KR100882902B1 - Non-linear optical film and manufacturing method thereof - Google Patents

Abstract

A method of manufacturing a non-linear optical film is provided to form a crystallization area within a film by self-aligning octupolar molecule and to ensure excellent nonlinearly and thermal stability. A method of manufacturing a non-linear optical film comprises (S1) a step for obtaining a mixture solution by dissolving octupolar molecule of the following chemical formula (1) and polymer in a solvent, wherein A is CN, D is NR2, R is C_mH_(2m+1), n is an integer of 1-5 and m is an integer of 1-100; (S2) a step for applying the mixture solution on the plate; and (S3) a step for performing the crystal growth and self alignment of the octupolar molecule by evaporating the solvent from the mixture solution. The octupolar molecule is 1,3,5-tricyano-2,4,6-tris (paradiethylamino styryl) benzene.

Description

Non-linear optical film and manufacturing method thereof

The present invention relates to a nonlinear optical film and a method of manufacturing the same, and more particularly, to a nonlinear optical film having excellent nonlinear effects and a method of manufacturing the same.

Non-linear optical materials have the characteristics of rectifying, modulating and switching optical signals because they act on the electric field of incident light to change the frequency phase, amplitude, etc. of the incident light, which is the key material used for optical communication and optical recording. The most widely used nonlinear optical materials are inorganic materials such as LiNbO ₃ and GaAs. However, these materials are economically limited to meet the demand of huge information devices that are being developed recently due to difficulties in the production process.

As an alternative to the inorganic material, organic nonlinear optical materials have been developed by various synthetic methods, and generally have a dipole structure in which electron donors and electron acceptors are substituted at both ends of a conjugated double bond. Such organic nonlinear optics have relatively low dielectric constants and refractive indices in that molecules with desired electronic and optical properties can be synthesized relatively easily, achieve ultrafast response speeds essential for processing optical signals and computational information. This has the industrial advantage over the inorganic material in that it can be used in a wide frequency range and is excellent in workability.

However, the dipole molecules have a limitation such that the nonlinear optical properties increase when the conjugation length is increased, but the absorption wavelength is shifted toward the long wavelength. The biggest drawback of the dipole molecules is that the nonlinear optical properties as molecular aggregates cancel out because the dipole arrangement in the opposite direction in the solid state is thermodynamically stable. In addition, in the manufacturing process of the nonlinear optical film using the dipole molecules, a polling process for applying a high electric field is used to align the dipole molecules in one direction. The polling process using such a high electric field has the side effect of raising the cost of manufacturing the nonlinear optical film, and furthermore, as described above, the dipoles oriented in the same direction by the polling process tend to be oriented thermodynamically in the opposite direction. This tends to degrade the performance of nonlinear optical films containing dipole molecules.

As a material for overcoming the technical shortcomings of the dipole, the applicant has proposed an octapole molecule through Patent Application No. 1999-0054553.

Since the polar dipole molecules have no polarity in the ground state, they are easily crystallized by non-centrosymmetry compared to the conventional dipole molecules, which are very strong second harmonic waves having no polarization-dependence on incident light. (second-harmonic generation, 'SHG') as well as has the advantage of excellent thermal stability. That is, compared to the dipole molecules, the octapole molecules of the above structural formula have a wider range of nonlinear coefficients, i.e., tensor coefficients, which provide an optimal nonlinear effect of SHG without polarization-dependence on incident light.

However, in order to apply such materials directly to an optical device, it is necessary to prepare a film having high SHG and thermal stability, and to prepare a nonlinear optical film containing the octapole molecules, The electrical polling process used to make the film is undesirable. Because the dipole molecules do not have a dipole moment in the ground state unlike the dipole molecules. On the other hand, the method of optical polling in the polymer can also be considered, but this method also has a property that the molecule can be photoisomerized, and requires a process of resonance excitation (resonant excitation) of the molecule by a strong laser pulse. In other words, the electrical and optical polling processes are both uneconomical in that they require a separate high energy consumption step (high electric field injection step in the case of electrical polling, and resonance excitation step by laser pulse in the case of optical polling), and furthermore, specific conditions of the molecule. The application is limited in that it must satisfy (the dipole moment for electrical polling and photoisomerization for optical polling).

A first object of the present invention for solving the above problems is to provide a method for economically manufacturing a non-linear optical film of excellent performance.

