JPS61167930A - Production of material for non-linear optical element which can be patterned and non-linear optical element - Google Patents

Abstract

PURPOSE:To make possible fine working by high energy rays with less light injuries and to improve mechanical strength by using a material which is expressed by the specific formula and can be patterned. CONSTITUTION:The material expressed by the formula is used as the material for the non-linear optical element which can be patterned. The above-mentioned optical element is produced by dissolving the material for the non-linear optical element in a suitable solvent and coating the resultant soln. by a spin coating method, spray method, etc. on a substrate on which an optical waveguide is formed. The substrate is then prebaked by an electric furnace, IR heating, etc. in a dry atmosphere, by which the org. solvent in the film is removed and the adhesiveness to the substrate is improved. The pattern is then backed by the irradiation of far UV rays or X-rays through a mask or the direct irradiation of electron rays and ion beam thereon. The backed pattern is developed with a suitable developing soln. and is washed and thereafter the pattern is post-baked to have the higher adhesiveness and to remove the solvent picked up during the development. The element is thus made less susceptible to the injury by light and the mechanical strength thereof is much improved as compared with a low-molecular org. compd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a patternable material for a nonlinear optical element and a method for manufacturing a nonlinear optical element using the same.

[Prior art and its problems]

Conventionally, nonlinear optical elements have been developed by fixing an inorganic or organic crystal that exhibits optical nonlinearity on a vibration isolating table using a holder, etc., and injecting a laser beam into the crystal to produce a light rectification effect, light mixing, Kamo's work utilized nonlinear optical effects such as the generation of second and third harmonics to function as an active optical device. However, when such an optical system is assembled, the system as a whole becomes large, and
However, by creating an optical waveguide on the substrate and incorporating a nonlinear optical material into it, these drawbacks can be eliminated. (This becomes possible.

However, when increasing the density of optical waveguides to form optical integrated circuits, fine nonlinear optical materials are added to the necessary parts of the circuit.
Incorporating one is quite difficult. Therefore, it is essentially impossible to fabricate high-density optical integrated circuits by incorporating nonlinear optical materials in irregularly formed optical waveguides.

On the other hand, as a nonlinear optical material, LINb (
Inorganic crystals such as J3 have been used most often, but organic crystals such as benzene derivatives and stilbene derivatives are attracting attention as materials with significantly higher nonlinearity than these. However, these organic compounds have drawbacks such as being easily damaged by laser light and having poor mechanical strength, which prevents their application to nonlinear optical elements. The purpose of the invention is to solve these drawbacks, to enable microfabrication using high-energy beams, to reduce photodamage, and to
The object of the present invention is to provide a nonlinear optical material with excellent mechanical strength.

Furthermore, another object is to provide a method for producing a nonlinear optical element using the material.

Third Means for Solving Problem C] In view of the current state of organic nonlinear optical element materials and nonlinear optical element manufacturing methods, the present inventors have conducted various studies to solve the conventional problems. As a result of the research, it was possible to achieve the above-mentioned objective by introducing a material for nonlinear optical elements of living organisms into polymers that are sensitive to high energy rays, and making it possible to pattern with high energy rays. fl:, t) E2 found to be extremely effective,
Completed the invention.

That is, the /9 turnable nonlinear optical element material of the present invention has the following general formula 1, where 88 is hydrogen, halogen, or methyl group, R8 is water f1 aromatic group, t or furkyl group, R .

is aromatic group, substituted aromatic group, pyridine base, nitro group,
r represents an aromatic group, X represents a halogen, and 1 represents a helogenated alkyl group; is Ol or a positive integer, ! II,
n indicates a positive integer.

It is characterized by the following.

The material VcN for nonlinear optical elements of the present invention is m and n.
The ratio of *VC* is as follows, but the halogen group sensitive to high energy rays is the ^rodan 1-furkyl group (general f:, (1
)) shows sufficient practical sensitivity with 20 mol % of stripes.

In the material of general formula (I), examples of the alkyl group of R2 include methyl group, ethyl group, butyl group, butyl group, etc., and examples of the aromatic group include phenyl group, naphthyl group, methyl group, etc. Killers include phenyl groups, carbazole groups, etc. Furthermore, examples of the halogenated alkyl group of X include pa-miromethyl, bromomethyl group, methyl iodide group, chromityl group, and chloropropyl group. Examples of the aromatic group and substituted aromatic group for R3 include a phenyl group, a naphthyl group, a methylphenyl group, a carbazole group, a ria-rophenyl group, a nido-a-phenyl group, and a nitrophenylethyl group. The ttl pyridine base includes the overbasic acid group of N-methylpyridine, the cinnamate of N-methylpyridine, the heptafluoroborate of N-methylpyridine, the rhenium salt of N-methylpyridine, and the rhenium salt of N-methylpyridine. Examples include methylsulfonate of methylpyridine and methylsulfonate of N-methylpyridine.

