KR20050051289A - 2-(3-[2-(9-decyl-9h-carbazole-3-yl)-vinyl]-5,5-dimethylcyclohex-2-enylidene)malononitrile and its preparing method - Google Patents

Abstract

The present invention is represented by the following general formula (1), and having both photoconductivity and nonlinear optical properties at the same time including a carbazole having a characteristic that can be used as an excellent photorefractive material 2- {3- [2- (9-decyl-9H- Carbazol-3-yl) -vinyl] -5,5-dimethylcyclohex-2-enylidene} malonononitrile and a process for preparing the same:

Description

2- (3- [2- (9-decyl-9H-carbazol-3-yl) -vinyl] -5,5-dimethylcyclohex-2-enylidene) malononnitrile and its preparation method {2- (3- [2- (9-Decyl-9H-carbazole-3-yl) -vinyl] -5,5-dimethylcyclohex-2-enylidene) malononitrile and its preparing method}

The present invention is represented by the following general formula (1), and having both photoconductivity and nonlinear optical properties at the same time including a carbazole having a characteristic that can be used as an excellent photorefractive material 2- {3- [2- (9-decyl-9H- Carbazol-3-yl) -vinyl] -5,5-dimethylcyclohex-2-enylidene} malononnitrile and a method for producing the same.

[Formula 1]

In general, all molecules have an induced dipole moment under the influence of an external electric field, where the induced dipole moment of the molecule due to the external electric field can be expressed by Equation 1 below.

In Equation 1, E is the intensity of the external electric field, α is linear polarizability, β and γ are primary and secondary hyperpolarizability, respectively, and μ is microscopically one molecule. When the full length E is applied at, it is the induced dipole moment of the molecule.

P, the macroscopic polarization that appears when the electric field E is applied to a nonlinear optical material, is given by Equation 2 below.

In Equation 2, χ ⁽¹⁾ is linear susceptibility, χ ⁽²⁾ is second order nonlinear susceptibility, and χ ⁽³⁾ is third order nonlinear susceptibility.

If the molecule is polar, the total dipole moment is the sum of the permanent dipole moment and the induced dipole moment. If the molecule has a center of inversion symmetry, β and χ ⁽²⁾ are zero. . Therefore, in order to have a large second order nonlinear optical property, a material having a center of symmetry and β and χ ⁽²⁾ must be large, and χ ⁽²⁾ is a nonlinear susceptibility induced by macroscopic polarization. If the moments are arranged in disorder, the value becomes zero, so the process of aligning the molecular structure in one direction is required.

Nonlinear optical phenomena are classified into secondary and tertiary nonlinear optical phenomena. Higher order linears exist, but are usually ignored because of their small quantities. Next, the second-order nonlinear optical phenomenon will be described, and the macroscopic polarization phenomenon, the second harmonic generation (SHG), the linear electro-optic effect, and the conjugated molecule will be described in detail. .

An electric field traveling in a z direction and traveling at a single frequency having an amplitude of E _o may be expressed by Equation 3 below, and the polarization induced when the electric field E is incident on a nonlinear optical material may be derived from Equation 2, It is expressed as Equation 4 below. In this case, when [E _o cos (ωt- k _ω z )] ² terms and [E _o cos (ωt- k _ω z )] ³ terms are expanded in Equation 4, the following Equation 5 can be expressed.

In this case, it can be seen that a high frequency component such as 2ω, 3ω, etc. is generated in addition to the fundamental frequency ω as a nonlinear phenomenon. When the light having the frequency of ω is incident on the material, 2ω is called second harmonic generation. 1A shows a model of the second harmonic generation, and FIG. 1B shows a simple diagram of the energy level model of the second harmonic.

The second order nonlinear optical coefficient χ ⁽²⁾ of the nonlinear optical polymer thin film may be expressed as d according to the researcher, and d and χ ⁽²⁾ have a relationship as shown in Equation 6 below.

In Equation 6, i, j and k represent the index of the axis.

When light passes through a nonlinear optical medium, a strong electric field is applied from the outside to change the refractive index of the medium. The light emitted from the medium causes phase modulation or amplitude modulation. It is possible to implement the core high speed optical signal processing of the optical switch. When the above effect is shown in proportion to the electric field, it is called a linear electro-optic or Pockels effect, and when it is proportional to the square of the electric field, it is called a Kerr effect. The change of the refractive index due to the electric field E is shown in Equation 7 below.

