KR100341532B1 - Method for producing a fluorescent material - Google Patents

Abstract

In order to limit the donor concentration, the luminous efficiency is high, and various emission colors can be realized by electron beam excitation by selection of additional elements, thereby providing a phosphor having excellent life characteristics.

23.5 g (0.1 mol) of Ga ₂ S ₃ is added and 0.02 g (0.1 mol% / Ga) of MgCl ₂ . Again, 0.05 g of polysilazane 20% solution is added so that the Si and Mg concentrations are equal. The mixture was kept at 1100 ° C. for 10 hours in an ammonia atmosphere to obtain GaN: Mg and Si phosphors. By varying the amount of polysilazane, the amount of Si is varied from 0.001 mol to 10 mol% to obtain a plurality of types of samples. Samples without Si and samples using SiO ₂ instead of polysilazane were also prepared. These samples were used for the anode of the fluorescent display tube and lit to evaluate the phosphor luminance characteristics. The emission color of each sample was all blue. The luminance of light emitted is low in the region where the doping amount of Si is low, and the brightness is low when excessive. The concentration M of Mg is preferably 0.01 <M <0.3, and the concentration X of Si is preferably 0.005 <X <0.3.

Description

Manufacturing method of phosphor {METHOD FOR PRODUCING A FLUORESCENT MATERIAL}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phosphor in which a dopant is doped in gallium nitride and an indium nitride solid solution, and emits light by electron beam excitation, and has excellent luminance and lifespan characteristics capable of realizing various emission colors by selection of a raw material.

Japanese Patent Application Laid-Open No. 51-41686 discloses a phosphor doped with Cd using GaN obtained by nitriding Ga ₂ O ₃ in an ammonia atmosphere as a matrix. This phosphor is not applied to light emission by electron beam excitation, and there is no description of light emission by electron beam excitation in the above document.

When Ga ₂ O ₃ is nitrided in a nitrogen atmosphere, Ga ₂ O ₃ is nitrided on the surface of the material, but when heated to a high temperature, the surface is oxidized again. That is, gallium nitride has the property that nitrogen is easy to fall out, and therefore, it is n type, very low resistance, and emits light even in non-dope.

The light emission of gallium nitride is a pair light emission of the donor (D) and the acceptor (A). Although the acceptor uses Zn, Mg, etc., the donor is a nitrogen defect that is naturally formed, and according to the conventional method, if the donor concentration is to be increased, defects in the material are increased and crystallinity is reduced. As described above, in the conventional gallium nitride, the donor number could not be controlled and produced.

In addition, gallium nitride has a possibility of being oxidized due to the presence of oxygen. Therefore, if Ga ₂ O ₃ is used as the raw material, it is difficult to completely nitrate the gallium nitride, and the obtained gallium nitride also adversely affects luminescence. Such quality cannot be said to be good.

The present invention provides a phosphor having a high luminous efficiency and realizing various luminous colors by electron beam excitation by selection of an additional element because the donor temperature is controlled without being influenced by oxygen at the time of manufacture, and excellent in luminance and lifetime characteristics. It aims to do it.

(Means to solve the task)

Phosphor of the present invention is Ga _1-x In _x N: M, X (where 0≤x <0.8, M is at least one element selected from the set of Be, Mg, Ca, Sr, Ba, Zn, Cd, Hg) , X is at least one element selected from the set of C, Si, Ge, Sn, Pb).

The phosphor of the present invention is characterized in that the concentration range (mol%) of M and X is 0.005 <M <0.7 and 0.002 <X <0.8, respectively.

Preferably, the phosphor of the present invention is characterized in that the concentration range (mol%) of M and X is 0.01 <M <0.3 and 0.005 <X <0.3, respectively.

The phosphor of the present invention is characterized in that the phosphor is made of a raw material containing no oxygen.

The phosphor of the present invention is characterized in that the Si raw material is (SiH _a N _b ) _n (where a = 1 to 3, b = O or 1) containing no oxygen.

