CN103160278A - Red long-lasting phosphor material and preparation method thereof - Google Patents

Abstract

The invention discloses a red long-lasting phosphor material and a preparation method thereof. A light-emitting substrate of the red long-lasting phosphor material is ZnGa2O4, and the chemical formula of the red long-lasting phosphor material is ZnGa2O4: aCr<3+>, bDy<3+>, wherein a is more than or equal to 0.01 and less than or equal to 0.05, and b is more than or equal to 0.01 and less than or equal to 0.05. The red long-lasting phosphor material provided by the invention has the characteristics that red luminescence is strong, afterglow can be more than one hour, light-emitting wavelength is wide, and wavelength ranges from 640nm to 720 nm; and the red long-lasting phosphor material also has the characteristics of cheap raw materials, simple preparation method and stable chemical stability. The red long-lasting phosphor material prepared by the invention is fine in granularity, high in crystalline degree and complete in crystal form, can be effectively activated by sunlight or a sunlight lamp to give out red afterglow and can also be applied to the fields of printing, luminescence decoration, noctilucent marking and the like.

Description

A red long afterglow luminescent material and preparation method thereof

technical field

The invention relates to a red long afterglow luminescent material and a preparation method thereof, belonging to the field of luminescent materials.

Background technique

Long afterglow luminescent material is a kind of photoluminescent material, that is, it emits light under the excitation of external light. The difference between long afterglow luminescence and ordinary photoluminescence is that the decay time of this luminescent material is very long after light excitation, and some can reach several Hours or even dozens of hours, so it can be used in emergency lighting, handicraft decoration and low-light lighting and other fields. At present, the development of green and blue long-lasting luminescent materials is relatively good, and some materials can achieve the effect of practical application, but the red long-lasting luminescent materials have always been a hot spot for people to explore, and there are many reports about red long-lasting luminescent materials. ZnGa ₂ O ₄ is an excellent matrix luminescent material. The matrix has a strong absorption of ultraviolet light and near ultraviolet light. Red luminescent material can be obtained by adding Cr ³⁺ ions in the matrix, but the afterglow performance is not good. The afterglow performance of the material after doping Dy3 ⁺ ions is significantly enhanced, the main reason is that the introduction of Dy3+ ions effectively increases the defect concentration in the matrix, and these defects act as a carrier trap in the matrix, thereby achieving enhanced afterglow. ability.

Contents of the invention

The invention provides a red long-lasting luminescent material, the luminescent substrate is ZnGa ₂ O ₄ , and its chemical expression is: ZnGa ₂ O ₄ : aCr ³⁺ , b Dy ³⁺ , wherein: 0.01≤a≤0.05, 0.01≤ b≤0.05.

The present invention also provides a preparation method of the red long afterglow luminescent material, which has the following steps:

1) The high-purity oxides ZnO, Ga ₂ O _{3 ,} Cr ₂ O ₃ and Dy ₂ O ₃ with a purity of not less than 99.99% are prepared according to the formula of Zn:Ga:Cr:Dy=1:2:0.01～0.05:0.01～0.05 Weigh the molar ratio, then mix and grind for more than an hour, make sure the mixture is uniform;

2) Put the ground mixture into a crucible, and then place it in a high-temperature furnace for high-temperature solid-state reaction; the heating process is carried out in 4 steps:

从室温经过6小时升至1350°C ；

From room temperature rise to 1350 DEG C through 6 hours;

Insulated at 1350°C for 5 hours;

从1350°C经过4小时降温至800°C；

Cooling from 1350°C to 800°C in 4 hours;

Natural cooling from 800°C to room temperature;

3) Take out the sample, and then grind it into powder; that is, obtain the red long-lasting luminescent material ZnGa ₂ O ₄ : aCr ³⁺ , bDy ³⁺ , 0.01≤a≤0.05, 0.01≤b≤0.05.

