Patent Grant
10559762
One embodiment of the present invention relates to an organic compound, a light-emitting element, a light-emitting device, an electronic device, and a lighting device. 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 power storage device, a storage device, a method for driving any of them, and a method for manufacturing any of them.
In recent years, research and development of light-emitting elements using electroluminescence (EL) have been actively conducted. In a basic structure of such a light-emitting element, a layer containing a light-emitting substance (an EL layer) is interposed between a pair of electrodes. By applying a voltage between the pair of electrodes of this element, light emission from the light-emitting substance is obtained.
Since the above light-emitting element is a self-luminous type, a display device using this light-emitting element has advantages such as high visibility, no necessity of a backlight, and low power consumption. Further, such a light-emitting element also has advantages in that the element can be formed to be thin and lightweight, and that response time is high.
It is said that the light emission mechanism of a light-emitting element is as follows: when a voltage is applied between a pair of electrodes with an EL layer including a light-emitting substance provided therebetween, electrons injected from a cathode and holes injected from an anode recombine in the light emission center of the EL layer to form molecular excitons, and energy is released and light is emitted when the molecular excitons relax to the ground state.
The excited states of an organic compound in which molecular excitons are formed include a singlet excited state (S*) and a triplet excited state (T*), and light emission from the singlet excited state is referred to as fluorescence, and light emission from the triplet excited state is referred to as phosphorescence. The statistical generation ratio thereof in the light-emitting element is considered to be S*:T*=1:3. In other words, a light-emitting element containing a compound emitting phosphorescence has higher emission efficiency than a light-emitting element containing a compound emitting fluorescence. Therefore, light-emitting elements containing phosphorescent compounds capable of converting a triplet excited state into light emission has been actively developed in recent years.
Among light-emitting elements containing phosphorescent compounds, in particular, a light-emitting element that emits blue light has not yet been put into practical use because it is difficult to develop a stable compound having a high triplet excited energy level. For this reason, as a light-emitting element that emits blue light, a light-emitting element containing a more stable fluorescent compound has been developed and high efficiency of a light-emitting element containing a fluorescent compound (fluorescent light-emitting element) has been required.
In the light-emitting element containing a fluorescent compound, triplet-triplet annihilation (TTA) is known as a light emission mechanism capable of converting part of a triplet excited state into light emission. The term TTA refers to a process in which, when two triplet excitons approach each other, excited energy and spin angular momentum are exchanged and transferred to form singlet excitons.
As a compound in which TTA occurs, a compound including an anthracene skeleton is known. Non-Patent Document 1 discloses that the use of a compound including an anthracene skeleton as a host material achieves high external quantum efficiency in a light-emitting element that emits blue light. It also discloses that the proportion of the delayed fluorescence due to TTA to the total light emitted from the light-emitting element using a compound including an anthracene skeleton is approximately 10%.
An object of one embodiment of the present invention is to provide a novel fluorescent organic compound (a fluorescent compound). Note that 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 a substance that emits fluorescence and is an organic compound (a host material) in which TTA can occur efficiently. Furthermore, one embodiment of the present invention is an organic compound in which triplet excitons, which do not contribute to light emission, can be efficiently converted into singlet excitons.
Note that as one of methods for efficiently converting the energy of triplet excitons into the energy of singlet excitons, energy transfer and intersystem crossing which are caused by the Förster mechanism are used. The Förster mechanism is a mechanism in which energy is transferred by resonance, which occurs more easily when the following conditions are satisfied: organic compounds (host materials) containing triplet excitons approach each other with an intermolecular distance of 1 nm to 10 nm, the oscillator strength for transition from the lowest triplet excited level (referred as a T1 level) of the organic compound (host material) to one of levels of triplet excited states which are higher than the T1 level of the organic compound (referred as Tn levels) is high (energy absorption in transition is high), and the like.
Note that one embodiment of the present invention is an organic compound in which energy transfer by the Förster mechanism is likely to occur and an organic compound in which the probability of TTA can be increased when the organic compound is used in an EL layer of a light-emitting element. Such an organic compound preferably includes a tetracene skeleton or an anthracene skeleton.
In the case where an EL layer of a light-emitting element includes, as a first organic compound (a host material), an organic compound in which the probability of TTA is high as described above and, as a second organic compound (a dopant), a fluorescent compound, the emission efficiency of the light-emitting element can be improved by converting energy of triplet excitons, which does not contribute to light emission in the first organic compound, into energy of singlet excitons and making the fluorescent compound emit light by energy transfer of the singlet excitons.
One embodiment of the present invention is an organic compound represented by General Formula (G) shown below. Note that the organic compound represented by General Formula (G) shown below is the first organic compound in the above-described light-emitting element.
Note that in General Formula (G), either of A1 and A2 is represented by General Formula (G-1) shown above, and the other is hydrogen or another substituent. Furthermore, α1 and α2 each represent a substituted or unsubstituted phenylene group. Furthermore, n and m each independently represent 1 or 2. P1 and P2 each independently represent hydrogen, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group. The substituent in General Formula (G) or, when substituents are further included in General Formula (G), the substituent and the substituents each independently represent an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkylphenyl group, or a phenyl group.
In one embodiment of the present invention, when P1 and P2 in General Formula (G) shown above each independently represent a substituted or unsubstituted phenylene group or a substituted or unsubstituted biphenylene group, P1 and P2 are each represented by any one of Structure Formulae (Ar-1) to (Ar-6) shown below.
In one embodiment of the present invention, the phenylene groups represented by α1 and α2 in General Formula (G) and General Formula (G-1) shown above each independently represent any one of a para-phenylene group, a meta-phenylene group, and an ortho-phenylene group.
In one embodiment of the present invention, the phenylene groups represented by α1 and α2 in General Formula (G) and General Formula (G-1) shown above are each represented by any one of Structure Formulae (α-1) to (α-5) shown below.
In one embodiment of the present invention, in the case where the phenylene groups represented by α1 and α2 in General Formula (G) and General Formula (G-1) shown above include substituents, the substituents each independently represent any one of an alkyl group having 1 to 6 carbon atoms and a cycloalkyl group having 3 to 6 carbon atoms, and more specifically, any one of a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a hexyl group, an isohexyl group, and a cyclohexyl group.
In one embodiment of the present invention, in the case where the phenylene groups represented by α1 and α2 in General Formula (G) and General Formula (G-1) shown above include a substituent, the substituent is represented by any one of Structure Formulae (R-1) to (R-11) shown below.
One embodiment of the present invention is an organic compound represented by any one of the following Structure Formula (100), Structure Formula (110), and Structure Formula (120) or the first organic compound.
The above-described first organic compound is an organic compound (a host material) in which TTA can be efficiently caused, triplet excitons, which do not contribute to light emission, can be efficiently converted into singlet excitons, and the proportion of delayed fluorescence to the total light emitted from the organic compound is high because the triplet exciton has long excitation lifetime.
One embodiment of the present invention includes, in its category, not only a light-emitting element including the first organic compound and a light-emitting device including the light-emitting element but also a lighting device including the light-emitting device. Therefore, the light-emitting device in this specification refers to an image display device and a light source (e.g., a lighting device). In addition, the light-emitting device includes, in its category, all of a module in which a connector such as a flexible printed circuit (FPC) or a tape carrier package (TCP) is connected to a light-emitting device, a module in which a printed wiring board is provided on the tip 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.
According to one embodiment of the present invention, a novel fluorescent organic compound (a fluorescent compound) can be provided. According to one embodiment of the present invention, a light-emitting element containing a fluorescent compound, which has high efficiency, can be provided. According to one embodiment of the present invention, a light-emitting element in which the proportion of delayed fluorescence to the total light emitted from the light-emitting element is higher than that in a conventional light-emitting element can be provided. According to one embodiment of the present invention, a novel light-emitting element can be provided. According to one embodiment of the present invention, a novel light-emitting device can be provided. According to one embodiment of the present invention, a novel light-emitting device, a novel electronic device, or a novel lighting device can be provided.
Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. Note that the present invention is not limited to the following description, and modes and details thereof can be variously changed without departing from the spirit and scope of the present invention. Therefore, the present invention should not be construed as being limited to the description in the following embodiments.
Note that the terms “film” and “layer” can be interchanged with each other according to circumstances. For example, in some cases, the term “conductive film” can be used instead of the term “conductive layer,” and the term “insulating layer” can be used instead of the term “insulating film”.
In this embodiment, a mechanism of occurrence of triplet-triplet annihilation (TTA) in an EL layer of a light-emitting element is described.
There are various theories on the detail of the mechanism of TTA, and it is not defined clearly. In one embodiment of the present invention, energy transfer shown in schemes in
First, in the case where triplet excitons of two molecules of the same kind (a molecule A and a molecule B) exist adjacently as shown in
Next, as shown in
Then, by transition of a triplet exciton at the S1 level to the S0 level as shown in
As described above, using the excitation energy of one of two molecules, the other molecule undergoes transition to a higher level; thus, up to half of 75% of T1 excitons can be extracted as emission. Since there is also 25% of S1 excitons generated by current excitation, the total internal quantum efficiency can be 62.5% at the maximum.
Note that in the case where intermolecular energy transfer through TTA described in
In the Dexter mechanism, electron spins of both two molecules are stored before and after energy transfer. Thus, when the electron spins of both two molecules are stored before and after energy transfer, energy transfer by the Dexter mechanism is allowed. Note that energy transfer through TTA has been mainly described using the Dexter mechanism.
Meanwhile, the rate constant kET of energy transfer in the Förster mechanism is expressed by Formula (1) below.
c: The velocity of light, n: refractive index, NA: Avogadro number, τ0: donor duration, R: intermolecular distance, x: relative orientation factor of transition dipole moments of A and B, {tilde over (v)}: wave number, f: light intensity per wave number standardized to Area 1, et absorption coefficient.
Note that to in Formula (1) is the reciprocal number of radiation speed kr. Here, x is expressed as follows.
Thus, Formula (1) can be represented by Formula (1′) below.
kET=xkr (1′)
Furthermore, energy transfer efficiency ϕET by the Förster mechanism is represented by Formula (2) below.
kr: radiative rate constant, knr: non-radiative rate constant.
Formula (2′) can be derived from Formula (2) and Formula (1′) as follows.
ϕp: phosphorescence quantum efficiency.
In the case where the molecule A and the molecule B are anthracene derivatives, a radiation rate constant (kr) of phosphorescent emission obtained from the anthracene derivatives is 1×103 (s−1) to 1×104 (s−1) and a non-radiation rate constant (knr) thereof is 1×107 (s−1) to 1×108 (s−1). Accordingly, the phosphorescence quantum efficiency (ϕp) can be estimated to be 1×10−3 to 1×10−5.
Here, when the phosphorescence quantum efficiency (q) is 1×10−4 and x is 100, the energy transfer efficiency (ϕET) is 1.0%. If x is 1000, the energy transfer efficiency (ϕET) is 9.1%. Note that there is a positive correlation between x and an absorption coefficient; thus, as the absorption coefficient is increased, x is also increased. That is, even in the case where the phosphorescence quantum efficiency of the molecule on a donor side (the molecule B in
As described above, energy transfer between triplet excitons can partly occur by the Förster mechanism. Thus, here, the energy transfer through TTA by not only the Dexter mechanism but also that by the Förster mechanism are considered.
In the case where the energy transfer by the Förster mechanism is caused, as shown in the following Formula (3), generally, the absorption coefficient of the molecule is high when the oscillator strength (f) of the molecule is large.
f=4.32×10−9∫ε({tilde over (v)})d{tilde over (v)} (3)
f: oscillator strength, ε: absorption coefficient.
Hence, a molecular design is performed using quantum chemical calculations so that the oscillator strength (f) between the triplet excited state (T1) that is the lowest level and the triplet excited state (Tn) that is higher than the T1 is increased. However, in the case where there is a plurality of triplet excited states (Tn) that is higher than T1, the total of the oscillator strengths in the triplet excited states is considered to be the oscillator strength (J). Note that by the molecular design, it is found that the oscillator strength (f) of the molecule is increased when a compound including an anthracene skeleton is used. Structure Formulae of the compounds each including an anthracene skeleton are shown below.
The quantum chemical calculation method of the above compound is as follows. Note that Gaussian 09 is used as the quantum chemistry computational program. A high performance computer (ICE X manufactured by SGI Japan, Ltd.) is used for the calculation.
First, stable structures and electron states in the singlet ground state (S0) and the T1 state are calculated using the density functional theory (DFT). After that, vibration analysis is conducted, and the T1 level is calculated from the energy difference between the stable structures in the S0 state and in the T1 state. As a basis function, 6-311G(d,p) is used. As a functional, B3LYP is used. In the DFT, the total energy of the molecules 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; thus, electron states can be obtained with high accuracy.
Next, a time-dependent density functional theory (TD-DFT) is used to calculate the transition dipole moment and the oscillator strength (f) which relate to the transition from the T1 level to the Tn level. As a basis function, 6-311G(d,p) is used, and as a functional, CAM-B3LYP is used. In the calculation using TD-DFT, stable structures and electron states in the T1 state obtained from the calculation using CAM-B3LYP as a functional of DFT are used.
Note that a Tn state in TD-DFT indicates a triplet excited state at an energy level lower than a value obtained by adding 0.6 eV to excitation energy corresponding to twice the T1 level by the calculation using TD-DFT. However, even if an excited state satisfying the above condition is included in a portion other than an anthracene skeleton in the compound including the anthracene skeleton, it is excluded from the Tn state because of being not involved in triplet excitation of the entire compound.
From the calculation using TD-DFT, the T1 level of 1,5CzP2A is 1.67 eV and the T1 level of 1,8CzP2A is 1.66 eV. From the calculation using TD-DFT, it is found that there are two triplet excited states corresponding to the Tn levels where excitation energy from the T1 level is higher than the T1 level by less than 0.6 eV in each of 1,5CzP2A and 1,8CzP2A. Note that excitation energies from the T1 level to the Tn level in 1,5CzP2A are 1.80 eV and 2.07 eV, and excitation energies from the T1 level to the Tn level in 1.8CzP2A was 1.81 eV and 2.06 eV.
As shown in
The magnitude of the transition dipole moment and the oscillator strength (f) have a relation shown in the following Formula (4) in which the oscillator strength (f) is proportional to the square of the magnitude of the transition dipole moment.
f: oscillator strength, μmn: transition dipole moment, μ0: oscillation electric dipole moment, h: Planck constant, e: quantum of electricity, m: mass of electrons, v: wave number.
In each of 1,5CzP2A and 1,8CzP2A, the compound is divided into an anthracene skeleton 501 and carbazole skeletons 502 as units (skeletons) constituting the compound, and the transition dipole moment in the transition from the T1 level to the Tn level in each of the units is analyzed. Here, only the transition between the main molecular orbitals of the transition with the largest oscillator strength among the transitions from the T1 level to the Tn level, is analyzed.
From the results in
Furthermore, quantum chemical calculation of 1,5-bis[4-(9H-carbazol-9-yl)phenyl]-9,10-diphenylanthracene (abbreviation: 1,5CzP2PA), an organic compound that has an anthracene skeleton and is represented by Structure Formula (120), was performed.
