CN101560680A - Terbium-doped gadolinium oxide green light luminescent film and preparation method thereof - Google Patents

Abstract

The invention discloses a terbium-doped gadolinium oxide green light luminescent film and a preparation method thereof. A layer of terbium-doped gadolinium oxide green light luminescent film is deposited on a conductive glass substrate. The preparation method comprises the following steps: selecting a soluble gadolinium salt solution and a soluble terbium salt as raw materials; carrying out thin film deposition on the conductive glass substrate by an electrochemical method; inserting a three-electrode into an evenly mixed solution of a gadolinium salt and the terbium salt, and depositing the mixture in a constant temperature water bath at a temperature of between 50 and 70 DEG C, wherein regulation voltage is between -0.90 and -1.4V (vs an SCE saturation calomel reference electrode), and the deposition time is 15 to 60 minutes; washing and drying the obtained film; and then carrying out rapid annealing on the film for 3 to 5 minutes at a temperature of between 400 and 700 DEG C under the protection of argon gas. The prepared luminescent film is even and compact and has no cracking; the film material has a sharp green light emission spectrum at 545 nanometers and 491 nanometers; the luminescent film has the advantages of simple technique, easily-obtained raw materials, low cost, low energy consumption and no toxicity; and the formed film is even and compact and has no cracking.

Description

A green light-emitting film doped with terbium-gadolinium oxide and its preparation method

technical field

The invention relates to a terbium-doped gadolinium oxide green light-emitting thin film and a preparation method thereof.

Background technique

Rare earth doped luminescence is the 4f inner electron transition luminescence of rare earth ions. Due to the shielding effect of outer electrons, the 4f inner electrons of rare earth ions are less affected by external environmental factors, with good monochromaticity, high brightness, long life and high efficiency. . The luminescent spectrum ranges from ultraviolet, visible to near-infrared, and has a wide range of applications in optical communication, flat display, lighting, optical storage and other fields. [Wang Tao, Pan Xiaojun, Zhang Zhenxing, Li Hui, Xie Erqing, Room temperature visible luminescence of terbium-doped nanocrystalline GaN films, Chinese Journal of Rare Earth 26(2008): 244-247]. Due to the limited content of rare earth elements, in order to make the performance of rare earth elements get better application, there have been research reports on rare earth ion-doped nano-luminescent materials in the last ten or twenty years [Zhou Jianguo, Li Zhenquan, Zhao Fengying, Xia Shuping, Gao Shiyang, Nano A review of research on Y ₂ O ₃ :Eu ³⁺ luminescent materials, Advances in Chemical Industry, 6(2003):573-577].

With the rapid development of information technology, people's requirements for living standards are getting higher and higher, and the demand for large-screen high-definition color TVs, high-resolution displays, projection TVs, and high-efficiency energy-saving lamps is growing rapidly. At the same time, with the requirements of a friendly society and an energy-saving society, people require displays to have the characteristics of thinness, light weight, low-voltage drive, and low power consumption in addition to the diversification of functions. This requires phosphors to have Multi-performance, strong luminescence, high color rendering, long life and so on.

The main peak of Tb ³⁺ intrinsic luminescence spectrum is around 550nm, which just corresponds to the green color of the standard chromaticity system (CIE). Therefore, terbium-gadolinium oxide is a green fluorescent material with excellent performance. Tricolor fluorescent lamps and stained glass, etc. Tb ³⁺ doping has attracted people's attention. Electrochemical coating method to prepare terbium-doped gadolinium oxide thin film is a new preparation method, and can prepare thin film with excellent properties. Through the adjustment of reaction parameters, co-deposited films of gadolinium oxide and terbium oxide can be uniformly grown on the substrate material, which can not only reduce the reaction materials, but also save the subsequent coating process, which greatly reduces the production cost. In addition, the electrochemical method has uniform film formation, controllable deposition thickness, simple equipment and operation, mild reaction conditions, and less environmental pollution. It is a new, clean, mild, and environmentally friendly method.

Contents of the invention

The object of the present invention is to propose a terbium-doped gadolinium oxide green light-emitting film and a preparation method thereof. Using soluble gadolinium salt and terbium salt solution as raw materials, a terbium-doped gadolinium oxide film is deposited on a conductive glass substrate by an electrochemical method. Terbium-doped gadolinium oxide green light-emitting film was obtained by rapid annealing at high temperature.

The technical scheme step that the present invention adopts is as follows:

1. A green luminescent film doped with terbium-gadolinium oxide:

A green light-emitting thin film of gadolinium oxide and terbium oxide is deposited on one surface of a conductive glass substrate.

The chemical formula of the luminescent film is Gd ₂ O ₃ :Tb ³⁺ , and the film material has sharp green emission spectra at 545 nm and 491 nm.

