Patent Application
20170271600
1. Field of the Invention
One embodiment of the present invention relates to an organometallic complex, and a light-emitting element, a display module, a lighting module, a display device, a light-emitting device, an electronic device, and a lighting device each including the organometallic complex. Note that one embodiment of the present invention is not limited to the above technical field. The technical field of one embodiment of the invention disclosed in this specification and the like relates to an object, a method, or a manufacturing method. Furthermore, one embodiment of the present invention relates to a process, a machine, manufacture, or a composition of matter. Specifically, examples of the technical field of one embodiment of the present invention disclosed in this specification include a semiconductor device, a display device, a liquid crystal display device, a light-emitting device, a lighting device, a power storage device, a memory device, a method for driving any of them, and a method for manufacturing any of them.
2. Description of the Related Art
As lighting devices or display devices, display devices using light-emitting elements (organic EL elements) in which organic compounds or organometallic complexes are used as light-emitting substances have been developed and reported because of their potential for thinness, lightness, high-speed response to input signals, low power consumption, and the like.
In an organic EL element, voltage application between electrodes between which a light-emitting layer is provided causes recombination of electrons and holes injected from the electrodes, which brings a light-emitting substance into an excited state, and the return from the excited state to the ground state is accompanied by light emission. Since the spectrum of light emitted from a light-emitting substance depends on the light-emitting substance, the use of light-emitting substances having different molecular structures makes it possible to obtain light-emitting elements which emit light of various colors.
Although displays or lighting devices including light-emitting elements can be suitably used for a variety of electronic devices as described above, their performance has plenty of room to improve. In order to achieve this, materials that have good characteristics are required.
Patent Document 1 discloses an organometallic complex having a 1,2,4-triazole skeleton.
An object of one embodiment of the present invention is to provide a novel organometallic complex. Another object of one embodiment of the present invention is to provide an organometallic complex emitting green to blue phosphorescence. Another object of one embodiment of the present invention is to provide an organometallic complex having a deep LUMO level and emitting green to blue phosphorescence. Another object of one embodiment of the present invention is to provide a light-emitting element with high emission efficiency. Another object of one embodiment of the present invention is to provide a light-emitting element emitting green to blue phosphorescence and having low drive voltage. Another object of one embodiment of the present invention is to provide a light-emitting device with low power consumption.
Another object of one embodiment of the present invention is to provide a novel light-emitting element. Another object of one embodiment of the present invention is to provide a display module, a lighting module, a light-emitting device, a display device, an electronic device, and a lighting device each having low power consumption.
It is only necessary that at least one of the above objects be achieved in one embodiment of the present invention. Note that the descriptions of these objects do not disturb the existence of other objects. In one embodiment of the present invention, there is no need to achieve all the objects. Other objects will be apparent from and can be derived from the description of the specification, the drawings, the claims, and the like.
One embodiment of the present invention is an organometallic complex including iridium and a ligand having a triazole skeleton. The triazole skeleton has a group including a pyridine ring or a group including a pyrimidine ring and an aryl group. One of nitrogen atoms included in the triazole skeleton is coordinated to the iridium. The aryl group is bonded to the iridium at the ortho position.
Another embodiment of the present invention is an organometallic complex represented by General Formula (G1) below.
Note that in General Formula (G1), each of R1 to R4 independently represents any of hydrogen, a saturated hydrocarbon group having 1 to 6 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 8 carbon atoms, and an aromatic hydrocarbon group having 6 to 13 carbon atoms. At least one of R1 and R20 represents a group including a pyridine ring or a group including a pyrimidine ring, and the other represents any of a saturated hydrocarbon group having 1 to 6 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 8 carbon atoms, an aromatic hydrocarbon group having 6 to 13 carbon atoms, a group including a pyridine ring, and a group including a pyrimidine ring.
Another embodiment of the present invention is an organometallic complex represented by General Formula (G2) below.
Note that in General Formula (G2), each of R1 to R4 and R11 to R14 independently represents any of hydrogen, a saturated hydrocarbon group having 1 to 6 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 8 carbon atoms, and an aromatic hydrocarbon group having 6 to 13 carbon atoms. R20 represents any of a saturated hydrocarbon group having 1 to 6 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 8 carbon atoms, an aromatic hydrocarbon group having 6 to 13 carbon atoms, a group including a pyridine ring, and a group including a pyrimidine ring.
Another embodiment of the present invention is an organometallic complex represented by General Formula (G3) below.
Note that in General Formula (G3), each of R1 to R4, R11 to R14, and R21 to R25 independently represents any of hydrogen, a saturated hydrocarbon group having 1 to 6 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 8 carbon atoms, and an aromatic hydrocarbon group having 6 to 13 carbon atoms.
Another embodiment of the present invention is an organometallic complex represented by General Formula (G4) below.
Note that in General Formula (G4), each of R11, R13, R14, and R21 independently represents any of hydrogen, a saturated hydrocarbon group having 1 to 6 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 8 carbon atoms, and an aromatic hydrocarbon group having 6 to 13 carbon atoms.
Another embodiment of the present invention is an organometallic complex represented by Structural Formula (100) below.
Another embodiment of the present invention is an organometallic complex represented by Structural Formula (101) below.
Another embodiment of the present invention is an organometallic complex represented by Structural Formula (102) below.
Another embodiment of the present invention is a light-emitting element including any one of the above organometallic complexes.
Another embodiment of the present invention is a light-emitting device including the above light-emitting element, and a transistor or a substrate.
Another embodiment of the present invention is an electronic device including the above light-emitting device, and a sensor, an operation button, a speaker, or a microphone.
Another embodiment of the present invention is a lighting device including the above light-emitting device and a housing.
Note that the light-emitting device in this specification includes, in its category, an image display device that uses a light-emitting element. The light-emitting device may be included in a module in which a light-emitting element is provided with a connector such as an anisotropic conductive film or a tape carrier package (TCP), a module in which a printed wiring board is provided at the end of a TCP, and a module in which an integrated circuit (IC) is directly mounted on a light-emitting element by a chip on glass (COG) method. The light-emitting device may be included in lighting equipment.
One embodiment of the present invention makes it possible to provide a novel organometallic complex. One embodiment of the present invention makes it possible to provide an organometallic complex emitting green to blue phosphorescence. One embodiment of the present invention makes it possible to provide an organometallic complex having a deep LUMO level and emitting green to blue phosphorescence. One embodiment of the present invention makes it possible to provide a light-emitting element with high emission efficiency. One embodiment of the present invention makes it possible to provide a light-emitting element emitting green to blue phosphorescence and having low drive voltage. One embodiment of the present invention makes it possible to provide a light-emitting device with low power consumption.
Another embodiment of the present invention makes it possible to provide a novel light-emitting element. Another embodiment of the present invention makes it possible to provide a display module, a lighting module, a light-emitting device, a display device, an electronic device, and a lighting device each having low power consumption.
It is only necessary that at least one of the above effects be achieved in one embodiment of the present invention. Note that the description of these effects does not preclude the existence of other effects. One embodiment of the present invention does not necessarily achieve all the effects listed above. Other effects will be apparent from and can be derived from the description of the specification, the drawings, the claims, and the like.
An embodiment and examples of the present invention will be described in detail below with reference to the drawings. It will be readily appreciated by those skilled in the art that modes and details of the present invention can be modified in various ways without departing from the spirit and scope of the present invention. Thus, the present invention should not be construed as being limited to the description in the following embodiment and examples.
One embodiment of the present invention is an organometallic complex having a 1,2,4-triazole skeleton. The organometallic complex includes a ligand having a group including a pyridine ring or a group including a pyrimidine ring at at least one of the 4-position and the 5-position of the 1,2,4-triazole skeleton. The organometallic complex includes iridium as a central metal. Note that the organometallic complex is preferably a tris-type organometallic complex in which three ligands as described above are coordinated.
The organometallic complex emits green to blue phosphorescence and has high efficiency. A light-emitting element including the organometallic complex as a light-emitting substance can emit green to blue phosphorescence. Note that although many light-emitting elements that emit green to blue phosphorescence have a high drive voltage and high power consumption, a light-emitting element which includes the organometallic complex of one embodiment of the present invention and emits green to blue phosphorescence can have a low drive voltage and low power consumption.
The organometallic complex of one embodiment of the present invention can be regarded as an organometallic complex having the structure represented by General Formula (G1) below.
Note that in General Formula (G1), each of R1 to R4 independently represents any of hydrogen, a saturated hydrocarbon group having 1 to 6 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 8 carbon atoms, and an aromatic hydrocarbon group having 6 to 13 carbon atoms. At least one of R10 and R20 represents a group including a pyridine ring or a group including a pyrimidine ring, and the other represents any of a saturated hydrocarbon group having 1 to 6 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 8 carbon atoms, an aromatic hydrocarbon group having 6 to 13 carbon atoms, a group including a pyridine ring, and a group including a pyrimidine ring.
The organometallic complex of one embodiment of the present invention preferably has a group including a pyridine ring at the 4-position of the 1,2,4-triazole skeleton because the LUMO level of the organometallic complex is lowered and electrons are easily injected into the organometallic complex when the organometallic complex is used for a light-emitting element. That is, the organometallic complex represented by General Formula (G2) below is preferable.
In General Formula (G2), each of R1 to R4 and R11 to R14 independently represents any of hydrogen, a saturated hydrocarbon group having 1 to 6 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 8 carbon atoms, and an aromatic hydrocarbon group having 6 to 13 carbon atoms. R20 represents any of a saturated hydrocarbon group having 1 to 6 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 8 carbon atoms, an aromatic hydrocarbon group having 6 to 13 carbon atoms, a group including a pyridine ring, and a group including a pyrimidine ring.
It is preferable that R20 be a phenyl group because the structure of the organometallic complex in an excited state is stabilized and high emission efficiency is obtained. Furthermore, the use of a phenyl group as R20 is effective in fabrication of an element by evaporation because the thermophysical property can be improved and a more excellent sublimation property can be obtained. Such an organometallic complex can be represented by General Formula (G3) below.
Note that in General Formula (G3), each of R1 to R4, R11 to R14, and R21 to R25 independently represents any of hydrogen, a saturated hydrocarbon group having 1 to 6 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 8 carbon atoms, and an aromatic hydrocarbon group having 6 to 13 carbon atoms.
Both the HOMO level and the LUMO level of such an organometallic complex are low in the case where R1 to R4, R11 to R14, and R21 to R25 are all hydrogen, so that a light-emitting element having a lower drive voltage can be provided.
It is preferable that some of R1 to R4, R11 to R14, and R21 to R25 be not hydrogen but saturated hydrocarbon groups because the organometallic complex can have an excellent sublimation property and a highly reliable light-emitting element can be provided easily.
That is, another embodiment of the present invention is the organometallic complex represented by General Formula (G4) below.
Note that in General Formula (G4), each of R11, R13, R14, and R21 independently represents any of hydrogen, a saturated hydrocarbon group having 1 to 6 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 8 carbon atoms, and an aromatic hydrocarbon group having 6 to 13 carbon atoms.
In this specification, specific examples of a saturated hydrocarbon group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a 1-methylethyl group (an isopropyl group), an n-butyl group, a 1-methylpropyl group (a sec-butyl group), a 2-methylpropyl group (an isobutyl group), a 1,1-dimethylethyl group (a tert-butyl group), an n-pentyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylpropyl group, a 1,1-dimethylpropyl group, a 1,2-dimethylpropyl group, a 2,2-dimethylpropyl group (a neopentyl group), and a branched or non-branched hexyl group. Specific examples of a cyclic saturated hydrocarbon group having 3 to 8 carbon atoms include a cyclopentyl group, a cyclohexyl group, a 1-methylcyclohexyl group, a 2,6-dimethylcyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of an aromatic hydrocarbon group having 6 to 13 carbon atoms include a phenyl group, a naphthyl group, a 9,9-dimethylfluorenyl group, a phenyl group substituted by one or more methyl groups, a phenyl group substituted by one or more ethyl groups, a phenyl group substituted by one or more isopropyl groups, a phenyl group substituted by a tert-butyl group, and a phenyl group substituted by a phenyl group.
Note that the above cyclic saturated hydrocarbon group and the above aromatic hydrocarbon group may have a substituent, an example of which is an alkyl group having 1 to 4 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, and a tert-butyl group.
Some specific examples of the organometallic complexes of embodiments of the present invention with the above-described structures are shown below.
A variety of reactions can be employed as a method for synthesizing the organometallic complex of one embodiment of the present invention described above. An example of a method for synthesizing the organometallic complex of one embodiment of the present invention is described.
First, an example of a method for synthesizing a 1,2,4-triazole derivative represented by General Formula (G0) below is described using Synthesis Scheme (a).
In General Formula (G0), each of R1 to R4 independently represents any of hydrogen, a substituted or unsubstituted saturated hydrocarbon group having 1 to 6 carbon atoms, a substituted or unsubstituted cyclic saturated hydrocarbon group having 3 to 8 carbon atoms, and a substituted or unsubstituted aromatic hydrocarbon group having 6 to 13 carbon atoms. Each of R10 and R20 independently represents any of a substituted or unsubstituted saturated hydrocarbon group having 1 to 6 carbon atoms, a substituted or unsubstituted cyclic saturated hydrocarbon group having 3 to 8 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 13 carbon atoms, a group including a pyridine skeleton, and a group including a pyrimidine skeleton. At least one of R10 and R20 represents a group including a pyridine skeleton or a group including a pyrimidine skeleton.
As shown in Synthesis Scheme (a) below, a hydrazide compound having a substituted or unsubstituted phenyl group (A1) is reacted with a thioether compound having R10 and R20 or an N-substituted thioamide compound having R10 and R20 (A2), whereby the 1,2,4-triazole derivative can be obtained.
Note that the method for synthesizing the 1,2,4-triazole derivative is not limited to Synthesis Scheme (a). For example, as another synthesis method, a method in which a thioether compound having a substituted or unsubstituted phenyl group and R20, or an N-substituted thioamide compound having a substituted or unsubstituted phenyl group is reacted with a hydrazide compound having R10 can be given.
As shown in Scheme (a′) below, there is also a method in which a dihydrazide compound (A1′) and a primary amine compound (A2′) are reacted.
As described above, the 1,2,4-triazole derivative represented by General Formula (G0) can be synthesized by a simple synthesis scheme.
<Method for Synthesizing Organometallic Complex which is One Embodiment of the Present Invention and Represented by General Formula (G1)>
Next, a method for synthesizing the organometallic complex which is one example of the organometallic complex of one embodiment of the present invention and represented by General Formula (G1) below is described.
