JP2008247810A - Polycyclic heterocyclic compound, hole transport material comprising the compound, hole light-emitting material, field effect transistor and organic EL device using the compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new polycyclic heterocyclic compound, to provide a hole transport material and a hole light-emitting material composed of the compound and to provide a field-effect transistor and an organic EL device using the compound. <P>SOLUTION: The polycyclic heterocyclic compound is represented by the general formula (1) (wherein, Z is carbon or nitrogen; R<SP>1</SP>to R<SP>4</SP>represents each hydrogen, an alkyl group or an alkoxy group; and A is a quinoline ring or the like). The hole transport material and the hole light-emitting material are composed of the compound. The field-effect transistor and the organic EL device are obtained by using the compound. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a polycyclic heterocyclic compound, a hole transport material comprising the compound, a hole light emitting material, a field effect transistor and an organic EL device using the compound.

  In recent years, the information society has drastically developed, and based on this, functions and miniaturization of mobile devices such as mobile phones, portable audio systems, and digital cameras are progressing. It is no exaggeration to say that the advancement of semiconductor technology is creating new products due to the development of the semiconductor field.

Organic semiconductor devices have been studied as a major field of semiconductor technology, and include organic EL devices that have reached a practical level in recent years. Furthermore, research on organic transistors as organic semiconductor devices along with organic EL has been actively conducted. The organic field effect transistor (OFET) was first confirmed in the world in 1986 by Hizuka et al. The device created by Hizuka et al. Is a film in which polythiophene is formed on a silicon wafer by electrolytic polymerization, and gold is formed as a drain / source electrode. The FET mobility is about 10 ⁻⁵ (cm ² / Vsec). And succeeded in obtaining an On / Off ratio of about 10 ³ (Non-patent Document 1). Although the characteristics of FETs using Si were not at all reached, they had features such as flexibility, weight reduction, and simplification of the production process and cost reduction by application of coating technology.

In material development, materials with high mobility are required for both p-type (hole transportability) and n-type (electron transportability). To date, for p-type, 10 ^-2 to 10 ⁰ (pentacene or sesquithiophene). (cm / Vsec) The latter half of mobility is reported (Non-Patent Documents 2 to 3). In n-type, PICBI, fluorinated pentacene, fullerene, etc. report mobility of about 10 ⁻² to 10 ⁻¹ (cm / Vsec). (Non-Patent Documents 4 to 6). What can be said in common to these is that the material has excellent flatness and high crystallinity. There are many π electrons as a molecular design guideline for high mobility materials, and there is a tendency to introduce more planar molecules. However, such high-mobility materials have very long π conjugation, so that many of the materials with poor light-emitting properties cannot be extracted as visible light or aggregate, and high-mobility materials have high fluorescence. There are few reports on materials at present.

  Polythiophene, polyfluorene, oligothiophene and thiophene-polyacene oligomers have been reported as organic semiconductors having light-emitting properties. Especially in polymer semiconductor materials, there are many applications in both organic FETs and organic ELs, which are highly useful. It is difficult to achieve high purity compared to low molecular weight materials, and structural defects are also generated at the synthesis stage. Therefore, the problem is that the mobility in OFETs is low, and it is said that it is difficult to increase the efficiency in organic EL as well. .

Hiroshi Hitsuka Chemical Vol. 56 No. 10 (2001) A. Dodabalapur, L .; Torsh and H.M. E. Katz, Science 268, 270, 1995 J. et al. H. Schoon, C.I. Kloc and B.M. Batlog, Org. Electron 1,57,2000 C. Rost, D.C. J. et al. Gundlach, S.M. Karg and E.K. Riess, J. et al. Appl. Phys. 95, 5782, 2004 Y. Sakamoto, T .; Suzuki, F.A. Sato and S. Tokyo, J. et al. Am. Chem. Soc. 126, 8138, 2004 R. C. Haddon, A .; S. Perel and R.M. M.M. Fleming, Appl. Phys. Lett. 67, 121, 1995

  An object of the present invention is to provide a novel bithiophene compound or polycyclic heterocyclic compound containing a bithiazole compound, a hole transport material comprising the same, a hole light emitting material, a field effect transistor and an organic EL device using the same. It is in.

The first of the present invention is the following general formula (1)
(In the formula, Z represents a carbon element or a nitrogen element, and R ^{1 to} R ⁴ represent hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, and a linear or branched alkoxy group having 1 to 6 carbon atoms. R ¹ and R ⁴ are not present when Z is a nitrogen element, and A is represented by the following formula:
Wherein R ^{10 to} R ¹⁸ and R ^{20 to} R ⁴⁰ are hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, and 1 carbon atom. A group selected from the group consisting of a linear or branched alkoxy group of ˜6 and a linear or branched alkylamino group of 1 to 6 carbon atoms)
It is related with the polycyclic heterocyclic compound characterized by these.
The second of the present invention relates to a hole transport material comprising the polycyclic heterocyclic compound according to claim 1.
A third aspect of the present invention relates to a hole light-emitting material comprising the polycyclic heterocyclic compound according to claim 1.
4th of this invention is related with the field effect transistor using the polycyclic heterocyclic compound of Claim 1.
5th of this invention is related with the organic EL element using the polycyclic heterocyclic compound of Claim 1.

When the compound represented by the general formula (1) is shown more specifically, the following general formulas (2) to (11) are obtained.
(Wherein R ^{1 to} R ⁴ are selected from the group consisting of hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, and a linear or branched alkoxy group having 1 to 6 carbon atoms, R ^{10 to} R ¹⁸ and R ^{20 to} R ⁴⁰ are hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms, and a straight chain having 1 to 6 carbon atoms. A group selected from the group consisting of chain or branched alkylamino groups).
Those of the general formulas (2) to (6) can be referred to as bithiophene compounds, and those of the general formulas (7) to (11) can be referred to as bithiazole compounds.

The bithiophene compound and the bithiazole compound of the present invention can be produced by the following method. In the following formulae, R ^{1 to} R ⁴ are selected from the group consisting of hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, and a linear or branched alkoxy group having 1 to 6 carbon atoms. R ^{10 to} R ¹⁸ and R ^{20 to} R ⁴⁰ are hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms. These are groups selected from the group consisting of linear or branched alkylamino groups.
(I) Production of bithiophene compound of general formula (2)
(II) Production of bithiophene compound of general formula (3)
(III) Production of bithiophene compound of general formula (4)
(IV) Production of bithiophene compound of general formula (5)
(V) Production of bithiophene compound of general formula (6)
(VI) Production of a bithiazole compound of the general formula (7)
(VII) Production of a bithiazole compound of the general formula (8)
(VIII) Production of a bithiazole compound of the general formula (9)
(IX) Production of a bithiazole compound of the general formula (10)
(X) Production of a bithiazole compound of the general formula (11)
(note)
In the above (VI) to (X), when R ² and R ³ are the same, it is a raw material
Only if R ² and R ³ are not identical,
Will be used together.

As the linear or branched alkyl group moiety having 1 to 6 carbon atoms that forms an alkyl group, an alkoxy group, or an alkylamino group in R ^{1 to} R ⁴ , R ^{10 to} R ^18, and R ^{20 to} R ⁴⁰ in the present invention, Methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-heptyl, sec-heptyl, iso-heptyl, n-hexyl, sec-hexyl, iso-hexyl, etc. Can be mentioned.

  Specific examples of the compound of the present invention are shown below.

Examples of compounds of general formula (2)

Examples of compounds of general formula (3)

Examples of compounds of general formula (4)

Examples of compounds of general formula (5)

Examples of compounds of general formula (6)

Examples of compounds of general formula (7)

Examples of compounds of general formula (8)

Examples of compounds of general formula (9)

Examples of compounds of general formula (10)

Examples of compounds of general formula (11)

The polycyclic heterocyclic compound containing the bithiophene compound or the bithiazole compound of the present invention has high hole transport performance. Therefore, it can be used as a hole transport material. Further, the bithiophene compound and the bithiazole compound of the present invention can be used as a hole light-emitting material since light emission from the compound is observed.
Therefore, it can be used in a field effect transistor or an organic EL element to make use of these characteristics.

  When the bithiophene compound and the bithiazole compound of the present invention are used for a field effect transistor, a silicon wafer with a thermal oxide film is used as a substrate, and a film is formed thereon by vacuum deposition or spin coating.

  The bithiophene compound and the bithiazole compound of the present invention are used in an active layer when used in a field effect transistor.

  Next, the field effect transistor of the present invention will be described. In the field effect transistor of the present invention, a silicon oxide film insulating layer is stacked between a substrate and a source / drain electrode, and the bithiophene compound and the bithiazole compound of the present invention are stacked by a vacuum deposition method or a spin coating method. This field effect transistor is referred to as a top contact type. The top contact type has the advantage that the manufacturing process is simpler than the bottom top type and has the advantage that the width of the insulating layer and electrode that can be used is widened. There is a risk of receiving. As the material of the source / drain electrodes, gold, gold-titanium alloy, gold-magnesium alloy or the like can be used, but gold is preferably used. The silicon wafer substrate is sharpened with a file to expose the heavily doped silicon to form a gate electrode.

  As a substrate for the field effect transistor of the present invention, a glass substrate, a plastic substrate, or the like can be used. As long as the gate electrode has a small sheet resistance compared to the on-resistance of the transistor, it is not necessary to pay particular attention to the material. The source / drain electrodes need not be limited to metals and organic conductive films as long as they can make good contact with the bithiophene compound and the bithiazole compound of the present invention.

  When the bithiophene compound and the bithiazole compound of the present invention are used in an organic EL device, they can be used in combination with an appropriate electron transport material or light emitting material.

