CN115246655A - Terbium stannate and preparation method thereof - Google Patents

Abstract

The invention relates to the field of luminescent materials, in particular to a stannic terbium chlorate and a preparation method thereof, wherein the preparation method of the stannic terbium chlorate comprises the steps of dissolving stannous chloride dihydrate and terbium salt serving as precursors in a solvent at room temperature to form a solution A; and spin-coating the solution A on a substrate to form a film, and heating to obtain the substrate-based terbium stannate film. The method has the advantages of simple preparation process, low requirement on equipment, high controllability, less thermal budget involved in the preparation process, and excellent photoluminescence performance of the product.

Description

Terbium stannous chlorate and preparation method thereof

technical field

The invention relates to the field of luminescent materials, in particular to terbium tin chlorate and a preparation method thereof.

Background technique

SnO ₂ is a wide band gap semiconductor with a band gap of 3.6eV, high carrier mobility, low phonon energy, and high transmittance in the visible and near-infrared bands. Doping Sb or F can greatly increase the electron concentration in _SnO2 , making it an excellent conductive material. As a commercialized transparent conductive material, the current process for preparing _SnO2 is very mature, and high-quality thin films can be obtained by vacuum vapor deposition. The solid solubility of rare earth elements in _SnO2 is high (up to ~10 mol%), and its oxygen-rich environment is conducive to the optical transition of rare earth ions. How to develop and prepare materials with photoluminescence properties is an urgent research topic.

SUMMARY OF THE INVENTION

The primary technical problem to be solved by the present invention is to provide a terbium tin chlorate with simple process, low cost, short reaction period and strong photoluminescence performance and a preparation method thereof.

In order to solve the above-mentioned technical problems, a technical solution provided by the present application is: a preparation method of terbium stannous chlorate, comprising: using stannous chloride dihydrate and terbium salt as precursors, dissolving in a solvent at room temperature to form a solution A; The solution A is spin-coated on a substrate to form a film, and heated to obtain a substrate-based terbium tin chlorate thin film.

Wherein, the heating temperature is 10-250°C.

The terbium salt is terbium chloride hexahydrate.

Wherein, the mass ratio of stannous chloride dihydrate to terbium chloride hexahydrate is (0.1-1):(0.0001-0.1).

Among them, the solvent includes ethanol.

Wherein, the mass volume ratio of stannous chloride dihydrate, terbium chloride hexahydrate and ethanol is (0.1-1) g:(0.0001-0.1) g:(0.5-50) ml.

Wherein, the substrate includes a silicon substrate, a germanium substrate, a gallium arsenide substrate or a gallium nitride substrate.

Among them, the number of layers of spin coating is 1-10 layers.

The application also includes a second technical solution: a kind of terbium tin chlorate prepared by the above-mentioned preparation method of terbium tin chlorate. luminescence.

Among them, the terbium tin chlorate thin film has a luminescence intensity of 3.8×10 ³ in the 550nm band.

Beneficial effects of the present invention:

(1) the preparation method of a kind of terbium stannous chlorate of the present invention, the terbium tin chlorate thin film is prepared by combining the sol-gel method and the heat treatment on the heating stage, without expensive instruments and equipment, through reasonable process control, can obtain stannous chloric acid Terbium thin film, and terbium stannochlorate has strong photoluminescence properties in the visible band. It can be applied to the fields of silicon-based light sources, LED light sources, integrated circuits and display devices.

(2) the preparation method of a kind of terbium stannous chlorate of the present invention, the raw material is cheap and easy to obtain, the synthesis process is simple, the controllability is high, the cost is low, the reaction cycle is short, and does not pollute the environment, the terbium stannous chlorate prepared by the preparation Thin film materials have strong photoluminescence properties.

(3) the preparation method of a kind of terbium stannous chlorate of the present invention, the reaction temperature is low, the thermal budget is few, can reduce energy consumption.

Description of drawings

FIG. 1 is a photoluminescence diagram of the terbium tin chlorate thin film prepared in Example 1 of the present application.

2 is a scanning electron microscope image of the terbium tin chlorate thin film prepared in Example 1 of the present application.

3 is another scanning electron microscope image of the terbium tin chlorate thin film prepared in Example 1 of the present application.

4 is the EDS diagram of the terbium tin chlorate thin film prepared in Example 1 of the present application.