As shown in Synthesis Scheme (b) below, the 1,2,4-triazole derivative represented by General Formula (G0) is mixed with an iridium metal compound including a halogen (e.g., iridium chloride hydrate or ammonium hexachloroiridate) or an iridium organometallic complex compound (e.g., an acetylacetonato complex or a diethylsulfide complex), and the mixture is heated in the absence of a solvent or the mixture is dissolved in an alcohol-based solvent (e.g., glycerol, ethylene glycol, 2-methoxyethanol, or 2-ethoxyethanol) and then heated, whereby the organometallic complex having a structure represented by General Formula (G1) or a precursor thereof can be obtained. Note that in the case where the precursor is obtained, the precursor may be reacted with a ligand, so that the organometallic complex having the structure represented by General Formula (G1) can be obtained.
Note that in order to obtain an ortho-metalated complex including the 1,2,4-triazole derivative as a ligand in the present invention, as described above, it is preferable that any of the following substituents of a substituted or unsubstituted saturated hydrocarbon group having 1 to 6 carbon atoms, a substituted or unsubstituted cyclic saturated hydrocarbon group having 3 to 8 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 13 carbon atoms, a group including a pyridine skeleton, and a group including a pyrimidine skeleton be bonded to the 5-position of the 1,2,4-triazole derivative, i.e., R20 in which case the yield under Synthesis Scheme (b) can be increased as compared with the case where hydrogen is used as R20.
Here, for example, the lowest triplet excitation energy levels (T1 levels) and the molecular orbitals of the organometallic complexes each of which is one embodiment of the present invention were calculated by quantum chemistry calculation. The structures of compounds used in the calculation are shown below. Note that organometallic complexes represented by Structural Formulae (301) to (306) and (308) to (313) are each the organometallic complex of one embodiment of the present invention, and organometallic complexes represented by Structural Formulae (300) and (307) are each a comparative organometallic complex.
The calculating method is described below. Note that Gaussian 09 was used as the quantum chemistry computational program. A high performance computer (ICE X, manufactured by SGI Japan, Ltd.) was used for the calculation.
First, the most stable structure in the singlet ground state was calculated using the density functional theory (DFT). As a basis function, 6-311G(d,p) was used for H, C, and N atoms, and LanL2DZ was used for Ir atoms. As a functional, B3PW91 was used. By the above basis function, for example, orbits of is to 3s are considered in the case of hydrogen atoms while orbits of 1s to 4s and 2p to 4p are considered in the case of carbon atoms. Furthermore, to improve calculation accuracy, the p function and the d function, respectively, were added as polarization basis sets to hydrogen atoms and atoms other than hydrogen atoms.
Next, energy required for the transition from the most stable structure in the singlet ground state to the triplet excited state was calculated using the time-dependent density functional theory (TD-DFT). In the DFT, the total energy is represented as the sum of potential energy, electrostatic energy between electrons, electronic kinetic energy, and exchange-correlation energy including all the complicated interactions between electrons. Also in the DFT, an exchange-correlation interaction is approximated by a functional (a function of another function) of one electron potential represented in terms of electron density to enable high-accuracy calculations.
Table 1 shows the HOMO levels, the LUMO levels, and the T1 levels, which were obtained by the calculation.
A pyridine ring and a pyrimidine ring have a higher electron-accepting property than a benzene ring. Therefore, as shown in the above calculation results, the LUMO levels of the organometallic complexes represented by Structural Formulae (301) to (306) are each lower than the LUMO level of the organometallic complex represented by Structural Formula (300). Furthermore, the LUMO levels of the organometallic complexes represented by Structural Formulae (308) to (313) are each lower than the LUMO level of the organometallic complex represented by Structural Formula (307). That is, the organometallic complex having a ligand having a group including a pyridine skeleton or a group including a pyrimidine skeleton, which is one embodiment of the present invention, has a low LUMO level.
The calculation results reveal that the T1 levels of the organometallic complexes represented by Structural Formulae (301) to (313) enable green to blue light emission. Accordingly, the organometallic complex of one embodiment of the present invention is preferable as an organometallic complex that emits green to blue phosphorescence.
Next, an example of a light-emitting element which is one embodiment of the present invention is described in detail below with reference to
In this embodiment, the light-emitting element includes a pair of electrodes (a first electrode 101 and a second electrode 102), and an EL layer 103 provided between the first electrode 101 and the second electrode 102. Note that the first electrode 101 functions as an anode and the second electrode 102 functions as a cathode.
To function as an anode, the first electrode 101 is preferably formed using any of metals, alloys, conductive compounds having a high work function (specifically, a work function of 4.0 eV or more), mixtures thereof, and the like. Specific examples include indium oxide-tin oxide (ITO: indium tin oxide), indium oxide-tin oxide containing silicon or silicon oxide, indium oxide-zinc oxide, and indium oxide containing tungsten oxide and zinc oxide (IWZO). Films of such conductive metal oxides are usually formed by a sputtering method, but may be formed by application of a sol-gel method or the like. In an example of the formation method, indium oxide-zinc oxide is deposited by a sputtering method using a target obtained by adding 1 wt % to 20 wt % of zinc oxide to indium oxide. Furthermore, a film of indium oxide containing tungsten oxide and zinc oxide (IWZO) can be formed by a sputtering method using a target in which tungsten oxide and zinc oxide are added to indium oxide at 0.5 wt % to 5 wt % and 0.1 wt % to 1 wt %, respectively. Other examples are gold (Au), platinum (Pt), nickel (Ni), tungsten (W), chromium (Cr), molybdenum (Mo), iron (Fe), cobalt (Co), copper (Cu), palladium (Pd), nitrides of metal materials (e.g., titanium nitride), and the like. Graphene can also be used. Note that when a composite material described later is used for a layer which is in contact with the first electrode 101 in the EL layer 103, an electrode material can be selected regardless of its work function.
It is preferable that the EL layer 103 have a stacked-layer structure and any of the layers of the stacked-layer structure include the organometallic complex which is one embodiment of the present invention and represented by any of General Formulae (G1) to (G4) above.
The stacked-layer structure of the EL layer 103 can be formed by combining a hole-injection layer, a hole-transport layer, a light-emitting layer, an electron-transport layer, an electron-injection layer, a carrier-blocking layer, an intermediate layer, and the like as appropriate. In this embodiment, the EL layer 103 has a structure in which a hole-injection layer 111, a hole-transport layer 112, a light-emitting layer 113, an electron-transport layer 114, and an electron-injection layer 115 are stacked in this order over the first electrode 101. Specific examples of the materials forming the layers are given below.
The hole-injection layer 111 is a layer containing a substance having a high hole-injection property. The hole-injection layer 111 can be formed using molybdenum oxide, vanadium oxide, ruthenium oxide, tungsten oxide, manganese oxide, or the like. Alternatively, the hole-injection layer 111 can be formed using a phthalocyanine-based compound such as phthalocyanine (abbreviation: H2Pc) or copper phthalocyanine (abbreviation: CuPc), an aromatic amine compound such as 4,4′-bis[N-(4-diphenylaminophenyl)-N-phenylamino]biphenyl (abbreviation: DPAB) or N,N′-bis{4-[bis(3-methylphenyl)amino]phenyl}-N,N′-diphenyl-(1,1′-biphenyl)-4,4′-diamine (abbreviation: DNTPD), a high molecule such as poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonic acid) (PEDOT/PSS), 7,7, 8,8-tetracyano-2,3,5,6-tetrafluoroquinodimethane (abbreviation: F4-TCNQ), chloranil, or the like.
Alternatively, a composite material in which a substance with a hole-transport property contains a substance with an acceptor property can be used for the hole-injection layer 111. Note that the use of the composite material in which a substance having a hole-transport property contains a substance having an acceptor property enables selection of a material used to form an electrode regardless of its work function. In other words, besides a material having a high work function, a material having a low work function can be used for the first electrode 101. As examples of the substance having an acceptor property, 7,7, 8,8-tetracyano-2,3,5,6-tetrafluoroquinodimethane (abbreviation: F4-TCNQ), chloranil, and the like can be given. In addition, transition metal oxides can be given. Moreover, oxides of metals belonging to Groups 4 to 8 of the periodic table can be given. Specifically, it is preferable to use vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide, tungsten oxide, manganese oxide, and rhenium oxide because of their high electron accepting properties. In particular, molybdenum oxide is more preferable because of its stability in the atmosphere, low hygroscopic property, and easiness of handling.
As the substance with a hole-transport property which is used for the composite material, any of a variety of organic compounds such as aromatic amine compounds, carbazole derivatives, aromatic hydrocarbons, and high molecular compounds (e.g., oligomers, dendrimers, or polymers) can be used. Note that the substance with a hole-transport property which is used for the composite material is preferably a substance having a hole mobility of 10−6 cm2/Vs or more. Organic compounds that can be used as the substance with a hole-transport property in the composite material are specifically given below.
Examples of the substance with a hole-transport property that can be used for the composite material are aromatic amine compounds such as N,N′-di(p-tolyl)-N,N′-diphenyl-p-phenylenediamine (abbreviation: DTDPPA), 4,4′-bis[N-(4-diphenylaminophenyl)-N-phenylamino]biphenyl (abbreviation: DPAB), N,N′-bis{4-[bis(3-methylphenyl)amino]phenyl}-N,N′-diphenyl-(1,1′-biphenyl)-4,4′-diamine (abbreviation: DNTPD), and 1,3,5-tris[N-(4-diphenylaminophenyl)-N-phenylainino]benzene (abbreviation: DPA3B); carbazole derivatives such as 3-[N-(9-phenylcarbazol-3-yl)-N-phenylamino]-9-phenylcarbazole (abbreviation: PCzPCA1), 3,6-bis[N-(9-phenylcarbazol-3-yl)-N-phenylamino]-9-phenylcarbazole (abbreviation: PCzPCA2), 3-[N-(1-naphthyl)-N-(9-phenylcarbazol-3-yl)amino]-9-phenylcarbazole (abbreviation: PCzPCN1), 4,4′-di(N-carbazolyl)biphenyl (abbreviation: CBP), 1,3,5-tris[4-(N-carbazolyl)phenyl]benzene (abbreviation: TCPB), 9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole (abbreviation: CzPA), and 1,4-bis[4-(N-carbazolyl)phenyl]-2,3,5,6-tetraphenylbenzene; and aromatic hydrocarbons such as 2-tert-butyl-9,10-di(2-naphthyl)anthracene (abbreviation: t-BuDNA), 2-tert-butyl-9,10-di(1-naphthyl)anthracene, 9,10-bis(3,5-diphenylphenyl)anthracene (abbreviation: DPPA), 2-tert-butyl-9,10-bis(4-phenylphenyl)anthracene (abbreviation: t-BuDBA), 9,10-di(2-naphthyl)anthracene (abbreviation: DNA), 9,10-diphenylanthracene (abbreviation: DPAnth), 2-tert-butylanthracene (abbreviation: t-BuAnth), 9,10-bis(4-methyl-1-naphthyl)anthracene (abbreviation: DMNA), 2-tert-butyl-9,10-bis[2-(1-naphthyl)phenyl]anthracene, 9,10-bis[2-(1-naphthyl)phenyl]anthracene, 2,3,6,7-tetramethyl-9,10-di(1-naphthyl)anthracene, 2,3,6,7-tetramethyl-9,10-di(2-naphthyl)anthracene, 9,9′-bianthryl, 10,10′-diphenyl-9,9′-bianthryl, 10,10′-bis(2-phenylphenyl)-9,9′-bianthryl, 10,10′-bis[(2,3,4,5,6-pentaphenyl)phenyl]-9,9′-bianthryl, anthracene, tetracene, rubrene, perylene, and 2,5,8,11-tetra(tert-butyl)perylene. Besides, pentacene, coronene, or the like can also be used. The aromatic hydrocarbons may have a vinyl skeleton. Examples of the aromatic hydrocarbon having a vinyl skeleton are 4,4′-bis(2,2-diphenylvinyl)biphenyl (abbreviation: DPVBi), 9,10-bis[4-(2,2-diphenylvinyl)phenyl]anthracene (abbreviation: DPVPA), and the like.
A high molecular compound such as poly(N-vinylcarbazole) (abbreviation: PVK), poly(4-vinyltriphenylamine) (abbreviation: PVTPA), poly[N-(4-{N-[4-(4-diphenylamino)phenyl]phenyl-N′-phenylamino}phenyl)methacrylamide] (abbreviation: PTPDMA), or poly[N,N′-bis(4-butylphenyl)-N,N′-bis(phenyl)benzidine] (abbreviation: poly-TPD) can also be used.
By providing the hole-injection layer 111, a high hole-injection property can be achieved to allow a light-emitting element to be driven at a low voltage.
The hole-transport layer 112 is a layer that contains a substance with a hole-transport property. Examples of the substance with a hole-transport property are aromatic amine compounds such as 4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (abbreviation: NPB), N,N′-bis(3-methylphenyl)-N,N′-diphenyl-[1,1′-biphenyl]-4,4′-diamine (abbreviation: TPD), 4,4′,4″-tris(N,N′-diphenylamino)triphenylamine (abbreviation: TDATA), 4,4′,4″-tris[N-(3-methylphenyl)-N-phenylamino]triphenylamine (abbreviation: MTDATA), 4,4′-bis[N-(spiro-9,9′-bifluoren-2-yl)-N-phenylamino]biphenyl (abbreviation: BSPB), 4-phenyl-4′-(9-phenylfluoren-9-yl)triphenylamine (abbreviation: BPAFLP), and the like. The substances mentioned here have high hole-transport properties and are mainly ones that have a hole mobility of 10−6 cm2/Vs or more. An organic compound given as an example of the substance with a hole-transport property in the composite material described above can also be used for the hole-transport layer 112. Note that the layer that contains a substance with a hole-transport property is not limited to a single layer, and may be a stack of two or more layers including any of the above substances.
The light-emitting layer 113 may be a layer that emits fluorescence, a layer that emits phosphorescence, or a layer emitting thermally activated delayed fluorescence (TADF). Furthermore, the light-emitting layer 113 may be a single layer or include a plurality of layers containing different light-emitting substances. In the case where the light-emitting layer including a plurality of layers is formed, a layer containing a phosphorescent substance and a layer containing a fluorescent substance may be stacked. In that case, an exciplex described later is preferably utilized for the layer containing the phosphorescent substance.
