Water-soluble dye functionalized hydrogen phthalate nonlinear optical crystal, preparation method and application thereof

Abstract

The application discloses a water-soluble dye functionalized potassium hydrogen phthalate nonlinear optical crystal and a preparation method and application thereof. The chemical formula of the potassium hydrogen phthalate crystal matrix is C8H5O4K, the water-soluble dye functionalized potassium hydrogen phthalate nonlinear optical crystal belongs to an orthorhombic system, a space group is Pca21, and the cell parameters are alpha = beta = gamma = 90 degrees. The crystal material has good third-order nonlinear optical performance and shows a significant saturated absorption effect. A large-size water-soluble dye functionalized potassium hydrogen phthalate nonlinear optical crystal is grown by using a constant-temperature evaporation method, and the preparation method has the advantages of simple operation, low cost, less pollution, low toxicity of raw materials, and short growth cycle. The water-soluble dye functionalized potassium hydrogen phthalate nonlinear optical crystal is not deliquescent in air, has stable physical and chemical properties, is easy to cut and polish, and is suitable for manufacturing nonlinear optical devices.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of functional materials. More particularly, it relates to a water-soluble dye functionalized hydrogen potassium phthalate nonlinear optical crystal, a preparation method and application thereof. BACKGROUND

[0002] In recent years, organic third-order nonlinear optical materials have attracted extensive attention due to their large nonlinear optical coefficient, wide light transmission range, fast response speed, and other advantages, as well as their structural diversity, easy molecular tailoring, structural modification, and high integration performance. Among them, water-soluble dyes with π electron conjugated system are a kind of excellent organic third-order nonlinear optical materials, which can produce large molecular polarizability and fast response time under non-resonant excitation, and have low dielectric constant, flexible chemical structure and physical properties, easy preparation and integration into devices. Using these water-soluble dyes, the frequency, intensity, phase and other parameters of laser can be effectively controlled, and they are applied in the field of all-optical switching. However, dye molecules also have some disadvantages, such as easy aging, easy damage, and difficult to grow large size single crystals.

[0003] Crystal materials are an important class of second-order nonlinear optical materials, which can convert the wavelength of laser, thereby expanding the tunable range of laser, so nonlinear crystal materials are the preferred materials for making optical devices, and have wide application in the field of electro-optic switching. Crystals have good mechanical properties and high laser damage threshold, but also have some disadvantages, such as low nonlinear coefficient, narrow light transmission range, and stringent phase matching conditions.

[0004] Therefore, it is necessary to provide a water-soluble dye functionalized hydrogen potassium phthalate nonlinear optical crystal, so as to enhance the efficiency and stability of the second-order nonlinear optical effect of the crystal, and the crystal as a matrix can play a protective role to improve the easy aging and damage of organic molecules. SUMMARY

[0005] A first object of the present application is to provide a water-soluble dye functionalized hydrogen potassium phthalate nonlinear optical crystal. The water-soluble dye functionalized hydrogen potassium phthalate nonlinear optical crystal of the present application has good saturated absorption characteristics and can be used as a nonlinear optical absorption material.

[0006] A second object of the present application is to provide a preparation method of the above-mentioned water-soluble dye functionalized hydrogen potassium phthalate nonlinear optical crystal.

[0007] A third object of the present application is to provide an application of the above-mentioned water-soluble dye functionalized hydrogen potassium phthalate nonlinear optical crystal in third-order nonlinear optical materials.

[0008] To achieve the above object, the application adopts the following technical scheme:

[0009] In a first aspect, a water-soluble dye functionalized hydrogen phthalate nonlinear optical crystal has a chemical formula of C8H5O4K, and belongs to an orthorhombic system with a space group of Pca21 and a cell parameter of a=0.7 nm, b=1.4 nm, and c=0.5 nm.

[0010] In a second aspect, a preparation method of the water-soluble dye functionalized hydrogen phthalate nonlinear optical crystal includes the following steps:

[0011] 1) A saturated solution of hydrogen phthalate is prepared at a temperature of 20-30°C, and is left to stand for 3-7 days to obtain a seed crystal;

[0012] 2) The water-soluble dye is added to the saturated solution of hydrogen phthalate and stirred uniformly, and the seed crystal obtained in step 1) is added, and a constant-temperature evaporation method is used to grow the crystal at a temperature of 20-30°C, so as to obtain the water-soluble dye functionalized hydrogen phthalate nonlinear optical crystal.

[0013] Further, the water-soluble dye has a π-electron conjugated system composed of three benzene rings.