From the calculation using DFT, the T1 level of 1,5CzP2PA was determined to be 1.52 eV. From the calculation using TD-DFT, it is found that there are seven triplet excited states corresponding to the Tn levels which are each higher than the T1 level by less than 0.6 eV. Note that excitation energies from the T1 level to the Tn level in 1,5CzP2PA are 1.87 eV and 1.92 eV. Furthermore, the sum of oscillator strengths (f) of 1,5CzP2PA between the T1 level and the Tn level that are obtained from the calculation using TD-DFT were determined to be 0.0089. At this time, it is confirmed that the orbital relating to a transition from T1 to Tn is mainly distributed on anthracene.
Note that a structure described in this embodiment can be used in appropriate combination with any of the structures described in the other embodiments.
In this embodiment, an organic compound of one embodiment of the present invention will be described. The organic compound described in this embodiment is an organic compound in which the probability of TTA caused by energy transfer by the Förster mechanism can be increased, as in 1,5CzP2A, 1,8CzP2A, and 1,5CzP2PA described as examples in Embodiment 1.
The organic compound described in this embodiment has a feature in that a carbazole skeleton is bonded to an anthracene skeleton directly or through an arylene group. The organic compound described in this embodiment is an organic compound having a structure represented by General Formula (G0) or General Formula (G1) shown below.
Note that either of A1 and A2 in General Formula (G0) shown above is represented by General Formula (G0-1) shown above, and the other is hydrogen or another substituent. That is, α2 is bonded to the 5-position or 8-position of the anthracene skeleton in General Formula (G0). Furthermore, α1 and α2 each represent a substituted or unsubstituted phenylene group. Furthermore, n and m each individually represent 1 or 2. The substituent in General Formula (G0) or, when substituents are further included in General Formula (G0), the substituent and the substituents each independently represent an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkylphenyl group, or a phenyl group. Ar1 and Ar2 each independently represent a substituted or unsubstituted phenylene group or a substituted or unsubstituted biphenylene group.
Specific examples of the phenyl group or the biphenyl group that is represented by Ar1 and Ar2 in General Formula (G0) shown above are represented by Structure Formulae (Ar-1) to (Ar-6).
It is preferable that an alkyl group be bonded as shown in (Ar-2) to (Ar-5), in which case high solubility in an organic solvent can be obtained and easy synthesis is possible. It is preferable that a substituent not be included or a substituent be bonded at the para-position as shown in (Ar-1), (Ar-2), (Ar-5), and (Ar-6), in which case a transition dipole moment is large.
The organic compound described in this embodiment is an organic compound having a structure represented by General Formula (G1) shown below.
Note that either of A1 and A2 in General Formula (G1) shown above is represented by General Formula (G1-1) shown above, and the other is hydrogen or another substituent. That is, α2 is bonded to the 5-position or 8-position of the anthracene skeleton in General Formula (G1). In addition, α1 and α2 each represent a substituted or unsubstituted phenylene group. Furthermore, n and m each individually represent 1 or 2. The substituent in General Formula (G1) or, when substituents are further included in General Formula (G1), the substituent and the substituents each independently represent an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkylphenyl group, or a phenyl group.
Note that as the substitution site of General Formula (G0-1) and General Formula (G1-1), A1 is preferred to A2 in General Formula (G0) and General Formula (G1) because the total of the oscillator strengths for excitation from the T1 level to the Tn level tends to be larger.
Furthermore, as the substitution site of General Formula (G0-1) and General Formula (G1-1), A1 is preferred to A2 in General Formula (G0) and General Formula (G1) because the two substituents each including the carbazole skeleton are bonded to a 1-position and a 5-position of the anthracene skeleton, and steric repulsion of the two substituents each including the carbazole skeleton is prevented. Similarly, when General Formula (G1) has other substituents, it is preferable that the substituents be provided so as not to be adjacent (e.g., at the 1- and 2-positions, the 2- and 3-positions, and the 1- and 9-positions) to each other at the same time because the steric repulsion can be prevented.
Note that in General Formula (G0), General Formula (G0-1), General Formula (G1), or General Formula (G1-1) shown above, examples of phenylene groups represented by α1 and α2 include a para-phenylene group, a meta-phenylene group, and an ortho-phenylene group.
Specific examples of the phenylene groups represented by α1 and α2 in General Formula (G0), General Formula (G0-1), General Formula (G1), or General Formula (G1-1) shown above are represented by Structure Formulae (α-1) to (α-5).
In the phenylene groups represented by a and α2 in General Formulae (G0), (G0-1), (G1), and (G1-1) shown above, the substitution sites of the carbazole skeleton and the anthracene skeleton can be any positions of a para-position, a meta-position, and an ortho-position. When the phenylene group has the substituents at the para-position, a high carrier-transport property is obtained, which is preferable. When the phenylene group has the substituents at the meta-position, a bulky structure is obtained and thus evaporation temperature can be low, which is preferable.
In the case where General Formulae (G0), (G0-1), (G1), and (G1-1) shown above include substituents and in the case where the phenylene groups represented by α1 and α2 in General Formulae (G0), (G0-1), (G1), and (G1-1) shown above include substituents, examples of the substituents include an alkyl group having 1 to 6 carbon atoms and a cycloalkyl group having 3 to 6 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a hexyl group, an isohexyl group, and a cyclohexyl group.
Furthermore, specific examples of the substituents of the phenylene groups represented by α1 and α2 in General Formulae (G0), (G0-1), (G1), and (G1-1) shown above are represented by Structure Formulae (R-1) to (R-11).
In the case where the phenylene groups represented by α1 and α2 in General Formulae (G0), (G0-1), (G1), and (G1-1) shown above have the substituents, improvement in solubility and improvement in thermophysical property can be expected, which is preferable. Meanwhile, in the case where the phenylene groups represented by α1 and α2 in General Formulae (G0), (G0-1), (G1), and (G1-1) do not have the substituents, synthesis is performed easily, which is preferable.
A structure of another organic compound is represented by General Formula (G2) shown below.
Note that either of A1 and A2 in General Formula (G2) shown above is represented by General Formula (G2-1) shown above, and the other is hydrogen or another substituent. The substituent in General Formula (G2) or, when substituents are further included in General Formula (G2), the substituent and the substituents each independently represent an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkylphenyl group, or a phenyl group.
Specific examples of the structure formulae of the above-described organic compound are shown below. Note that the present invention is not limited to these formulae.
Note that in an organic compound represented by Structure Formula (103), n and m each represent 2, and α1 and α2 each have a structure in which a phenylene group 5 and an alkylphenylene group are bonded to each other in General Formula (G1). As described above, also in the case where n and m each represent 2, phenylene groups with different structures may be bonded to each other in α1 and α2
Note that the organic compounds represented by Structure formulae (103) to (109), (115), (122), (124), and (125) shown above are organic compounds of the case where General Formula (G) and General Formulae (G0) to (G2) (and General Formulae (G-1) and (G1-1) to (G2-1)) include substituents. For example, Structure Formulae (103), (106), (107), (113), (115), (122), and (124) are organic compounds each including an alkyl group having 1 to 6 carbon atoms as a substituent, Structure Formulae (109), (113), (122), and (124) are organic compounds each including an alkylphenyl group as a substituent, and Structure Formulae (105), (108), and (125) are organic compounds each including a phenyl group as a substituent.
Examples of a method for synthesizing the organic compound represented by General Formula (G0) and General Formula (G0-1) shown below are described referring to Synthesis Schemes (F0-1) and (F0-2). That is, by application of reactions shown in Synthesis Schemes (F0-1) and (F0-2), the organic compound represented by General Formula (G0) and General Formula (G0-1) can be synthesized. As in the above case, either of A1 and A2 in General Formula (G0) is the substituent represented by General Formula (G0-1), and the other is hydrogen or another substituent.
In Synthesis Schemes (F0-1) and (F0-2), either of X1 and X2 and X3 represent halogen. Specifically, iodine, bromine, and chlorine have higher reactivity in this order and are preferred in this order. B1 and B2 each represent a boron compound; specifically, represent boronic acid or alkoxy boron. Note that an aryl aluminum compound, an aryl zirconium compound, an aryl zinc compound, an aryl tin compound, or the like may also be used. In addition, α1 and α2 each represent a substituted or unsubstituted phenylene group. Furthermore, n and m each individually represent 1 or 2. Ar1 and Ar2 each independently represent a substituted or unsubstituted phenylene group or a substituted or unsubstituted biphenylene group. M1 and M2 each independently represent lithium or magnesium halogen. The halogen specifically represents iodine, bromine, and chlorine, and bromine is easy to handle.
There are a variety of reaction conditions for the coupling reaction in Synthesis Scheme (F0-1). As an example, a synthesis method using a metal catalyst in the presence of a base, such as a Suzuki-Miyaura reaction, can be employed. In the above-described synthesis method, a compound (a12) and a compound (a13) are made to react with a compound (a11) at the same time, but in the case where α1 in the compound (a12) is different from α2 in the compound (a13) or n in the compound (a12) is different from m in the compound (a13), the reaction is preferably performed in two steps because high purity can be obtained.
There are a variety of reaction conditions for the reaction in Synthesis Scheme (F0-2). A compound (a15) and a compound (a16) that are lithiated or prepared as a Grignard reagent are made to react with a compound (a14) in an ether solvent, whereby a compound (a17) is synthesized. Then, dehydroxylation is performed using potassium iodide and sodium phosphinate in the presence of acid, whereby an organic compound that is a target substance and represented by General Formula (G0-1) can be synthesized.
Examples of a method for synthesizing the organic compound represented by General Formula (G1) and General Formula (G1-1) shown below are described referring to Synthesis Schemes (F1-1) and (F1-2). That is, by application of coupling reactions shown in Synthesis Schemes (F1-1) and (F1-2), the organic compound represented by General Formula (G1) and General Formula (G1-1) can be synthesized. As in the above case, either of A1 and A2 in General Formula (G1) is the substituent represented by General Formula (G1-1), and the other is hydrogen or another substituent.
In Synthesis Schemes (F1-1) and (F1-2), either of X1 and X2 and X3 represent halogen. Specifically, iodine, bromine, and chlorine have higher reactivity in this order and are preferred in this order. B1 and B2 each represent a boron compound; specifically, represent boronic acid or alkoxy boron. Note that an aryl aluminum compound, an aryl zirconium compound, an aryl zinc compound, an aryl tin compound, or the like may also be used. In addition, α1 and α2 each represent a substituted or unsubstituted phenylene group. Note that n and m each individually represent 1 or 2.
There are a variety of reaction conditions for the coupling reactions in Synthesis Schemes (F1-1) and (F1-2). As an example, a synthesis method using a metal catalyst in the presence of a base, such as a Suzuki-Miyaura reaction, can be employed. In the above synthesis method, the synthesis is carried out in two steps of a synthesis step represented by Synthesis Scheme (F1-1) and a synthesis step represented by Synthesis Scheme (F1-2). However, in the case where α1 in a compound (a2) and α2 in a compound (a4) are the same and n in the compound (a2) and m in the compound (a4) are the same, two or more equivalents of the compound (a2) may be added to the compound (a1), in which case the organic compound can be easily synthesized in one step.
Although the example of a method for synthesizing the organic compound is described above, the present invention is not limited thereto and any other synthesis method may be employed.
The above-described organic compound can be used alone or in combination with a light-emitting substance (guest), another organic compound, or the like in a light-emitting element.
In addition, the above-described organic compound can be used in an organic thin film solar cell. More specifically, the organic compound can be used in a carrier-transport layer or a carrier-injection layer since the organic compound has a carrier-transport property. In addition, a mixed layer of the organic compound and an acceptor substance can be used as a charge generation layer. The organic compound can be photoexcited and hence can be used for a power generation layer.
Note that a structure described in this embodiment can be used in appropriate combination with any of the structures described in the other embodiments.
In this embodiment, light-emitting elements of the present invention will be described with reference to
In the light-emitting element described in this embodiment, an EL layer 102 including a light-emitting layer 113 is provided between a pair of electrodes (a first electrode (anode) 101 and a second electrode (cathode) 103). The EL layer 102 includes, in addition to the light-emitting layer 113, a hole-injection layer 111, a hole-transport layer 112, an electron-transport layer 114, an electron-injection layer 115, and the like.
When a voltage is applied to the light-emitting element, holes injected from the first electrode 101 side and electrons injected from the second electrode 103 side recombine in the light-emitting layer 113; with energy generated by the recombination, a light-emitting substance such as an organometallic complex that is contained in the light-emitting layer 113 emits light.
The hole-injection layer 111 in the EL layer 102 can inject holes into the hole-transport layer 112 or the light-emitting layer 113 and can be formed of, for example, a substance having a high hole-transport property and a substance having an acceptor property, in which case electrons are extracted from the substance having a high hole-transport property by the substance having an acceptor property to generate holes. Thus, holes are injected from the hole-injection layer 111 into the light-emitting layer 113 through the hole-transport layer 112. For the hole-injection layer 111, a substance having a high hole-injection property can also be used. For example, molybdenum oxide, vanadium oxide, ruthenium oxide, tungsten oxide, manganese oxide, or the like can be used. Alternatively, the hole-injection layer 111 can be formed using a phthalocyanine-based compound such as phthalocyanine (abbreviation: H2Pc) and copper phthalocyanine (CuPc), an aromatic amine compound such as 4,4′-bis[N-(4-diphenylaminophenyl)-N-phenylamino]biphenyl (abbreviation: DPAB) and N,N′-bis{4-[bis(3-methylphenyl)amino]phenyl}-N,N-diphenyl-(1,1′-biphenyl)-4,4′-diamine (abbreviation: DNTPD), or a high molecular compound such as poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonic acid) (PEDOT/PSS).
A preferred specific example in which the light-emitting element described in this embodiment is fabricated is described below.
For the first electrode (anode) 101 and the second electrode (cathode) 103, a metal, an alloy, an electrically conductive compound, a mixture thereof, and the like can be used. Specific examples are indium oxide-tin oxide (indium tin oxide), indium oxide-tin oxide containing silicon or silicon oxide, indium oxide-zinc oxide (indium zinc oxide), indium oxide containing tungsten oxide and zinc oxide, gold (Au), platinum (Pt), nickel (Ni), tungsten (W), chromium (Cr), molybdenum (Mo), iron (Fe), cobalt (Co), copper (Cu), palladium (Pd), and titanium (Ti). In addition, an element belonging to Group 1 or Group 2 of the periodic table, for example, an alkali metal such as lithium (Li) or cesium (Cs), an alkaline earth metal such as calcium (Ca) or strontium (Sr), magnesium (Mg), and an alloy containing such an element (MgAg or AlLi); a rare earth metal such as europium (Eu) or ytterbium (Yb) and an alloy containing such an element; and a graphene compound such as graphene or graphene oxide can be used. The first electrode (anode) 101 and the second electrode (cathode) 103 can be formed by, for example, a sputtering method or an evaporation method (including a vacuum evaporation method).
As the substance having a high hole-transport property which is used for the hole-injection layer 111 and the hole-transport layer 112, 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. The organic compound used for the composite material is preferably an organic compound having a high hole-transport property. Specifically, a substance having a hole mobility of 1×106 cm2/Vs or more is preferably used. The layer formed using the substance having a high hole-transport property is not limited to a single layer and may be formed by stacking two or more layers.