In Equation 7, r _ikj is a linear electro-optic coefficient, and the relationship between the linear electro-optic coefficient and the nonlinear optical sensitivity χ _ijk ⁽²⁾ is expressed by Equation 8 below.

In general, a material having a large secondary nonlinear optical characteristic has a large linear electro-optic coefficient (r _ijk ) and a large asymmetry of molecules is required for the secondary nonlinear optical characteristic to be large, and conventionally, phenyl, stilben ( conjugation pathways such as stilbene and polyene and electron donors (D) such as -NH ₂ , -N (Me) ₂ and -N (Et) ₂ , and -NO ₂ , A material containing an electron acceptor (A) such as dicyanovinyl was used.

The molecular structure of dimethyl- {4- [2- (4-nitro-phenyl) -vinyl] -phenyl] -amine (DANS), which is a typical nonlinear optical dye, is as follows.

In addition, three forms of asymmetric polarization of π-electrons and the D-π-A type molecules are as follows.

As described above, the material having the structure of the electron donor (D) -π-electron acceptor (A) is characterized by the fact that charge flow is disturbed in one direction and improved in the other direction when an electric field is applied from the outside. Since π-electrons are more easily polarized by an electric field than σ-electrons, they include a long conjugated bond structure between the electron donor (D) and the electron acceptor (A), if the molecule is a symmetric center point ( If a symmetrical element such as a center of inversion is used, the secondary nonlinear optical characteristic is lost.

Therefore, the higher the polarization degree of π-electrons induced by an external electric field, that is, the higher the polarization phenomenon, the higher the secondary nonlinear optical characteristics can be expected.

In general, materials exhibiting photorefractive phenomena should have both nonlinear optical and photoconductive properties. The principle of the photorefractive phenomenon is briefly explained in FIG. When two light beams coherent to the photorefractive material cross each other and are incident on each other, light interference causes light intensity and weakness. Charges are generated in the strong light part, and the charge is drifted or diffused by the conductive material. The drifted charge is trapped by impurities and the like to form an electric field E _sc in the space. The internal electric field created by light varies the refractive index distribution of the material by the Pockels effect. The change in refractive index due to the internal electric field (E _sc ) is shown in Equation 9 below.

In Equation 9, r _eff is an electro-optic coefficient.

As described above, if the distribution of the refractive index in one material can be freely changed, it can be used as an information storage device and an image display device (hologram).

Linear optical materials are applied to optical fibers and optical waveguides that transmit information in optical communication, while nonlinear optical materials are mainly used to control light. Among the second nonlinear optical effects, the application of the laser to the double frequency using the second harmonic generation can selectively use the high power laser wavelength, and the high frequency is also possible for the high density information storage application.

In other words, optical technology is inevitably necessary to realize high-speed communication and information recording and processing in response to the information and communication society of the future, and if it utilizes the characteristics of light compared to electronic technology using copper wire, It will solve the high speed of recording and processing. For example, optical signal processing elements such as optical modulators and optical switches using the Pockels effect can be used to implement core ultrafast optical signal processing.

Just as electro-optic technology requires a great deal of effort to research semiconductor materials, the development of photon optics requires intensive research on the development of nonlinear optical materials. Photorefractive materials using nonlinear optical phenomena and photoconductive phenomena can be applied as information storage and display devices.

The photorefractive material approach is to chemically combine several functional materials in one polymer to form a single phase. Although the efficiency is still low, many studies have been attempted to solve the problem of phase separation by preventing each component from moving independently in a material.

Accordingly, the present invention is part of a research effort to develop a material having high non-conductive optical properties and high photoconductivity, and by introducing an electron acceptor group into a carbazole having photoconductivity, a novel compound having both of the above properties can be obtained. Synthesized.

That is, by condensation reaction between a compound containing a chromophore and a carbazole aldehyde derivative, a novel compound having excellent nonlinear optical properties can be prepared, and the novel compound prepared as described above is easily lighted even when a high content of chromophore is contained in a molecule. It has been found that the conductivity is not degraded and thus applicable to photorefractive materials.

Thus, the present invention is a novel compound 2- {3- [2- (9-decyl-9H-carbazol-3-yl)-as an organic pigment comprising carbazole and simultaneously containing photoconductivity and nonlinear optical properties. It is an object of the present invention to provide a vinyl] -5,5-dimethylcyclohex-2-enylidene} malononnitrile and a preparation method thereof.

The present invention is a 2- {3- [2- (9-decyl-9H-carbazol-3-yl) -vinyl] -5,5-dimethylcyclohex-2-enylidene} Nonnitrile and its manufacturing method are characterized.

