JPS5940177B2 - borate phosphor - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel phosphors, and more particularly to cerium-activated or cerium and terbium-activated borate phosphors that exhibit high brightness blue to green emission.

Cerium-activated magnesium aluminate phosphor (CeMgAllOl9), cerium and terbium-activated magnesium aluminate phosphor [(Ce, Tb ) MgAllOl9] (Japanese Patent Publication No. 52-22836), cerium-activated yttrium silicate phosphor (Y2SlO5:Ce, Japanese Patent Publication No. 48-37914)
), cerium and terbium activated yttrium silicate phosphor (Y2SiO5:Ce.Tb, JP-A-53127)
384), cerium-activated calcium phosphate phosphor [Ca
3Ce(PO4)3], cerium and terbium activated calcium phosphate phosphor [Ca3(CelTb)(PO4
)3] (Japanese Unexamined Patent Publication No. 54-57480), cerium and terbium activated boron oxide phosphor [(Ce.T
b) 203.3B203, JP-A No. 53-33986]
etc. are known.

Generally, these cerium-activated or cerium and terbium-activated oxide-based phosphors emit blue to green light.
That is, among these phosphors, phosphors activated solely with cerium emit blue light due to cerium, but in phosphors co-activated with cerium and terbium, as the relative amount of terbium to cerium increases, Therefore, the energy transferred from cerium to terbium increases, which causes the terbium to gradually emit green light, and when the relative amount of terbium to cerium exceeds a certain level, the phosphor begins to emit green light. The above-mentioned conventionally known cerium-activated or cerium and terbium-activated oxide-based phosphors emit considerably high-intensity blue to green light under various excitations such as ultraviolet rays, electron beams, X-rays, and vacuum ultraviolet rays. It is useful for a wide range of applications such as fluorescent lamps, cathode ray tubes, X-ray image converters, and plasma display devices.

Some of them are already in practical use for specific purposes.
From a practical point of view, it goes without saying that it is desirable that the luminance of these phosphors be as high as possible. A cerium-activated or cerium and terbium-activated oxide-based phosphor that emits more luminous light than a phosphor is desired.

The present invention discloses a novel cerium-activated or cerium- and terbium-activated oxide-based phosphor that emits blue to green light with higher brightness than conventional cerium-activated or cerium- and terbium-activated oxide-based phosphors. The purpose is to provide a light body.

The present applicant previously reported that its composition formula was a(Ml.-X.MIrX)0.B2O3:YCe,.
ZTb (where M is at least one of magnesium, beryllium, zinc and cadmium, M is at least one of calcium hestrontium and barium)
species, A. x. y and z are respectively O<a≦2,
0, 0≦x≦0.25, 0<y≦0.4 and O≦z≦
A new cerium-activated or cerium and terbium-activated 2 expressed as
A patent application was filed for a valent metal borate phosphor (patent application filed in 1986-1999).
No. 316).

This phosphor emits high-intensity blue to green light when excited by ultraviolet rays, electron beams, It achieves the above object by emitting blue to green light with higher brightness than physical phosphors. The present inventors discovered that the compositional formula of the cerium-activated or cerium and terbium-activated divalent metal borate phosphor disclosed in the above-mentioned Japanese Patent Application No. 54-99316 is AMI [
O-B2O3:YCe,. zTb (where M is at least one of magnesium, beryllium, zinc, cadmium, calcium hestrontium and barium; A.
y and z are each O<a≦2.010 and y≦0.4
Various studies have been carried out on cerium-activated and cerium- and terbium-activated divalent metal borate phosphors expressed by the following formulas: and Z<-0.4.