Next, the organic EL element of the present invention will be described. The organic EL device of the present invention is a device in which a single layer or a multilayer organic compound is laminated between an anode and a cathode, and at least one layer of the organic compound layer contains the bithiophene compound and the bithiazole compound of the present invention. When the organic EL element is a single layer, a light emitting layer is provided between the anode and the cathode. The light-emitting layer contains the light-emitting material, and in addition to that, the compound of the present invention or the existing hole transport material or electron transport material is used for transporting holes injected from the anode or electrons injected from the cathode to the light-emitting material. It may contain. Examples of the configuration of the multilayer organic EL element include, for example, an anode (ITO) / hole transport layer / light emitting layer / electron transport layer / cathode, ITO / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode,
ITO / hole transport layer / light emitting layer / hole block layer / electron transport layer / cathode, ITO / hole transport layer / light emitting layer / hole block layer / electron transport layer / electron injection layer / cathode, ITO / hole injection layer / hole transport Examples of such layers include a layer / light-emitting layer / hole block layer / electron transport layer / electron injection layer / cathode multilayered structure. Moreover, you may have a sealing layer on a cathode as needed.

  Each of the hole transport layer, the electron transport layer, and the light emitting layer may have a single layer structure or a multilayer structure. In addition, the hole transport layer and the electron transport layer should be provided separately with a layer responsible for the injection function (hole injection layer and electron injection layer) and a layer responsible for the transport function (hole transport layer and electron transport layer). You can also.

  The organic EL element of the present invention is not limited to the above configuration example, and can have various configurations. If necessary, a layer in which a hole transport layer component and a light emitting layer component or an electron transport layer component and a light emitting layer component are mixed may be provided.

  Hereinafter, the constituent elements of the organic EL device of the present invention will be described by taking as an example the device configuration composed of anode / hole transport layer / light emitting layer / electron transport layer / cathode. The organic EL element of the present invention is preferably supported on a substrate.

  There is no restriction | limiting in particular about the raw material of a board | substrate, What is necessary is just what is conventionally used for the conventional organic EL element, For example, what consists of glass, quartz glass, a transparent plastic etc. can be used.

As an anode of the organic EL device of the present invention, it is preferable to use a single metal having a high work function (4 eV or more), an alloy of metals having a high work function (4 eV or more), a conductive substance, or a mixture thereof as an electrode material. . Specific examples of such electrode materials include metals such as gold, silver, and copper, conductive transparent materials such as ITO (indium-tin oxide), tin oxide (SnO ₂ ), and zinc oxide (ZnO), polypyrrole, and polythiophene. Examples thereof include conductive polymer materials such as For the anode, these electrode materials can be formed by a method such as vapor deposition, sputtering, or coating. The sheet electrical resistance of the anode is preferably several hundred Ω / cm ² or less. The thickness of the anode depends on the material, but is generally about 5 to 1,000 nm, preferably 10 to 500 nm.

As the cathode, an electrode material is preferably a single metal having a small work function (4 eV or less), an alloy of metals having a small work function (4 eV or less), a conductive substance, or a mixture thereof. Specific examples of such electrode materials include lithium, lithium-indium alloy, sodium, sodium-potassium alloy, magnesium, magnesium-silver alloy, magnesium-indium alloy, aluminum, aluminum-lithium alloy, and aluminum-magnesium alloy. Can be mentioned. The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet electrical resistance of the cathode is preferably several hundred Ω / cm ² or less. The thickness of the cathode depends on the material, but is generally about 5 to 1,000 nm, preferably 10 to 500 nm. In order to efficiently extract light emitted from the organic EL device of the present invention, at least one of the anode and the cathode is preferably transparent or translucent.

The electron transport layer of the organic EL element of the present invention is made of an electron transfer material and has a function of transmitting electrons injected from the cathode to the light emitting layer. When an electron transfer substance is disposed between two electrodes to which an electric field is applied and electrons are injected from the cathode, an electron transfer substance having an electron mobility of at least 10 ⁻⁶ cm ² / V · sec or more is preferable. The electron transfer material used for the electron transport layer used in the organic EL device of the present invention is not particularly limited as long as it has the above-mentioned preferable performance. Any one of materials conventionally used as electron charge injection materials in photoconductive materials and known materials used for electron transport layers of organic EL elements can be selected and used.

Examples of the electron transfer material include tris (8-hydroxyquinolinolato) aluminum complex (Alq ₃ ), bis (2-methyl-8-hydroxyquinolinolato) (p-phenylphenolato) aluminum complex (BAlq). Quinoline complexes such as 1-N-phenyl-2- (p-biphenyl) -5- (p-tert-butylphenyl) -1,3,5-triazine (TAZ), 1,4 -Phenanthroline derivatives such as di (1,10-phenanthroline-2-yl) benzene (DPB), alkali metal halides such as lithium fluoride, and the like. The electron transport layer may be composed of one or more of these other electron transfer materials, or may be a stack of electron transport layers made of a compound different from the electron transfer material. .
Examples of the electron injecting material include lithium fluoride and 8-hydroxyquinolinolatolithium complex (Liq) represented by the following chemical formula, and lithium of a phenanthroline derivative according to Japanese Patent Application No. 2006-292032 of the present applicant. It is also possible to use a complex (LiPB) or a phenoxypyridine lithium complex (LiPP) described in Japanese Patent Application No. 2007-29695.
Examples of the electron transport material include Alq ₃ , TAZ, and DPB represented by the following chemical formula.

  For the light emitting layer of the organic EL device of the present invention, the bithiophene compound and the bithiazole compound of the present invention can be used. Moreover, there is no restriction | limiting in particular also about the conventionally well-known material, Arbitrary things can be selected and used.

Examples of the light-emitting material include perylene derivatives, naphthacene derivatives, quinacridone derivatives, coumarin derivatives (eg, coumarin 1, coumarin 540, coumarin 545, etc.), pyran derivatives (eg, DCM-1, DCM-2, DCJTB, etc.), organometallic complexes, such as Fluorescent materials such as tris (8-hydroxyquinolinolato) aluminum complex (Alq ₃ ), tris (4-methyl-8-hydroxyquinolinolato) aluminum complex (Almq ₃ ) and [2- (4,6-difluorophenyl ) Pyridyl-N, C2 ′] iridium (III) picolylate (FIrpic), tris {1- [4- (trifluoromethyl) phenyl] -1H-pyrazolate-N, C2 ′} iridium (III) (Irtfmpppz ₃ ), Bis [2- (4 ′, 6′-difluorophenyl) pyridy DOO -N, C2 '] iridium (III) tetrakis (1-pyrazolyl) borate (FIr6), tris (2-phenylpyridinato) iridium (III) (Irppy ₃₎ and the like phosphorescent material such as .

  The light-emitting layer can also be formed of a host material and a guest material (dopant) [Appl. Phys. Lett. 65 3610 (1989)]. In particular, when a phosphorescent material is used for the light emitting layer, it is necessary to use a host material. As the host material used at this time, 4,4′-di (N-carbazolyl) -1,1′-biphenyl (CBP) ), 1,4-di (N-carbazolyl) benzene-2,2′-di [4 ″-(N-carbazolyl) phenyl] -1,1′-biphenyl (4CzPBP) and the like.

The guest material is preferably 0.01 to 40% by weight, more preferably 0.1 to 20% by weight with respect to the host material. Examples of guest materials include conventionally known FIrpic, Irppy ₃ , FIr _{6 and the} like shown below.

  As the material for the hole transport layer of the organic EL device of the present invention, the bithiophene compound and the bithiazole compound of the present invention are preferable. This can be used alone, but may be used in combination with other hole transport materials.

  In the organic EL device of the present invention, a hole injection layer composed of an organic conductor may be further provided between the anode and the organic layer for the purpose of further improving the hole injection property. Examples of the conductor used here include phthalocyanine derivatives such as copper phthalocyanine, polyphenylenediamine derivatives, polythiophene derivatives, and PEDOT-PSS (polyethylenedioxythiophene-polystyrenesulfonic acid).

  The formation method of the hole transport layer and the light emitting layer containing the compound of the present invention is not particularly limited. For example, a dry film forming method (for example, vacuum vapor deposition method, ionization vapor deposition method, etc.) or a wet film forming method [solvent coating method (for example, spin coating method, cast method, ink jet method, etc.)] can be used. The bithiophene compound and the bithiazole compound of the present invention are preferably dry film forming methods (for example, vacuum deposition method, ionization deposition method, etc.). The film formation of the electron transport layer is limited to a dry film formation method (for example, a vacuum vapor deposition method, an ionization vapor deposition method, etc.) because the lower layer may be eluted when the wet film formation method is used. For the production of the element, the above film forming method may be used in combination.

When forming each layer such as a hole transport layer, a light emitting layer, and an electron transport layer by a vacuum deposition method, the vacuum deposition conditions are not particularly limited. Usually, a boat temperature (deposition source temperature) of about 50 to 500 ° C. under a vacuum of about 10 ⁻⁵ Torr or less, a substrate temperature of about −50 to 300 ° C., and 0.01 to 50 nm / sec. Vapor deposition is preferred. When forming each layer of a positive hole transport layer, a light emitting layer, and an electron carrying layer using a some compound, it is preferable to co-evaporate the boat which put the compound, respectively controlling temperature.

  When forming the hole transport layer and the light emitting layer by a solvent coating method, the components constituting each layer are dissolved or dispersed in a solvent to obtain a coating solution. Solvents include hydrocarbon solvents (eg, heptane, toluene, xylene, cyclohexane, etc.), ketone solvents (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), halogen solvents (eg, dichloromethane, chloroform, chlorobenzene, dichlorobenzene, etc.) Ester solvents (eg, ethyl acetate, butyl acetate, etc.), alcohol solvents (eg, methanol, ethanol, butanol, methyl cellosolve, ethyl cellosolve, etc.), ether solvents (eg, dibutyl ether, tetrahydrofuran, 1,4-dioxane, 1 , 2-dimethoxyethane, etc.), aprotic solvents (eg, N, N′-dimethylacetamide, dimethyl sulfoxide, etc.), water and the like. The solvent may be used alone, or a plurality of solvents may be used in combination.

  The thickness of each layer such as the hole transport layer, the light emitting layer, and the electron transport layer is not particularly limited, but is usually 5 to 5,000 nm.

