Metal-organic photon glass material with near-infrared light waveguide characteristic and application of metal-organic photon glass material in optical storage

Abstract

The invention discloses a metal-organic photon glass material with near-infrared light waveguide characteristics and application of the metal-organic photon glass material in optical storage. The method specifically comprises the following steps: mixing zinc nitrate, lanthanide metal nitrate and 4-cyano imidazole, adding water for ultrasonic dissolution, heating for 12-18 hours at 370-375K, and volatilizing a solvent to obtain a glassy substance, namely the metal-organic photon glass material with the near-infrared light waveguide characteristic. The material can be prepared into a one-dimensional glass optical fiber or two-dimensional photon glass after being heated and melted. Different signal emission is obtained by exciting metal-organic photon glass materials which are doped with lanthanide series metals in different proportions and have near-infrared light waveguide characteristics, and optical information storage is achieved. The invention provides a new thought and method for preparing a novel glass material with high optical property and a photon storage material with low light transmission loss.

Description

Technical Field

[0001] The present invention belongs to the technical field of optical functional materials, and particularly relates to a metal-organic photonic glass material with near-infrared optical waveguide characteristics and its application in optical storage. Background Art

[0002] Near-infrared luminescent materials have wide applications in the fields of biomedicine, military reconnaissance, optical storage, etc. Lanthanide ion doping is an effective strategy to achieve near-infrared luminescence. However, the 4f-4f transition of lanthanide ions is parity-forbidden, making it difficult to achieve efficient luminescence in the near-infrared region and hindering its applications. Therefore, it is necessary to select a suitable host material to sensitize the luminescence of lanthanide metals. Generally speaking, the host material needs to meet the following conditions: one is that the lowest excited triplet state energy level matches the resonance energy level of lanthanide metals, and the other is that it has a long triplet excited state lifetime. As a material with great development prospects in the 21st century, optical functional metal-organic framework materials have received extensive attention due to their structural flexibility and adjustable porosity. Summary of the Invention

[0003] The purpose of the present invention is to provide a metal-organic photonic glass material with near-infrared optical waveguide characteristics and its application in optical storage. The present invention adopts an easy-to-operate solvothermal synthesis method to integrate efficient near-infrared emission and excellent processability into the metal-organic photonic glass to transmit and modulate light. The present invention provides new ideas and methods for preparing new glass materials with excellent optical properties and photon storage materials with low light transmission loss.

[0004] The preparation method of the metal-organic photonic glass material with near-infrared optical waveguide characteristics is as follows: Mix zinc nitrate, lanthanide metal nitrate and 4-cyanoimidazole, add water and dissolve them by ultrasonic wave, then heat at 370-375K for 12-18 hours. After the solvent volatilizes, a glassy substance is obtained, which is the metal-organic photonic glass material with near-infrared optical waveguide characteristics.

[0005] The lanthanide metal nitrate is europium nitrate or neodymium nitrate.

[0006] The molar ratio range of the zinc nitrate and the lanthanide metal nitrate is 1:0.01-0.50.

[0007] The molar ratio range of the zinc nitrate and the 4-cyanoimidazole is 1-3:4.

[0008] After heating and melting the metal-organic photonic glass material with near-infrared optical waveguide characteristics, a one-dimensional glass optical fiber or a two-dimensional photonic glass can be made.

[0009] Application of the above-prepared metal-organic photonic glass material with near-infrared optical waveguide properties in optical storage. By exciting the metal-organic photonic glass material with near-infrared optical waveguide properties doped with lanthanide metals in different proportions, different signal emissions are obtained to achieve optical information storage.