As the fluorescent substance, any of the following substances can be used, for example. Fluorescent substances other than those given below can also be used. Examples of the fluorescent substance are 5,6-bis[4-(10-phenyl-9-anthryl)phenyl]-2,2′-bipyridine (abbreviation: PAP2BPy), 5,6-bis[4′-(10-phenyl-9-anthryl)biphenyl-4-yl]-2,2′-bipyridine (abbreviation: PAPP2BPy), N,N′-diphenyl-N,N′-bis[4-(9-phenyl-9H-fluoren-9-yl)phenyl]pyrene-1,6-diamine (abbreviation: 1,6FLPAPrn), N,N′-bis(3-methylphenyl)-N,N′-bis[3-(9-phenyl-9H-fluoren-9-yl)phenyl]pyrene-1, 6-diamine (abbreviation: 1,6mMemFLPAPrn), N,N′-bis[4-(9H-carbazol-9-yl)phenyl]-N,N′-diphenylstilbene-4,4′-diamine (abbreviation: YGA2S), 4-(9H-carbazol-9-yl)-4′-(10-phenyl-9-anthryl)triphenylamine (abbreviation: YGAPA), 4-(9H-carbazol-9-yl)-4′-(9,10-diphenyl-2-anthryl)triphenylamine (abbreviation: 2YGAPPA), N,9-diphenyl-N-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazol-3-amine (abbreviation: PCAPA), perylene, 2,5,8,11-tetra-tert-butyl-perylene (abbreviation: TBP), 4-(10-phenyl-9-anthryl)-4′-(9-phenyl-9H-carbazol-3-yl)triphenylamine (abbreviation: PCBAPA), N,N″-(2-tert-butylanthracene-9,10-diyldi-4,1-phenylene)bis[N,N′,N′-triphenyl-1,4-phenylenediamine] (abbreviation: DPABPA), N,9-diphenyl-N-[4-(9,10-diphenyl-2-anthryl)phenyl]-9H-carbazol-3-amine (abbreviation: 2PCAPPA), N-[4-(9,10-diphenyl-2-anthryl)phenyl]-N,N′,N′-triphenyl-1,4-phenylenediamine (abbreviation: 2DPAPPA), N,N,N′,N′,N″,N″,N′″,N′″-octaphenyldibenzo[g,p]chrysene-2,7,10,15-tetraamine (abbreviation: DBC1), coumarin 30, N-(9,10-diphenyl-2-anthryl)-N,9-diphenyl-9H-carbazol-3-amine (abbreviation: 2PCAPA), N-[9,10-bis(1,1′-biphenyl-2-yl)-2-anthryl]-N,9-diphenyl-9H-carbazol-3-amine (abbreviation: 2PCABPhA), N-(9,10-diphenyl-2-anthryl)-N,N′,N′-triphenyl-1,4-phenylenediamine (abbreviation: 2DPAPA), N-[9,10-bis(1,1′-biphenyl-2-yl)-2-anthryl]-N,N′,N′-triphenyl-1,4-phenylenediamine (abbreviation: 2DPABPhA), 9,10-bis(1,1′-biphenyl-2-yl)-N-[4-(9H-carbazol-9-yl)phenyl]-N-phenylanthracen-2-amine (abbreviation: 2YGABPhA), N,N,9-triphenylantlracen-9-amine (abbreviation: DPhAPhA), coumarin 545T, N,N′-diphenylquinacridone (abbreviation: DPQd), rubrene, 5,12-bis(1,1′-biphenyl-4-yl)-6,11-diphenyltetracene (abbreviation: BPT), 2-(2-{2-[4-(dimethylamino)phenyl]ethenyl}-6-methyl-4H-pyran-4-ylidene)propanedinitrile (abbreviation: DCM1), 2-{2-methyl-6-[2-(2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizin-9-yl)ethenyl]-4H-pyran-4-ylidene}propanedinitrile (abbreviation: DCM2), N,N,N′,N′-tetrakis(4-methylphenyl)tetracene-5,11-diamine (abbreviation: p-mPhTD), 7,14-diphenyl-N,N,N′,N-tetrakis(4-methylphenyl)acenaphtho[1,2-a]fluoranthene-3,10-diamine (abbreviation: p-mPhAFD), 2-{2-isopropyl-6-[2-(1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizin-9-yl)ethenyl]-4H-pyran-4-ylidene}propanedinitrile (abbreviation: DCJTI), 2-{2-tert-butyl-6-[2-(1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizin-9-yl)ethenyl]-4H-pyran-4-ylidene}propanedinitrile (abbreviation: DCJTB), 2-(2,6-bis{2-[4-(dimethylamino)phenyl]ethenyl}-4H-pyran-4-ylidene)propanedinitrile (abbreviation: BisDCM), 2-{2,6-bis[2-(8-methoxy-1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H,5H-benzo[j]quinolizin-9-yl)ethenyl]-4H-pyran-4-ylidene}propanedinitrile (abbreviation: BisDCJTM), and the like. Condensed aromatic diamine compounds typified by pyrenediamine compounds such as 1,6FLPAPrn and 1,6mMemFLPAPrn are preferable because of their high hole-trapping properties, high emission efficiency, and high reliability.
Examples of a material which can be used as a phosphorescent substance in the light-emitting layer 113 are as follows. The examples include organometallic iridium complexes having 4H-triazole skeletons, such as tris{2-[5-(2-methylphenyl)-4-(2,6-dimethylphenyl)-4H-1,2,4-triazol-3-yl-κN2]phenyl-κC}iridihnm(III) (abbreviation: [Ir(mpptz-dmp)3]), tris(5-methyl-3,4-diphenyl-4H-1,2,4-triazolato)iridium(III) (abbreviation: [Ir(Mptz)3]), and tris[4-(3-biphenyl)-5-isopropyl-3-phenyl-4H-1,2,4-triazolato]iridium(III) (abbreviation: [Ir(iPrptz-3b)3]); organometallic iridium complexes having 1H-triazole skeletons, such as tris[3-methyl-1-(2-methylphenyl)-5-phenyl-1H-1,2,4-triazolato]iridium(III) (abbreviation: [Ir(Mptz1-mp)3]) and tris(1-methyl-5-phenyl-3-propyl-1H-1,2,4-triazolato)iridium(III) (abbreviation: [Ir(Prptz1-Me)3]); organometallic iridium complexes having imidazole skeletons, such as fac-tris[1-(2,6-diisopropylphenyl)-2-phenyl-1H-imidazole]iridium(III) (abbreviation: [Ir(iPrpmi)3]) and tris[3-(2,6-dimethylphenyl)-7-methylimidazo[1,2-f]phenanthridinato]iridium(III) (abbreviation: [Ir(dmpimpt-Me)3]); and organometallic iridium complexes in which a phenylpyridine derivative having an electron-withdrawing group is a ligand, such as bis[2-(4′,6′-difluorophenyl)pyridinato-N,C2′]iridium(III) tetrakis(1-pyrazolyl)borate (abbreviation: FIr6), bis[2-(4′,6′-difluorophenyl)pyridinato-N,C2′]iridium(III) picolinate (abbreviation: Flrpic), bis {2-[3′,5′-bis(trifluoromethyl)phenyl]pyridinato-N,C2′}iridium(III) picolinate (abbreviation: [Ir(CF3ppy)2(pic)]), and bis[2-(4′,6′-difluorophenyl)pyridinato-N,C2′]iridium(III) acetylacetonate (abbreviation: FIr(acac)). These are compounds emitting blue phosphorescence and have an emission peak at 440 nm to 520 nm.
Other examples include organometallic iridium complexes having pyrimidine skeletons, such as tris(4-methyl-6-phenylpyrinidinato)iridium(III) (abbreviation: [Ir(mppm)3]), tris(4-t-butyl-6-phenylpyrinidinato)iridium(III) (abbreviation: [Ir(tBuppm)3]), (acetylacetonato)bis(6-methyl-4-phenylpyrimidinato)iridium(III) (abbreviation: [Ir(mppm)2(acac)]), (acetylacetonato)bis(6-tert-butyl-4-phenylpyrinidinato)iridium(III) (abbreviation: [Ir(tBuppm)2(acac)]), (acetylacetonato)bis[6-(2-norbomyl)-4-phenylpyrimidinato]iridium(III) (abbreviation: [Ir(nbppm)2(acac)]), (acetylacetonato)bis[5-methyl-6-(2-methylphenyl)-4-phenylpyrimidinato]iridium(III) (abbreviation: [Ir(mpmppm)2(acac)]), and (acetylacetonato)bis(4,6-diphenylpyrimidinato)iridium(III) (abbreviation: [Ir(dppm)2(acac)]); organometallic iridium complexes having pyrazine skeletons, such as (acetylacetonato)bis(3,5-dimethyl-2-phenylpyrazinato)iridium(III) (abbreviation: [Ir(mppr-Me)2(acac)]) and (acetylacetonato)bis(5-isopropyl-3-methyl-2-phenylpyrazinato)iridium(III) (abbreviation: [Ir(mppr-iPr)2(acac)]); organometallic iridium complexes having pyridine skeletons, such as tris(2-phenylpyridinato-N,C2′)iridium(III) (abbreviation: [Ir(ppy)3]), bis(2-phenylpyridinato-N,C2′)iridium(III) acetylacetonate (abbreviation: [Ir(ppy)2(acac)]), bis(benzo[h]quinolinato)iridium(III) acetylacetonate (abbreviation: [Ir(bzq)2(acac)]), tris(benzo[h]quinolinato)iridium(III) (abbreviation: [Ir(bzq)3]), tris(2-phenylquinolinato-N,C2′)iridium(IlI) (abbreviation: [Ir(pq)3]), and bis(2-phenylquinolinato-N,C2′)iridium(III) acetylacetonate (abbreviation: [Ir(pq)2(acac)]); and rare earth metal complexes such as tris(acetylacetonato)(monophenanthroline)terbium(III) (abbreviation: [Tb(acac)3(Phen)]). These are mainly compounds emitting green phosphorescence and have an emission peak at 500 nm to 600 nm. Note that organometallic iridium complexes having pyrimidine skeletons have distinctively high reliability and emission efficiency and thus are especially preferable.
Other examples include organometallic iridium complexes having pyrimidine skeletons, such as (diisobutyrylmethanato)bis[4,6-bis(3-methylphenyl)pyrimidinato]iridium(III) (abbreviation: [Ir(5mdppm)2(dibm)]), bis[4,6-bis(3-methylphenyl)pyrimnidinato](dipivaloylmethanato)iridium(III) (abbreviation: [Ir(5mdppm)2(dpm)]), and bis[4,6-di(naphthalen-1-yl)pyrimidinato](dipivaloylmethanato)iridium(III) (abbreviation: [Ir(d1npm)2(dpm)]); organometallic iridium complexes having pyrazine skeletons, such as (acetylacetonato)bis(2,3,5-triphenylpyrazinato)iridium(III) (abbreviation: [Ir(tppr)2(acac)]), bis(2,3,5-triphenylpyrazinato)(dipivaloyhnethanato)iridium(III) (abbreviation: [Ir(tppr)2(dpm)]), and (acetylacetonato)bis[2,3-bis(4-fluorophenyl)quinoxalinato]iridium(III) (abbreviation: [Ir(Fdpq)2(acac)]); organometallic iridium complexes having pyridine skeletons, such as tris(1-phenylisoquinolinato-N,C2′)iridium(III) (abbreviation: [Ir(piq)3]) and bis(1-phenylisoquinolinato-N,C2′)iridium(III) acetylacetonate (abbreviation: [Ir(piq)2(acac)]); platinum complexes such as 2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphyrin platinum(II) (abbreviation: PtOEP); and rare earth metal complexes such as tris(1,3-diphenyl-1,3-propanedionato)(monophenanthroline)europium(I) (abbreviation: [Eu(DBM)3(Phen)]) and tris[1-(2-thenoyl)-3,3,3-trifluoroacetonato](monophenanthroline)europium(III) (abbreviation: [Eu(TTA)3(Phen)]). These are compounds emitting red phosphorescence and have an emission peak at 600 nm to 700 nm. Furthermore, organometallic iridium complexes having pyrazine skeletons can provide red light emission with favorable chromaticity.
As well as the above phosphorescent compounds, a variety of phosphorescent substances may be selected and used.
Note that the organometallic complex of one embodiment of the present invention is preferably used as the phosphorescent substance. The organometallic complex of one embodiment of the present invention emits green to blue phosphorescence efficiently, which allows fabrication of a light-emitting element with high emission efficiency. The organometallic complex which is one embodiment of the present invention and has a ligand having the 1,2,4-triazole skeleton has a deep LUMO level and thus has an excellent electron-injection property and an excellent electron-transport property. A light-emitting element including the organometallic complex as a phosphorescent substance can have low drive voltage. Accordingly, a light-emitting device including the light-emitting element can have low power consumption.
Examples of the TADF material include a fullerene, a derivative thereof, an acridine, derivative thereof, and an eosin derivative. Furthermore, a metal-containing porphyrin, such as a porphyrin containing magnesium (Mg), zinc (Zn), cadmium (Cd), tin (Sn), platinum (Pt), indium (In), or palladium (Pd) can be used. Examples of the metal-containing porphyrin include a protoporphyrin-tin fluoride complex (SnF2(Proto IX)), a mesoporphyrin-tin fluoride complex (SnF2(Meso IX)), a hematoporphyrin-tin fluoride complex (SnF2(Hemato IX)), a coproporphyrin tetramethyl ester-tin fluoride complex (SnF2(Copro III-4Me)), an octaethylporphyrin-tin fluoride complex (SnF2(OEP)), an etioporphyrin-tin fluoride complex (SnF2(Etio I)), and an octaethylporphyrin-platinum chloride complex (PtCl2(OEP)), which are shown in the following structural formulae.
Alternatively, a heterocyclic compound having both of a π-electron rich heteroaromatic ring and a π-electron deficient heteroaromatic ring, such as 2-(biphenyl-4-yl)-4,6-bis(12-phenylindolo[2,3-a]carbazol-11-yl)-1,3,5-triazine (abbreviation: PIC-TRZ), 9-(4,6-diphenyl-1,3,5-triazin-2-yl)-9′-phenyl-9H,9′H-3,3′-bicarbazole (abbreviation: PCCzTzn), 9-[4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl]-9′-phenyl-9H,9′H-3,3′-bicarbazole (abbreviation: PCCzPTzn), 2-[4-(10H-phenoxazine-10-yl)phenyl]-4,6-diphenyl-1,3,5-triazine (abbreviation: PXZ-TRZ), 3-[4-(5-phenyl-5,10-dihydrophenazin-10-yl)phenyl]-4,5-diphenyl-1,2,4-triazole (abbreviation: PPZ-3 TPT), 3-(9,9-dimethyl-9H-acridin-10-yl)-9H-xanthen-9-one (abbreviation: ACRXTN), bis[4-(9,9-dimethyl-9,10-dihydroacridine)phenyl]sulfone (abbreviation: DMAC-DPS), or 10-phenyl-10H, 10′H-spiro[acridin-9,9′-anthracen]-10′-one (abbreviation: ACRSA) shown in Structural Formulae below, can be used. The heterocyclic compound is preferable because of having the π-electron rich heteroaromatic ring and the π-electron deficient heteroaromatic ring, for which the electron-transport property and the hole-transport property are high. Note that a substance in which the π-electron rich heteroaromatic ring is directly bonded to the π-electron deficient heteroaromatic ring is particularly preferably used because the donor property of the π-electron rich heteroaromatic ring and the acceptor property of the π-electron deficient heteroaromatic ring are both increased, the energy difference between the S1 level and the T1 level becomes small, and thus thermally activated delayed fluorescence can be obtained with high efficiency. Note that an aromatic ring to which an electron-withdrawing group such as a cyano group is bonded may be used instead of the π-electron deficient heteroaromatic ring.