The substance used for the hole-transport layer 112 preferably has higher S1 and T1 levels than the light-emitting layer 113 that is adjacent to the hole-transport layer 112 because diffusion of excitation energy to the hole-transport layer 112 can be suppressed. Furthermore, the substance used for the hole-transport layer 112 preferably has a higher LUMO level (a larger value) than the light-emitting layer 113 that is adjacent to the hole-transport layer 112 because passage of electrons through the light-emitting layer 113 to the hole-transport layer 112 can be suppressed. Furthermore, a HOMO level of the substance used for the hole-transport layer 112 is preferably deeper (a smaller value) than or substantially equal to the HOMO level of the light-emitting layer 113 that is adjacent to the hole-transport layer 112 because easier hole-injection into the light-emitting layer 113 can be achieved. Organic compounds that can be used as the substance having a hole-transport property are specifically given below.
Examples of the aromatic amine compounds are N,N-di(p-tolyl)-N,N′-diphenyl-p-phenylenediamine (abbreviation: DTDPPA), 4,4′-bis[N-(4-diphenylaminophenyl)-N-phenylamino]biphenyl (abbreviation: DPAB), DNTPD, 1,3,5-tris[N-(4-diphenylaminophenyl)-N-phenylamino]benzene (abbreviation: DPA3B), 4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (abbreviation: NPB or α-NPD), N,N-bis(3-methylphenyl)-N,N-diphenyl-[1,1′-biphenyl]-4,4′-diamine (abbreviation: TPD), 4,4′,4″-tris(carbazol-9-yl)triphenylamine (abbreviation: TCTA), 4,4′,4″-tris(N,N-diphenylamino)triphenylamine (abbreviation: TDATA), 4,4′,4″-tris[N-(3-methylphenyl)-N-phenylamino]triphenylamine (abbreviation: MTDATA), and 4,4′-bis[N-(spiro-9,9′-bifluoren-2-yl)-N-phenylamino]biphenyl (abbreviation: BSPB), and the like.
Specific examples of carbazole derivatives are 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), and the like. Other examples are 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), 1,4-bis[4-(N-carbazolyl)phenyl]-2,3,5,6-tetraphenylbenzene, and the like.
Examples of aromatic hydrocarbons are 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, 2,5,8,11-tetra(tert-butyl)perylene, and the like. Besides, pentacene, coronene, or the like can also be used. The aromatic hydrocarbon which has a hole mobility of 1×10−6 cm2/Vs or more and which has 14 to 42 carbon atoms is particularly preferable. The aromatic hydrocarbons may have a vinyl skeleton. Examples of the aromatic hydrocarbon having a vinyl group 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.
Examples of the substance having an acceptor property which is used for the hole-injection layer 111 and the hole-transport layer 112 are compounds having an electron-withdrawing group (a halogen group or a cyano group) such as 7,7,8,8-tetracyano-2,3,5,6-tetrafluoroquinodimethane (abbreviation: F4-TCNQ), chloranil, and 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HAT-CN). In particular, a compound in which electron-withdrawing groups are bonded to a condensed aromatic ring having a plurality of heteroatoms, like HAT-CN, is thermally stable and preferable. Oxides of metals belonging to Groups 4 to 8 of the periodic table can be given. Specifically, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide, tungsten oxide, manganese oxide, and rhenium oxide are preferable because of their high electron-accepting properties. Among these, molybdenum oxide is especially preferable because it is stable in the air, has a low hygroscopic property, and is easy to handle.
The light-emitting layer 113 is a layer containing a light-emitting substance (guest material). Examples of the light-emitting substance include a light-emitting substances that convert singlet excitation energy into luminescence and light-emitting substances that convert triplet excitation energy into luminescence. In the case of a structure in which triplet excitons are converted into singlet excitons by TTA so that emission efficiency of the singlet excitons is improved as described in Embodiment 1, a light-emitting substance that converts singlet excitation energy into luminescence is preferably used. As an example of the light-emitting substance that converts singlet excitation energy into luminescence, a substance that emits fluorescence (a fluorescent compound) can be given.
Examples of the substance that emits fluorescence are 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-pheny lenediamine] (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-9yl)phenyl]-N-phenylanthracen-2-amine (abbreviation: 2YGABPhA), N,N,9-triphenylanthracen-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)propanedinit rile (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-d iamine (abbreviation: p-mPhAFD), 2-{2-isopropyl-6-[2-(1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H, 5H-benzo[j]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[if]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[ij]quinolizin-9-yl)ethenyl]-4H-pyran-4-ylidene}propanedinitrile (abbreviation: BisDCJTM), and the like.
In the case where the light-emitting substance that converts triplet excitation energy into luminescence is used in the light-emitting layer 113, it is preferable that an organic compound (a host material) used with a light-emitting substance (referred to as a dopant or a guest material) have a higher probability of TTA. Specifically, an organic compound where the oscillator strength (f) is 0.0015 or more, preferably 0.0020 or more is preferably used. That is, an organic compound in which the transition between the T1 level and the Tn level easily occurs, and which has a higher probability of TTA caused by energy transfer by the Förster mechanism, is preferably used. As an example of the organic compound which has a higher probability of TTA, the organic compound described in Embodiment 2 can be used.
In the case where the light-emitting substance that converts triplet excitation energy into luminescence is used in the light-emitting layer 113, it seems that when the organic compound (the host material) used with the light-emitting substance (the dopant) is designed such that the T1 level of the organic compound (the host material) is the lowest, the triplet excitation energy is collected at the host material and thus the probability of TTA is increased.
Furthermore, in the light-emitting layer 113 of the light-emitting element in this embodiment, not only a structure in which a substance that emits fluorescence (a fluorescence compound) is used for a light-emitting substance by utilizing TTA, but also a structure in which a light-emitting substance that converts triplet excitation energy into luminescence can be used together with the substance that emits fluorescence (a fluorescence compound). Examples of the light-emitting substance that converts triplet excitation energy into luminescence include a substance which emits phosphorescence (a phosphorescent compound) and a thermally activated delayed fluorescent (TADF) material which emits thermally activated delayed fluorescence. Note that “delayed fluorescence” exhibited by the TADF material refers to light emission having the same spectrum as normal fluorescence and an extremely long lifetime. The lifetime is 1×10−6 seconds or longer, preferably 1×10−3 seconds or longer.
Examples of the substance that emits phosphorescence are bis{2-[3′,5′-bis(trifluoromethyl)phenyl]pyridinato-N, C2′}iridium(III) picolinate (abbreviation: [Ir(CF3ppy)2(pic)], bis[2-(4′,6′-difluorophenyl)pyridinato-N,C2′]iridium(III) acetylacetonate (abbreviation: Flracac), tris(2-phenylpyridinato)iridium(III) (abbreviation: [Ir(ppy)3]), bis(2-phenylpyridinato)iridium(III) acetylacetonate (abbreviation: [Ir(ppy)2(acac)]), tris(acetylacetonato)(monophenanthroline)terbium(III) (abbreviation: [Tb(acac)3(Phen)]), bis(benzo[h]quinolinato)iridium(III) acetylacetonate (abbreviation: [Ir(bzq)2(acac)]), bis(2,4-diphenyl-1,3-oxazolato-N,C2′)iridium(III) acetylacetonate (abbreviation: [Ir(dpo)2(acac)]), bis {2-[4′-(perfluorophenyl)phenyl]pyridinato-N,C2′}iridium(III) acetylacetonate (abbreviation: [Ir(p-PF-ph)2(acac)]), bis(2-phenylbenzothiazolato-N, C2′)iridium(III) acetylacetonate (abbreviation: [Ir(bt)2(acac)]), bis[2-(2′-benzo[4,5-a]thienyl)pyridinato-N,C3′]iridium(III) acetylacetonate (abbreviation: [Ir(btp)2(acac)]), bis(1-phenylisoquinolinato-N,C2′)iridium(III) acetylacetonate (abbreviation: [Ir(piq)2(acac)]), (acetylacetonato)bis[2,3-bis(4-fluorophenyl)quinoxalinato]iridium(III) (abbreviation: [Ir(Fdpq)2(acac)]), (acetylacetonato)bis(3,5-dimethyl-2-phenylpyrazinato)iridium(III) (abbreviation: [Ir(mppr-Me)2(acac)]), (acetylacetonato)bis(5-isopropyl-3-methyl-2-phenylpyrazinato)iridium(III) (abbreviation: [Ir(mppr-iPr)2(acac)]), (acetylacetonato)bis(2,3,5-triphenylpyrazinato)iridium(III) (abbreviation: [Ir(tppr)2(acac)]), bis(2,3,5-triphenylpyrazinato)(dipivaloylmethanato)iridium(III) (abbreviation: [Ir(tppr)2(dpm)], (acetylacetonato)bis(6-tert-butyl-4-phenylpyrimidinato)iridium(III) (abbreviation: [Ir(tBuppm)2(acac)]), (acetylacetonato)bis(4,6-diphenylpyrimidinato)iridium(III) (abbreviation: [Ir(dppm)2(acac)]), 2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphyrin platinum(II) (abbreviation: PtOEP), tris(1,3-diphenyl-1,3-propanedionato)(monophenanthroline)europium(III) (abbreviation: [Eu(DBM)3(Phen)]), tris[1-(2-thenoyl)-3,3,3-trifluoroacetonato](monophenanthroline)europium(III) (abbreviation: [Eu(TTA)3(Phen)]), and the like.
Examples of the TADF material are fullerene, a derivative thereof, an acridine derivative such as proflavine, eosin, and the like. Other examples are a metal-containing porphyrin, such as a porphyrin containing magnesium (Mg), zinc (Zn), cadmium (Cd), tin (Sn), platinum (Pt), indium (In), or palladium (Pd). Examples of the metal-containing porphyrin are a protoporphyrin-tin fluoride complex (abbreviation: SnF2(Proto IX)), a mesoporphyrin-tin fluoride complex (abbreviation: SnF2(Meso IX)), a hematoporphyrin-tin fluoride complex (abbreviation: SnF2(Hemato IX)), a coproporphyrin tetramethyl ester-tin fluoride complex (abbreviation: SnF2(Copro III-4Me)), an octaethylporphyrin-tin fluoride complex (abbreviation: SnF2(OEP)), an etioporphyrin-tin fluoride complex (abbreviation: SnF2(Etio I)), an octaethylporphyrin-platinum chloride complex (abbreviation: PtCl2OEP), and the like. Alternatively, a heterocyclic compound including a i-electron rich heteroaromatic ring and a π-electron deficient heteroaromatic ring can be used, such as 2-(biphenyl-4-yl)-4,6-bis(12-phenylindolo[2,3-a]carbazol-11-yl)-1,3,5-triazine (abbreviation: PIC-TRZ). Note that a material in which the n-electron rich heteroaromatic ring is directly bonded to the it-electron deficient heteroaromatic ring is particularly preferably used because the donor property of the in-electron rich heteroaromatic ring and the acceptor property of the in-electron deficient heteroaromatic ring are both increased and the energy difference between the S1 level and the T1 level becomes small.
When the light-emitting substance that converts triplet excitation energy into luminescence is used in the light-emitting layer 113, other than a structure in which one kind of organic compound (host material) is used in addition to the light-emitting substance, the following structure may be employed: a structure where two kinds of organic compounds (the two kinds of organic compounds may include the above host material) that can form an excited complex (also called an exciplex) at the time of recombination of carriers (electrons and holes) in the light-emitting layer 113 are contained in addition to the light-emitting substance. In order to form an excited complex efficiently, it is particularly preferable to combine a compound which easily accepts electrons (a material having an electron-transport property) and a compound which easily accepts holes (a material having a hole-transport property). In the case where the combination of a material having an electron-transport property and a material having a hole-transport property is used as a host material which forms an excited complex as described above, the carrier balance between holes and electrons in the light-emitting layer can be easily optimized by adjustment of the mixture ratio of the material having an electron-transport property and the material having a hole-transport property. The optimization of the carrier balance between holes and electrons in the light-emitting layer can prevent a region in which electrons and holes are recombined from existing on one side in the light-emitting layer. By preventing the region in which electrons and holes are recombined from existing to one side, the reliability of the light-emitting element can be improved.
As the material having an electron-transport property that is preferably used to form the above excited complex, a π-electron deficient heteroaromatic compound such as a nitrogen-containing heteroaromatic compound, a metal complex, or the like can be used. Specific examples include 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: COll), 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[fh]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), 2-[4-(3,6-diphenyl-9H-carbazol-9-yl)phenyl]dibenzo[f,h]quinoxaline (abbreviation: 2CzPDBq-III), 7-[3-(dibenzothiophen-4-yl)phenyl]dibenzo[f,h]quinoxaline (abbreviation: 7mDBTPDBq-II); 6-[3-(dibenzothiophen-4-yl)phenyl]dibenzo[f,h]quinoxaline (abbreviation: 6mDBTPDBq-II), 4,6-bis[3-(phenanthren-9-yl)phenyl]pyrimidine (abbreviation: 4,6mPnP2Pm), 4,6-bis[3-(4-dibenzothienyl)phenyl]pyrimidine (abbreviation: 4,6mDBTP2Pm-II), or 4,6-bis[3-(9H-carbazol-9-yl)phenyl]pyrimidine (abbreviation: 4,6mCzP2Pm); a heterocyclic compound having a triazine skeleton such as 2-{4-[3-(N-phenyl-9H-carbazol-3-yl)-9H-carbazol-9-yl]phenyl}-4,6-diphenyl-1,3,5-tria zine (abbreviation: PCCzPTzn); 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, heterocyclic compounds having diazine skeletons and triazine skeletons and heterocyclic compounds having pyridine skeletons have high reliability and are thus preferable. Heterocyclic compounds having diazine (pyrimidine or pyrazine) skeletons and triazine skeletons have an excellent electron-transport property and contribute to a decrease in drive voltage.
