JPH01185527A - Nonlinar optical material - Google Patents

Abstract

PURPOSE:To obtain a novel org. compd. which exhibits a high nonlinear optical effect by consisting the title material of a specific heterocyclic compd. CONSTITUTION:This optical material consists of the compd. expressed by the formula I. In the formula I, R1, R2 denote a substd. or unsubstd. alkyl group, substd. or unsubstd. aryl group, substd. or unsubstd. amino group, arom. group contg. a substd. or unsubstd. heteroatom, -CH=CH-nR3, etc., which may be the same or different; Z denotes O, S, NH. The substd. or unsubstd. alkyl groups of low carbon numbers such as methyl group, ethyl group and butyl groups are more preferably but the number of carbon atoms. is generally not limited. The novel high-performance org. compd. which exhibits the nonlinear optical effect is thereby obtd.

Description

[Detailed Description of the Invention] [Technical Field] The present invention relates to an electro-optical device, a second harmonic generation device,
The present invention relates to novel nonlinear optical materials useful for piezoelectric devices, optical waveguides, etc., optical memory light sources, laser printer light sources, optical switches, etc.

[Prior art] In recent years, materials that have a nonlinear optical effect - a phenomenon in which when intense laser light is incident on a material, an emitted light with a different component from the incident light is obtained due to the interaction - have attracted attention. . Such materials are generally known as nonlinear optical materials and are described in detail in, for example:

“Nonliner Optical Prope
rties or Organicand Poly
meric Materlls” A CS SYM
PO3ILIMSIEl? IIES 233. Davj
d J, W1111ams (AmericanChe
liical 5ociety, 1983), "Organic Nonlinear Optical Materials" edited by Masao Kato and He Nakanishi (CMC Publishing Co., Ltd., 1983), "Organic Electronic Materials" edited by Akio Taniguchi (Science Forum Co., Ltd., 1986).
Annual publication).

One of the applications of nonlinear optical materials is second harmonic generation (SHG) based on second-order nonlinear optical effects and wavelength conversion devices using sum frequency and difference frequency. Potassium dihydrogen phosphate (K
DP), ammonium dihydrogen phosphate (ADP), lithium niobate, and the like. However, in recent years, it has become known that π-electron conjugated slave compounds having an electron-donating group and an electron-withdrawing group have various performances as nonlinear optical materials that far exceed those of the above-mentioned inorganic materials.

In general, the nonlinear optical performance of a molecule is determined by its molecular hyperpolarizability: β
(molecular hyperpolarzab
Although it depends on the magnitude of the When crystallized, many molecules do not exhibit any second-order nonlinear optical effects in their crystalline state because their molecular arrangement has central symmetry. In addition, MNA (2-methyl-4 Nitroaniline) has a large SHG density d 11 [B, P, Levlne, eL al, J.

Appl, Phys, 50.2523 (I970)],
Since this component does not satisfy the phase matching condition for efficiently extracting SHG, it is difficult to effectively utilize this large nonlinear optical performance.

Furthermore, it is difficult to obtain a single crystal of MNA, and there are many problems in applying it as a device.

In addition, asymmetric carbon atoms are introduced into known SHG active skeletons [
: J, L, Oudar, et al, J, Appl P
hys, 48°2699 (I977)], and methods such as dispersing high-performance molecules in polymers and poling them using an electric field (Japanese Patent Application Laid-open No. 188942/1983) have not necessarily yielded good results. Not yet.

[Objective] In view of the above circumstances, the object of the present invention is to provide a novel organic compound exhibiting a high nonlinear optical effect.

[Structure] In order to solve the above-mentioned problems, research has been carried out in the past, and it was discovered that a specific heterocyclic compound is effective, leading to the present invention.

That is, the present invention is a nonlinear optical material characterized by comprising a compound represented by the following general formula (I).

General formula (I) [However, R1 and R2 may be the same or different, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted amino group, substituted or unsubstituted hetero Represents an aromatic group containing an atom, an unsubstituted aryl group, and R4
represents a hydrogen atom, a substituted or unsubstituted alkyl group, and n
represents l or 2, m represents an integer from 1 to 5), and
represents O,5SNH] The substituted or unsubstituted alkyl group is preferably one having a low carbon number such as a methyl group, ethyl group, or butyl group, but the number of carbon atoms is generally not limited.

