。発光材料からの発光は、色素セル62の外部に放出され、部分反射鏡62および回折格子63間で反射、増幅される。増幅された光は、部分反射鏡65を通過して外部へと射出される。このように、本実施形態の発光材料は、色素レーザーにも応用することができる。
<表示装置>
本実施形態の表示装置は、画像信号出力部と、駆動部と、発光部とを有する。画像信号出力部は、画像信号を発生する。駆動部は、画像信号出力部からの信号に基づき電流もしくは電圧を発生する。発光部は、駆動部からの電流もしくは電圧により発光する。本実施形態の表示装置において、発光部は、前記した本実施形態の有機発光素子、波長変換発光素子、光変換発光素子のいずれかより構成されている。以下の説明においては、発光部が本実施形態の有機発光素子である場合を例示して説明するが、本実施形態はこれに限定されず、本実施形態の表示装置において、発光部は波長変換発光素子や光変換発光素子より構成されることもできる。
図8に示すように、本実施形態の表示装置70は、有機発光素子20の基板1に対し平面視マトリクス状に走査線101と信号線102とが配線されている。各走査線101は基板1の一側縁部に設けられる走査回路103に接続されている。各信号線102は基板1の他側縁部に設けられる映像信号駆動回路104に接続されている。より具体的には走査線101と信号線102との交差部分のそれぞれの近傍に、図2に示す有機発光素子20の薄膜トランジスタなどの駆動素子(TFT回路2)が設けられている。各駆動素子には、画素電極が接続されている。これらの画素電極が図2に示す構造の有機発光素子20の反射電極11に対応し、これらの反射電極11が第1電極12に対応されている。
有機発光素子20の有機EL発光部10を駆動させる駆動部は、走査回路103、映像信号駆動回路104、有機EL電源回路112を有する。走査線101および信号線102により区画された各領域内に、図2に示す有機発光素子20のTFT回路2が形成されている。
本実施形態の表示装置は、本実施形態の発光材料を用いてなる有機発光素子、波長変換発光素子または光変換発光素子のいずれかを発光部として備えることにより、良好な発光効率の表示装置となる。
図10は、本実施形態に係る照明装置の一実施形態を示す概略斜視図である。図10に示す照明装置70は、電流もしくは電圧を発生する駆動部71と、この駆動部71からの電流もしくは電圧により発光する発光部72とを備えてなる。本実施形態の照明装置において、発光部72は、前記した実施形態の有機発光素子、波長変換発光素子、光変換発光素子のいずれかより構成されている。以下の説明においては、発光部が実施形態の有機発光素子10である場合を例示して説明するが、本実施形態はこれに限定されず、本実施形態の照明装置において、発光部は波長変換発光素子や光変換発光素子より構成されることもできる。
なお、照明装置70の発光部72として本実施形態の有機発光素子10を使用する場合、有機発光素子10の有機発光層14には、本実施形態の遷移金属錯体に加えて、従来公知の有機EL発光材料が含有されていてもよい。
本実施形態の照明装置70は、本実施形態の発光材料を用いてなる有機発光素子、波長変換発光素子または光変換発光素子のいずれかを発光部として備えることにより、良好な発光効率の照明装置70となる。
以下の合成例において、各段階の化合物、及び最終化合物(遷移金属錯体)は、MSスペクトル(FAB-MS)により同定した。
(合成例1;化合物1の合成)
以下のルートで化合物1を合成した。
化合物A(0.1mol)をメチルアミン(0.5mol)水溶液に滴下した。数分間撹拌後、固体が析出した。反応溶液に水を添加し、分液処理により固体を濾過し、乾燥させて化合物Bを得た。収率:82%。
化合物Cの合成:
化合物B(10.2mmol)をTHF(テトラヒドロフラン)に溶解させた溶液中に、n-BuLi(10.2mmol)の ヘキサン溶液をゆっくりと室温下、添加した。30分後、トリメチルシリルクロライド(10.2mmol)を添加した。その後、溶媒を減圧除去し、エーテルで抽出して化合物Cを得た。収率:93%。
化合物Dの合成:
BBr3(10mol)に-50℃中、攪拌下、Sn(CH3)4(5mol)を添加し、1時間攪拌した。その後、溶媒を減圧除去し、エーテルで抽出して化合物Dを得た。収率:80%。
化合物Eの合成:
メチルアミン(10mmol)の溶解したヘキサン溶液中に、n-BuLi(9mmol)を-10℃で滴下し、この溶液中にジブロモメチルボラン(化合物D:9mmol)のヘキサン溶液(50mL)を-20℃でゆっくり滴下した。室温に戻し、1日攪拌を続けた。その後、LiCl及び、過剰のLi[N(H)CH3]を取り除くために濾過し、溶媒を減圧除去し、エーテルで再結晶化して化合物Eを得た。収率:70%。