[0014] Further, the water-soluble dye is selected from basic fuchsin or acid fuchsin.

[0015] Further, the basic fuchsin has a structural formula of:

[0016]

[0017] The acid fuchsin has a structural formula of:

[0018]

[0019] Hydrogen phthalate is the basic framework of the dyeing crystal, and is an ionic organic salt compound formed through ionic bonds and coulomb forces. The anion group in the structural composition is a π-electron conjugated system, and the carboxyl group COOH and the carboxylate COO - X-ray single crystal diffraction test results show that the incorporation of the basic fuchsin dye does not affect the crystal structure of hydrogen phthalate.

[0020] Further, in step 2), the molar ratio of the saturated solution of hydrogen phthalate to the water-soluble dye is 400:1-800:1.

[0021] Further, the crystal growth in step 2) is carried out in a clean, non-polluted, non-air-convection static environment.

[0022] Further, the evaporation rate of the water solvent in the saturated solution of the potassium hydrogen phthalate in step 2) is 0.05-0.1 kg m -2 h -1 .

[0023] In a third aspect, the present application provides an application of the above-mentioned water-soluble dye functionalized potassium hydrogen phthalate nonlinear optical crystal in a third-order nonlinear optical material.

[0024] It can be understood that the third-order nonlinear optical material containing the above-mentioned water-soluble dye functionalized potassium hydrogen phthalate nonlinear optical crystal in the raw material is also within the protection scope of the present application.

[0025] It should be noted that, if not specifically stated, any range described in the present application includes the end values and any numerical value between the end values and any sub-range formed by the end values or any numerical value between the end values. The preparation method in the present application is a conventional method if not specifically stated, and the raw materials used are available from public commercial channels or prepared according to the prior art if not specifically stated.

[0026] The beneficial effects of the present application are as follows:

[0027] The incorporation of the dye in the water-soluble dye functionalized potassium hydrogen phthalate nonlinear optical crystal of the present application does not affect the crystal structure of the potassium hydrogen phthalate.

[0028] The water-soluble dye functionalized potassium hydrogen phthalate nonlinear optical crystal involved in the present application has nonlinear optical properties and can be used as a nonlinear optical absorption material. The experimental results of Z-scan show that the crystal has obvious nonlinear saturated absorption characteristics. The water-soluble dye functionalized potassium hydrogen phthalate nonlinear optical crystal involved in the present application has good saturated absorption characteristics (third-order nonlinear optical effect) and has potential application value in all-optical switching devices and the like. BRIEF DESCRIPTION OF DRAWINGS

[0029] The specific embodiments of the present application will be further described in detail below with reference to the accompanying drawings.

[0030] Figure 1 A photo of the basic fuchsin functionalized potassium hydrogen phthalate nonlinear optical crystal in the present application is shown.

[0031] Figure 2 A powder diffraction pattern of the basic fuchsin functionalized potassium hydrogen phthalate nonlinear optical crystal in the present application is shown.

[0032] Figure 3A powder diffraction pattern of the acid fuchsin functionalized potassium hydrogen phthalate nonlinear optical crystal in the present application is shown.

[0033] Figure 4 A powder diffraction pattern of the crystal violet functionalized potassium hydrogen phthalate nonlinear optical crystal in the present application is shown.

[0034] Figure 5 A UV-Vis spectrum of the acid fuchsin functionalized potassium hydrogen phthalate nonlinear optical crystal in the present application is shown.

[0035] Figure 6 A UV-Vis spectrum of the acid fuchsin functionalized potassium hydrogen phthalate nonlinear optical crystal in the present application is shown.

[0036] Figure 7 A UV-Vis spectrum of the acid fuchsin functionalized potassium hydrogen phthalate nonlinear optical crystal in the present application is shown.

[0037] Figure 8 A nonlinear optical performance chart of the acid fuchsin functionalized potassium hydrogen phthalate nonlinear optical crystal in the present application is shown.

[0038] Figure 9 A nonlinear optical performance chart of the acid fuchsin functionalized potassium hydrogen phthalate nonlinear optical crystal in the present application is shown.

[0039] Figure 10 A nonlinear optical performance chart of the acid fuchsin functionalized potassium hydrogen phthalate nonlinear optical crystal in the present application is shown. DETAILED DESCRIPTION

[0040] In order to more clearly illustrate the present application, the present application will be further described below with reference to the preferred embodiments and the accompanying drawings. Like components are denoted by the same reference numerals in the drawings. It should be understood by those skilled in the art that the specific descriptions below are illustrative rather than limiting, and should not limit the scope of protection of the present application.

