JPS604855B2 - phosphor - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a halophosphate lamp activated with divalent europium and having an emission spectrum distribution mainly in the blue region, a light body, and a method for producing the same.

Conventionally, the halophosphate poppy activated with divalent europium, the light body, was published in Tokuko No. 46-40604 or Tsubaki Kosho 48.
It has the parent crystal structure of apatite as described in No. 13315y, etc., and has the general formula aM3(P04)2・b
M'X2, where M and M' are alkali metals, x represents a halogen element, and a/b=3. In other words, this poppy light body has a composition in which the molar ratio of orthophosphate and halogen compound is 3:1, and divalent europium is activated, and antimony, lead, cadmium, etc. are effective additives. It is said that there is. However, these conventional phosphors have not been fully satisfactory in terms of color tone, luminous efficiency, etc.

An object of the present invention is to provide a new poppy, a light body, and a method for manufacturing the same, which improve these problems.

Another object of the present invention is to provide a poppy, a luminous body, and a method for producing the same, which produce luminescence with high luminous efficiency and stimulation purity when excited with ultraviolet rays or electron beams. The poppy and light body of the present invention have the general formula a (Sr.~1 YM vine M history Euzo) 3 (P).

4) 2-bM'X2 (Mh is at least one element selected from the group consisting of Zn, Ca, and Mm
is at least one element selected from the group consisting of AI, Y, Buddha, and Gd; M is at least one element selected from the group consisting of Ca, Sr, and shear; X is one or more halogens; , provided that when 1 is used as X, it is less than 20 mol% of the total amount of X, and z is 0.00
Values in the range of 15mm x 30.20, x and y are values in the range of 0mm x mi 0.999 and 0mm ymi 0.999, respectively, x + y + z is (a/b is a value in the range of 0.3 mya/b31.2), and can be applied to illumination light sources and various picture tubes. .

If the value of z is less than 0.0015, the brightness is not sufficient and the value is 0.0015.
．． If it exceeds 20, the color tone changes, so it is determined as described above. The reason why the value of a/b is limited to the above range is that in this range, the E
This is because the luminous efficiency increases.

Furthermore, it is preferable to set this value in the range of 0.4 to 0.7 because greater luminous efficiency can be obtained.
As for the above x, it is preferable that CI and/or Br be contained in an amount of 50 mol % or more because the luminous efficiency of Eu20 increases.

In particular, those containing only CI and/or Br or containing 80 mol % or more of CI and/or Br are more preferable because they exhibit higher luminous efficiency. Furthermore, the value of x + y is 0 < x y
It is preferable to set 0<x+y30.2, more preferably 0<x+y30.2, because the luminous efficiency increases significantly. Also X
When 1 is contained as 1, the amount of 1 is preferably 20 mol%. If 1 is 20 mol% or more, the luminance will decrease and the color tone will become reddish.

Furthermore, as the above M', only Ca or 90% of Ca is used.
Those containing mol% or more are preferable because they have excellent color purity.
The poppy and luminous bodies of the present invention have an average emission peak wavelength of 456
nm, half width 41 nm, as an example (Sr..9
Z ratio of 0. . , 67Eu. ．． 083)3(P04)2
・Book aC12 Narukeshi ・The light body has chromaticity coordinates x=0.14
9 y=0.108, and the well-known poppy, light body $r3 (
P04) 2SrC12:Eu2 chromaticity coordinate x=0.1
50y: Compared to 0.032, this value is closer to the blue origin of the NTSC system. Also, the specific surface area is on average 25
It is evening of 00.

The poppy and luminous material of the present invention are effective when applied to illumination light sources and display devices, but especially the blue component of the high-efficiency, high color rendering poppy and light lamp that produces white color when mixed with other poppy and luminous materials. Poppies have a remarkable effect as a light source. To produce the poppy and light bodies of the invention, various raw material mixtures are used, supplying the required amounts of alkali metals, phosphate groups, halogens and metals represented by MU and Mm.

Examples of these raw materials include carbonates, phosphates, and halides of Sr, carbonates, phosphates, and halides of metals represented by MO or Mm, and halides or carbonates of alkali metals. These include ammonium halides and ammonium phosphate.

