JPH1039348A - Organic nonlinear optical material, organic conductive material and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an org. nonlinear optical material and org. conductive material having excellent nonlinear optical characteristics and electrical conduction characteristics. SOLUTION: The thin film of an org. compd. which has vinylene groups in its molecular structure and in which at least one of these vinylene groups are cis substances and which has nonlinear optical characteristics, is formed by vacuum vapor deposition. This thin film is photoirradiated to convert all the vinylene groups existing in this org. compd. to trans substances by photoisomerization reaction. As a result, the nonlinear org. material is provided with a plane structure and the π conjugation length is made longer. An electron withdrawing compd. is deposited by evaporation and is dispersed into the thin film described above at the time of vacuum vapor deposition, by which the org. conductive material is obtd. Since these materials have the long π conjugation length, the materials have the excellent nonlinear optical characteristics and electrical conduction characteristics.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an organic nonlinear optical material, an organic conductive material, and a method for producing the same.

[0002]

2. Description of the Related Art A nonlinear optical material is a material having an electro-optic effect in which the refractive index changes according to a change in light intensity or an applied voltage, and an effect such as light-light conversion for converting the frequency of incident light. Currently, it is regarded as a key material in developing frequency conversion elements and optical switching elements. In particular, nonlinear optical materials composed of organic compounds are attracting attention because of their high nonlinear optical properties and high-speed response. [D.J. Williams (DJ
Williams) ed., ACS Symp. Ser. Series, Volume 233, "Nonlinear Optical Properties of Organic and Polymeric Materials (Nonlinear Optical Propertie)
s of Organic and polymeric Materials) "(198
3)]. Organic compounds are also expected to be conductive materials because of their semiconducting properties, light weight and low cost [W.P. Sui (WPSu), J.R.
JRSurieffer, AJHeeger, Physical Review Phy
s. Rev. B) 226, pp. 2099-2111 (198
0)].

[0003] In order to use such an organic compound having excellent characteristics as a nonlinear optical material, it is indispensable to make them into a thin film to form a device. Known methods for thinning an organic compound include a vacuum deposition method such as an LB method, a spin coating method, and a molecular beam deposition method, and a method such as a CVD method. In the LB method, an organic compound having both a hydrophilic group and a hydrophobic group is dissolved in a solvent and dropped on a water surface to form a monomolecular film of the organic compound on the water surface, and the formed film is scooped. This is a method of accumulating on a substrate.
The spin coating method is a method in which a solution of an organic compound is dropped on a high-speed rotating substrate to uniformly deposit the organic compound on the substrate to form a film. However, in these methods, since a step of dissolving the organic compound in a solvent is indispensable, an organic compound having low solubility cannot be formed into a film.

[0004] The vacuum deposition method is a method of forming a film by irradiating a vapor of an organic compound onto a substrate and depositing the vapor on the substrate. However, in this method, since the step of sublimating the organic compound is indispensable, thermal decomposition and thermal reaction occur at a temperature similar to or lower than the sublimation under the pressure conditions usually used in the vacuum deposition method. Organic compounds cannot form films.

[0005] Unlike the above three methods, the CVD method does not use an organic compound itself as a raw material, but reacts a reactive gas with heat, plasma or light under normal pressure or reduced pressure to obtain an organic compound obtained as a reaction product. Is deposited on a substrate. However, in this method, since a reaction product by a gas phase reaction is deposited, a film cannot be formed unless an organic compound is obtained by a gas reaction.

As described above, the application of any of the above-mentioned film forming methods is limited, and in practice, a film cannot be formed unless an organic compound having a solubility or sublimability higher than a certain level is used. Is the current situation. Therefore, since the solubility and sublimability of an organic compound become lower as the π-conjugation length in the compound becomes longer, it is difficult to form a film by forming such an organic compound directly into a device by a conventional method. there were. However, it is considered that the longer the π-conjugation length, the better the nonlinear optical properties and electric conduction properties are, and the development of nonlinear optical materials and organic conductive materials made of such organic compounds has been expected.

For example, an organic compound which is a phenylene vinylene derivative in which all vinylene groups are in the trans form,
In particular, when the number of repetitions is large, it has a planar structure and a long π conjugation length and is excellent in non-linear optical properties and electric conduction properties.However, since its thermal decomposition initiation temperature or thermal reaction temperature is lower than the sublimation temperature, vacuum It is difficult to form a device by directly forming a film by vapor deposition. On the other hand, when the ratio of the cis-vinylene group in the phenylene vinylene derivative is increased, the sublimation temperature is lowered and the film can be directly formed relatively easily by vacuum deposition. On the other hand, a planar structure is formed due to steric hindrance and the like. Π conjugation length is shortened.