[Formula 1]

The present invention will be described in detail as follows.

In general, polymers containing carbazole have the properties of photoconductivity, nonlinear optical properties, photorefraction, and electroluminescence, and have been used as various functional materials using the above properties. Specific examples of the photorefractive material including a carbazole having the above characteristics are as follows.

In the present invention, in order to prepare a material having both photoconductivity and nonlinear optical properties, an electron acceptor group was introduced to a photoconductive carbazole, and a novel compound of the present invention prepared by condensation reaction of a carbazole derivative and a compound containing a chromophore. One compound exhibits excellent properties that, when applied to photorefractive materials, do not readily degrade the photoconductivity even with high chromophore content. The novel compound prepared in the present invention as a light-bending material was measured through nonlinear optical properties and photoconductivity and two-wave mixing experiments, which can be known by measuring the electro-optic coefficient and the second harmonic intensity.

The linear electro-optic coefficient r ₃₃ includes a simple reflection method, an electrooptic amplitude modulation and an interferometric method, a prism coupling method, and the like. Simple reflection method was used.

When light passes through a nonlinear optical medium, an electric field is applied externally, and the refractive index of the medium is changed by the electric field, and the light emitted through the medium causes phase modulation or amplitude modulation. When the modulation voltage (V = V _m sinω _m t) is supplied to the sample, the intensity (Io) of the light output is expressed by Equation 10 below.

In Equation 10, Φ _sp is the phase difference between the s wave and p wave of the light reflected from the sample, I _c represents half of the maximum intensity, the phase change λ Φ _sp is the refractive index change derived from the electro-optic effect Is determined. The relationship between the light intensity and the phase difference is shown in FIG. 3. When the sample is biased at a position where the value of the output light intensity (I _o ) becomes I _c , it can be seen that the I _o value is the area that varies most linearly with respect to the phase difference. Therefore, the ratio of the intensity I _m and I _c of the modulated light by the electric field can be expressed by the following equation (11).

The electro-optic coefficients are arranged as in Equation 12 below, and the phase refractive index and the ideal refractive index are almost equal to ( ), Which takes into account the symmetry of r ₃₃ = 3r ₃₁ .

In Equation 12, λ is the wavelength of the laser used, θ is the incident angle of light, V _m is the amplitude of the alternating voltage applied to the sample, n is the refractive index of the material.

Methods of measuring χ ⁽²⁾ , which is a secondary nonlinear optical coefficient, include a powder method, a phase matching method, and a Maker-Fringe method. In the present invention, a Maker-Fringe method is applied. The second harmonic was measured by the maker-fringe method. Since the above method obtains the nonlinear coefficient by comparing the sample to be measured with the reference material, the second harmonic generation coefficient can be measured by a relatively simple method compared to other methods. . When light is incident on the crystal of the sample to be measured at an arbitrary angle, the inheritance varies according to the difference in the thickness of the sample. Therefore, a pattern is formed by interference between free and harmonic waves. It is a function of angle.

Two-wave mixing experiments were carried out to confirm the photorefractive properties of the photorefractive materials. When light of the same wavelength forming the refraction grating is incident at the same angle, the phase condition of Bragg scattering is established by itself and the incident light is diffracted by the refraction grating. Incident light 1 is diffracted by the refraction grating, and the diffracted light travels along the traveling path of the incident light 2. Incident light 2 is also diffracted and progresses along the path of incident light 1. This is called energy coupling by self diffraction.

As shown in FIG. 2, when two lights are irradiated, a photo lattice is formed by interference. This phase shift results in an asymmetric energy transfer between the two lights, with the largest energy exchange when the two phase differences are 90 °. Although diffraction by the diffraction grating can be observed in other cases than the photorefractive phenomenon, gain efficient by energy transfer is an important means of proving that it is a photorefractive material.

The value (gain, Γ) representing the degree of energy transfer of the two beams obtained from the two-wave mixing (TBC) experiment is expressed by Equation 13.

In Equation 13, d is the thickness of the thin film, Θ is the incident angle of the incident light 2, β is the ratio of the intensity of the two incident light, γ is the energy coupling ratio, the intensity of the incident light 2 with and without incident light 1 Is rain.

2- {3- [2- (9-decyl-9H-carbazol-3-yl) -vinyl] -5,5-dimethylcyclohex-2- represented by Chemical Formula 1 as a novel compound of the present invention Nilidene} malononenitrile (Caz-Vm-MN) is prepared by the method shown in Scheme 1 below.