It also includes cases where a substituent is introduced that does not significantly affect the electron donating property of the alkyl group (for example, a 4-chlorobutyl group).

Examples of the substituted or unsubstituted amino group include an alkylamino group, a dialkylamino group, a diphenylamino group, a dibenzylamino group, a di-4-alkylphenylamino group, and a di-4-alkoxyphenylamino group.

The substituted or unsubstituted aryl has the following general formula (I
Particularly preferred are compounds represented by I) or (II[).

In the formula, q is an integer of 1 or 2, and p is an integer of 1 to 5. Furthermore, R5 and R6 are hydrogen atoms, alkyl groups, amino groups,
Examples include an alkoxycarbonyl group, an aryloxycarbonyl group, an alkoxy group, an aryloxy group, an aryl group, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, and a halogen atom. In addition, the phenyl group in the formula includes a benzene ring,
The indole ring or the like may be fused.

Here, examples of the alkyl moiety of the alkyl group include the same alkyl groups as mentioned above.

Aryl moieties such as aryl groups include phenyl group, 4-
Alkylphenyl group, 4-alkoxyphenyl group, 4-
Examples include halogenated phenyl groups. Examples of the amino group include those mentioned above. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The aromatic group containing a hetero atom is preferably represented by the general formula (rV) or (V).

In the formula, Zl, Z2, Z3, Z 4 , Z s SZ & represent a c-y4.0 atom, a N atom, or an S atom.

Y has the same meaning as R5 or R6 above.

Furthermore, a benzene ring or the like may be condensed to the 6-membered ring or the 5-membered ring in the formula.

Among the above-mentioned compounds, R
1. It is preferable that R2 is the above aryl group, the blade m is the same as above), and X is O. In particular, for the above aromatic group, an aromatic group having 1 or 2 N atoms as heteroatoms is preferable. A family group is preferable.

Next, preferred examples of compounds in the present invention will be shown, but the present invention is not limited thereto.

t Next, the present invention will be explained in detail based on examples.

The above compound can be produced by dehydration condensation of hydrazine and the corresponding aromatic carboxylic acid derivative, or by JP-A-51-128971.
JP-A-52-139063, JP-A-52-139084
, JP-A-52-139085 or JP-A-52-13
This can be easily carried out by the method described in, for example, 9068.

[Example] The nonlinear optical performance of the compound was measured.

Second harmonic generation (
SHG) was measured by S, K, Kurtz and T, T, P.
erry is J, Appl, Phys, 39.3798 (
The method was published in 1968). In this method, the compound powder to be measured is irradiated with a strong laser beam, and the intensity of the generated SHG is measured against a reference material.
Approximate second-order nonlinear performance can be estimated.

We used a high-power Nd":YAG laser (250J/pulse, pulse width ~20ns) as the light source laser.The oscillation wavelength of the Nd":YAG laser is 1.084.
μm, and when this light is irradiated on SHG active material, 5
(32 nm green SHG is obtained) SHG from the sample filled in the quartz glass cell is scattered and seen on both sides of the front and back with respect to the laser beam traveling direction, so the SHG intensity is was measured. The detector at this time is a photomultiplier tube, which cuts the laser light with an infrared absorption filter, and an interference filter that cuts the laser beam at 532 ns.
Only HG was taken out.

At this time, the particle size of the sample was not screened, and the reference material was urea with an average particle size of about 100 microns.

Otori NH4H2PO4 As is clear from the examples, the compound of the present invention is effective as a nonlinear optical material, and for example, by making this material into a single crystal, it can be applied to an SHG device as shown in FIG.

[Effects] As explained above, the present invention makes it possible to provide a novel high-performance nonlinear optical material.

[Brief explanation of the drawing]

FIG. 1 is a diagram schematically showing an example of an SHG device using the nonlinear optical material of the present invention. 1... Semiconductor laser, 2... Single crystal of the present invention material.

Claims (1)

[Claims] A nonlinear optical material comprising a compound represented by the following general formula (I). General formula (I) ▲ Numerical formula, chemical formula, table, etc. ▼ [However, in the formula, R_1 and R_2 may be the same or different, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or an unsubstituted amino group, an aromatic group containing a substituted or unsubstituted heteroatom, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R_3 is substituted or unsubstituted. represents an aryl group, R_4 represents a hydrogen atom, a substituted or unsubstituted alkyl group, n represents 1 or 2, m represents an integer of 1 to 5), X represents O, S, NH]