[0010] In the present invention, a series of novel near-infrared-emitting metal-organic photonic glass materials are synthesized by the "bottom-up" supramolecular coordination self-assembly of zinc nitrate, lanthanide metal nitrates and 4-cyanoimidazole in different proportions. The rigidity of the metal-organic framework glass helps to stabilize triplet excitons, and the plasticity of the glass network topology is conducive to the effective transmission and conversion of photons. The metal-organic photonic glass matrix prepared in the present invention has ultra-long-lived all-phosphorescence emission. Based on the effective energy transfer from the metal-organic photonic glass matrix to the doped lanthanide metal ions, sensitizing the luminescence of rare earth ions, and the atomic-level dispersion of lanthanide metal ions in the glass matrix, long-lived emission in the near-infrared regions I and II is achieved. In addition, the metal-organic photonic glass has good processing performance and mass transfer ability, and can prepare one-dimensional glass optical fibers and two-dimensional photonic glasses with low-loss active photon transmission. Using the long-lived near-infrared emission and spatially resolved optical waveguide properties of this material, the potential application of this new type of photonic glass material in the field of optical information storage is demonstrated. Description of the Drawings

[0011] Figure 1 XRD and optical microscope images of the metal-organic photonic glass powders prepared in Examples 1, 2, and 3.

[0012] Figure 2 Emission spectra of the metal-organic photonic glasses prepared in Examples 2 and 3.

[0013] Figure 3 Optical waveguide attenuation curve of the metal-organic photonic glass prepared in Example 3. Detailed Description of the Invention Example 1

[0014] Dissolve 148.8 mg of zinc nitrate and 93.1 mg of 4-cyanoimidazole in 10 mL of deionized water. After ultrasonic treatment for 10 minutes, place it in a 20 mL glass bottle. Then heat the reaction mixture to 373 K and maintain this temperature for 12 hours. After the solvent evaporates, the target product, the metal-organic photonic glass matrix, can be obtained.

[0015] Analysis of the product by powder X-ray diffraction, X-ray photoelectron spectroscopy, and nuclear magnetic resonance spectroscopy shows that Zn 2+ Coordinates with nitrogen atoms and oxygen atoms in a six-coordinate manner. There is no long-range order in the amorphous photonic glass, and the metal-organic photonic glass material matrix is obtained. The optical microscope shows that the surface of the prepared glass material matrix is smooth. Example 2

[0016] Dissolve 125.0 mg of zinc nitrate, 35.7 mg of europium nitrate, and 93.1 mg of 4-cyanoimidazole in 10 mL of deionized water. After ultrasonic treatment for 10 minutes, transfer it into a 20 mL glass bottle. Then heat the reaction mixture to 373 K and maintain this temperature for 12 hours. After the solvent evaporates, the target product, metal-organic photonic glass, can be obtained. Adjust the addition amount of europium nitrate to obtain metal-organic photonic glasses with different doping ratios.

[0017] Analysis of the product by powder X-ray diffraction, X-ray photoelectron spectroscopy, nuclear magnetic resonance spectroscopy, and scanning electron microscopy shows that there is no long-range order in the amorphous photonic glass, and Eu 3+ is densely and evenly dispersed without agglomeration, and Eu 3+ -doped metal-organic photonic glass materials are obtained. The optical microscope shows that the surface of the prepared glass material is smooth.

[0018] Through spectral analysis, it can be seen that at a low doping ratio (Eu 3+ : Zn 2+ = 1:99), the emission peak of this Eu 3+ -doped metal-organic photonic glass material is mainly located at 440 nm, and the luminescence lifetime is 66.13 ms. In addition, small characteristic peaks appear at 593, 617, 695, and 819 nm. As the doping ratio increases, the emission at 440 nm gradually weakens, the luminescence lifetime gradually shortens to 16.92 ms, and the emission of the characteristic peaks at 593, 617, 695, and 819 nm gradually increases. By adjusting the doping ratio, the emission color and lifetime of the metal-organic photonic glass material can be controlled.

[0019] Thermogravimetric-differential scanning calorimetry (TGA-DSC) characterization shows that the glass transition temperature of this metal-organic photonic glass material is 304 K, and the weight loss temperature is 409 K. Example 3

[0020] Dissolve 125.0 mg of zinc nitrate, 26.4 mg of neodymium nitrate, and 93.1 mg of 4-cyanoimidazole in 10 mL of deionized water. After ultrasonic treatment for 10 minutes, transfer it into a 20 mL glass bottle. Then heat the reaction mixture to 373 K and maintain this temperature for 12 hours. After the solvent evaporates, the target product, metal-organic photonic glass, can be obtained. Adjust the addition amount of neodymium nitrate to obtain metal-organic photonic glasses with different doping ratios. After heating and melting, one-dimensional glass optical fibers and two-dimensional photonic glasses are made.