That is, a carbazole aldehyde derivative is prepared by a condensation reaction with a malononitrile derivative under a piperidine catalyst. The preparation method will be described in detail as follows.

First, 9-decyl-9H-carbazole-3-carbaaldehyde is prepared from poly (9-vinylcarbazole).

That is, 9-decyl-9H-carbazole is prepared by reacting poly (9-vinylcarbazole) with 1-bromodecane. Then, 9-decyl-9H-carbazole and phosphorus oxychloride (POCl ₃ ) are reacted to prepare 9-decyl-9H-carbazole-3-carbaaldehyde.

In other words, POCl ₃ was added while the temperature of the organic solvent was cooled to about 0 ° C., the temperature was raised to about room temperature, stirred for 30 minutes to 2 hours, and then 9-decyl was cooled to about 0 ° C. again. The reaction is carried out by addition of -9H-carbazole. At this time, the reaction temperature after the addition of 9-decyl-9H-carbazole is the refluxable temperature range of the organic solvent used, preferably in the range of 60 ~ 90 ℃, the reaction time is 18 to 24 hours, preferably It is about 19 to 20 hours. If the reaction temperature and the reaction time are not maintained in the above range, there is a problem such that the reaction efficiency is lowered. Therefore, the above range is preferably maintained.

Next, the condensation reaction of the carbaaldehyde derivative and the malonononitrile derivative is 2- {3- [2- (9-decyl-9H-carbazol-3-yl) represented by Chemical Formula 1, which is the object of the present invention. -Vinyl] -5,5-dimethylcyclohex-2-enylidene} malononnitrile is prepared.

That is, malononitrile is dissolved in an organic solvent and then reacted under isophorone, glacial acetic acid, acetic anhydride, and piperidine catalyst. The reaction temperature is controlled by reacting at room temperature and increasing the reaction temperature to the refluxable temperature of the organic solvent used, followed by cooling to room temperature. In other words, the used organic solvent is reacted at room temperature for 30 minutes to 2 hours, preferably 50 minutes to 80 minutes, and then refluxable temperature range of the organic solvent, preferably 10 to 24 hours in the range of 50 to 80 ℃. During the reaction, the reaction is preferably carried out for 15 to 20 hours, and then cooled to room temperature again to prepare a malononitrile derivative including a chromophore.

Then, the reaction product containing the malononitrile derivative including the chromophore is cooled to room temperature, and then the 9-decyl-9H-carbazole-3-carbaaldehyde is added to the condensation reaction. At this time, the reaction temperature is carried out in the refluxable temperature range of the organic solvent used, preferably in the range of 70 to 80 ℃ for 10 to 24 hours, preferably for 14 to 16 hours. When the reaction temperature and the reaction time are out of the above range, the reaction efficiency may decrease, so it is preferable to maintain the temperature range and time.

After the condensation reaction is completed, the product is extracted with an organic solvent, concentrated and purified, and then recrystallized to obtain 2- {3- [2- (9-decyl-9H-carbazole) represented by Chemical Formula 1, which is an object of the present invention. 3-yl) -vinyl] -5,5-dimethylcyclohex-2-enylidene} malonononitrile (Caz-Vm-MN) is obtained.

The organic solvent that can be used in the preparation of the novel compound Caz-Vm-MN of the present invention is a commonly used organic solvent, dimethylformamide (DMF), tetrahydrofuran (THF), CH ₂ Cl ₂ , CHCl ₃ Etc. can be used.

The characteristics of the optical refractive material as described above are mainly characterized by four-wave mixing for obtaining the diffraction efficiency of light due to lattice formation and two-wave mixing for obtaining the degree of asymmetric energy transfer between two lights in phase shift of the material. It is evaluated by a beam coupling experiment. In addition, a method of measuring electro-optic coefficient or examining photoconductivity may be applied.

Caz-Vm-MN prepared as described above is excellent in photoconductivity and nonlinear optical properties, and thus can be applied as an information storage and display device.

Such a present invention will be described in detail based on the following examples, but the present invention is not limited by the following examples.

Example 1.Preparation of 9-decyl-9H-carbazole-3-carbaaldehyde

The reaction vessel was well dried and prepared to have no moisture, and the reaction was performed under a nitrogen atmosphere. NaH (6.0 g, 0.25 mol) was added to a 500 mL three-necked flask, and 100 mL of purified THF was added slowly. At this time, NaH reacts violently with water, so be careful in handling, and avoid the reaction on wet days. To this, slowly add poly (9-vinylcarbazole) (33.4 g, 0.2 mol) dissolved in 200 mL of THF in a separate flask, and 1-bromodecan (55.30 g, 0.25 mol) dissolved in 50 mL of THF. The addition was slow and the mixture was refluxed for 18 hours.

