阅读说明：本技术 一种掺杂Mn4+的高色纯度氟化物红光材料及制备方法 (Mn-doped steel wire4+High-color-purity fluoride red-light material and preparation method thereof ) 是由 周强 施栋鑫 汪正良 普海琦 谢晓玲 张茜 叶艳青 于 2020-05-28 设计创作，主要内容包括：本发明涉及无机发光材料领域,公开了一种掺杂Mn<Sup>4+</Sup>的高色纯度氟化物红光材料及制备方法。本发明所述掺杂Mn<Sup>4+</Sup>的氟化物红光材料,其化学组成为Na<Sub>5</Sub>Al<Sub>3(1-x)</Sub>F<Sub>14</Sub>:3xMn<Sup>4+</Sup>,x为所掺杂的Mn<Sup>4+</Sup>离子相对Al<Sup>3+</Sup>离子所占的摩尔百分比系数,0.0<x≤0.10。本发明所述高色纯度,是指材料在蓝光(460 nm)照射下产生的红光发射以629 nm为主,且在621 nm处有强的零声子振动峰。本发明所述的红光材料,是在水热条件下,将碳酸钠或氟化钠、氧化铝或氢氧化铝、六氟锰酸钾或高锰酸钾溶解在装有氢氟酸的水热反应釜中,在一定温度和pH值条件下反应得到的。(The invention relates to the field of inorganic luminescent materials, and discloses Mn-doped luminescent material 4+ The high-color-purity fluoride red-light material and the preparation method. The doped Mn of the invention 4+ Fluoride red light emitting material of chemical composition Na 5 Al 3(1‑x) F 14 :3xMn 4+ X is Mn as doped 4+ Ion-relative Al 3+ Molar percentage coefficient of ion, 0.0<x is less than or equal to 0.10. The high color purity of the invention means that the red light emission of the material under the irradiation of blue light (460 nm) is mainly 629 nm, and a strong zero phonon vibration peak is at 621 nm. The red light material is obtained by dissolving sodium carbonate or sodium fluoride, aluminum oxide or aluminum hydroxide, potassium hexafluoromanganate or potassium permanganate in a hydrothermal reaction kettle filled with hydrofluoric acid under a hydrothermal condition and reacting at a certain temperature and pH value.)

1. Mn-doped steel wire⁴⁺The fluoride red light material comprises the following chemical components: na (Na)₅Al_3(1-x)F₁₄:3xMn⁴⁺X is Mn as doped⁴⁺Ion-relative Al³⁺Molar percentage coefficient of ion, 0.0<x ≤ 0.10。

2. Mn doping according to claim 1⁴⁺The fluoride red light material is characterized in that the used excitation light source is blue light with the wavelength of 420-470 nm, and the obtained emission light is a series of narrow-band red light with the wavelength of 610-650 nm.

3. Mn doping according to claim 1⁴⁺The fluoride red material is characterized in that the high color purity means that the CIE value of the emission spectrum of the sample is close to the Standard value (x = 0.67, y = 0.33) of red NTSC (national Television Standard Committee).

4. Mn doping according to claim 1⁴⁺The fluoride red light material is characterized in that a series of narrow-band emission peaks of a sample have a strong zero-phonon vibration peak, and the peak is positioned at 621 nm.

5. Mn doping according to claim 1⁴⁺The fluoride red-light material is characterized in that the used raw materials and the mass percentage of each raw material are respectively as follows: sodium carbonate: 60.0-90.0%; sodium fluoride: 50.0-80.0%; aluminum oxide: 70.0-80.0%; 70.0 to 95.0 percent of aluminum hydroxide; hydrofluoric acid: 10.0-40.0%; acetic acid: 50.0-85.0%; ethanol: 70.0-90.0%; potassium permanganate: 50.0-75.0%; potassium hexafluoromanganate: 60.0-80.0%; 20.0 to 30.0 percent of hydrogen peroxide.

6. Mn doping according to claim 1⁴⁺The preparation method of the fluoride red-light material is characterized in that the preparation method is a hydrothermal method, and comprises the following steps: dissolving sodium carbonate or sodium fluoride, aluminum oxide or aluminum hydroxide, potassium hexafluoromanganate or potassium permanganate and other raw materials according to a certain proportion into a polytetrafluoroethylene lining containing 10ml of hydrofluoric acid, stirring at a constant speed for 15 minutes at room temperature, then placing the lining into a reaction kettle for sealing, reacting in an oven at 120-180 ℃ for 6-24 hours, cooling to room temperature, washing with acetic acid and ethanol for 3 times respectively, and then placing the product into an oven at 80 ℃ for drying for 8 hours to obtain light red powder as a final product.

Technical Field

The invention relates to Mn doping⁴⁺The high-color-purity fluoride red-light material and the preparation method thereof, in particular to a fluoride red-light material which generates high color purity under the irradiation of blue light (420-470 nm) ((>96%) red light, and has a chemical composition of Na₅Al_3(1-x)F₁₄:3xMn⁴⁺Belonging to the field of inorganic luminescent material preparation.

Background

Energy is a major strategic problem which puzzles human development, and reducing energy consumption is a major direction of scientific research. At present, Light Emitting Diodes (LEDs) have been widely used in the field of lighting because of their excellent properties such as low power consumption (1/10 for incandescent lamps, 1/4 for energy saving lamps), small size, long life, good applicability, short response time, environmental protection (no harmful metals), and the like.