As a result, in addition to the parent constituents of this phosphor, MO (where M is at least one of magnesium, beryllium, zinc, cadmium, calcium, strontium, and barium) and B2O3, M
[V'02 (where M is at least one of silicon, titanium, germanium, zirconium, tin, thorium, and lead)
species), MV2O5 (MV is phosphorus, vanadium,
niobium, antimony, tantalum and arsenic) MI2O (where MI is at least one of lithium, sodium, potassium rubidium and cesium), M2O3 (where M is aluminum, hescandium, gallium, yttrium, indium, lanthanum, lutetium, gadolinium, bismuth, and thallium) and MO3 (where M is at least one of molybdenum, tellurium, and tungsten). When a borate base, which is used as a constituent component and has these base constituents dissolved in an appropriate ratio, is activated with an appropriate amount of cerium or cerium and terbium,
Similar to the cerium-activated or cerium and terbium-activated divalent metal borate phosphor disclosed in the above-mentioned Japanese Patent Application No. 54-99316, it exhibits high brightness under excitation with ultraviolet rays, electron beams, X-rays, vacuum ultraviolet rays, etc. It is possible to obtain a phosphor that emits blue to green light and exhibits blue to green light emission with higher brightness than conventional cerium-activated or cerium and terbium-activated oxide-based phosphors, especially under ultraviolet and vacuum ultraviolet excitation. This discovery led to the completion of the present invention. The cerium-activated or cerium- and terbium-activated borate phosphor of the present invention has a compositional formula (where M is at least one of magnesium, beryllium, zinc, cadmium, calcium, strontium, and barium, and M is silicon). , titanium, germanium, zirconium, tin, thorium, and at least one of lead; MV is phosphorus, vanadium,
at least one of niobium, antimony, tantalum and arsenic; M is at least one of lithium, sodium, potassium, rubidium and cesium; M is aluminum, scandium, gallium, yttrium, indium, lanthanum, lutetium, gadolinium;
at least one of bismuth and thallium; M is at least one of molybdenum, tellurium, and tungsten; A. b. c. d, E, . x,. y and Z are O<a≦2.0, 0≦b≦0.3, O≦c≦0.
3.0kud≦0.4, O≦e≦0.4, O≦x≦0.6
, O≦y≦0.35, 0≦Z≦0.01 and b+c+
This is a number that satisfies the condition x+y+z'80).

From the viewpoint of luminance, the above A. b. c,. d. e. x,. y
The more preferable range of and z is 0.07≦a≦, respectively.
135, 0≦b≦0.2, 0≦c≦0.2, 0.005
≦d≦0.3, 0.0001≦e≦0.3, O≦X≦0
．． 4, 0≦y≦0.2 and 0<z≦0.005. The phosphor of the present invention emits high-intensity blue to green light under excitation with ultraviolet rays, electron beams, It emits blue to green light with higher brightness than terbium-activated oxide phosphors.

The present invention will be explained in detail below.

The phosphor of the present invention represented by the above compositional formula is manufactured by the manufacturing method described below.