In the case where a fluorescent light-emitting substance is used as a host material in the light-emitting layer, a material having an anthracene skeleton is preferred such as 9-phenyl-3-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole (abbreviation: PCzPA), 3-[4-(1-naphthyl)-phenyl]-9-phenyl-9H-carbazole (abbreviation: PCPN), 9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole (abbreviation: CzPA), 7-[4-(10-phenyl-9-anthryl)phenyl]-7H-dibenzo[c,g]carbazole (abbreviation: cgDBCzPA), 6-[3-(9,10-diphenyl-2-anthryl)phenyl]-benzo[b]naphtho[1,2-d]furan (abbreviation: 2mBnfPPA), and 9-phenyl-10-{4-(9-phenyl-9H-fluoren-9-yl)biphenyl-4′-yl}anthracene (abbreviation: FLPPA). The use of a substance having an anthracene skeleton as the host material for the fluorescent substance makes it possible to obtain a light-emitting layer with high emission efficiency and high durability. In particular, CzPA, cgDBCzPA, 2mBnfPPA, and PCzPA are preferable choices because of their excellent characteristics.
In the case where a material other than the above-mentioned materials is used as a host material, various carrier-transport materials, such as a material with an electron-transport property or a material with a hole-transport property, can be used.
Examples of the material with an electron-transport property are a metal complex such as bis(10-hydroxybenzo[h]quinolinato)beryllium(II) (abbreviation: BeBq2), bis(2-methyl-8-quinolinolato)(4-phenylphenolato)aluminum(III) (abbreviation: BAlq), bis(8-quinolinolato)zinc(II) (abbreviation: Znq), bis[2-(2-benzoxazolyl)phenolato]zinc(II) (abbreviation: ZnPBO), or bis[2-(2-benzothiazolyl)phenolato]zinc(II) (abbreviation: ZnBTZ); a heterocyclic compound having a polyazole skeleton such as 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (abbreviation: PBD), 3-(4-biphenylyl)-4-phenyl-5-(4-tert-butylphenyl)-1,2,4-triazole (abbreviation: TAZ), 1,3-bis[5-(p-tert-butylphenyl)-1,3,4-oxadiazol-2-yl]benzene (abbreviation: OXD-7), 9-[4-(5-phenyl-1,3,4-oxadiazol-2-yl)phenyl]-9H-carbazole (abbreviation: CO11), 2,2′,2″-(1,3,5-benzenetriyl)tris(1-phenyl-1H-benzimidazole) (abbreviation: TPBI), or 2-[3-(dibenzothiophen-4-yl)phenyl]-1-phenyl-1H-benzimidazole (abbreviation: mDBTBIm-II); a heterocyclic compound having a diazine skeleton such as 2-[3-(dibenzothiophen-4-yl)phenyl]dibenzo[f,h]quinoxaline (abbreviation: 2mDBTPDBq-II), 2-[3′-(dibenzothiophen-4-yl)biphenyl-3-yl]dibenzo[f,h]quinoxaline (abbreviation: 2mDBTBPDBq-II), 2-[3′-(9H-carbazol-9-yl)biphenyl-3-yl]dibenzo[f,h]quinoxaline (abbreviation: 2mCzBPDBq), 4,6-bis[3-(phenanthren-9-yl)phenyl]pyrimidine (abbreviation: 4,6mPnP2Pm), or 4,6-bis[3-(4-dibenzothienyl)phenyl]pyrimidine (abbreviation: 4,6mDBTP2Pm-II); and a heterocyclic compound having a pyridine skeleton such as 3,5-bis[3-(9H-carbazol-9-yl)phenyl]pyridine (abbreviation: 35DCzPPy) or 1,3,5-tri[3-(3-pyridyl)phenyl]benzene (abbreviation: TmPyPB). Among the above materials, a heterocyclic compound having a diazine skeleton and a heterocyclic compound having a pyridine skeleton have high reliability and are thus preferable. Specifically, a heterocyclic compound having a diazine (pyrimidine or pyrazine) skeleton has a high electron-transport property to contribute to a reduction in drive voltage.
Examples of the material with a hole-transport property include a compound having an aromatic amine skeleton such as 4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (abbreviation: NPB), N,N′-bis(3-methylphenyl)-N,N′-diphenyl-[1,1′-biphenyl]-4,4′-diamine (abbreviation: TPD), 4,4′-bis[N-(spiro-9,9′-bifluoren-2-yl)-N-phenylamino]biphenyl (abbreviation: BSPB), 4-phenyl-4′-(9-phenylfluoren-9-yl)triphenylamine (abbreviation: BPAFLP), 4-phenyl-3′-(9-phenylfluoren-9-yl)triphenylamine (abbreviation: mBPAFLP), 4-phenyl-4′-(9-phenyl-9H-carbazol-3-yl)triphenylamine (abbreviation: PCBA1BP), 4,4′-diphenyl-4″-(9-phenyl-9H-carbazol-3-yl)triphenylamine (abbreviation: PCBBi1BP), 4-(1-naphthyl)-4′-(9-phenyl-9H-carbazol-3-yl)triphenylamine (abbreviation: PCBANB), 4,4′-di(1-naphthyl)-4″-(9-phenyl-9H-carbazol-3-yl)triphenylamine (abbreviation: PCBNBB), 9,9-dimethyl-N-phenyl-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]fluoren-2-amine (abbreviation: PCBAF), or N-phenyl-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]spiro-9,9′-bifluoren-2-amine (abbreviation: PCBASF); a compound having a carbazole skeleton such as 1,3-bis(N-carbazolyl)benzene (abbreviation: mCP), 4,4′-di(N-carbazolyl)biphenyl (abbreviation: CBP), 3,6-bis(3,5-diphenylphenyl)-9-phenylcarbazole (abbreviation: CzTP), or 3,3′-bis(9-phenyl-9H-carbazole) (abbreviation: PCCP); a compound having a thiophene skeleton such as 4,4′,4″-(benzene-1,3,5-triyl)tri(dibenzothiophene) (abbreviation: DBT3P-II), 2,8-diphenyl-4-[4-(9-phenyl-9H-fluoren-9-yl)phenyl]dibenzothiophene (abbreviation: DBTFLP-III), or 4-[4-(9-phenyl-9H-fluoren-9-yl)phenyl]-6-phenyldibenzothiophene (abbreviation: DBTFLP-IV); and a compound having a furan skeleton such as 4,4′,4″-(benzene-1,3,5-triyl)tri(dibenzofuran) (abbreviation: DBF3P-II) or 4-{3-[3-(9-phenyl-9H-fluoren-9-yl)phenyl]phenyl}dibenzofuran (abbreviation: mmDBFFLBi-II). Among the above materials, a compound having an aromatic amine skeleton and a compound having a carbazole skeleton are preferable because these compounds are highly reliable and have high hole-transport properties to contribute to a reduction in drive voltage. Hole-transport materials can be selected from a variety of substances as well as from the hole-transport materials given above.
Note that the host material may be a mixture of a plurality of kinds of substances, and in the case of using a mixed host material, it is preferable to mix a material having an electron-transport property with a material having a hole-transport property. By mixing the material having an electron-transport property with the material having a hole-transport property, the transport property of the light-emitting layer 113 can be easily adjusted and a recombination region can be easily controlled. The ratio of the content of the material having a hole-transport property to the content of the material having an electron-transport property may be 1:9 to 9:1.
These mixed host materials may form an exciplex. When a combination of these materials is selected so as to form an exciplex that exhibits light emission whose wavelength overlaps the wavelength of a lowest-energy-side absorption band of the fluorescent substance, the phosphorescent substance, or the TADF material, energy is transferred smoothly and light emission can be obtained efficiently. Such a structure is preferable in that drive voltage can be reduced.
The light-emitting layer 113 having the above-described structure can be formed by co-evaporation by a vacuum evaporation method, or a gravure printing method, an offset printing method, an inkjet method, a spin coating method, a dip coating method, or the like using a solution of the materials.
The electron-transport layer 114 contains a substance with an electron-transport property. As the substance with an electron-transport property, the materials having an electron-transport property or having an anthracene skeleton, which are described above as materials for the host material, can be used.
Between the electron-transport layer and the light-emitting layer, a layer that controls transport of electron carriers may be provided. This is a layer formed by addition of a small amount of a substance having a high electron-trapping property to the aforementioned material having a high electron-transport property, and the layer is capable of adjusting carrier balance by retarding transport of electron carriers. Such a structure is very effective in preventing a problem (such as a reduction in element lifetime) caused when electrons pass through the light-emitting layer.
In addition, the electron-injection layer 115 may be provided in contact with the second electrode 102 between the electron-transport layer 114 and the second electrode 102. For the electron-injection layer 115, an alkali metal, an alkaline earth metal, or a compound thereof, such as lithium fluoride (LiF), cesium fluoride (CsF), or calcium fluoride (CaF2), can be used. For example, a layer that is formed using a substance having an electron-transport property and contains an alkali metal, an alkaline earth metal, or a compound thereof can be used. In addition, an electride may be used for the electron-injection layer 115. Examples of the electride include a substance in which electrons are added at high concentration to calcium oxide-aluminum oxide. Note that a layer that is formed using a substance having an electron-transport property and contains an alkali metal or an alkaline earth metal is preferably used as the electron-injection layer 115, in which case electron injection from the second electrode 102 is efficiently performed.
Instead of the electron-injection layer 115, a charge-generation layer 116 may be provided (
Note that the charge-generation layer 116 preferably includes either an electron-relay layer 118 or an electron-injection buffer layer 119 or both in addition to the p-type layer 117.
The electron-relay layer 118 contains at least the substance with an electron-transport property and has a function of preventing an interaction between the electron-injection buffer layer 119 and the p-type layer 117 and smoothly transferring electrons. The LUMO level of the substance with an electron-transport property contained in the electron-relay layer 118 is preferably between the LUMO level of an acceptor substance in the p-type layer 117 and the LUMO level of a substance contained in a layer of the electron-transport layer 114 in contact with the charge-generation layer 116. As a specific value of the energy level, the LUMO level of the substance with an electron-transport property contained in the electron-relay layer 118 is preferably higher than or equal to −5.0 eV, more preferably higher than or equal to −5.0 eV and lower than or equal to −3.0 eV. Note that as the substance with an electron-transport property in the electron-relay layer 118, a phthalocyanine-based material or a metal complex having a metal-oxygen bond and an aromatic ligand is preferably used.
A substance having a high electron-injection property can be used for the electron-injection buffer layer 119. For example, an alkali metal, an alkaline earth metal, a rare earth metal, or a compound thereof (e.g., an alkali metal compound (including an oxide such as lithium oxide, a halide, and a carbonate such as lithium carbonate or cesium carbonate), an alkaline earth metal compound (including an oxide, a halide, and a carbonate), or a rare earth metal compound (including an oxide, a halide, and a carbonate)) can be used.
In the case where the electron-injection buffer layer 119 contains the substance having an electron-transport property and a donor substance, an organic compound such as tetrathianaphthacene (abbreviation: TTN), nickelocene, or decamethylnickelocene can be used as the donor substance, as well as an alkali metal, an alkaline earth metal, a rare earth metal, a compound of the above metal (e.g., an alkali metal compound (including an oxide such as lithium oxide, a halide, and a carbonate such as lithium carbonate or cesium carbonate), an alkaline earth metal compound (including an oxide, a halide, and a carbonate), and a rare earth metal compound (including an oxide, a halide, and a carbonate)). Note that as the substance having an electron-transport property, a material similar to the above-described material used for the electron-transport layer 114 can be used. Furthermore, the organic compound of the present invention can be used.
For the second electrode 102, any of metals, alloys, electrically conductive compounds, and mixtures thereof which have a low work function (specifically, a work function of 3.8 eV or less) or the like can be used. Specific examples of such a cathode material are elements belonging to Groups 1 and 2 of the periodic table, such as alkali metals (e.g., lithium (Li) and cesium (Cs)), magnesium (Mg), calcium (Ca), and strontium (Sr), alloys thereof (e.g., MgAg and AlLi), rare earth metals such as europium (Eu) and ytterbium (Yb), alloys thereof, and the like. However, when the electron-injection layer is provided between the second electrode 102 and the electron-transport layer, for the second electrode 102, any of a variety of conductive materials such as Al, Ag, ITO, or indium oxide-tin oxide containing silicon or silicon oxide can be used regardless of the work function. Films of these conductive materials can be formed by a dry method such as a vacuum evaporation method or a sputtering method, an inkjet method, a spin coating method, or the like. In addition, the films of these conductive materials may be formed by a wet method using a sol-gel method, or by a wet method using paste of a metal material.
Any of a variety of methods can be used to form the EL layer 103 regardless of whether it is a dry process or a wet process. For example, a vacuum evaporation method, a gravure printing method, an offset printing method, a screen printing method, an inkjet method, a spin coating method, or the like may be used.
Here, a method for forming the EL layer 786 by a droplet discharge method is described with reference to
First, the conductive film 772 is formed over the planarization insulating film 770, and an insulating film 730 is formed to cover part of the conductive film 772 (see
Next, a droplet 784 is discharged to an exposed portion of the conductive film 772, which is an opening of the insulating film 730, from a droplet discharge apparatus 783, so that a layer 785 containing a composition is formed. The droplet 784 is a composition containing a solvent and is attached over the conductive film 772 (see
Note that the method for discharging the droplet 784 may be performed under reduced pressure.
Then, the solvent is removed from the layer 785 containing the composition, and the resulting layer is solidified to form the EL layer 786 (see
The solvent may be removed by drying or heating.
Next, the conductive film 788 is formed over the EL layer 786; thus, the light-emitting element 782 is formed (see
When the EL layer 786 is formed by a droplet discharging method as described above, the composition can be selectively discharged; accordingly, waste of material can be reduced. Furthermore, a lithography process or the like for shaping is not needed, and thus, the process can be simplified and cost reduction can be achieved.