化合物E(10.2mmol)をトルエン20mLに溶解させた溶液を、-78℃中、化合物C(10.2mmol)をトルエン10mLに溶解させた溶液に、攪拌下、滴下した。室温下に戻し、1時間攪拌を行い、溶媒を減圧除去した。その後、ヘキサンで抽出して化合物Fを得た。収率:80%。
化合物Gの合成:
ジブロモフェニルボラン(化合物D)と化合物Fをクロロホルム20mLに溶解させ、1.5日間還流させた。室温に戻し、溶媒を減圧除去し、ヘキサンで残留物を洗い流して化合物Gを得た。収率:82%。
化合物1の合成:
2-エトキシエタノール(10mL)中に[IrCl(COD)]2(COD=1,5-シクロオクタジエン)(0.15mmol)と化合物G(0.90mmol)と酸化銀(0.90mmol)を添加し、24時間遮光下、還流した。フラッシュクロマトグラフィー(シリカゲル/クロロホルム)により精製した。更に、ジクロロメタンに溶解させ、ヘキサンを添加して再結晶化させ、目的のmer体の化合物1を得た。収率:45%、FAB-MS(+):m/e=832。
以下のルートで化合物2を合成した。
ジエトキシメタン (0.05mol)とアニリン(化合物A’、0.1mol)と氷酢酸0.25mLの混合物を2時間還流し、副生成物と未反応物を減圧除去して化合物B’を得た。収率:80%。
化合物D、化合物Eは化合物1の合成と同じ化合物であり、化合物C’、化合物F’及び化合物G’の合成は、化合物1と同じ当量関係、反応温度で行った。
化合物2の合成:
化合物2の合成は、化合物1と同じ当量関係、反応温度で行った。クロロホルムにより再結晶することにより、目的のmer体の化合物2を白い固体として得た。収率:80%、FAB-MS(+):m/e=1018。
化合物Eを、N-(ブロモ(メチル)ボリル)-2-メチルプロパン-2-アミンに置き換えた以外は、合成例2と同様にして化合物3(mer体)を得た。収率:60%、FAB-MS(+):m/e=1143。
(合成例4;化合物4の合成)
化合物Aを、(E)-N-シアノ-N-(2,4-ジメチルフェニル)ホルムアミジンに置き換えた以外は、合成例1と同様にして化合物4(mer体)を得た。収率:70%、FAB-MS(+):m/e=915。
(合成例5;化合物5の合成)
化合物Aを、(E)-N’-(4-tert-ブチルフェニル)-N-シアノホルムアミジンに置き換えた以外は、合成例1と同様にして化合物5(mer体)を得た。収率:72%、FAB-MS(+):m/e=999。
(合成例6;化合物6の合成)
化合物DをN-(ブロモ(フェニル)ボリル)メタンアミンに置き換え、化合物Eをジブロモ(フェニル)ボランに置き換えた以外は、合成例2と同様にして化合物6(mer体)を得た。収率:65%、FAB-MS(+):m/e=1516。
以下のルートで化合物7を合成した。
[IrCl(COD)]2(COD=1,5-シクロオクタジエン)1当量に対し、4当量の化合物Hと、過剰量のメトキシナトリウムを混合した2-エトキシエタノール溶液を3時間加熱還流後、クロマトグラフィーにより分離し、化合物Jを得た。収率:50%。
化合物7の合成:
化合物J(0.08mmol)と化合物G(0.16mmol)と酸化銀(1.0mmol)とTHF20mLの混合溶液を、3時間加熱還流した後、反応溶液をクロマトグラフィーにより分離し、化合物7(mer体)を得た。収率:60%、FAB-MS(+):m/e=691。
化合物1と化合物3について、fac体とmer体の混合錯体(fac体:mer体=5:1)と、mer体のみの錯体について、脱気したトルエン溶液中のPL量子収率を測定した。PL量子収率の測定は以下の手順で行った。まず、各化合物の発光スペクトルをPL測定装置FluoroMax-4(HORIBA社製、励起波長380nm)で測定し、吸光度を吸光度測定装置UV-2450(島津製作所社製)で測定した。次に、PL量子収率が既知の参照資料fac-Ir(ppy)3と各化合物の励起波長(380nm)における吸光度を合わせ、その発光強度を比較することにより、PL量子収率を算出した。結果を表1に示す。
(実施例2)
ガラス基板上にプラズマ化学蒸着(プラズマCVD)法によってシリコン半導体膜を形成し、結晶化処理を施した後、多結晶半導体膜(多結晶シリコン薄膜)を形成した。続いて多結晶シリコン薄膜をエッチング処理し、複数の島状パターンを形成した。次に多結晶シリコン薄膜の各島の上に窒化ケイ素(SiN)をゲート絶縁膜として形成した。その後、チタン(Ti)-アルミニウム(Al)-チタン(Ti)の積層膜をゲート電極として順次形成し、エッチング処理によってパターニングを行った。当該ゲート電極の上に、Ti-Al-Tiを用いてソース電極およびドレイン電極を形成し、複数の薄膜トランジスタ(薄膜TFT)を作製した。