[0008]

Conventionally, organic compounds having a long π-conjugation length have a thermal reaction or thermal decomposition prior to sublimation. Therefore, it is difficult to form a device by directly forming a film by vacuum deposition. There is a problem that it is difficult to obtain an organic nonlinear optical material and an organic conductive material made of such an organic compound. The present invention has been made in order to solve such problems, and all vinylene groups in an organic compound are trans-forms, and it is practically impossible to form a film directly by vacuum deposition. An object of the present invention is to provide an amorphous or crystalline organic nonlinear optical material made of an organic compound having an excellent optical property and electric conduction property and having a long conjugate length.

Another object of the present invention is to provide a polymerizable organic nonlinear optical material obtained by polymerizing such an organic nonlinear optical material by heat or light. Still another object of the present invention is to provide an organic conductive material obtained by dispersing an electron-withdrawing compound in the organic nonlinear optical material of the present invention. In addition to the above, an object of the present invention is to provide a method for producing such an organic nonlinear material and an organic conductive material.

[0010]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in view of the above problems, and found that the ratio of isomers of vinylene groups in an organic compound having a vinylene group in the molecular structure, for example, a phenylenevinylene derivative By utilizing the property that various physicochemical properties of the organic compound change depending on the abundance ratio of the vinylene group isomer in the above, an organic nonlinear optical material and an organic conductive material composed of an organic compound having a long π-conjugated length are utilized. They found that a film could be formed directly, and completed the present invention.

Thus, according to the present invention, an organic compound having nonlinear optical properties and / or a polymer of the organic compound having a vinylene group in the molecular structure and all of the vinylene groups being in a trans form is provided. An organic nonlinear optical material is provided. Further, according to the present invention, there is provided an organic nonlinear optical material comprising a phenylenevinylene derivative, wherein all vinylene groups are in a trans form, and / or a polymer of the organic compound. Further, according to the present invention, the following chemical structural formula (1):

[0012]

Embedded image

[Wherein R ₁ and R ₂ are each independently a hydrogen atom, a halogen atom, a carboxyl group, a hydroxyl group, a mercapto group, a nitro group, a nitroso group, an amino group,
A cyano group, an isocyano group, a cyanato group, an isocyanato group, an azide group, or an alkyl group having 5 or less carbon atoms,
It is any one of an alkenyl group, an alkynyl group, an ether group, an ester group and an acyl group, and n is an integer of any of 1 to 5. Wherein all vinylene groups in the formula are in the trans form and / or an organic nonlinear optical material comprising a polymer of the organic compound.

Further, according to the present invention, the following chemical structural formula (2):

[0015]

Embedded image

[Wherein R ₁ and R ₂ are each independently a hydrogen atom, a halogen atom, a carboxyl group, a hydroxyl group, a mercapto group, a nitro group, a nitroso group, an amino group,
A cyano group, an isocyano group, a cyanato group, an isocyanato group, an azide group, or an alkyl group, an alkenyl group, an alkynyl group, an ether group, an ester group or an acyl group having 5 or less carbon atoms, and m and n are each independently And the sum of m and n is 5 or less. Wherein all vinylene groups in the formula are in the trans form and / or an organic nonlinear optical material comprising a polymer of the organic compound.

According to the present invention, an organic compound having a nonlinear optical characteristic and / or a polymer of the organic compound having a vinylene group in the molecular structure and all the vinylene groups being in a trans form. Provided is an organic conductive material obtained by dispersing an electron-withdrawing compound in an optical material. Further, according to the present invention, an electron-withdrawing compound is dispersed in an organic nonlinear optical material comprising a phenylene vinylene derivative in which all vinylene groups are in a trans form and / or a polymer of the organic compound. Provided is an organic conductive material. Furthermore, according to the present invention,
An electron withdrawing property is represented by an organic compound represented by the chemical structural formula (1) or (2), wherein all vinylene groups in the formula are in a trans form and / or an organic nonlinear optical material comprising a polymer of the organic compound. An organic conductive material having a compound dispersed therein is provided.