The mixture solution was cooled to room temperature, vacuum distilled to remove THF, and then the product was extracted with ethyl acetate (EA), concentrated, n-hexane was added, and the precipitate generated was filtered off. The solution from which the precipitate was removed was concentrated and then purified by vacuum distillation to obtain 9-decyl-9H-carbazole as a transparent liquid at room temperature.

Mol. Wt = 307.47; Thin-layer chromatogram (TLC) R _f = 0.76 (EA / Hexane (2/8)) .; ¹ H NMR (CDCl ₃ , ppm) δ8.11 (d, 2H, ArH), 7.43 (m, 4H, ArH), 7.28 (d, 2H, ArH), 4.32 (t, 2H, -NCH _2- ), 1.90 (m, 2H, -CH _2- ), 1.27 (m, 16H, -CH _2- ), 0.95 (t, 3H, -CH ₃ ).

DMF (86 mL, d = 0.994, 1.18 mol) and 50 mL of CH ₂ C1 ₂ were added to the reaction vessel, the temperature was lowered to 0 ° C., and POCl ₃ (53.5 mL, d = 1.645, 0.57 mol) was added slowly. After the temperature was raised to 30 ℃ reacted for 1 hour. After the temperature of the reaction vessel was lowered to 0 ° C., the 9-decyl-9H-carbazole (10 g, 32.5 mmol) was dissolved in 10 ml of CH ₂ C1 ₂ , and then slowly added to the mixture at 80 ° C. for 20 hours. Reacted.

The reaction was cooled to room temperature and slowly poured into iced water. The resulting compound was extracted with CHCl ₃ and n-hexane was added to obtain a precipitate. The precipitate was purified by silica gel column using CHCl ₃ as the developing solvent to give 9-decyl-9H-carbazole-3-carbaaldehyde as a white solid.

TLC R _f = 0.52 (EA / hexanes (2/8)); mp = 66 ° C .; Mol. Wt = 335.48; ¹ H NMR (CDCl ₃ , ppm) δ 10.10 (s, 1H, -CHO), 8.62 (s, 1H, ArH), 8.15 (d, 1H, ArH), 8.00 (d, 1H, ArH), 7.46 ( m, 4H, ArH), 4.34 (t, 2H, -NCH _2- ), 1.89 (m, 2H, -CH _2- ), 1.24 (m, 16H, -CH _2- ), 0.87 (t, 3H,- CH ₃ ); FT-IR (KBr pellet, cm ⁻¹ ) 2921 (HC (SP ² )), 2851 (HC (SP ³ ), 2716 (HC = O), 1691 (C = O).

Example 2: 2- {3- [2- (9-decyl-9H-carbazol-3-yl) -vinyl] -5,5-dimethylcyclohex-2-enylidene} malononnitrile (Caz- Vm-MN) Preparation

Malononnitrile (0.66 g, 10 mmol) was dissolved in 25 mL of DMF in a reaction vessel, followed by isophorone (1.52 g, 11 mmol), piperidine (0.15 g, 1.82 mmol) and glacial acetic acid. (42 mg, 0.7 mmol) and acetic anhydride (41 mg, 0.2 mmol) were added sequentially, followed by reaction at room temperature for 1 hour, and then the temperature was raised to 80 ° C. for 1 hour.

After the reaction was completed, the reaction mixture was cooled to room temperature, and 9-decyl-9H-carbazole-3-carbaaldehyde (1.68 g, 5 mmol) was added to the reaction mixture, followed by reaction at 80 ° C. for 16 hours. After cooling to room temperature again, the product was extracted with CHCl ₃ and concentrated to obtain a precipitate with n-hexane (hexane), the precipitate was purified by silica gel column using CHCl ₃ . The purified was recrystallized again with hexane to give needle-shaped red crystals. The characteristics of the obtained Caz-Vm-MN is shown as follows, ¹ H NMR spectrum is shown in the accompanying drawings, Figure 4a, UV-visible spectrum is shown in Figure 4b, Figure 4c shows the spectrum of the thermal analysis results .