  The organic EL device of the present invention can be protected by providing a protective layer (sealing layer) for the purpose of blocking the contact of oxygen, moisture, etc., or encapsulating the device in an inert material. Examples of the inert substance include paraffin, silicon oil, and fluorocarbon. Examples of the material used for the protective layer include fluororesin, epoxy resin, silicone resin, polyester, polycarbonate, and photocurable resin.

  The organic EL device of the present invention can be usually used as a direct-current drive device. When a DC voltage is applied, light emission is usually observed when about 1.5 to 20 V is applied with the positive polarity of the anode and the negative polarity of the cathode. The organic EL element of the present invention can also be used as an AC drive element. When an AC voltage is applied, light is emitted when the anode is in a positive state and the cathode is in a negative state. The organic EL element of the present invention includes, for example, a flat light emitter such as an electrophotographic photosensitive member and a flat panel display, a copying machine, a printer, a backlight of a liquid crystal display, a light source such as an instrument, various light emitting elements, various display devices, various signs, It can be used for various sensors and various accessories.

When an organic field effect transistor was prepared using the bithiophene compound and the bithiazole compound synthesized this time, both showed p-type characteristics and no n-type characteristics. From this, the compound of this invention shows the usefulness as a hole transport material. Particularly, a structure in which a condensed polycycle such as pyrene is introduced into bithiophene exhibits good characteristics, and has high FET characteristics with an On / Off ratio:> 10 ⁵ , mobility:> 10 ⁻² [cm ² / Vsec]. I was able to get it. Similar results were obtained with a bithiophene compound or a bithiazole compound having a heterocyclic ring such as a quinoline ring.
Moreover, when the compound used for organic field effect transistor evaluation this time was used as an organic EL light emitting material, light emission was seen from any compound and good characteristics were exhibited. In particular, the dipyrene-substituted bithiophene compound [compound of Example 2 (2): DPylBT] exhibited high emission characteristics both in solution and in film form, and showed strong fluorescence even at a high concentration of 25 wt%.
With the material of the present invention, a thin film can be easily formed by vapor deposition, and film defects are less likely to occur. By using the material of the present invention, it becomes possible to produce an organic field transistor with high efficiency, and application in fields such as a mobile phone and a digital camera can be expected.

  Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.

Reference example 1
(1) 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -naphthalene {2- (4,4,5,5-tetramethyl-1,3,2) -Dioxabololane-2-yl) -naphthalene} [2DOBNap]
14.49 mmol of 2-bromonaphthalene [2BrNap] was dissolved in 50 ml of dehydrated tetrahydrofuran (THF), cooled to −78 ° C., and 17.39 mmol of n-butyllithium (n-BuLi) was slowly added. The mixture was added dropwise and allowed to react for 1 hour. 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2) -Dioxaborane) [DOB] 14.49 mmol was slowly added dropwise and reacted at -78 ° C for 1 hour, slowly returned to room temperature and reacted for 12 hours to obtain 2DOBNap. The reaction was carried out under a nitrogen stream.
After completion of the reaction, water was added and the mixture was extracted with chloroform, washed with brine and dried over anhydrous magnesium sulfate. Purification was performed by column chromatography (developing solvent: chloroform) and recrystallization (n-hexane) to obtain 2 g of white (2DOBNap) crystals. Identification was performed by ¹ H-NMR.
(2) Synthesis of 2,2′-di (naphthyl-2-yl) -5,5′-bithiophene [2,2′-Di (naphthyl-2-yl) -5,5′-bithiophene] [DNpBT]
2.93 mmol of 2DOBNap and 1.31 mmol of 2,2′-dibromobithiophene (2DBrBT) were dissolved in 50 ml of tetrahydrofuran (THF), and tetrakis (triphenylphosphine) palladium (0) {Pd (PPh ₃ ) ₄ } 0. 0.07 mmol and an aqueous solution of K ₂ CO ₃ (2 mmol) were added, and the mixture was stirred at 60 ° C. for 48 hours under a nitrogen stream to obtain DNpBT.
After completion of the reaction, the precipitated solid was collected by suction filtration and dried in vacuum. Purification was performed three times by the train sublimation method (high temperature part: 230 ° C., low temperature part: 100 ° C., nitrogen flow rate: 50 cc / min) to obtain 0.5 g of yellow DNpBT crystals. Identification was performed by elemental analysis.
The decomposition state of DNpBT by TGA-7 (thermogravimetric analyzer) and the thermal behavior by DSC (differential scanning calorimeter) are shown in FIGS. 1 and 2, respectively. The electrochemical characteristics are shown in Table 1.

Example 1
(1) 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -pyrene {2- (4,4,5,5-tetramethyl-1,3,2) -Dioxabololane-2-yl) -pyrene} [DOBPyl]
17.8 mmol of 2-bromopyrene (2BrPyl) was dissolved in 150 ml of dehydrated diethyl ether, cooled to −78 ° C., and 21.3 mmol of n-butyllithium (n-BuLi) was slowly added dropwise. Reaction for 2 hours, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxabololane) [DOB] 21.3 mmol was slowly added dropwise and reacted at −78 ° C. for 1 hour, slowly returned to room temperature and reacted for 12 hours to obtain DOBPyl. The reaction was carried out under a nitrogen stream.
After completion of the reaction, water was added and the mixture was extracted with chloroform, washed with brine and dried over anhydrous magnesium sulfate. Purification was performed by column chromatography (developing solvent; chloroform: n-hexane = 1: 1) and recrystallization (n-hexane) to obtain 5.6 g of white DOBPyl crystals. Identification was performed by ¹ H-NMR and elemental analysis.
(2) Synthesis of 2,2′-di (pyren-2-yl) -5,5′-bithiophene [2,2′-Di (pyrene-2-yl) -5,5′-bithiophene] [DPylBT]
DOBPyl 6.09 mmol and 2DBrBT 2.44 mmol were dissolved in 100 mL of THF, 0.12 mmol of Pd (PPh ₃ ) _{4 and an} aqueous solution of K ₂ CO ₃ (2 mmol) were added, and the mixture was stirred at 60 ° C. for 48 hours under a nitrogen stream. DPylBT was obtained.
After completion of the reaction, the precipitated solid was collected by suction filtration and dried in vacuum. Purification was performed three times by a train sublimation method (high temperature part: 380 ° C., low temperature part: 100 ° C., nitrogen flow rate: 50 cc / min) to obtain 1.26 g of yellow-orange DPylBT crystals. Identification was performed by elemental analysis.
The decomposition state of DPylBT by TGA-7 and the thermal behavior by DSC are shown in FIGS. 3 and 4, respectively. The electrochemical characteristics are shown in Table 1.
The value of ionization potential (Ip) was estimated by Riken Keiki AC-3, and the energy gap (Eg) was estimated by the absorption edge of the UV-vis absorption spectrum. The electron affinity was estimated by Ip-Eg.
Ip: ionization potential value (HOMO value) measured by electron analysis in air
Ea: electron affinity value calculated by subtracting Eg value from Ip value
(Energy affinity: LUMO value)
Eg: Energy gap value calculated from the absorption edge of the UV absorption spectrum
(Difference between HOMO value and LUMO value)

Example 2
(1) 6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -quinoline {6- [4,4,5,5-tetramethyl-1,3,2 -Dioxabololane-2-yl] -quinoline} [6DOBQ]
6-Bromoquinoline (6-BrQ) is dissolved in dehydrated diethyl ether, cooled to −30 ° C., 1.6 mol / liter of n-butyllithium (n-BuLi) is slowly added and reacted for 30 minutes. Propoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaboranene) [DOB] was slowly added at room temperature. The mixture was reacted for 12 hours to obtain 6DOBQ.
After completion of the reaction, water was poured, extracted with ethyl acetate, washed with water and brine, and dried over anhydrous magnesium sulfate.
Purification was performed by a column chromatography method [developing solvent: ethyl acetate] to obtain a light yellow solid 6DOBQ. Identification was performed by ¹ H-NMR and elemental analysis.
(2) Synthesis of 2,2′-di (quinolin-6-yl) -5,5′-bithiophene {2,2′-Di (quinolin-6-yl) -5,5′-bithiophene} [6DQBT]
Dissolve 4.70 mmol of 6DOBQ and 1.88 mmol of 2,2'-dibromo-5,5'-bithiophene {2,2'-Dibromo-5,5'-bithiophene} [DBrBT] in 100 ml of 1,4-dioxane. Then, tetrakis (triphenylphosphine) palladium (0) [Pd (PPh ₃ ) ₄ ] 0.09 mmol, K ₂ CO ₃ (2 mmol) aqueous solution was added and stirred at 80 ° C. for 24 hours under nitrogen stream.
After completion of the reaction, ethyl acetate and water were poured and the precipitated solid 6DQBT was washed, and the solid was collected by suction filtration and dried by vacuum drying.
Purification was carried out three times by a toilet insublimation method [high temperature part: 280 ° C., low temperature part: 100 ° C., nitrogen flow rate: 100 cc / min] to obtain 0.68 g of orange 6DQBT solid. Identification was performed by elemental analysis.
FIG. 5 is a graph showing a decomposition state of 6DQBT by TGA-7.
FIG. 6 is a graph showing the thermal behavior of 6DQBT by DSC.
The thermal and electrochemical properties of 6DQBT are shown in Table 2.
Tg: Glass transition temperature Tm: Melting temperature Td: Thermal decomposition temperature

Example 3
(1) Synthesis of 6-bromoquinoxaline [6BrQx]
3-Bromophenylenediamine (BrphDA) 21.39 mmol and Glyoxal [GOx] 21.39 mmol were dissolved in 100 ml of ethanol and refluxed for 4 hours under a nitrogen stream to obtain 6BrQx.
After completion of the reaction, the mixture was extracted with chloroform, washed several times with 10% dilute hydrochloric acid and water, washed with brine, and dried over anhydrous magnesium sulfate.
Purification was performed by a column chromatography method [developing solvent; chloroform: n-hexane = 10: 1] to obtain 3.5 g of a light yellow 6BrQx solid. Identification was performed by ¹ H-NMR.
(2) Synthesis of 2,2′-di (quinoxalin-6-yl) -5,5′-bithiophene [2,2′-Di (quinoxaline-6-yl) -5,5′-bithiophene] [6DQxBT]
5.4 mmol of 6BrQx and 2,2'-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -2,2'-bithiophene {2,2'-Bis ( 4,4,5,5-tetramethyl-1,3,2-dioxabololane-2-yl) -2,2'-bithiophene} [DBrBT] is dissolved in 100 ml of 1,4-dioxane, and Pd (PPh ₃ ) ₄ 0.09 mmol, K ₂ CO ₃ (2 mmol) aqueous solution was added, and the mixture was stirred at 80 ° C. for 24 hours under a nitrogen stream to obtain 6DQxBT.
After completion of the reaction, ethyl acetate and water were poured to wash the precipitated solid, and the solid was collected by suction filtration and dried by vacuum drying.
Purification was performed three times by a toilet insublimation method [high temperature part: 250 ° C., low temperature part: 100 ° C., nitrogen flow rate: 100 cc / min] to obtain 0.28 g of orange 6DQxBT solid. Identification was performed by elemental analysis.
The thermal and electrochemical properties of 6DQxBT are shown in Table 2.