According to the present invention, an organic compound having a non-linear optical property and having a vinylene group in the molecular structure and at least one of the vinylene groups being a cis-form is thinned by vacuum deposition, and the thin film is formed into a light-emitting layer. A method for producing an organic nonlinear optical material is provided, wherein all vinylene groups present in the organic compound upon irradiation are converted into a trans form by a photoisomerization reaction. According to the present invention, an organic compound having a non-linear optical property, which has a vinylene group in a molecular structure and at least one of the vinylene groups is a cis body, is formed into a thin film by vacuum deposition, and at the same time, an electron-withdrawing compound is formed. And dispersing the electron-withdrawing compound in the thin film, irradiating the thin film with light to convert all vinylene groups present in the organic compound into a trans form by a photoisomerization reaction, A method for manufacturing an organic conductive material is provided.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The organic nonlinear optical material of the present invention comprises:
An organic nonlinear optical material having a vinylene group in the molecular structure, and all of the vinylene groups being in a trans form, comprising an organic compound having nonlinear optical characteristics and / or a polymer of the organic compound. Further, the organic nonlinear optical material of the present invention is an organic nonlinear optical material which is a phenylenevinylene derivative, wherein all vinylene groups are trans-forms, and / or a polymer of the organic compound.
Further, the organic nonlinear optical material of the present invention has the following chemical structural formula (1):

[0020]

Embedded image

[Wherein R ₁ and R ₂ each independently represent a hydrogen atom, a halogen atom, a carboxyl group, a hydroxyl group, a mercapto group, a nitro group, a nitroso group, an amino group,
A cyano group, an isocyano group, a cyanato group, an isocyanato group, an azide group, or an alkyl group having 5 or less carbon atoms,
It is any one of an alkenyl group, an alkynyl group, an ether group, an ester group and an acyl group, and n is an integer of any of 1 to 5. Or the following chemical structural formula (2):

[0022]

Embedded image

Wherein R ₁ and R ₂ each independently represent a hydrogen atom, a halogen atom, a carboxyl group, a hydroxyl group, a mercapto group, a nitro group, a nitroso group, an amino group,
A cyano group, an isocyano group, a cyanato group, an isocyanato group, an azide group, or an alkyl group, an alkenyl group, an alkynyl group, an ether group, an ester group or an acyl group having 5 or less carbon atoms, and m and n are each independently And the sum of m and n is 5 or less. And all the vinylene groups in the formula are trans-forms, and / or a polymer of the organic compound.

As the organic compound represented by the chemical structural formula (1), 4,4′-distyrylbenzene, 4,4′-
Distyrylstilbene, 4,4'-distyrylbylbenzene, 4,4'-distyrylvirstilbene, 4,4'-bis (3,4,5-trimethoxy-styryl) benzene, 4,4 '
-Bis (3,4,5-trimethoxy-styryl) stilbene, 4,4'-bis (3,4,5-trimethoxy-styrylvir) benzene, 4,4'-bis (3,4,5-trimethoxy-)
Styrylvir) stilbene, 4,4'-bis (3,5-isobutyl-styryl) benzene, 4,4'-bis (3,5-isobutyl-styryl) stilbene, 4,4'-bis (3,5-isobutyl) -Styrylvir) benzene, 4,4'-bis (3,
5-isobutyl-styrylvir) stilbene, 4,4'-bis (4-ethynyl-styryl) benzene, 4,4'-bis (4-ethynyl-styryl) stilbene, 4,4'-bis (4-ethynyl-styrylvir) ) Benzene, 4,4'-bis (4-ethynyl-styrylville) stilbene, 4,4'-bis (4-hydroxy-styryl) benzene, 4,4'-bis (4-hydroxy-styryl) stilbene, 4'-bis (4-hydroxy-styrylvir) benzene, 4,4'-bis (4-hydroxy-styrylvir) stilbene, 4,4 '
-Bis (4-mercapto-styryl) benzene, 4,4'-bis (4-mercapto-styryl) stilbene, 4,4'-bis (4-mercapto-styrylvir) benzene, 4,4'-
Bis (4-mercapto-styrylvir) stilbene, 4,
4'-bis (4-cyano-styryl) benzene, 4,4'-bis (4-cyano-styryl) stilbene, 4,4'-bis (4-cyano-styrylvir) benzene, 4,4'-bis ( 4-cyano-styrylvir) stilbene, 4,4'-bis (4-isocyano-styryl) benzene, 4,4'-bis (4-isocyano-styryl) stilbene, 4,4'-bis (4-isocyano-styrylvir) ) Benzene, 4,4'-bis (4-isocyano-styrylvir) stilbene, 4,4 '
-Bis (4-formyl-styryl) benzene, 4,4'-bis (4-formyl-styryl) stilbene, 4,4'-bis (4-formyl-styrylvir) benzene, 4,4'-bis (4- Formyl-styrylvir) stilbene, 4,4'-bis (4-carboxy-styryl) benzene, 4,4'-bis (4-carboxy-styryl) stilbene, 4,4'-bis (4-carboxy-styrylvir) benzene 4,4'-bis (4-carboxy-styrylvir) stilbene, 4,4 '
-Bis (4-chloro-styryl) benzene, 4,4'-bis (4-chloro-styryl) stilbene, 4,4'-bis (4-
Chloro-styrylvir) benzene, 4,4'-bis (4-chloro-styrylvir) stilbene, 4,4'-bis (4-nitro-styryl) benzene, 4,4'-bis (4-nitro-styryl) stilbene 4,4'-bis (4-nitro-styrylvir) benzene, 4,4'-bis (4-nitro-styrylvir) stilbene, 4,4'-bis (4-nitroso-styryl) benzene, 4,4 ' -Bis (4-nitroso-styryl)
Stilbene, 4,4'-bis (4-nitroso-styrylvir) benzene, 4,4'-bis (4-nitroso-styrylvir) stilbene, 4,4'-bis (4-amino-styryl)
Benzene, 4,4'-bis (4-amino-styryl) stilbene, 4,4'-bis (4-amino-styrylvir) benzene, 4,4'-bis (4-amino-styrylvir) stilbene, 4,4 '-Bis (4-cyanato-styryl) benzene,
4,4'-bis (4-cyanato-styryl) stilbene
4'-bis (4-cyanato-styrylvir) benzene, 4,
4'-bis (4-cyanato-styrylvir) stilbene,
4,4′-bis (4-isocyanato-styryl) benzene,
4,4′-bis (4-isocyanato-styryl) stilbene, 4,4′-bis (4-isocyanato-styrylvir) benzene, 4,4′-bis (4-isocyanato-styrylvir) stilbene, 4,4′- Bis (4-azido-styryl)
Benzene, 4,4'-bis (4-azido-styryl) stilbene, 4,4'-bis (4-azido-styrylvir) benzene and 4,4'-bis (4-azido-styrylvir) stilbene are exemplified. You.