The 2nd subject of this invention is providing the nonlinear optical film which is excellent in a nonlinear characteristic and is thermally stable.

One embodiment of the present invention for solving the first problem comprises the steps of dissolving the octapole molecules and polymer of the formula (1) in a solvent to obtain a mixed solution;

(Wherein A is CN, D is NR ₂ , R is C _m H _{2m +1} , n is an integer from 1 to 5, m is an integer from 1 to 100)

Applying the mixed solution onto a plate; And evaporating the solvent from the applied mixed solution to perform crystal growth and self-alignment of the octapole molecules.

Here, the octapole molecule is 1,3,5-tricyano-2,4,6-tris (paradiethylaminostyryl) benzene (hereinafter referred to as' TTB '), and the polymer is polymethylmethacrylate (hereinafter referred to as' PMMA '), and the solvent in which the octapole molecules and the polymer are dissolved may be chlorobenzene.

In addition, the mixed solution is applied to the plate after obtaining the mixed solution, and the mixed solution may be filtered to remove impurities and the like before applying to the plate. The filtration step is carried out by passing the mixed solution through a filter having a diameter of 0.1 to 0.3㎛.

After coating on the plate, the mixed solution is subjected to the step of performing the crystal growth and self-alignment of the octapole molecules by evaporation of the solvent by evaporation, the temperature conditions of 20 to 30 ℃ over 5 days to 9 days You can proceed.

An embodiment of the present invention for solving the second problem is disclosed by the manufacturing method, and discloses a nonlinear optical film comprising a polymer and the octapole molecule of the formula (1).

The octapole molecule may be TTB, and the polymer may be PMMA. The nonlinear optical film may include a crystalline domain, and the crystalline region may have a cylindrical shape including a plurality of octapole molecules.

In the case where the octapole molecule of the crystal region is TTB, the distance between the centers of the TTB molecules is 7.5 Å and the branch length of the TTB molecules is 15 으로부터 from the center. In addition, the content of the octapole molecules in the nonlinear optical film is 10 to 30% by weight relative to the polymer.

The method for producing a nonlinear optical film according to the present invention forms a crystal region by orienting nonlinear molecules without separately applying a high electric field or a laser pulse, thereby making it possible to economically manufacture an optical film having excellent nonlinear optical properties.

In addition, the film produced according to the above-described method forms a crystal region and includes self-orientated octapole molecules, so that the nonlinear optical effect is excellent and thermally stable.

As described above, the non-linear optical film manufacturing method according to an embodiment of the present invention comprises the steps of dissolving the octapole molecule and the polymer of Formula 1 in a solvent to obtain a mixed solution; Applying the mixed solution onto a plate; And evaporating the solvent from the applied mixed solution to perform crystal growth and self-orientation of the octapole molecules.

In one embodiment of the present invention, the octapole molecule is TTB, and the polymer is PMMA having excellent optical properties as the main material of the film. In addition, since the octapole molecule such as TTB and the polymer such as PMMA are organic materials, the solvent is preferably an organic solvent, and in one embodiment of the present invention, chlorobenzene.

After the octapole molecules and the polymer are dissolved in an organic solvent such as chlorobenzene, a mixed solution is obtained. The mixed solution is then applied onto a plate, and then the solvent is removed by evaporating the solvent from the applied mixed solution.

As described above, the solvent contained in the mixed solution is removed by evaporation. In the evaporation step, the octapole molecules of the mixture undergo crystal growth and self-orientation. Therefore, it is essential to secure evaporation time for achieving sufficient crystal growth and self-orientation of the octahedral molecules.

In the production method according to the invention, the evaporation step is carried out for 5 days 9 days. If the evaporation is shorter than the time range, sufficient crystallization is not achieved, and if the evaporation is longer than the time range, it is uneconomical.

In addition, crystal growth and self-orientation of the octapole molecules are also dependent on the evaporation temperature of the solvent, the evaporation process in the production method according to the invention is carried out at a temperature condition of 20 to 30 ℃. If the solvent is evaporated at a temperature lower than the temperature range, the manufacturing process is too long, so the economical efficiency is low. On the contrary, if the solvent is evaporated too fast at a temperature higher than the temperature range, sufficient crystal growth and self No orientation can be obtained.