A more excellent method for producing the poppy seeds and light bodies of the present invention is to add the halogen element, which is a component element of the poppy seeds and light bodies, in an amount in excess of the stoichiometric amount, more preferably 1.25 to 3.5%.
In this method, a double amount of a halogen compound is used and fired in a reducing atmosphere to produce a poppy and a light body represented by the above general formula.

The halogen compounds used here include Sr×2,
There are Mn×2 and Mm×3 (where x, Mh and Mm have the above-mentioned meanings).

In this case, since the elements Sr, M mountain, and Mm are constituent elements of the poppy/light body, the amounts of these elements cannot be greater than the stoichiometric amount. Therefore, the amount of halogen element added cannot exceed a certain amount. In other words, using such a halogen compound will reduce the amount of S, M in the raw materials.
This means that part or all of the elements m and Mm are used in the form of a halide. In this case, preferred halogen compounds from the viewpoint of brightness improvement are halides of elements Mh and Mm, and preferred halogen is chlorine.

Other halogen compounds include ammonium halides.

In this case, an arbitrary amount of ammonium halide can be added since ammonium groups are not included in the opium or the light material. A preferred halogen from the viewpoint of improving brightness is chlorine. The above-mentioned excessive amount of halogen element is avoided for the following reasons. If the amount of the halogen compound is even slightly in excess of the stoichiometric amount of the halogen element, a corresponding effect will be recognized, but in general, the effect of improving brightness is obvious at pitches of 1.2 or higher, and especially Significant improvement occurs at 1.5 times or more. Also, the amount of halogen element in the raw material is 3.5% of the stoichiometric amount. Although the brightness is improved even beyond vowels, for example, when using N ratio CI as a raw material for halogen elements, adding too much will cause sublimation of NH4C during firing.
This is unfavorable in terms of piping clogging due to I. Therefore, the amount of halogen element added in excess in the raw material is preferably 1.25 to 3.5 times the stoichiometric amount, more preferably 1.5 to 2. It's painful. Firing is 900-13000
It is preferable to carry out the reaction at 0 for 1 to 6 hours.

Alternatively, a first reactant solution containing the required Sr, Mm, Mm, and Eu ions and a second reactant solution containing the required phosphate ions and halogen ions are mixed, and the resulting coprecipitate is dried. It can also be used as a raw material.

The present invention will be explained below with reference to Examples.

Example 1 SrC.

3 2,75 moles (NH4)2H
P04 2.00″CaC2
2.00″Eu203 0.12
After accurately weighing 5″ and mixing thoroughly, add 5% hydrogen.
Calcinate at 1000qC for 3 hours in a nitrogen atmosphere containing
=0, z=0.083, a/b;0. FuM NiCa, X=
A phosphor called CI, ie (Sto.9, 7 E~.
o83)3(PQ)2・shio aC12 was obtained.

In this poppy, the mercury vapor resonance line excitation of 254n of the light body has a powder brightness of 339 (known poppy, light body $ 3 (P04) 2
-SrC12:Eu is assumed to be 100 (the same applies hereinafter unless otherwise specified), and the emission spectrum was as shown in 1 in FIG.

Examples 2 to 4 The raw material mixtures in Table 1 were treated in the same manner as in Example 1, and in the general formula x = 00 5, y = 0, z = 0.0833 a/
b=o. 5 M positive = zn, M' = Ca, X = CI Narukeshi light body (Example 2), x = 0, y = 0.0667, z
=0.0833, a/b=o. 5, Mm=M, M=Ca
, ×=CI Narukeshi, light body (Example 3) and x=0,
y=0.0167, z=0.083 a/b=o. 5
, Mm=Y, M=Ca, x=CI, a light body (Example 4) was obtained.

Table 1 The emission spectra of these poppies and luminaries are shown in Figures 2 and 3.
and FIG. 2 4, and the powder brightness is 44, respectively.
They were 0,512,432.