First, the raw materials for the phosphor are (1) boron oxide (B2O3) and boric acid (H3BO3).
), metaboric acid (HBO2), ammonium borate [(NH
4) at least one compound selected from the group consisting of boron compounds that can be easily converted to B2O3 at high temperatures such as 3B03], (il) magnesium oxide (MgO), beryllium oxide (BeO), zinc oxide (ZnO), Cadmium oxide (CdO), calcium oxide (CaO), strontium oxide (SrO) and barium oxide (BaO)
), as well as nitrates, carbonates, sulfates, hydroxides,...logenides, etc., which easily convert Mg at high temperatures.
O, BeO, ZnO. CdO, CaO, SrO and B
At least one compound selected from the second compound group consisting of magnesium compounds, beryllium compounds, zinc compounds, cadmium compounds, calcium compounds, strontium compounds, and barium compounds that can replace aO, (111) silicon dioxide ( SiO2),
Titanium oxide (TiO2), germanium oxide (GeO2)
), zirconium oxide. ``mu (ZrO2), tin oxide (S
nO2), thorium oxide (ThO2) and oxide salts (P
The first group of compounds consisting of
2, TlO2, GeO2, ZrO2, SnO2, ThO
2 and a second compound group consisting of silicon compounds, titanium compounds, germanium compounds, zirconium compounds, tin compounds, thorium compounds, and lead compounds that can be converted into PbO2; (:V) Phosphorous pentoxide (P2
O5), vanadium oxide (V2O5), niobium oxide (N
b2O5), antimony oxide (Sb2O5), tantalum oxide (Ta2O5) and diarsenic pentoxide (As2O5)
The first group of compounds consisting of
, poor V2O5, Nb2O5, Sb2O5, Ta2
At least one compound selected from the second compound group consisting of phosphorus compounds, vanadium compounds, niobium compounds, antimony compounds, tantalum compounds, and arsenic compounds that can be converted into O5 and AS2O5, (
V) Lithium oxide (Li2O), sodium oxide (Na
2O), potassium oxide (K2O), rubidium oxide (R
b2O) and cesium oxide (Cs2O).
, as well as nitrates, carbonates, sulfates, hydroxides, halides, etc., can easily be converted into Ll2O, Na2O, etc. at high temperatures.
A second group of compounds consisting of lithium compounds, sodium compounds, potassium compounds, rubidium compounds and cesium compounds that can be converted into , K2O, Rb2O and CS2O. - at least one compound selected from the group of compounds consisting of aluminum oxide (Al2O3), scandium oxide (SC2O3), gallium oxide (Ga2O3),
Yttrium oxide (Y2O3), indium oxide (In
2O3), lanthanum oxide (La2O3), lutetium oxide (LU2O3), gadolinium oxide (Gd2O3),
Bismuth oxide (Bi2O3) and thallium oxide (Tl
2O3), as well as nitrates, carbonates, sulfates, hydroxides, halides, etc., can be easily converted to Al2O3, Se2O3, Ga2O3, Y2O3, In
2O3, La2O3, LU2O3, Gd2O3, Bi2
A compound selected from the compound group consisting of a second compound group consisting of aluminum compounds, scandium compounds, potassium compounds, yttrium compounds, indium compounds, lanthanum compounds, lutetium compounds, gadolinium compounds, bismuth compounds, and thallium compounds that can be converted into O3 and Tl2O3 At least one of (Vil) molybdenum oxide (MOO3), tellurium trioxide (TeO3)
and tungsten oxide (WO3), as well as MOO3, TeO3 and W
At least one compound selected from the second compound group consisting of a molybdenum compound, a tellurium compound, and a tungsten compound that can be converted into O3, 411
1) Cerium oxide (CeO2) and nitrates, carbonates,
At least one compound selected from the group consisting of cerium compounds that can be easily converted into oxides at high temperatures, such as sulfates and halides, and (sub) terbium oxide (T
At least one compound selected from the group consisting of nitrates, carbonates, sulfates, terbium compounds that can be easily converted into oxides at high temperatures, such as nitrates, carbonates, sulfates, etc., is used.

Each of the above phosphor raw materials is stoichiometrically prepared (M is at least one of magnesium, beryllium, zinc, cadmium, calcium, strontium, and barium, M
is at least one of silicon, titanium, germanium, zirconium, tin, thorium, and lead, M is at least one of phosphorus, vanadium, niobium, antimony, tantalum, and arsenic, and MI is lithium, sodium, potassium, and rubidium. and at least one of cesium, M is aluminum, scandium, gallium, yttrium, indium, at least one of lanthanum, lutetium, gadolinium, bismuth, and thallium, M is at least one of molybdenum, tellurium, and tungsten. And. ,B. c. d, E. x.
y and z are O<a≦2.0, O≦b≦0.3, 0≦c
≦0,3, 0kudku0.4, O≦e≦0.4, O≦x≦
0.6, 0≦y≦0.35, O≦Z≦0.01 and b
+c+x+y+Z8O) is weighed out and mixed thoroughly.