Detailed ways

The following specific examples are used to further illustrate the method described in the present invention, but it does not mean that the present invention is limited to these examples.

An embodiment of the present application provides a method for preparing terbium tin chlorate, including: using stannous chloride dihydrate and terbium salt as precursors, dissolving in a solvent at room temperature to form solution A; spin-coating solution A on a substrate Film formation and heating to obtain a substrate-based terbium tin chlorate thin film.

The preparation method of terbium tin chlorate in the embodiment of the present application is simple. The sol is formed at room temperature, and the film is formed by spin coating to form a gel, and then the terbium tin chlorate film can be obtained by heating; The method is simple, the cost of raw materials is low, the preparation period is short, the prepared film is uniform and strong, and the preparation process does not pollute the environment. The terbium stannous chlorate prepared in the examples of the present application has strong photoluminescence performance in the visible wavelength band, and can be used in the fields of light sources, such as silicon-based light sources, LED light sources, and display devices.

In the examples of the present application, the heating temperature is 10-250°C. In the present application, the terbium tin chlorate thin film can be prepared by heating at a low temperature, the required thermal budget is low, and the prepared terbium tin chlorate thin film has photoluminescence properties. In the embodiments of the present application, the heating temperature may be 25°C, 50°C, 60°C, 80°C, 100°C, 120°C, 150°C, 180°C, 210°C, or 250°C.

In the embodiments of the present application, the terbium salt includes terbium chloride hexahydrate. In the embodiments of the present application, the terbium salt is terbium chloride hexahydrate, so that the prepared terbium tin chlorate has a higher purity. In other embodiments, the terbium salt may also include terbium nitrate and the like.

In the embodiments of the present application, the mass ratio of stannous chloride dihydrate to terbium chloride hexahydrate is (0.1-1): (0.0001-0.1). In the examples of the present application, by controlling the mass ratio of stannous chloride dihydrate to terbium chloride hexahydrate, the prepared terbium tin chlorate thin film has the best photoluminescence performance.

In the embodiments of the present application, the solvent includes ethanol. Among them, stannous chloride dihydrate and terbium chloride hexahydrate can be dissolved in ethanol, and ethanol is volatile, which can shorten the preparation time of terbium tin chlorate thin film products. In other embodiments, the solvent can also be a mixture of water and ethanol.

In the examples of this application, the mass volume ratio of stannous chloride dihydrate, terbium chloride hexahydrate and ethanol is (0.1-1) g:(0.0001-0.1) g:(0.5-50) ml. By reasonably controlling the mass volume ratio of stannous chloride dihydrate, terbium chloride hexahydrate and ethanol in the examples of the present application, stannous chloride dihydrate and terbium chloride hexahydrate can be completely dispersed in ethanol, and can be prepared Terbium tin chlorate.

In the embodiments of the present application, the substrate is a silicon substrate. In other embodiments, the substrate may also be a germanium substrate, a gallium arsenide substrate, or a gallium nitride substrate. The photoluminescence performance of the substrate can be improved, so that a terbium tin chlorate film based on a silicon lining can be formed, which can be applied to the fields of silicon-based light sources, LED light sources, integrated circuits and the like.

In the examples of the present application, the number of layers of spin coating is 1-10 layers. In the examples of the present application, the number of layers of spin coating is 1 layer, 2 layers, 3 layers, 5 layers, 6 layers, 8 layers, 10 layers, etc., by spin coating solution A with different layers, so that the thickness of the film is prepared It can be set as desired, and at this thickness, the photoluminescence performance is optimal. In the embodiments of the present application, the thickness of the terbium tin chlorate thin film is 1-100 nm.

The application also includes a second technical solution: a kind of terbium tin chlorate prepared by the above-mentioned preparation method of terbium tin chlorate. luminescence. The terbium tin chlorate thin film of the embodiments of the present application can be applied to the fields of silicon-based light sources, LED light sources, display devices, integrated circuits, and the like.

In the examples of the present application, the terbium tin chlorate thin film has a luminescence intensity of 3.8×10 ³ in the wavelength band of 550 nm. The terbium tin chlorate implemented in this application has extremely strong photoluminescence properties.

In order to facilitate the understanding of the technical solutions of the present application, the following specific examples are provided.