Further, FIG. 3 shows the relative brightness when the a/b ratio was changed by increasing or decreasing the amount of CaC12 in Example 2. As shown in the figure, the brightness increases when the a/b ratio is in the range of 0.3 to 1.2. In particular, in the range of 0.4 to 0.7, the powder brightness increases significantly, and becomes 3.0 times or more compared to the secondary poppy and light body. Figure 4 shows the relationship between X-ray diffraction intensity and interplanar spacing for the poppy and light body of Example 2 (lower figure) and for the known poppy and light body $r3 (
P04)2・SrC12:Eu20 (upper figure) is compared and contrasted.

As is clear from the figure, the diffraction intensity distributions in the upper and lower figures are different, and in the region of a/b = 0.3 to 1.2, the same intensity distribution as in the lower figure is shown. Therefore, the increase in relative strength is
This is thought to be due to the crystal structure different from that of apatite. In addition, FIG. 5 shows the excitation spectrum of Eze+ emission for the phosphor of Example 2 doped with ZnC12 (dashed line).
and the poppy light material of Example 1 (solid line) in which no ZnC12 was added, and the emission intensity was at the mercury resonance line 25.
It can be seen that the broken lines uniformly increase compared to the solid lines in areas other than 4n.

Example 5 The same raw material mixture as in Example 1 was fired at 1200 qo.

The emission spectrum of the obtained poppy and luminous material was as shown in FIG. 6, and the powder brightness was 355. Example 6Sr
C03 2.700 Mol ZnC Buddha 2
0.050″(NH4)2HP04 2.
000″BaCmu2 2.000 〃E
U203 0.125 〃Using a raw material with a composition of
Process in the same manner as (Sro.9).

Z~. o, 67E ratio. o833)3(P04)2・Hiroshi2
CI2 Narukeshi obtained a light body. The emission spectrum of this poppy luminous substance is as shown in Fig. 6, and the powder brightness is 50
It was 4. Example 7 The same process was carried out using Mother CQ in place of SrC03 in Example 6 (B was also .9).

Sail Zno. oM Eu side spot 3) 3 (P04) 2・ is aC
12 Narukeshi obtained a light body. The emission spectrum of this poppy luminous substance is as shown in Figure 6 and 7, and the powder brightness is 178
Met. Examples 8 and 9 Instead of BaC12 in Example 6, 1 of CaC12
．． 80 mol and 0.20 mol of BaC12 (Example 8)
, 1.00 mol of CaC12 and 1.00 mol of BaC12 (Example 9) were fired at 1000 qo, and (Sr
Zn side of side o, 67E ratio. O83)3(P04)2・2
(C et al. 9B fever.,) CI2 and (S~.9oooZn
〇． 67E ratio. 33) 3 (P04) 2.2 (Ca〇.5 Ba〇.5) CI2 Narukeshi, a light object was obtained.

The emission spectrum of this poppy luminous material is as shown in Fig. 7 8 (Example 8) and 9 (Example 9), and the powder brightness is 4
They were 33 and 548.

Examples 10 and 11 CaF2 was substituted for CaC12 in Example 1 (Example 10
) Also, in place of CaC12 in Example 2, CaF2 (Example 11) was used and treated in the same manner, and the corresponding poppy seeds,
Obtained a light object.

The emission spectrum of this phosphor is as shown in FIG. 8 (Example 10) and 11 (Example 11), and
The powder brightness of Example 11 to which ZnC12 was added was 1.61 times that of Example 10 to which ZnC12 was not added. Example 1
2-14 The raw material mixture in Table 2 was processed in the same machine as in Example 1, and the mixture in Table 3 was
Nokeshi obtained a light body.

Table 2 Table 3 The emission spectra of these poppies and luminaries are shown in 12 in Figure 9.
(Example 12), 13 (Example 13) and 14 (Example 14), and the powder brightness was 29k269 and 269k, respectively.
It was 69.

Example 15 SrC.

3 2.7 mole GdP04・day2
0 0.051″(NH4)2HP04 2.
0 ″CaC Must 2 2.0 〃
A raw material mixture of Eu203 0.1245 was treated in the same manner as in Example 2, and (Sro.9Gdo.o
, 7E ratio. 3) 3 (P04) 2・This aC12 Narukeshi, a light body was obtained.