The droplet discharge method described above is a general term for a means including a nozzle equipped with a composition discharge opening or a means to discharge droplets such as a head having one or a plurality of nozzles.
Next, a droplet discharge apparatus used for the droplet discharge method is described with reference to
The droplet discharge apparatus 1400 includes a droplet discharge means 1403. In addition, the droplet discharge means 1403 is equipped with a head 1405, a head 1412, and a head 1416.
The heads 1405 and 1412 are connected to a control means 1407, and this control means 1407 is controlled by a computer 1410; thus, a preprogrammed pattern can be drawn.
The drawing may be conducted at a timing, for example, based on a marker 1411 formed over a substrate 1402. Alternatively, the reference point may be determined on the basis of an outer edge of the substrate 1402. Here, the marker 1411 is detected by an imaging means 1404 and converted into a digital signal by an image processing means 1409. Then, the digital signal is recognized by the computer 1410, and then, a control signal is generated and transmitted to the control means 1407.
An image sensor or the like using a charge coupled device (CCD) or a complementary metal oxide semiconductor (CMOS) can be used as the imaging means 1404. Data about a pattern to be formed over the substrate 1402 is stored in a storage medium 1408, and the control signal is transmitted to the control means 1407 based on the data, so that each of the heads 1405, 1412, and 1416 of the droplet discharging means 1403 can be individually controlled. The heads 1405, 1412, and 1416 are supplied with a material to be discharged from material supply sources 1413, 1414, and 1415 through pipes, respectively.
Inside each of the heads 1405, 1412, and 1416, a space as indicated by a dotted line 1406 to be filled with a liquid material and a nozzle which is a discharge outlet are provided. Although it is not shown, an inside structure of the head 1412 is similar to that of the head 1405. When the nozzle sizes of the heads 1405 and 1412 are different from each other, different materials with different widths can be discharged simultaneously. Each head can discharge and draw a plurality of light emitting materials. In the case of drawing over a large area, the same material can be simultaneously discharged to be drawn from a plurality of nozzles in order to improve throughput. When a large substrate is used, the heads 1405, 1412, and 1416 can freely scan the substrate in directions indicated by arrows X, Y, and Z in
Further, a step of discharging the composition may be performed under reduced pressure. Also, a substrate may be heated when the composition is discharged. After discharging the composition, either drying or baking or the both is performed. Both the drying and baking are heat treatments but different in purpose, temperature, and time period. The steps of drying and baking are performed under normal pressure or under reduced pressure by laser irradiation, rapid thermal annealing, heating using a heating furnace, or the like. Note that the timing of the heat treatment and the number of times of the heat treatment are not particularly limited. The temperature for performing each of the steps of drying and baking in a favorable manner depends on the materials of the substrate and the properties of the composition.
In the above manner, the EL layer 786 can be formed with the droplet discharge apparatus.
In the case where the EL layer 786 is formed with the droplet discharge apparatus, the EL layer 786 can be formed by a wet method using a composition in which the organometallic complex of the present invention is dissolved in a solvent. In that case, the following various organic solvents can be used to form a coating composition: benzene, toluene, xylene, mesitylene, tetrahydrofuran, dioxane, ethanol, methanol, n-propanol, isopropanol, n-butanol, t-butanol, acetonitrile, dimethylsulfoxide, dimethylformamide, chloroform, methylene chloride, carbon tetrachloride, ethyl acetate, hexane, cyclohexane, and the like. In particular, less polar benzene derivatives such as benzene, toluene, xylene, and mesitylene are preferable because a solution with a suitable concentration can be obtained and the organometallic complex of the present invention contained in ink can be prevented from deteriorating due to oxidation or the like. Furthermore, to achieve a uniform film or a film with a uniform thickness, a solvent with a boiling point of 100° C. or higher is preferably used, and more preferably, toluene, xylene, or mesitylene is used.
Note that the above structure can be combined with any of the structures in this embodiment and the other embodiments as appropriate.
In addition, the electrode may be formed by a wet method using a sol-gel method, or by a wet method using paste of a metal material. Alternatively, the electrode may be formed by a dry method such as a sputtering method or a vacuum evaporation method.
Light emission from the light-emitting element is extracted out through one or both of the first electrode 101 and the second electrode 102. Therefore, one or both of the first electrode 101 and the second electrode 102 are formed as a light-transmitting electrode.
The structure of the layers provided between the first electrode 101 and the second electrode 102 is not limited to the above-described structure. Preferably, a light-emitting region where holes and electrons recombine is positioned away from the first electrode 101 and the second electrode 102 so that quenching due to the proximity of the light-emitting region and a metal used for electrodes and carrier-injection layers can be prevented.
Furthermore, in order that transfer of energy from an exciton generated in the light-emitting layer can be suppressed, preferably, the hole-transport layer and the electron-transport layer which are in contact with the light-emitting layer 113, particularly a carrier-transport layer in contact with a side closer to the recombination region in the light-emitting layer 113, are formed using a substance having a wider band gap than the light-emitting substance of the light-emitting layer or the emission center substance included in the light-emitting layer.
Next, a mode of a light-emitting element with a structure in which a plurality of light-emitting units are stacked (this type of light-emitting element is also referred to as a stacked element) is described with reference to
In
The charge-generation layer 513 has a function of injecting electrons into one of the light-emitting units and injecting holes into the other of the light-emitting units when a voltage is applied between the first electrode 501 and the second electrode 502. That is, in
The charge-generation layer 513 preferably has a structure similar to the structure of the charge-generation layer 116 described with reference to
In the case where the electron-injection buffer layer 119 is provided, the electron-injection buffer layer serves as the electron-injection layer in the light-emitting unit on the anode side and the light-emitting unit does not necessarily further need an electron-injection layer.
Note that when a layer in contact with a surface of the charge-generation layer 513 on the anode side in a light-emitting unit (typically, the electron-transport layer in the light-emitting unit on the anode side) contains the organometallic complex of one embodiment of the present invention, a light-emitting element with low power consumption can be obtained.
The light-emitting element having two light-emitting units is described with reference to
Furthermore, when emission colors of the light-emitting units are made different, light emission of a desired color can be obtained from the light-emitting element as a whole. For example, it is easy to enable a light-emitting element having two light-emitting units to emit white light as the whole element when the emission colors of the first light-emitting unit are red and green and the emission color of the second light-emitting unit is blue.
A light-emitting element with a microcavity structure is formed with the use of a reflective electrode and a semi-transmissive and semi-reflective electrode as the pair of electrodes. The reflective electrode and the semi-transmissive and semi-reflective electrode correspond to the first electrode and the second electrode described above. The light-emitting element with a microcavity structure includes at least an EL layer between the reflective electrode and the semi-transmissive and semi-reflective electrode. The EL layer includes at least a light-emitting layer serving as a light-emitting region.
Light emitted from the light-emitting layer included in the EL layer is reflected and resonated by the reflective electrode and the semi-transmissive and semi-reflective electrode. Note that the reflective electrode has a visible light reflectivity of 40% to 100%, preferably 70% to 100% and a resistivity of 1×10−2 Ωcm or lower. In addition, the semi-transmissive and semi-reflective electrode has a visible light reflectivity of 20% to 80%, preferably 40% to 70%, and a resistivity of 1×10−2 Ωcm or lower.
In the light-emitting element, by changing thicknesses of the transparent conductive film, the composite material, the carrier-transport material, and the like, the optical path length between the reflective electrode and the semi-transmissive and semi-reflective electrode can be changed. Thus, light with a wavelength that is resonated between the reflective electrode and the semi-transmissive and semi-reflective electrode can be intensified while light with a wavelength that is not resonated therebetween can be attenuated.
Note that light that is emitted from the light-emitting layer and reflected back by the reflective electrode (first reflected light) considerably interferes with light that directly enters the semi-transmissive and semi-reflective electrode from the light-emitting layer (first incident light). For this reason, the optical path length between the reflective electrode and the light-emitting layer is preferably adjusted to (2n−1)λ/4 (n is a natural number of 1 or larger and 2 is a wavelength of color to be amplified). In that case, the phases of the first reflected light and the first incident light can be aligned with each other and the light emitted from the light-emitting layer can be further amplified.
Note that in the above structure, the EL layer may be formed of light-emitting layers or may be a single light-emitting layer. The tandem light-emitting element described above may be combined with the EL layers; for example, a light-emitting element may have a structure in which a plurality of EL layers is provided, a charge-generation layer is provided between the EL layers, and each EL layer is formed of light-emitting layers or a single light-emitting layer.
A light-emitting device of one embodiment of the present invention is described using
Reference numeral 608 denotes a wiring for transmitting signals to be input to the source line driver circuit 601 and the gate line driver circuit 603 and receiving signals such as a video signal, a clock signal, a start signal, and a reset signal from a flexible printed circuit (FPC) 609 serving as an external input terminal. Although only the FPC is illustrated here, a printed wiring board (PWB) may be attached to the FPC. The light-emitting device in the present specification includes, in its category, not only the light-emitting device itself but also the light-emitting device provided with the FPC or the PWB.
Next, a cross-sectional structure will be described with reference to
As the source line driver circuit 601, a CMOS circuit in which an n-channel FET 623 and a p-channel FET 624 are combined is formed. In addition, the driver circuit may be formed with any of a variety of circuits such as a CMOS circuit, a PMOS circuit, or an NMOS circuit. Although a driver integrated type in which the driver circuit is formed over the substrate is described in this embodiment, the driver circuit is not necessarily formed over the substrate, and the driver circuit can be formed outside, not over the substrate.
The pixel portion 602 includes a plurality of pixels including a switching FET 611, a current controlling FET 612, and a first electrode 613 electrically connected to a drain of the current controlling FET 612. One embodiment of the present invention is not limited to the structure. The pixel portion may include three or more FETs and a capacitor in combination.
The kind and crystallinity of a semiconductor used for the FETs is not particularly limited; an amorphous semiconductor or a crystalline semiconductor may be used. Examples of the semiconductor used for the FETs include Group 13 semiconductors, Group 14 semiconductors, compound semiconductors, oxide semiconductors, and organic semiconductor materials. Oxide semiconductors are particularly preferable. Examples of the oxide semiconductor include an In—Ga oxide and an In-M-Zn oxide (M is Al, Ga, Y, Zr, La, Ce, or Nd). Note that an oxide semiconductor material that has an energy gap of 2 eV or more, preferably 2.5 eV or more, further preferably 3 eV or more is preferably used, in which case the off-state current of the transistors can be reduced.
Note that to cover an end portion of the first electrode 613, an insulator 614 is formed. The insulator 614 can be formed using a positive photosensitive acrylic resin film here.
The insulator 614 is formed to have a curved surface with curvature at its upper or lower end portion in order to obtain favorable coverage. For example, in the case where positive photosensitive acrylic is used for a material of the insulator 614, only the upper end portion of the insulator 614 preferably has a curved surface with a curvature radius (0.2 μm to 3 μm). As the insulator 614, either a negative photosensitive resin or a positive photosensitive resin can be used.
An EL layer 616 and a second electrode 617 are formed over the first electrode 613. The first electrode 613, the EL layer 616, and the second electrode 617 correspond, respectively, to the first electrode 101, the EL layer 103, and the second electrode 102 in
The EL layer 616 preferably contains the organometallic complex of one embodiment of the present invention. The organometallic complex is preferably used as an emission center substance in the light-emitting layer.
The sealing substrate 604 is attached to the element substrate 610 with the sealing material 605, so that a light-emitting element 618 is provided in the space 607 surrounded by the element substrate 610, the sealing substrate 604, and the sealing material 605. The space 607 is filled with a filler, and may be filled with an inert gas (such as nitrogen or argon) or the sealing material 605. It is preferable that the sealing substrate 604 be provided with a recessed portion and a drying agent be provided in the recessed portion, in which case deterioration due to influence of moisture can be suppressed.
An epoxy-based resin or glass frit is preferably used for the sealing material 605. It is preferable that such a material do not transmit moisture or oxygen as much as possible. As the element substrate 610 and the sealing substrate 604, a glass substrate, a quartz substrate, or a plastic substrate formed of fiber reinforced plastic (FRP), polyvinyl fluoride (PVF), polyester, or acrylic can be used.
Note that in this specification and the like, a transistor or a light-emitting element can be formed using any of a variety of substrates, for example. The type of a substrate is not limited to a certain type. As the substrate, a semiconductor substrate (e.g., a single crystal substrate or a silicon substrate), an SOI substrate, a glass substrate, a quartz substrate, a plastic substrate, a metal substrate, a stainless steel substrate, a substrate including stainless steel foil, a tungsten substrate, a substrate including tungsten foil, a flexible substrate, an attachment film, paper including a fibrous material, a base material film, or the like can be used, for example. As an example of a glass substrate, a barium borosilicate glass substrate, an aluminoborosilicate glass substrate, a soda lime glass substrate, or the like can be given. Examples of the flexible substrate, the attachment film, the base material film, and the like are substrates of plastics typified by polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polyether sulfone (PES). Another example is a synthetic resin such as acrylic. Alternatively, polytetrafluoroethylene (PTFE), polypropylene, polyester, polyvinyl fluoride, polyvinyl chloride, or the like can be used. Alternatively, polyamide, polyimide, aramid, epoxy, an inorganic vapor deposition film, paper, or the like can be used. Specifically, the use of semiconductor substrates, single crystal substrates, SOI substrates, or the like enables the manufacture of small-sized transistors with a small variation in characteristics, size, shape, or the like and with high current capability. A circuit using such transistors achieves lower power consumption of the circuit or higher integration of the circuit.
Alternatively, a flexible substrate may be used as the substrate, and the transistor or the light-emitting element may be provided directly on the flexible substrate. Still alternatively, a separation layer may be provided between the substrate and the transistor or the substrate and the light-emitting element. The separation layer can be used when part or the whole of a semiconductor device formed over the separation layer is separated from the substrate and transferred onto another substrate. In such a case, the transistor can be transferred to a substrate having low heat resistance or a flexible substrate. For the separation layer, a stack including inorganic films, which are a tungsten film and a silicon oxide film, or an organic resin film of polyimide or the like formed over a substrate can be used, for example.
In other words, a transistor or a light-emitting element may be formed using one substrate, and then transferred to another substrate. Examples of a substrate to which a transistor or a light-emitting element is transferred include, in addition to the above-described substrates over which transistors can be formed, a paper substrate, a cellophane substrate, an aramid film substrate, a polyimide film substrate, a stone substrate, a wood substrate, a cloth substrate (including a natural fiber (e.g., silk, cotton, or hemp), a synthetic fiber (e.g., nylon, polyurethane, or polyester), a regenerated fiber (e.g., acetate, cupra, rayon, or regenerated polyester), or the like), a leather substrate, and a rubber substrate. When such a substrate is used, a transistor with excellent characteristics or a transistor with low power consumption can be formed, a device with high durability or high heat resistance can be provided, or reduction in weight or thickness can be achieved.