As the compound that is preferably used to form the above excited complex, a π-electron rich heteroaromatic compound (e.g., a carbazole derivative or an indole derivative), an aromatic amine compound, or the like can be favorably used. Specific examples are compounds having aromatic amine skeletons, such as 2-[N-(9-phenylcarbazol-3-yl)-N-phenylamino]spiro-9,9′-bifluorene (abbreviation: PCASF), 4,4′,4″-tris[N-(1-naphthyl)-N-phenylamino]triphenylamine (abbreviation: 1′-TNATA), 2,7-bis[N-(4-diphenylaminophenyl)-N-phenylamino]-spiro-9,9′-bifluorene (abbreviation: DPA2SF), N,N-bis(9-phenylcarbazol-3-yl)-N,N-diphenylbenzene-1,3-diamine (abbreviation: PCA2B), N-(9,9-dimethyl-2-diphenylamino-9H-fluoren-7-yl)diphenylamine (abbreviation: DPNF), N,N,N″-triphenyl-N,N′,N′-tris(9-phenylcarbazol-3-yl)benzene-1,3,5-triamine (abbreviation: PCA3B), 2-[N-(4-diphenylaminophenyl)-N-phenylamino]spiro-9,9′-bifluorene (abbreviation: DPASF), N,N-bis[4-(carbazol-9-yl)phenyl]-N,N-diphenyl-9,9-dimethylfluorene-2,7-diamine (abbreviation: YGA2F), NPB, N,N-bis(3-methylphenyl)-N,N-diphenyl-[1,1′-biphenyl]-4,4′-diamine (abbreviation: TPD), 4,4′-bis[N-(4-diphenylaminophenyl)-N-phenylamino]biphenyl (abbreviation: DPAB), BSPB, 4-phenyl-4′-(9-phenylfluoren-9-yl)triphenylamine (abbreviation: BPAFLP), 4-phenyl-3′-(9-phenylfluoren-9-yl)triphenylamine (abbreviation: mBPAFLP), N-(9,9-dimethyl-9H-fluoren-2-yl)-N-{9,9-dimethyl-2-[N-phenyl-N-(9,9-dimethyl-9H-fluoren-2-yl)amino]-9H-fluoren-7-yl}phenylamine (abbreviation: DFLADFL), PCzPCA1, 3-[N-(4-diphenylaminophenyl)-N-phenylamino]-9-phenylcarbazole (abbreviation: PCzDPA1), 3,6-bis[N-(4-diphenylaminophenyl)-N-phenylamino]-9-phenylcarbazole (abbreviation: PCzDPA2), DNTPD, 3,6-bis[N-(4-diphenylaminophenyl)-N-(1-naphthyl)amino]-9-phenylcarbazole (abbreviation: PCzTPN2), PCzPCA2, 4-phenyl-4′-(9-phenyl-9H-carbazol-3-yl)triphenylamine (abbreviation: PCBA1BP), 4,4′-diphenyl-4″-(9-phenyl-9H-carbazol-3-yl)triphenylamine (abbreviation: PCBBilBP), 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), 3-[N-(1-naphthyl)-N-(9-phenylcarbazol-3-yl)amino]-9-phenylcarbazole (abbreviation: PCzPCN1), 9,9-dimethyl-N-phenyl-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]fluoren-2-amine (abbreviation: PCBAF), N-phenyl-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]spiro-9,9′-bifluoren-2-amine (abbreviation: PCBASF), N-(4-biphenyl)-N-(9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazol-3-amine (abbreviation: PCBiF), and N-(1,1′-biphenyl-4-yl)-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-9,9-dimethyl-9H-fluor en-2-amine (abbreviation: PCBBiF); compounds having carbazole skeletons, such as 1,3-bis(N-carbazolyl)benzene (abbreviation: mCP), CBP, 3,6-bis(3,5-diphenylphenyl)-9-phenylcarbazole (abbreviation: CzTP), and 9-phenyl-9H-3-(9-phenyl-9H-carbazol-3-yl)carbazole (abbreviation: PCCP); compounds having thiophene skeletons, 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), and 4-[4-(9-phenyl-9H-fluoren-9-yl)phenyl]-6-phenyldibenzothiophene (abbreviation: DBTFLP-IV); and compounds having furan skeletons, such as 4,4′,4″-(benzene-1,3,5-triyl)tri(dibenzofuran) (abbreviation: DBF3P-II) and 4-{3-[3-(9-phenyl-9H-fluoren-9-yl)phenyl]phenyl}dibenzofuran (abbreviation: mmDBFFLBi-II). Among the above materials, the compounds having aromatic amine skeletons and the compounds having carbazole skeletons are preferred because these compounds are highly reliable and have an excellent hole-transport property and contribute to a reduction in drive voltage.
In the light-emitting element, the light-emitting layer 113 does not necessarily have the single-layer structure illustrated in
Note that in the case where the light-emitting layer 113 has a stacked-layer structure, a light-emitting substance converting singlet excitation energy into light emission or a light-emitting substance converting triplet excitation energy into light emission can be used alone or in combination, for example. In that case, the following substances can be used.
The electron-transport layer 114 is a layer containing a substance having a high electron-transport property (also referred to as an electron-transport compound). For the electron-transport layer 114, a metal complex such as tris(8-quinolinolato)aluminum (abbreviation: Alq3), tris(4-methyl-8-quinolinolato)aluminum (abbreviation: Almq3), BeBq2, BAlq, bis[2-(2-hydroxyphenyl)benzoxazolato]zinc (abbreviation: Zn(BOX)2), or bis[2-(2-hydroxyphenyl)benzothiazolato]zinc (abbreviation: Zn(BTZ)2) can be used. Alternatively, a heteroaromatic compound such as PBD, 1,3-bis[5-(p-tert-butylphenyl)-1,3,4-oxadiazol-2-yl]benzene (abbreviation: OXD-7), TAZ, 3-(4-tert-butylphenyl)-4-(4-ethylphenyl)-5-(4-biphenylyl)-1,2,4-triazole (abbreviation: p-EtTAZ), bathophenanthroline (abbreviation: Bphen), bathocuproine (abbreviation: BCP), or 4,4′-bis(5-methylbenzoxazol-2-yl)stilbene (abbreviation: BzOs) can also be used. A high molecular compound such as poly(2,5-pyridinediyl) (abbreviation: PPy), poly[(9,9-dihexylfluorene-2,7-diyl)-co-(pyridine-3,5-diyl)](abbreviation: PF-Py), or poly[(9,9-dioctylfluorene-2,7-diyl)-co-(2,2′-bipyridine-6,6′-diyl)] (abbreviation: PF-BPy) can also be used. The substances listed here are mainly ones that have an electron mobility of 1×10−6 cm2/Vs or more. Note that any substance other than the substances listed here may be used for the electron-transport layer 114 as long as the electron-transport property is higher than the hole-transport property.
The substance used for the electron-transport layer 114 preferably has higher S1 and T1 levels than the light-emitting layer 113 that is adjacent to the electron-transport layer 114 because diffusion of excitation energy to the electron-transport layer 114 can be prevented. Furthermore, the substance used for the electron-transport layer 114 preferably has a deeper HOMO level (a smaller value) than the light-emitting layer 113 adjacent to the electron-transport layer 114 because passage of holes through the light-emitting layer 113 to the electron-transport layer 114 can be suppressed. Furthermore, a LUMO level of the substance used for the electron-transport layer 114 is preferably higher (a larger value) than or substantially equal to the LUMO level of the light-emitting layer 113 that is adjacent to the electron-transport layer 114 because easier electron-injection into the light-emitting layer 113 can be achieved.
The electron-transport layer 114 is not limited to a single layer, but may be a stack of two or more layers each containing any of the substances listed above.
The electron-injection layer 115 is a layer containing a substance having a high electron-injection property. 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), calcium fluoride (CaF2), or lithium oxide (LiOx) can be used. A rare earth metal compound like erbium fluoride (ErF3) can also be used. An electride may also 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. Any of the substances for forming the electron-transport layer 114, which are given above, can be used.
A composite material in which an organic compound and an electron donor (donor) are mixed may also be used for the electron-injection layer 115. Such a composite material is excellent in an electron-injection property and an electron-transport property because electrons are generated in the organic compound by the electron donor. In this case, the organic compound is preferably a material that is excellent in transporting the generated electrons. Specifically, for example, the substances for forming the electron-transport layer 114 (e.g., a metal complex or a heteroaromatic compound), which are given above, can be used. As the electron donor, a substance showing an electron-donating property with respect to the organic compound may be used. Specifically, an alkali metal, an alkaline earth metal, and a rare earth metal are preferable, and lithium, cesium, magnesium, calcium, erbium, ytterbium, and the like are given. In addition, an alkali metal oxide or an alkaline earth metal oxide is preferable, and lithium oxide, calcium oxide, barium oxide, and the like are given. A Lewis base such as magnesium oxide can also be used. An organic compound such as tetrathiafulvalene (abbreviation: TTF) can also be used.
Note that each of the hole-injection layer 111, the hole-transport layer 112, the light-emitting layer 113, the electron-transport layer 114, and the electron-injection layer 115 can be formed by any one or any combination of the following methods: an evaporation method (including a vacuum evaporation method), a printing method (such as relief printing, intaglio printing, gravure printing, planography printing, and stencil printing), an ink-jet method, a coating method, and the like. Besides the above-mentioned materials, an inorganic compound such as a quantum dot or a high molecular compound (e.g., an oligomer, a dendrimer, or a polymer) may be used for the hole-injection layer 111, the hole-transport layer 112, the light-emitting layer 113, the electron-transport layer 114, and the electron-injection layer 115, which are described above.
In the above light-emitting element, current flows due to a potential difference applied between the first electrode 101 and the second electrode 103 and holes and electrons recombine in the EL layer 102, whereby light is emitted. Then, the emitted light is extracted outside through one or both of the first electrode 101 and the second electrode 103. Therefore, one or both of the first electrode 101 and the second electrode 103 are electrodes having a light-transmitting property.
As described above, in the light-emitting element of this embodiment, the characteristics of the light-emitting element can be improved by the use of the above-described desired structure for a light-emitting layer. Specifically, when TTA is utilized, light efficiency due to singlet excitation energy can be improved, whereby the light-emitting element can have higher efficiency than a conventional fluorescent light-emitting element.
Note that the structure described in this embodiment can be used in combination with any of the structures described in the other embodiments, as appropriate.
In this embodiment, a light-emitting element (hereinafter referred to as a tandem light-emitting element) including a plurality of EL layers is described.
A light-emitting element described in this embodiment is a tandem light-emitting element including, between a pair of electrodes (a first electrode 201 and a second electrode 204), a plurality of EL layers (a first EL layer 202(1) and a second EL layer 202(2)) and a charge-generation layer 205 provided therebetween, as illustrated in
In this embodiment, the first electrode 201 functions as an anode, and the second electrode 204 functions as a cathode. Note that the first electrode 201 and the second electrode 204 can have structures similar to those described in Embodiment 3. In addition, either or both of the EL layers (the first EL layer 202(1) and the second EL layer 202(2)) may have structures similar to those described in Embodiment 3. In other words, the structures of the first EL layer 202(1) and the second EL layer 202(2) may be the same as or different from each other. When the structures are the same, Embodiment 3 can be referred to.
The charge-generation layer 205 provided between the plurality of EL layers (the first EL layer 202(1) and the second EL layer 202(2)) has a function of injecting electrons into one of the EL layers and injecting holes into the other of the EL layers when a voltage is applied between the first electrode 201 and the second electrode 204. In this embodiment, when a voltage is applied such that the potential of the first electrode 201 is higher than that of the second electrode 204, the charge-generation layer 205 injects electrons into the first EL layer 202(1) and injects holes into the second EL layer 202(2).
Note that in terms of light extraction efficiency, the charge-generation layer 205 preferably has a property of transmitting visible light (specifically, the charge-generation layer 205 has a visible light transmittance of 40% or more). The charge-generation layer 205 functions even when it has lower conductivity than the first electrode 201 or the second electrode 204.
The charge-generation layer 205 may have either a structure in which an electron acceptor (acceptor) is added to an organic compound having a high hole-transport property or a structure in which an electron donor (donor) is added to an organic compound having a high electron-transport property. Alternatively, both of these structures may be stacked.
In the case of the structure in which an electron acceptor is added to an organic compound having a high hole-transport property, as the organic compound having a high hole-transport property, the substances having a high hole-transport property which are given in Embodiment 3 as the substances used for the hole-injection layer 111 and the hole-transport layer 112 can be used. For example, an aromatic amine compound such as NPB, TPD, TDATA, MTDATA, or BSPB, or the like can be used. The substances listed here are mainly ones that have a hole mobility of 1×10−6 cm2/Vs or more. Note that any organic compound other than the compounds listed here may be used as long as the hole-transport property is higher than the electron-transport property.
As the electron acceptor, 7,7,8,8-tetracyano-2,3,5,6-tetrafluoroquinodimethane (abbreviation: F4-TCNQ), chloranil, and the like can be given. Oxides of metals belonging to Groups 4 to 8 of the periodic table can also be given. Specifically, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide, tungsten oxide, manganese oxide, and rhenium oxide are preferable because of their high electron-accepting properties. Among these, molybdenum oxide is especially preferable because it is stable in the air, has a low hygroscopic property, and is easy to handle.
In the case of the structure in which an electron donor is added to an organic compound having a high electron-transport property, as the organic compound having a high electron-transport property, the substances having a high electron-transport property which are given in Embodiment 3 as the substances used for the electron-transport layer 114 can be used. For example, a metal complex having a quinoline skeleton or a benzoquinoline skeleton, such as Alq, Almq3, BeBq2, or BAlq, or the like can be used. Alternatively, a metal complex having an oxazole-based ligand or a thiazole-based ligand, such as Zn(BOX)2 or Zn(BTZ)2, can be used. Alternatively, in addition to such a metal complex, PBD, OXD-7, TAZ, Bphen, BCP, or the like can be used. The substances listed here are mainly ones that have an electron mobility of 1×10−6 cm2/Vs or more. Note that any organic compound other than the compounds listed here may be used as long as the electron-transport property is higher than the hole-transport property.
As the electron donor, it is possible to use an alkali metal, an alkaline earth metal, a rare earth metal, metals belonging to Groups 2 and 13 of the periodic table, or an oxide or carbonate thereof. Specifically, lithium (Li), cesium (Cs), magnesium (Mg), calcium (Ca), ytterbium (Yb), indium (In), lithium oxide, cesium carbonate, or the like is preferably used. Alternatively, an organic compound such as tetrathianaphthacene may be used as the electron donor.
Note that forming the charge-generation layer 205 by using any of the above materials can suppress a drive voltage increase caused by the stack of the EL layers. The charge-generation layer 205 can be formed by any one or any combination of the following methods: an evaporation method (including a vacuum evaporation method), a printing method (such as relief printing, intaglio printing, gravure printing, planography printing, and stencil printing), an ink-jet method, a coating method, and the like.
Although the light-emitting element including two EL layers is described in this embodiment, the present invention can be similarly applied to a light-emitting element in which n EL layers (202(1) to 202(n)) (n is three or more) are stacked as illustrated in
When the EL layers have different emission colors, a desired emission color can be obtained from the whole light-emitting element. For example, in a light-emitting element having two EL layers, when an emission color of the first EL layer and an emission color of the second EL layer are complementary colors, the light-emitting element can emit white light as a whole. Note that “complementary colors” refer to colors that can produce an achromatic color when mixed. In other words, mixing light of complementary colors allows white light emission to be obtained. Specifically, a combination in which blue light emission is obtained from the first EL layer and yellow or orange light emission is obtained from the second EL layer is given as an example. In that case, it is not necessary that both of blue light emission and yellow (or orange) light emission are fluorescence, and the both are not necessarily phosphorescence. For example, a combination in which blue light emission is fluorescence and yellow (or orange) light emission is phosphorescence or a combination in which blue light emission is phosphorescence and yellow (or orange) light emission is fluorescence may be employed.
The same can be applied to a light-emitting element having three EL layers. For example, the light-emitting element as a whole can provide white light emission when the emission color of the first EL layer is red, the emission color of the second EL layer is green, and the emission color of the third EL layer is blue.
Note that the structure described in this embodiment can be combined as appropriate with any of the structures described in the other embodiments.