次に、形成した薄膜トランジスタ上にスルーホールを有する層間絶縁膜を形成して平坦化した。そして、当該スルーホールを介して酸化インジウムスズ(ITO)電極を陽極として形成した。ポリイミド系樹脂の単層でITO電極の周辺を取り囲むようにしてパターニングした後、ITO電極を形成した基板を超音波洗浄し、200℃の減圧下で3時間ベークした。
その後、正孔注入層上にN,N-ジカルバゾイル-3,5-ベンゼン(mCP)を真空蒸着法によって蒸着速度1Å/secで蒸着して、正孔注入層上に膜厚15nmの正孔輸送層を形成した。
次に、正孔輸送層上に2,8-ビス(ジフェニルフォスフォリル)ジベンゾチオフェン(PPT)を蒸着した(膜厚:50nm)。
次いで、正孔輸送層上に、UGH2(1,4-ビストリフェニルシリルベンゼン)と、化合物1(mer体)とを真空蒸着法によって共蒸着して有機発光層を形成した。この際、ホスト材料であるUGH2中に化合物1が7.5%程度含まれるようにドープした。続いて、有機発光層上に、膜厚5nmのUGH2を正孔ブロック層として形成し、さらに、正孔ブロック層上に1,3,5-トリス(N-フェニルベンズイミダゾル-2-イル)ベンゼン(TPBI)を真空蒸着法によって蒸着して、正孔ブロック層上に膜厚30nmの電子輸送層を形成した。
続いて、電子輸送層上にフッ化リチウム(LiF)を真空蒸着法によって蒸着速度1Å/secで蒸着し、膜厚0.5nmのLiF膜を形成した。その後、LiF膜上にアルミニウム(Al)を用いて膜厚100nmのAl膜を形成した。このようにして、LiFとAlとの積層膜を陰極として形成し、有機EL素子(有機発光素子)を作製した。
得られた有機EL素子の1000cd/m2における電流効率(発光効率)を測定した。その結果、電流効率は12.2cd/A、発光波長は2.8eV(440nm)となり、良好な効率の青色発光を示した。
有機発光層にドープするドーパント(発光材料)を、表2記載の化合物に変更したこと以外は、実施例2と同様の手法で有機EL素子(有機発光素子)を作製し、得られた有機EL素子の1000cd/m2における電流効率(発光効率)及び発光波長を測定した。
結果を表2に併記した。なお、実施例3~8ではいずれもmer体を使用し、比較例1及び2ではmer体を使用した。
(実施例9)
本実施例では、本発明の一態様の発光材料を含む青色の有機発光素子(有機EL素子)を利用して、この有機発光素子からの光を赤色へ色変換する波長変換発光素子と、この有機発光素子からの光を緑色への色変換する波長変換発光素子をそれぞれ作製した。
〈有機EL基板の形成〉
0.7mmの厚みのガラス基板上に、スパッタ法により銀を膜厚100nmとなるよう成膜して反射電極を形成し、その上にインジウム-スズ酸化物(ITO)を、膜厚20nmとなるようスパッタ法により成膜することによって、第1電極として反射電極(陽極)を形成した。その後、従来のフォトリソグラフィー法により、第1電極を電極幅が2mm幅の90本のストライプにパターニングした。
次に、第1電極(反射電極)上に、スパッタ法によりSiO2を200nm積層し、従来のフォトリソグラフィー法により第1電極(反射電極)のエッジ部を覆うようにパターン化することによって、エッジカバーを形成した。エッジカバーは、反射電極の短辺を端から10μm分だけSiO2で覆う構造とした。これを水洗後、純水超音波洗浄を10分、アセトン超音波洗浄を10分、イソプロピルアルコール蒸気洗浄を5分行い、100℃にて1時間乾燥させた。
まず、正孔注入材料として1,1-ビス-ジ-4-トリルアミノ-フェニル-シクロヘキサン(TAPC)を用い、抵抗加熱蒸着法により膜厚100nmの正孔注入層を形成した。
次いで、正孔輸送材料としてN,N’-ジ-1-ナフチル-N,N’-ジフェニル-1,1’-ビフェニル-1,1’-ビフェニル-4,4’-ジアミン(NPD)を用い、抵抗加熱蒸着法により正孔注入層上に膜厚40nmの正孔輸送層を形成した。
次に、正孔輸送層上の所望の画素位置に、青色の有機発光層(厚さ:30nm)を形成した。この青色の有機発光層は、1,4-ビス-トリフェニルシリル-ベンゼン(UGH-2)(ホスト材料)と、化合物1とを、それぞれ1.5Å/sec、0.2Å/secの蒸着速度で共蒸着することによって作製した。
続いて、有機発光層上に、2,9-ジメチルー4,7-ジフェニル-1,10-フェナントロリン(BCP)を用いて、正孔防止層(厚さ:10nm)を形成した。
次いで、正孔防止層上に、トリス(8-ヒドロキシキノリン)アルミニウム(Alq3)を用いて電子輸送層(厚さ:30nm)を形成した。
次に、電子輸送層上に、フッ化リチウム(LiF)を用いて電子注入層(厚さ:0.5nm)を形成した。
以上の処理によって、有機EL層の各有機層を成膜した。
以上の処理によって、有機EL部が形成された有機EL基板を作製した。
次に、赤色蛍光体層を0.7mmの赤色カラーフィルター付きガラス基板上に、緑色蛍光体層を0.7mmの緑色カラーフィルター付きガラス基板上に、それぞれ別々に形成した。