Reference example 2
(1) Synthesis of 2- (naphthalen-2-yl) -4-bromothiazole [2- (Naphthalene-2-yl) -4-Bromthiazole] [BrNpTz]
Naphthalene-2-boronic acid [NpBA] 4.11 mmol and 2,5-dibromothiazole [DBrTz] 4.11 mmol in tetrahydrofuran (THF) 100 ml After dissolving, 0.2 Pm of Pd (PPh ₃ ) _{4 and an} aqueous solution of K ₂ CO ₃ (2 mol / liter) were added, and the mixture was stirred at 60 ° C. for 24 hours under a nitrogen stream to obtain BrNpTz.
After completion of the reaction, the mixture was extracted with ethyl acetate, washed with water and saturated brine, and dried over anhydrous magnesium sulfate. Purification was carried out by a column chromatography method [developing solvent: n-hexane: chloroform = 1: 1] to obtain 0.58 g of a light yellow BrNpTz solid. Identification was performed by ¹ H-NMR and a mass spectrum.
(2) Synthesis of 2,2′-di (naphthalen-2-yl) -5,5′-bithiazole [2,2′-Di (naphthalene-2-yl) -5,5′-bithiazole] [DNpBTz]
50 ml of dimethylformamide (DMF) obtained by dehydrating and deoxygenating 1.03 mmol of 2- (naphthalen-2-yl) -4-bromothiazole (BrNpTz) and 1.03 mmol of Bispinacolatodiboron [DOB2] Bis (diphenylphosphinoferrocene) dichloropalladium (0) {Bis (diphenylphosphinoferrocene) dichloroparadium (0)} and 3.09 mmol of potassium acetate were added and reacted at 80 ° C. for 24 hours under nitrogen atmosphere. DNpBTz was obtained.
After completion of the reaction, water was poured to precipitate a solid, and then the solid was suction filtered and vacuum dried. Purification was performed by a train sublimation method [high temperature part: 250 ° C., low temperature part: 100 ° C., nitrogen flow rate: 100 cc / min] to obtain 0.2 g of orange DNpBTz needle crystals. Identification was performed by ¹ H-NMR, elemental analysis, and mass spectrum.

Example 4
2,2'-di (naphthyl-2-yl) -5,5'-bithiophene (DNpBT) obtained in Reference Example 1 and 2,2'-di (pyren-2-yl) obtained in Example 1 ) -5,5′-bithiophene (DPylBT) was used to prepare organic field effect transistors (Field Effect Transistor = FET) having the following configuration.
Device _{1: n-Si / SiO 2} (300nm) / DNpBT (50nm) / Au (50nm)
Device 2: n-Si / SiO ₂ (300 nm) / DPylBT (50 nm) / Au (50 nm)
The relationship between the drain voltage and the drain current (current flowing from the source to the drain) of the device 1 is shown in FIG.
The gate voltage-drain current relationship of device 1 is shown in FIG.
The relationship of the gate voltage of device 1− (drain current) ^1/2 is shown in FIG.
The drain voltage-drain current relationship of device 2 is shown in FIG.
The gate voltage-drain current relationship of device 2 is shown in FIG.
The relationship of the gate voltage of device 2− (drain current) ^1/2 is shown in FIG.
The On / Off ratio in FIG. 8 and FIG. 11 is the ratio of the drain current value when the gate voltage is 0V and the drain current value when the gate voltage is −100V, and it should be larger. In FIG. 9 and FIG. 12, (drain current) ^1/2 is the value of the square root of the drain current value flowing from the source to the drain. When the drain voltage is fixed at −100 V and the square root of the current value flowing from the source to the drain when the gate voltage is changed is plotted, the slope of the curve corresponds to “mobility μ”, and the tangent of the curve is the X axis. The crossing point corresponds to the “threshold voltage V _T ”. The mobility μ should be fast, and the threshold voltage V _T should be low.
The curves shown at the top in FIG. 7 and FIG. 10 show changes in the drain current value when the gate voltage is fixed to −100 V and the drain voltage is changed, and the second shows the gate voltage − In the case of 75V, the lower curve is for the gate voltage of -50V. The bottom curve (substantially straight line) overlaps when the gate voltage is −25V and when it is 0V.

Example 5
Using 2,2′-di (quinolin-6-yl) -5,5′-bithiophene (6DQBT) obtained in Example 2, an organic field effect transistor having the following constitution was prepared.
Device _{^{3: n ++ Si / SiO 2}} (300nm) / 6DQBT (50nm) / Au (50nm)
Device 3 characteristics
* 1) There are NPN and PNP structures as semiconductor structures, but those using NPN are called N-channel and those using PNP are called P-channel. In this case, P-channel.
* 2) The ON / OFF ratio is the ratio of the drain current value in the ON state (gate voltage: 100V) to the drain current value in the OFF state (gate voltage: 0V).
* 3) The _{V T,} it is the threshold voltage. As the gate voltage is applied, current suddenly begins to flow between the source and drain. The voltage at this time is a threshold voltage. The lower this value, the faster the response.
FIG. 13 shows a cross-sectional view of the device. W is the depth length, and L is the distance between the source and drain.
The relationship between the drain voltage and the drain current of device 3 is shown in FIG.
The gate voltage-drain current relationship of device 3 and the gate voltage- (drain current) ^1/2 relationship of device 3 are shown in FIG.
The curve shown at the top in FIG. 14 shows the change in drain current value when the gate voltage is fixed to −100V and the drain voltage is changed. The second curve is −75V. In this case, the lower curve is obtained when the gate voltage is -50V. The bottom curve (substantially straight line) overlaps when the gate voltage is −25V and when it is 0V.

Example 6
Was obtained in Example 1 2,2'-di (pyrene-2-yl) -5,5'-bithiophene (DPylBT) a light emitting material, the Alq ₃ as a host material An organic EL device was fabricated. Device 4 is for comparison.
The device configuration is as follows.
Device 4: ITO / α-NPD (40 nm) / Alq ₃ (60 nm) / LiF (0.5 nm) / Al (100 nm) [Ref. ]
Device 5: ITO / α-NPD (40 nm) / Alq ₃ : DPylBT (5 wt%) (30 nm) / Alq ₃ (30 nm) / LiF (0.5 nm) / Al (100 nm)
Device 6: ITO / α-NPD (40 nm) / Alq ₃ : DPylBT (10 wt%) (30 nm) / Alq ₃ (30 nm) / LiF (0.5 nm) / Al (100 nm)
Device 7: ITO / α-NPD (40 nm) / Alq ₃ : DPylBT (15 wt%) (30 nm) / Alq ₃ (30 nm) / LiF (0.5 nm) / Al (100 nm)
Device 8: ITO / α-NPD (40 nm) / Alq ₃ : DPylBT (20 wt%) (30 nm) / Alq ₃ (30 nm) / LiF (0.5 nm) / Al (100 nm)
Device 9: ITO / α-NPD (40 nm) / Alq ₃ : DPylBT (25 wt%) (30 nm) / Alq ₃ (30 nm) / LiF (0.5 nm) / Al (100 nm)
Device 10: ITO / α-NPD (40 nm) / DPylBT (100 wt%) (30 nm) / Alq ₃ (30 nm) / LiF (0.5 nm) / Al (100 nm)
The voltage-current density relationship of the devices 4 to 10 is shown in FIG.
The relationship between voltage and luminance is shown in FIG.
The relationship between voltage and luminous efficiency is shown in FIG.
The relationship between voltage and current efficiency is shown in FIG.
The relationship between current density and luminance is shown in FIG.
The relationship between wavelength and standardized EL intensity is shown in FIG.
Also,
The relationship between the wavelength of device 5 and the standardized EL intensity is shown in FIG.
The relationship between the wavelength of device 6 and the standardized EL intensity is shown in FIG.
The relationship between the wavelength of device 7 and the standardized EL intensity is shown in FIG.
The relationship between the wavelength of device 8 and the standardized EL intensity is shown in FIG.
The relationship between the wavelength of the device 9 and the standardized EL intensity is shown in FIG.
The energy diagram of the organic EL elements of devices 5 to 9 is shown in FIG.
Each is shown.
The standardized absorption of the Alq ₃ film, the standardized absorption of the DPylBT film, the standardized PL strength of the Alq ₃ film, and the standardized PL strength of the DPylBT film are shown in FIG.
The PL intensity of each single vapor deposition film of the co-deposition film of Alq ₃ and DPylBT is shown in FIG.
FIG. 30 shows the standardized PL intensity of each single vapor deposition film of the co-deposition film of Alq ₃ and DPylBT.
Each is shown.
In FIG. 27, the energy diagrams of ITO from the left side, the next is the α-NPD layer, the portion surrounded by the dotted line is the Alq ₃ layer containing DPylBT 5 to 25 wt%, and the next is the Alq ₃ layer. It is.
Note that the PL intensity indicates the intensity of the PL as measured, but the standardized PL intensity depends on the PL intensity, so the PL intensity is aligned with the largest peak, and the PL maximum The position is made easier to understand.
Table 4 below shows the EL characteristics at 100 cd / m ² of devices 4 to 10, Table 5 shows the EL characteristics at 1000 cd / m ² of devices 4 to 10, and Table 6 shows the highest characteristics of devices 4 to 10. The EL characteristic at the time is shown.
The devices indicated by (100 wt%) in Table 4 and Tables 5, 11, and 12 below are 100 wt%, and therefore are not doped, and thus do not emit light. From this point of view, it is not appropriate to use the compound of the present invention alone, and it is preferable to mix the compound of the present invention with components such as Alq ₃ and BAlq. The mixing ratio may be determined in a form corresponding to the desired performance.
P. E. : Power efficiency
C. E. : Current efficiency
Q. E. : Quantum efficiency
As a result of an attempt to manufacture an EL device using Alq ₃ as a host, the optimum doping concentration was obtained when the doping concentration was DPylBT / Alq ₃ = 20 wt%, the driving voltage was 2.5 (V), and the maximum luminance was 75000 (cd / m ² ). The luminous efficiency was 9.02 (lm / w), the maximum current efficiency was 11.8 (cd / A), and the maximum external quantum efficiency was 3.6%.
In addition, as the doping concentration of DPylBT increased, carriers were more likely to enter, and a tendency for the drive voltage to decrease was observed. This is probably because DPylBT has a relatively high carrier transport property. Alternatively, Alp _{3 has} an Ip of about 5.7 (eV) and DPylBT has an Ip of 5.5 (eV), and as the doping concentration increases, it becomes easier to inject holes directly from α-NPD to DPylBT. The voltage is thought to have dropped.
The obtained EL spectrum is similar to the EL spectrum of Alq ₃ , but the half width is narrower than that of the Alq ₃ spectrum, and it is red-shifted as the doping concentration increases, and is close to the PL spectrum of DPylBT film. From this, it is considered that DPylBT emits light. The reason why the emission color of the obtained EL is shorter than the PL spectrum of the DPylBT film is considered that Alq ₃ caused the solvatochromism effect. When a fluorescent material is dissolved in a solvent and its emission spectrum is measured, the emission spectrum may differ depending on the polarity of the solvent. When a fluorescent material is excited in a state dissolved in a polar solvent, the electronic state is polarized and the exciton becomes unstable. As a result, the emission spectrum shifts to the short wavelength side, or conversely stabilizes and becomes longer. It may shift to the wavelength side. This phenomenon is called the solvatochromism effect. In general, when a red shift occurs due to aggregation, a decrease in characteristics due to excimer or exciplex formation, or a decrease in characteristics due to concentration quenching, etc. is observed. The solvent effect of the material is thought to cause the red shift.