The organic compounds represented by the chemical structural formula (2) include 4,4′-distyrylbiphenyl,
Styryl-4'-styrylvirbiphenyl, 4,4'-distyrylvirbiphenyl, 4,4'-bis (3,4,5-trimethoxy-styryl) biphenyl, 4- (3,4,5-trimethoxy-styryl ) -4 '-(3,4,5-trimethoxy-styrylvir) biphenyl, 4,4'-bis (3,4,5-trimethoxy
-Styrylvir) biphenyl, 4,4'-bis (3,5-isobutyl-styryl) biphenyl, 4- (3,5-isobutyl-
(Styryl) -4 '-(3,5-isobutyl-styrylvir) biphenyl, 4,4'-bis (3,5-isobutyl-styrylvir) biphenyl, 4,4'-bis (4-ethynyl-styryl) biphenyl, 4 -(4-ethynyl-styryl) -4 '-(4-
Ethynyl-styrylvir) biphenyl, 4,4'-bis (4
-Ethynyl-styrylvir) biphenyl, 4,4'-bis (4-hydroxy-styryl) biphenyl, 4- (4-hydroxy-styryl) -4 '-(4-hydroxy-styrylvir)
Biphenyl, 4,4'-bis (4-hydroxy-styrylvir) biphenyl, 4,4'-bis (4-mercapto-styryl) biphenyl, 4- (4-mercapto-styryl) -4'-
(4-Mercapto-styrylvir) biphenyl, 4,4'-bis (4-mercapto-styrylvir) biphenyl, 4,4 '
-Bis (4-cyano-styryl) biphenyl, 4- (4-cyano-styryl) -4 ′-(4-cyano-styrylvir) biphenyl, 4,4′-bis (4-cyano-styrylvir) biphenyl, 4, 4'-bis (4-isocyano-styryl) biphenyl, 4- (4-isocyano-styryl) -4 '-(4-isocyano
-Styrylvir) biphenyl, 4,4'-bis (4-isocyano-styrylvir) biphenyl, 4,4'-bis (4-formyl-styryl) biphenyl, 4- (4-formyl-styryl) -4 '-(4 -Formyl-styrylvir) biphenyl,
4,4'-bis (4-formyl-styrylvir) biphenyl, 4,4'-bis (4-carboxy-styryl) biphenyl, 4- (4-carboxy-styryl) -4 '-(4-carboxy
-Styrylvir) biphenyl, 4,4'-bis (4-carboxy-styrylvir) biphenyl, 4,4'-bis (4-chloro-styryl) biphenyl, 4- (4-chloro-styryl)
-4 '-(4-Chloro-styrylvir) biphenyl, 4,4'-
Bis (4-chloro-styrylvir) biphenyl, 4,4'-
Bis (4-nitro-styryl) biphenyl, 4- (4-nitro-styryl) -4 '-(4-nitro-styrylvir) biphenyl, 4,4'-bis (4-nitro-styrylvir) biphenyl, 4.4 '-Bis (4-nitroso-styryl) biphenyl, 4- (4-nitroso-styryl) -4'-(4-nitroso-styrylvir) biphenyl, 4,4'-bis (4-nitroso-
Styrylvir) biphenyl, 4,4'-bis (4-amino-
Styryl) biphenyl, 4- (4-amino-styryl) -4'-
(4-amino-styrylvir) biphenyl, 4,4'-bis (4-amino-styrylvir) biphenyl, 4,4'-bis (4-cyanato-styryl) biphenyl, 4- (4-cyanato-styryl) -4 '-(4-Cyanato-styrylvir) biphenyl, 4,4'-bis (4-cyanato-styrylvir) biphenyl, 4,4'-bis (4-isocyanato-styryl) biphenyl, 4- (4-isocyanato-styryl) -4 '-(4-Isocyanato-styrylvir) biphenyl, 4,4'-bis (4-isocyanato-styrylvir) biphenyl, 4,4'
Examples include -bis (4-azido-styryl) biphenyl, 4- (4-azido-styryl) -4 '-(4-azido-styrylvir) biphenyl and 4,4'-bis (4-azido-styrylvir) biphenyl and the like. Is done.