赤色蛍光体層の形成は、次の手順で行った。まず、平均粒径5nmのエアロゾル0.16gにエタノール15g及びγ-グリシドキシプロピルトリエトキシシラン0.22gを加えて、開放系室温下で1時間攪拌した。この混合物と、赤色蛍光体(顔料)K5Eu2.5(WO4)6.2520gとを乳鉢に移し、よくすり混ぜた後、70℃のオーブンで2時間加熱し、さらに120℃のオーブンで2時間加熱することによって、表面改質したK5Eu2.5(WO4)6.25を得た。次に、表面改質を施したK5Eu2.5(WO4)6.2510gに、水/ジメチルスルホキシド=1/1の混合溶液(300g)で溶解されたポリビニルアルコール30gを加え、分散機により攪拌することによって、赤色蛍光体層形成用塗液を作製した。作製された赤色蛍光体層形成用塗液を、スクリーン印刷法により3mm幅で、CF付きガラス基板上における赤色画素位置に塗布した。その後、真空オーブン(200℃、10mmHgの条件)で4時間加熱乾燥し、厚さ90μmの赤色蛍光体層を形成した。
以上の処理により赤色蛍光体層が形成された蛍光体基板、及び緑色蛍光体層が形成された蛍光体基板をそれぞれ作製した。
赤色の波長変換発光素子及び緑色の波長変換発光素子の各々について、以上のようにして作製した有機EL基板と蛍光体基板とを、画素配置位置の外側に形成されている位置合わせマーカーにより位置合わせを行った。なお、蛍光体基板には、位置合わせ前に熱硬化樹脂を塗布した。
位置合わせ後、熱硬化樹脂を介して両基板を密着し、90℃、2時間加熱することによって硬化を行った。なお、両基板の貼り合わせ工程は、有機EL層が水分により劣化することを防止するために、ドライエアー環境下(水分量:-80℃)で行った。
得られた各波長変換発光素子について、周辺に形成した端子を外部電源に接続した。その結果、良好な緑色発光、および赤色発光が得られた。
(実施例10)
実施例2~8で作成した有機発光素子(有機EL素子)をそれぞれ100×100のマトリクス状に配列した表示装置を作成し、動画を表示させた。表示装置は、画像信号を発生する画像信号出力部と、前記画像信号出力部からの画像信号を発生する走査電極駆動回路と信号駆動回路を有する駆動部と100×100のマトリクス状に配列された有機発光素子(有機EL素子)を有する発光部とを備えている構成とした。いずれの表示装置も色純度の高い良好な画像が得られた。また、繰り返し表示装置を作成しても、装置間のばらつきがなく、面内均一性の優れた表示装置が得られた。
(実施例11)
電流を発生する駆動部と前記駆動部から発生した電流に基づいて発光する発光部とを備えている照明装置を作製した。本実施例では、フィルム基板上に有機発光素子(有機EL素子)を形成したこと以外は、実施例2~8と同様の手法で有機発光素子(有機EL素子)を作製し、この有機発光素子を発光部とした。この有機発光装置に電圧を印加し点灯したところ、輝度の損失につながる間接照明を用いることなく、局面状の均一な面発光照明装置が得られた。また作製した照明装置は、液晶表示パネルのバックライトとして用いることもできた。
(実施例12)
図5に示す光変換発光素子を作製した。
光変換発光素子は、次の手順で作製した。まず、実施例1の電子輸送層形成までの工程を同様の方法で行い、その後、電子輸送層上に、光電材料層としてNTCDA(ナフタレンテトラカルボン酸)を500nm形成した。次に、NTCDA層上に厚さ20nmのAu薄膜で形成されたAu電極を形成した。ここで、Au電極の一部は、同一材料により一体形成された所定パターンの配線を介して素子基板の端部に引き出され、駆動電源の-極に接続されるようにした。同様に、ITO電極の一部も、同一材料により一体形成された所定パターンの配線を介して素子基板の端部に引き出されて、駆動電源の+極に接続されるようにした。また、これら一対の電極(ITO電極、Au電極)間には所定の電圧が印加されるようにした。
以上の工程により作製した光変換発光素子について、ITO電極側をプラスに電圧印加し、波長335nmの単色光をAu電極側に照射した時の室温における光電流と、その時の化合物1から発光された発光照度(波長442nm)をそれぞれの印加電圧に対して測定し、印加電圧に対して測定を行ったところ、20V駆動時、光電子増倍効果を観測した。
(実施例13)
図7に示す色素レーザーを作製した。
XeClエキシマー中(励起波長:308nm)中に、レーザー色素として化合物1(脱気したアセトニトリル溶液中:濃度1×10-4M)を用いる構成として色素レーザーを作製したところ、発振波長が430~450nmで、強度が440nm付近で強くなる現象を観測した。
(実施例14)
H. Yamamoto et al., Appl. Phys. Lett., 2004, 84, 1401を参照して、図6に示す構成の有機レーザーダイオード発光素子を作製した。