According to the present invention, there is also provided a method for manufacturing a nonlinear optical element, in which a material for a nonlinear optical element that can be patterned is coated on a substrate, and after patterning is irradiated with high-energy rays, the material is coated and placed at a desired position. When manufacturing an optical waveguide-shaped nonlinear optical element by forming a nonlinear optical material having a desired shape on a substrate, use a patternable nonlinear optical element material represented by the above general formula ()l. It is characterized by

Further, high-energy rays that can be used in patterning include deep ultraviolet rays, X-rays, electron beams, and ion beams, and the material of the present invention functions as a negative type with respect to these high-energy rays.

The method for producing the material for nonlinear optical elements of the present invention is as follows: General formula + CH2-C-)-(1) Ar ■ In the formula, R1 is hydrogen, halogen or a methyl group, Ar is an aromatic group, and X is a halogen or Indicates a halogenated alkyl group.

In the general formula, R, Fi, hydrogen, an aromatic group, or an alkyl group, using potassium carbonate as a catalyst in an organic polymer represented by
R3 represents an aromatic group, a substituted aromatic group, a pyridine base, or a nitro group.

It can be obtained by reacting the compound shown below.

Further, it may be copolymerized with a monomer of the compound of general formula 1.

Furthermore, the organic polymer of the general formula 1 can be obtained by polymerizing its monomers, Ar In the formula, R□ is hydrogen, the halogen te is a methyl group, and %Ar is an aromatic group.

It can also be obtained by introducing a halogen or a halogenated methyl group into the organic polymer represented by.

In the method for manufacturing a nonlinear optical element of the present invention, first,
The material for a nonlinear optical element of the present invention is dissolved in a suitable solvent on a substrate on which an optical waveguide is formed, and the resulting solution is applied by a spin code method, a spray method, or the like. Next, the film is prebaked in a dry atmosphere using an electric furnace, infrared heating, etc. to remove the organic solvent in the film and improve its adhesion to the substrate. The pattern is then printed by irradiation through a mask with deep ultraviolet rays, X-rays, or directly with electron beams or ion beams, and then with a suitable liquid, e.g.
The pattern is washed with a solvent such as methyl ethyl ketone, xylene, or a mixed solvent of these with isopropyl alcohol or cyclohexane, and then a boost bake is performed to further improve the adhesion of the pattern and to remove the solvent in the current coating.

According to the present invention, a nonlinear optical material of a desired size can be placed at a desired position on a substrate having an optical waveguide. Since the material of the present invention has high sensitivity to high-energy radiation and excellent decomposition properties, it can be used with sufficient productivity even when it is highly densified and becomes an optical integrated circuit.

Furthermore, we have discovered that materials exhibiting nonlinearity solidify through crosslinking and become organic polymers, which retain the high nonlinearity of organic materials and are less susceptible to damage by light. It can be significantly improved compared to organic compounds.

Hereinafter, the present invention will be explained in more detail with reference to Production Examples and Examples, but the scope of the present invention is not limited in any way by these Examples.6 Production Example 1 Chloromethylated constant polystyrene C TOYOBEAM-EX,
A mixture of Toyo 1 and 13 gsp was dissolved in 3 g of p-aminodiphenyl diacetylene and 11 um of carbon dioxide and 50 g of t-N,N-dimethylformamide and reacted at 60°C for 8 hours. The resulting deep red solution was mixed with water-methanol=3=
By pouring into the mixed solvent of 1 to precipitate the polymer, washing the polymer with water and methanol, and vacuum drying,
A good friend of polymers.

) Conventional Examples 2 to 7 In Production Example 1, s'9-'N-methylamino)diphenylacetylene (#Unusual Example 2), p -(N-methylamino)-
p'-Chlorodiphenylacetylene C type preparation example 3), p-
Amino-p'-diphenylacetylene (Production Example 4)
1, p-(N-methyamino)-p'-nitrodiphenylacetylene C Production Example 51.1-2) ct-2-(p-
(N-methylamino)phenyl)acetylene tIJ Typical 61.1-(p-nitro)phenyl-4-(P-(N-
Using methylamino)phenyl)butadiin C Production Example 7), the same operation as in Production Example 1 was carried out to obtain a polymer.