In this embodiment, a light-emitting device will be described.
The light-emitting device may be either a passive matrix light-emitting device or an active matrix light-emitting device. Any of the light-emitting elements described in other embodiments can be used in the light-emitting device described in this embodiment.
In this embodiment, first, an active matrix light-emitting device is described with reference to
Note that
In addition, over the element substrate 301, a lead wiring 307 for connecting an external input terminal, through which a signal (e.g., a video signal, a clock signal, a start signal, or a reset signal) or an potential from the outside is transmitted to the driver circuit portion 303 and the driver circuit portions 304a and 304b, is provided. Here, an example is described in which a flexible printed circuit (FPC) 308 is provided as the external input terminal. Although only the FPC is illustrated here, the FPC may be provided with a printed wiring board (PWB). The light-emitting device in this 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 is described with reference to
The driver circuit portion 303 is an example in which FETs 309 and 310 are combined. Note that the driver circuit portion 303 may be formed with a circuit including transistors having the same conductivity type (either n-channel transistors or p-channel transistors) or a CMOS circuit including an n-channel transistor and a p-channel transistor. Although this embodiment shows a driver integrated type in which the driver circuit is formed over the substrate, the driver circuit is not necessarily formed over the substrate, and may be formed outside the substrate.
The pixel portion 302 includes a switching FET (not illustrated) and a current control FET 312, and a wiring of the current control FET 312 (a source electrode or a drain electrode) is electrically connected to a first electrode (anode) (313a or 313b) of a light-emitting element 317a or 317b. Although the pixel portion 302 includes two kinds of FETs (the switching FET and the current control FETs 312) in this embodiment, one embodiment of the present invention is not limited thereto. The pixel portion 302 may include, for example, three or more kinds of FETs and a capacitor in combination.
As the FETs 309, 310, and 312, for example, a staggered transistor or an inverted staggered transistor can be used. Examples of a semiconductor material that can be used for the FETs 309, 310, and 312 are a Group 13 semiconductor, a Group 14 semiconductor (e.g., silicon), a compound semiconductor, an oxide semiconductor, and an organic semiconductor. In addition, there is no particular limitation on the crystallinity of the semiconductor material, and an amorphous semiconductor or a crystalline semiconductor can be used. In particular, an oxide semiconductor is preferably used for the FETs 309, 310, and 312. Examples of the oxide semiconductor are In—Ga oxides, In-M-Zn oxides (M is Al, Ga, Y, Zr, La, Ce, Hf, or Nd), and the like. For example, an oxide semiconductor that has an energy gap of 2 eV or more, preferably 2.5 eV or more and further preferably 3 eV or more, is used, so that the off-state current of the transistors can be reduced.
In addition, conductive films (320a and 320b) for optical adjustment are stacked over the first electrodes 313a and 313b. For example, as illustrated in
The insulator 314 preferably has a curved surface with curvature at an upper end portion or a lower end portion thereof. This enables favorable coverage by a film to be formed over the insulator 314. The insulator 314 can be formed using, for example, either a negative photosensitive resin or a positive photosensitive resin. The material for the insulator 314 is not limited to an organic compound and an inorganic compound such as silicon oxide, silicon oxynitride, or silicon nitride can also be used.
An EL layer 315 and a second electrode 316 are stacked over the first electrodes (313a and 313b). In the EL layer 315, at least a light-emitting layer is provided. In the light-emitting elements (317a and 317b) including the first electrodes (313a and 313b), the EL layer 315, and the second electrode 316, an end portion of the EL layer 315 is covered with the second electrode 316. The structure of the EL layer 315 may be the same as or different from the single-layer structure and the stacked layer structure described in Embodiments 2 and 3. Furthermore, the structure may differ between the light-emitting elements.
For the first electrode 313, the EL layer 315, and the second electrode 316, any of the materials given in Embodiment 3 can be used. The first electrodes (313a and 313b) of the light-emitting elements (317a and 317b) are electrically connected to the lead wiring 307 in a region 321, so that an external signal is input through the FPC 308. The second electrode 316 of the light-emitting elements (317a and 317b) is electrically connected to a lead wiring 323 in a region 322, so that an external signal is input through the FPC 308 although it is not illustrated.
Although the cross-sectional view in
The sealing substrate 306 is attached to the element substrate 301 with the sealant 305, whereby the light-emitting elements 317a and 317b are provided in a space 318 surrounded by the element substrate 301, the sealing substrate 306, and the sealant 305.
The sealing substrate 306 is provided with coloring layers (color filters) 324, and a black layer (black matrix) 325 is provided between adjacent coloring layers. Note that one or both of the adjacent coloring layers (color filters) 324 may be provided so as to partly overlap with the black layer (black matrix) 325. Light emission obtained from the light-emitting elements 317a and 317b is extracted through the coloring layers (color filters) 324.
Note that the space 318 may be filled with an inert gas (such as nitrogen or argon) or the sealant 305. In the case where the sealant is applied for attachment of the substrates, one or more of UV treatment, heat treatment, and the like are preferably performed.
An epoxy-based resin or glass frit is preferably used for the sealant 305. The material preferably allows as little moisture and oxygen as possible to penetrate. As the sealing substrate 306, a glass substrate, a quartz substrate, or a plastic substrate formed of fiber-reinforced plastic (FRP), poly(vinyl fluoride) (PVF), polyester, acrylic, or the like can be used. In the case where glass frit is used as the sealant, the element substrate 301 and the sealing substrate 306 are preferably glass substrates for high adhesion.
Structures of the FETs electrically connected to the light-emitting elements may be different from those in
As described above, an active matrix light-emitting device can be obtained.
Note that the light-emitting device can be a passive matrix light-emitting device as well as the above active matrix light-emitting device.
As illustrated in
Since the insulating film 406 has openings in part of the first electrode 402, the EL layers (403a, 403b, and 403c) and second electrodes 404 which are divided as desired can be formed over the first electrode 402. In the example in
After the formation of the EL layers (403a, 403b, and 403c), the second electrodes 404 are formed. Thus, the second electrode 404 is formed over the EL layers (403a, 403b, and 403c) without contact with the first electrode 402.
Note that sealing can be performed by a method similar to that used for the active matrix light-emitting device, and description thereof is not made.
As described above, the passive matrix light-emitting device can be obtained.
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 film, and the like are substrates of plastics typified by polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyether sulfone (PES), and polytetrafluoroethylene (PTFE). Another example is a synthetic resin such as acrylic. Alternatively, 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 supply capability. A circuit using such transistors achieves low power consumption of the circuit or high integration of the circuit.
Alternatively, a flexible substrate may be used as the substrate, and a transistor or a 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 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 or the light-emitting element 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 are, in addition to the above-described substrates over which a transistor or a light-emitting element 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, a rubber substrate, and the like. 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 a reduction in weight or thickness can be achieved.
Note that the structure described in this embodiment can be combined as appropriate with any of the structures described in the other embodiments.
In this embodiment, examples of a variety of electronic devices and an automobile manufactured using a light-emitting device which is one embodiment of the present invention are described.
Examples of the electronic device including the light-emitting device are television devices (also referred to as TV or television receivers), monitors for computers and the like, digital cameras, digital video cameras, digital photo frames, cellular phones (also referred to as portable telephone devices), portable game consoles, portable information terminals, audio playback devices, large game machines such as pachinko machines, and the like. Specific examples of the electronic devices are illustrated in
The television device 7100 can be operated by 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 7100 is provided with a receiver, a modem, and the like. With the use of the receiver, general television broadcasts 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.
The display portion 7304 mounted in the housing 7302 serving as a bezel includes a non-rectangular display region. The display portion 7304 can display an icon 7305 indicating time, another icon 7306, and the like. The display portion 7304 may be a touch panel (an input/output device) including a touch sensor (an input device).
The smart watch illustrated in
The housing 7302 can include a speaker, a sensor (a sensor having a function of measuring force, displacement, position, speed, acceleration, angular velocity, rotational frequency, distance, light, liquid, magnetism, temperature, chemical substance, sound, time, hardness, electric field, current, voltage, electric power, radiation, flow rate, humidity, gradient, oscillation, odor, or infrared rays), a microphone, and the like. Note that the smart watch can be manufactured using the light-emitting device for the display portion 7304.
When the display portion 7402 of the cellular phone 7400 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 data 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 e-mail, a character input mode mainly for inputting characters is selected for the display portion 7402 so that characters displayed on the 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 such as a gyroscope sensor or an acceleration sensor is provided inside the cellular phone 7400, display on the screen of the display portion 7402 can be automatically changed by determining the orientation of the cellular phone 7400 (whether the cellular phone is placed horizontally or vertically for a landscape mode or a portrait mode).
The screen modes are changed by touch on the display portion 7402 or operation with the operation button 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, if a signal detected by an optical sensor in the display portion 7402 is detected and the input by touch on the display portion 7402 is not performed for a certain period, the screen mode may be controlled so as to be changed 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 touch on the display portion 7402 with the palm or the finger, whereby personal authentication can be performed. In addition, by providing a backlight or a sensing light source that emits near-infrared light in the display portion, an image of a finger vein, a palm vein, or the like can be taken.
The light-emitting device can be used for a cellular phone having a structure illustrated in
Note that in the case of the structure illustrated in
Another electronic device including a light-emitting device is a foldable portable information terminal illustrated in
A display portion 9311 is supported by three housings 9315 joined together by hinges 9313. Note that the display portion 9311 may be a touch panel (an input/output device) including a touch sensor (an input device). By bending the display portion 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. A light-emitting device of one embodiment of the present invention can be used for the display portion 9311. A display region 9312 in the display portion 9311 is a display region that is positioned at a 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.
As described above, the electronic devices and automobiles can be obtained using the light-emitting device which is one embodiment of the present invention. Note that the light-emitting device can be used for electronic devices and automobiles in a variety of fields without being limited to the electronic devices described in this embodiment.
Note that the structure described in this embodiment can be combined as appropriate with any of the structures described in the other embodiments.
In this embodiment, a structure of a lighting device fabricated using the light-emitting element which is one embodiment of the present invention will be described with reference to
A lighting device 4000 illustrated in
The first electrode 4004 is electrically connected to an electrode 4007, and the second electrode 4006 is electrically connected to an electrode 4008. In addition, an auxiliary wiring 4009 electrically connected to the first electrode 4004 may be provided. Note that an insulating layer 4010 is formed over the auxiliary wiring 4009.
The substrate 4001 and a sealing substrate 4011 are bonded to each other by a sealant 4012. A desiccant 4013 is preferably provided between the sealing substrate 4011 and the light-emitting element 4002. The substrate 4003 has the unevenness illustrated in
Instead of the substrate 4003, a diffusion plate 4015 may be provided on the outside of the substrate 4001 as in a lighting device 4100 illustrated in
A lighting device 4200 illustrated in
The first electrode 4204 is electrically connected to an electrode 4207, and the second electrode 4206 is electrically connected to an electrode 4208. An auxiliary wiring 4209 electrically connected to the second electrode 4206 may be provided. An insulating layer 4210 may be provided under the auxiliary wiring 4209.
The substrate 4201 and a sealing substrate 4211 with unevenness are bonded to each other by a sealant 4212. A barrier film 4213 and a planarization film 4214 may be provided between the sealing substrate 4211 and the light-emitting element 4202. The sealing substrate 4211 has the unevenness illustrated in
Instead of the sealing substrate 4211, a diffusion plate 4215 may be provided over the light-emitting element 4202 as in a lighting device 4300 illustrated in
Note that the structure described in this embodiment can be combined as appropriate with any of the structures described in the other embodiments.
In this embodiment, examples of a lighting device which is an application of the light-emitting device of one embodiment of the present invention will be described with reference to
Besides the above examples, when the light-emitting device is used as part of furniture in a room, a lighting device that functions as the furniture can be obtained.
In this manner, a variety of lighting devices to which the light-emitting device is applied can be obtained.
Note that the structure described in this embodiment can be combined as appropriate with any of the structures described in the other embodiments.
In this embodiment, touch panels including a light-emitting element of one embodiment of the present invention or a light-emitting device of one embodiment of the present invention will be described with reference to
The touch panel 2000 includes a display panel 2501 and a touch sensor 2595 (see
The display panel 2501 includes a plurality of pixels over the substrate 2510, and a plurality of wirings 2511 through which signals are supplied to the pixels. The plurality of wirings 2511 are led to a peripheral portion of the substrate 2510, and part of the plurality of wirings 2511 forms a terminal 2519. The terminal 2519 is electrically connected to an FPC 2509(1).
The substrate 2590 includes the touch sensor 2595 and a plurality of wirings 2598 electrically connected to the touch sensor 2595. The plurality of wirings 2598 are led to a peripheral portion of the substrate 2590, and part of the plurality of wirings 2598 forms a terminal 2599. The terminal 2599 is electrically connected to an FPC 2509(2). Note that in
As the touch sensor 2595, a capacitive touch sensor can be used, for example. Examples of the capacitive touch sensor are a surface capacitive touch sensor, a projected capacitive touch sensor, and the like.
Examples of the projected capacitive touch sensor are a self-capacitive touch sensor, a mutual capacitive touch sensor, and the like, which differ mainly in the driving method. The use of a mutual capacitive touch sensor is preferable because multiple points can be sensed simultaneously.
First, an example of using a projected capacitive touch sensor is described with reference to
The projected capacitive touch sensor 2595 includes electrodes 2591 and 2592. The electrodes 2591 are electrically connected to any of the plurality of wirings 2598, and the electrodes 2592 are electrically connected to any of the other wirings 2598. The electrodes 2592 each have a shape of a plurality of quadrangles arranged in one direction with one corner of a quadrangle connected to one corner of another quadrangle with a wiring 2594 in one direction, as illustrated in
The intersecting area of the wiring 2594 and one of the electrodes 2592 is preferably as small as possible. Such a structure allows a reduction in the area of a region where the electrodes are not provided, reducing unevenness in transmittance. As a result, unevenness in the luminance of light from the touch sensor 2595 can be reduced.
Note that the shapes of the electrodes 2591 and the 2592 are not limited to the above-described shapes and can be any of a variety of shapes. For example, the plurality of electrodes 2591 may be provided so that a space between the electrodes 2591 is reduced as much as possible, and the plurality of electrodes 2592 may be provided with an insulating layer sandwiched between the electrodes 2591 and 2592. In that case, it is preferable to provide, between two adjacent electrodes 2592, a dummy electrode which is electrically insulated from these electrodes because the area of a region having a different transmittance can be reduced.
Next, the touch panel 2000 is described in detail with reference to
The touch panel 2000 includes the touch sensor 2595 and the display panel 2501.
The touch sensor 2595 includes the electrodes 2591 and 2592 that are provided in a staggered arrangement and in contact with the substrate 2590, an insulating layer 2593 covering the electrodes 2591 and 2592, and the wiring 2594 that electrically connects the adjacent electrodes 2591 to each other. Between the adjacent electrodes 2591, the electrode 2592 is provided.