TLC R _f = 0.69 (CHCl ₃ ); mp = 119 ° C .; Mol. Wt = 503.72; ¹ H NMR (CDCl ₃ , ppm) δ 8.25 (s, 1H, ArH), 8.11 (d, 1H, ArH), 7.5 (m), 7.05 (d, 1H, -CH = CH-), 6.86 (s , 1H,> C = CH-), 4.31 (t, 2H, -NCH _2- ), 2.61 (s, 2H, -CH _2- ), 2.53 (s, 2H, -CH _2- ), 1.88 (m, 2H, -CH _2- ), 1.24 (m, 16H, -CH _2- ), 1.10 (s, 6H, (CH ₃ ) ₂ C), 0.87 (t, 3H, -CH ₃ ) .; FT-IR (KBr pellet, cm ⁻¹ ) 2921 (HC (SP ² )), 2851 (HC (SP ³ )), 2213 (CN) .; Anal. Calcd. for C ₃₅ H ₄₁ N ₃ ; C: 83.45, H: 8.20, N: 8.34; Found: 83.45, H: 8.32, N: 8.42

Example 3 Preparation of Sample for Second Harmonic Measurement

Caz-Vm-MN prepared in Example 2 was dissolved in CHCl ₃ at a concentration of about 2% by weight and filtered through a 0.45 μm filter to prepare a sample solution. The slide glass substrate was immersed in piranha solution [sulfuric acid: hydrogen peroxide (70:30)] for 1 hour, taken out, rinsed thoroughly in water, dried, and spin-coated the sample solution at 1000 rpm, followed by drying for 12 hours or more in vacuum. I was. At this time, if the ambient temperature is high during the spin-coating process, the solvent will fly quickly so that the surface becomes cloudy.

Example 4 Preparation of Sample for Electro-optic Coefficient and Photocurrent Measurement

The sample solution prepared in Example 3 was used as it is, and a glass substrate coated with indium tin oxide (ITO), which is a transparent conductive material, was used as the substrate. The edge of the ITO glass was etched with aqua regia (hydrochloric acid: nitric acid = 3: 1), the sample solution was spin-coated on an ITO glass substrate, and dried in vacuo for at least 12 hours to remove the solvent. The edge of the ITO part was wiped off with a solvent (CHCl ₃ ), the wire was connected with silver paste, the ITO electrode was grounded and then polarized. After masking so that only necessary portions of the Al electrode were coated, the electrodes were coated on the polymer membrane using DC magnetron sputtering. The photocurrent measurement sample was prepared by omitting the polarization process, and the process of preparing the electro-optic coefficient and the photocurrent measurement sample was briefly illustrated in FIG. 5.

Example 5 Preparation of Sample for Measuring Two-beam Coupling

Only the necessary portions of the ITO glass substrate were covered with masking tape and the remaining portions were etched. The polymer was dissolved in CHCl ₃ at a concentration of about 2% by weight, filtered through a 0.45 μm filter, and all the solvents of the filtered solution were removed by vacuum distillation.

Caz-Vm-MN prepared according to Example 2 was concentrated in a small amount of toluene / CHCl ₃ solvent, poured onto the prepared two ITO glass substrates, and the solvent was slowly evaporated at room temperature (about 2 days). Slowly raise the temperature to 120 ° C and completely remove the solvent in the polymer, and then two ITO substrates coated with Caz-Vm-MN are superimposed on each other while applying more than T _g of heat, whereby air between the two ITO substrates (electrodes) Care should be taken to ensure no drops are present. In the accompanying drawings, the manufacturing process of the sample for measuring the mixing of light waves is simply illustrated.

Experimental Example 1: Corona poling

Since the dipole of Caz-Vm-MN spin-coated in Example 3 (hereinafter, "polymer" refers to Caz-Vm-MN in the Experimental Example) is disordered or has a very low degree of orientation. Corona polar alignment is required to align the irregular polarization in one direction (see attached drawing FIG. 7A).

In other words, in order to orient the chromophore in the polymer by applying a temperature of T _g or higher and a high electric field to the polymer, corona poling was used. A self-made corona polar alignment device as shown in FIG. 8 was used. The ground plate was grounded at, and the distance between the needle and the sample was 1 cm, and a high voltage of 7 kV was applied at a temperature of T _g + 15 ° C. Polar orientation was carried out for about 30 minutes to 1 hour, and cooled to room temperature while maintaining an electric field to maintain polarization of the polymer even at room temperature. If the polymer suddenly applied a high electric field before reaching a temperature above T _g , the surface becomes cloudy. To prevent this, after raising the temperature above T _g , waiting for 5 minutes and then slowly raising the electric field.

Figure 7b shows the UV-visible light spectrum before and after the polar alignment of the Caz-Vm-MN prepared in the present invention.