有機レーザーダイオード発光素子は、次の手順で作製した。まず、実施例1と同様にして陽極まで作製した。
続いて、陽極上に4,4’-ビス[N-(1-ナフチル)-N-フェニル-アミノ]ビフェニル(α-NPD)を真空蒸着法によって蒸着速度1Å/secで蒸着して、陽極上に膜厚20nmの正孔注入層を形成した。
その後、N,N-ジカルバゾイル-3,5-ベンゼン(mCP)と化合物1(mer体)とを真空蒸着法によって共蒸着して有機発光層を形成した。この際、ホスト材料であるmCP中に化合物1が5.0%程度含まれるようにドープした。次に、有機発光層上に膜厚5nmの1,4-ビス-トリフェニルシリル-ベンゼン(UGH-2)を正孔ブロック層として形成し、その上に1,3,5-トリス(N-フェニルベンズイミダゾル-2-イル)ベンゼン(TPBI)を真空蒸着法によって蒸着して、正孔ブロック層上に膜厚30nmの電子輸送層を形成した。
続いて、電子輸送層上にMgAg(9:1、膜厚2.5nm)を真空蒸着法によって蒸着し、ITO膜をスパッタ法により20nm形成することにより、有機レーザーダイオード発光素子を作製した。
作製した有機レーザーダイオード発光素子について、陽極側からレーザー(Nd:YAG laser SHG、532nm、10Hz、0.5ns)を当てて、ASE発振特性について調べた。レーザーによる励起強度を変えて当てたところ、1.0μJ/cm2で発振が始まり、励起強度に比例してピーク輝度が増大するASE発振が観測された。
Claims (24)
- 中心金属がIr、OsまたはPtのいずれかであり、
配位子として、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるカルベン配位子、または、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるシリレン配位子を、少なくとも1つ有する遷移金属錯体からなる発光材料。 - 前記遷移金属錯体が、3つの2座配位子が配位したトリス体であり、mer体(meridional)がfac体(facial)よりも多く含有されてなる請求項1に記載の発光材料。
- 発光層を含む少なくとも一層の有機層と、
前記有機層を狭持する一対の電極からなり、
前記有機層は、中心金属がIr、OsまたはPtのいずれかであり、配位子として、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるカルベン配位子、または、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるシリレン配位子を、少なくとも1つ有する遷移金属錯体を含有する有機発光素子。 - 前記遷移金属錯体が前記発光層に含有されている請求項8に記載の有機発光素子。
- 有機発光素子と、
前記有機発光素子の光を取り出す面側に配され、前記有機発光素子からの発光を吸収して、吸収光とは異なる波長の発光を行うよう構成された蛍光体層とを備え、
前記有機発光素子は、発光層を含む少なくとも一層の有機層と、前記有機層を狭持する一対の電極からなり、前記有機層は、中心金属がIr、OsまたはPtのいずれかであり、配位子として、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるカルベン配位子、または、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるシリレン配位子を、少なくとも1つ有する遷移金属錯体を含有する波長変換発光素子。 - 発光素子と、
前記発光素子の光を取り出す面側に配され、前記発光素子からの発光を吸収して、吸収光とは異なる波長の発光を行うよう構成された蛍光体層とを備え、
前記蛍光体層は、中心金属がIr、OsまたはPtのいずれかであり、配位子として、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるカルベン配位子、または、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるシリレン配位子を、少なくとも1つ有する遷移金属錯体を含有する波長変換発光素子。 - 発光層を含む少なくとも一層の有機層と、
電流を増幅させる層と、
前記有機層と前記電流を増幅させる層狭持する一対の電極とを備え、
前記発光層は、ホスト材料と、中心金属がIr、OsまたはPtのいずれかであり、配位子として、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるカルベン配位子、または、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるシリレン配位子を、少なくとも1つ有する遷移金属錯体とを有する光変換発光素子。 - 励起光源と前記励起光源が照射される共振器構造とを含み、