Since the crystal growth of the octahedral molecules proceeds in the mixed solution, the mixed solution should be free of impurities such as dust that inhibit the growth of the crystal. Accordingly, after the octapole molecules and the polymer are mixed in a solvent to obtain a mixed solution, a filtration process may be performed to remove impurities from the mixed solution that inhibit growth of crystals before applying the mixed solution on a plate. In the present invention, the filtration process is performed by passing the mixed solution through a filter having a diameter of 0.1 μm to 0.3 μm. In the case of a filter having a diameter smaller than the above range, the filtration process proceeds for too long, so that the filtration performance is rather low, and the entire manufacturing process becomes long. On the contrary, when a filter having a diameter larger than the above range is used, there is a risk that impurities which will inhibit crystal growth of the octahedral molecules remain.

The nonlinear optical film obtained through the manufacturing process has a crystal region essential for nonlinear optical characteristics. The crystal region may have a cylindrical shape including a plurality of octapole molecules, and the octapole molecules may be spaced apart from each other. When the octapole molecule is TTB, the distance between the centers of the TTB molecules is about 7.5 m 3, and the branching length of the TTB molecules is about 15 m 3 from the center.

In the nonlinear optical film prepared according to the present invention, the content of the octahedron molecules is 10 to 30% by weight based on the polymer. If the content of the octahedron molecules is lower than the above range, sufficient nonlinear optical effects cannot be achieved, and if higher than the above range, the material properties of the film are deteriorated.

A nonlinear optical film manufacturing method and a nonlinear optical film manufactured according to the present invention will be described below in detail with reference to the following drawings and examples. However, the scope of the present invention is not limited by the following examples and the like.

Example 1

1,3,5- Triciano -2,4,6- Tris ( Paradiethylaminostyryl Preparation of Benzene (TTB)

1,3,5-tricyano-2,4,6-trimethylbenzene and 4-diethylaminobenzaldehyde were added to ethanol / benzene and refluxed, followed by the slow addition of piperidine. After refluxing this solution for 3-5 days, the solvent was evaporated under reduced pressure and the product was adsorbed onto silica gel. Thereafter, hexane / ethyl acetate (4/1) was used as an eluent to purify by column chromatography to obtain TTB, an octapole molecule.

Example 1- (1)

Preparation of nonlinear optical film TTB  Content: 10% by weight)

TTB (0.1 g) was dissolved in 17 mL of chlorobenzene with 0.9 g of PMMA (Mw = 100,000) to obtain a mixed solution. Then, the mixed solution was filtered by passing the mixed solution through a 0.2 μm diameter Teflon filter. The filtered mixed solution was applied to a BK7 plate (roughness of λλ / 10) and then covered with a glass cap. Thereafter, for one week at 25 ° C., the solvent was evaporated from the mixed solution to obtain a nonlinear optical film.

Example 1- (2)

Preparation of nonlinear optical film TTB  Content: 20% by weight)

Except that the TTB content is 20% by weight, the manufacturing process was carried out under the same conditions as in Example 1- (1) to obtain a nonlinear scientific film.

Comparative Example 1

Preparation of Spin Coated Nonlinear Optical Films

After obtaining a mixed solution of TTB and PMMA in the same manner as in Example 1- (1), the mixed solution was applied onto a plate of the same kind as the plate used in Example 1- (1), and at a speed of 1000 rpm. Spin-coated. After leaving for 1 day at room temperature, the solvent was evaporated to a temperature of 100 ℃ for 3 days.

Test Example 1

Absorption Spectrum of Nonlinear Optical Film

1 shows absorption spectra for the films of Example 1- (1) and Comparative Example 1. FIG.

Referring to FIG. 1, the film of Comparative Example 1 shows almost the same spectrum (a) as the mixed solution, but the spectrum (b) of Example 1- (1) is wider. From these results, the film of Comparative Example 1 is uniform and has amorphous properties, but in the case of the film according to Example 1- (1), the micro-area makes the spectrum wider by dispersing light. -domain) is included in the film.

Test Example 2

Morphological Analysis of Nonlinear Optical Films

FIG. 2A is a polarizing microscope image of the nonlinear optical film of Example 1- (1), and FIG. 2B is a polarizing microscope image of the nonlinear optical film when the nonlinear optical film of FIG. 2A is rotated 45 degrees. 2C is a polarization microscope image of the nonlinear optical film of Example 1- (2), and FIG. 2D is a polarization microscope image of the nonlinear optical film when the film of FIG. 2C is rotated 45 degrees.

