JP5590553B2 - Organic semiconductor materials - Google Patents

Description

  The present invention relates to a novel amine compound and an organic optoelectronic device using the same.

  In recent years, organic optoelectronic devices using organic solid thin films, such as organic EL elements and organic thin film solar cells, have been vigorously developed. The thickness of the organic solid thin film constituting these devices is generally several tens to several hundreds nm. Accordingly, materials that form a uniform and smooth amorphous thin film during film formation are used in organic EL elements and organic thin film solar cells. On the other hand, in the amorphous state, the arrangement of molecules is random, and it can be said that this is a disadvantageous arrangement in terms of charge transport compared to a crystalline state in which the molecules are completely oriented. The charge transport property of the organic solid thin film affects the driving voltage in the organic EL element and the photoelectric conversion efficiency in the organic thin film solar cell. Therefore, materials used for these elements are required to form an amorphous state during film formation and have high charge transport characteristics. Under such circumstances, in recent years, a phenomenon has been reported in which an oxadiazole derivative (Bpy-OXD) having an electron transport property is oriented in the substrate surface direction in an amorphous thin film (for example, see Non-Patent Document 1). Analysis of the Bpy-OXD thin film by multi-incidence angle spectroscopic ellipsometry revealed that Bpy-OXD was oriented in the direction parallel to the substrate during film formation and stacked in the thickness direction of the film. Furthermore, there is a correlation between the molecular orientation and the electron mobility, and it has been shown that the molecular orientation in the thin film is effective in improving the charge transport property of the amorphous thin film. From such a background, in the organic optoelectronic device using an organic solid thin film, the development of a material having orientation is effective in improving the device characteristics.

  Amine compounds are widely used in organic optoelectronic devices because they have hole transport properties and form an amorphous thin film by vapor deposition or spin coating. For example, 4,4′-bis [N- (1-naphthyl) -N-phenyl] biphenyl (hereinafter abbreviated as NPD) has an appropriate ionization potential and forms a homogeneous amorphous thin film by vacuum deposition. Therefore, it is widely used as a hole transport material for organic EL elements. However, it cannot be said that the hole transport characteristics of NPD are sufficient, and the driving voltage of the organic EL element using NPD as the hole transport layer and the photoelectric conversion efficiency of the organic thin film solar cell using NPD as the p layer are improved. There is a need for. Regarding the NPD amorphous thin film, orientation analysis by multi-incidence angle spectroscopic ellipsometry has been performed, but it has been reported that the molecular orientation in the NPD thin film is almost random (for example, see Non-Patent Document 2). Therefore, in order to obtain an amorphous film having excellent hole transport properties, it is necessary to develop an amine compound in which molecules are oriented during film formation.

Applied Physics Letter, 2009, 95, 243303. Applied Physics Letter, 2008, 93, 173302.

  An object of the present invention is to provide an amine compound suitable for a hole transport material of an organic optoelectronic device, and further a high performance organic optoelectronic device using a thin film of the compound.

As a result of intensive studies, the present inventors have found that the amine compound represented by the following general formula (1) having a specific substituent has excellent hole transport properties, and the compound is used as a hole transport layer and / or a hole injection. The drive voltage of the organic EL element used for the layer was improved, and the photoelectric conversion efficiency of the organic thin-film solar cell using the compound for the p-layer was found, and the present invention was completed.
That is, the present invention relates to an amine compound represented by the general formula (1) and its use.

(Wherein, X ^{1 to} X ⁴ and R ^{1 to} R ²⁰ are each independently a hydrogen atom, a halogen atom, a straight chain having 1 to 18 carbon atoms, a branched or cyclic alkyl group, or a straight chain having 1 to 18 carbon atoms. A branched or cyclic alkoxy group, an amino group which may have a substituent, an aryl group having 6 to 50 carbon atoms which may have a substituent, or an alkyl group which has 4 to 50 carbon atoms which may have a substituent. Represents a heteroaryl group, provided that at least two of X ^{1 to} X ⁴ are substituents represented by the following general formula (2) or (3).

Wherein R ^{21 to} R ²⁸ are each independently a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms. A group, an amino group which may have a substituent, an aryl group having 6 to 50 carbon atoms which may have a substituent or a heteroaryl group having 4 to 50 carbon atoms which may have a substituent; n is an integer of 1 to 3.)

  Since the amine compound represented by the general formula (1) according to the present invention has higher hole transport properties than those of conventional materials, it is possible to realize high performance of organic optoelectronic devices such as organic EL elements and organic thin film solar cells. it can.