Example 1:

A kind of preparation method of terbium stannous chlorate, its steps comprise:

Step 1: Dissolve 0.4516g of stannous chloride dihydrate and 0.0216g of terbium chloride hexahydrate in sequence in 15ml of absolute ethanol, and stir at room temperature until completely dissolved to form mixed solution A;

Step 2, take 40 μl of solution A, prepare a film on a silicon substrate by spin coating, spin-coat 3 layers, and heat on a heating table at 150° C. to obtain a silicon substrate-based terbium tin chlorate film.

As shown in Figure 1, the photoluminescence diagram of the terbium tin chlorate thin film prepared in this example, it can be seen from Figure 1 that the prepared terbium tin chlorate thin film has strong photoluminescence performance in the visible band; 550nm In the wavelength band, the luminous intensity is 3.8×10 ³ , in the 490 nm band, the luminous intensity is 1.8×10 ³ , in the 590 nm band, the luminous intensity is 1.45×10 ³ ; in the 628 nm band, the luminous intensity is 1.2×10 ³ . As shown in FIG. 2 and FIG. 3 , the scanning electron microscope images of the terbium tin chlorate thin films prepared in the examples of the present application, it can be seen from the figures that the prepared terbium tin chlorate thin films have strong compactness and uniform distribution, The particle size of the terbium stannous chlorate particles is between 100nm and 800nm. As shown in Figure 4, the EDS diagram of the product prepared in the embodiment of the application, it can be seen from the figure that the prepared product contains the elements oxygen, tin, chlorine and terbium, indicating that the product prepared in the embodiment of the application is tin chloride Terbium acid.

Example 2:

The difference between this embodiment and embodiment 1 is that in step 1, the amount of terbium chloride hexahydrate is changed to 0.0036g, as follows:

The preparation method of terbium stannous chlorate, comprising:

Step 1: Dissolve 0.4516g of stannous chloride dihydrate and 0.0036g of terbium chloride hexahydrate in sequence in 15ml of absolute ethanol, and stir at room temperature until completely dissolved to form mixed solution A;

Step 2, take 40 μl of solution A, prepare a film on a silicon substrate by spin coating, spin coat 3 layers, and place it on a heating table at 150 ° C for heating for 10 minutes to obtain a silicon substrate-based tin Terbium chlorate film.

In this embodiment of the present application, a terbium tin chlorate thin film can be formed on a silicon substrate, and the morphology and performance of the terbium tin chlorate thin film are the same as or similar to those in Embodiment 1. The preparation of the terbium tin chlorate thin film in the examples of the present application is short in time, low in temperature, and requires small thermal preheating.

Example 3:

The difference between this embodiment and embodiment 1 is that the amount of ethanol in step 1 is changed to 20ml, as follows:

The preparation method of terbium stannous chlorate, comprising:

Step 1: Dissolve 0.4516g of stannous chloride dihydrate and 0.0216g of terbium chloride hexahydrate in sequence in 20ml of absolute ethanol, and stir at room temperature until completely dissolved to form mixed solution A;

Step 2, take 40 μl of solution A, prepare a film on a silicon substrate by spin coating, spin-coat 3 layers, and heat on a heating table at 150° C. to obtain a silicon substrate-based terbium tin chlorate film.

Example 4:

The difference between this embodiment and embodiment 1 is that the temperature of the heating table treatment in step 2 becomes 50°C, and the others are the same as those in embodiment 1, as follows:

The preparation method of terbium stannous chlorate, comprising:

Step 1: Dissolve 0.4516g of stannous chloride dihydrate and 0.0216g of terbium chloride hexahydrate in sequence in 15ml of absolute ethanol, and stir at room temperature until completely dissolved to form mixed solution A;

Step 2, take 40 μl of solution A, prepare a film on a silicon substrate by spin coating, spin coat 3 layers, and place it on a 50°C heating table to heat to obtain a silicon substrate-based terbium tin chlorate film.

Example 5:

The difference between this embodiment and embodiment 1 is that the temperature of the heating table treatment in step 2 becomes 60°C, and the other is the same as embodiment 1, and the details are as follows:

The preparation method of terbium stannous chlorate, comprising:

Step 1: Dissolve 0.4516g of stannous chloride dihydrate and 0.0216g of terbium chloride hexahydrate in sequence in 15ml of absolute ethanol, and stir at room temperature until completely dissolved to form mixed solution A;

Step 2, take 40 μl of solution A, prepare a film on a silicon substrate by spin coating, spin coat 3 layers, and place it on a 60°C heating table to heat to obtain a silicon substrate-based terbium tin chlorate film.