2A to 2D, both the images of the nonlinear optical films of Examples 1- (1) and 1- (2) show light and dark areas. These areas show various shapes such as stacked leaves, triangles, and polyhedrons, and look like well-woven fabrics of 0.1 to 2 mm in size (see FIGS. 2A and 2C), and the film is uniform in thickness of about 1 μm. When this film is rotated in the plane of 45 to 50 degrees, the bright areas become dark, while the dark areas appear bright (see FIGS. 2B and 2D). This change in color means that the regions are aligned in different polarization directions. On the other hand, in the case of the nonlinear optical film of Comparative Example 1, these areas were not observed. This means the amorphous properties of the film according to Comparative Example 1, similar to the results of Test Example 1.

The presence of the crystal region of TTB molecules in the nonlinear optical film according to the present invention is clearly demonstrated by the following X-ray diffraction analysis (XRD).

3A to 3C show the results of X-ray diffraction analysis on the TTB powder, the film of Example 1- (1), and the film of Comparative Example 1, respectively.

When FIG. 3a and FIG. 3b, it can be seen that the two spectra match at 2 θ = 5.86, 11.72. However, FIG. 3C does not exhibit the same or similar spectrum as the TTB molecular crystal spectrum shown in FIG. 3A. This means that the TTB molecules of the spin-coated Comparative Example 1 do not form a crystal region in PMMA and have amorphous properties.

On the other hand, the distance between the centers of TTB molecules calculated from the spectra for the film of Example 1- (1) was found to be 7.5 mW. Accordingly, it can be seen from the polarization microscope image and the result of X-ray diffraction analysis that the crystal region of Example 1- (1) includes TTB molecules having a distance of 7.5 중심 between centers. In addition, it is understood that the film of Example 1- (1) showing the same peak also has the crystal of the cylinder structure from the fact that the TTB powder forms the crystal of the cylinder shape. In addition, it can be seen that the length of the branch of the TTB molecule of the film according to Example 1- (1) is also 15 Å from the length of 15 인 that the branch of the TTB molecule has in the TTB powder.

Test Example 3

SHG and two-photon of nonlinear optical film Excitation  analysis

4 is an SHG and two-photon excited fluorescence (“TPF”) analytical spectra for the film of Example 1- (1).

Referring to FIG. 4, it can be seen that when pumped at 1064 nm, the film emits strong SHG at 532 nm and weak TPF at 620 nm. Similar results can be obtained when a 1560 nm laser photon is used as the pump beam. Interestingly, the TPF emitted from the crystal is almost always destroyed by the PMMA matrix. Thus, all photons obtained at 532 nm can be seen to be entirely due to SHG.

In contrast, the film of Comparative Example 1 did not show any peaks in X-ray diffraction analysis and also showed no SHG. Since the TTB molecules in the film of Comparative Example 1 do not form a crystal region, it can be seen from the results that the crystal region must be present in the film in order to exhibit SHG, which is a nonlinear optical characteristic of the film.

Test Example 4

SHG Polarization  Structural Analysis of Crystal Region Using Reaction

Prior to the analysis result according to this Test Example 4, a variable that quantitatively represents the amorphous optical effect is first examined.

The nonlinear optical effect of the crystal is defined by the non-linearity suceptibility tensor d, which is derived from the oriented gas model. Assuming that the crystal region has symmetry of the octapole, adopting a model developed by Zyss et al . (See J. Zyss, S. Brasselet, VR Thalladi, GR Desiraju, J. Chem . Phys . 1998, 109,658) , The only non-deleted coefficient in the (1,2,3) unit loss structure is d ₁₁₁ = Nf ₁ ^{2 ω} (f ₁ ^ω ) ² β ₁₁₁ , d ₁₂₂ = -Nf ₁ ^{2 ω} (f ₂ ^ω ) β ₁₁₁ And d ₂₁₂ = d ₂₂₁ = Nf ₂ ^{2 ω} f ₁ ^ω f ₂ ^ω β ₁₁₁ , where N is the number density of the octapole molecules. The local field correction factor f _i is determined by f _i ^ω = ((n _i ^ω ) ² +2) / 3 according to the Lorentz-Lorentz model, where n _i ^ω is the refractive index at the frequency ω. Due to the triangular symmetry of the crystals of the octapole molecule, n ₁ ^ω = n ₂ ^ω , d ₁₁₁ = -d ₁₂₂ = -d ₂₁₂ = ∥d∥ / 2, where d ∥ d ∥ absolute of d tenso Value.