The emission spectrum of this phosphor was as shown in 15 in FIG. 10, and the powder brightness was 422. Example 16 Using CaBr2 in place of the late CI2 in Example 6, and setting the firing temperature to 1000 oo, a poppy and light body of X=Br was synthesized.

The emission spectrum of this poppy luminous material was as shown in 16 in FIG. 10, and the powder brightness was 336. Example 1
7 Using NH41 and CaC12 in place of BaC12 in Example 6, the firing temperature was 1000oo, and X=lo. , CI
■Nokeshi obtained a light body.

The emission spectrum of this poppy and the luminous material was almost the same as in Example 1, and the powder luminance was 280. Example 18 SrC.

3 2,652 moles YC 3
0.099″(NH4)2HP04 2.0
00 ″CaC Must 2 2.000 ″E
A raw material mixture of u203 0.1245'' was treated in the same manner as in Example 2.
U skin 83) 3 (P04) 2nd aC12 Narukeshi, a light body was obtained.

The emission spectrum of this poppy luminous material was as shown in 17 in FIG. 11, and the powder brightness was 454. Example 1
9 Instead of GdP04 and Day 20 in Example 15, CI3 was used to obtain Mm=Buddha poppy light body.

The emission spectrum of this poppy luminous material was as shown in 18 in FIG. 11, and the powder luminance was 394. Example 2
0 The number of moles of YC13 in Example 18 was 0.051 mole,
Furthermore, 0.051 mol of LaC13 was added and the same treatment was carried out to obtain a light body with Mm=Y+La.

The emission spectrum of this poppy luminous material was almost the same as that of Example 19, and the powder brightness was 405. Example 2
1. In place of CaBr2 in Example 16, 12 was used for S, and the same treatment was carried out to obtain a poppy light body with M'=Sr.

The emission spectrum of this poppy luminous substance was as shown in 19 in FIG. 11, and the powder luminance was 123, emission peak wavelength 44, and half width 3. Example 22 The amount of Eu203 in Example 1 was increased or decreased, and the amount of SrC03 was also increased or decreased accordingly, and the same treatment was carried out to obtain light bodies with various concentrations of Eze+.

The powder brightness of these poppies and luminaries is 0.0 for Eu203.
025 (z=0.00167) moles and 122, and E
The brightness also increases as the amount of glaze increases. But 0.075
The peak height decreases when exceeding molar (z = 0.05);
When the amount exceeds 0.225 mol (z=0.15), the light emission becomes slightly blue-colored. and 0.275 mol (z=0.18
When exceeding 3), the blue line color becomes a little stronger. Example 23 SrC.

32.4 mol, BaC.

30.3 mol, ZnC 120.05 mol, (NH4)2
HP042.0 mol, E average 030.125 mol, CaC
122.0 mol and N ratio CII. 0 mol was mixed well, placed in an alumina boat, and fired at 1000 qo for 3 hours in a reducing atmosphere containing 5% molasses and 95% N2.

After firing, the whole boat is immersed in water for several hours to separate the fired product.
After water-bending with 270-mesh knots, repeated washing and tilting, drying at 140 to 160 oo for several hours (Sro.
8BaMZn skin, 67E ratio. Snake 33) 3 (P04) 2・
A phosphor called aC12 was obtained. Relative brightness when changing the amount of NACI (10 without adding NHCI)
0) is shown in FIG. As seen in the figure, NH
1 mol of 4CI (25% as halogen amount for 122.0 mol of CaC, 1 stoichiometric amount as total halogen amount)
．． By adding 25 tones) or more, the relative brightness is improved by 1.2 times or more. Example 24 YC13 was used instead of ZnC12 in Example 23, and NH3.H was used instead of N-stop CI.
The same process as in Example 23 was performed using F, and (Sr
o. 8 Europe o. , Yo. o, Nail E ratio. .

83) 3 (P04) 2.Xa (FM CI side) 2 Narukeshi, a light body was obtained.

This poppy light showed a powder brightness of 1.1 tones compared to the poppy light obtained using the same amount of yttrium as Y203 and without excessive use of halogen.