The electrodes 2591 and 2592 can be formed using a light-transmitting conductive material. As a light-transmitting conductive material, a conductive oxide such as indium oxide, indium tin oxide, indium zinc oxide, zinc oxide, or zinc oxide to which gallium is added can be used. A graphene compound may be used as well. When a graphene compound is used, it can be formed, for example, by reducing a graphene oxide film. As a reducing method, a method with application of heat, a method with laser irradiation, or the like can be employed.
For example, the electrodes 2591 and 2592 can be formed by depositing a light-transmitting conductive material on the substrate 2590 by a sputtering method and then removing an unneeded portion by any of various patterning techniques such as photolithography.
Examples of a material for the insulating layer 2593 are a resin such as acrylic or epoxy resin, a resin having a siloxane bond, and an inorganic insulating material such as silicon oxide, silicon oxynitride, or aluminum oxide.
The adjacent electrodes 2591 are electrically connected to each other with the wiring 2594 formed in part of the insulating layer 2593. Note that a material for the wiring 2594 preferably has higher conductivity than materials for the electrodes 2591 and 2592 to reduce electrical resistance.
One wiring 2598 is electrically connected to any of the electrodes 2591 and 2592. Part of the wiring 2598 serves as a terminal. For the wiring 2598, a metal material such as aluminum, gold, platinum, silver, nickel, titanium, tungsten, chromium, molybdenum, iron, cobalt, copper, or palladium or an alloy material containing any of these metal materials can be used.
Through the terminal 2599, the wiring 2598 and the FPC 2509(2) are electrically connected to each other. The terminal 2599 can be formed using any of various kinds of anisotropic conductive films (ACF), anisotropic conductive pastes (ACP), and the like.
An adhesive layer 2597 is provided in contact with the wiring 2594. That is, the touch sensor 2595 is attached to the display panel 2501 so that they overlap with each other with the adhesive layer 2597 provided therebetween. Note that the substrate 2570 as illustrated in
The adhesive layer 2597 has a light-transmitting property. For example, a thermosetting resin or an ultraviolet curable resin can be used; specifically, a resin such as an acrylic-based resin, a urethane-based resin, an epoxy-based resin, or a siloxane-based resin can be used.
The display panel 2501 in
In
The pixel 2502R includes a light-emitting element 2550R and a transistor 2502t that can supply electric power to the light-emitting element 2550R.
The transistor 2502t is covered with an insulating layer 2521. The insulating layer 2521 covers unevenness caused by the transistor and the like that have been already formed to provide a flat surface. The insulating layer 2521 may serve also as a layer for preventing diffusion of impurities. That is preferable because a reduction in the reliability of the transistor or the like due to diffusion of impurities can be prevented.
The light-emitting element 2550R is electrically connected to the transistor 2502t through a wiring. It is one electrode of the light-emitting element 2550R that is directly connected to the wiring. An end portion of the one electrode of the light-emitting element 2550R is covered with an insulator 2528.
The light-emitting element 2550R includes an EL layer between a pair of electrodes. A coloring layer 2567R is provided to overlap with the light-emitting element 2550R, and part of light emitted from the light-emitting element 2550R is transmitted through the coloring layer 2567R and extracted in the direction indicated by an arrow in the drawing. A light-blocking layer 2567BM is provided at an end portion of the coloring layer, and a sealing layer 2560 is provided between the light-emitting element 2550R and the coloring layer 2567R.
Note that when the sealing layer 2560 is provided on the side from which light from the light-emitting element 2550R is extracted, the sealing layer 2560 preferably has a light-transmitting property. The sealing layer 2560 preferably has a higher refractive index than the air.
The scan line driver circuit 2503g includes a transistor 2503t and a capacitor 2503c. Note that the driver circuit and the pixel circuits can be formed in the same process over the same substrate. Thus, in a manner similar to that of the transistor 2502t in the pixel circuit, the transistor 2503t in the driver circuit (scan line driver circuit 2503g) is also covered with the insulating layer 2521.
The wirings 2511 through which a signal can be supplied to the transistor 2503t are provided. The terminal 2519 is provided in contact with the wiring 2511. The terminal 2519 is electrically connected to the FPC 2509(1), and the FPC 2509(1) has a function of supplying signals such as an image signal and a synchronization signal. Note that a printed wiring board (PWB) may be attached to the FPC 2509(1).
Although the case where the display panel 2501 illustrated in
In the touch panel 2000 illustrated in
For the substrates 2510, 2570, and 2590 in
Next, a touch panel 2000′ having a structure different from that of the touch panel 2000 illustrated in
The coloring layer 2567R overlaps with the light-emitting element 2550R. Light from the light-emitting element 2550R illustrated in
The touch sensor 2595 is provided on the transistor 2502t side (the far side from the light-emitting element 2550R) of the display panel 2501 (see
The adhesive layer 2597 is in contact with the substrate 2510 of the display panel 2501 and attaches the display panel 2501 and the touch sensor 2595 to each other in the structure illustrated in
As in the touch panel 2000, transistors with a variety of structures can be used for the display panel 2501 in the touch panel 2000′. Although a bottom-gate transistor is used in
An example of a driving method of the touch panel is described with reference to
The pulse voltage output circuit 2601 is a circuit for sequentially applying a pulse voltage to the wirings X1 to X6. By application of a pulse voltage to the wirings X1 to X6, an electric field is generated between the electrodes 2621 and 2622 of the capacitor 2603. When the electric field between the electrodes is shielded, for example, a change occurs in the capacitor 2603 (mutual capacitance). The approach or contact of a sensing target can be sensed by utilizing this change.
The current sensing circuit 2602 is a circuit for sensing changes in current flowing through the wirings Y1 to Y6 that are caused by the change in mutual capacitance in the capacitor 2603. No change in current value is sensed in the wirings Y1 to Y6 when there is no approach or contact of a sensing target, whereas a decrease in current value is sensed when mutual capacitance is decreased owing to the approach or contact of a sensing target. Note that an integrator circuit or the like is used for sensing of current.
A pulse voltage is sequentially applied to the wirings X1 to X6, and the waveforms of the wirings Y1 to Y6 change in accordance with the pulse voltage. When there is no approach or contact of a sensing target, the waveforms of the wirings Y1 to Y6 change uniformly in accordance with changes in the voltages of the wirings X1 to X6. The current value is decreased at the point of approach or contact of a sensing target and accordingly the waveform of the voltage value changes. By sensing a change in mutual capacitance in this manner, the approach or contact of a sensing target can be sensed.
Although
The sensor circuit illustrated in
A signal G2 is input to a gate of the transistor 2613. A voltage VRES is applied to one of a source and a drain of the transistor 2613, and one electrode of the capacitor 2603 and a gate of the transistor 2611 are electrically connected to the other of the source and the drain of the transistor 2613. One of a source and a drain of the transistor 2611 is electrically connected to one of a source and a drain of the transistor 2612, and a voltage VSS is applied to the other of the source and the drain of the transistor 2611. A signal G1 is input to a gate of the transistor 2612, and a wiring ML is electrically connected to the other of the source and the drain of the transistor 2612. The voltage VSS is applied to the other electrode of the capacitor 2603.
Next, the operation of the sensor circuit illustrated in
In reading operation, a potential for turning on the transistor 2612 is supplied as the signal G1. A current flowing through the transistor 2611, that is, a current flowing through the wiring ML is changed in accordance with the potential of the node n. By sensing this current, the approach or contact of a sensing target can be sensed.
In each of the transistors 2611, 2612, and 2613, an oxide semiconductor layer is preferably used as a semiconductor layer in which a channel region is formed. In particular, such a transistor is preferably used as the transistor 2613, so that the potential of the node n can be held for a long time and the frequency of operation of resupplying VRES to the node n (refresh operation) can be reduced.
At least part of this embodiment can be implemented in combination with any of the embodiments described in this specification as appropriate.
In this embodiment, as an example of a display device including a light-emitting element in which an organic compound of one embodiment of the present invention is used, a display device that includes a liquid crystal element and a light-emitting element and that can display an image both in a transmissive mode and a reflective mode will be described with reference to
The display device described in this embodiment can be driven with extremely low power consumption for display using the reflective mode in a bright place such as outdoors. Meanwhile, in a dark place such as indoors at night, an image can be displayed at an optimal luminance with the use of the transmissive mode. Thus, by combination of these modes, the display device can display an image with lower power consumption and a higher contrast compared to a conventional display panel.
As an example of the display device of this embodiment, description is made on a display device in which a liquid crystal element provided with a reflective electrode and a light-emitting element are stacked and an opening of the reflective electrode is provided in a position overlapping with the light-emitting element. Visible light is reflected by the reflective electrode in the reflective mode and light emitted from the light-emitting element is emitted through the opening of the reflective electrode in the transmissive mode. Note that transistors used for driving these elements (the liquid crystal element and the light-emitting element) are preferably formed on the same plane. It is preferable that the liquid crystal element and the light-emitting element be stacked through an insulating layer.
Each of the plurality of pixels 604 includes a liquid crystal element and a light-emitting element. The liquid crystal element and the light-emitting element include portions overlapping with each other.
FIG. 18B1 shows the shape of a conductive film 605 serving as a reflective electrode of the liquid crystal element included in the pixel 604. Note that an opening 607 is provided in a position 606 which is part of the conductive film 605 and which overlaps with the light-emitting element. That is, light emitted from the light-emitting element is emitted through the opening 607.
The pixels 604 in FIG. 18B1 are arranged such that adjacent pixels 604 in the R direction exhibit different colors. Furthermore, the openings 607 are provided so as not to be arranged in a line in the R direction. Such arrangement has an effect of suppressing crosstalk between the light emitting elements of adjacent pixels 604.
The opening 607 can have a polygonal shape, a quadrangular shape, an elliptical shape, a circular shape, a cross shape, a stripe shape, or a slit-like shape, for example.
FIG. 18B2 illustrates another example of the arrangement of the conductive films 605.
The ratio of the opening 607 to the total area of the conductive film 605 (excluding the opening 607) affects the display of the display device. That is, a problem is caused in that as the area of the opening 607 is larger, the display using the liquid crystal element becomes darker; in contrast, as the area of the opening 607 is smaller, the display using the light-emitting element becomes darker. Furthermore, in addition to the problem of the ratio of the opening, a small area of the opening 607 itself also causes a problem in that extraction efficiency of light emitted from the light-emitting element is decreased. The ratio of opening 607 to the total area of the conductive film 605 (other than the opening 607) is preferably 5% or more and 60% or less for maintaining display quality at the time of combination of the liquid crystal element and the light-emitting element.
Next, an example of a circuit configuration of the pixel 604 is described with reference to
The pixel 604 includes a transistor SW1, a capacitor C1, a liquid crystal element 610, a transistor SW2, a transistor M, a capacitor C2, a light-emitting element 611, and the like. Note that these components are electrically connected to any of the wiring G1, the wiring G2, the wiring ANO, the wiring CSCOM, the wiring S1, and the wiring S2 in the pixel 604. The liquid crystal element 610 and the light-emitting element 611 are electrically connected to a wiring VCOM1 and a wiring VCOM2, respectively.
A gate of the transistor SW1 is connected to the wiring G1. One of a source and a drain of the transistor SW1 is connected to the wiring S1, and the other of the source and the drain is connected to one electrode of the capacitor C and one electrode of the liquid crystal element 610. The other electrode of the capacitor C1 is electrically connected to the wiring CSCOM. The other electrode of the liquid crystal element 610 is connected to the wiring VCOM1.
A gate of the transistor SW2 is connected to the wiring G2. One of a source and a drain of the transistor SW2 is connected to the wiring S2, and the other of the source and the drain is connected to one electrode of the capacitor C2 and a gate of the transistor M. The other electrode of the capacitor C2 is connected to one of a source and a drain of the transistor M and the wiring ANO. The other of the source and the drain of the transistor M is connected to one electrode of the light-emitting element 611. Furthermore, the other electrode of the light-emitting element 611 is connected to the wiring VCOM2.
Note that the transistor M includes two gates between which a semiconductor is provided and which are electrically connected to each other. With such a structure, the amount of current flowing through the transistor M can be increased.
The on/off state of the transistor SW1 is controlled by a signal from the wiring G1. A predetermined potential is supplied from the wiring VCOM1. Furthermore, orientation of liquid crystals of the liquid crystal element 610 can be controlled by a signal from the wiring S1. A predetermined potential is supplied from the wiring CSCOM.
The on/off state of the transistor SW2 is controlled by a signal from the wiring G2. By the difference between the potentials applied from the wiring VCOM2 and the wiring ANO, the light-emitting element 611 can emit light. Furthermore, the conduction state of the transistor M can be controlled by a signal from the wiring S2.
Accordingly, in the structure of this embodiment, in the case of the reflective mode, the liquid crystal element 610 is controlled by the signals supplied from the wiring G1 and the wiring S1 and optical modulation is utilized, whereby display can be performed. In the case of the transmissive mode, the light-emitting element 611 can emit light when the signals are supplied from the wiring G2 and the wiring S2. In the case where both modes are performed at the same time, desired driving can be performed based on the signals from the wiring G1, the wiring G2, the wiring S1, and the wiring S2.
Next, specific description will be given with reference to
The display device 600 includes a light-emitting element 623 and a liquid crystal element 624 between substrates 621 and 622. Note that the light-emitting element 623 and the liquid crystal element 624 are formed with an insulating layer 625 positioned therebetween. That is, the light-emitting element 623 is positioned between the substrate 621 and the insulating layer 625, and the liquid crystal element 624 is positioned between the substrate 622 and the insulating layer 625.
A transistor 615, a transistor 616, a transistor 617, a coloring layer 628, and the like are provided between the insulating layer 625 and the light-emitting element 623.
A bonding layer 629 is provided between the substrate 621 and the light-emitting element 623. The light-emitting element 623 includes a conductive layer 630 serving as one electrode, an EL layer 631, and a conductive layer 632 serving as the other electrode which are stacked in this order over the insulating layer 625. In the light-emitting element 623 that is a bottom emission light-emitting element, the conductive layer 632 and the conductive layer 630 contain a material that reflects visible light and a material that transmits visible light, respectively. Light emitted from the light-emitting element 623 is transmitted through the coloring layer 628 and the insulating layer 625 and then transmitted through the liquid crystal element 624 via an opening 633, thereby being emitted to the outside of the substrate 622.
In addition to the liquid crystal element 624, a coloring layer 634, a light-blocking layer 635, an insulating layer 646, a structure 636, and the like are provided between the insulating layer 625 and the substrate 622. The liquid crystal element 624 includes a conductive layer 637 serving as one electrode, a liquid crystal 638, a conductive layer 639 serving as the other electrode, alignment films 640 and 641, and the like. Note that the liquid crystal element 624 is a reflective liquid crystal element and the conductive layer 639 serves as a reflective electrode; thus, the conductive layer 639 is formed using a material with high reflectivity. Furthermore, the conductive layer 637 serves as a transparent electrode, and thus is formed using a material that transmits visible light. Alignment films 640 and 641 may be provided on the conductive layers 637 and 639 and in contact with the liquid crystal 638. The insulating layer 646 is provided so as to cover the coloring layer 634 and the light-blocking 635 and serves as an overcoat layer. Note that the alignment films 640 and 641 are not necessarily provided.
