KR840000445B1 - Composition of phosphors - Google Patents

Abstract

Fluorescent compositions are prepared by adding 100-10000 ppm of P to alkaline metal sulfides activated by a kind of element selected from the group of Mn, Cu, Ag, Pb, Au, and La-series elements. The process occurs at 1000-1400oC in the presence of halogen elements (PCl3 and halogenated ammonium are prefd.). As Lanthanum series elements, Eu and Ce are desirable.

Description

Phosphor Composition

1 to 9 are diagrams showing emission spectra of phosphors which are one embodiment of the present invention, respectively.

10 to 13 show changes in relative luminance for explaining the effect of the phosphor of the present invention.

14 is a view for explaining the deviation of the chromaticity table according to the emission temperature of the phosphor of the present invention.

The present invention relates to a phosphor composition. In particular, the present invention relates to a phosphor composition suitable for use in color cathode ray tubes. The present invention also relates to a color cathode ray tube, and more particularly, to a high density current wave color cathode ray tube.

Alkali-type metal sulfide phosphors activated by circuits or transition metals, in particular CaS and SrS-based phosphors, are known to luminesce with high efficiency in response to electron beam stimulation. In particular, Eu activation, or Eu and Ce joints, and activating phosphors are red light-emitting phosphors whose main emission wavelength is 650 to 653 mm (Cas crab) or 609 to 612 mm (SrS crab). On the other hand, Ce-activated phosphor is a green light-emitting phosphor whose main emission wavelength is 520-523 mm (Cas crab) or 503-506 mm (SrS-based). It is also known that in the (CaSr) S-based phosphor, its main emission wavelength is in the middle of that of the CaS-based phosphor.

In order to improve the luminance of these phosphors, coating treatment of halogen elements such as Cl, Br, and I is described in Japanese Patent Application Laid-Open No. 47-38747. These halogen elements are called coactivators and have a role of emphasizing the light emission of the activators Eu ²⁺ and Ce ³⁺ , rather than themselves. In addition, Ce ³⁺ is itself a luminescence, when used with Eu ²⁺ has the role of increasing the light emission of Eu ^2+, is called as sensitized material (sensitizer).

Similarly, an attempt to apply a treatment to the alkaline earth metal sulfide phosphor of P-rule for the purpose of improving the luminance of the phosphor is also described in Japanese Patent Laid-Open No. 47-38747.

However, these effects of brightness enhancement are not yet sufficient. On the other hand, in a typical cathode ray tube for display, the phosphor applied to the screen-in is stimulated with an electron beam having a density of approximately 1 mA / cm ^{2 in} order to obtain practical brightness. The phosphor used in such a cathode ray tube is mainly ZnS: CuAl (zinc sulfide activated with European and aluminum) or (Zn, Cd) S: Ag, and its energy efficiency is 21 ~ 22%, luminous efficiency reaches 6 ~ 7lm / W. In the case of forming a color cathode ray tube, in addition to the green phosphor, Y ₂ O ₂ S: Eu (energy efficiency 12-13%) as a red phosphor, and ZnS: Ag, Cl (energy efficiency 20-23%) as a blue phosphor Is being used. In the color cathode ray tube, mainly due to the lack of luminance of the red phosphor, the luminous efficiency when white is emitted remains at about 3 lm / W. In recent years, however, cathode ray tubes have been developed to excite high-density currents of approximately 100 mA / cm ² to obtain high-brightness or large-area television images. It is known that the use of the above conventional conventional fluorescent substance for this cathode ray tube causes a significant decrease in efficiency in the high current density region and thus saturation of luminance. Such luminance saturation is particularly pronounced in the green phosphor and then in the blue phosphor. For example, when the green phosphor (Zn, Cd) S: Ag is excited with a pulsed electron beam of 10 KV, 10 μsec, the efficiency is 100 mA / cm ² when the energy efficiency at a current density of 10 ^-4 A / cm ² is 100. About 10.

Thus, such a high-density current-excited cathode ray tube phosphor, in particular, green phosphor, instead of the ZnS-based phosphor, for example Zn ₂ SiO ₄ : Mn. Or Gd ₂ O ₂ S: Td and Y ₂ O ₂ S: Td has recently been developed. The large current density characteristics of these phosphors are clearly superior to the ZnS system, and it has been suggested that the luminance saturation is small in the high current density region. However, when the arrow tube is driven by driving the cathode ray tube coated with the phosphor, it has been found that a new problem arises in that the temperature of the phosphor surface rises around 100 ° C in the high current density region. It has also been found that under such high temperature, new deterioration of the phosphor (a decrease in luminance and a change in color tone) occurs.