FIG. 1 is a graph showing current-voltage characteristics of the devices manufactured in Examples 5 and 6 and Comparative Examples 3 and 4. In FIG.

Hereinafter, the present invention will be described in detail.
[About amine compounds]
In the amine compound represented by the general formula (1) of the present invention, R ^{1 to} R ²⁰ are each independently a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, or a carbon number. 1-18 linear, branched or cyclic alkoxy groups, optionally substituted amino groups, optionally substituted aryl groups having 6 to 50 carbon atoms or substituents. A heteroaryl group having 4 to 50 carbon atoms is represented.

Examples of the halogen atom represented by R ^{1 to} R ²⁰ include a fluorine, chlorine, bromine or iodine atom.

Specific examples of the linear, branched or cyclic alkyl group having 1 to 18 carbon atoms represented by R ^{1 to} R ²⁰ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a sec-butyl group. , Tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, stearyl group, trichloromethyl group, trifluoromethyl group, cyclopropyl group, cyclohexyl group and the like, but are not limited thereto. It is not a thing.

Specific examples of the linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms represented by R ^{1 to} R ²⁰ include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, sec -Butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, stearyloxy group and the like can be exemplified, but are not limited thereto.

Examples of the amino group optionally having a substituent represented by R ^{1 to} R ²⁰ include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, a diphenylamino group, a di (m-tolyl) amino group, Di (p-tolyl) amino group, N- (m-tolyl) phenylamino group, N- (p-tolyl) phenylamino group, N- (1-naphthyl) phenylamino group, N- (2-naphthyl) phenyl An amino group, an N- (4-biphenyl) phenylamino group, a di (4-biphenyl) amino group, a di (2-naphthyl) amino group, and the like can be exemplified, but are not limited thereto.

Examples of the substituted or unsubstituted aryl group having 6 to 50 carbon atoms represented by R ^{1 to} R ²⁰ include a phenyl group, a 4-methylphenyl group, a 3-methylphenyl group, a 2-methylphenyl group, and a 4-ethylphenyl group. 3-ethylphenyl group, 2-ethylphenyl group, 4-n-propylphenyl group, 4-isopropylphenyl group, 2-isopropylphenyl group, 4-n-butylphenyl group, 4-isobutylphenyl group, 4-sec -Butylphenyl group, 4-tert-butylphenyl group, 4-n-pentylphenyl group, 4-isopentylphenyl group, 4-neopentylphenyl group, 4-n-hexylphenyl group, 4-n-octylphenyl group 4-n-decylphenyl group, 4-n-dodecylphenyl group, 4-cyclopentylphenyl group, 4-cyclohexylpheny Group, 4-tritylphenyl group, 3-tritylphenyl group, 4-triphenylsilylphenyl group, 3-triphenylsilylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 3,4- Dimethylphenyl group, 3,5-dimethylphenyl group, 2,6-dimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 4-methoxyphenyl group, 3-methoxyphenyl group, 2-methoxyphenyl group, 4-ethoxyphenyl group, 3-ethoxyphenyl group, 2-ethoxyphenyl group, 4-n-propoxyphenyl group, 3-n-propoxyphenyl Group, 4-isopropoxyphenyl group, 2-isopropoxyphenyl group, 4-n-butoxyphenyl group, 4-isobutyl Xiphenyl group, 2-sec-butoxyphenyl group, 4-n-pentyloxyphenyl group, 4-isopentyloxyphenyl group, 2-isopentyloxyphenyl group, 4-neopentyloxyphenyl group, 2-neopentyloxyphenyl Group, 4-n-hexyloxyphenyl group, 2- (2-ethylbutyl) oxyphenyl group, 4-n-octyloxyphenyl group, 4-n-decyloxyphenyl group, 4-n-dodecyloxyphenyl group, 4 -N-tetradecyloxyphenyl group, 4-cyclohexyloxyphenyl group, 2-cyclohexyloxyphenyl group, 4-phenoxyphenyl group, 2-methyl-4-methoxyphenyl group, 2-methyl-5-methoxyphenyl group, 3 -Methyl-4-methoxyphenyl group, 3-methyl-5-methoxyphene Nyl group, 3-ethyl-5-methoxyphenyl group, 2-methoxy-4-methylphenyl group, 3-methoxy-4-methylphenyl group, 2,4-dimethoxyphenyl group, 2,5-dimethoxyphenyl group, 2 , 6-dimethoxyphenyl group, 3,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3,5-diethoxyphenyl group, 3,5-di-n-butoxyphenyl group, 2-methoxy-4- Ethoxyphenyl group, 2-methoxy-6-ethoxyphenyl group, 3,4,5-trimethoxyphenyl group, 4-fluorophenyl group, 3-fluorophenyl group, 2-fluorophenyl group, 2,3-difluorophenyl group 2,4-difluorophenyl group, 2,5-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluorophenyl group, , 5-difluorophenyl group, 4- (1-naphthyl) phenyl group, 4- (2-naphthyl) phenyl group, 3- (1-naphthyl) phenyl group, 3- (2-naphthyl) phenyl group, 1-naphthyl Group, 2-naphthyl group, 4-methyl-1-naphthyl group, 6-methyl-2-naphthyl group, 4-phenyl-1-naphthyl group, 6-phenyl-2-naphthyl group, 2-anthryl group, 9- Anthryl group, 10-phenyl-9-anthryl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, 9,9-diethyl-2-fluorenyl group, 9,9-di-n-propyl-2 -Fluorenyl group, 9,9-di-n-octyl-2-fluorenyl group, 9,9-diphenyl-2-fluorenyl group, 9,9'-spirobifluorenyl group, 9-phenanthryl group, 2-phen Enthryl group, benzofluorenyl group, dibenzofluorenyl group, fluoranthenyl group, pyrenyl group, chrysenyl group, perylenyl group, picenyl group, 4-biphenylyl group, 3-biphenylyl group, 2-biphenylyl group, p-ter Examples thereof include, but are not limited to, a phenyl group, an m-terphenyl group, and an o-terphenyl group.