The opening 633 is provided in part of the conductive layer 639. A conductive layer 643 is provided in contact with the conductive layer 639 and has a light-transmitting property because of being formed using a material transmitting visible light.
The structure 636 serves as a spacer that prevents the substrate 622 from coming closer to the insulating layer 625 than required. The structure 636 is not necessarily provided.
One of a source and a drain of the transistor 615 is electrically connected to the conductive layer 630 in the light-emitting element 623. For example, the transistor 615 corresponds to the transistor M in
One of a source and a drain of the transistor 616 is electrically connected to the conductive layer 639 and the conductive layer 643 in the liquid crystal element 624 through a terminal portion 618. That is, the terminal portion 618 electrically connects the conductive layers provided on both surfaces of the insulating layer 625. The transistor 616 corresponds to the transistor SW1 in
A terminal portion 619 is provided in a region where the substrates 621 and 622 do not overlap with each other. Similarly to the terminal portion 618, the terminal portion 619 electrically connects the conductive layers provided on both surfaces of the insulating layer 625. The terminal portion 619 is electrically connected to a conductive layer obtained by processing the same conductive film as the conductive layer 643. Thus, the terminal portion 619 and the FPC 644 can be electrically connected to each other through a connection layer 645.
A connection portion 647 is provided in part of a region where a bonding layer 642 is provided. In the connection portion 647, the conductive layer obtained by processing the same conductive film as the conductive layer 643 and part of the conductive layer 637 are electrically connected with a connector 648. Accordingly, a signal or a potential input from the FPC 644 can be supplied to the conductive layer 637 through the connection portion 647.
The structure 636 is provided between the conductive layer 637 and the conductive layer 643. The structure 636 maintains a cell gap of the liquid crystal element 624.
As the conductive layer 643, a metal oxide, a metal nitride, or an oxide such as an oxide semiconductor whose resistance is reduced is preferably used. In the case of using an oxide semiconductor, a material in which at least one of the concentrations of hydrogen, boron, phosphorus, nitrogen, and other impurities and the number of oxygen vacancies is made to be higher than those in a semiconductor layer of a transistor is used for the conductive layer 643.
Note that the structure described in this embodiment can be combined as appropriate with any of the structures described in the other embodiments.
In this embodiment, a light-emitting element is described. The light-emitting element described in this embodiment has a structure different from that described in Embodiment 2. An element structure and a manufacturing method of the light-emitting element is described with reference to
The light-emitting element described in this embodiment has a structure in which an EL layer 3202 including a light-emitting layer 3213 is sandwiched between a pair of electrodes (a cathode 3201 and an anode 3203) formed over a substrate 3200. The EL layer 3202 can be formed by stacking a light-emitting layer, a hole-injection layer, a hole-transport layer, an electron-injection layer, an electron-transport layer, and the like as in the EL layer described in Embodiment 2.
In this embodiment, as shown in
In the above-described light-emitting element, current flows due to a potential difference applied between the cathode 3201 and the anode 3203, and holes and electrons recombine in the EL layer 3202, whereby light is emitted. Then, this light emission is extracted to the outside through one or both of the cathode 3201 and the anode 3203. Therefore, one or both of the cathode 3201 and the anode 3203 are electrodes having light-transmitting properties; light can be extracted through the electrode having a light-transmitting property.
In the light-emitting element described in this embodiment, end portions of the cathode 3201 are covered with insulators 3217 as shown in
As the insulator 3217, an inorganic compound or an organic compound having an insulating property can be used. As the organic compound, a photosensitive resin such as a resist material, e.g., an acrylic-based resin, a polyimide-based resin, a fluorine-based resin, or the like can be used. As the inorganic material, silicon oxide, silicon oxynitride, silicon nitride, or the like can be used, for example. Note that the insulator 3217 preferably has a water-repellent surface. As its treatment method, plasma treatment, chemical treatment (using an alkaline solution or an organic solvent), or the like can be employed.
In this embodiment, the electron-injection layer 3214 formed over the cathode 3201 is formed using a high molecular compound. It is preferable to use a high molecular compound which does not dissolve in the nonaqueous solvent and which has a high electron-transport property. Specifically, the electron-injection layer 3214 is formed using an appropriate combination of any of the materials (including not only a high molecular compound but also an alkali metal, an alkaline earth metal, or a compound thereof) which can be used for the electron-injection layer 115 and electron-transport layer 114 in Embodiment 2. The materials are dissolved in a polar solvent, and the layer is formed by a coating method.
Here, examples of the polar solvent include methanol, ethanol, propanol, isopropanol, butyl alcohol, ethylene glycol, and glycerin.
The light-emitting layer 3213 is formed over the electron-injection layer 3214. The light-emitting layer 3213 is formed by depositing (or applying) ink in which any of the materials (a light-emitting substance) which can be used for the light-emitting layer 3213 in Embodiment 2 are combined as appropriate and dissolved (dispersed) in a polar solvent, by a wet method (an ink-jet method or a printing method). Although the electron-injection layer 3214 is used in common in light-emitting elements of different emission colors, a material corresponding to an emission color is selected for the light-emitting layer 3213. As the polar solvent, an aromatic-based solvent such as toluene or xylene, or a heteroaromatic-based solvent such as pyridine can be used. Alternatively, a solvent such as hexane, 2-methylhexane, cyclohexane, or chloroform can be used.
As shown in
The ink 3303a to ink 3303c are sprayed from the respective spraying portions 3301a to 3301c, whereby light-emitting layers 3213a to 3213c emitting different colors are formed.
The hole-transport layer 3215 is formed over the light-emitting layer 3213. The hole-transport layer 3215 can be formed by a combination of any of the materials which can be used for the hole-transport layer 3215 in Embodiment 2. The hole-transport layer 3215 can be formed by a vacuum evaporation method or a coating method. In the case of employing a coating method, the material which is dissolved in a solvent is applied to the light-emitting layer 3213 and the insulator 3217. As a coating method, an ink-jet method, a spin coating method, a printing method, or the like can be used.
The hole-injection layer 3216 is formed over the hole-transport layer 3215. The anode 3203 is formed over the hole-injection layer 3216. They are formed using an appropriate combination of the materials described in Embodiment 2 by a vacuum evaporation method.
The light-emitting element can be formed through the above steps. Note that in the case of using an organometallic complex in the light-emitting layer, phosphorescence due to the organometallic complex is obtained. Thus, the light-emitting element can have higher efficiency than a light-emitting element formed using only fluorescent compounds.
Note that the structure described in this embodiment can be used in combination with any of the structures described in the other embodiments, as appropriate.
In this example, light-emitting elements were fabricated and characteristics thereof were shown. Specifically, Light-emitting element 1 in which only 1,5-bis[4-(9H-carbazol-9-yl)phenyl]anthracene (abbreviation: 1,5CzP2A) (Structure Formula 100) was used in a light-emitting layer, Light-emitting element 2 in which 1,5CzP2A and 1,6mMemFLPAPrn that was a dopant (a light-emitting substance) were used in a light-emitting layer, Light-emitting element 3 in which only 1,8-bis[4-(9H-carbazol-9-yl)phenyl]anthracene (abbreviation: 1,8CzP2A) (Structure Formula 110) was used in a light-emitting layer, Light-emitting element 4 in which 1,8CzP2A and 1,6mMemFLPAPrn that was a dopant (a light-emitting substance) was used in a light-emitting layer, and Light-emitting element 5 in which only 1,5-bis[4-(9H-carbazol-9-yl)phenyl]-9,10-diphenylanthracene (abbreviation: 1,5CzP2PA) (Structure Formula 120) was used in a light-emitting layer were fabricated. Note that the fabrication of Light-emitting elements 1 to 5 is described with reference to
<<Fabrication Method of Light-Emitting Elements 1 to 5>>
First, indium tin oxide (ITO) containing silicon oxide was deposited over a 5 glass substrate 900 by a sputtering method, whereby a first electrode 901 functioning as an anode was formed. The thickness of the first electrode 901 was set to 70 nm and the area of the electrode was set to 2 mm×2 mm.
Next, as pretreatment for fabricating the light-emitting element over the substrate 900, UV ozone treatment was performed for 370 seconds after washing of a surface of the substrate with water and baking that was performed at 200° C. for 1 hour.
After that, the substrate 900 was transferred into a vacuum evaporation apparatus where the pressure had been reduced to approximately 1×10−4 Pa, and was subjected to vacuum baking at 170° C. for 30 minutes in a heating chamber of the vacuum evaporation apparatus. Then, the substrate 900 was cooled down for approximately 30 minutes.
Next, the substrate 900 over which the first electrode 901 was formed was fixed to a holder provided inside a vacuum evaporation apparatus so that the surface over which the first electrode was formed faced downward. In this example, a case will be described in which a hole-injection layer 911, a hole-transport layer 912, a light-emitting layer 913, an electron-transport layer 914, and an electron-injection layer 915 which are included in an EL layer 902 are sequentially formed by a vacuum evaporation method.
The pressure in the vacuum evaporation apparatus was reduced to 1×10−4 Pa. Then, 3-[4-(9-phenanthryl)-phenyl]-9-phenyl-9H-carbazole (abbreviation: PCPPn) and molybdenum oxide were deposited by co-evaporation with a mass ratio of PCPPn to molybdenum oxide being 4:2, thereby forming the hole-injection layer 911 on the first electrode 901. A thickness thereof was set to be 10 nm. Note that a co-evaporation method is an evaporation method in which a plurality of different substances is concurrently vaporized from respective different evaporation sources.
Next, PCPPn was deposited to a thickness of 20 nm by evaporation to form the hole-transport layer 912. Note that only in the case of Light-emitting element 5, PCPPn was deposited to a thickness of 30 nm by evaporation to form the hole-transport layer 912.
Next, the light-emitting layer 913 was formed over the hole-transport layer 912.
In the case of Light-emitting element 1, the light-emitting layer 913 was deposited to a thickness of 25 nm by evaporation of 1,5CzP2A.
In the case of Light-emitting element 2, 1,5CzP2A and 1,6mMemFLPAPrn that was a dopant (a light-emitting substance) were deposited by co-evaporation so that the mass ratio of 1,5CzP2A and 1,6mMemFLPAPrn was 1:0.03, whereby the light-emitting layer 913 was formed to a thickness of 25 nm.
In the case of Light-emitting element 3, the light-emitting layer 913 was deposited to a thickness of 25 nm by evaporation of 1,8CzP2A.
In the case of Light-emitting element 4, 1,8CzP2A and 1,6mMemFLPAPrn that was a dopant (a light-emitting substance) were deposited by co-evaporation such that the mass ratio of 1,8CzP2A and 1,6mMemFLPAPrn was 1:0.03, whereby the light-emitting layer 913 was formed to a thickness of 25 nm.
In the case of Light-emitting element 5, the light-emitting layer 913 was deposited to a thickness of 25 nm by evaporation of 1,5CzP2PA.
Next, over the light-emitting layer 913, 2,2′-(pyridine-2,6-diyl)bis(4,6-diphenylpyrimidine) (abbreviation: 2,6(P2Pm)2Py) was deposited by evaporation to a thickness of 25 nm, whereby the electron-transport layer 914 was formed. Note that in the case of Light-emitting element 5, 2,2′-(pyridine-2,6-diyl)bis(4-phenylbenzo[h]quinazoline) (abbreviation: 2,6(P-Bqn)2Py) was deposited to a thickness of 25 nm by evaporation, whereby the electron-transport layer 914 was formed.
Furthermore, lithium fluoride was deposited by evaporation to a thickness of 1 nm over the electron-transport layer 914, whereby the electron-injection layer 915 was formed.
Lastly, aluminum was deposited by evaporation to a thickness of 200 nm over the electron-injection layer 915, whereby a second electrode 903 serving as a cathode was formed. Thus, Light-emitting elements 1 to 5 were fabricated. It is to be noted that an evaporation method using resistive heating was employed for all the evaporation steps.
Table 1 shows element structures of Light-emitting elements 1 to 5 obtained as described above.
The fabricated Light-emitting elements 1 to 5 were sealed in a glove box under a nitrogen atmosphere so as not to be exposed to the air (a sealant was applied to surround the elements, and at the time of sealing, UV treatment was performed and heat treatment was performed at 80° C. for 1 hour).
<Delayed Fluorescence Measurement of Light-Emitting Element>
Delayed fluorescence measurement was performed on Light-emitting elements 1 to 5. A picosecond fluorescence lifetime measurement system (manufactured by Hamamatsu Photonics K.K.) was used for the measurement. To measure the lifetimes of fluorescence obtained from the light-emitting layers of Light-emitting elements 1 to 5, the light-emitting elements were made to emit light by applying a square wave pulse voltage, and time-resolved measurements of light, which was attenuated from the falling of the voltage, were performed using a streak camera. The pulse voltage was applied at a frequency of 10 Hz. By integrating data obtained by repeated measurements, data with a high S/N ratio was obtained. The measurement was performed at room temperature (in an atmosphere kept at 23° C.) under the conditions of a pulse voltage of approximately 3 V, a pulse time width of 100 μsec, a negative bias voltage of −5 V, and a measurement time of 50 μsec.
The attenuation curves obtained by the measurement are shown in
In Formula (5), L and t represent normalized emission intensity and elapsed time, respectively.
As the results of the fitting of attenuation curves in
<<Operation Characteristics of Light-Emitting Elements 1 to 5>>
Operation characteristics of Light-emitting elements 1, 3, and 5 in which dopant (a light-emitting substance) was not included in the respective light-emitting layers, and Light-emitting elements 2 and 4 in which dopant (a light-emitting substance) was included in the respective light-emitting layers were measured. It is to be noted that the measurements were performed at room temperature (in an atmosphere kept at 25° C.).
Table 2 shows initial values of main characteristics of Light-emitting elements 1, 3, and 5 at a luminance of approximately 1000 cd/m2.
Note that the above results show that Light-emitting elements 1, 3, and 5 can emit light even when the driving voltage is comparatively low.
Table 3 shows initial values of main characteristics of Light-emitting elements 2 and 4 at a luminance of approximately 1000 cd/m2.
When the external quantum efficiencies of Light-emitting elements 2 and 4 containing dopant (here, 1,6mMemFLPAPrn) are compared with each other, Light-emitting element 2 in which 1,5CzP2A was used as a host material used in the light-emitting layer of the light-emitting element had a higher external quantum efficiency than that of Light-emitting element 4. This indicates that the use of the material (1,5CzP2A) having a larger oscillator strength (f) was one factor allowing easy occurrence of TTA.
In this example, a synthesis method of 1,5-bis[4-(9H-carbazol-9-yl)phenyl]-9,10-diphenylanthracene (abbreviation: 1,5CzP2PA) (Structure Formula 120), which is an organic compound, is described. The structure of 1,5CzP2PA is shown below.