[0041] Example 1

[0042] The synthesis steps of the potassium hydrogen phthalate nonlinear optical crystal functionalized based on the basic fuchsin dye in the present embodiment are as follows:

[0043] An analytical pure potassium hydrogen phthalate (125.00 g, 0.61 mol) was prepared into a saturated solution with 500 mL of distilled water at room temperature, and was left to stand for 3-7 days to obtain high-quality seed crystals;

[0044] The constant temperature evaporation method was used to add basic fuchsin (50.00 mg, 0.15 mmol) into 50 mL of a saturated solution of potassium hydrogen phthalate at room temperature and stir until uniform. The temperature was kept constant during the crystal growth process. The container was placed in a static environment without shaking, contamination, or air convection. A porous polyethylene plate was placed above the container to adjust the evaporation rate of the aqueous solvent to 0.05-0.1 kg m -2 h -1 .

[0045] As shown in Figure 1 , the water-soluble dye functionalized potassium hydrogen phthalate nonlinear optical crystal prepared in this example. The powder diffraction pattern is shown in Figure 2 , and the test results are consistent with those of pure potassium hydrogen phthalate crystals, indicating that the incorporation of basic fuchsin dye has no effect on the crystal structure of potassium hydrogen phthalate. The UV-Vis spectrum is shown in Figure 5 , and the functionalized crystal exhibits an absorption peak centered at 565 nm.

[0046] The third-order nonlinear effect of the basic fuchsin dye functionalized potassium hydrogen phthalate nonlinear optical crystal is saturated absorption: the third-order nonlinear optical properties of the material were tested using the Z-scan method.

[0047] The test laser was a Nd:YAG pulse laser with a pulse width of 8 ns, a pulse frequency of 10 Hz, a laser wavelength of 532 nm, and a laser incident energy of 10 μJ. The basic fuchsin dye functionalized potassium hydrogen phthalate nonlinear optical crystal was found to have obvious saturated absorption characteristics, as shown in Figure 8 , with a normalized transmittance of 3.51 and a nonlinear absorption coefficient of -802.62 cm·GW 1 .

[0048] Example 2

[0049] The synthesis steps of the acid fuchsin dye functionalized potassium hydrogen phthalate nonlinear optical crystal of this example are as follows:

[0050] An analytical pure potassium hydrogen phthalate (125.00 g, 0.61 mol) was prepared into a saturated solution with 500 mL of distilled water at room temperature, and the solution was left to stand for 3-7 days to obtain high-quality seed crystals;

[0051] The constant temperature evaporation method was used to add acid fuchsin (50.00 mg, 0.085 mmol) into 50 mL of a saturated solution of potassium hydrogen phthalate at room temperature and stir until uniform. The temperature was kept constant during the crystal growth process. The container was placed in a static environment without shaking, contamination, or air convection. A porous polyethylene plate was placed above the container to adjust the evaporation rate of the aqueous solvent to 0.05-0.1 kg m-2 h -1 .

[0052] The powder diffraction pattern is shown in FIG. 3, and the test results are consistent with those of pure potassium hydrogen phthalate crystals, indicating that the incorporation of the acid fuchsin dye has not affected the crystal structure of potassium hydrogen phthalate. Figure 3 The UV-visible spectrum is shown in FIG. 4, and the functionalized crystal exhibits an absorption peak centered at 568 nm. Figure 6 The third-order nonlinear effect of the acid fuchsin dye functionalized potassium hydrogen phthalate nonlinear optical crystal—saturation absorption characteristics: the third-order nonlinear optical properties of the material were tested by the Z-scan method.

[0053] The test laser was a Nd:YAG pulse laser with a pulse width of 8 ns, a pulse frequency of 10 Hz, a laser wavelength of 532 nm, and a laser incident energy of 10 μJ. The acid fuchsin dye functionalized potassium hydrogen phthalate nonlinear optical crystal was found to have obvious saturation absorption characteristics, as shown in FIG. 5, with the normalized transmittance rising to 2.23 and the nonlinear absorption coefficient being -390.41 cm·GW 1 .