前記共振器構造は、レーザー活性層を含む少なくとも一層の有機層と、前記有機層を狭持する一対の電極とを備え、
前記レーザー活性層は、ホスト材料と、中心金属がIr、OsまたはPtのいずれかであり、配位子として、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるカルベン配位子、または、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるシリレン配位子を、少なくとも1つ有する遷移金属錯体とを有する有機レーザーダイオード発光素子。 - 発光材料を含むレーザー媒質と、
前記レーザー媒質の前記発光材料からの燐光を誘導放出させてレーザー発振させる励起用光源を備え、
前記発光材料は、中心金属がIr、OsまたはPtのいずれかであり、配位子として、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるカルベン配位子、または、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるシリレン配位子を、少なくとも1つ有する遷移金属錯体である色素レーザー。 - 画像信号を発生する画像信号出力部と、
前記画像信号出力部からの信号に基づき電流もしくは電圧を発生する駆動部と、
前記駆動部からの電流もしくは電圧により発光する発光部とを備え、
前記発光部は、発光層を含む少なくとも一層の有機層と、前記有機層を狭持する一対の電極からなり、前記有機層は、中心金属がIr、OsまたはPtのいずれかであり、配位子として、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるカルベン配位子、または、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるシリレン配位子を、少なくとも1つ有する遷移金属錯体を含有する有機発光素子である表示装置。 - 画像信号を発生する画像信号出力部と、
前記画像信号出力部からの信号に基づき電流もしくは電圧を発生する駆動部と、
前記駆動部からの電流もしくは電圧により発光する発光部とを備え、
前記発光部が有機発光素子と、前記発光素子の光を取り出す面側に配され、前記有機発光素子からの発光を吸収して、吸収光とは異なる波長の発光を行うよう構成された蛍光体層とを備え、前記有機発光素子は、発光層を含む少なくとも一層の有機層と、前記有機層を狭持する一対の電極からなり、前記有機層は、中心金属がIr、OsまたはPtのいずれかであり、配位子として、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるカルベン配位子、または、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるシリレン配位子を、少なくとも1つ有する遷移金属錯体を含有する波長変換発光素子である表示装置。 - 画像信号を発生する画像信号出力部と、
前記画像信号出力部からの信号に基づき電流もしくは電圧を発生する駆動部と、
前記駆動部からの電流もしくは電圧により発光する発光部とを備え、
前記発光部が発光層を含む少なくとも一層の有機層と、電流を増幅させる層と、前記有機層と前記電流を増幅させる層狭持する一対の電極とを備え、前記発光層は、ホスト材料と、中心金属がIr、OsまたはPtのいずれかであり、配位子として、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるカルベン配位子、または、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるシリレン配位子を、少なくとも1つ有する遷移金属錯体とを有する光変換発光素子である表示装置。 - 前記発光部の陽極と陰極がマトリックス状に配置されている請求項15に記載の表示装置。
- 前記発光部が、薄膜トランジスタによって駆動される請求項19に記載の表示装置。
- 請求項15の表示装置を有する電子機器。
- 電流もしくは電圧を発生する駆動部と、
前記駆動部からの電流もしくは電圧により発光する発光部とを備え、
前記発光部が発光層を含む少なくとも一層の有機層と、前記有機層を狭持する一対の電極からなり、前記有機層は、中心金属がIr、OsまたはPtのいずれかであり、配位子として、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるカルベン配位子、または、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるシリレン配位子を、少なくとも1つ有する遷移金属錯体を含有する有機発光素子である照明装置。 - 電流もしくは電圧を発生する駆動部と、