Example 6:

The difference between this embodiment and embodiment 1 is that the temperature of the heating table treatment in step 2 is changed to 70 ° C, and the other is the same as embodiment 1, and the details are as follows:

The preparation method of terbium stannous chlorate, comprising:

Step 1: Dissolve 0.4516g of stannous chloride dihydrate and 0.0216g of terbium chloride hexahydrate in sequence in 15ml of absolute ethanol, and stir at room temperature until completely dissolved to form mixed solution A;

Step 2, take 40 μl of solution A, prepare a film on a silicon substrate by spin coating, spin coat 3 layers, and place it on a heating table at 70° C. to heat to obtain a silicon substrate-based terbium tin chlorate film.

Example 7:

The difference between this embodiment and embodiment 1 is that the temperature of the heating table treatment in step 2 becomes 80°C, and the others are the same as those in embodiment 1, as follows:

The preparation method of terbium stannous chlorate, comprising:

Step 1: Dissolve 0.4516g of stannous chloride dihydrate and 0.0216g of terbium chloride hexahydrate in sequence in 15ml of absolute ethanol, and stir at room temperature until completely dissolved to form mixed solution A;

Step 2, take 40 μl of solution A, prepare a film on a silicon substrate by spin-coating, spin-coat 3 layers, and heat on a heating table at 80° C. to obtain a silicon-substrate-based terbium tin chlorate film.

Example 8:

The difference between this embodiment and embodiment 1 is that the temperature of the heating table treatment in step 2 becomes 90°C, and the others are the same as those in embodiment 1, as follows:

The preparation method of terbium stannous chlorate, comprising:

Step 1: Dissolve 0.4516g of stannous chloride dihydrate and 0.0216g of terbium chloride hexahydrate in sequence in 15ml of absolute ethanol, and stir at room temperature until completely dissolved to form mixed solution A;

Step 2, take 40 μl of solution A, prepare a film on a silicon substrate by spin coating, spin coat 3 layers, and place it on a heating table at 90° C. to heat to obtain a silicon substrate-based terbium tin chlorate film.

Example 9:

The difference between this embodiment and embodiment 1 is that the temperature of the heating table treatment in step 2 becomes 100°C, and the others are the same as those in embodiment 1, as follows:

The preparation method of terbium stannous chlorate, comprising:

Step 1: Dissolve 0.4516g of stannous chloride dihydrate and 0.0216g of terbium chloride hexahydrate in sequence in 15ml of absolute ethanol, and stir at room temperature until completely dissolved to form mixed solution A;

Step 2, take 40 μl of solution A, prepare a film on a silicon substrate by spin coating, spin coat 3 layers, and place it on a 100°C heating table to heat to obtain a silicon substrate-based terbium tin chlorate film.

Example 10:

The preparation method of terbium stannous chlorate, comprising:

Step 1: Dissolve 0.4516g of stannous chloride dihydrate and 0.0216g of terbium chloride hexahydrate in sequence in 15ml of absolute ethanol, and stir at room temperature until completely dissolved to form mixed solution A;

Step 2, take 40 μl of solution A, prepare a film on a silicon substrate by spin coating, spin coat 3 layers, and place it on a heating table at 250° C. for 20 min to obtain a silicon substrate-based terbium tin chlorate film.

Example 11:

The preparation method of terbium stannous chlorate, comprising:

Step 1: Dissolve 0.4516g of stannous chloride dihydrate and 0.0216g of terbium chloride hexahydrate in sequence in 15ml of absolute ethanol, and stir at room temperature until completely dissolved to form mixed solution A;

Step 2, take 40 μl of solution A, prepare a film on a silicon substrate by spin coating, spin coat 3 layers, and place it on a heating table at 10°C for 2 hours to obtain a silicon substrate-based terbium tin chlorate film.

Example 12:

The preparation method of terbium stannous chlorate, comprising:

Step 1: Dissolve 0.4516g of stannous chloride dihydrate and 0.0216g of terbium chloride hexahydrate in sequence in 15ml of absolute ethanol, and stir at room temperature until completely dissolved to form mixed solution A;

Step 2, take 40 μl of solution A, prepare a film on a silicon substrate by spin coating, spin coat 3 layers, and place it on a heating table at 10°C for 2 hours to obtain a silicon substrate-based terbium tin chlorate film.

