Water-soluble dye functionalized potassium hydrogen phthalate nonlinear optical crystal as well as preparation method and application thereof

Abstract

The invention discloses a water-soluble dye functionalized potassium hydrogen phthalate nonlinear optical crystal as well as a preparation method and application thereof. The chemical formula of a potassium hydrogen phthalate crystal matrix is C8H5O4K, the water-soluble dye functionalized potassium hydrogen phthalate nonlinear optical crystal belongs to an orthorhombic system, the space group is Pca21, the cell parameters are # imgabs 0 # alpha = beta = gamma = 90 degrees, # imgabs 1 #, and the crystal material has good third-order nonlinear optical performance and shows a remarkable saturated absorption effect; the large-size water-soluble dye functionalized potassium hydrogen phthalate nonlinear optical crystal is grown by adopting a constant-temperature evaporation method, the preparation method is simple and convenient to operate, low in cost and less in pollution, and the used raw materials are low in toxicity and short in growth cycle; the water-soluble dye functionalized potassium hydrogen phthalate nonlinear optical crystal does not deliquesce 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 invention relates to the field of functional materials, and more specifically to a water-soluble dye functionalized potassium hydrogen phthalate nonlinear optical crystal, and a preparation method and application thereof. Background Art

[0002] In recent years, organic third-order nonlinear optical materials have attracted extensive attention. They have the advantages of large nonlinear optical coefficients, wide light transmission range, fast response speed, etc., and also have the characteristics of structural diversity, easy molecular tailoring, structural modification and high integrated performance. Among them, water-soluble dyes with π-electron conjugated system are a class of organic third-order nonlinear optical materials with excellent performance. They can produce large molecular polarizability and fast response time under non-resonant excitation. At the same time, they also have the advantages of low dielectric constant, flexible change of chemical structure and physical properties, easy preparation and integration into devices. Using these water-soluble dyes, it is possible to effectively control the frequency, intensity, phase and other parameters of the laser, and they are applied in fields such as all-optical switching. However, dye molecules also have some disadvantages, such as easy aging, easy damage, and difficulty in growing large-sized single crystals.

[0003] Crystal materials are an important type of second-order nonlinear optical materials. They can change the wavelength of lasers, thereby expanding the tunable range of lasers. Therefore, nonlinear crystal materials are the preferred materials for making optical devices and are widely used in fields such as electro-optical switches. Crystals have good mechanical properties and high laser damage thresholds, but they also have some disadvantages, such as low nonlinear coefficients, narrow light transmission range, and harsh phase matching conditions.

[0004] Therefore, it is necessary to provide a water-soluble dye functionalized potassium hydrogen phthalate nonlinear optical crystal to enhance the efficiency and stability of the crystal's second-order nonlinear optical effect. At the same time, the crystal can play a protective role as a matrix to improve the aging and damage problems of organic molecules. Summary of the invention

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

[0006] The second object of the present invention is to provide a method for preparing the above-mentioned water-soluble dye functionalized potassium hydrogen phthalate nonlinear optical crystal.

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

[0008] In order to achieve the above object, the present invention adopts the following technical solutions:

[0009] In a first aspect, a water-soluble dye functionalized potassium hydrogen phthalate nonlinear optical crystal, wherein the chemical formula of the potassium hydrogen phthalate crystal matrix is ​​C 8 H 5 O 4 K; The water-soluble dye-functionalized potassium hydrogen phthalate nonlinear optical crystal belongs to the orthorhombic system with a space group of Pca2 1 , its unit cell parameters are:

[0010] In a second aspect, a method for preparing a water-soluble dye functionalized potassium hydrogen phthalate nonlinear optical crystal comprises the following steps:

[0011] 1) Prepare a saturated solution of potassium hydrogen phthalate at a temperature of 20-30°C, and let it stand for 3-7 days to obtain a seed crystal;

[0012] 2) adding a water-soluble dye to a saturated potassium hydrogen phthalate solution and stirring the mixture evenly, and then adding the seed crystal obtained in step 1), and growing the crystal by a constant temperature evaporation method at 20-30° C. to obtain a water-soluble dye functionalized potassium hydrogen phthalate nonlinear optical crystal.

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

[0014] Furthermore, the water-soluble dye is basic fuchsin or acid fuchsin.

[0015] Furthermore, the basic fuchsin structural formula is:

[0016]

[0017] The acid fuchsin structural formula is:

[0018]

[0019] Potassium hydrogen phthalate is the basic framework of the dyed crystal. It is an ionic organic salt compound formed by anion-cation bonds and Coulomb forces. The anion group in the structural composition is a π-electron conjugated system, with carboxyl -COOH and carboxylate COO - , which are connected by OH···O hydrogen bonds. The test results of X-ray single crystal diffraction show that the incorporation of basic fuchsin dye has no effect on the crystal structure of potassium hydrogen phthalate.

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

[0021] Furthermore, in step 2), crystal growth is performed in a clean, pollution-free, and air-convection-free static environment.