Beneficial effects of the present invention:

The biggest feature of the red long afterglow luminescent material provided by the invention is that the red luminescence is strong, the afterglow can reach more than one hour, the luminescence wavelength is wide, and the wavelength range is from 640nm to 720nm. At the same time, it has the characteristics of cheap raw materials, simple preparation method, stable chemical performance and the like.

The chromium-dysprosium co-doped zinc gallate red long-lasting luminescent material prepared by the method has fine particle size, high degree of crystallization, complete crystal form, can be effectively excited by sunlight or fluorescent lamps to emit red afterglow, and can be applied to printing, luminous decoration, and luminous marking and other fields.

Description of drawings

Figure 1 is the emission spectrum of ZnGa ₂ O ₄ : 0.01Cr ³⁺ , 0.01Dy ³⁺ prepared by the invention.

Fig. 2 is the afterglow attenuation diagram of ZnGa ₂ O ₄ : 0.01Cr ³⁺ , 0.01Dy ³⁺ prepared by the invention.

Fig. 3 is the emission spectrum diagram of ZnGa ₂ O ₄ : 0.02Cr ³⁺ , 0.02Dy ³⁺ prepared by the invention.

Fig. 4 is the afterglow attenuation diagram of ZnGa ₂ O ₄ : 0.02Cr ³⁺ , 0.02Dy ³⁺ prepared by the invention.

Fig. 5 is the emission spectrum diagram of ZnGa ₂ O ₄ : 0.03Cr ³⁺ , 0.03Dy ³⁺ prepared by the invention.

Fig. 6 is the afterglow attenuation diagram of ZnGa ₂ O ₄ : 0.03Cr ³⁺ , 0.03Dy ³⁺ prepared by the invention.

Fig. 7 is the emission spectrum of ZnGa ₂ O ₄ : 0.01Cr ³⁺ , 0.03Dy ³⁺ prepared by the invention.

Fig. 8 is the afterglow attenuation diagram of ZnGa ₂ O ₄ : 0.01Cr ³⁺ , 0.03Dy ³⁺ prepared by the invention.

Fig. 9 is the emission spectrum of ZnGa ₂ O ₄ : 0.03Cr ³⁺ , 0.01Dy ³⁺ prepared by the invention.

Fig. 10 is the afterglow attenuation diagram of ZnGa ₂ O ₄ : 0.03Cr ³⁺ , 0.01Dy ³⁺ prepared by the invention.

Detailed ways

Embodiment one:

Weigh high-purity raw materials ZnO, Ga ₂ O ₃ , Cr ₂ O ₃ , and Dy ₂ O ₃ with a purity of not less than 99.99% in molar ratios, according to the molar ratio of Zn:Ga:Cr:Dy=1:2:0.01:0.01 Compare batching, then put into high-temperature furnace and be heated to 1350 ℃, keep warm for 5 hours, slowly cool to 800 ℃, then cool to room temperature, obtain required sample. The sample showed red luminescence under ultraviolet light excitation, and a red afterglow visible to the naked eye after the excitation stopped.

Embodiment two:

Weigh high-purity raw materials ZnO, Ga ₂ O ₃ , Cr ₂ O ₃ , and Dy ₂ O ₃ with a purity of not less than 99.99% in molar ratios, according to the molar ratio of Zn:Ga:Cr:Dy=1:2:0.02:0.02 Compare batching, then put into high-temperature furnace and be heated to 1350 ℃, keep warm for 5 hours, slowly cool to 800 ℃, then cool to room temperature, obtain required sample. The sample showed red luminescence under ultraviolet light excitation, and a red afterglow visible to the naked eye after the excitation stopped.

Embodiment three:

Weigh the high-purity raw materials ZnO, Ga ₂ O ₃ , Cr ₂ O ₃ , and Dy ₂ O ₃ with a purity not less than 99.99% in molar ratio, according to the molar ratio of Zn:Ga:Cr:Dy=1:2:0.03:0.03 Compare batching, then put into high-temperature furnace and be heated to 1350 ℃, keep warm for 5 hours, slowly cool to 800 ℃, then cool to room temperature, obtain required sample. The sample showed red luminescence under ultraviolet light excitation, and a red afterglow visible to the naked eye after the excitation stopped.