Further, examples of the substituted or unsubstituted carbon atoms 4-50 heteroaryl group represented by R ¹ to R ^20, an aromatic group containing at least one hetero atom of oxygen atom, nitrogen atom and sulfur atom, For example, 4-quinolyl group, 4-pyridyl group, 3-pyridyl group, 2-pyridyl group, 3-furyl group, 2-furyl group, 3-thienyl group, 2-thienyl group, 2-oxazolyl group, 2-thiazolyl Group, 2-benzoxazolyl group, 2-benzothiazolyl group, 2-carbazolyl group, benzothiophenyl group, benzoimidazolyl group, dibenzothiophenyl group and the like can be exemplified, but not limited thereto.

In the amine compound represented by the general formula (1), X ^{1 to} X ⁴ are each independently a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, or 1 to 1 carbon atoms. 18 linear, branched or cyclic alkoxy groups, amino groups which may have substituents, aryl groups having 6 to 50 carbon atoms which may have substituents, or carbon atoms which may have substituents Represents 4-50 heteroaryl groups. However, at least two of X ^{1 to} X ⁴ are substituents represented by the following general formula (2) or (3).

Wherein R ^{21 to} R ²⁸ are each independently a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms. A group, an amino group which may have a substituent, an aryl group having 6 to 50 carbon atoms which may have a substituent or a heteroaryl group having 4 to 50 carbon atoms which may have a substituent; n is an integer of 1 to 3.)

It may have a halogen atom represented by X ^{1 to} X ⁴ , a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 18 carbon atoms, or a substituent. Examples of the good amino group, the aryl group having 6 to 50 carbon atoms that may have a substituent, or the heteroaryl group having 4 to 50 carbon atoms that may have a substituent include those exemplified for R ^{1 to} R ²⁰ above. A substituent is mentioned.

In the general formulas (2) and (3), R ^{21 to} R ²⁸ are each independently a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, or a C 1 to 18 carbon atoms. A linear, branched or cyclic alkoxy group, an amino group that may have a substituent, an aryl group having 6 to 50 carbon atoms that may have a substituent, or a carbon number that has 4 to 5 carbon atoms that may have a substituent Although 50 heteroaryl groups are represented, Specific examples of these include the substituents exemplified for R ^{1 to} R ²⁰ .
In the general formula (2), n represents an integer of 1 to 3.

[Orientation parameter S]
Among the amine compounds represented by the general formula (1), those having a molecular plane oriented in a direction parallel to the substrate when the film is formed on the substrate are preferable. Specifically, the angle formed between the molecular axis and the substrate normal direction in the thin film formed on the substrate is θ, and the extinction coefficients in the substrate parallel direction and the vertical direction obtained by multi-incidence angle spectroscopic ellipsometry measurement of the thin film are respectively shown. If the k _o and _{k e,} an amine compound represented by the general formula orientation parameter S represented by the following formula (4) is -0.50～-0.15 (1).
^{S = (1/2) <3cos 2} θ-1> = (k e -k o) / (k e + 2k o) (4)

  The method for evaluating the molecular orientation in the thin film used here is a known technique, and details are described in Organic Electronics, 2009, Vol. 10, page 127. As a method for forming a thin film, a known method such as a vacuum deposition method, a spin coating method, or a casting method can be applied.