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

[0023] In a third aspect, the present invention 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 whose raw materials include the above-mentioned water-soluble dye functionalized potassium hydrogen phthalate nonlinear optical crystal is also within the protection scope of the present invention.

[0025] It should also be noted that, unless otherwise specified, any range described in the present invention includes the end value and any value between the end values ​​and any sub-range formed by the end value or any value between the end values. The preparation methods in the present invention are conventional methods unless otherwise specified, and the raw materials used can be obtained from public commercial channels or prepared according to the prior art unless otherwise specified.

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

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

[0028] The water-soluble dye functionalized potassium hydrogen phthalate nonlinear optical crystal involved in the present invention 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 saturation absorption characteristics. The water-soluble dye functionalized potassium hydrogen phthalate nonlinear optical crystal involved in the present invention has good saturation absorption characteristics (third-order nonlinear optical effect) and has potential application value in all-optical switch devices and the like. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] The specific implementation modes of the present invention will be further described in detail below in conjunction with the accompanying drawings.

[0030] Figure 1 A photograph showing the nonlinear optical crystal of potassium hydrogen phthalate functionalized with basic fuchsin in the present invention.

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

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

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

[0034] Figure 5 The UV-visible spectrum of the basic fuchsin functionalized potassium hydrogen phthalate nonlinear optical crystal of the present invention is shown.

[0035] Figure 6 The ultraviolet-visible spectrum of the acid fuchsin functionalized potassium hydrogen phthalate nonlinear optical crystal of the present invention is shown.

[0036] Figure 7 The ultraviolet-visible spectrum of the crystal violet functionalized potassium hydrogen phthalate nonlinear optical crystal of the present invention is shown.

[0037] Figure 8 The nonlinear optical performance diagram of the basic fuchsin functionalized potassium hydrogen phthalate nonlinear optical crystal in the present invention is shown.

[0038] Fig. 9 The nonlinear optical performance diagram of the acid fuchsin functionalized potassium hydrogen phthalate nonlinear optical crystal in the present invention is shown.

[0039] Fig.10 The nonlinear optical performance diagram of the crystal violet functionalized potassium hydrogen phthalate nonlinear optical crystal of the present invention is shown. DETAILED DESCRIPTION

[0040] In order to more clearly illustrate the present invention, the present invention is further described below in conjunction with preferred embodiments and accompanying drawings. Similar components in the accompanying drawings are represented by the same reference numerals. It should be understood by those skilled in the art that the content specifically described below is illustrative rather than restrictive, and should not be used to limit the scope of protection of the present invention.

[0041] Example 1

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

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

[0044] Using the constant temperature evaporation method, add basic fuchsin (50.00 mg, 0.15 mmol) to 50 mL of saturated potassium hydrogen phthalate solution at room temperature and stir evenly, then add seed crystals. Keep the temperature constant during the crystal growth process. Place the container in a static environment without shaking, pollution, or air convection, and cover the container with a porous polyethylene sheet to adjust the evaporation rate of the water solvent to 0.05-0.1 kg m -2 h -1 .

[0045] like Figure 1 As shown in FIG. 1 , the water-soluble dye functionalized potassium hydrogen phthalate nonlinear optical crystal prepared in this embodiment is shown in FIG. Figure 2 As shown in the figure, 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. Figure 5 As shown, the functionalized crystal exhibits an absorption peak centered at 565 nm.

[0046] The third-order nonlinear effect-saturation absorption characteristic of the potassium hydrogen phthalate nonlinear optical crystal functionalized with basic fuchsin dye: the third-order nonlinear optical performance of the material is tested by a Z-scan method.

[0047] The test laser is a Nd:YAG pulse laser with a pulse width of 8ns, a pulse frequency of 10Hz, a laser wavelength of 532nm, and a laser incident energy of 10μJ. It is measured that the basic fuchsin dye functionalized potassium hydrogen phthalate nonlinear optical crystal has obvious saturation absorption characteristics, such as Figure 8 As shown, the normalized transmittance rises to 3.51, and the nonlinear absorption coefficient is -802.62 cm·GW 1 .

[0048] Example 2

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

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

[0051] Using the constant temperature evaporation method, add acid fuchsin (50.00 mg, 0.085 mmol) to 50 mL of saturated potassium hydrogen phthalate solution at room temperature and stir evenly, then add seed crystals. Keep the temperature constant during the crystal growth process. Place the container in a static environment without shaking, pollution, or air convection, and cover the container with a porous polyethylene sheet to adjust the evaporation rate of the water solvent to 0.05-0.1 kg m-2 h -1 .

[0052] Powder diffraction pattern Figure 3 As shown in the figure, the test results are consistent with those of pure potassium hydrogen phthalate crystals, indicating that the incorporation of acid fuchsin dye has no effect on the crystal structure of potassium hydrogen phthalate. Figure 6 As shown, the functionalized crystal exhibits an absorption peak centered at 568 nm.

[0053] The third-order nonlinear effect-saturation absorption characteristic of the acid fuchsin dye functionalized potassium hydrogen phthalate nonlinear optical crystal: the Z-scan method is used to test the third-order nonlinear optical performance of the material.