Experimental Example 2 Second Harmonic Measurement

The second harmonic generation coefficient d ₃₃ of Caz-Vm-MN polarly oriented in Experimental Example 1 was measured by the maker-fringe method, and the maker-fringe method measuring device is simply illustrated in FIG. 9.

As a reference material, Y-cut quartz (d ₁₁ = 0.33 pm / V) having a thickness of 3 mm was used, and an Nd-YAG laser having a wavelength of 1064 nm was used as the incident light source. Harmonic light at 532 nm was measured as a function of incidence angle. 10A is a graph showing a result of measuring a second harmonic of a reference material, and FIG. 10B is a graph showing a result of measuring a second harmonic of Caz-Vm-MN of the present invention prepared in Example 3. FIG. The polar alignment conditions applied at this time was 45 kV, 30 minutes, 165 ℃, the thickness of the sample used was 0.38 ㎛.

Experimental Example 3 Measurement of Linear Electro-optic Coefficient by Simple Reflection Method

The electro-optic coefficient of Caz-Vm-MN of the present invention was measured by a simple reflection method, and FIG. 11 is a schematic diagram of an electro-optic coefficient measuring apparatus used.

The light source used for the measurement is a 632.8 nm He-Ne laser (or 1550 nm diode laser). The polarizer in front of the light source was set at 45 ° so that the p-wave and s-wave intensity of the light source were equal, and the laser was incident on the glass substrate at an angle of 45 °. The light passing through the glass substrate is reflected by the Al electrode after passing through the ITO and the polymer thin film, and the reflected light reaches the detector through the λ / 4 plate and a -45 ° analyzer.

If there is no electric field, rotate the λ / 4 plate to find the maximum and minimum value of the light passing through it, then fix the λ / 4 plate to have an intermediate value between them, and change the AC voltage of 1 kHz from the function generator. (V _m ) was added to the sample. An AC voltage of the same frequency was supplied as a reference of a lock-in amplifier, and a change in the intensity of light according to the change of the electric field was amplified by a fixed amplifier, and the result was obtained by an oscilloscope.

I _m is the intensity of the modulated light and the electro-optic coefficient of the nonlinear optical material can be obtained from the slope of I _m / V _m (see Equation 12). The gain coefficient of the energy transfer degree of the fixed amplifier used was calculated using a voltage divider. The role of the [lambda] / 4 plate is shown in FIG. 12, which converts the light into circular polarization when the linearly polarized light is incident at 45 [deg.] of the [lambda] / 4 plate optical axis.

Experimental Example 4 Photocurrent Measurement

Photocurrent was measured to examine the potential of nonlinear optical materials as photorefractive materials. First, in order to obtain the laser power density, the beam size and power of the laser light must be obtained. The cross-sectional area of the laser light incident on the sample was calculated as follows. Move the well-cut face (razor) to a micro linear stage, obscuring the laser light, and finding the distance between the quarter of the maximum intensity of the light and the quarter of the radius of the laser light It is done. The output of the laser was measured by Newport's Picowatt Digital Optical Power Meter (Model 1830-C), and the power density (97 mW / cm ² ) of the used He-Ne laser was obtained. .

13 is a schematic view of a photocurrent measuring device. The laser beam was choked at 400 Hz and the reflected light incident at 45 ° on the sample was used as the reference signal of the lock-in amplifier. The photocurrent was calculated by obtaining the voltage across the resistor R (20 mA) from both sides of the polymer from the fixed amplifier. The voltage across R is subtracted from the voltage V * applied to find the actual voltage across polymer.

Experimental Example 5 Measurement of Two-beam Coupling (TBC)

A schematic diagram of the apparatus used for the two-wave mixing measurement is shown in the accompanying drawings, and the P-polarized light was divided by a beam splitter and incident on the samples at angles a and b, respectively. The change in the intensity of the two lights was observed while applying high voltage to the two ITO electrodes. An optical detector circuit configured for converting the current difference obtained from the detector into a voltage difference is shown in FIG. 15.