In consideration of the above nonlinear accommodating tenso d, the analysis result of the region structure according to the SHG signal will be described in detail below with reference to the accompanying drawings.

5A and 5B show SHG polarization and marker fringe measurement methods.

5C shows laboratory coordinates (X, Y, Z) and molecular coordinates [1 (U)._One), 2 (U₂), 3 (U₃Euler angle at)]θ, Ø, Ψ5D shows the hexagonal structure of the TTB crystal region in the film, and FIG. 5E shows the arrangement of the TTB molecules.

In this test example, the SHG signal has the advantage of being sensitive to the crystal structure and orientation as well as the polarization of the incident electric field, the crystal region structure was measured using the SHG polarization reaction. To this end, as shown in FIG. 5A, a linearly polarized 1064 nm (or 1560 nm) incident beam was irradiated to the film of Example 1- (1) in the Z-axis direction, where the polarization angle Φ = (X, E ^ω ) was rotated from 0 ^o to 360 ^o (see FIGS. 5A and 5D). The focused beam was irradiated to one crystal region having a diameter of 1 mm with a diameter of ˜400 μm and a thickness of 0.96 μm, and the results are shown in FIGS. 6A to 6F.

6A and 6B show polarization diagrams of Example 1- (1) at wavelengths of 1064 and 1560 nm.

6A and 6B, the polarization diagram shows two lobes. This indicates that the TTB plane is perpendicular to the (X, Y) plane, ie θ (Z, z) = 90 ^o , which is illustrated in FIG. 5C. When changing φ, the general shape represented by the polarization diagrams of FIGS. 6A and 6B shows that the theoretical model is in agreement with the experimental data, especially with regard to the geometry of the molecular arrangement.

6A and 6B also show that the polar dipole molecules are perpendicular to the plane of polarization light. Indeed in this structure, the molecular-field coupling occurs perpendicular to the plane of the octapole, which appears as two lobes "similar to the dipole" of the polarization reaction. This feature is also observed in TTB bulk crystals.

6C and 6D show marker fringe results for Y-cut quartz at wavelengths of 532 nm and 780 nm, respectively. FIGS. 6E and 6F show Example 1 at wavelengths of 532 nm and 780 nm, respectively. Marker fringe results for the film of-(1) are shown.

In order to apply the measurement results shown in the figure to the structural analysis, first look at the following equation (1).

And I, J, K are X, Y, which are laboratory coordinates.

to be.

는 Ψ에 대하여 독립적인 비율의 하기의 간단한 수학식 2로 정리된다.When an electric field is incident on X ( Φ = 0 ^o ),

Is summarized by the following simple equation (2) of the ratio independent of Ψ .

Where I represents the intensity of the SHG reaction.

From the analytical results at 532 nm, from the measured I ^{2 ω} _X / I ^{2 ω} _Y ratio when Φ = 0 ^o , tan ² Ø was inverted and Ø was 69.2 ^o . This means that the molecular plane xy is inclined by the 69.2 ^o axis from the XZ plane. In the 780 nm measurement, I ^{2 ω} _Y = 0 where Ø is 90 ^° considering the above equation. In other words, this means that the molecular plane xy is parallel to the XZ plane. As such, the discrepancy in the Ø values measured in the two wavelength bands is due to the different arrangement of the films in the two experiments. Similarly, when the same crystal region is rotated by 90 ^° on the XY plane, the two lobes also rotate by 90 ^° , involving the exchange of I ^{2 ω} _X and I ^{2 ω} _Y.

7A and 7B show polarization diagrams and marker fringe measurement results for the film of Example 1- (2) at a wavelength of 780 nm.

Referring to FIGS. 7A and 7B, it can be seen that the film of Example 1- (2) also shows a result similar to that of the film of Example 1- (1).

Assuming _octapole symmetry in the crystal region, d _2eff measured from the marker fringe shown in FIG. 5B is represented by the following equation (3) as the input pump beam ω of the P-polarization and the output beam _2ω of the P-polarization.