The mixing may be carried out in a dry manner using a ball mill, mixer mill, mortar, etc., or may be carried out in a wet manner in a paste state using water, acid, etc. as a medium. In particular, from the viewpoint of luminance of the obtained phosphor, A. b. O. d. e
．． The values of x, y and Z are each 0.07≦a≦1.5
, 0≦b≦0.2, 0≦c≦0.2, 0.005≦d≦
0.3, 0.0001≦e≦0.3, 0≦x≦0.4,
More preferably, O≦y≦0.2 and O≦z≦0.005. In the production of phosphors, a fluxing agent is often added to the phosphor raw material mixture for the purpose of improving the luminance, powder properties, etc. of the phosphor obtained. In the production of the phosphor of the invention, ammonium chloride (NH4Ci), ammonium fluoride (NH4
F), acidic ammonium fluoride (NH4HF2), ammonium bromide (NH4Br), ammonium iodide (NH4
1), ammonium carbonate [(NH4)2C03], ammonium nitrate (NH4NO3), etc. as a flux and are added to the phosphor raw material mixture in appropriate amounts to improve luminance. In addition, in the above mixed composition formula, if b=O, the phosphor raw material of the above 0V), if c1O, the phosphor raw material of the above (v), and if e-0, the phosphor raw material of the above (sub) Fluorescent raw material, in the case of x-0, the above (111)
It goes without saying that it is not necessary to use the above (Vi) phosphor raw material in the case of y-0 and the upper MD phosphor raw material in the case of z-0. .x,.
y and z cannot be zero at the same time). Next, the phosphor raw material mixture is filled into a heat-resistant container such as an alumina crucible or a quartz crucible, and fired. Firing is performed once at a temperature of 800 to 1100°C in a neutral atmosphere such as air, argon gas atmosphere, nitrogen gas atmosphere, or a reducing atmosphere such as nitrogen gas atmosphere containing a small amount of hydrogen gas or carbon atmosphere. Or do it more than once. In this case, in order to ensure that the valence of cerium and terbium, which are the activators, is trivalent, at least the final firing (or the firing if only one firing) is performed in a neutral atmosphere or in a reducing atmosphere. Preferably, it is carried out in an atmosphere. The firing time varies depending on the amount of the phosphor raw material mixture filled in the heat-resistant container, the firing temperature employed, etc., but in general, 0.5 to 6 hours is appropriate within the above firing temperature range, and is more preferable. is 1 to 5 hours. Note that, before performing the above-mentioned firing, it is preferable to pre-fire the phosphor raw material mixture filled in the heat-resistant container. This pre-firing is carried out for the purpose of converting each phosphor raw material into an oxide in advance and increasing the reactivity of each phosphor raw material during firing, and is generally performed in air for approximately 40 min.
It is carried out once or twice or more at a temperature of 0 to 800°C. A suitable pre-baking time is 0.5 to 6 hours. After firing, the resulting fired product is processed through various operations generally employed in the production of phosphors, such as crushing, washing, drying, and sieving, to obtain the phosphor of the present invention. By the manufacturing method described above, the composition formula (MI, .M, M, M, MV
、． M, Alb. c. d. e. x. y and z have the same definitions as above) of the present invention (when the e value is zero) or cerium and terbium activation (when the e value is O<e≦0.4) Borate phosphors can be obtained.

This phosphor emits high-intensity blue to green light when excited by ultraviolet rays, electron beams, X-rays, vacuum ultraviolet rays, and the like. That is, the phosphor of the present invention exhibits blue light emission due to cerium when the terbium activation amount (e value) is zero, but as the e value increases, the green light emission due to terbium gradually becomes stronger.
Although it depends on the amount of cerium activation (d value), generally when the e value is about 10-4 or more, the emitted light color is green. Note that the luminescent color of the phosphor of the present invention is MI. M, M, M,
Types of MV and M, and (MP-o, M-stand/2) 0
amount (a value), MyO5 amount (b value), M2lO amount (c value)
There is almost no change in any of the M value (x/2 value), the M amount (y value), and the M amount (z/2 value).

Figure 1 shows the 0.33Mg0-0.05L120 of the present invention.
The emission spectrum of B2O3:0.11Ce, 0.06Tb phosphor is shown.

Table 1 below shows the cerium and terbium activated borate phosphor of the present invention (/F6.8~46) at 253.7 Nm.
The emission brightness under ultraviolet excitation was determined from the above-mentioned Japanese Patent Application Laid-Open No. 53-33.
Cerium and terbium activated boron acid phosphor (716.1) described in No.
A comparison is made with the cerium and terbium activated divalent metal borate phosphors (/F6.2-7) disclosed in No. 316. Note that in Table 1, the luminance is compared to the conventional (Ce
, Tb)203・3B203 phosphor luminance to 100
It is expressed as a relative value.

As is clear from Table 1 above, the phosphor of the present invention exhibits higher luminance than the conventional (Ce.Tb) 203.3B203 phosphor.