前記駆動部からの電流もしくは電圧により発光する発光部とを備え、
前記発光部が有機発光素子と、前記有機発光素子の光を取り出す面側に配され、前記有機発光素子からの発光を吸収して、吸収光とは異なる波長の発光を行うよう構成された蛍光体層とを備え、前記有機発光素子は、発光層を含む少なくとも一層の有機層と、前記有機層を狭持する一対の電極からなり、前記有機層は、中心金属がIr、OsまたはPtのいずれかであり、配位子として、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるカルベン配位子、または、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるシリレン配位子を、少なくとも1つ有する遷移金属錯体を含有する波長変換発光素子である照明装置。 - 電流もしくは電圧を発生する駆動部と、
前記駆動部からの電流もしくは電圧により発光する発光部とを備え、
前記発光部が発光層を含む少なくとも一層の有機層と、電流を増幅させる層と、前記有機層と前記電流を増幅させる層狭持する一対の電極とを備え、前記発光層は、ホスト材料と、中心金属がIr、OsまたはPtのいずれかであり、配位子として、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるカルベン配位子、または、骨格中にホウ素原子を含む中性あるいはモノアニオン性、及び単座、二座あるいは三座であるシリレン配位子を、少なくとも1つ有する遷移金属錯体とを有する光変換発光素子である照明装置。 - 請求項21に記載の照明装置を有する照明機器。
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| CN201180048338.9A CN103154188B (zh) | 2010-10-06 | 2011-10-04 | 发光材料 |
| US13/877,901 US20130303777A1 (en) | 2010-10-06 | 2011-10-04 | Luminescent material, and organic light-emitting element, wavelength-converting light-emitting element, light-converting light-emitting element, organic laser diode light-emitting element, dye laser, display device, and illumination device using same |
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| JP2010-226740 | 2010-10-06 | ||
| JP2010226740 | 2010-10-06 |
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| WO2012046715A1 true WO2012046715A1 (ja) | 2012-04-12 |
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| PCT/JP2011/072833 Ceased WO2012046715A1 (ja) | 2010-10-06 | 2011-10-04 | 発光材料、及びこれを用いた有機発光素子、波長変換発光素子、光変換発光素子、有機レーザーダイオード発光素子、色素レーザー、表示装置並びに照明装置 |
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| US (1) | US20130303777A1 (ja) |
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| WO (1) | WO2012046715A1 (ja) |
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| WO2013172163A1 (ja) * | 2012-05-16 | 2013-11-21 | 株式会社ブイ・テクノロジー | 露光装置 |
| WO2014072874A1 (en) * | 2012-11-06 | 2014-05-15 | Empire Technology Development Llc | Organic phosphorescent materials and methods for their preparation and use |
