CN105038787A - Ce, Tb and Mn-coactivated single-matrix phosphate white phosphor powder and preparation method thereof - Google Patents

Abstract

The present invention is a cerium, terbium, and manganese co-activated single-matrix phosphate white light phosphor, the general formula of which is Ba _{2 (1-xyz)} Mg (PO ₄ ) ₂ : xCe ³⁺ , yTb ³⁺ , zMn ²⁺ , Wherein 0<x≤0.2, 0<y≤0.2, 0<z≤0.4. The invention also discloses a preparation method of the above-mentioned white light fluorescent powder. The carbonate corresponding to Ba, Mg and Mn, ammonium dihydrogen phosphate and the oxide or nitrate of Ce and Tb are uniformly mixed and ground according to the stoichiometric ratio to obtain the mixture , put the mixture into a crucible boat and place it in a dual temperature zone tube furnace quartz tube, use aluminum powder as a reducing agent to calcinate at high temperature, cool and grind into powder to obtain a single-matrix phosphate white phosphor. Under the excitation of ultraviolet light, the fluorescent powder of the invention emits white light composed of 380nm blue light, 550nm green light and 600nm red light by adjusting the concentration of doped cerium, terbium and manganese ions.

Description

A kind of cerium, terbium, manganese co-activated single matrix phosphate white light phosphor and preparation method thereof

technical field

The invention belongs to the field of material science, and relates to a rare earth luminescent material, specifically a cerium, terbium and manganese co-activated single-matrix phosphate white light phosphor and a preparation method thereof.

Background technique

White light-emitting diodes (WLEDs) have broad application prospects in the field of lighting and display due to their remarkable advantages such as long life, low energy consumption, no pollution, high efficiency, and small size, and are called a new generation of lighting sources.

At present, the preparation scheme of using ultraviolet-near-ultraviolet chips to excite three primary color phosphors to realize white light has become the focus of the current WLEDs industry development. Due to the insensitivity of vision to ultraviolet-near ultraviolet light, the color of this type of white light LED is only determined by phosphor powder. low-level disadvantages. However, due to problems such as color reabsorption and ratio control among multi-phase phosphor mixtures, lumen efficiency and color reproduction performance are greatly affected. In addition, the coating process of several phosphor mixtures also increases the white LED manufacturing process. The difficulty increases the production cost.

Therefore, it is of great significance to develop new high-efficiency single-matrix white light-emitting materials, and it has become a research hotspot in the new generation of white LED lighting. In recent years, some new single-matrix white light phosphor systems have been reported in the literature, most of which are concentrated in silicate matrix. For example, Eu ²⁺ /Tb ³⁺ /Mn ²⁺ co-activated silicate BaMg ₂ Al ₆ Si ₉ O ₃₀ , Ce ³⁺ /Tb ³⁺ /Mn ²⁺ co-activated silicate CaScAlSiO ₆ and other systems white light emission. However, the preparation temperature of the silicate system is high, and due to the strong inertness of SiO ₂ , it is difficult to confirm the phase and structure.

Contents of the invention

Aiming at the above-mentioned technical problems in the prior art, the present invention provides a cerium, terbium, and manganese co-activated single-matrix phosphate white light phosphor and a preparation method thereof. The described cerium, terbium, and manganese co-activated single-matrix The phosphate white light phosphor and the preparation method solve the technical problems of high preparation temperature and difficult phase and structure confirmation of the white light phosphor in the prior art.

The present invention is a cerium, terbium and manganese co-activated single-matrix phosphate white light phosphor, and its combination formula is Ba _2(1-xyz) Mg(PO ₄ ) ₂ :xCe ³⁺ ,yTb ³⁺ ,zMn ²⁺ , where 0<x≤0.2, 0<y≤0.2, 0<z≤0.4.

The present invention also provides a method for preparing the above-mentioned cerium, terbium, and manganese co-activated single-matrix phosphate white light phosphor,

(1) Weigh barium carbonate, basic magnesium carbonate, ammonium dihydrogen phosphate, cerium oxide or cerium nitrate, terbium oxide or terbium nitrate, manganese carbonate, barium carbonate, basic magnesium carbonate, ammonium dihydrogen phosphate, The mass ratio of cerium or cerium nitrate, terbium oxide or terbium nitrate, and manganese carbonate is 2(1-x-y-z):1:2:x:y:z, the above-mentioned substances are mixed uniformly, and then ground, and the mixture obtained after grinding Put it into the crucible boat and place it on one end of the quartz tube of the dual-temperature zone tube furnace, and place the crucible boat filled with aluminum powder on the other end of the quartz tube of the dual-temperature zone tube furnace;

(2) Place the above-mentioned dual temperature zone tube furnace in a vacuum environment, the sintering temperature of one end of the mixture is 1000-1300°C, the calcination time is 3-10 hours, the sintering temperature of one end of the aluminum powder is 700-900°C, the calcination time is 3-10 hours; after the tube furnace is cooled to room temperature, turn off the vacuum pump, take out the sintered material and grind to obtain a single-matrix phosphate white light phosphor co-activated by cerium, terbium and manganese.

The invention uses aluminum powder as a reducing agent to prepare the fluorescent powder. Under the excitation of a 307nm light source, the energy transfer from Ce ³⁺ to Tb ³⁺ greatly improves the emission intensity of green light with an emission peak wavelength of 550nm. At the same time, Ce ^{3 +} sensitizes the emission of Mn ²⁺ , increases the emission intensity of red light with a peak emission wavelength of 600nm, and obtains a white light phosphor with chromaticity coordinates of (0.263, 0.240). The fluorescent powder of the present invention is excited by ultraviolet light, and by adjusting the concentration of doped cerium, terbium and manganese ions, the sample emits white light composed of 380nm blue light, 550nm green light and 600nm red light.