  The amine compound represented by the general formula (1) in which the orientation parameter S obtained from multi-incidence angle spectroscopic ellipsometry measurement is −0.50 to −0.15 is an overlap of π electrons between molecules in the thin film. Increases and the hole transport property is improved.

  The orientation parameter S obtained from multi-incidence angle spectroscopic ellipsometry measurement is −0.50 when all molecules are oriented in a direction parallel to the substrate. Further, when the molecules are random without being oriented, the value is 0.00. In organic optoelectronic devices that flow charge in a direction perpendicular to the substrate, such as organic EL elements and organic thin-film solar cells, a thin film with molecules aligned in a direction parallel to the substrate and having a large overlap of orbits between molecules is more charged. This is advantageous for transportation. Therefore, as compared with a thin film with molecular orientation close to random, a thin film having an orientation parameter S of −0.50 to −0.15 has a large overlap of orbits between molecules and exhibits high charge transport characteristics.

Preferred compounds are illustrated below, but are not limited to these compounds.

[Production method of amine compound]
The amine compound represented by the general formula (1) can be synthesized by a known method. For example, it can be synthesized by coupling a halogenated tetraphenylphenylenediamine represented by the following general formula (5) and a boronic acid compound represented by the following general formula (6) in the presence of a catalyst. .

(Wherein R ^{1 to} R ²⁰ and X represent the same substituents as R ^{1 to} R ²⁰ and X ^{1 to} X ⁴ represented by the general formula (1), Y represents a halogen atom, m represents Represents an integer of 0 or 1. At least two of m are m = 1.)

[About organic EL elements and organic thin-film solar cells]
Since the amine compound represented by the general formula (1) of the present invention is excellent in hole transport ability, it can be used in a layer responsible for hole transport in an organic optoelectronic device.

  Specifically, it can be used as a hole transport layer and / or a hole injection layer of an organic EL device. The organic EL device using the amine compound represented by the general formula (1) as a hole transport layer and / or a hole injection layer is improved in driving voltage, light emission efficiency, and durability.

  When forming the hole injection layer and / or hole transport layer made of the amine compound represented by the general formula (1), two or more kinds of materials may be contained or laminated as necessary. For example, oxides such as molybdenum oxide, 7,7,8,8-tetracyanoquinodimethane, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, hexacyanohexahexa A known electron-accepting material such as azatriphenylene may be contained or laminated.

  Moreover, since the amine compound represented by the general formula (1) is excellent in hole transport ability, it can also be used as a p layer of an organic thin film solar cell. The device using the amine compound represented by the general formula (1) as the p layer can obtain higher photoelectric conversion efficiency as compared with a device using a conventionally known amine compound.

  Examples of a method for forming a thin film (for example, a hole transport layer, a hole injection layer, or a p layer) made of an amine compound represented by the general formula (1) include a vacuum deposition method, a spin coating method, a cast method, and the like. The known methods can be applied.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited by these Examples.

¹ H-NMR measurement was performed using ECP400 manufactured by JEOL Ltd.
Multi-incidence angle spectroscopic ellipsometry measurements are described in J. A. This was performed using M-2000U manufactured by Woollam.
The current-voltage characteristics of the organic EL element were measured using an Agilent 4155C semiconductor parameter analyzer manufactured by Agilent Technology, Inc. by applying a direct current to the manufactured element.

Synthesis Example 1 (Synthesis of 1,4-bis (diphenylamino) benzene [see the following formula (7)])
Under a stream of argon, 2.97 g (17.5 mmol) of diphenylamine was charged into a 100 ml flask and dissolved in 30 ml of tetrahydrofuran. At room temperature, 2.41 g (18.3 mmol) of ethylmagnesium bromide was added dropwise over 1 hour, and the mixture was further stirred for 4 hours. After the tetrahydrofuran was distilled off, 50 ml of toluene, 2.08 g (0.38 mmol) of dichloro (1,2-bis (diphenylphosphinopropane)) nickel, 2.02 g (0.76 mmol) of triphenylphosphine, 1,4- Dibromobenzene 1.8g (7.6mmol) was added, and it stirred at 80 degreeC for 12 hours. After cooling to room temperature, the reaction solution was poured into a 5% aqueous hydrochloric acid solution. After neutralizing with sodium carbonate, the organic layer was washed with pure water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained solid was recrystallized from acetone, and 1.88 g of a white solid of 1,4-bis (diphenylamino) benzene was isolated (yield 59%).