| JP2017034281A (ja) * | 2016-10-31 | 2017-02-09 | コニカミノルタ株式会社 | 有機エレクトロルミネッセンス素子、表示装置及び照明装置 |
| JP2019090025A (ja) * | 2013-01-04 | 2019-06-13 | 日東電工株式会社 | 波長変換のための高蛍光性光安定性発色団 |
| JP2024107045A (ja) * | 2018-06-06 | 2024-08-08 | 株式会社半導体エネルギー研究所 | 発光装置、電子機器及び表示装置 |
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| CN103154189B (zh) * | 2010-10-06 | 2016-04-13 | 夏普株式会社 | 发光材料和使用其的有机发光元件、波长变换发光元件、光变换发光元件、有机激光二极管发光元件、色素激光器、显示装置以及照明装置 |
| US10622310B2 (en) | 2012-09-26 | 2020-04-14 | Ping-Jung Yang | Method for fabricating glass substrate package |
| US9615453B2 (en) | 2012-09-26 | 2017-04-04 | Ping-Jung Yang | Method for fabricating glass substrate package |
| TWI569491B (zh) * | 2012-10-11 | 2017-02-01 | Joled Inc | Organic EL display device and manufacturing method thereof, ink and electronic machine |
| US9590209B2 (en) * | 2012-11-08 | 2017-03-07 | Pioneer Corporation | Mirror device |
| KR102054369B1 (ko) * | 2013-05-30 | 2019-12-11 | 삼성디스플레이 주식회사 | 유기 발광 표시 장치 |
| DE102014106952A1 (de) * | 2014-05-16 | 2015-11-19 | Osram Oled Gmbh | Optoelektronisches Bauelement, Verfahren zum Herstellen eines optoelektronischen Bauelements |
| JPWO2016047229A1 (ja) * | 2014-09-26 | 2017-07-13 | コニカミノルタ株式会社 | 発光装置 |
| US10996515B2 (en) * | 2015-08-28 | 2021-05-04 | Samsung Display Co., Ltd. | Color conversion panel, display device comprising the same and manufacturing method of the color conversion panel |
| TWI621256B (zh) * | 2015-09-09 | 2018-04-11 | 群創光電股份有限公司 | 顯示裝置 |
| KR102609932B1 (ko) * | 2015-09-09 | 2023-12-04 | 이노럭스 코포레이션 | 디스플레이 디바이스 |
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| JP6613213B2 (ja) * | 2016-07-26 | 2019-11-27 | 株式会社Kokusai Electric | 半導体装置の製造方法、基板処理装置、およびプログラム |
| KR102477103B1 (ko) * | 2017-09-27 | 2022-12-13 | 삼성디스플레이 주식회사 | 표시 장치 및 그 제조방법 |
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| JP2024107045A (ja) * | 2018-06-06 | 2024-08-08 | 株式会社半導体エネルギー研究所 | 発光装置、電子機器及び表示装置 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103154188A (zh) | 2013-06-12 |
| US20130303777A1 (en) | 2013-11-14 |
| CN103154188B (zh) | 2015-05-20 |
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