In
Note that a light-emitting element including the organometallic complex of one embodiment of the present invention as a light-emitting substance can have high emission efficiency and low power consumption.
The above-described light-emitting device is a light-emitting device having a structure in which light is extracted from the substrate 1001 side where the FETs are formed (a bottom emission structure), but may be a light-emitting device having a structure in which light is extracted from the sealing substrate 1031 side (a top emission structure).
The first electrodes 1024W, 1024R, 1024G, and 1024B of the light-emitting elements each serve as an anode here, but may serve as a cathode. Furthermore, in the case of a light-emitting device having a top emission structure as illustrated in
In the case of a top emission structure as illustrated in
Although an example in which full color display is performed using four colors of red, green, blue, and white is shown here, there is no particular limitation and full color display using three colors of red, green, and blue or four colors of red, green, blue, and yellow may be performed.
Since many minute light-emitting elements arranged in a matrix can each be controlled with the FETs formed in the pixel portion, the above-described light-emitting device can be suitably used as a display device for displaying images.
A lighting device which is one embodiment of the present invention is described with reference to
In the lighting device, a first electrode 401 is formed over a substrate 400 which is a support and has a light-transmitting property. The first electrode 401 corresponds to the first electrode 101 in
A pad 412 for applying a voltage to a second electrode 404 is provided over the substrate 400.
An EL layer 403 is formed over the first electrode 401. The EL layer 403 corresponds to, for example, the EL layer 103 in
The second electrode 404 is formed to cover the EL layer 403. The second electrode 404 corresponds to the second electrode 102 in
A light-emitting element is formed with the first electrode 401, the EL layer 403, and the second electrode 404. The light-emitting element is fixed to a sealing substrate 407 with sealing materials 405 and 406 and sealing is performed, whereby the lighting device is completed. It is possible to use only either the sealing material 405 or the sealing material 406. In addition, the inner sealing material 406 (not shown in
When parts of the pad 412 and the first electrode 401 are extended to the outside of the sealing materials 405 and 406, the extended parts can serve as external input terminals. An IC chip 420 mounted with a converter or the like may be provided over the external input terminals.
Examples of an electronic device which is one embodiment of the present invention are described. Examples of the electronic device are television devices (also referred to as TV or television receivers), monitors for computers and the like, cameras such as digital cameras and digital video cameras, digital photo frames, mobile phones (also referred to as cell phones or mobile phone devices), portable game machines, portable information terminals, audio playback devices, and large game machines such as pachinko machines. Specific examples of these electronic devices are given below.
The television device can be operated with an operation switch of the housing 7101 or a separate remote controller 7110. With operation keys 7109 of the remote controller 7110, channels and volume can be controlled and images displayed on the display portion 7103 can be controlled. Furthermore, the remote controller 7110 may be provided with a display portion 7107 for displaying data output from the remote controller 7110.
Note that the television device is provided with a receiver, a modem, and the like. With the use of the receiver, general television broadcasting can be received. Moreover, when the television device is connected to a communication network with or without wires via the modem, one-way (from a sender to a receiver) or two-way (between a sender and a receiver or between receivers) information communication can be performed.
FIG. 7B1 illustrates a computer, which includes a main body 7201, a housing 7202, a display portion 7203, a keyboard 7204, an external connection port 7205, a pointing device 7206, and the like. Note that this computer is manufactured by using light-emitting elements arranged in a matrix in the display portion 7203. The computer illustrated in FIG. 7B1 may have a structure illustrated in FIG. 7B2. A computer illustrated in FIG. 7B2 is provided with a second display portion 7210 instead of the keyboard 7204 and the pointing device 7206. The second display portion 7210 is a touchscreen, and input can be performed by operation of display for input on the second display portion 7210 with a finger or a dedicated pen. The second display portion 7210 can also display images other than the display for input. The display portion 7203 may also be a touchscreen. Connecting the two screens with a hinge can prevent troubles; for example, the screens can be prevented from being cracked or broken while the computer is being stored or carried.
Information can be input to the portable information terminal illustrated in
There are mainly three screen modes of the display portion 7402. The first mode is a display mode mainly for displaying an image. The second mode is an input mode mainly for inputting information such as characters. The third mode is a display-and-input mode in which two modes of the display mode and the input mode are combined.
For example, in the case of making a call or creating an e-mail, a text input mode mainly for inputting text is selected for the display portion 7402 so that text displayed on a screen can be input. In this case, it is preferable to display a keyboard or number buttons on almost the entire screen of the display portion 7402.
When a detection device including a sensor such as a gyroscope sensor or an acceleration sensor for sensing inclination is provided inside the mobile phone, screen display of the display portion 7402 can be automatically changed by determining the orientation of the mobile phone (whether the mobile phone is placed horizontally or vertically).
The screen modes are switched by touch on the display portion 7402 or operation with the operation buttons 7403 of the housing 7401. The screen modes can be switched depending on the kind of images displayed on the display portion 7402. For example, when a signal of an image displayed on the display portion is a signal of moving image data, the screen mode is switched to the display mode. When the signal is a signal of text data, the screen mode is switched to the input mode.
Moreover, in the input mode, when input by touching the display portion 7402 is not performed for a certain period while a signal detected by an optical sensor in the display portion 7402 is detected, the screen mode may be controlled so as to be switched from the input mode to the display mode.
The display portion 7402 may function as an image sensor. For example, an image of a palm print, a fingerprint, or the like is taken by the display portion 7402 while in touch with the palm or the finger, whereby personal authentication can be performed. Furthermore, by providing a backlight or a sensing light source which emits near-infrared light in the display portion, an image of a finger vein, a palm vein, or the like can be taken.
Note that in the above electronic devices, any of the structures described in this specification can be combined as appropriate.
The display portion preferably includes a light-emitting element including the organometallic complex of one embodiment of the present invention. The light-emitting element can have high emission efficiency. Furthermore, the light-emitting element can be driven at low voltage. Thus, the electronic device including the organometallic complex of one embodiment of the present invention can have low power consumption.
As the light-emitting element, a light-emitting element including the organometallic complex of one embodiment of the present invention is preferably used. By including the light-emitting element, the backlight of the liquid crystal display device can have low power consumption.
An automobile which is one embodiment of the present invention is illustrated in
The display regions 5000 and 5001 are display devices which are provided in the automobile windshield and which include the light-emitting elements. When a first electrode and a second electrode are formed of electrodes having light-transmitting properties in these light-emitting elements, what is called a see-through display device, through which the opposite side can be seen, can be obtained. Such a see-through display device can be provided even in the automobile windshield, without hindering the vision. Note that in the case where a transistor for driving or the like is provided, a transistor having a light-transmitting property, such as an organic transistor using an organic semiconductor material or a transistor using an oxide semiconductor, is preferably used.
The display region 5002 is a display device which is provided in a pillar portion and which includes the light-emitting element. The display region 5002 can compensate for the view hindered by the pillar portion by showing an image taken by an imaging unit provided in the car body. Similarly, a display region 5003 provided in the dashboard can compensate for the view hindered by the car body by showing an image taken by an imaging unit provided in the outside of the car body, which leads to elimination of blind areas and enhancement of safety. Showing an image so as to compensate for the area which a driver cannot see makes it possible for the driver to confirm safety easily and comfortably.
The display region 5004 and the display region 5005 can provide a variety of kinds of information such as navigation information, a speedometer, a tachometer, a mileage, a fuel meter, a gearshift indicator, and air-condition setting. The content or layout of the display can be changed freely by a user as appropriate. Note that such information can also be shown by the display regions 5000 to 5003. The display regions 5000 to 5005 can also be used as lighting devices.
Part of the display portion 9631a can be a touchscreen region 9632a and data can be input when a displayed operation key 9637 is touched. Although half of the display portion 9631a has only a display function and the other half has a touchscreen function, one embodiment of the present invention is not limited to the structure. The whole display portion 9631a may have a touchscreen function. For example, a keyboard can be displayed on the entire region of the display portion 9631a so that the display portion 9631a is used as a touchscreen, and the display portion 9631b can be used as a display screen.
Like the display portion 9631a, part of the display portion 9631b can be a touchscreen region 9632b. When a switching button 9639 for showing/hiding a keyboard on the touchscreen is touched with a finger, a stylus, or the like, the keyboard can be displayed on the display portion 9631b.
Touch input can be performed in the touchscreen region 9632a and the touchscreen region 9632b at the same time.
The display mode switch 9034 can switch the display between portrait mode, landscape mode, and the like, and between monochrome display and color display, for example. The power-saving mode switch 9036 can control display luminance in accordance with the amount of external light in use of the tablet terminal sensed by an optical sensor incorporated in the tablet terminal. Another sensing device including a sensor such as a gyroscope sensor or an acceleration sensor for sensing inclination may be incorporated in the tablet terminal, in addition to the optical sensor.
Although
Since the tablet terminal is foldable, the housing 9630 can be closed when the tablet terminal is not in use. As a result, the display portion 9631a and the display portion 9631b can be protected, thereby providing a tablet terminal with high endurance and high reliability for long-term use.
The tablet terminal illustrated in
The solar cell 9633 provided on a surface of the tablet terminal can supply power to the touchscreen, the display portion, a video signal processing portion, or the like. Note that a structure in which the solar cell 9633 is provided on one or both surfaces of the housing 9630 is preferable because the battery 9635 can be charged efficiently.
The structure and operation of the charge and discharge control circuit 9634 illustrated in
First, description is made on an example of the operation in the case where power is generated by the solar cell 9633 with the use of external light. The voltage of the power generated by the solar cell is raised or lowered by the DCDC converter 9636 so as to be voltage for charging the battery 9635. Then, when power from the solar cell 9633 is used for the operation of the display portion 9631, the switch SW1 is turned on and the voltage of the power is raised or lowered by the converter 9638 so as to be voltage needed for the display portion 9631. When images are not displayed on the display portion 9631, the switch SW1 is turned off and the switch SW2 is turned on so that the battery 9635 is charged.
Although the solar cell 9633 is described as an example of a power generation unit, the power generation unit is not particularly limited, and the battery 9635 may be charged by another power generation unit such as a piezoelectric element or a thermoelectric conversion element (Peltier element). The battery 9635 may be charged by a non-contact power transmission module capable of performing charging by transmitting and receiving power wirelessly (without contact), or another charge unit used in combination, and the power generation unit is not necessarily provided.
Note that the organometallic complex of one embodiment of the present invention can be used for an organic thin-film solar cell. Specifically, the organometallic complex can be used in a carrier-transport layer since the organometallic complex has a carrier-transport property. The organometallic complex can be photoexcited and hence can be used in a power generation layer.
One embodiment of the present invention is not limited to the tablet terminal having the shape illustrated in
A display panel 9311 is supported by three housings 9315 joined together by hinges 9313. Note that the display panel 9311 may be a touch panel (an input/output device) including a touch sensor (an input device). By bending the display panel 9311 at a connection portion between two housings 9315 with the use of the hinges 9313, the portable information terminal 9310 can be reversibly changed in shape from an opened state to a folded state. The light-emitting device of one embodiment of the present invention can be used for the display panel 9311. A display region 9312 in the display panel 9311 is a display region that is positioned at the side surface of the portable information terminal 9310 that is folded. On the display region 9312, information icons, file shortcuts of frequently used applications or programs, and the like can be displayed, and confirmation of information and start of application can be smoothly performed.
In this example, a method for synthesizing tris{2-[5-(2-methylphenyl)-4-(2,6-dimethylpyridin-3-yl)-4H-1,2,4-triazol-3-yl-κN2]phenyl-κC}iridium(III) (abbreviation: [Ir(mpptz-dmpy)3]), which is one embodiment of the present invention and represented by Structural Formula (100) in the above embodiment, is described. The structure of [Ir(mpptz-dmpy)3] is shown below.
Into a 300 mL three-neck flask were put 10 g (34.2 mmol) of N-(chlorophenylmethylene)-2-methyl-benzenecarbohydrazoylchloride, 20 g (163.7 mmol) of 3-amino-2,4-dimethylpyridine, and 100 mL of N,N-dimethylaniline, and the mixture was stirred at 180° C. under a nitrogen stream for 35 hours to be reacted. After the reaction, 1M hydrochloric acid was added to the reacted solution to neutralize the mixed solution. An organic layer was extracted from the neutralized solution with the use of ethyl acetate. This organic layer was washed with a saturated aqueous solution of sodium hydrogen carbonate, water, and saturated saline in this order. Anhydrous magnesium sulfate was added to the washed organic layer for drying, and the resulting mixture was subjected to gravity filtration to give a filtrate. Ethyl acetate of this filtrate was distilled off, and then purification was performed by silica column chromatography. As a developing solvent, ethyl acetate and hexane were used. The solvent of the resulting fraction was distilled off and recrystallization was performed, so that 1.5 g (4.4 mmol) of a white solid was obtained in a yield of 13%. The obtained white solid was identified as Hmpptz-dmpy by nuclear magnetic resonance (NMR). A synthesis scheme of Step 1 is shown in (a-1) below.
Into a reaction container were put 1.5 g (4.4 mmol) of Hmpptz-dmpy and 0.43 g (0.88 mmol) of tris(acetylacetonato)iridium(III), and the mixture was stirred under an argon stream at 250° C. for 35 hours to be reacted. After the reaction, ethyl acetate was added to the obtained reaction mixture, and the mixture was subjected to filtration to give a filtrate. Ethyl acetate of the filtrate was distilled off, so that a solid was obtained. This solid was purified by silica column chromatography. As a developing solvent, ethyl acetate and dichloromethane were used. The solvent of the obtained fraction was distilled off, recrystallization was performed, and then the obtained solid was purified by a train sublimation method, so that 60 mg (50 μmol) of a yellow solid was obtained in a yield of 5.7%. A synthesis scheme of Step 2 is shown in (b-1) below.
The mass spectrum of the yellow solid obtained in Step 2 was measured. The results are shown below.
ESI-MS (m/z): Calcd, C66H57IrN12: 1210.4, found: 1211.0[M+H+].
These results reveal that [Ir(mpptz-dmpy)3], which is represented by Structural Formula (100), was obtained in this synthesis example.