In the chemical formula (1), the number of repetitions n is limited to any integer of 1 to 5, and in the chemical formula (2), the numbers of repetitions m and n are each independently an integer of 1 or more. The reason for limiting the sum to 5 or less is that an organic compound having a repetition number exceeding this range has a sublimation temperature lower than a thermal decomposition starting temperature or a thermal reaction temperature and cannot be subjected to vacuum deposition. . From the viewpoint of suppressing the sublimability of the organic nonlinear optical material and the organic conductive material of the present invention and increasing the stability, the number of repetitions n in the chemical structural formula (1) is 2 or more, and the chemical structure In the formula (2), the sum of the number of repetitions m and n is preferably 3 or more. The functional group at the terminal of the organic compound used as a raw material of the present invention is preferably a functional group such as an ethynyl group or an azide group which can be easily polymerized by a photoreaction or a thermal reaction.

The organic conductive material of the present invention is obtained by dispersing an appropriate electron-withdrawing compound in the organic nonlinear optical material of the present invention. The electron-withdrawing compound dispersed in the organic conductive material of the present invention is not particularly limited, and a compound such as iodine that can be usually used in this technical field can be appropriately selected and used.

The thickness of the organic nonlinear optical material and the organic conductive material of the present invention can be appropriately set according to the purpose of use and the like, but is preferably in the range of 100 ° to 3 μm.
Organic nonlinear optical material and organic conductive material of the present invention,
Under a pressure of at least about 1 × 10 ⁻⁹ Torr or 10 ⁻⁶ Pa, the thermal decomposition start temperature or the thermal reaction temperature is lower than the sublimation temperature, and the thin film is formed by vacuum deposition (film formation).
Can be effectively impossible.

The organic nonlinear optical material according to the present invention has a vinylene group in its molecular structure, and at least one of the vinylene groups is a cis isomer. It can be obtained by irradiating the thin film with light to convert all vinylene groups present in the organic compound into a trans form by a photoisomerization reaction. This organic nonlinear optical material is amorphous or crystalline. The photoisomerization from the cis-form to the trans-form can be carried out simultaneously with thinning by vacuum evaporation.

The photoisomerization is not particularly limited, but is usually performed under a pressure of 1 × 10 ⁻⁶ to 1 × 10 ⁻¹⁰ Torr, preferably 1 × 10 ⁻⁸ to 1 × 10 ⁻¹⁰ Torr. ,
On a substrate kept at a constant temperature in the temperature range of 20 to 100 ° C., preferably 40 to 60 ° C., 0.1 to 10 mJ / cm ^2.
Irradiation energy of pulse, preferably 1 to 5 mJ / cm ² · pulse and 1 to 30 Hz, preferably 1 to 10 H
The irradiation can be performed by irradiating light having a wavelength of 190 to 500 nm, preferably 250 to 500 nm, which is set to an oscillation frequency of z. As a light source, for example, K
rF excimer laser, ArF excimer laser, XeF excimer laser, XeCl excimer laser, mercury lamp,
A xenon lamp or the like can be used. Generally, the total light irradiation amount is set to about 10 to 50 J / cm ² . Further, after the photoisomerization reaction, it is preferable that all cis-forms initially present become trans-forms, but the organic nonlinear optical material of the present invention is not limited thereto.
Those in which a part of the originally existing cis form remains may be included in the present invention. In addition, the photoisomerization reaction of a phenylenevinylene derivative is a one-way isomerization reaction, and the state in which all of the isomers in which all vinylene groups are in the trans form is in a steady state is a steady state. Can stably maintain the trans form.