Further, a part of the phosphor of the present invention is disclosed in the above-mentioned Japanese Patent Application No. 54-993.
It exhibits higher luminance than the phosphor disclosed in No. 16. That is, a phosphor (waste 8
~12), phosphors containing M2l[103 where M is other than bismuth (Taki 13-21), phosphors containing SiO2 (Waterfall 24)
) and P2O5 (A6.32) are the phosphors disclosed in the above-mentioned Japanese Patent Application No. 54-199316 (respectively 應2, SEKI3, HAIL4, and TAKI5) that do not have these as base components.
) shows higher luminance than that of Especially M2lO and MI[[
is M other than bismuth! The phosphor of the present invention containing 03 as a base component (for example /F6.23) emits light with extremely high brightness. Note that praseodymium (
Pr), neodymium (Nd), samarium (Sm), europium (Eu), dysprosium (Dy), holcium (HO), erbium (Er), itterbium (
A phosphor that emits high-intensity light can also be obtained by activating an appropriate amount of Yb), thulium (Tm), or the like.

The fluorescent material of the present invention emits high-intensity blue to green light when excited by ultraviolet rays, electron beams, X-rays, vacuum ultraviolet rays, etc., so it can be used in fluorescent lamps, cathode ray tubes, X-ray image converters, plasma display devices, etc. It can be used for.

As explained in Table 1, the phosphor of the present invention emits light with higher brightness than conventionally known cerium-activated or cerium and terbium-activated oxide-based phosphors under ultraviolet excitation; Even under excitation, it exhibits higher luminance than conventional cerium-activated or cerium and terbium-activated oxide-based phosphors. For example, 0.33 of the present invention
Mg0-0.05L120・B2O3:0.11Ce1
The 0.06Tb phosphor is a conventional (CeO.65, TbO.35) 203″3B2 under 147nm vacuum ultraviolet excitation.
The luminance was 22 times higher than that of 03 phosphor.

Next, the present invention will be explained with reference to Examples.

Example 1 After the terbium oxide described above was dissolved in nitric acid, the other phosphor raw materials described above were added to this solution and thoroughly mixed.

After drying and pulverizing the resulting paste-like mixture, it was filled into an aluminum pot, placed in an electric furnace, and heated in air for 500 min.
Pre-calcination was carried out for 2 hours at a temperature of .degree. After this preliminary firing, the obtained fired product was pulverized, filled into an alumina crucible, placed in an electric furnace, and subjected to a second round firing under the same conditions as above. After the second firing, the resulting fired product is crushed,
The mixture was filled into an aluminum crucible, placed in an electric furnace, and fired at a temperature of 1050° C. for 2 hours in a carbon atmosphere.

After firing, the resulting fired product was crushed, washed, dried, and then sieved. In this way, the 0.33Mg of the present invention
0-0.05L120-B2O3: 0.11Ce, 0.
A 06Tb phosphor was obtained. This phosphor can be used for ultraviolet rays, electron beams,
It exhibited high-intensity green light emission under excitation with X-rays, vacuum ultraviolet rays, etc. The emission spectrum of this phosphor is shown in FIG. Furthermore, the luminance of this phosphor under 253.7 nm ultraviolet excitation is higher than that of conventional (CeO.65, TbO.35) 20
It was about 2.1 times that of the 3.3B203 phosphor.

Example 2 0.86Mg0 (BO.9,
AlO. l) 203:0.11Ce, 0.17Tb phosphor was obtained.

This phosphor exhibited high-intensity green light emission under excitation with ultraviolet rays, electron beams, X-rays, vacuum ultraviolet rays, etc. Furthermore, the luminance of this phosphor under excitation of 253.7 nm ultraviolet light was about 2.1 times that of Jumei's (CeO.65, TbO.35) 203.3B203 phosphor. Example 3 Using each of the above phosphor raw materials and flux, the firing temperature was set to 950℃.
0.degree. C. of the present invention in the same manner as in Example 1 except that the temperature was 0.degree.
71(BeO.8, SiO.l)O-B2O3:0.1
1Ce,. A 0.17Tb phosphor was obtained.