Embodiment of the Invention

The phosphor of the present invention controls the donor concentration by adding an element which becomes a donor, and improves luminous efficiency. In addition, during the production, it is prepared using a raw material that will not be affected by oxygen. The chemical formula is represented by Ga _1-x In _x N: M, X (where 0 ≦ x <0.8). The element X serving as a donor is preferably a Group 4 element such as C, Si, Ge, Sn, or Pb. Addition element M is preferably Be, Mg, Ca, Sr, Ba, Zn, Cd, Hg. In particular, in order to add Si to the phosphor, polysilazane (trademark of Tonen Co., Ltd.) may be used. Polysilazane is a perhydropolysilazane of the formula (SiH _a N _b ) _n (where a = 1 to 3, b = 0 or 1). By using this substance, the number of Si atoms added to the phosphor can be precisely controlled. In addition, this material does not contain C or O, which is advantageous for the production of nitrides. In addition, materials such as GeS ₂ for adding Ge and SnCl ₂ for adding Sn are used. When the amount of donor material added is controlled in this way, it is possible to produce a phosphor having excellent luminance characteristics and lifetime characteristics which emit light in various emission colors by electron beam excitation.

(Example)

(1) First Embodiment GaN: Mg, Si

23.5 g (0.1 mol) of Ga ₂ S ₃ is weighed. To this was added 0.02 g (0.1 mol% / Ga) of MgCl ₂ . In addition, 0.05 g of polysilazane 20% solution is added so that the Si concentration and the Mg concentration are the same. These are mixed and placed on a quartz board and placed in a quartz tube. The solution was maintained at 1100 ° C. for 10 hours while flowing ammonia at 10 ml / min in the quartz tube. GaN: Mg and Si were obtained.

In the manufacturing process, a plurality of samples were prepared in which the amount of Si was changed to 0.001 mol% to 10 mol% by fixing the amount of Mg and varying the amount of the polysilazane 20% solution. The particle shape of the phosphor of this Example thus produced was flat, rather than acicular, as in the conventional gallium nitride phosphor.

In Fig sample was prepared using the Si-free sample, and a polysilazane instead of SiO _2.

These samples were applied onto an anode conductor on a glass substrate using an organic binder, and then fired at 500 ° C. in the air to remove the binder to prepare a cathode substrate on which a phosphor layer was formed. A control electrode or a cathode is disposed on the upper surface of the positive electrode substrate, and a box-shaped container is sealed with fritted glass on the upper surface of the positive electrode substrate to form an envelope. The inside of the envelope was evacuated in a high vacuum state, and the envelope was sealed at about 500 ° C. to manufacture a fluorescent display tube. A voltage of about 50 V was applied to the anode conductor, and the phosphor was made to emit light, and the luminance characteristics thereof were compared and evaluated.

As shown in FIG. 1, the light emission color of each sample was all blue. As shown in Fig. 2, the luminance of light emission changes according to the amount of Si doping, and the luminance is low in a region where the amount of doping is small. In addition, when Si is excessive, extra Si is precipitated and the luminance is lowered. At that time, the light emitting state of the phosphor becomes nonuniform, and charge up appears everywhere. The luminance of the sample using SiO ₂ was about 75% of the sample luminance using polysilazane.

(2) Second Embodiment GaN: Mg, Ge

23.5 g (0.1 mol) of Ga ₂ S ₃ were weighed. MgCl _2, that is, 0.01 g (0.05 mol% / Ga) is added thereto. In addition, 0.014 g of GeS ₂ is added and mixed well so that the Mg concentration and the Ge concentration are the same. They are placed on a quartz pod and placed in a quartz tube. The solution was maintained at 1100 ° C. for 10 hours while flowing ammonia at 10 ml / min in the quartz tube. GaN: Mg, Ge was obtained.

In Fig was produced in the sample and, GeS ₂ instead of the sample with no GeO ₂ Ge.

Using these samples, a fluorescent display tube was produced in the same manner as in the first embodiment. A voltage of about 50 V was applied to the anode conductor, and the phosphor was made to emit light, and the luminance characteristics thereof were compared and evaluated.

The emission color of each sample was all blue. When the luminance of the sample without using Ge was 100%, the luminance of the sample of the present example was 170%, and the effect of adding Ge was confirmed. The luminance of the sample using GeO ₂ was 130%.