The polymerizable organic nonlinear optical material is obtained by polymerizing the amorphous or crystalline organic nonlinear material produced as described above. This polymerization is generally performed by thermal polymerization or photopolymerization. The isomerization reaction can be carried out simultaneously using the same or another means, or separately. Further, an organic conductive material obtained by dispersing the electron-withdrawing compound in the organic nonlinear optical material of the present invention can be obtained by vapor-depositing the electron-withdrawing compound and dispersing the electron-withdrawing compound in the thin film simultaneously with thinning by vacuum deposition. Can be.

[0032]

The present invention will be described below with reference to examples.
The present invention is not limited in any way by the following examples. Example 1 cis, cis-4,4'-bis (4-ethynylstyryl) benzene in which all vinylene groups are cis (hereinafter referred to as cis, cis-
Abbreviated as BESB. Compound No. (1) in Table 1 below) was accommodated in a Knunsen cell (K cell), and the degree of vacuum was 10 ^-6 P
A molecular beam was generated by heating and sublimation in a vacuum chamber of a or less. Irradiation energy 4mJ
/ cm ² · Kr set to pulse and oscillation frequency 5Hz
By irradiating the molecular beam to a quartz glass substrate maintained at a constant temperature of 45 ° C. to 60 ° C. while irradiating an F excimer laser, a thin film having a thickness of about 1000 ° was deposited on the substrate. The total light irradiation during deposition was set to 40 J / cm ² .

All cis, cis-BESB are converted to trans, trans-4,4'-bis (4-ethynylstyryl) by photoisomerization.
The change to benzene (hereinafter abbreviated as trans, trans-BESB) was confirmed by an infrared absorption spectrum. FIG. 1 shows the infrared absorption spectrum. As described above,
A crystalline thin film of trans, trans-BESB was obtained. Next, the THG characteristics of this thin film were evaluated by a maker fringe method using a YAG laser (1.06 μm). Table 1 below shows the structural formulas of the organic compounds used as raw materials in this example, the following examples and the following comparative examples, and Table 2 below shows the THG characteristics of the produced organic nonlinear optical materials.

[0034]

[Table 1]

[0035]

[Table 2]

[0036]

[Table 3]

[0037]

[Table 4]

[0038]

[Table 5]

As shown in Table 2 above, the thin film of this example exhibited a high Δ ⁽³⁾ . FIG. 2 shows how the χ ⁽³⁾ value of the thin film changes according to the amount of light irradiation. The maker fringe method used here is a method generally used to evaluate a thin film material, and determines χ ⁽³⁾ of a test sample in comparison with a standard sample (quartz single crystal). Furthermore, in this method, the sample is rotated with respect to the incident light,
By performing a combination of setting the polarization of the incident light and the emission TH light to be P-polarized light or S-polarized light, it is possible to determine each component of the nonlinear optical constant tensor.

Examples 2 to 26 In the same manner as in Example 1 except that all the vinylene groups of the organic compounds shown in Table 1 as compound numbers (2) to (26) were cis isomers. The thin films were prepared by the above method, and the values of χ ⁽³⁾ of the thin films were measured. As shown in Table 2, high χ ⁽³⁾ values were obtained for all the thin films.

Comparative Examples 1-26 Isomers in which all vinylene groups are trans isomers of the organic compounds shown in Table 1 as compound numbers (1) to (26) were subjected to the same vacuum deposition as in Example 1. Was served. But,
When heated in a vacuum chamber having a degree of vacuum of 10 ⁻⁶ Pa or less, all organic compounds started to decompose before sublimation occurred.

Comparative Example 27 cis, cis-BES which is an organic compound represented by the compound number (1) in the above Table 1 and in which all vinylene groups are cis isomers
B is accommodated in a Knunsen cell and heated and sublimated in a vacuum chamber having a degree of vacuum of 10 ⁻⁶ Pa or less.
A molecular beam was generated. By irradiating this molecular beam onto a quartz glass substrate, a film thickness of 1000
A crystalline thin film was deposited. Χ ⁽³⁾ of this thin film was measured in the same manner as in Example 1. As a result, as shown in Table 2, only an extremely low χ ⁽³⁾ value was obtained.