,From here

,

이고,

ego,

, n_ω=ω에서의 필름이 갖는 굴절율, n_{2 ω}=2ω에서의 필름이 갖는 굴절율, θ는 펌프빔의 입사각을 의미한다.

, the refractive index of the film at n _ω = ω, the refractive index of the film at n _{2 ω} = 2ω, θ means the incident angle of the pump beam.

Using the above equation, Ψ can be determined at 3 ^o (see FIGS. 6D and 6F), the angle at which the maximum intensity value is obtained at two wavelengths of 532 nm and 780 nm. Since the thickness of the film is much smaller than the coherence length of SHG (4.3 μm at 1064 nm, 32 μm at 1560 nm), the shape shown in FIG. 6 is in fact represented by an envelope fringe.

Test Example 5

Nonlinear Coefficient Analysis of Film

Test Example 5- (1)

Nonlinear coefficients for the films of Examples 1- (1) were measured quantitatively, using the general Herman and Hayder theory (WNHerman, LM Hayder, J. Opt . Soc . Am . B 1995, 12,416; TKLim, M.-Y. Jeong) , C. Song, DCKim, Applied Opts . 1998,37,2723), were used to calculate the nonlinear acceptor tens, ie the second order nonlinear optical coefficient d ₁₁₁ . The thickness and refractive index of the quartz and film used in this calculation are as follows.

1. Thickness

Quartz 990㎛,

0.96 μm film

2. Refractive index at 532, 780, 1064, 1560nm

Quartz 1.54690, 1.53878, 1.53410, 1.52735 (CVI laser Corporation optics catalog book)

Films 1.6720 1.6110, 1.5167, 1.3025 (wherein the measurement results of the refractive index for the film of Example 1- (1) are shown in FIG. 8).

The second order nonlinear coefficient calculated based on the thickness and refractive index was d ₁₁₁ = 11.8 pm / V (28.2 × 10 ⁻⁹ esu) at 1064 nm, and d ₁₁₁ = 14.6 pm / V (34.9 × 10 ^{−9 at} 1560 nm). esu). These two values could not be directly compared because the first value was obtained at resonance, where both increase and reuptake of SHG were expected. In fact, referring to FIG. 1, the absorption coefficient of the film at 780 nm was 0.02, which was more than 10 times less than 0.25 at 532 nm.

As a result, the modified nonlinear modulus in consideration of absorption is 21.1 pm / V at 1064 nm and 15.3 pm / V at 1560 nm, which confirms the resonance that occurs in nonlinear progression at 1064 nm.

Test Example 5- (2)

In addition to using the film of Experimental Example 1- (2), the nonlinear coefficient was analyzed and computed on the same conditions as Test Example 5- (1).

The d ₁₁₁ value of the film of Experimental Example 1- (2) calculated using the refractive index was 22.4 pm / V (53.3 × 10 ⁻⁹ esu). The high d ₁₁₁ value in the lattice is due in part to the increased number density of TTB molecules. Instead, higher TTB concentrations provide the conditions to produce regions with a higher number density than expected from the concentration of the stock solution in the PPMA matrix. As a comparison, the d value of TTB bulk crystals measured femto-second at 1028 nm was 1580 × 10 ⁻⁹ esu, which is about 20 times larger than the film. In addition to uniformly high nonlinear effects in the film, the non-planar orientation of the molecules appears to be the same in all observed regions, confirming the cylindrical symmetry and uniformity of molecular behavior of each crystal region. As such, the difference between the TTB bulk crystal and the film is believed to be due to the difference in structure. That is, in bulk crystals, there is a uniform crystal matrix, but in thin films, regions with different planar orientations are connected.

As described above, although the nonlinear coefficient of the film of Example 1- (2) is lower than that of the TTB bulk crystal, the film of Example 1- (2) includes the TTB crystal region, thereby satisfying the industrially required nonlinear optical effect. You can. In addition, unlike the TTB bulk crystals, since it is in the form of a film, it can be directly applied to the device. Furthermore, the film of Example 1- (2) has an advantage of being stable for 1 year at room temperature and 3 days at 100 ° C.

1 shows absorption spectra for the films of Example 1- (1) and Comparative Example 1. FIG.

2A is a polarized light microscope image of the nonlinear optical film of Example 1- (1).

FIG. 2B is a polarization microscope image of the nonlinear optical film when the nonlinear optical film of FIG. 2A is rotated 45 degrees. FIG.