An object of the present invention is to provide an improved phosphor. Another object of the present invention is to provide a phosphor having more excellent luminous luminance. Another object of the present invention is to provide an improved cathode ray tube. These and other objects are based on the presence of halogen elements in alkaline earth metal sulfides activated by lanthanides and at least one element selected from the group consisting of Mn, Cu, Ag, Pb and Au. It achieves with the fluorescent substance characterized by adding P which is the amount of the range of 10000 ppm.

The phosphor of the present invention is alkaline earth such as Cas, SrS, MgS, Bas, CaSrS or CaMgs activated with a lanthanide group and at least one element selected from the group consisting of Mn, Cu, Ag, Pb and Ag. It is characterized in that 100 to 10000 ppm of P is added to the metal sulfide phosphor in the presence of halogen elements such as Cl, Br, I, and F. Compared with the phosphor added only halogen element by adding P together with the halogen element Energy efficiency improves by more than about 1%, as an example of adding P and Cl simultaneously to CaS, by Journal of Luminescence 5 / 87,1972 by W. Lehmann. However, in this case, it does not contain Eu or Ce, etc., and it is thought that the electron beam stimulation emission is probably due to P ³⁺ .Cl ⁻ pair, and the main emission wavelength is 582 nm different from that of the present invention. , Yellow light emission, thus added P and Cl There are different from the case of the present invention that significantly emphasizing the light emission, such as red light-emitting Ce ³⁺ or Eu ²⁺ green light emission of the alkaline-earth metal sulfide phosphor containing a small amount of Ba, i.e. the formula M1-x BaxS: Ln, where M represents at least one element selected from the group consisting of Ca, Sr, and Mg, except that the bonds of Sr and Mg are excluded. Ln represents a lanthanide group and Mn, Cu, Ag, Pb and Au At least one element selected from the group consisting of x is a value in the range of 0.00005? X? 0.01. The phosphor represented by increases in luminescence intensity as compared with a phosphor containing no Ba.

This phosphor does not contain halogen or P and also has high luminance. In addition, the phosphor to which 100-10000 ppm of P is added in the presence of a halogen element, that is, the phosphor represented by the general formula M _1- x Baz: Ln, X, P (where X represents a halogen element) is higher in luminance. Even if the amount of x is less than the above range or exceeds the above range, the increase in luminescence intensity is hardly seen.

Moreover, it is represented by general formula M1'-x (Ba, Mg) x S: Ln (M 'represents at least 1 sort (s) of element chosen from the group which consists of Ca and Sr, and Ln and x have the meaning mentioned above). Phosphors and phosphors in which 100 to 10000 ppm of P is added in the presence of halogen elements also increase in luminescence intensity as compared with phosphors containing no Ba or Mg.

The element represented by Ln is preferably Eu ²⁺ or Ce ³⁺ or both thereof. The amount is preferably 10 ⁻⁵ to 10 ⁻² gram atoms per mole of alkaline earth metal sulfide. Below this amount, there is little effect as an activator, and above this amount, the luminescence brightness decreases. The amount of halogen element is preferably 10 ⁻⁵ to 10 ⁻¹ gram atoms per mole of alkaline earth metal sulfide. Moreover, it is preferable that the quantity of P is 100-10000 ppm as mentioned above. This is because neither of these is less than the amount of transition, and if the amount exceeds this amount, the increase in the emission intensity is not seen.

The phosphor of the present invention,

(1) alkaline earth metal sulfides or

(1 ') alkaline earth metal compounds and sulfur or sulfur compounds, which may be sulfides by heating together with sulfur or sulfur compounds, and

(2) Lanthanides such as Eu, Ce, Mn, Cu, Ag, Pb and or Au compounds, if necessary

(3) P or P compounds and

(4) It can be obtained by heating a halogen group or a halogen compound.

When PCl ₃ is used as the compound of the above-mentioned (3) and (4), one kind of compound is sufficient. When ammonium halide is used as the halogen compound, part of the ammonium halide acts as a coagulant and is preferable because some halogen elements tend to be contained in the phosphor.