This phosphor exhibited high-intensity green light emission under excitation with ultraviolet rays, electron beams, X-rays, vacuum ultraviolet rays, etc. Furthermore, the luminance of this phosphor under excitation of 253.7 nm ultraviolet light was about 1.9 times that of the conventional (CeO.65, TbO.3,)203.3B203 phosphor. Example 4 The 0.5zn0-
0.1p205・B2O3: 0.06ce, 0.06T
b A phosphor was obtained.

This phosphor exhibited high-intensity green light emission under excitation with ultraviolet rays, electron beams, X-rays, vacuum ultraviolet rays, etc. Furthermore, the luminance of this phosphor under excitation of 253.7 nm ultraviolet light was about 1.7 times that of the conventional (CeO.651Tb0.35) 203-3B203 phosphor. Example 5 0.64Mg03 (BO.99
6) MOO. OO2) 203:0.06Ce, 0.29
A Tb phosphor was obtained.

This phosphor exhibited high-intensity green light emission under excitation with ultraviolet rays, electron beams, X-rays, vacuum ultraviolet rays, etc. Furthermore, the luminance of this phosphor under excitation of 253.7 nm ultraviolet light was about 1.1 times that of the conventional (CeO.65, TbO.35) 203°3B203 phosphor. Example 6 The 0.29(MgO.7, ZnO.3)O-
0.05Na20・(BO.,,YO.l)203:0
．． A 11Ce, 0.06Tb phosphor was obtained.

This phosphor exhibited high-intensity green light emission under excitation with ultraviolet rays, electron beams, X-rays, vacuum ultraviolet rays, etc. Furthermore, the luminance of this phosphor under excitation of 253.7 nm ultraviolet light was about 2.0 times that of the conventional (CeO.65, TbO.35) 203.3B203 phosphor.

[Brief explanation of the drawing]

The drawing shows 0.33Mg0-0.05Li20・B of the present invention.
2 is a graph showing the emission spectrum of a 2O3:0.11Ce, 0.06Tb phosphor.

Claims (1)

[Claims] 1. The compositional formula is a(M_1^II_-_x, M_x^IV_/_2)O・b
M^V_2O_5・cM_2^ I O・B_1_-_y
____z, M_y^III, M_z^VI_/2)_2O_
3: dCe, eTb (However, M^II is at least one of magnesium, beryllium, zinc, cadmium, calcium, strontium, and barium, and M^IV is silicon, titanium, germanium, zirconium, tin, thorium, and lead. M^V is at least one of phosphorus, vanadium, niobium, antimony, tantalum and arsenic, M^I is at least one of lithium, sodium, potassium, rubidium and cesium, M^III is at least one of aluminum, scandium, gallium, yttrium, indium, lanthanum, lutetium, gadolinium, bismuth, and thallium; M^VI is at least one of molybdenum, delurium, and tungsten; a, b, c
, d, e, x, y and z are 0<a≦2.0, 0≦b≦
0.3, 0≦c≦0.3, 0<d≦0.4, 0≦e≦0
．． 4, 0≦x≦0.6, 0≦y≦0.35, 0≦z≦0
．． 01 and b+c+x+y+z≠0). 2 The above a, b, c, x, y and z are each 0.0
7≦a≦1.5, 0≦b≦0.2, 0≦c≦0.2, 0
≦x≦0.4, 0≦y≦0.2 and 0≦z≦0.00
The borate phosphor according to claim 1, wherein the number satisfies the condition of 5. 3 The above d and e are each 0.005≦d≦0.3
and 0.0001≦e≦0.3.
Borate phosphor as described in Section. 4. The borate phosphor according to claim 1, 2 or 3, wherein c is c≠0. 5. Claim No. 5, characterized in that y≠0, and M^III is at least one of aluminum, scandium, gallium, yttrium, indium, lanthanum, lutetium, gadolinium, and thallium. The borate phosphor according to any one of items 1 to 4. 6. The borate phosphor according to claim 1, 2 or 3, wherein x is x≠0 and M^IV is silicon. 7 Claims 1, 2, or 3, characterized in that the above b is b≠0, and the above M^V is phosphorus.
Borate phosphor as described in Section.