Comparative Examples 28 to 52 In the same manner as in Comparative Example 27, using the isomers in which all vinylene groups are cis isomers of the organic compounds shown in Table 1 as Compound Nos. (2) to (26). When a thin film was prepared by using the method described above and the χ ^{(3) of the} thin film was measured, as shown in Table 2, only extremely low χ ⁽³⁾ values were obtained for all the thin films.

Example 27 A trans-trans-BESB crystalline thin film produced in the same manner as in Example 1 was irradiated with a KrF excimer laser set at an irradiation energy of 4 mJ / cm ² · pulse and an oscillation frequency of 20 Hz. The total light irradiation amount was set to 400 J / cm ² . After irradiation, [pi-[pi * the absorption lambda _max is shifted to the long wavelength side, and since the thin film is insolubilized, the polymerization reaction was confirmed that progressed. FIG. 3 shows an ultraviolet-visible absorption spectrum measured at the end of 400 J / cm ² irradiation. When χ ⁽³⁾ of this thin film was measured in the same manner as in Example 1, a high χ ⁽³⁾ value was obtained as shown in Table 2 above.

Examples 28 to 34 KrF excimer laser was irradiated to the crystalline thin film prepared in the same manner as in Examples 2 to 8 under the same conditions as in Example 27. When χ ⁽³⁾ of these thin films was measured after irradiation,
As shown in Table 2, higher in all of the thin film chi ⁽³⁾
The value was obtained.

Example 35 In the same manner as in Example 1, cis, cis-BESB was accommodated in a Knunsen cell, and heated in a vacuum chamber having a degree of vacuum of 10 ⁻⁶ Pa or less to sublimate the molecular beam. Occurred. While irradiating a KrF excimer laser set to an irradiation energy of 4 mJ / cm ² · pulse and an oscillation frequency of 5 Hz, and a molecular beam of iodine, the cis, cis-BESB molecular beam is kept at a constant temperature between 45 ° C and 60 ° C. By irradiating the gold comb-shaped electrode substrate with a film thickness of 1000
About の thin films were deposited. Total light irradiation during deposition is 40J
/ cm ² . It was confirmed by infrared absorption spectrum that all cis, cis-BESB was changed to trans, trans-BESB by photoisomerization reaction. Thus, a trans, trans-BESB crystalline thin film in which iodine was dispersed was obtained. Iodine in the thin film acts as an electron-withdrawing dopant. FIG. 4 shows the I- of the thin film of this example doped with iodine.
The V characteristics are shown in comparison with a thin film not doped with iodine. FIG. 4 shows that the iodine-doped thin film exhibits excellent conductivity.

Example 36 A crystalline thin film of cis, cis-4,4'-bis (4-ethynyl-styryl) biphenyl was obtained in the same manner as in Example 35. When the IV characteristic was measured, a high characteristic value was obtained as in Example 35.

[0048]

The organic nonlinear optical material of the present invention has a vinylene group in the molecular structure, and the vinylene group is all in a trans form. Since they are formed of a united structure and have a planar structure and a long π-conjugated length, they have an effect of being excellent in non-linear optical characteristics and electric conductive characteristics. Also,
Since the organic conductive material of the present invention is also obtained by dispersing an electron-withdrawing compound in the organic nonlinear material of the present invention, it has an effect of being excellent in nonlinear optical characteristics and electric conductive characteristics. Since these materials according to the present invention can be manufactured without using special equipment and raw materials, there is also an effect that a product exhibiting excellent characteristics can be provided at low cost.

[Brief description of the drawings]

FIG. 1 is a diagram showing an infrared absorption spectrum of a crystalline thin film of trans, trans-BESB. Each spectral line shows a KrF excimer laser at 0, 1, 10, and 40 J /
It was measured at the time of irradiation with cm ² .

Fig. 2 Crystalline thin film of trans, trans-BESB
FIG. 3C is a diagram illustrating a state of a change in (3) value according to a light irradiation amount.

FIG. 3 is a view showing an ultraviolet-visible absorption spectrum measured after polymerizing a crystalline thin film of trans, trans-BESB. Each spectral line indicates, in order from the bottom, the total light irradiation of a KrF excimer laser during polymerization. 0, 100 and 400 J /
It is a measurement of a thin film obtained by setting to cm ² .