As for the said heating temperature, the range of 1000-1400 degreeC is preferable. In case of BaS, about 100 ℃ is good.

The phosphor of the present invention exhibits excellent luminescent color, particularly for use in color cathode ray tubes. For example, Ce-activated alkaline earth metal sulfide is a green light-emitting phosphor, and Eu- or alkaline earth sulfide of Eu-Ce co-activation is a red light-emitting phosphor, Mn-activated Cu-activated Pb-activated, Ag-activated, Au-activated or AuX The co-activated alkaline earth metal sulfide is a blue light emitting phosphor. In addition, the addition of P in the presence of a halogen element in all phosphors shows a light emission wavelength approximately equal to the light emission wavelength.

Among these phosphors, the red light-emitting phosphor is colored in red, so that high contrast similar to that of the pigment-adhered type in the case of other phosphors can be obtained even when the pigment is not attached to the phosphor when used in a color cathode ray tube. Therefore, since the cost of adhering a pigment to a phosphor can be omitted, and the fall of the brightness | luminance by adhesion can be prevented, it is a preferable fluorescent substance also in this point.

In the case where the phosphor is applied to the screen of the cathode ray tube, it is preferable to use the aromatic diazo compound in which adhesiveness occurs due to exposure, not the method of using a generally used phosphor and a dough which is a photosensitive composition. Do. This is because alkaline earth metal sulfide phosphors generally have low water resistance, and in the case of the kneading method, their brightness tends to decrease because they are in contact with moisture in the dough for a long time.

According to the latter method, since the fluorescent substance, which is substantially dried, is brought into contact with a portion in which adhesion occurs due to exposure, the fluorescent substance does not come into contact with moisture for a long time.

However, the phosphors with F and P addition in the phosphors exhibit good water resistance compared to those containing no F. Therefore, a bright cathode ray tube can also be formed by the kneading method.

When at least one of the above phosphors contains only Au as the phosphor or activator, the cathode ray tube activated by Au and a halogen element and having a phosphor containing no P on the inner surface of the face plate has excellent characteristics as a high current density cathode ray tube. When the current density is increased by two orders of magnitude or more, the luminance saturation hardly occurs, and it is used as a high current cathode ray tube having a commercial stimulation current density of up to 50 mA / cm ² or more. Hereinafter, the present invention will be described according to examples.

[Examples 1-5]

CaS, EuS, 0.1 mol% (the same as below for CaS) and 0.005 mol% of Ce ₂ S ₃ are mixed well, divided into 5 and filled into quartz containers, respectively, 0.5 atm of pressure and H ₂ S containing PCl ₃ It baked at 1200 degreeC for 1 hour in 0.5 atmosphere of atmosphere. At this time, the temperature of PCl _{3 in} Ar was changed by changing the heating temperature of the container holding PCl ₃ , respectively. In this way, red phosphor colored as CaS: Eu, Ce, P, Cl was obtained. The amounts of P and Cl in the phosphor are shown in Table 1. Table 1 also shows the relative energy efficiency when these phosphors were irradiated with an electron beam of 10 kV and 1 x 10 ^-6 A at 2 x 10 ^-6 Torr.

For comparison, CaS, 0.1 mol% EuS, 0.005 mol% Ce ₂ S ₃ and 10 mol% NH 4 Cl were mixed well and filled into a quartz container, and placed under an atmosphere of Ar 0.5 atmosphere and H ₂ S 0.5 atmosphere. It baked at 1200 degreeC for 1 hour, and obtained phosphor which is CaS: Eu, Ce, Cl which does not contain P. The Cl content of this phosphor was about 5 mol%. By changing the amount of NH ₄ Cl, three kinds of phosphors having different Cl contents were obtained. These results are also shown in Table 1. Energy efficiency was based on Comparative Example 1.

TABLE 1

As apparent from Table 1, the Eu ²⁺ and Ce ³⁺ activated Cas phosphors coated with P at 100 ppm or more simultaneously with Cl showed an energy efficiency improvement of 10% or more compared to the phosphors coated with Cl only.

The emission spectrum of the phosphor of Example 1 was the same as that in FIG. 1, and the main emission wavelength was 652 mm, which was the same as in Comparative Example 1.

In addition, the same effect was seen even if Cl was changed into Br or I.