[0021] Analysis of the product by powder X-ray diffraction, X-ray photoelectron spectroscopy, nuclear magnetic resonance spectroscopy, and scanning electron microscopy shows that there is no long-range order in the amorphous photonic glass, and Nd3+ are densely and evenly dispersed without agglomeration, and Nd 3+ -doped metal-organic photon glass materials are obtained. Optical microscopy shows that the surface of the prepared glass materials is smooth.

[0022] It can be seen from spectral analysis that this Nd 3+ -doped metal-organic photon glass materials exhibit characteristic fine emission peaks of Nd at 864, 1048, and 1315 nm. The emission intensity gradually increases with the increase of the doping ratio. The time-resolved lifetime decay curve shows that the luminescence lifetime of this Nd 3+ -doped metal-organic photon glass materials is 2226.10 - 755.98 μs, showing long-lived near-infrared emission. 3+ Thermogravimetric-differential scanning calorimetry measurement, i.e., TGA-DSC characterization, shows that the glass transition temperature of this metal-organic photon glass material is 308 K, and the weight loss temperature is 409 K.

[0023] Waveguide characterization shows that this Nd

[0024] -doped metal-organic photon glass materials have near-infrared optical waveguide properties. The loss coefficient of the one-dimensional glass fiber optical waveguide prepared above is 0.0081 dB / μm, and the loss coefficient of the two-dimensional photon glass longitudinal optical waveguide is 0.0051 dB / μm, which is lower than that of most molecular optical waveguide materials. 3+ Using the above-prepared one-dimensional glass fiber and two-dimensional photon glass, potential applications of photon information storage can be realized. For example,

[0025] as shown, when a laser is excited at one end, the signals output from the other end include multiple signals at 864, 897, 1048, 1067, and 1315 nm. When the signal intensity at 1048 nm in the second near-infrared region is greater than the signal intensity at 864 nm in the first near-infrared region, it is recorded as binary "1". When the signal intensity at 1048 nm in the second near-infrared region is less than the signal intensity at 864 nm in the first near-infrared region, it is recorded as binary "0". Binary "1" and "0" can be achieved by exciting photon glasses with different Nd Figure 3 doping ratios. 3+ -doped photon glasses.

Claims

1. A method for preparing a metal-organic photonic glass material having near-infrared optical waveguide properties, characterized in that: The specific operation of the preparation method is: zinc nitrate, lanthanide metal nitrate and 4-cyanoimidazole are mixed, water is added for ultrasonic dissolution, and then heated at 370-375K for 12-18 hours to obtain a glassy substance after the solvent evaporates, that is, a metal-organic photonic glass material with near-infrared optical waveguide characteristics.

2. The preparation method according to claim 1, characterized in that: The lanthanide metal nitrate is europium nitrate or neodymium nitrate.

3. The preparation method according to claim 1, characterized in that: The molar ratio of the zinc nitrate to the lanthanide metal nitrate is in the range of 1:0.01-0.

50.

4. The preparation method according to claim 1, characterized in that: The molar ratio of the zinc nitrate to 4-cyanoimidazole is in the range of 1-3:

4.

5. The preparation method according to claim 1, characterized in that: Metal-organic photonic glass materials with near-infrared optical waveguide properties can be heated and melted to produce one-dimensional glass optical fibers or two-dimensional photonic glass.

6. Application of the metal-organic photonic glass material with near-infrared optical waveguide characteristics prepared by the method according to any one of claims 1 to 5 in optical storage, characterized in that: By exciting metal-organic photonic glass materials with near-infrared optical waveguide properties doped with lanthanide metals in different proportions, different signal emissions are obtained to achieve optical information storage.

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