Compared with the prior art, the technical progress of the present invention is remarkable. Phosphate is a kind of matrix material with good luminescence performance. Its preparation temperature is low, its luminescence efficiency is high, its physical and chemical properties are stable, and it can effectively absorb ultraviolet photon energy. Therefore, it is of great significance to obtain a single-matrix phosphate white light phosphor with low synthesis temperature, high luminous efficiency, more stable physical and chemical properties, and simple preparation process.

Description of drawings

Fig. 1 is the emission spectrum of Ba _1.88 Mg(PO ₄ ) ₂ :0.04Ce ³⁺ , 0.01Tb ³⁺ , 0.01Mn ²⁺ of the present invention.

Fig. 2 is a chromaticity coordinate diagram of Ba _1.88 Mg(PO ₄ ) ₂ :0.04Ce ³⁺ , 0.01Tb ³⁺ , 0.01Mn ²⁺ of the present invention.

Detailed ways

Example 1:

Preparation of Ba _1.92 Mg(PO ₄ ) ₂ : 0.04Ce ³⁺ , 0.01Tb ³⁺ , 0.01Mn ²⁺ .

Weigh 2.0668g of barium carbonate, 0.5411g of basic magnesium carbonate, 0.0767g of cerium oxide, 0.0208g of terbium oxide, 0.0128g of manganese carbonate, and 1.2817g of ammonium dihydrogen phosphate, grind and mix them in a mortar for 120min, then add alcohol and grind for 60min to obtain The mixture, the mixture was put into a crucible boat and placed in a tube furnace with two temperature zones, calcined at 1100° C. for 5 hours under an aluminum reducing atmosphere, cooled naturally and ground into powder.

Example 2:

Preparation of Ba _1.74 Mg(PO ₄ ) ₂ : 0.04Ce ³⁺ , 0.03Tb ³⁺ , 0.06Mn ²⁺ .

Weigh 1.9193g of barium carbonate, 0.5429g of basic magnesium carbonate, 0.1458g of cerium nitrate, 0.0289g of terbium nitrate, 0.0771g of manganese carbonate, and 1.2859g of ammonium dihydrogen phosphate, grind and mix in a mortar for 120min, then add alcohol and grind for 60min The obtained mixture was put into a crucible boat and placed in a double temperature zone tube furnace, calcined at 1100° C. for 5 hours under an aluminum reducing atmosphere, cooled naturally and ground into powder.

Example 3:

Preparation of Ba _1.72 Mg(PO ₄ ) ₂ : 0.2Ce ³⁺ , 0.1Tb ³⁺ , 0.3Mn ²⁺ .

Weigh 0.9564g of barium carbonate, 0.5884g of basic magnesium carbonate, 0.4171g of cerium oxide, 0.2265g of terbium oxide, 0.4178g of manganese carbonate, and 1.3937g of ammonium dihydrogen phosphate, grind and mix in a mortar for 120min, then add acetone and grind for 10min After the mixture is obtained, the mixture is put into a crucible boat and placed in a double temperature zone tube furnace, calcined at 1000° C. for 10 hours under an aluminum reducing atmosphere, cooled naturally and ground into powder.

Example 4:

Preparation of Ba _1.72 Mg(PO ₄ ) ₂ : 0.2Ce ³⁺ , 0.2Tb ³⁺ , 0.4Mn ²⁺ .

Weigh 0.4921g of barium carbonate, 0.6055g of magnesium carbonate, 0.4291g of cerium oxide, 0.4661g of terbium oxide, 0.5732g of manganese carbonate, and 1.4341g of ammonium dihydrogen phosphate, put them in a mortar and grind and mix for 120min, then add acetone and grind for 10min to obtain Mixture, the mixture was put into a crucible boat and placed in a tube furnace with two temperature zones, calcined at 1300° C. for 3 hours under an aluminum reducing atmosphere, cooled naturally and ground into powder.

Claims (2)

1. cerium, terbium, the coactivated single matrix phosphoric acid salt white emitting fluorescent powder of manganese, is characterized in that: its combination matching general formula is Ba _{2 (1-x-y-z)}mg (PO ₄) ₂: xCe ³⁺, yTb ³⁺, zMn ²⁺, wherein 0<x≤0.2,0<y≤0.2,0<z≤0.4.

2. the preparation method of a kind of cerium according to claim 1, terbium, the coactivated single matrix phosphoric acid salt white emitting fluorescent powder of manganese, is characterized in that:

(1) barium carbonate, magnesium basic carbonate, primary ammonium phosphate, cerium oxide (cerous nitrate), terbium sesquioxide (Terbium trinitrate), manganous carbonate is taken according to the mol ratio of 2 (1-x-y-z): 1:2:x:y:z, mix after grinding, put into crucible boat and be placed in one end of two temperature-area tubular furnace silica tube, the crucible boat that aluminium powder is housed being placed in the other end of two temperature-area tubular furnace silica tube;

(2) under above-mentioned pair of temperature-area tubular furnace being placed in vacuum environment, one end sintering temperature of mixture is 1000-1300 DEG C, and calcination time is 3-10 hour, and one end sintering temperature of aluminium powder is 700-900 DEG C, and calcination time is 3-10 hour; Be cooled to after room temperature until tube furnace, close vacuum pump, take out sinter grinding and namely obtain cerium, terbium, the coactivated single matrix phosphoric acid salt white emitting fluorescent powder of manganese.