Production Examples 8 to 12 In Production Example 1, N-methyl-p-(2-(p'-N-methylanilino-1-ethynyl)pyridinicum perchlorate C Production Example 8) was used instead of p-aminodiphenylacetylene. , N-methyl-p-(2-(p' -N-methylanilino)ethynyl)bi-11dinium perchlorate cinnamate C Preparation Example 9), N-methyl-p-(2-(p' −
N-Methylanilino)ethynyl)pyridinium heptafluoride boronate C2), N-methyl-p-(2-(
p'-N-/chiruayu 11]) ethynyl) pyridinium rhenate (i customary 11), N-methyl-p-r2
-(p'-N-Methyanilino)ethynyl)pyridinium methylsulfone manufactured by C. (Example 12) was used and the same procedure as in Production Example 1 was carried out to obtain a polymer.

Production Examples 13 to 17 In Production Example 5, p-(N-methylaki))-p'-
The amount of diphenylacetylene charged was 0.5g (Production Example 13)%, 1-Og (Production Example 14), 1.
5g (Production Example 15), 2.0g (Production Example 16), 2.5
g (Production Example 17), the same operation as in Production Example 7 was carried out, and polymer f! -Gain7'j.

5j! Examples 1 to 17 The t-polymers obtained in Production Examples 1 to 17 were dissolved in methyl isobutyl ketone, applied to a 5 in 2 substrate on which a waveguide was formed, and prebaked at 100° C. for 30 minutes in a N 2 stream. After that, the pattern was burnt by irradiating electrons and beams with an acceleration voltage of 20 KV, and was developed with a 1:1 mixed solvent of methyl ethyl ketone and inopropyl alcohol. However, the polymer in the area irradiated with the electron beam remained and the conductive material remained. A nonlinear optical material with a film thickness of 20 μm11 and a length of 1lIIJ was formed at the desired position of the wave path. Next, wavelength 1.
064 μm.

Output IKW Nd: When the YAG laser is passed through a nonlinear optical material, the second harmonic wavelength is 0.532μ.
Light of m was observed.

Table 1 shows the electron beam irradiation amount and second harmonic output required for pattern formation. However, the output of the second harmonic is shown as a relative value to the case t when urea powder is incorporated into the same waveguide.

Practical examples 18 to 20 In Example 5, R1 on the polymer main chain was replaced with hydrogen, methyl group C Practical example 18), chlorine [Example 19),
Three types of polymers containing bromine C (Example 20) were patterned onto the same optical waveguide t-8iO□ as in Examples 1 to 17, and the generation of the second harmonic was observed.

The results are shown in Table 2.

Table 2 Actual Examples 21 to 23 In Example 1, instead of the electron beam, xmr Example 21
), deep ultraviolet II (Example 22), and ion beam C (Example 23), a pattern was formed in the same manner as in Example 1. At this time, the irradiation amount of high-energy rays necessary for pattern formation was as shown in Table 3).

[Effects of the Invention] As explained above, the patternable material for nonlinear optical elements according to the present invention has high sensitivity to high-energy radiation. can be patterned.

Moreover, the material itself is highly nonlinear,
Furthermore, it is not susceptible to optical damage and has excellent mechanical strength C:.

Therefore, the material and manufacturing method of the present invention have an extremely large effect on the production of waveguide-type nonlinear optical elements and, ultimately, integrated circuits.

Claims (1)

[Claims] 1) The following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the formula, R_1 is hydrogen, halogen, or a methyl group, R_
2 is hydrogen, aromatic group, or alkyl group, R_3 is aromatic group, substituted aromatic group, pyridine base, nitro group, Ar
represents an aromatic group, X represents a halogen or a halogenated alkyl group, l represents 0 or a positive integer, and m and n represent positive integers. A patternable nonlinear optical element material characterized by: 2) A nonlinear optical material that can be patterned is coated on a substrate, irradiated with high-energy rays in a pattern, and then developed to form a nonlinear optical material having a desired shape at a desired position on the substrate. In the method of manufacturing a wave-shaped nonlinear optical element, the following general formula ▲ mathematical formula, chemical formula, table, etc. are used as patternable nonlinear optical materials ▼ In the formula, R_1 is hydrogen, halogen, or methyl group, R_
2 is hydrogen, aromatic group, or alkyl group, R_3 is aromatic group, substituted aromatic group, pyridine base, nitro group, Ar
represents an aromatic group, X represents a halogen or a halogenated alkyl group, l represents 0 or a positive integer, and m and n represent positive integers. A method for manufacturing a nonlinear optical element, characterized by using a material shown in . 3) As high-energy rays, far ultraviolet rays, X-rays, electron beams,
3. The method of manufacturing a nonlinear optical element according to claim 2, wherein an ion beam is used.