Example 25SrC03, SrHP04, ZnC12,
The same treatment as in Example 23 was carried out using BaC03, Eu203, CaC03 and NH4CI (S et al. 8
BaM Zn side, 67 Euo. Side 3) 3 (P04)
In 2. aC12, a photobody was obtained. NH4CI to the stoichiometric amount of chlorine in this poppy/light body, 1.5, 1
．． 75 and 2. When M sound was used, the powder brightness was improved by 1.2 times or more compared to when stoichiometric amount was used. Example 26 When the same poppy and light body as in Example 2 were excited with an electron beam at an accelerating voltage of 10 to 2 V, the poppy and light body emitted blue light.

Brightness is 30 for $ et al. (P04)2 SrC12:Eu
9% (10 KV, 1 μA').

[Brief explanation of the drawing]

Figures 1, 2, 6, 7, 8, 9, 10, and 11 are diagrams showing the emission spectra of the poppy and the light body of one embodiment of the present invention. , FIG. 3, FIG. 4, FIG. 5, and FIG. 12 are diagrams for explaining the present invention. Younger brother 'Zuji Z Zukai 3 Figure 4 Figure 5 Figure 3 Figure 7 Zuji Zu group? Zuji ′o Zubo ′′ Zukan 'Z diagram

Claims (1)

[Claims] 1 General formula a(Sr_1_-_x_-_y_-_zM^I^I_xM
^I^I^I_yEu^2^+_2)_3(PO_4)_
2・bM'X_2 (where M^I^I is at least one element selected from the group consisting of Zn, Ca and Ba,
M^I^I^I is at least one element selected from the group consisting of Al, Y, La, and Gd; M' is Ca, Sr;
and at least one element selected from the group consisting of Ba, X represents one or more halogens, provided that when I is used as X, it is less than 20 mol% of the total amount of Value in the range of ≦z≦0.20, x
and y is 0≦x≦0.999, 0≦y≦0.999,
Value in the range of x+y+z≦1, a/b is 0.3≦a/b
≦1.2). 2. The phosphor according to claim 1, wherein X in the general formula contains 50 mol% or more of Cl, Br, or both. 3. The phosphor according to claim 1 or 2, wherein X in the general formula contains 80 mol% or more of Cl or Br, or both. 4. The phosphor according to any one of claims 1 to 3, wherein X in the general formula consists of Cl, Br, or both. 5 The ratio of a/b in the general formula is 0.4≦a/b≦
Claims 1 to 4 have a value in the range of 0.7.
A phosphor according to any of paragraphs. 6 General formula a(Sr_1_-_x_-_y_-_zM^I^I_xM
^I^I^I_yEu^2^+_z)_3(PO_4)_
2・bM'X_2 (where M^I^I is at least one element selected from the group consisting of Zn, Ca and Ba,
M^I^I^I is at least one element selected from the group consisting of Al, Y, La, and Gd; M' is Ca, Sr;
At least one element selected from the group consisting of Values in the range of z≦0.20, x and y are 0≦x≦0.999, 0≦y≦0.999, x
+y+z≦1), the raw material composition is mixed with a/b ratio of 0.
．． 3≦a/b≦1.2, and the halogen compound is blended in such a way that the halogen element is in excess of the stoichiometric amount, and is fired in a reducing atmosphere. A method for producing a phosphor. 7. The method for producing a phosphor according to claim 6, characterized in that the halogen element is added as a halogen compound in an amount of at least 1.25 times the stoichiometric amount. 8 The halogen element is 1.25% higher than the stoichiometric amount.
7. The method for producing a phosphor according to claim 6, wherein the halogen compound is added in excess so that the amount is 3.5 times as much. 9 Halogen compounds are SrX_2, M^I^I_xX_2
, M^I^I^I_yX_3, and NH_4X, the method for producing a phosphor according to any one of claims 6 to 8. 10. The method for producing a phosphor according to claim 9, wherein the halogen compound is NH_4X. 11 Claims 6 to 10 in which X is chlorine
A method for producing a phosphor according to any of paragraphs. 12. The method for manufacturing a phosphor according to any one of claims 6 to 11, wherein the firing is performed at a temperature of 900 to 1300°C.