Example 7
An organic EL device was produced using 2,2′-di (pyren-2-yl) -5,5′-bithiophene (DPylBT) obtained in Example 1 as a light emitting material and BAlq as a host material. The device configuration is as follows.
Device 11: ITO / α-NPD (40 nm) / BAlq: DPylBT (15 wt%) (30 nm) / Alq ₃ (30 nm) / LiF (0.5 nm) / Al (100 nm)
Device 12: ITO / α-NPD (40 nm) / BAlq: DPylBT (20 wt%) (30 nm) / Alq ₃ (30 nm) / LiF (0.5 nm) / Al (100 nm)
Device 13: ITO / α-NPD (40 nm) / BAlq: DPylBT (25 wt%) (30 nm) / Alq ₃ (30 nm) / LiF (0.5 nm) / Al (100 nm)
BAlq: bis (2-methyl-8-quinolinolato) (p-phenylphenolato) aluminum
The voltage-current density relationship of the devices 11 to 13 is shown in FIG.
The relationship between voltage and luminance is shown in FIG.
The relationship between voltage and luminous efficiency is shown in FIG.
The relationship between voltage and current efficiency is shown in FIG.
The relationship between current density and luminance is shown in FIG.
Each is shown.
Also,
The standardized EL intensity at 5 mA of devices 11 to 13 is shown in FIG.
The standardized EL intensity at 1 mA to 100 mA of the device 11 is shown in FIG.
The standardized EL intensity of the device 12 at 1 mA to 100 mA is shown in FIG.
FIG. 39 shows the standardized EL intensity of the device 13 at 1 mA to 100 mA.
Table 7 below shows the EL characteristics of the devices 11 to 13 at 100 cd / m ² .
In the above table, 1 cd / m ² Turn on [V] indicates a voltage when a luminance of 1 cd / m ² or more is obtained.
Table 8 below shows the EL characteristics of the devices 11 to 13 at 1000 cd / m ² .
Fig. 40 shows the photochemical characteristics of 2,2'-di (pyren-2-yl) -5,5'-bithiophene (DPylBT) as the luminescent material and BAlq as the host material, and PL intensity of the BAlq: DPylBT co-adhered film. 41 shows the standardized PL intensity in FIG.
The broken line on the left side in FIG. 40 is the measurement result of UV absorption spectrum of BAlq, the broken line on the right side is the measurement result of UV absorption spectrum of DPylBT, the solid line on the left side is the measurement result of PL spectrum of BAlq, and the solid line on the right side These are the PL spectrum measurement results of DPylBT.
One of the conditions for determining the combination of the host and guest in the light-emitting layer is that the overlap between the PL spectrum of the host and the absorption spectrum of the guest is large. When the host (BAlq) is excited, the host itself tries to emit light. However, if there is an overlap between the host PL spectrum and the guest absorption spectrum, the guest (DPylBT) absorbs the energy emitted by the host and the guest (DPylBT) absorbs the guest. Is considered to emit light.
Looking at FIG. 40, there is an overlap (400 to 550 nm) of the absorption spectrum of DPylBT (dashed line on the right side) and the PL spectrum of BAlq (solid line on the left side), so it is estimated that energy transfer from the host to the guest takes place. .
In addition, since the PL spectrum of the guest (DPylBT) (solid line on the right) is on the longer wavelength side than the PL spectrum of the host (BAlq) (solid line on the left), it is estimated that the emission from the guest is stronger. The
FIG. 41 is a comparison of PL spectra when the doping concentration of the guest (DPylBT) is changed.
When the dope concentration was varied between 5 and 25% by weight, the PL spectrum at 20% by weight was the highest, so it was estimated that high efficiency could be obtained when the dope concentration was about 20% by weight. it can.
However, in the case of an EL element, there is an influence such as a carrier balance between holes and electrons, and therefore it cannot always be said that 20% by weight is good.
FIG. 42 shows a comparison in which the peak tops of the spectra are aligned and normalized.
This indicates that the emission color changes when the doping concentration of the guest (DPylBT) is changed.
The single curve on the left is the PL spectrum of a single film of BAlq as a host. As the doping concentration of the guest (DPylBT) is increased, it shifts to the right side. This shows that the energy transfer from the host to the guest is not sufficiently performed. That is, when the guest doping concentration is low, light emission is obtained not only from the guest but also from the host, and thus such a change in spectrum is observed.
In the EL element, it is preferable that the emission color does not change even if the doping concentration is changed.
Taking the above data together, the optimum doping concentration in PL was 20 wt%, and no light emission derived from BAlq was observed from the doped film. This suggests that energy transfer is occurring efficiently.
As a result of attempts to fabricate an organic EL device using the optimum doping concentration in PL and the concentration before and after that, carriers are introduced by increasing the doping concentration, and at 100 cd / m ² emission and 1000 cd / m ² emission. The luminous efficiency of 20 wt% showed the best characteristics. However, the current efficiency is preferably 15 wt%, and from this, it is considered that the carrier balance is easily lost due to the increase in the doping concentration, but the carrier is more likely to enter.
Comparing the one using BAlq as the host (devices 11, 12, 13) and the one using Alq ₃ (devices 5 to 10), the one using BAlq used Alq ₃ for the emission starting voltage and each efficiency. You can see that it is worse than the thing. This is because the difference between the HOMO of the hole transport material α-NPD and BAlq is large, and it is difficult for the holes to enter the BAlq layer. In addition, since the electron mobility of BAlq is lower than that of Alq ₃ , the driving voltage increases as a result. It is conceivable that the characteristics have deteriorated. Therefore, it is considered that the characteristics can be improved by improving the device structure so as to reduce the difference in the HOMO level between α-NPD and BAlq.

Example 8
A 25 mm x 25 mm ITO (sheet resistance = 10 Ω / □) substrate is masked with a mending tape, left in an aqua regia atmosphere for about 10 minutes to etch the ITO, and then the ITO substrate is made of special grade acetone, substrate cleaning solution Semico Clean 56 ( The product was subjected to ultrasonic cleaning for 15 minutes each in the order of (trade name). Semi-clean 56 [Semiconductor cleaning solution manufactured by Furuuchi Chemical Co., Ltd.] was washed off with ion-exchanged water, and then ultrasonically washed with ion-exchanged water for 5 minutes, electronic industrial 2-propanol for 15 minutes, and electronic industrial methanol for 15 minutes. Then, it was washed by boiling for 5 minutes in boiling 2-propanol for electronics industry. The ITO substrate to be used immediately before use is wiped off with THF, ultrasonically cleaned with 2-propanol for electronics industry for 15 minutes, boiled and washed in 2-propanol for electronics industry for 5 minutes, and then UVO-Clener Model 42 (Jelight Company Inc. )) Was irradiated with UV-ozone for 30 minutes to clean the surface. The cleaning process immediately before use was performed in a clean bench.
The organic material deposition is performed using ULVAC's new organic glass chamber at a vacuum degree of 1.0 × 10 ⁻⁴ Pa, and the hole transport material α-NPD is performed at a deposition rate of 0.2 nm / sec. Alq ₃ or BAlq as a transport material was performed at a deposition rate of 0.2 nm / sec. The host material was selected in consideration of the overlap between the emission spectrum of the host material and the absorption spectrum of the luminescent material used.
The electrode and the electron injection layer are formed at a vacuum of 1.0 × 10 ⁻³ [Pa] or less using a new metal glass chamber vapor deposition machine manufactured by ULVAC, and LiF as the electron injection layer is 0.01 to 0.02 nm / A device was fabricated so that 0.5 nm was deposited at a rate of sec, and Al as an electrode was further deposited by 100 nm, so that the light emitting area was 5 mm × 5 mm.
The following measurement method is a measurement method applied to the whole of the present invention.
The film thickness was measured using DEKTAK ³ ST manufactured by Sloan. The measurement conditions were as follows: measurement distance = 1,000 μm, measurement speed = Low (50 seconds), data analysis ability = High, measurement range = 65 KA, stylus pressure = 1 mg.
As the measurement of the device, BM-8 manufactured by TOPCON was used for luminance measurement, Kikusui PBX40-2.5 was used for the DC power supply, and a digital multimeter (Advantest TR6846) was used for measurement of the current value.
A direct current was applied to the EL element in steps of 0.5 V at intervals of about 2 seconds, and the current density and luminance at that time were measured after about 1 second.
The EL spectrum measurement was carried out in the atmosphere using a Photo Multi-Channel Analyzer (PMA-10) manufactured by Hamamatsu Photonics and F-4010 manufactured by Hitachi. Light emission when the element is made to emit light by applying a direct current by connecting the ITO to the anode and the metal electrode to the cathode by placing the glass substrate surface of the EL element perpendicular to the light receiving part of the spectrometer The spectrum was measured. The measurement was performed for each current density by changing the current density of the light emitting surface to 1,2.5, 5, 10, 25, 50, and 100 mA / cm ² .