[0054] Figure 9 Comparative Example 1

[0055] The synthesis steps of the crystal violet dye functionalized potassium hydrogen phthalate nonlinear optical crystal of the present comparative example are as follows:

[0056] Analytically pure potassium hydrogen phthalate (125.00 g, 0.61 mol) was prepared into a saturated solution with 500 mL of distilled water at room temperature, and was left to stand for 3-7 days to obtain high-quality seed crystals;

[0057] A constant temperature evaporation method was used, and at room temperature, crystal violet (50.00 mg, 0.12 mmol) was added to 50 mL of a potassium hydrogen phthalate saturated solution and stirred uniformly, and seed crystals were added. The temperature was kept constant during the crystal growth process. The container was placed in a static environment without shaking, contamination, or air convection, and a porous polyethylene plate was used to cover the top of the container to adjust the evaporation rate of the aqueous solvent to 0.05-0.1 kg m -2 h -1 .

[0058] The powder diffraction pattern is shown in FIG. 6, and the test results are consistent with those of pure potassium hydrogen phthalate crystals, indicating that the incorporation of the crystal violet dye has not affected the crystal structure of potassium hydrogen phthalate.

[0059] The UV-visible spectrum is shown in FIG. 7, and the functionalized crystal exhibits a wide absorption band centered at 546 nm and 585 nm. Figure 4 Figure 7 The third-order nonlinear effect of the crystal violet dye functionalized potassium hydrogen phthalate nonlinear optical crystal—saturation absorption characteristics: the third-order nonlinear optical properties of the material were tested by the Z-scan method. ​​

[0060] The third-order nonlinear effect-saturated absorption characteristics of potassium hydrogen phthalate nonlinear optical crystal functionalized with crystal violet dye were tested using the Z-scan method.

[0061] The laser used in the test was an Nd:YAG pulsed laser with a pulse width of 8 ns, a pulse frequency of 10 Hz, a laser wavelength of 532 nm, and an incident laser energy of 10 μJ. The crystal violet dye-functionalized potassium hydrogen phthalate nonlinear optical crystal was found to exhibit significant saturation absorption characteristics, such as... Figure 10 As shown, the normalized transmittance increased to 1.67, and the nonlinear absorption coefficient was -293.89 cm·GW. 1 .

[0062] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. For those skilled in the art, other variations or modifications can be made based on the above description. It is impossible to exhaustively list all the implementation methods here. All obvious variations or modifications derived from the technical solutions of the present invention are still within the protection scope of the present invention.

Claims

1. A water-soluble dye functionalized Potassium hydrogen phthalate nonlinear optical crystal, characterized in that: The chemical formula of the potassium hydrogen phthalate crystal matrix is C8H5O4K; the water-soluble dye functionalized potassium hydrogen phthalate nonlinear optical crystal belongs to an orthorhombic system, a space group is Pca21, and cell parameters are as follows: a=9.6119(8) Å, b=13.3370(11) Å, c=6.4797(4) Å, α=β=γ=90°, V=830.66(11) Å 3 ; and the water-soluble dye is basic fuchsin or acid fuchsin.

2. A method for the preparation of water soluble dye functionalized Potassium hydrogen phthalate nonlinear optical crystal as claimed in claim 1, wherein, The application discloses a water-soluble dye functionalized hydrogen phthalate nonlinear optical crystal prepared by a constant-temperature evaporation method, and specifically comprises the following steps: 1) a saturated hydrogen phthalate solution is prepared under the condition of a temperature of 20-30 DEG C, and is left to stand for 3-7 days to obtain a seed crystal; 2) the saturated hydrogen phthalate solution is stirred uniformly with water-soluble dye, and then the seed crystal obtained in step 1) is added, and the crystal growth is carried out by a constant-temperature evaporation method under the condition of a temperature of 20-30 DEG C and keeping the temperature unchanged to obtain the water-soluble dye functionalized hydrogen phthalate nonlinear optical crystal.

3. The preparation method according to claim 2, characterized in that, The basic fuchsin has the structural formula as shown in the following formula: ； The acid fuchsin has the structural formula as shown in the following formula: 。 4. The preparation method according to claim 2, characterized in that, In step 2), the molar ratio of the saturated hydrogen phthalate solution to the water-soluble dye is 400:1-800:

1.

5. The preparation method according to claim 2, characterized in that, In step 2), the crystal growth is carried out in a clean, non-polluted and non-air convection static environment.

6. The preparation method according to claim 2, characterized in that, Step 2) The evaporation rate of the aqueous solvent in the saturated solution of potassium hydrogen phthalate during the crystal growth process is 0.05-0.1 kg m -2 h -1 .

7. Application of the water-soluble dye functionalized hydrogen phthalate nonlinear optical crystal according to claim 1 or the water-soluble dye functionalized hydrogen phthalate nonlinear optical crystal obtained by the preparation method according to any one of claims 2-6 to preparation of a third-order nonlinear optical material.

Images