<Synthesis of 1,5-bis[4-(9H-carbazol-9-yl)phenyl]-9,10-anthraquinone>
Into a 200 mL three-neck flask were put 1.6 g (4.3 mmol) of 1,5-dibromo-9,10-anthraquinone, 2.7 g (9.6 mmol) of 4-(9H-carbazol-9-yl)phenylboronic acid, and 2.6 g (19 mmol) of potassium carbonate. To this mixture, 30 mL of toluene, 10 mL of ethanol, and 10 mL of water were added. The resulting mixture was degassed by being stirred while the pressure was reduced. To the mixture, 100 mg (87 μmol) of tetrakis(triphenylphosphine)palladium(0) was added and stirring was performed at 90° C. under a nitrogen stream for 4 hours. After the stirring, the mixture was filtered, and the obtained residue was washed with water, ethanol, and ethyl acetate and then collected. Thus, 3.0 g of a crude-like yellow solid was obtained. A synthesis scheme of the above-described synthesis method is shown in (c-1).
Note that the above-described yellow solid is 1,5-bis[4-(9H-carbazol-9-yl)phenyl]-9,10-anthraquinone, an intermediate obtained at the time of synthesizing 1,5CzP2PA. The intermediate is represented by m1 in (c-1) and is a compound effective for synthesis of 1,5CzP2PA.
<Synthesis of 1,5-bis[4-(9H-carbazol-9-yl)phenyl]-9,10-diphenylanthracene-9, 10-diol>
Into a 200 mL three-neck flask was put 3.0 g (4.3 mmol) of 1,5-bis[4-(9H-carbazol-9-yl)phenyl]-9,10-anthraquinone, the atmosphere in the flask was substituted by nitrogen, and then, 45 mL of tetrahydrofuran was added to the flask. The mixture was cooled with ice, and 4.6 mL (9.55 mmol) of phenyl lithium was dropped into the mixture. After the dropping, the resulting solution was stirred at room temperature. After the stirring, the temperature was set at 0° C., 1 M dilute hydrochloric acid was added, and stirring was performed for 30 minutes. Then, water and ethyl acetate were added to separate the organic layer and the aqueous layer of this mixture, and the aqueous layer was subject to extraction with ethyl acetate twice. This extracted solution and the organic layer were together washed with a saturated aqueous solution of sodium chloride. The obtained organic layer was dried with magnesium sulfate. This mixture was separated by gravity filtration, and the filtrate was concentrated to give 3.8 g of a crude-like pale yellow solid. A synthesis scheme of the above-described synthesis method is shown in (c-2).
<Synthesis of 1,5-bis[4-(9H-carbazol-9-yl)phenyl]-9,10-diphenylanthracene (abbreviation: 1,5CzP2PA)>
Into a 200 mL three-neck flask were put 3.8 g of 1,5-bis[4-(9H-carbazol-9-yl)phenyl]-9,10-diphenylanthracene-9,10-diol, which is a crude-like solid, 1.5 g (9.1 mmol) of potassium iodide, 2.4 g (23 mmol) of sodium phosphine acid monohydrate, and 45 mL of glacial acetic acid. The mixture was stirred at 120° C. for 12 hours. After the stirring, the mixture was filtered, and the obtained solid was washed with acetic acid, ethanol, and water and then collected. The obtained residue was purified by silica gel column chromatography (developing solvent: toluene). The resulting solid was recrystallized by toluene twice, so that 1.1 g of a pale yellow solid was obtained in a yield of 31%. A synthesis scheme of the above-described synthesis method is shown in (c-3).
The following shows analysis results by nuclear magnetic resonance (1H-NMR) spectroscopy of the pale yellow solid obtained by the above-described synthesis method.
1H NMR (Cl2CDCDCl2, 300 MHz): δ=7.21-7.56 (m, 34H), 7.72 (dd, J1=8.4 Hz, J2=1.5 Hz, 2H), 8.18 (d, J1=7.5 Hz, 4H)
Next, ultraviolet-visible absorption spectra (hereinafter simply referred to as “absorption spectra”) and emission spectra of 1,5CzP2PA in a toluene solution and 1,5CzP2PA in a solid thin film were measured. The solid thin film was formed over a quartz substrate by a vacuum evaporation method. The absorption spectra were measured using an ultraviolet-visible light spectrophotometer (V-550 type manufactured by JASCO Corporation). The emission spectra were measured using a fluorescence spectrophotometer (FS920 manufactured by Hamamatsu Photonics K.K.).
As shown in
These results show that the organic compound 1,5CzP2PA can be used as a blue fluorescent material.
Furthermore, 1,5CzP2PA was subjected to mass spectrometric (MS) analysis by liquid chromatography mass spectrometry (LC/MS). The measurement results are shown in
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) analysis was carried out with Xevo G2 Tof MS (manufactured by Waters Corporation).
For the LC separation, ACQUITY UPLC BEH C8 (2.1×100 mm, 1.7 μm) was used as a column, and a mixed solution of acetonitrile and a 0.1% formic acid aqueous solution was used for a mobile phase.
In the MS analysis, ionization was carried out by an electrospray ionization (ESI) method, and the analysis was performed in a positive mode. A component that underwent the ionization 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. A mass range for the measurement was m/z=100-1120.
The result in
The product ion detected at around m/z=569 is presumed to be a cation in the state where one carbazolyl group and one phenyl group are dissociated from 1,5CzP2PA, which means that 1,5CzP2PA contains a carbazolyl group and a phenyl group.
The product ion detected at around m/z=647 is presumed to be a cation in the state where one carbazolyl group is dissociated from 1,5CzP2PA, which means that 1,5CzP2PA contains a carbazolyl group.
The product ion detected at around m/z=735 is presumed to be a cation in the state where one phenyl group is dissociated from 1,5CzP2PA, which means that 1,5CzP2PA contains a phenyl group.
In this synthesis example, a synthesis method of 1,5-bis[4-(9H-carbazol-9-yl)phenyl]anthracene (abbreviation: 1,5CzP2A) (Structure Formula 100), which is an organic compound, is described. Note that the structure of 1,5CzP2A is shown below.
A mixture of 1.2 g (3.6 mmol) of 1,5-dibromoanthracene, 2.3 g (7.9 mmol) of 4-(9H-carbazol-9-yl)phenylboronic acid, 2.2 g (16 mmol) of potassium carbonate, 30 mL of toluene, 10 mL of ethanol, 8 mL of water, and 83 mg (71 μmol) of tetrakis(triphenylphosphine)palladium(0) was stirred under a nitrogen stream at 90° C. for 14 hours.
After the stirring, the mixture was filtered and the obtained solid was washed with water and ethanol and then collected. This solid was purified by silica gel column chromatography (developing solvent: toluene) to give a solid. The obtained solid was recrystallized, so that 2.0 g of a pale yellow solid was obtained in a yield of 86%.
By a train sublimation method, 2.0 g of the obtained solid was purified under a pressure of 2.7 Pa in an argon stream at 343° C. After the purification, 1.8 g of a pale yellow solid was obtained at a collection rate of 90%. A synthesis scheme of the above-described synthesis method is shown in (a).
The following shows analysis results by nuclear magnetic resonance (1H-NMR) spectroscopy of the pale yellow solid obtained by the above-described synthesis method. The 1H-NMR charts are shown in
1H-NMR (CDCl3, 300 MHz): δ=7.36 (t, J1=7.8 Hz, 4H), 7.51 (t, J1=8.4 Hz, 4H), 7.57 (s, 2H), 7.58 (dd, J1=6.9 Hz, J2=11.7 Hz, 2H), 7.65 (d, J1=7.8 Hz, 4H), 7.80 (d, J1=8.4 Hz, 4H), 7.88 (d, J1=8.7 Hz, 4H), 8.07 (dd, J1=2.4 Hz, J2=6.6 Hz, 2H), 8.22 (d, J1=7.5 Hz, 4H), 8.72 (s=2H).
Next, ultraviolet-visible absorption spectra (hereinafter simply referred to as “absorption spectra”) and emission spectra of 1,5CzP2A in a toluene solution and 1,5CzP2A in a solid thin film were measured. The toluene solution and the solid thin film were each measured in a manner similar to that in Example 2.
These results show that the organic compound 1,5CzP2A can be used as a blue fluorescent material.
Next, LC/MS analysis was performed. The measurement results are shown in
In the LC/MS analysis, liquid chromatography (LC) separation was carried out with ACQUITY UPLC (registered trademark) (manufactured by Waters Corporation) and mass spectrometric (MS) analysis was carried out with Xevo G2 Tof MS (manufactured by Waters Corporation).
For the LC separation, ACQUITY UPLC BEH C8 (2.1×100 mm, 1.7 m) was used as a column, and a mixed solution of acetonitrile and a 0.1% formic acid aqueous solution was used for a mobile phase.
In the MS analysis, ionization was carried out by an electrospray ionization (ESI) method, and the analysis was performed in a positive mode. A component that underwent the ionization 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. A mass range for the measurement was m/z=100-1200.
The result shows that a precursor ion of 1,5CzP2A was detected at around m/z=661, and product ions of 1,5CzP2A were detected at around m/z=495 and around m/z=707. This result is characteristically derived from 1,5CzP2A and thus can be regarded as important data in identification of 1,5CzP2A contained in the mixture.
Note that the product ion around m/z=495 is presumed to be a hydrogen ion adduct of a radical expressed as C38H25N.+ in the state where one carbazole is dissociated, and the product ion around m/z=707 is presumed to be acetonitrile and a hydrogen ion adduct. These indicate that a terminal of 1,5CzP2A has a carbazole skeleton and that acetonitrile is easily added. Note that acetonitrile was used for sample adjustment at the time of the analysis and for the mobile phase. Note that there is a possibility that the above m/z values±1 are detected as protonation or deprotonation products of the product ions.
In this synthesis example, a synthesis method of 1,8-bis[4-(9H-carbazol-9-yl)phenyl]anthracene (abbreviation: 1,8CzP2A) (Structure Formula 110), which is an organic compound, is described. Note that the structure of 1,8CzP2A is shown below.
In a 200 mL three-neck flask, a mixture of 1.2 g (3.7 mmol) of 1,8-dibromoanthracene, 2.3 g (8.1 mmol) of 4-(9H-carbazol-9-yl)phenylboronic acid, 2.2 g (16 mmol) of potassium carbonate, 30 mL of toluene, 10 mL of ethanol, 8 mL of water, and 85 mg (74 μmol) of tetrakis(triphenylphosphine)palladium(0) was stirred under a nitrogen stream at 90° C. for 14 hours.
After the stirring, the mixture was filtered and the obtained solid was washed with water and ethanol and then collected. This solid was purified by silica gel column chromatography (developing solvent: toluene). The purified solid was recrystallized by toluene, so that 2.3 g of a pale yellow solid was obtained in a yield of 93%. By a train sublimation method, 2.2 g of the obtained solid was purified under a pressure of 2.9 Pa in an argon stream at 295° C. After the purification, 1.9 g of a pale yellow solid was obtained at a collection rate of 83%. A synthesis scheme of the above-described synthesis method is shown in (b).
The following shows analysis results by nuclear magnetic resonance (1H-NMR) spectroscopy of the pale yellow solid obtained by the above-described synthesis method. 1H-NMR charts are shown in
1H NMR (CDCl3, 300 MHz): δ=6.88 (t, J1=7.2 Hz, 4H), 7.08 (t, J1=7.8 Hz, 4H), 7.31 (d, J1=8.1 Hz, 4H), 7.55 (dd, J1=1.5 Hz, J2=6.9 Hz, 2H), 7.60-7.68 (m, 6H), 7.80 (d, J1=8.1 Hz, 4H), 8.03 (d, J1=7.8 Hz, 4H), 8.14 (d, J1=7.8 Hz, 2H), 8.66 (s, 1H), 8.95 (s, 1H).
Next, ultraviolet-visible absorption spectra (hereinafter simply referred to as “absorption spectra”) and emission spectra of 1,8CzP2A in a toluene solution and 1,8CzP2A in a solid thin film were measured. The solution and the solid thin film were each measured in a manner similar to that in Example 2.
The result in
These results show that the organic compound 1,8CzP2A can be used as a blue fluorescent material.
Next, LC/MS analysis was performed. The measurement method was similar to that used in Example 2. The measurement result is shown in
The result shows that precursor ions of 1,8CzP2A were detected at around m/z=661, and product ions of 1,8CzP2A were detected at around m/z=243, nm/z=329, and m/z=495. This result is characteristically derived from 1,8CzP2A and thus can be regarded as important data in identification of 1,8CzP2A contained in a mixture.
Note that the product ion around m/z=243 is presumed to be a proton adduct of a radical of phenylcarbazole expressed as C18H13N.+; the product ion around m/z=329 is presumed to be a hydrogen ion adduct of a biradical expressed as C26H172.+ in the state where two carbazoles are dissociated; and the product ion around m/z=495 is presumed to be a hydrogen ion adduct of a radical expressed as C38H25N.+ in the state where one carbazole is dissociated. These indicate that a terminal of 1,8CzP2A includes two carbazole skeletons and a phenylcarbazole skeleton. Note that there is a possibility that the above m/z values±1 are detected as protonation or deprotonation products of the product ions.
In this example, a light-emitting element was fabricated and characteristics thereof were shown. In this example, Light-emitting element 6 was used. Light-emitting element 6 was obtained such that the material of the light-emitting layer of Light-emitting element 5 described in Example 1 was changed to 1,5CzP2PA and 9,10mMemFLPA2A that was a dopant (a light-emitting substance). Note that the fabrication of Light-emitting element 6 is described with reference to
<<Fabrication of Light-Emitting Element 6>>
Light-emitting element 6 was fabricated in a manner similar to the manner in which Light-emitting element 5 described in Example 1 was fabricated. In the case of Light-emitting element 6, 1,5CzP2PA and 9,10mMemFLPA2A that was a dopant (a 5 light-emitting substance) were deposited by co-evaporation so that the mass ratio of 1,5CzP2PA and 9,10mMemFLPA2A was 1:0.05, whereby the light-emitting layer 913 was formed to a thickness of 25 nm.
Table 4 shows an element structure of Light-emitting element 6 obtained as described above.
<Delayed Fluorescence Measurement of Light-Emitting Element>
Delayed fluorescence measurement was performed on Light-emitting element 6. The measurement was performed by a method similar to that in Example 1. The measurement result is shown in
As a result of the measurement, a delayed fluorescence component obtained from Light-emitting element 6 was calculated to be approximately 10%. In other words, 5% or more of the delayed fluorescence component was observed. It can be said that TTA occurs efficiently in 1,5CzP2PA of one embodiment of the present invention. This indicates that a large oscillator strength (f) of 1,5CzP2PA is one factor allowing efficient TTA.
<<Operation Characteristics of Light-Emitting Element 6>>
Table 5 below shows initial values of main characteristics of Light-emitting element 6 at a luminance of about 1000 cd/m2.
Table 5 shows that Light-emitting element 6 in which 1,5CzP2PA of one embodiment of the present invention is used as a host is a highly efficient light-emitting element that is driven at low voltage.
This application is based on Japanese Patent Application Serial No. 2016-142447 filed with Japan Patent Office on Jul. 20, 2016, the entire contents of which are hereby incorporated by reference.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2016-142447 | Jul 2016 | JP | national |
This application is a continuation of copending U.S. application Ser. No. 15/652,799, filed on Jul. 18, 2017 which is incorporated herein by reference.
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| Number | Date | Country | |
|---|---|---|---|
| 20190036036 A1 | Jan 2019 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 15652799 | Jul 2017 | US |
| Child | 16151659 | US |