Production of device 14 using DNpBT obtained in Reference Example 1 as a luminescent material 2,2′-Di (naphthyl-2-yl) -5,5′-bithiophene [DNpBT] was applied as a luminescent material.
Device 14: ITO / α-NPD (40 nm) / t-BuDNA: DNpBT (3 wt%) (30 nm) / Alq ₃ (30 nm) / LiF (0.5 nm) / Al (100 nm)
The chemical structural formula of t-BuDNA is as shown below.
The solid line in FIG. 43 is the PL spectrum measurement result in the DNpBT solution state, the broken line is the UV absorption spectrum measurement result in the DNpBT solution state, and the dotted line is the PL spectrum measurement in the t-BuDNA thin film state. It is a result.
One of the conditions for determining the combination of the host and guest (DNpBT) in the light-emitting layer is that the overlap between the PL spectrum of the host and the absorption spectrum of the guest is large.
When the host (t-BuDNA) is excited, it emits itself, but when the PL spectrum of the host and the absorption spectrum of the guest overlap, the guest absorbs the energy emitted by the host and the guest emits light. It is considered.
When FIG. 43 is seen, since there exists an overlap (400-450 nm) of the absorption spectrum (dashed line) of DNpBT and PL spectrum (dotted line) of t-BuDNA, it seems that energy transfer is performed.
Moreover, since the PL spectrum (solid line) of the guest is on the longer wavelength side than the PL spectrum (dotted line) of the host, it can be estimated that the emission from the guest is stronger.
FIG. 44 shows the EL spectrum of the device 14 and the PL spectrum of the co-deposited film of t-BuDNA and DNpBT.
45 to 49 show the characteristics of the device 14 obtained in Reference Example 1. FIG.
FIG. 45 shows the EL spectrum.
FIG. 46 shows the voltage-luminance relationship.
FIG. 47 shows the voltage-current density relationship.
FIG. 48 shows the relationship between voltage and luminous efficiency.
FIG. 49 shows CIE color coordinate at 5 mA.
Table 9 below shows the EL characteristics of the device 14 at 100 cd / m ² , and Table 10 shows the EL characteristics of the device 14 at 1000 cd / m ² .
In the table below, 1 cd / m ² Turn on [V] indicates a voltage when a luminance of 1 cd / m ² or more is obtained. P. E. (Power Efficiency) is luminous efficiency, C.I. E. (Current Efficiency) is current efficiency, Q.V. E. (Quantum Efficiency) is an external quantum efficiency, CIEc. c. (CIE color coordinate) is a chromaticity coordinate.

Example 9
Using a silicon wafer with a 300 nm thermally oxidized film cut into 20 mm × 24 mm (formed by forming a SiO ₂ film on a silicon wafer by a thermal oxidation method) as a base, an organic semiconductor compound was deposited to a thickness of 50 nm, followed by As a source / drain electrode, 50 nm of Au is deposited (only in the case of the device 20, Ca 2 nm and Ag 100 nm are deposited after the organic semiconductor compound formation film), top contact type (insulating layer, organic semiconductor layer on the silicon substrate) And a device having a source and drain electrode attached thereto was fabricated.
The silicon wafer substrate is sharpened with a file to make heavy-doped silicon (the resistance value is lowered by increasing the doping amount, n ⁺⁺ is indicated in the figure), and the gate electrode is exposed to form a gate electrode, manufactured by Kanto Chemical Co., Ltd. Scrub clean using glass cleaner neutral detergent deer clean, sprinkle with pure water, wash in running water, ultrasonic clean (15 min), then ultrasonic ultrasonic clean (15 min), isopropyl alcohol ( IPA) What was subjected to ultrasonic cleaning (15 min), IPA boiling cleaning, and UV-O ₃ cleaning was used.
As a method for forming the organic film, a vacuum evaporation method was used. Organic vapor deposition was carried out using a new glass chamber for organics manufactured by ULVAC at a vacuum degree of 1.0 × 10 ⁻⁴ [Pa] and a vapor deposition rate of 0.1 [nm / sec].
Measurements are performed in a glove box (O ₂ concentration <0.1 ppm, H ₂ O concentration <0.1 ppm), and an Agilent semiconductor parameter analyzer (apparatus for examining the amount of current flowing from the source to the drain by applying a voltage to the gate and drain) It was performed using. The stacked structure of each device is shown in FIG.
FIG. 51 shows the relationship between drain voltage and drain current when a voltage of 25 V, 50 V, 75 V, and 100 V is applied to the device 15.
The relationship between the gate voltage-drain current and gate voltage- (drain current) ^1/2 of the device 15 is shown in FIG.
FIG. 53 shows the relationship between drain voltage and drain current when a voltage of 25 V, 50 V, 75 V, and 100 V is applied to the device 16.
54 shows the relationship between the gate voltage-drain current and gate voltage- (drain current) ^1/2 of the device 16.
FIG. 55 shows the relationship between drain voltage and drain current when voltages of 25 V, 50 V, 75 V, and 100 V are applied to the device 17.
The relationship between the gate voltage-drain current and gate voltage- (drain current) ^1/2 of the device 17 is shown in FIG.
FIG. 57 shows the relationship between drain voltage and drain current when a voltage of 25 V, 50 V, 75 V, and 100 V is applied to the device 18.
FIG. 58 shows the relationship between drain voltage and drain current when a voltage of 25 V, 50 V, 75 V, and 100 V is applied to the device 19.
FIG. 59 shows the relationship between drain voltage and drain current when a voltage of 25 V, 50 V, 75 V, and 100 V is applied to the device 20.
The relationship between the gate voltage-drain current and gate voltage- (drain current) ^1/2 of the device 20 is shown in FIG.
Each is shown.
51, 53, 55 and 59, the curve shown at the top shows the change in the drain current value when the gate voltage is fixed to -100V and the drain voltage is changed, and the second is the gate. When the voltage is -75V, the lower curve is when the gate voltage is -50V. The bottom curve (substantially straight line) overlaps when the gate voltage is −25V and when it is 0V.
52, 54, 56 and 60, the on / off ratio is the ratio between the drain current value in the on state (gate voltage 100V) and the drain current value in the off state (gate voltage 0V). .
V _T in FIG 52,54,56,60 is that threshold voltage, the Yuku over this if voltage to the gate, there is a time when the current starts to flow between the sudden drain. The voltage value at this time is a threshold voltage. In FIG. 52, 54, 56 and 60, μ is the mobility. These data indicate that the compound of the present invention has a hole transport property.
The configuration of each device as a P-type transistor is as follows.
Device _{^{15: n ++ Si / SiO 2}} (300nm) / DNpBT obtained in Reference Example 1 (50nm) / Au (50nm )
Device 16: n ⁺⁺ Si / SiO ₂ (300 nm) / DPylBT (50 nm) / Au (50 nm) obtained in Example 1
Device 17: n ⁺⁺ Si / SiO ₂ (300 nm) / 6DQBT obtained in Example 2 (50 nm) / Au (50 nm)
Device 18: n ⁺⁺ Si / SiO ₂ (300 nm) / 6DQxBT obtained in Example 3 (50 nm) / Au (50 nm)
Device 19: n ⁺⁺ Si / SiO ₂ (300 nm) / 6DQxBT obtained in Example 3 (50 nm) / Ca (2 nm) / Ag (100 nm)
Device _{^{20: n ++ Si / SiO 2}} (300nm) / DNpBTz obtained in Reference Example 2 (50nm) / Au (50nm )