Two, a kind of preparation method of terbium-doped gadolinium oxide green light emitting thin film, the steps of this method are as follows:

1) Dissolve soluble gadolinium salt and terbium salt in deionized water respectively, stir, and prepare gadolinium salt solution and terbium salt solution with molar concentration of 0.05-0.2mol/L;

2) Take the above-mentioned gadolinium salt and terbium salt solution to form a uniformly mixed solution, and control the solution temperature at 50°C to 70°C through a constant temperature water bath;

3) A three-electrode electrochemical cell composed of a working electrode, a counter electrode and a reference electrode is used to deposit thin films on a conductive glass substrate. The three electrodes are inserted into a mixed solution composed of gadolinium salt and terbium salt solution, and the working electrode and terbium salt solution are adjusted. The voltage between the SCE saturated calomel reference electrodes is between -0.9V and -1.4V, and the deposition time is controlled between 15 minutes and 60 minutes;

4) The deposited film is washed with deionized water and dried, and then the film is rapidly annealed under the protection of argon at 400° C. to 700° C. for 3 minutes to 5 minutes.

In the described three-electrode electrochemical cell, the working electrode is a conductive glass substrate, the counter electrode is a platinum electrode, a gold electrode or a graphite electrode, and the reference electrode is a SCE saturated calomel reference electrode.

The soluble gadolinium salt and terbium salt are nitrates.

The chemical formula of the luminescent film is Gd ₂ O ₃ :Tb ³⁺ , the film is formed uniformly and densely without cracks, and has sharp green light emission spectra at 546 nanometers and 491 nanometers. The beneficial effects that the present invention has are:

The present invention prepares a novel terbium-doped gadolinium oxide green light-emitting film through a simple electrochemical deposition method and a subsequent high-temperature annealing process. The film material is uniform and dense without cracking, and there are sharp green lights at 546 nanometers and 491 nanometers ll. The invention has the advantages of simple process, easy-to-obtain raw materials, low cost, low energy consumption, non-toxicity, uniform and compact film formation without cracking.

Description of drawings

Figure 1 is a schematic diagram of the structure of a terbium-doped gadolinium oxide green light-emitting thin film on a conductive glass substrate

In Fig. 1: 1. a green light-emitting film doped with terbium-gadolinium oxide; 2. a conductive glass substrate.

Fig. 2 is the energy spectrogram of the product obtained in embodiment 1.

Fig. 3 is the XRD spectrogram of the product obtained in Example 1.

Figure 4 is an electron micrograph (low magnification) of the product obtained in Example 1.

Figure 5 is an electron micrograph (high magnification) figure of the product obtained in Example 1.

6 is the photoluminescence emission spectrum of the product obtained in Example 1.

Detailed ways

As shown in FIG. 1 , the present invention deposits a layer of terbium-doped gadolinium oxide green light-emitting thin film 1 on a conductive glass substrate 2 . The chemical formula of the luminescent film is Gd ₂ O ₃ :Tb ³⁺ , and the film material has sharp green emission spectra at 546 nm and 491 nm.

Example 1:

Terbium-doped gadolinium oxide green light-emitting film and its synthesis, 4.513g gadolinium nitrate hexahydrate was dissolved in 100mL deionized water, stirred, and made into a gadolinium salt solution with a molar concentration of 0.1mol/L; 4.529g terbium nitrate hexahydrate was dissolved in 100mL of deionized water, stirred, and made into a terbium salt solution with a molar concentration of 0.1mol/L.

The above-mentioned gadolinium salt and terbium salt were mixed according to a certain ratio, and the mixed solution was 12 mL in total, and the temperature of the solution was controlled at 60° C. by means of a constant temperature water bath. Terbium-doped gadolinium oxide films were deposited using a three-electrode electrochemical cell. The working electrode is conductive glass. The counter electrode is a high-purity platinum electrode. The reference electrode is SCE saturated calomel reference electrode. Insert the three electrodes into the mixed solution of gadolinium salt and terbium salt, and keep the temperature constant for 30 minutes. The voltage was adjusted at -1.20V (vs SCE saturated calomel reference electrode), and the deposition time was controlled at 30 minutes. The deposited films were washed with deionized water and dried. Subsequently, the film was rapidly annealed at 700 °C under the protection of argon for 3 min. Figure 2 is the EDS spectrum of the film product, which shows that there are mainly three elements: oxygen, gadolinium and terbium. The atomic number ratio of yttrium and terbium is about 10.2:1:, indicating that the obtained film is terbium-doped gadolinium oxide. Figure 3 is the XRD spectrum of the film, which is completely consistent with the standard card (JCPDS#43-1014) of cubic phase gadolinium oxide. Figure 4 is a low magnification electron micrograph of the product obtained in this example. It can be seen from the figure that the particles of the film are uniform, and the film is dense without cracking. Figure 5 is a high-magnification electron micrograph of the product obtained in this example. It can be seen from Figure 6 that the product of this example has a strong photoluminescence emission spectrum, and there are sharp green light emission spectra at 546 nm and 491 nm.