(3) Third Example Ga _0.7 InN: Zn, Ge

16.4 g of Ga ₂ S ₃ and 9.8 g of In ₂ S ₃ are used. Here, 0.02 g of ZnS (0.1 mol% / Ga) and 0.027 g of GeS ₂ are added and mixed well so that Zn and Ge have the same concentration. They are placed on a quartz board and placed in a quartz tube. It is maintained at 1150 ° C. for 6 hours while flowing ammonia at 10 ml / min in the quartz tube. Ga _0.7 InN: Zn, Ge was obtained.

In the manufacturing process, a plurality of samples were prepared in which the amount of Zn was changed at the same time the amount of ZnS was changed and the amount of Zn was changed to 0.001 mol% to 10 mol%. In Fig sample was prepared using a Ge-free sample, and a polysilazane instead of SiO _2. In addition, a plurality of samples in which the amount of Zn was fixed and Ge was changed to 0.001 to 5 mol% were also produced.

Slurry liquids are prepared using these samples and PVA, and the slurry liquid is applied to an ITO electrode on a glass substrate. This was fired at 480 ° C. in the air to prepare a positive electrode substrate on which a phosphor layer was formed. A negative electrode substrate having a field emission-type negative electrode formed on the inner surface side thereof is prepared, and the inner surface side thereof faces the upper surface side of the positive electrode substrate at predetermined intervals, and the outer periphery is sealed between the outer circumferences of the two substrates through a spacer member. The inside of the enclosure was evacuated and sealed in a high vacuum state to fabricate a field emission display device (FED, Field Emission Cathode). A voltage was applied to the anode conductor, and the electrons emitted from the field emission cathode were adolescent to the phosphor layer of the anode to emit phosphors, and the luminance characteristics thereof were compared and evaluated.

As shown in Fig. 3, the luminance of light emission changes according to the amount of Ge doping, and the luminance is low in a region where the amount of doping is small. In addition, when Ge is excessive, the luminance is lowered. Also for Zn, as shown in Fig. 5, the relative intensity of luminance changes with the amount of dope around the optimum value.

(4) Fourth Example Ga _0.7 InN: Mg, Zn, Si

16.4 g of Ga ₂ S ₃ and 9.8 g of In ₂ S ₃ are used. 0.01 g (0.05 mol% / Ga) of MgCl _{2 and} 0.01 g (0.05 mol% / Ga) of ZnS were added thereto, and 0.05 g of a 20% aqueous polysilazane solution was added so that the Si concentration was equal to the concentration of Zn and Mg. Add. These are mixed well and placed on a quartz board and placed in a quartz tube. The solution was maintained at 1180 ° C. for 6 hours while flowing ammonia at 10 ml / min in the quartz tube. Ga _0.7 InN: Mg, Zn, and Si were obtained. Si-free samples were also prepared.

Using these samples, FED was produced similarly to the first example. A phosphor of about 100V was applied to the anode conductor to emit light, and the luminance characteristics thereof were compared and evaluated.

The phosphor of this example emitted green light. When the emission luminance of the sample without Si was 100%, the phosphor of this example obtained 180% luminance, and the Si addition effect was confirmed.

(5) Fifth Embodiment GaN: Mg, Sn

23.5 g (0.1 mol) of Ga ₂ S ₃ is weighed. 0.02 g of MgCl ₂ (0.1 mol% / Ga) and 0.04 g of SnCl ₂ are added and mixed well so that the Sn concentration is equal to the Mg concentration. They are placed on a quartz board and placed in a quartz tube. It is maintained at 1200 ° C. for 10 hours while flowing ammonia at 10 ml / min in the quartz tube. GaN: Mg and Sn were obtained.

In the manufacturing process, a plurality of types of samples were prepared in which the amount of Sn was fixed and the amount of Mg was changed from 0.001 mol% to 10 mol%. Sn-free samples were also prepared. In addition, a plurality of samples in which the amount of Mg was fixed and the Sn was changed to 0.001 to 5 mol% were also produced.

Using these samples, a fluorescent display tube was produced in the same manner as in the first embodiment. A voltage of about 50 V was applied to the anode conductor, and the phosphor was emitted to compare and evaluate the luminance characteristics.