Example 10
A 25 mm x 25 mm ITO (sheet resistance = 10 Ω / □) substrate is masked with a mending tape, left in an aqua regia atmosphere for about 10 minutes to etch the ITO, and then the ITO substrate is made of special grade acetone, substrate cleaning solution Semico Clean 56 ( The product was subjected to ultrasonic cleaning for 15 minutes each in the order of (trade name). Semi-clean 56 [Semiconductor cleaning solution manufactured by Furuuchi Chemical Co., Ltd.] was washed off with ion-exchanged water, and then ultrasonically washed with ion-exchanged water for 5 minutes, electronic industrial 2-propanol for 15 minutes, and electronic industrial methanol for 15 minutes. Then, it was washed by boiling for 5 minutes in boiling 2-propanol for electronics industry. The ITO substrate to be used immediately before use is wiped off with THF, ultrasonically cleaned with 2-propanol for electronics industry for 15 minutes, boiled and washed in 2-propanol for electronics industry for 5 minutes, and then UVO-Clener Model 42 (Jelight Company Inc. )) Was irradiated with UV-ozone for 30 minutes to clean the surface. The cleaning process immediately before use was performed in a clean bench.
The organic material deposition is performed using ULVAC's new organic glass chamber at a vacuum degree of 1.0 × 10 ⁻⁴ Pa, and the hole transport material α-NPD is performed at a deposition rate of 0.2 nm / sec. Alq ₃ or BAlq as a transport material was performed at a deposition rate of 0.2 nm / sec. The host material was selected in consideration of the overlap between the emission spectrum of the host material and the absorption spectrum of the luminescent material used. As the luminescent material, the compounds of the present invention defined in the following (Part 1) to (Part 4) were used.
The electrode and the electron injection layer are formed at a vacuum of 1.0 × 10 ⁻³ [Pa] or less using a new metal glass chamber vapor deposition machine manufactured by ULVAC, and LiF as the electron injection layer is 0.01 to 0.02 nm / A device was fabricated so that 0.5 nm was deposited at a rate of sec, and Al as an electrode was further deposited by 100 nm, so that the light emitting area was 5 mm × 5 mm.
The film thickness was measured using DEKTAK ³ ST manufactured by Sloan. The measurement conditions were as follows: measurement distance = 1,000 μm, measurement speed = Low (50 seconds), data analysis ability = High, measurement range = 65 KA, stylus pressure = 1 mg.
As the measurement of the device, BM-8 manufactured by TOPCON was used for luminance measurement, Kikusui PBX40-2.5 was used for the DC power supply, and a digital multimeter (Advantest TR6846) was used for measurement of the current value.
A direct current was applied to the EL element in steps of 0.5 V at intervals of about 2 seconds, and the current density and luminance at that time were measured after about 1 second.
The EL spectrum measurement was carried out in the atmosphere using a Photo Multi-Channel Analyzer (PMA-10) manufactured by Hamamatsu Photonics and F-4010 manufactured by Hitachi. Light emission when the element is made to emit light by applying a direct current by connecting the ITO to the anode and the metal electrode to the cathode by placing the glass substrate surface of the EL element perpendicular to the light receiving part of the spectrometer The spectrum was measured. The measurement was performed for each current density by changing the current density of the light emitting surface to 1,2.5, 5, 10, 25, 50, and 100 mA / cm ² .

(Part 1)
Production of device 21 using DPylBT obtained in Example 1 as a luminescent material 2,2′-Di (pyrene-2-yl) -5,5′-bithiophene [DPylBT] was applied as a luminescent material. Alq ₃ was used as a host, and devices were prepared at doping concentrations of 5 wt%, 10 wt%, 15 wt%, 20 wt%, and 25 wt%. 61 shows the structure of the device 21, and FIG. 62 shows the energy diagram of the device 21.
The solid line in FIG. 63 shows the PL spectrum of the DPylBT solution.
The broken line shows the UV spectrum of the DPylBT solution.
The dotted line shows the PL spectrum of the Alq ₃ thin film.
FIG. 64 shows the PL intensity of the co-deposited film of Alq ₃ and DPylBT and the PL intensity of each single-deposited film.
FIG. 65 shows the EL spectra of devices 21-R to 21-6 and the PL spectrum of DPylBT film.
FIG. 66 shows the EL spectrum of device 21-R.
FIG. 67 shows the EL spectrum of device 21-1.
FIG. 68 shows the EL spectrum of device 21-2.
FIG. 69 shows the EL spectrum of device 21-3.
FIG. 70 shows the EL spectrum of device 21-4.
FIG. 71 shows the EL spectrum of device 21-5.
FIG. 72 shows voltage-luminance characteristics of devices 21-R and 21-1 to 21-6.
FIG. 73 shows the voltage-current density relationship of devices 21-R and 21-1 to 21-6.
FIG. 74 shows the voltage-luminous efficiency relationship of devices 21-R and 21-1 to 21-6.
FIG. 75 shows CIE color coordinate at the time of 5 mA of the device 21-4.
Device 21-R: ITO / α-NPD (40 nm) / Alq ₃ (60 nm) / LiFnm) / Al (100 nm) [Ref. ]
Device 21-1: ITO / α-NPD (40 nm) / Alq ₃ : DPylBT (5 wt%) (30 nm) / Alq ₃ (30 nm) / LiF (0.5 nm) / Al (100 nm)
Device 21-2: ITO / α-NPD (40 nm) / Alq ₃ : DPylBT (10 wt%) (30 nm) / Alq ₃ (30 nm) / LiF (0.5 nm) / Al (100 nm)
Device 21-3: ITO / α-NPD (40 nm) / Alq ₃ : DPylBT (15 wt%) (30 nm) / Alq ₃ (30 nm) / LiF (0.5 nm) / Al (100 nm)
Device 21-4: ITO / α-NPD (40 nm) / Alq ₃ : DPylBT (20 wt%) (30 nm) / Alq ₃ (30 nm) / LiF (0.5 nm) / Al (100 nm)
Device 21-5: ITO / α-NPD (40 nm) / Alq ₃ : DPylBT (25 wt%) (30 nm) / Alq ₃ (30 nm) / LiF (0.5 nm) / Al (100 nm)
Device 21-6: ITO / α-NPD (40 nm) / DPylBT (30 nm) / Alq ₃ (30 nm) / LiF (0.5 nm) / Al (100 nm)
Table 11 below shows the EL characteristics of the devices 21-R to 21-6 at 100 cd / m ² , and Table 12 shows the EL characteristics of the devices 21-R to 21-6 at 1000 cd / m ² .

(Part 2)
Production of device 22 using 6DQBT obtained in Example 2 as light emitting material 2,2′-Di (quinolin-6-yl) -5,5′-bithiophene [6DQBT] was applied as the light emitting material. A device 22 was prepared using t-BuDNA as a host and a doping concentration of 3 wt%. The device structure is shown below.
Device 22: ITO / α-NPD (40 nm) / t-BuDNA: 6DQBT (3 wt%) (30 nm) / Alq ₃ (30 nm) / LiF (0.5 nm) / Al (100 nm)
FIG. 76 shows an energy diagram of the device 22 (the structure of the device 22 is the same as that of FIG. 61).
FIG. 77 shows a standardized EL spectrum of device 22 (at 5 mA) and a PL spectrum of a co-deposited film (3 wt%) of t-BuDNA and 6DQBT.
FIG. 78 shows the EL spectrum of device 22.
FIG. 79 shows the voltage-luminance relationship of the device 22.
FIG. 80 shows the voltage-current density relationship of the device 22.
FIG. 81 shows the voltage-luminous efficiency relationship of the device 22.
FIG. 82 shows CIE color coordinate of the device 22 at 5 mA.
Table 13 below shows EL characteristics of the device 22 at 100 cd / m ² , and Table 14 shows EL characteristics of the device 22 at 1000 cd / m ² .

(Part 3)
Preparation of device 23 using 6DQxBT obtained in Example 3 as light emitting material 2,2'-Di (quinoxaline-6-yl) -5,5'-bithiophene [6DQxBT] was applied as the light emitting material. BAlq was used as a host, and a device 23 was prepared at a doping concentration of 3 wt%. The device structure is shown below.
Device 23: ITO / α-NPD (40 nm) / BAlq: 6DQxBT (3 wt%) (30 nm) / BAlq (30 nm) / LiF (0.5 nm) / Al (100 nm)
Table 15 below shows the EL characteristics of the device 23 at 100 cd / m ² , and Table 16 shows the EL characteristics of the device 23 at 1000 cd / m ² .
FIG. 83 shows the energy diagram of device 23 (structure identical to FIG. 61).
FIG. 84 shows the standardized PL intensity and standardized absorption spectrum of 6DQxBT obtained in Example 3, and the standardized PL intensity of the BAlq thin film.
FIG. 85 shows the standardized EL intensity (at 5 mA) of the device 23 and the standardized PL intensity of the 6DQxBT and BAlq co-deposited film (3 wt%).
FIG. 86 shows the EL spectrum of device 23.
FIG. 87 shows the voltage-luminance relationship of the device 23.
FIG. 88 shows the voltage-current density relationship of the device 23.
FIG. 89 shows the relationship between voltage and luminous efficiency of the device 23.
FIG. 90 shows CIE color coordinate of the device 23 at 5 mA.

(Part 4)
Production of device 24 using DNpBTz obtained in Reference Example 2 as a luminescent material 2,2'-Di (naphthalene-2-yl) -5,5'-bithiazole [DNpBTz] was applied as a luminescent material. A device 24 was prepared using t-BuDNA as a host and a doping concentration of 3 wt%. The device structure is shown below.
Device 24: ITO / α-NPD (40 nm) / t-BuDNA: DNpBTz (3 wt%) (30 nm) / Alq ₃ (30 nm) / LiF (0.5 nm) / Al (100 nm)
Table 17 below shows the EL characteristics of the device 24 at 100 cd / m ² , and Table 18 shows the EL characteristics of the device 24 at 1000 cd / m ² .
FIG. 91 shows an energy diagram of device 24. The structure of the device 24 is the same as that shown in FIG.
FIG. 92 shows the PL spectrum and EL spectrum of the DNpBTz solution obtained in Reference Example 2 and the PL spectrum of the t-BuDNA film.
FIG. 93 shows the standardized EL intensity (at 5 mA) of the device 24 and the standardized PL intensity of the DNpBT and t-BuDNA co-deposited film (3 wt%).
FIG. 94 shows the EL spectrum of device 24.
FIG. 95 shows the voltage-luminance relationship of the device 24.
FIG. 96 shows the voltage-current density relationship of the device 24.
FIG. 97 shows the voltage-luminous efficiency relationship of the device 24.
FIG. 98 shows CIE color coordinate of the device 24 at 5 mA.