The optical properties of the compounds of the present invention measured by Experimental Examples 1 to 5 are summarized in the following Table 1, and the measurement graphs of the electro-optic coefficients are shown in the accompanying drawings.

r ₃₃ (pm / V) ^a d ₃₃ (esu) (pm / V) d ₃₁ (esu) λ _max (nm) ^b φ n ^x 532 nm 632.8 nm 1064 nm Caz-Vm-MN / PVK (0.1: 0.9) 4.03 7.3 × ^-9 3.06 1.9 × 10 ^-9 473 0.26 1.70 ^t 1.693 ^p 1.49 ^{t a} d ₃₃ = χ ⁽²⁾ / 2, 1 pm / V = 2.386 × 10 ^-9 esu. φ 1 = ^b - (A _p / A _o) A _p: absorbance at λmax after pole orientation .A _o: pole x .n ^X in absorbance at λmax alignment transition is how to measure the optical index of refraction .x = t (transmittance method) x = p (prism coupling method) x = e (ellipsometery method)

As shown in Table 1, 2- {3- [2- (9-decyl-9H-carbazol-3-yl) -vinyl] -5,5-dimethylcyclohex-2- is a compound of the present invention. Nilidene} malononitrile showed excellent electrooptic coefficient (r ₃₃ (pm / V)) and nonlinear optic coefficient (d ₃₃ ) through an efficient polling process. It can be seen that the photoconductivity and nonlinear electro-optic properties are simultaneously shown.

As described above, 2- {3- [2- (9-decyl-9H-carbazol-3-yl) -vinyl] -5,5 prepared by the condensation reaction of a carbazolealdehyde derivative with a specific chromophore-containing compound -Dimethylcyclohex-2-enylidene} malononitrile exhibited excellent photoconductivity and nonlinear electro-optic properties, which is expected to be widely used as a photorefractive material that can be applied to information storage and display devices.

1A is a diagram showing a model of the second harmonic generation, and FIG. 1B is a diagram showing an energy level model of the second harmonic.

2 is a simple diagram showing the principle of the photorefractive phenomenon.

3 is a graph showing the relationship between light intensity and phase difference.

4A shows 2- {3- [2- (9-decyl-9H-carbazol-3-yl) -vinyl] -5,5-dimethylcyclohex-2-enylidene} malononnitrile (Caz-Vm -MN), ¹ H-NMR spectrum, Figure 4b is a UV-visible spectrum of Caz-Vm-MN, Figure 4c is a spectrum showing the results of the thermal analysis of Caz-Vm-MN.

FIG. 5 is a diagram illustrating a sample preparation process for measuring electro-optic coefficient and photocurrent of Example 4. FIG.

6 is a schematic diagram illustrating a sample preparation process for measuring the mixing of light waves of Example 5. FIG.

FIG. 7A is a schematic of rearrangement of polarization after polar alignment, and FIG. 7B is a UV-visible spectrum before and after polar alignment of Caz-Vm-MN.

8 is a schematic view of the corona polar alignment device used in Experimental Example 1. FIG.

9 is a schematic diagram of a Maker-Fringe method measuring device used in Experimental Example 2. FIG.

FIG. 10A is a graph showing a second harmonic measurement result of a reference material measured by Experimental Example 2, and FIG. 10B is a graph summarizing nonlinear electro-optical characteristics, which is a second harmonic measurement result of Caz-Vm-MN.

11 is a schematic view of an electro-optic coefficient measuring device used in Experimental Example 3. FIG.

12 is an enlarged view of the λ / 4 plate of the electro-optic coefficient measuring device of FIG. 11.

13 is a schematic view of a photocurrent measuring device used in Experimental Example 4. FIG.

14 is a schematic diagram of a two-wave mixing measurement apparatus used in Experimental Example 5. FIG.

15 is a circuit diagram of a detector used in Experimental Example 5. FIG.

Fig. 16 shows the measurement results of the electro-optic coefficients of Caz-Vm-MN.

Claims (2)

2- {3- [2- (9-decyl-9H-carbazol-3-yl) -vinyl] -5,5-dimethylcyclohex-2-enylidene, which is represented by the following formula (1): Malononitrile (Caz-Vm-MN): [Formula 1] Reacting poly (9-vinylcarbazole) with 1-bromodecane to produce 9-decyl-9H-carbazole; Reacting the 9-decyl-9H-carbazole with phosphorus oxychloride (POCl ₃ ) to prepare 9-decyl-9H-carbazole-3-carbaaldehyde; Reacting malononitrile and isophorone under glacial acetic acid, acetic anhydride and piperidine catalyst to prepare a malononnitrile derivative comprising a chromophore; And 2- {3- [2- (9-decyl-9H-carba) represented by the following Chemical Formula 1 by condensation reaction of the malononitrile derivative including the chromophore with the 9-decyl-9H-carbazole-3-carbaaldehyde: Zol-3-yl) -vinyl] -5,5-dimethylcyclohex-2-enylidene} malononnitrile (Caz-Vm-MN). [Formula 1]