[0054] The test laser is a Nd:YAG pulse laser with a pulse width of 8ns, a pulse frequency of 10Hz, a laser wavelength of 532nm, and a laser incident energy of 10μJ. It is measured that the acid fuchsin dye functionalized potassium hydrogen phthalate nonlinear optical crystal has obvious saturation absorption characteristics, such as Fig. 9 As shown, the normalized transmittance rises to 2.23, and the nonlinear absorption coefficient is -390.41 cm·GW 1 .

[0055] Comparative Example 1

[0056] The synthesis steps of the nonlinear optical crystal based on the crystal violet dye functionalized potassium hydrogen phthalate in this comparative example are as follows:

[0057] At room temperature, analytically pure potassium hydrogen phthalate (125.00 g, 0.61 mol) was prepared into a saturated solution with 500 mL of distilled water and allowed to stand for 3-7 days to obtain high-quality seed crystals;

[0058] Using the constant temperature evaporation method, add crystal violet (50.00 mg, 0.12 mmol) to 50 mL of saturated potassium hydrogen phthalate solution at room temperature and stir evenly, then add seed crystals. Keep the temperature constant during the crystal growth process. Place the container in a static environment without shaking, pollution, or air convection, and cover the container with a porous polyethylene sheet to adjust the evaporation rate of the water solvent to 0.05-0.1 kg m -2 h -1 .

[0059] Powder diffraction pattern Figure 4 As shown in the figure, the test results are consistent with those of pure potassium hydrogen phthalate crystals, indicating that the incorporation of crystal violet dye has no effect on the crystal structure of potassium hydrogen phthalate. Figure 7 As shown, the functionalized crystals exhibited broad absorption bands centered at 546 nm and 585 nm.

[0060] The third-order nonlinear effect-saturation absorption characteristics of the potassium hydrogen phthalate nonlinear optical crystal functionalized with crystal violet dye: the Z-scan method is used to test the third-order nonlinear optical performance of the material.

[0061] The test laser is a Nd:YAG pulse laser with a pulse width of 8ns, a pulse frequency of 10Hz, a laser wavelength of 532nm, and a laser incident energy of 10μJ. It is measured that the crystal violet dye functionalized potassium hydrogen phthalate nonlinear optical crystal has obvious saturation absorption characteristics, such as Fig.10 As shown, the normalized transmittance rises to 1.67, and the nonlinear absorption coefficient is -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 limitations on the implementation methods of the present invention. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made based on the above description. It is impossible to list all the implementation methods here. All obvious changes or modifications derived from the technical solution 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, Features: The chemical formula of potassium hydrogen phthalate crystal matrix is ​​C 8 H 5 O 4 K; The water-soluble dye-functionalized potassium hydrogen phthalate nonlinear optical crystal belongs to the orthorhombic system with a space group of Pca2 1 , its unit cell parameters are: α=β=γ=90°, 2. A method for preparing the water-soluble dye functionalized potassium hydrogen phthalate nonlinear optical crystal as claimed in claim 1, It is characterized in that Water-soluble dye-functionalized potassium hydrogen phthalate nonlinear optical crystals were prepared by constant temperature evaporation method.

3. The preparation method according to claim 2, It is characterized in that The specific steps include: 1) Prepare a saturated solution of potassium hydrogen phthalate at a temperature of 20-30°C, and let it stand for 3-7 days to obtain a seed crystal; 2) adding a water-soluble dye to a saturated potassium hydrogen phthalate solution and stirring the mixture evenly, and then adding the seed crystal obtained in step 1), and growing the crystal by a constant temperature evaporation method at 20-30° C. to obtain a water-soluble dye functionalized potassium hydrogen phthalate nonlinear optical crystal.

4. The preparation method according to claim 3, It is characterized in that The water-soluble dye has a π-electron conjugated system consisting of three benzene rings.

5. The preparation method according to claim 3, It is characterized in that The water-soluble dye is basic fuchsin or acid fuchsin.

6. The preparation method according to claim 5, It is characterized in that The basic fuchsin structural formula is: The acid fuchsin structural formula is:

7. The preparation method according to claim 3, It is characterized in that In step 2), the molar ratio of the saturated potassium hydrogen phthalate solution to the water-soluble dye is 400:1-800:

1.

8. The preparation method according to claim 3, It is characterized in that In step 2), crystal growth is performed in a clean, pollution-free, and air-convection-free static environment.

9. The preparation method according to claim 3, It is characterized in that Step 2) During the crystal growth process, the evaporation rate of the water solvent in the saturated potassium hydrogen phthalate solution is 0.05-0.1 kg m -2 h -1 .

10. Use of the water-soluble dye functionalized potassium hydrogen phthalate nonlinear optical crystal as claimed in claim 1 or the water-soluble dye functionalized potassium hydrogen phthalate nonlinear optical crystal obtained by the preparation method as claimed in any one of claims 2 to 9 in the preparation of third-order nonlinear optical materials.

Images