Next, an ultraviolet-visible absorption spectrum (hereinafter, simply referred to as absorption spectrum) and an emission spectrum of a dichloromethane solution of [Ir(mpptz-dmpy)3] were measured. The measurement of the absorption spectrum was conducted at room temperature, for which an ultraviolet and visible spectrophotometer (V550 type manufactured by JASCO Corporation) was used and the dichloromethane solution (0.0100 mmol/L) of [Ir(mpptz-dmpy)3] was put in a quartz cell. In addition, the measurement of the emission spectrum was performed at room temperature in such a manner that an absolute PL quantum yield measurement system (C11347-01 manufactured by Hamamatsu Photonics K. K.) was used and a dichloromethane solution (0.0100 mmol/L) of [Ir(mpptz-dmpy)3] was adjusted with dichloromethane having 1 ppm or less of dissolved oxygen and was sealed in a quartz cell under a nitrogen atmosphere in a glove box (LABstar M13 (1250/780) manufactured by Bright Co., Ltd.).
As shown in
Next, [Ir(mpptz-dmpy)3] (abbreviation) obtained in this example was subjected to a MS analysis by liquid chromatography mass spectrometry (LC/MS).
In the LC-MS analysis, liquid chromatography (LC) separation was carried out with ACQUITY UPLC (registered trademark) manufactured by Waters Corporation, and mass spectrometry (MS) was carried out with Xevo G2 Tof MS manufactured by Waters Corporation. ACQUITY UPLC (registered trademark) BEH C8 (2.1×100 mm, 1.7 μm) was used as a column for the LC separation, and the column temperature was 40° C. Acetonitrile was used for Mobile Phase A and a 0.1% formic acid aqueous solution was used for Mobile Phase B. Furthermore, a sample was prepared in such a manner that [Ir(mpptz-dmpy)3] was dissolved in chloroform at a given concentration and the mixture was diluted with acetonitrile. The injection amount was 5.0 μL.
In the LC separation, a gradient method in which the composition of mobile phases is changed was employed. The ratio of Mobile Phase A to Mobile Phase B was 30:70 for 0 to 1 minute after the start of the measurement, and then the composition was changed such that the ratio of Mobile Phase A to Mobile Phase B after 30 minutes from the start of the measurement was 95:5. The composition was changed linearly.
In the MS analysis, ionization was carried out by an electrospray ionization (abbreviation: ESI) method. At this time, the capillary voltage and the sample cone voltage were set to 3.0 kV and 30 V, respectively, and detection was performed in a positive mode. A component with m/z of 1210.96 which underwent the ionization under the above-described conditions was collided with an argon gas in a collision cell to dissociate into product ions. Energy (collision energy) for the collision with argon was 50 eV. The mass range for the measurement was m/z=100 to 1500. The detection result of the dissociated product ions by time-of-flight (TOF) MS are shown in
It is presumed that the product ion around m/z=871 is a cation in a state where the ligand Hmpptz-dmpy is eliminated from [Ir(mpptz-dmpy)3]. It is presumed that the product ion around m/z=341 is a cation in a state where a proton was added to the ligand Hmpptz-dmpy, that the product ion around nm/z=224 is a cation in a state where dimethyl pyridine and methane are further eliminated from the product ion around m/z=341, and that the product ion around m/z=121 is a cation in a state where benzylamine is further eliminated from the product ion around m/z=224, which are characteristic of [Ir(mpptz-dmpy)3].
In this example, a method for synthesizing tris{2-[5-phenyl-4-(2,6-dimethylpyridin-3-yl)-4H-1,2,4-triazol-3-yl-κN2]phenyl-κC}iridium(III) (abbreviation: [Ir(taz-dmpy)3]), which is one embodiment of the present invention and represented by Structural Formula (101) in the above embodiment, is described. Note that a structure of [Ir(taz-dmpy)3] is shown below.
Into a 1-L three-neck flask was put 12 g (50 mmol) of N,N′-dibenzoylhydrazine, and the air in the flask was replaced with nitrogen. After that, 250 mL of dehydrated toluene was added, and stirring was performed. Then, 25 g (123 mmol) of phosphorus pentachloride was added under a nitrogen stream, the temperature was slowly raised up to 120° C., and the mixture was stirred for six hours to be reacted. After the reaction, the reacted solution was added to 500 mL of water, and stirring was performed for 3 hours. This mixture was separated into an aqueous layer and an organic layer, and the aqueous layer was subjected to extraction with toluene. A solution obtained by combining the solution of the extract and the organic layer was washed with a saturated aqueous solution of sodium hydrogen carbonate, water, and saturated saline in this order. Then, anhydrous magnesium sulfate was added to the washed organic layer for drying, and the resulting mixture was subjected to gravity filtration to give a filtrate. The solvent of the filtrate was distilled off, and then the remaining solvent was removed under a reduced pressure, so that 12.7 g (43 mmol) of a yellow oily substance was obtained in a yield of 87%. The obtained yellow oily substance was identified as bis(N-chlorophenylmethylidene)hydrazine by nuclear magnetic resonance (NMR). A synthesis scheme of Step 1 is shown in (al-2) below.
Into a 300 mL three-neck flask were put 12.5 g (42.8 mmol) of bis(N-chlorophenylmethylidene)hydrazine synthesized in Step 1, 25 g (206 mmol) of 3-amino-2,4-dimethylpyridine, and 100 mL of N,N-dimethylaniline, and the mixture was stirred under a nitrogen stream at 180° C. for 20 hours to be reacted. After the reaction, 1M hydrochloric acid was added to the reacted solution to neutralize the mixed solution. An organic layer was extracted from the neutralized solution with the use of ethyl acetate. This organic layer was washed with a saturated aqueous solution of sodium hydrogen carbonate, water, and saturated saline in this order. Anhydrous magnesium sulfate was added to the washed organic layer for drying, and the resulting mixture was subjected to gravity filtration to give a filtrate. Ethyl acetate of this filtrate was distilled off, and then purification was performed by silica column chromatography. As a developing solvent, ethyl acetate and toluene were used. The solvent of the resulting fraction was distilled off and recrystallization was performed, so that 6.3 g (19 mmol) of a white solid was obtained in a yield of 45%. The obtained white solid was identified as Htaz-dmpy by nuclear magnetic resonance (NMR). A synthesis scheme of Step 2 is shown in (a-2) below.
Into a reaction container were put 2 g (6.1 mmol) of Htaz-dmpy and 0.60 g (1.2 mmol) of tris(acetylacetonato)iridium (III), and the mixture was stirred under an argon stream at 250° C. for 17 hours to be reacted. After the reaction, ethyl acetate was added to the obtained reaction mixture, and the mixture was subjected to filtration to give a filtrate. Ethyl acetate of the filtrate was distilled off, so that a solid was obtained. This solid was purified by silica column chromatography. As a developing solvent, ethyl acetate and dichloromethane were used. The solvent of the obtained fraction was distilled off, recrystallization was performed, and then the obtained solid was purified by a train sublimation method, so that 134 mg (0.12 μmol) of a yellow solid was obtained in a yield of 20%. A synthesis scheme of Step 3 is shown in (b-2) below.
The mass spectrum of the yellow solid obtained in Step 3 was measured. The results are shown below.
ESI-MS (m/z): Calcd, C63H51IrN12: 1168.4, found: 1169.4[M+H+].
These results reveal that [Ir(taz-dmpy)3], which is represented by Structural Formula (101), was obtained in this synthesis example.
Next, an ultraviolet-visible absorption spectrum (hereinafter, simply referred to as absorption spectrum) and an emission spectrum of a dichloromethane solution of [Ir(taz-dmpy)3] were measured. The measurement of the absorption spectrum was conducted at room temperature, for which an ultraviolet and visible spectrophotometer (V550 type manufactured by JASCO Corporation) was used and the dichloromethane solution (0.0100 mmol/L) of [Ir(taz-dmpy)3] was put in a quartz cell. In addition, the measurement of the emission spectrum was performed at room temperature in such a manner that an absolute PL quantum yield measurement system (C11347-01 manufactured by Hamamatsu Photonics K. K.) was used and a dichloromethane solution (0.0100 mmol/L) of [Ir(taz-dmpy)3] was adjusted with dichloromethane having 1 ppm or less of dissolved oxygen and was sealed in a quartz cell under a nitrogen atmosphere in a glove box (LABstar M13 (1250/780) manufactured by Bright Co., Ltd.).
As shown in
Next, [Ir(taz-dmpy)3] obtained in this example was subjected to a MS analysis by liquid chromatography mass spectrometry (LC/MS).
In the LC-MS analysis, liquid chromatography (LC) separation was carried out with ACQUITY UPLC (registered trademark) manufactured by Waters Corporation, and mass spectrometry (MS) was carried out with Xevo G2 Tof MS manufactured by Waters Corporation. ACQUITY UPLC BEH C8 (2.1×100 mm, 1.7 m) was used as a column for the LC separation, and the column temperature was set to 40° C. Acetonitrile was used for Mobile Phase A and a 0.1% formic acid aqueous solution was used for Mobile Phase B. Furthermore, a sample was prepared in such a manner that [Ir(taz-dmpy)3] was dissolved in chloroform at a given concentration and the mixture was diluted with acetonitrile. The injection amount was 5.0 μL.
In the LC separation, a gradient method in which the composition of mobile phases is changed was employed. The ratio of Mobile Phase A to Mobile Phase B was 55:45 for 0 to 1 minute after the start of the measurement, and then the composition was changed such that the ratio of Mobile Phase A to Mobile Phase B after 10 minutes from the start of the measurement was 95:5. The composition was changed linearly.
In the MS analysis, ionization was carried out by an electrospray ionization (abbreviation: ESI) method. At this time, the capillary voltage and the sample cone voltage were set to 3.0 kV and 30 V, respectively, and detection was performed in a positive mode. A component with m/z of 1169.40 which underwent the ionization under the above-described conditions was collided with an argon gas in a collision cell to dissociate into product ions. Energy (collision energy) for the collision with argon was 50 eV. The mass range for the measurement was m/z=100 to 1500. The detection result of the dissociated product ions by time-of-flight (TOF) MS are shown in
It is presumed that the product ion around m/z=843 is a cation in a state where the ligand Htaz-dmpy is eliminated from [Ir(taz-dmpy)3]. It is presumed that the product ion around m/z=327 is a cation in a state where a proton was added to the ligand Htaz-dmpy, that the product ion around m/z=224 is a cation in a state where dimethyl pyridine is eliminated from the ligand Htaz-dmpy, and that the product ion around m/z=121 is a cation in a state where benzylamine is further eliminated from the product ion around m/z=224, which are characteristic of [Ir(taz-dmpy)3].
In this example, a method for synthesizing tris{2-[5-(2-methylphenyl)-4-(2,4,6-trimethylpyridin-3-yl)-4H-1,2,4-triazol-3-yl-κN2]phenyl-κC}iridium(III) (abbreviation: [Ir(mpptz-tmpy)3]), which is one embodiment of the present invention and represented by Structural Formula (102), is described. The structure of [Ir(mpptz-tmpy)3] is shown below.
Into a 300 mL three-neck flask were put 17.1 g (59 mmol) of N-(chlorophenylmethylene)-2-methyl-benzenecarbohydrazylchloride, 24 g (176 mmol) of 3-amino-2,4,6-trimethylpyridine, and 240 mL of N,N-dimethylaniline, and the mixture was stirred under a nitrogen stream at 180° C. for 32 hours to be reacted. After the reaction, 1M hydrochloric acid was added to the reacted solution to neutralize the mixed solution. An organic layer was extracted from the neutralized solution with the use of ethyl acetate. This organic layer was washed with a saturated aqueous solution of sodium hydrogen carbonate, water, and saturated saline in this order. Anhydrous magnesium sulfate was added to the washed organic layer for drying, and the resulting mixture was subjected to gravity filtration to give a filtrate. Ethyl acetate of this filtrate was distilled off, and then purification was performed by silica column chromatography. As a developing solvent, ethyl acetate was used. The solvent of the resulting fraction was distilled off and recrystallization was performed, so that 3.9 g (11 mmol) of a white solid was obtained in a yield of 19%. The obtained white solid was identified as Hmpptz-tmpy by nuclear magnetic resonance (NMR). A synthesis scheme of Step 1 is shown in (a-3) below.
Into a reaction container were put 3.8 g (11 mmol) of Hmpptz-tmnpy and 1.3 g (2.7 mmol) of tris(acetylacetonato)iridium (III), and the mixture was stirred under an argon stream at 250° C. for 35 hours to be reacted. After the reaction, ethyl acetate was added to the obtained reaction mixture, and the mixture was subjected to filtration, so that a yellow solid was collected. This yellow solid was recrystallized, and then purification was performed by a train sublimation method, so that 0.56 g (0.45 mmnol) of a yellow solid was obtained in a yield of 16%. A synthesis scheme of Step 2 is shown in (b-3) below.
The mass spectrum of the yellow solid obtained in Step 2 was measured. The results are shown below.
ESI-MS (m/z): Calcd, C69H63IrN12: 1252.5, found: 1253.5 [M+H+].
These results reveal that [Ir(mpptz-tmpy)3], which is the organometallic complex of one embodiment of the present invention represented by Structural Formula (102), was obtained in this synthesis example.
Next, an ultraviolet-visible absorption spectrum (hereinafter, simply referred to as absorption spectrum) and an emission spectrum of a dichloromethane solution of [Ir(mpptz-tmpy)3] were measured. The measurement of the absorption spectrum was conducted at room temperature, for which an ultraviolet and visible spectrophotometer (V550 type manufactured by JASCO Corporation) was used and the dichloromethane solution (0.0100 mmol/L) of [Ir(mpptz-tmpy)3] was put in a quartz cell. In addition, the measurement of the emission spectrum was performed at room temperature in such a manner that an absolute PL quantum yield measurement system (C11347-01 manufactured by Hamamatsu Photonics K. K.) was used and a dichloromethane solution (0.0100 mmol/L) of [Ir(mpptz-tmpy)3] was adjusted with dichloromethane having 1 ppm or less of dissolved oxygen and was sealed in a quartz cell under a nitrogen atmosphere in a glove box (LABstar M13 (1250/780) manufactured by Bright Co., Ltd.).
As shown in
Next, [Ir(mpptz-tmpy)3] obtained in this example was subjected to a MS analysis by liquid chromatography mass spectrometry (LC/MS).
In the LC-MS analysis, liquid chromatography (LC) separation was carried out with ACQUITY UPLC (registered trademark) manufactured by Waters Corporation, and mass spectrometry (MS) was carried out with Xevo G2 Tof MS manufactured by Waters Corporation. ACQUITY UPLC BEH C8 (2.1×100 mm, 1.7 μm) was used as a column for the LC separation, and the column temperature was set to 40° C. Acetonitrile was used for Mobile Phase A and a 0.1% formic acid aqueous solution was used for Mobile Phase B. Furthermore, a sample was prepared in such a manner that [Ir(mpptz-tmpy)3] was dissolved in chloroform at a given concentration and the mixture was diluted with acetonitrile. The injection amount was 5.0 μL.