Example 13:

The preparation method of terbium stannous chlorate, comprising:

Step 1: Dissolve 0.1 g of stannous chloride dihydrate and 0.0001 g of terbium chloride hexahydrate in sequence in 0.5 ml of absolute ethanol, stir at room temperature until completely dissolved, and stir for 2 minutes to form mixed solution A;

Step 2, take the above solution A, prepare a film on a germanium substrate by spin coating, spin one layer, and place it on a heating table at 50°C for 1 hour to obtain a germanium substrate-based terbium tin chlorate thin film.

Example 14:

The preparation method of terbium stannous chlorate, comprising:

Step 1: Dissolve 1g of stannous chloride dihydrate and 0.1g of terbium chloride hexahydrate in sequence in 50ml of absolute ethanol, and stir at room temperature until completely dissolved to form mixed solution A;

Step 2, take the above solution A, prepare a film on a gallium arsenide substrate by spin coating, spin coat 10 layers, and place it on a heating table at 80°C for 0.5h to obtain a tin chloride based on a gallium arsenide substrate. Terbium acid film.

Example 15:

The preparation method of terbium stannous chlorate, comprising:

Step 1: Dissolve 1g of stannous chloride dihydrate and 0.0001g of terbium chloride hexahydrate in sequence in 10ml of absolute ethanol, and stir at room temperature until completely dissolved to form mixed solution A;

Step 2, take the above solution A, prepare a film on a gallium nitride substrate by spin coating, spin coat 6 layers, and place it on a heating table at 80°C for 0.5h to obtain a gallium nitride substrate-based tin chloride Terbium acid film.

Example 16:

The preparation method of terbium stannous chlorate, comprising:

Step 1: Dissolve 0.1 g of stannous chloride dihydrate and 0.1 g of terbium chloride hexahydrate in sequence in 50 ml of absolute ethanol, and stir at room temperature until completely dissolved to form mixed solution A;

Step 2: Take the above solution A, prepare a film on a gallium nitride substrate by spin coating, spin coat 8 layers, and place it on a heating table at 80°C for 0.2 h to obtain a tin chloride based on gallium nitride substrate. Terbium acid film.

Although embodiments of the present invention have been disclosed above, they are not limited to the applications set forth in the specification and embodiments. It can be fully adapted to various fields suitable for the present invention. Additional modifications can be readily implemented by those skilled in the art. Therefore, the invention is not to be limited to the specific details and illustrations herein shown and described, without departing from the general concept defined by the appended claims and the scope of equivalents.

Claims (10)

1. A method for preparing terbium stannate, which is characterized by comprising the following steps:

dissolving stannous chloride dihydrate and terbium salt serving as precursors in a solvent at room temperature to form a solution A;

and spin-coating the solution A on a substrate to form a film, and heating to obtain the substrate-based terbium stannate film.

2. The method for the preparation of a terbium stannate chlorate according to claim 1, wherein the heating temperature is 10-250 ℃.

3. The method for the preparation of a terbium stannate chlorate according to claim 1, wherein said terbium salt is terbium chloride hexahydrate.

4. The method for the preparation of a terbium stannate chlorate according to claim 3, wherein the mass ratio of said stannous chloride dihydrate to said terbium chloride hexahydrate is (0.1-1) to (0.0001-0.1).

5. The method for the preparation of a terbium stannate chlorate according to claim 3, wherein said solvent comprises ethanol.

6. The method for preparing the terbium stannate chlorate according to claim 5, wherein the mass-to-volume ratio of the stannous chloride dihydrate, the terbium chloride hexahydrate and the ethanol is (0.1-1) g, (0.0001-0.1) g, (0.5-50) ml.

7. The method for preparing a terbium stannate chlorate according to claim 1, wherein the substrate comprises a silicon substrate, a germanium substrate, a gallium arsenide substrate or a gallium nitride substrate.

8. The method for preparing a terbium stannate chlorate according to claim 1, wherein the number of spin-coated layers is 1 to 10.

9. A terbium stannate prepared by the method for preparing a terbium stannate according to any one of claims 1 to 8, comprising a thin film of terbium stannate, wherein the thin film of terbium stannate exhibits photoluminescence in the visible wavelength range.

10. The terbium stannate chlorate of claim 9, wherein the terbium stannate film has a luminous intensity of 3.8 x 10 in the 550nm wavelength band ³ 。

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