As shown in Fig. 4, the luminance of light emission changes according to the amount of Sn doping, and the luminance is low in a region where the amount of doping is small. In addition, excessive Sn lowers the brightness. Also for Mg, as shown in Fig. 5, the relative intensity of luminance changes with the amount of dope around the optimum value.

(6) Sixth Embodiment Ga _0.5 InN: Zn, Sn

11.7g Ga ₂ S _{3 and} 16.3g In ₂ S ₃ are used.

0.004 g of ZnS (0.02 mol% / Ga) and 0.008 g of SnCl ₂ are added thereto so that the Sn concentration is equal to the Zn concentration. Mix them well and place them on a quartz board and place them in a quartz tube. It was maintained at 1150 ° C. for 8 hours while flowing ammonia at 10 ml / min in the quartz tube. Ga _0.5 InN: Zn, Sn was obtained. Sn-free samples were also prepared.

Using these samples, FED was produced similarly to the first example. Voltages of various values were applied to the anode conductors in the range of about 0 to 100 V, and the phosphors were made to emit light, and their luminance characteristics were compared and evaluated, respectively.

The phosphor of this example emitted orange. The relative luminance of the emitted light of the sample without Sn was approximately doubled, and the Sn addition effect was confirmed.

For Mg and Zn used in the above-described examples, the concentration M (mol%) is in the range of 0.005 <M <0.7, more preferably 0.01 <M <0.3. Be, Ca, Sr, Ba, Cd or Hg may be used instead of Mg or Zn.

For Si, Ge, and Sn used in the above-described examples, the concentration X (mol%) has a range of 0.002 <X <0.8, more preferably 0.005 <X <0.3. C or Pb may be used instead of Si, Ge, Sn.

1 is a view showing the effect of the first embodiment of the present invention,

2 is a view showing the effect of the first embodiment of the present invention,

3 is a view showing the effect of the third embodiment of the present invention;

4 is a view showing the effect of the fifth embodiment of the present invention;

5 is a view showing the effect of the third and fifth embodiments of the present invention,

6 is a view showing the effect of the sixth embodiment of the present invention.

The phosphor of the present invention is doped with additional elements such that the donor concentration is appropriately controlled in the matrix of Ga _1-x In _x N (where O ≦ _x <0.8). For this reason, the phosphor of the present invention is excellent in luminance characteristics and lifespan characteristics, and has the effect of realizing various emission colors by electron beam excitation depending on the selection of additional elements. In addition, if a raw material containing no oxygen is used, the oxygen is not adversely affected during production.

Claims (4)

A compound selected from the group consisting of Mg, Zn, Si, Ge, and Sn, which is a dope material containing no oxygen, is mixed with a phosphor matrix material composed of Ga sulfide containing no oxygen, and is subjected to 1100 DEG C. in an ammonia atmosphere. Represented by the general formula GaN: M, X obtained by heating to 1200 ° C., wherein M is at least one element selected from the group consisting of Mg and Zn, and X is at least one element selected from the group consisting of Si, Ge, and Sn; , Wherein the concentration range (mol%) of M and X is 0.01 <M <0.3 and 0.005 <M <0.3, respectively. The fluorescent compound according to claim 1, wherein the Si compound is polysilazane (SiH _a N _b ) _n ( _where a = 1 to 3, b = 0 or 1, and n is an integer of 1 or more). Manufacturing method. A compound selected from the group consisting of Ma, Zn, Si, Ge, and Sn, which is a dope substance containing no oxygen, is mixed with a phosphor matrix material composed of indium sulfide containing no oxygen, and then subjected to 1100 DEG C. in an ammonia atmosphere. Represented by general formula GaN: M, X (wherein M is at least one element selected from the group consisting of Mg and Zn, X is at least one element selected from the group consisting of Si, Ge, Sn) obtained by heating to 1200 ° C And the concentration range (mol%) of M and X is 0.01 <M <0.3 and 0.005 <M <0.3, respectively. The method of claim 3, wherein the Si compound is polysilazane (SiH _a N _b ) _n ( _where a = 1 to 3, b = 0 or 1, and n is an integer of 1 or more), the production of phosphor Way.

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