Example 2:

Terbium-doped gadolinium oxide green light-emitting film and its synthesis, 2.2565g gadolinium nitrate hexahydrate was dissolved in 100mL deionized water, stirred, and made into a gadolinium salt solution with a molar concentration of 0.05mol/L; 2.2645g terbium nitrate hexahydrate was dissolved in 100mL of deionized water, stirred, and made into a terbium salt solution with a molar concentration of 0.05mol/L.

The above-mentioned gadolinium salt and terbium salt were mixed according to a certain ratio, and the mixed solution was 12 mL in total, and the temperature of the solution was controlled at 70° C. by means of a constant temperature water bath. Terbium-doped gadolinium oxide films were deposited using a three-electrode electrochemical cell. The working electrode is conductive glass. The counter electrode is a high-purity platinum electrode. The reference electrode is SCE saturated calomel reference electrode. Insert the three electrodes into the mixed solution of gadolinium salt and terbium salt. The voltage was adjusted at -1.4V (vs SCE saturated calomel reference electrode), and the deposition time was controlled at 30 minutes. The deposited films were washed with deionized water and dried. Subsequently, the film was rapidly annealed at 700 °C under the protection of argon for 5 min. The specific test results of the prepared terbium-doped gadolinium oxide film are similar to those of Example 1.

Example 3:

Terbium-doped gadolinium oxide green light-emitting film and its synthesis, 9.0260g gadolinium nitrate hexahydrate was dissolved in 100mL deionized water, stirred, and made into a gadolinium salt solution with a molar concentration of 0.20mol/L; 9.0580g terbium nitrate hexahydrate was dissolved in 100mL of deionized water, stirred, and made into a terbium salt solution with a molar concentration of 0.20mol/L.

The above-mentioned gadolinium salt and terbium salt were mixed according to a certain ratio, and the mixed solution was 12 mL in total, and the temperature of the solution was controlled at 50° C. by means of a constant temperature water bath. Terbium-doped gadolinium oxide films were deposited using a three-electrode electrochemical cell. The working electrode is conductive glass. The counter electrode is a high-purity platinum electrode. The reference electrode is SCE saturated calomel reference electrode. Insert the three electrodes into the mixed solution of gadolinium salt and terbium salt. The voltage was adjusted at -0.9V (vs SCE saturated calomel reference electrode), and the deposition time was controlled at 15 minutes. The deposited films were washed with deionized water and dried. Subsequently, the films were rapidly annealed at 400 °C for 3 min under the protection of argon. The specific test results of the prepared terbium-doped gadolinium oxide film are similar to those of Example 1.

Claims (6)

1. A green light-emitting thin film doped with terbium-gadolinium oxide, characterized in that: a green light-emitting thin film (1) of gadolinium oxide and terbium oxide is deposited on one surface of a conductive glass substrate (2). 2. A terbium-doped gadolinium oxide green light-emitting thin film according to claim 1, characterized in that: the chemical formula of the light-emitting thin film is Gd ₂ O ₃ :Tb ³⁺ , and the thin film material has a thickness between 545 nm and 491 nm There is a sharp green emission spectrum. 3. A method for preparing a terbium-doped gadolinium oxide green light-emitting thin film, characterized in that the steps of the method are as follows: 1) Dissolve soluble gadolinium salt and terbium salt in deionized water respectively, stir, and prepare gadolinium salt solution and terbium salt solution with molar concentration of 0.05-0.2mol/L; 2) Take the above-mentioned gadolinium salt and terbium salt solution to form a uniformly mixed solution, and control the solution temperature at 50°C to 70°C through a constant temperature water bath; 3) A three-electrode electrochemical cell composed of a working electrode, a counter electrode and a reference electrode is used to deposit thin films on a conductive glass substrate. The three electrodes are inserted into a mixed solution composed of gadolinium salt and terbium salt solution, and the working electrode and terbium salt solution are adjusted. The voltage between the SCE saturated calomel reference electrodes is between -0.9V and -1.4V, and the deposition time is controlled between 15 minutes and 60 minutes; 4) The deposited film is washed with deionized water and dried, and then the film is rapidly annealed under the protection of argon at 400° C. to 700° C. for 3 minutes to 5 minutes. 4. A method for preparing a terbium-doped gadolinium oxide green light-emitting thin film according to claim 3, characterized in that: in the three-electrode electrochemical cell, the working electrode is a conductive glass substrate, and the counter electrode is a platinum electrode , gold electrode or graphite electrode, and the reference electrode is SCE saturated calomel reference electrode. 5. The method for preparing a terbium-doped gadolinium oxide green light-emitting thin film according to claim 3, characterized in that: the soluble gadolinium salt and terbium salt are nitrates. 6. A method for preparing a terbium-doped gadolinium oxide green luminescent film according to claim 3, characterized in that: the chemical formula of the luminescent film is Gd ₂ O ₃ :Tb ³⁺ , and the film is formed uniformly and densely No cracking, sharp green emission spectrum at 546 nm and 491 nm.

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