The compound was identified by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 7.24 (dd, 8H, J = 8.80 Hz, 7.30 Hz), 7.10 (d, 8H, J = 8.80 Hz), 6.98 (t, 4H) , J = 7.30 Hz), 6.98 (s, 4H)

Synthesis Example 2 (Synthesis of 1,4-bis (di- (4-bromophenyl) amino) benzene [see the following formula (7)])
Under an argon stream, 6.00 g (14.5 mmol) of 1,4-bis (diphenylamino) benzene obtained in Synthesis Example 1 was dissolved in 50 ml of dimethylformamide in a 200 ml flask at 0 ° C. Thereto was added dropwise 11.37 g (63.9 mmol) of N-bromosuccinimide dissolved in 50 ml of dimethylformamide, followed by stirring at room temperature for 1 hour. The reaction mixture was poured into ice water and extracted with dichloromethane. The dichloromethane layer was washed with pure water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained solid was recrystallized from ethanol to isolate 9.7 g (13.3 mmol) of white crystals of 1,4-bis (di- (4-bromophenyl) amino) benzene (yield 92%).

The compound was identified by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 7.35 (d, 8H, J = 8.80 Hz), 6.95 (s, 4H), 6.94 (d, 8H, J = 8.80 Hz)

Example 1 (Synthesis of Compound (A4))
In a 100 ml flask under an argon stream, 0.50 g (0.69 mmol) of 1,4-bis (di- (4-bromophenyl) amino) benzene obtained in Synthesis Example 2 and 0.53 g of 2-thiopheneboronic acid (4.12 mmol), 0.047 g (0.04 mmol) of tetrakis (triphenylphosphine) palladium, 50 ml of tetrahydrofuran and 6.6 ml of 20M aqueous potassium carbonate solution were added, and the mixture was heated to reflux for 48 hours. After cooling to room temperature, pure water was added and extracted twice with dichloromethane. The dichloromethane extract was washed with pure water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained solid was recrystallized from toluene, and 0.33 g (0.40 mmol) of the solid of the compound (A4) was isolated (yield 59%).

The compound was identified by ¹ H-NMR measurement.
¹ H-NMR (DMSO-d ₆ ); 7.61 (d, 8H, J = 8.80 Hz), 7.49 (d, 4H, J = 5.12 Hz), 7.42 (d, 4H, J = 5.12 Hz), 7.12 (t, 4H, J = 5.12 Hz), 7.10 (d, 8H, J = 8.80 Hz), 7.09 (s, 4H)

Example 2 (Synthesis of Compound (A8))
In a 100 ml flask under an argon stream, 0.50 g (0.69 mmol) of 1,4-bis (di- (4-bromophenyl) amino) benzene obtained in Synthesis Example 2 and 2-benzothiopheneboronic acid 72 g (4.12 mmol), tetrakis (triphenylphosphine) palladium 0.047 g (0.04 mmol), tetrahydrofuran 50 ml, 20 M aqueous potassium carbonate solution 6.6 ml were added, and the mixture was heated to reflux for 48 hours. After cooling to room temperature, pure water was added and extracted twice with dichloromethane. The dichloromethane extract was washed with pure water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained solid was recrystallized with toluene, and 0.41 g (0.42 mmol) of the solid of the compound (A8) was isolated (yield 62%).

The compound was identified by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 7.82 (d, 4H, J = 7.68 Hz), 7.76 (d, 4H, J = 7.68 Hz), 7.65 (d, 8H, J = 8) .80 Hz), 7.49 (s, 4H), 7.31-7.35 (m, 8H), 7.21 (d, 8H, J = 7.68 Hz), 7.14 (s, 4H)

Example 3 (Multi-incidence angle spectroscopic ellipsometry measurement of compound (A4))
After ultrasonic cleaning with neutral detergent, pure water, acetone and isopropyl alcohol, the silicon substrate boiled and cleaned with isopropyl alcohol was placed in a vacuum deposition apparatus and evacuated with a vacuum pump until 3 × 10 ⁻³ Pa. Compound (A4) was deposited to a thickness of 100 nm at a deposition rate of 0.1 nm / second to form a thin film for measurement. About the produced thin film, ellipsometry parameters were measured using a multi-incidence angle spectroscopic ellipsometer with an incident angle in the range of 45 ° to 75 ° every 5 ° and a wavelength in the range of 245 to 1000 nm. The data obtained is A. The orientation parameter S was calculated by analysis with Woollam analysis software WVASE32. The deposited film of the compound (A4) was S = −0.19, and the molecular plane of the compound (A4) was oriented in a direction parallel to the silicon substrate.