In the LC separation, a gradient method in which the composition of mobile phases is changed was employed. The ratio of Mobile Phase A to Mobile Phase B was 60:40 for 0 to 1 minute after the start of the measurement, and then the composition was changed such that the ratio of Mobile Phase A to Mobile Phase B after 10 minutes from the start of the measurement was 95:5. The composition was changed linearly.
In the MS analysis, ionization was carried out by an electrospray ionization (abbreviation: ESI) method. At this time, the capillary voltage and the sample cone voltage were set to 3.0 kV and 30 V, respectively, and detection was performed in a positive mode. A component with m/z of 1253.50 which underwent the ionization under the above-described conditions was collided with an argon gas in a collision cell to dissociate into product ions. Energy (collision energy) for the collision with argon was 50 eV. The mass range for the measurement was m/z=100 to 2000. The detection result of the dissociated product ions by time-of-flight (TOF) MS are shown in
It is presumed that the product ion around m/z=899 is a cation in a state where the ligand Hmnpptz-tmpy is eliminated from [Ir(mpptz-tmpy)3]. It is presumed that the product ion around m/z=355 is a cation in a state where a proton was added to the ligand Hmpptz-tmpy, that the product ion around m/z=238 is a cation in a state where trimethylpyridine is further eliminated from the product ion around m/z=355, and that the product ion around m/z=135 is a cation in a state where benzylamine is further eliminated from the product ion around m/z=238, which are characteristic of [Ir(mpptz-tmpy)3].
In this example, Light-emitting element 1, which is a light-emitting element of one embodiment of the present invention, is described. Structural formulae of organic compounds used for Light-emitting element 1 are shown below.
First, a film of indium tin oxide containing silicon oxide (ITSO) was formed over a glass substrate by a sputtering method, so that the first electrode 101 was formed. The thickness of the first electrode 101 was 110 nm and the electrode area was 2 mm×2 mm.
Next, in pretreatment for forming the light-emitting element over the substrate, a surface of the substrate was washed with water and baked at 200° C. for 1 hour, and then UV ozone treatment was performed for 370 seconds.
After that, the substrate was transferred into a vacuum evaporation apparatus where the pressure had been reduced to approximately 10−4 Pa, and was subjected to vacuum baking at 170° C. for 30 minutes in a heating chamber of the vacuum evaporation apparatus, and then the substrate was cooled down for about 30 minutes.
Then, the substrate over which the first electrode 101 was formed was fixed to a substrate holder provided in the vacuum evaporation apparatus so that the surface on which the first electrode 101 was formed faced downward. Over the first electrode 101, 4,4′,4″-(benzene-1,3,5-triyl)tri(dibenzothiophene) (abbreviation: DBT3P-II) represented by Structural Formula (i) and molybdenum(VI) oxide were deposited by co-evaporation to a thickness of 60 nm at a weight ratio of 2:1 (=DBT3P-II:molybdenum oxide) by an evaporation method using resistance heating, so that the hole-injection layer 111 was formed.
Next, 3,3′-bis(9-phenyl-9H-carbazole) (abbreviation: PCCP) represented by Structural Formula (ii) was deposited by evaporation to a thickness of 20 nm over the hole-injection layer 111 to form the hole-transport layer 112.
Then, PCCP, 3,5-bis[3-(9H-carbazol-9-yl)phenyl]pyridine (abbreviation: 35DCzPPy) represented by Structural Formula (iii), and tris{2-[5-(2-methylphenyl)-4-(2,6-dimethylpyridin-3-yl)-4H-1,2,4-triazol-3-yl-κN2]phenyl-κC}iridium(III) (abbreviation: [Ir(mpptz-dmpy)3]) represented by Structural Formula (iv) were deposited by co-evaporation to a thickness of 30 nm so that PCCP:35DCzPPy:[Ir(mpptz-dmpy)3])=1.0:0.3:0.1 (weight ratio), and then, 35DCzPPy and [Ir(mpptz-dmpy)3]) were deposited by co-evaporation to a thickness of 10 nm so that 35DCzPPy:[Ir(mpptz-dmpy)3])=1.0:0.06 (weight ratio), whereby the light-emitting layer 113 was formed.
Then, over the light-emitting layer 113, a film of 35DCzPPy was formed to a thickness of 10 nm by evaporation, and a film of bathophenanthroline (abbreviation: BPhen) represented by Structural Formula (v) was formed to a thickness of 15 nm by evaporation to form the electron-transport layer 114.
After the formation of the electron-transport layer 114, lithium fluoride (LiF) was deposited by evaporation to a thickness of 1 nm to form the electron-injection layer 115. Then, aluminum was deposited by evaporation to a thickness of 200 nm to form the second electrode 102. Through the above-described steps, Light-emitting element 1 of this example was fabricated.
The element structure of Light-emitting element 1 is shown in a table below.
Light-emitting element 1 was sealed using a glass substrate in a glove box containing a nitrogen atmosphere so as not to be exposed to the air (specifically, a sealing material was applied to surround the element and UV treatment and heat treatment at 80° C. for 1 hour were performed at the time of sealing). Then, the initial characteristics of Light-emitting element 1 were measured. Note that the measurement was carried out in an atmosphere kept at 25° C.
It is found from
In this example, Light-emitting element 2, which is a light-emitting element of one embodiment of the present invention, is described. Structural formulae of organic compounds used for Light-emitting element 2 are shown below.
First, a film of indium tin oxide containing silicon oxide (ITSO) was formed over a glass substrate by a sputtering method, so that the first electrode 101 was formed. The thickness of the first electrode 101 was 110 nm and the electrode area was 2 mm×2 mm.
Next, in pretreatment for forming the light-emitting element over the substrate, a surface of the substrate was washed with water and baked at 200° C. for 1 hour, and then UV ozone treatment was performed for 370 seconds.
After that, the substrate was transferred into a vacuum evaporation apparatus where the pressure had been reduced to approximately 10−4 Pa, and was subjected to vacuum baking at 170° C. for 30 minutes in a heating chamber of the vacuum evaporation apparatus, and then the substrate was cooled down for about 30 minutes.
Then, the substrate over which the first electrode 101 was formed was fixed to a substrate holder provided in the vacuum evaporation apparatus so that the surface on which the first electrode 101 was formed faced downward. Over the first electrode 101, 4,4′,4″-(benzene-1,3,5-triyl)tri(dibenzothiophene) (abbreviation: DBT3P-II) represented by Structural Formula (i) and molybdenum(VI) oxide were deposited by co-evaporation to a thickness of 70 nm at a weight ratio of 2:1 (=DBT3P-II:molybdenum oxide) by an evaporation method using resistance heating, so that the hole-injection layer 111 was formed.
Next, 3,3′-bis(9-phenyl-9H-carbazole) (abbreviation: PCCP) represented by Structural Formula (ii) was deposited by evaporation to a thickness of 20 nm over the hole-injection layer 111 to form the hole-transport layer 112.
Then, PCCP, 3,5-bis[3-(9H-carbazol-9-yl)phenyl]pyridine (abbreviation: 35DCzPPy) represented by Structural Formula (iii), and tris{2-[5-phenyl-4-(2,6-dimethylpyridin-3-yl)-4H-1,2,4-triazol-3-yl-κN2]phenyl-κC}iridium(III) (abbreviation: [Ir(taz-dmpy)3]) represented by Structural Formula (vi) were deposited by co-evaporation to a thickness of 30 nm so that PCCP:35DCzPPy:[Ir(taz-dmpy)3]=1.0:0.3:0.06 (weight ratio), and then, 35DCzPPy and [Ir(taz-dmpy)3] were deposited by co-evaporation to a thickness of 10 inn so that 35DCzPPy:[Ir(taz-dmpy)3]=1.0:0.06 (weight ratio), whereby the light-emitting layer 113 was formed.
Then, over the light-emitting layer 113, a film of 35DCzPPy was formed to a thickness of 10 nm by evaporation, and a film of bathophenanthroline (abbreviation: BPhen) represented by Structural Formula (v) was formed to a thickness of 15 nm by evaporation to form the electron-transport layer 114.
After the formation of the electron-transport layer 114, lithium fluoride (LiF) was deposited to a thickness of 1 nm by evaporation to form the electron-injection layer 115. Then, aluminum was deposited to a thickness of 200 nm by evaporation to form the second electrode 102. Through the above-described steps, Light-emitting element 2 of this example was fabricated.
The element structure of Light-emitting element 2 is shown in a table below.
Light-emitting element 2 was sealed using a glass substrate in a glove box containing a nitrogen atmosphere so as not to be exposed to the air (specifically, a sealing material was applied to surround the element and UV treatment and heat treatment at 80° C. for 1 hour were performed at the time of sealing). Then, the initial characteristics of Light-emitting element 2 were measured. Note that the measurement was carried out in an atmosphere kept at 25° C.
It is found from
In this example, Light-emitting element 3, which is a light-emitting element of one embodiment of the present invention, is described. Structural formulae of organic compounds used for Light-emitting element 3 are shown below.
First, a film of indium tin oxide containing silicon oxide (ITSO) was formed over a glass substrate by a sputtering method, so that the first electrode 101 was formed. The thickness of the first electrode 101 was 70 nm and the electrode area was 2 mm×2 mm.
Next, in pretreatment for forming the light-emitting element over the substrate, a surface of the substrate was washed with water and baked at 200° C. for 1 hour, and then UV ozone treatment was performed for 370 seconds.
After that, the substrate was transferred into a vacuum evaporation apparatus where the pressure had been reduced to approximately 10−4 Pa, and was subjected to vacuum baking at 170° C. for 30 minutes in a heating chamber of the vacuum evaporation apparatus, and then the substrate was cooled down for about 30 minutes.
Then, the substrate over which the first electrode 101 was formed was fixed to a substrate holder provided in the vacuum evaporation apparatus so that the surface on which the first electrode 101 was formed faced downward. Over the first electrode 101, 4,4′,4″-(benzene-1,3,5-triyl)tri(dibenzothiophene) (abbreviation: DBT3P-II) represented by Structural Formula (i) above and molybdenum(VI) oxide were deposited to a thickness of 15 nm by an evaporation method using resistance heating so that the weight ratio was 2:1 (=DBT3P-II:molybdenum oxide), whereby the hole-injection layer 111 was formed.
Next, 3,3′-bis(9-phenyl-9H-carbazole) (abbreviation: PCCP) represented by Structural Formula (ii) was deposited by evaporation to a thickness of 20 nm over the hole-injection layer 111 to form the hole-transport layer 112.
Then, PCCP, 3,5-bis[3-(9H-carbazol-9-yl)phenyl]pyridine (abbreviation: 35DCzPPy) represented by Structural Formula (iii), and tris{2-[5-(2-methylphenyl)-4-(2,4,6-trimethylpyridin-3-yl)-4H-1,2,4-triazol-3-yl-κN2]phenyl-κC}iridium (III)} (abbreviation: [Ir(mpptz-tmpy)3]) represented by Structural Formula (vii) were deposited by co-evaporation to a thickness of 30 nm so that PCCP:35DCzPPy:[Ir(mpptz-tmpy)3])=1.0:0.3:0.06 (weight ratio), and then, 35DCzPPy and [Ir(mpptz-tmpy)3]) were deposited by co-evaporation to a thickness of 10 in so that 35DCzPPy:[Ir(mpptz-tmpy)3])=1.0:0.06 (weight ratio), whereby the light-emitting layer 113 was formed.
Then, over the light-emitting layer 113, a film of 35DCzPPy was formed to a thickness of 10 nm by evaporation, and a film of bathophenanthroline (abbreviation: BPhen) represented by Structural Formula (v) was formed to a thickness of 15 nm by evaporation to form the electron-transport layer 114.
After the formation of the electron-transport layer 114, lithium fluoride (LiF) was deposited to a thickness of 1 nm by evaporation to form the electron-injection layer 115. Then, aluminum was deposited to a thickness of 200 nm by evaporation to form the second electrode 102. Through the above-described steps, Light-emitting element 3 of this example was fabricated.
The element structure of Light-emitting element 3 is shown in a table below.
Light-emitting element 3 was sealed using a glass substrate in a glove box containing a nitrogen atmosphere so as not to be exposed to the air (specifically, a sealing material was applied to surround the element and UV treatment and heat treatment at 80° C. for 1 hour were performed at the time of sealing). Then, the initial characteristics of Light-emitting element 3 were measured. Note that the measurement was carried out in an atmosphere kept at 25° C.
It is found from
As described in Embodiment, the organometallic complex of one embodiment of the present invention is an organometallic complex represented by General Formula (G1) and having a pyridine ring or a pyrimidine ring at any of R10 and R20.
In this example, the HOMO levels and the LUMO levels of the organometallic complexes each of which is one embodiment of the present invention and which are represented by Structural Formulae (100), (101), and (102) in Synthesis examples 1 to 3 and the HOMO level and the LUMO level of the comparative organometallic complex represented by Structural Formula (001), which has the structure represented by General Formula (G1) and has a pyridine ring or a pyrimidine ring at neither R10 nor R20, are described in detail. The structure of the organometallic complex represented by Structural Formula (001) is shown below.
The HOMO levels and the LUMO levels were estimated from an oxidation potential, a reduction potential, and the value of the potential energy of a reference electrode (Ag/Ag+) (the potential energy of the reference electrode with respect to the vacuum level is approximately −4.94 eV), which were obtained by cyclic voltammetry (CV) measurement in a dimethylformamide solvent. Specifically, −4.94 [eV]−(the value of the oxidation potential or the reduction potential)=the HOMO level or the LUMO level.
Table 8 shows the measured values of the HOMO levels and the LUMO levels calculated by the above method.
As shown in Table 8, the LUMO levels of the organometallic complexes each of which is one embodiment of the present invention are each lower than the LUMO level of the comparative organometallic complex which is represented by Structural Formula (001). It can be also found that among the organometallic complexes each of which is one embodiment of the present invention, the organometallic complex having fewer substituents bonded to a pyridine ring has a lower HOMO level and a lower LUMO level. Accordingly, it is preferable to use an organometallic complex having fewer substituents bonded to a pyridine ring or a pyrimidine ring in order to achieve a reduction in voltage.
This application is based on Japanese Patent Application serial no. 2016-055941 filed with Japan Patent Office on Mar. 18, 2016, the entire contents of which are hereby incorporated by reference.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2016-055941 | Mar 2016 | JP | national |