2C is a polarization microscope image of the nonlinear optical film of Example 1- (2).

FIG. 2D is a polarization microscope image of the nonlinear optical film when the film of FIG. 2C is rotated 45 degrees. FIG.

Figure 3a is the result of X-ray diffraction analysis on the TTB powder.

3B is an X-ray diffraction analysis of the film of Example 1- (1).

3C is an X-ray diffraction analysis of the film of Comparative Example 1.

4 shows SHG and two photon excitation fluorescence spectra for the film of Example 1- (1).

5A shows the SHG polarization analysis method.

Figure 5b shows a marker fringe measurement method.

5C shows laboratory coordinates (X, Y, Z) and molecular coordinates [1 (U)._One), 2 (U₂), 3 (U₃Euler angle at)]θ, Ø, Ψ) Is defined.

5D shows the hexagonal structure of the TTB crystal region in the film.

5E shows the arrangement of TTB molecules.

6A shows a polarization diagram for the film of Example 1- (1) at a wavelength of 1064 nm.

6B shows the polarization diagram for the film of Example 1- (1) at a wavelength of 1560 nm.

6C shows marker fringe measurement results for Y-cut quartz at a wavelength of 532 nm.

6D shows the marker fringe measurement results for the film of Example 1- (1) at a wavelength of 532 nm.

6E shows marker fringe measurement results for Y-cut quartz at a wavelength of 780 nm.

6E shows marker fringe measurement results for the film of Example 1- (1) at a wavelength of 780 nm.

7A shows a polarization diagram for the film of Example 1- (2) at a wavelength of 780 nm.

7B shows the marker fringe measurement results for the film of Example 1- (2) at a wavelength of 780 nm.

8 shows the refractive index of the film of Example 1- (1).

Claims (16)

Dissolving the octapole molecules and the polymer of the following formula (1) in a solvent to obtain a mixed solution;

(Wherein A is CN, D is NR ₂ , R is C _m H _{2m +1} , n is an integer from 1 to 5, m is an integer from 1 to 100) Applying the mixed solution onto a plate; And A method of manufacturing a nonlinear optical film comprising evaporating a solvent from the applied mixed solution to perform crystal growth and self-orientation of the octapole molecules. The method of claim 1, wherein the octapole molecule is 1,3,5-tricyano-2,4,6-tris (paradiethylaminostyryl) benzene (TTB). The method of claim 1, wherein the polymer is polymethyl methacrylate (PMMA). The method of claim 1, wherein the solvent is chlorobenzene. The method of claim 1, wherein the evaporation is performed at a temperature condition of 20 to 30 ℃. The method of claim 1, wherein the evaporation is performed for 5 to 9 days. The method of claim 1, further comprising filtering the mixed solution after obtaining the mixed solution and before applying the mixed solution onto a plate. The method of claim 7, wherein the filtration step is performed by passing the mixed solution through a filter having a diameter of 0.1 to 0.3 μm. A nonlinear optical film obtained by the manufacturing method of claim 1, comprising a polymer and octapole molecules of the following formula (1).

(Wherein A is CN, D is NR ₂ , R is C _m H _{2m +1} , n is an integer from 1 to 5, m is an integer from 1 to 100) 10. The nonlinear optical film of claim 9, wherein the nonlinear optical film includes a crystal region, and the crystal region has a cylindrical shape including octapole molecules. 10. The nonlinear optical film of claim 9, wherein the amount of the octapole molecule is 10 to 30% by weight based on the polymer. 11. The nonlinear optical film of claim 10, wherein the octapole molecules are formed spaced apart from each other in the crystal region. 13. The method according to any one of claims 9 to 12, wherein the octapole molecule is 1,3,5-tricyano-2,4,6-tris (paradiethylaminostyryl) benzene (TTB). Nonlinear optical film. The nonlinear optical film of claim 9, wherein the polymer is polymethylmethacrylate (PMMA). 14. The nonlinear optical film of claim 13, wherein the 1,3,5-tricyano-2,4,6-tris (paradiethylaminostyryl) benzene (TTB) is spaced at a distance of 7.5 kV. 14. The nonlinear optical film of claim 13, wherein the 1,3,5-tricyano-2,4,6-tris (paradiethylamino styryl) benzene has a branch length of 15 mm from the center.

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