Example 4 (Multi-incidence angle spectroscopic ellipsometry measurement of compound (A8))
The orientation parameter S was calculated in the same manner as in Example 3 except that the compound (A4) was changed to (A8). The deposited film of the compound (A8) was S = −0.24, and the molecular plane of the compound (A8) was oriented in a direction parallel to the silicon substrate.

Comparative Example 1 (NPD multiple incidence angle spectroscopic ellipsometry measurement)
The orientation parameter S was calculated in the same manner as in Example 3 except that the compound (A4) was changed to NPD. The deposited film of NPD was S = −0.01, and the arrangement of NPD molecules in the thin film was random.

Comparative Example 2 (multi-incidence angle spectroscopic ellipsometry measurement of comparative compound (a))
The orientation parameter S was calculated in the same manner as in Example 3 except that the compound (A4) was changed to the comparative compound (a). The deposited film of the comparative compound (a) was S = −0.11, and the molecular arrangement in the thin film was random as compared with the compounds (A4) and (A8).

Example 5 (Element evaluation of compound (A4))
The glass substrate on which the ITO transparent electrode (anode) having a thickness of 200 nm was laminated was subjected to ultrasonic cleaning with a neutral detergent, pure water, acetone and isopropyl alcohol, and then subjected to boiling cleaning with isopropyl alcohol. Further, ultraviolet ozone cleaning was performed, and after evacuation with a vacuum pump until 1 × 10 ⁻³ Pa or less after installation in a vacuum deposition apparatus. First, the compound (A4) was deposited on the ITO transparent electrode at a deposition rate of 0.3 nm / second to form a 45 nm hole injection layer. Subsequently, NPD was deposited at 5 nm at a deposition rate of 0.3 nm / second, and then tris (8-quinolinolato) aluminum was deposited at 50 nm at a deposition rate of 0.3 nm / second to form a light emitting layer. Subsequently, an alloy of magnesium and silver (10: 1) was deposited to 100 nm at 0.33 nm / second, and silver was further deposited to 10 nm at a deposition rate of 0.1 nm / second to form a cathode. did. FIG. 1 shows the current-voltage characteristics of the device thus fabricated, and Table 1 shows the drive voltage to which a current of 20 mA / cm ² was applied.

Example 6 (device evaluation of compound (A8))
An organic EL device was produced in the same manner as in Example 5 except that the compound (A4) was changed to the compound (A8). FIG. 1 shows the current-voltage characteristics of the fabricated device, and Table 1 shows the drive voltage to which a current of 20 mA / cm ² was applied.

Comparative Example 3 (NPD element evaluation)
An organic EL device was produced in the same manner as in Example 5 except that the compound (A4) was changed to NPD. FIG. 1 shows the current-voltage characteristics of the fabricated device, and Table 1 shows the drive voltage to which a current of 20 mA / cm ² was applied.

Comparative Example 4 (device evaluation of comparative compound (a))
An organic EL device was produced in the same manner as in Example 5 except that the compound (A4) was changed to the comparative compound (a). FIG. 1 shows the current-voltage characteristics of the fabricated device, and Table 1 shows the drive voltage to which a current of 20 mA / cm ² was applied.

  The amine compound of the present invention can be used as a material for a thin film of an organic optoelectronic device.

Claims (3)

An amine compound represented by the following (A4) or (A8) .
A thin film comprising the amine compound according to claim 1, wherein the angle formed between the molecular axis and the substrate normal direction in the thin film formed on the substrate is θ, and the substrate parallel direction obtained by multi-incidence angle spectroscopic ellipsometry measurement of the thin film and if the vertical extinction coefficient was _{k o} and _{k e,} respectively, a thin film orientation parameter S represented by the following formula (4) it is -0.50～-0.15.
^{S = (1/2) <3cos 2} θ-1> = (k e -k o) / (k e + 2k o) (4) An organic optoelectronic device using a thin film comprising the amine compound according to claim 1 .