Commercial white LEDs are fabricated from GaN chips (emitting 460 nm blue light) and yellow yttrium aluminum garnet (YAG: Ce)³⁺) And the fluorescent powder is packaged together. Part of the blue light emitted by the chip is absorbed by the fluorescent powder, and the other part of the blue light and the fluorescent powder YAG: Ce³⁺The emitted yellow light mixes to produce white light. However, the white light LED formed by combining the blue and the yellow has high color temperature>6,000K), which is prone to eyestrain; low color rendering index (Ra<80) The cold light can impair vision. Therefore, the requirement of people for the diversity of the illumination light sources cannot be met. To solve this problem, the "blue + yellow" combination is changed to "blue + yellow + red" combination, and a red phosphor which can be excited by blue light to generate red light is developed and is mixed with YAG: Ce³⁺The powder is mixed and coated on a blue light chip, and the composition of red, yellow and blue colors is realized so as to achieve the purposes of reducing the color temperature and improving the color rendering index. Currently, some rare earth ions such as Eu²⁺、Ce³⁺、Sm³⁺The activated nitrogen (oxide) can obtain proper red fluorescent powder, but the requirements of commercial production are difficult to completely meet due to the defects of high price of rare earth, high energy consumption of a synthesis method, low red light emission efficiency and the like. For example, (1) BaMoO₄: Sm³⁺The product can be prepared by presintering at 500 deg.C for 2h, and then firing at 850 deg.C for 4hJ. Am. Ceram. Soc., 2010, 93, 1397.]；（2）Lu₂CaMg₂(Si, Ge)₃O₁₂: Ce³⁺Reducing the mixture for 5 to 10 hours at the temperature of 1300 ℃ and 1450 ℃ to prepare the alpha-beta-cyclodextrin alpha-Chem. Mater.,2006, 18, 3314.]；（3）YAG:Ce³⁺,Eu³⁺The excitation efficiency in the blue region is low and the emission efficiency in the red region is lowJ. Electrochem. Soc., 2012, 159, H195.]。

At present, the research finds that Mn is doped⁴⁺The fluoride can generate high-efficiency blue light absorption band and red light emission peak, and can effectively improve the color temperature and color rendering index of the white light LED. For example, Ce can be added to YAG³⁺Yellow powder and K₂Si_1-xMn_xF₆The red powder is mixed and coated on a blue LED chip, and white light [ chem. mater, 2016, 28 and 1495 ] with high efficiency, good thermal stability, low color temperature and high color rendering index can be obtained.]. If it can realize Mn⁴⁺The spectral intensity of the ion is further improved by non-equivalent doping with other ions. Therefore, based on this objective, the present invention discloses a high color purity Na having a broad blue excitation band, a narrow red emission peak and a strong zero phonon vibration peak₅Al_3(1-x)F₁₄:3xMn⁴⁺A red luminescent material and a preparation method thereof.

Disclosure of Invention

The invention aims to provide a Mn-doped alloy⁴⁺And is suitable for high-color-purity fluoride red light materials excited by blue light.

Another object of the present invention is to provide a method for preparing the above red light emitting material.

In order to achieve the purpose, the invention relates to Mn doping⁴⁺The high-color-purity fluoride red-light material and the preparation method thereof comprise the following chemical components: na (Na)₅Al_3(1-x)F₁₄: 3xMn⁴⁺X is Mn as doped⁴⁺Ion-relative Al³⁺Molar percentage coefficient of ion, 0.0<x is less than or equal to 0.10. The raw materials used in the invention and the mass percentage of each raw material are respectively as follows: sodium carbonate: 60.0-90.0%; sodium fluoride: 50.0-80.0%; aluminum oxide: 70.0-80.0%; 70.0 to 95.0 percent of aluminum hydroxide; hydrofluoric acid: 10.0-40.0%; acetic acid: 50.0-85.0%; ethanol: 70.0-90.0%; potassium permanganate: 50.0-75.0%; potassium hexafluoromanganate: 60.0-80.0%; 20.0 to 30.0 percent of hydrogen peroxide.

The wavelength of the blue light is 420-470 nm.

The preparation of the red light material adopts a hydrothermal method, and comprises the following steps: dissolving sodium carbonate or sodium fluoride, aluminum oxide or aluminum hydroxide, potassium hexafluoromanganate or potassium permanganate and other raw materials according to a certain proportion into a polytetrafluoroethylene lining containing 10ml of hydrofluoric acid, stirring at a constant speed for 15 minutes at room temperature, then placing the lining into a reaction kettle for sealing, reacting in an oven at 120-180 ℃ for 6-24 hours, cooling to room temperature, washing with acetic acid and ethanol for 3 times respectively, and then placing the product into an oven at 80 ℃ for drying for 8 hours to obtain light red powder as a final product.

The red light material disclosed by the invention has stronger red light emission (the main emission peak is positioned at 629 nm) under the excitation of 420-470 nm blue light; a zero phonon oscillation peak at 621 nm, which makes the material show high red color purity (> 96%).

Drawings

FIG. 1 is an XRD diffraction pattern of a red light material of the present invention;

FIG. 2 shows the excitation spectrum of the red light material of the present invention at room temperature;

FIG. 3 shows the emission spectrum of the red-emitting material of the present invention at room temperature;

FIG. 4 is an XRD diffractogram of the red light material of the present invention;

FIG. 5 is an electroluminescence spectrum of a red LED fabricated by compounding the red light material and a blue GaN chip under a current of 20 mA.

Detailed Description