FIG. 4 IV of a crystalline thin film of trans, trans-BESB
It is a figure which shows a characteristic, and shows the thin film which doped iodine and the thin film which is not doped with iodine in comparison.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication location C23C 14/12 C23C 14/12 (72) Inventor Makoto Tsunoda 2-3-2 Marunouchi, Chiyoda-ku, Tokyo No. Mitsubishi Electric Corporation

Claims (19)

[Claims] An organic compound having a non-linear optical property and / or a polymer of the organic compound, wherein the organic compound has a vinylene group in the molecular structure, and the vinylene group is all in a trans form. Organic nonlinear optical material. 2. The organic nonlinear optical material according to claim 1, wherein the organic nonlinear optical material is a thin film having a thickness of 100 to 3 μm. 3. The organic nonlinear optical material according to claim 1, wherein the organic compound is a phenylene vinylene derivative, and all vinylene groups are in a trans form. 4. The organic compound has the following chemical structural formula (1): Wherein R ₁ and R ₂ are each independently a hydrogen atom,
Halogen atom, carboxyl group, hydroxyl group, mercapto group, nitro group, nitroso group, amino group, cyano group, isocyano group, cyanato group, isocyanato group, azide group, or alkyl group, alkenyl group, alkynyl group having 5 or less carbon atoms , An ether group, an ester group or an acyl group, and n is an integer of any of 1 to 5. The organic nonlinear optical material according to claim 3, wherein all the vinylene groups in the formula are an organic compound in a trans form. 5. The method according to claim 1, wherein the organic compound has the following chemical structural formula (2): Wherein R ₁ and R ₂ are each independently a hydrogen atom,
Halogen atom, carboxyl group, hydroxyl group, mercapto group, nitro group, nitroso group, amino group, cyano group, isocyano group, cyanato group, isocyanato group, azido group or an alkyl group having 5 or less carbon atoms, alkenyl group, alkynyl group, An ether group, an ester group, or an acyl group, m and n are each independently an integer of 1 or more, and the sum of m and n is 5 or less. The organic nonlinear optical material according to claim 3, wherein all the vinylene groups in the formula are an organic compound in a trans form. 6. An organic compound which is a phenylene vinylene derivative and has at least one cis vinylene group,
It is made into a thin film by vacuum evaporation, and a wavelength of 500 n
m, wherein all cis-vinylene groups present in the organic compound are subjected to photoisomerization to trans-vinylene groups by irradiation with light having a wavelength of m or less, wherein the organic compound is formed by photoisomerization. 5. The organic nonlinear optical material according to any one of 5. 7. The organic nonlinear optical material according to claim 6, wherein the thinning by vacuum deposition and the photoisomerization reaction are simultaneously performed. 8. The method according to claim 1, wherein a thermal decomposition temperature is lower than a sublimation temperature under a pressure of 1 × 10 ⁻⁹ Torr or less.
The organic nonlinear optical material according to claim 1. 9. The organic nonlinear optical material according to claim 1, wherein a thermal reaction initiation temperature is lower than a sublimation temperature under a pressure of 1 × 10 ⁻⁹ Torr or less. 10. The organic nonlinear optical material according to claim 1, wherein the organic nonlinear optical material is crystalline. 11. The organic nonlinear optical material according to claim 1, which is a polymer polymerized by heat or light. 12. An organic conductive material, wherein an electron-withdrawing compound is dispersed in the organic nonlinear optical material according to any one of claims 1 to 11. 13. The organic conductive material according to claim 12, wherein the dispersion of the electron-withdrawing compound and the thinning of the raw material compound of the organic nonlinear optical material are simultaneously performed by vacuum deposition. Material. 14. An organic compound having a non-linear optical property, having a vinylene group in a molecular structure and at least one of the vinylene groups being a cis-form, is thinned by vacuum deposition, and the thin film is irradiated with light to form the thin film. A method for producing an organic nonlinear optical thin film material, wherein all vinylene groups present in an organic compound are converted into a trans form by a photoisomerization reaction. 15. An organic compound having a non-linear optical property, which has a vinylene group in a molecular structure and at least one of the vinylene groups is a cis isomer, is thinned by vacuum deposition, and an electron-withdrawing compound is vapor-deposited. Dispersing the electron-withdrawing compound in the thin film, irradiating the thin film with light, and converting all vinylene groups present in the organic compound into a trans form by a photoisomerization reaction. Manufacturing method of thin film material. 16. The organic compound according to claim 14, wherein the organic compound is a phenylene vinylene derivative and has at least one cis-vinylene group.
16. The method according to any one of claims 15 to 15. 17. The phenylene vinylene derivative according to claim 16, wherein the phenylene vinylene derivative is represented by the chemical structural formula (1) according to claim 4 or the chemical structural formula (2) according to claim 5. Method. 18. The method according to claim 1, wherein the thinning by vacuum deposition and the photoisomerization reaction are performed simultaneously.
18. The method according to any one of 4 to 17. 19. The method according to claim 14, further comprising polymerizing the thin film by heat or light.
9. The method according to any one of items 8.