Embodiment four:

Weigh the high-purity raw materials ZnO, Ga ₂ O ₃ , Cr ₂ O ₃ , and Dy ₂ O ₃ with a purity not less than 99.99% in molar ratio, according to the molar ratio of Zn:Ga:Cr:Dy=1:2:0.01:0.03 Compare batching, then put into high-temperature furnace and be heated to 1350 ℃, keep warm for 5 hours, slowly cool to 800 ℃, then cool to room temperature, obtain required sample. The sample showed red luminescence under ultraviolet light excitation, and a red afterglow visible to the naked eye after the excitation stopped.

Embodiment five:

Weigh the high-purity raw materials ZnO, Ga ₂ O ₃ , Cr ₂ O ₃ , and Dy ₂ O ₃ with a purity of not less than 99.99% in molar proportions, according to the molar ratio of Zn:Ga:Cr:Dy=1:2:0.03:0.01 Compare batching, then put into high-temperature furnace and be heated to 1350 ℃, keep warm for 5 hours, slowly cool to 800 ℃, then cool to room temperature, obtain required sample. The sample showed red luminescence under ultraviolet light excitation, and a red afterglow visible to the naked eye after the excitation stopped.

Embodiment six:

Weigh high-purity raw materials ZnO, Ga ₂ O ₃ , Cr ₂ O ₃ , and Dy ₂ O ₃ with a purity of not less than 99.99% in molar proportions, according to the molar ratio of Zn:Ga:Cr:Dy=1:2:0.01:0.05 Compare batching, then put into high-temperature furnace and be heated to 1350 ℃, keep warm for 5 hours, slowly cool to 800 ℃, then cool to room temperature, obtain required sample. The sample showed red luminescence under ultraviolet light excitation, and a red afterglow visible to the naked eye after the excitation stopped.

Embodiment seven:

Weigh high-purity raw materials ZnO, Ga ₂ O ₃ , Cr ₂ O ₃ , and Dy ₂ O ₃ with a purity not less than 99.99% in molar proportions, according to the molar ratio of Zn:Ga:Cr:Dy=1:2:0.05:0.01 Compare batching, then put into high-temperature furnace and be heated to 1350 ℃, keep warm for 5 hours, slowly cool to 800 ℃, then cool to room temperature, obtain required sample. The sample showed red luminescence under ultraviolet light excitation, and a red afterglow visible to the naked eye after the excitation stopped.

Claims (2)

1. red long afterglow luminous material, it is characterized in that: luminous host is ZnGa ₂O ₄, its chemical expression is: ZnGa ₂O ₄: aCr ³⁺, b Dy ³⁺, wherein: 0.01≤a≤0.05,0.01≤b≤0.05.

2. the preparation method of a red long afterglow luminous material claimed in claim 1 is characterized in that having following steps:

1) purity is not less than 99.99% high pure oxide ZnO _,Ga ₂O _3,Cr ₂O ₃And Dy ₂O ₃According to the molar ratio weighing of Zn:Ga:Cr:Dy=1:2:0.01～0.05:0.01～0.05, then mixed grinding more than one hour, must make mixture even;

2) mixture after grinding is put into crucible, then is placed on and carries out high temperature solid state reaction in High Temperature Furnaces Heating Apparatus; Its heat-processed divided for 4 steps carried out:

From room temperature through rising to 1350 ° of C in 6 hours;

1350 ° of C insulations 5 hours;

From 1350 ° of C through being cooled to 800 ° of C in 4 hours;

Naturally cool to room temperature from 800 ° of C;

3） ₂₄ ^3+3+? ≤a≤0.05，0.01≤b≤0.05。

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