It is a graph which shows the decomposition | disassembly condition of 2,2'- di (naphthyl-2-yl) -5,5'-bithiophene (DNpBT) obtained by the reference example 1 by a thermogravimetric analyzer (TGA-7). It is a graph which shows the thermal behavior of 2,2'-di (naphthyl-2-yl) -5,5'-bithiophene (DNpBT) obtained by the reference example 1 by a differential scanning calorimeter (DSC). It is a graph which shows the decomposition | disassembly condition of 2,2'- di (pyren-2-yl) -5,5'-bithiophene (DPylBT) obtained in Example 1 by the thermogravimetric analyzer (TGA-7). It is a graph which shows the thermal behavior of 2,2'-di (pyren-2-yl) -5,5'-bithiophene (DPylBT) obtained in Example 1 by a differential scanning calorimeter (DSC). It is a graph which shows the decomposition | disassembly condition of 2,2'- di (quinolin-6-yl) -5,5'-bithiophene (6DQBT) obtained in Example 2 by the thermogravimetric analyzer (TGA-7). It is a graph which shows the thermal behavior of 2,2'-di (quinolin-6-yl) -5,5'-bithiophene (6DQBT) obtained in Example 2 by a differential scanning calorimeter (DSC). The relationship of the drain voltage-drain current of the device 1 described in Example 4 is shown. The gate voltage-drain current relationship of the device 1 described in Example 4 is shown. The gate voltage- (drain current) ^1/2 relationship of the device 1 described in Example 4 is shown. The relationship of the drain voltage-drain current of the device 2 described in Example 4 is shown. The gate voltage-drain current relationship of the device 2 described in Example 4 is shown. The gate voltage- (drain current) ^1/2 relationship of the device 2 described in Example 4 is shown. Sectional drawing of the device 3 of Example 5 is shown. The relationship of the drain voltage-drain current of the device 3 described in Example 5 is shown. The gate voltage-drain current relationship and gate voltage- (drain current) ^1/2 relationship of the device 3 described in Example 5 are shown. The voltage-current density relationship of the devices 4 to 10 described in Example 6 is shown. The voltage-brightness relationship of the devices 4 to 10 described in Example 6 is shown. The relationship of the voltage-luminous efficiency of the devices 4-10 of Example 6 is shown. The relationship of the voltage-current efficiency of the devices 4-10 of Example 6 is shown. The current density-luminance relationship of the devices 4 to 10 described in Example 6 is shown. The relationship of the wavelength-standardized EL intensity | strength of the devices 4-10 of Example 6 is shown. The relationship of the wavelength-standardized EL intensity | strength of the device 5 of Example 6 is shown. The relationship between the wavelength of the device 6 described in Example 6 and the standardized EL intensity is shown. The wavelength-standardized EL intensity | strength relationship of the device 7 of Example 6 is shown. The relationship between the wavelength of the device 8 described in Example 6 and the standardized EL intensity is shown. The relationship of the wavelength-standardized EL intensity | strength of the device 9 of Example 6 is shown. The energy diagram of the organic EL element of the devices 5-9 of Example 6 is shown. Shows the normalized absorption spectra and standardization PL intensity DPylBT film and Alq ₃ film obtained by in Example 6. It shows the co-deposition film and PL intensity of each single deposition film of Alq ₃ and DPylBT in Example 6. Indicating the normalized PL intensity of the co-deposited film and each single deposition film of Alq ₃ and DPylBT in Example 6. The voltage-current density relationship of the devices 11 to 13 described in Example 7 is shown. The voltage-brightness relationship of the devices 11-13 of Example 7 is shown. The relationship of the voltage-luminous efficiency of the devices 11-13 of Example 7 is shown. The relationship of the voltage-current efficiency of the devices 11-13 of Example 7 is shown. The current density-luminance relationship of the devices 11-13 of Example 7 is shown. The EL spectrum in 5 mA of the devices 11-13 of Example 7, and the standardized EL intensity | strength of BAlq are shown. The standardized EL intensity | strength at the time of 1 mA-100 mA of the device 11 of Example 7 is shown. The standardized EL intensity | strength at the time of 1 mA-100 mA of the device 12 of Example 7 is shown. The standardized EL intensity | strength at the time of 1 mA-100 mA of the device 13 of Example 7 is shown. The standardized absorption spectrum and standardized PL intensity | strength of DPylBT obtained in Example 1 and well-known BAlq are shown. The PL intensity | strength of the co-evaporation film | membrane of BAlq and DPylBT and each single vapor deposition film is shown. The standardized PL intensity | strength of the co-deposition film | membrane of BAlq and DPylBT and each single vapor deposition film is shown. The PL spectrum in the solution state of DNpBT obtained in Reference Example 1 is indicated by a solid line, the UV absorption spectrum is indicated by a broken line, and the PL spectrum in the thin film state of t-BuDNA is indicated by a dotted line. The standardized EL intensity | strength (at the time of 5 mA) of the device 14 and the standardized PL intensity | strength of the co-deposition film | membrane (3 wt%) of DNpBT and t-BuDNA are shown. The EL spectrum of the device 14 obtained in Reference Example 1 is shown. The voltage-luminance of the device 14 obtained in Reference Example 1 is shown. The voltage-current density of the device 14 obtained in Reference Example 1 is shown. The voltage-luminous efficiency of the device 14 obtained in Reference Example 1 is shown. The CIE color coordinate at 5 mA of the device 14 obtained in Reference Example 1 is shown. The laminated structure of the devices 15-20 obtained in Example 9 is shown. The relationship of the drain voltage-drain current of the device 15 obtained in Example 9 is shown. The gate voltage-drain current and gate voltage- (drain current) ^1/2 relationship of the device 15 obtained in Example 9 are shown. The relationship of the drain voltage-drain current of the device 16 obtained in Example 9 is shown. The relationship of the gate voltage-drain current of the device 16 obtained in Example 9, and gate voltage- (drain current) ^1/2 is shown. The relationship of the drain voltage-drain current of the device 17 obtained in Example 9 is shown. The gate voltage-drain current and gate voltage- (drain current) ^1/2 relationship of the device 17 obtained in Example 9 are shown. The relationship of the drain voltage-drain current of the device 18 obtained in Example 9 is shown. The relationship of the drain voltage-drain current of the device 19 obtained in Example 9 is shown. The drain voltage-drain current relationship of the device 20 obtained in Example 9 is shown. The relationship of the gate voltage-drain current of the device 20 obtained in Example 9 and gate voltage- (drain current) ^1/2 is shown. The laminated structure of the device 21 obtained in Example 10 is shown. The energy diagram of the device 21 obtained in Example 10 is shown. The PL spectrum of the DPylBT solution is indicated by a solid line, the UV spectrum of the DPylBT solution is indicated by a broken line, and the PL spectrum of the Alq ₃ thin film is indicated by a dotted line. It shows the PL intensity of the co-deposited film and the respective single deposited film of Alq ₃ and DPylBT. The EL spectrum of devices 21-R to 21-6 and the PL spectrum of DPylBT film are shown. 2 shows the EL spectrum of device 21-R. The EL spectrum of the device 21-1 is shown. 2 shows the EL spectrum of device 21-2. 2 shows the EL spectrum of device 21-3. 2 shows the EL spectrum of device 21-4. 2 shows the EL spectrum of device 21-5. The voltage-luminance characteristics of devices 21-R and 21-1 to 21-6 are shown. The voltage-current density relationship of devices 21-R and 21-1 to 21-6 is shown. The voltage-luminous efficiency relationship of devices 21-R and 21-1 to 21-6 is shown. The CIE color coordinate at the time of 5 mA of the device 21-4 is shown. The energy diagram of the device 22 (the structure of the device 22 is the same as FIG. 61) is shown. The standardized EL spectrum of the device 22 (at 5 mA) and the PL spectrum of the co-deposited film (3 wt%) of t-BuDNA and 6DQBT are shown. 2 shows the EL spectrum of device 22. The voltage-luminance relationship of the device 22 is shown. The voltage-current density relationship of the device 22 is shown. The voltage-luminous efficiency relationship of the device 22 is shown. The CIE color coordinate of the device 22 at 5 mA is shown. The energy diagram of the device 23 (structure is the same as FIG. 61) is shown. The standardized PL intensity and standardized absorption spectrum of the 6DQxBT solution obtained in Example 3 and the standardized PL intensity of the BAlq thin film are shown. The standardized EL intensity of the device 23 (at 5 mA) and the standardized PL intensity of the 6DQxBT and BAlq co-deposited film (3 wt%) are shown. The EL spectrum of the device 23 is shown. The voltage-luminance relationship of the device 23 is shown. The voltage-current density relationship of the device 23 is shown. The relationship between voltage and luminous efficiency of the device 23 is shown. The CIE color coordinate of the device 23 at 5 mA is shown. An energy diagram of device 24 is shown. The PL spectrum and EL spectrum of the DNpBTz solution obtained in Reference Example 2 and the PL spectrum of the t-BuDNA film are shown. The standardized EL intensity | strength (at the time of 5 mA) of the device 24 and the standardized PL intensity | strength of the co-deposition film | membrane (3 wt%) of DNpBT and t-BuDNA are shown. The EL spectrum of device 24 is shown. The voltage-luminance relationship of the device 24 is shown. The voltage-current density relationship of the device 24 is shown. The voltage-luminous efficiency relationship of the device 24 is shown. The CIE color coordinate of the device 24 at 5 mA is shown.

Claims (5)

The following general formula (1)
(In the formula, Z represents a carbon element or a nitrogen element, and R ^{1 to} R ⁴ represent hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, and a linear or branched alkoxy group having 1 to 6 carbon atoms. R ¹ and R ⁴ are not present when Z is a nitrogen element, and A is represented by the following formula:
Wherein R ^{10 to} R ¹⁸ and R ^{20 to} R ⁴⁰ are hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, and 1 carbon atom. A group selected from the group consisting of a linear or branched alkoxy group of ˜6 and a linear or branched alkylamino group of 1 to 6 carbon atoms)
The polycyclic heterocyclic compound characterized by these.   A hole transport material comprising the polycyclic heterocyclic compound according to claim 1.   A hole light-emitting material comprising the polycyclic heterocyclic compound according to claim 1.   A field effect transistor using the polycyclic heterocyclic compound according to claim 1.   An organic EL device using the polycyclic heterocyclic compound according to claim 1.