Example 6

CaCO ₃ containing 0.1 mol% of CeO ₂ was mixed well and maintained at 1300 ° C. for 6 hours in air. The obtained oxide was pulverized and maintained at 1200 ° C. for 2 hours under H ₂ S atmosphere to sulfide. Thereafter, the mixture was calcined at 1200 DEG C for 30 minutes while flowing a mixed gas of Ar0.5 and H ₂ S0.5 atm containing PCl3 as in Example 1, thereby obtaining a phosphor having CaS: Ce, P, Cl. The P concentration of the phosphor was 600 ppm and the Cl concentration was 2,800 ppm, 10 kV, and ^10-6 A excitation conditions. The main light emission wavelength was 521 mm and the energy efficiency was 22%. The emission spectrum is shown in FIG.

[Comparative Example 4]

CaCO 3 containing 0.1 mol% of CeO 2 was mixed well and held at 1300 ° C. for 4 hours in air. The obtained oxide was pulverized, and 10 mol% of NH 4 Cl was added to CaCO 3, and sulfated at 1200 ° C. for 2 hours under H ₂ S atmosphere. In this way, a phosphor having CaS: Ce, Cl was obtained. Under the same air condition as in Example 6, the main light emission wavelength was 521 mm and the same as in Example 6, but the energy efficiency was 20%. It is evident that the energy efficiency is improved by about 10% by applying P and Cl as in the phosphor of Example 6.

Example 7

SrSO ₄ and 0.1 mol% (relative to SrSO ₄ ) of CeO ₂ were mixed well and calcined by holding at 1200 ° C. for 5 hours in air. This fired product was pulverized, maintained at 1100 ° C. for 2 hours under H ₂ S atmosphere, and sulfided. Subsequently, the mixture was calcined for 30 minutes in a mixed gas of Ar 0.5 atm and H ₂ S 0.5 atm containing PCl ₃ to obtain a phosphor having SrS: Ce, P, Cl. The P concentration of the phosphor was 300 ppm and the Cl concentration was 1200 ppm. The emission spectrum of the electron beam breaking at 10 kV and 10-A was the same as in FIG. 3, and the main emission wavelength was 506 mm.

For comparison, the fired product and 10 mol% of NH ₄ Cl (relative to SrSO ₄ ) were sulfided at 1100 ° C. for 2 hours in an H ₂ S atmosphere. The main light emission wavelength of the phosphor containing no P was 506 mm in the same manner as above. On the other hand, the energy efficiency of the phosphor containing P was about 15% higher.

Example 8

BaCO ₃ was used instead of SrSO ₄ of Example 7, and the same treatment was performed at a sulfidation temperature of 800 ° C. Both the phosphor containing P and the phosphor containing no P had a main emission wavelength of 490 mm, but the energy efficiency of P containing phosphor was about 10% higher.

Example 9

MgCO ₃ was used in place of SrSO ₄ in Example 7, and the same treatment was performed at a sulfidation temperature of 1200 ° C. P-containing phosphors and P-free phosphors also had a main emission wavelength of 520 mm, but the energy efficiency of P-containing phosphors was about 12% higher.

Example 10

50 mol% of CaS, 50 mol% of SrS, 0.2 mol% of EuS, 0.01 mol% of CeS ₃ , 5 mol% of NH ₄ Cl, and 0.5 mol% of PSO were mixed well with Ar0.3 and H ₂ S0.7 atmospheres. It was maintained for 24 hours at 1100 ℃ in the mixed gas atmosphere to synthesize a phosphor of Ca0.5 Sr0.5 S: Eu, Ce, P, Cl. The P concentration of this fluorescent lamp was about 2000 ppm and the Cl concentration was about 18000 ppm. In addition, the emission spectrum inferred by the 10 kV, 10 ^-6 A electron beam was shown in FIG. 4, and the main emission wavelength was 642 mm, and the relative luminance was 138% based on Comparative Example 1.

For comparison, the same treatment was carried out except for P in the above raw material to obtain a phosphor containing no P. The dominant wavelength of the emission spectrum of this phosphor was 642 mm, which was the same as described above, but the relative luminance was 117%. Therefore, the luminance of the phosphor containing P was 18% higher than that containing no P.

[Examples 11-15]

CaCO ₃ and SrCO ₃ are each weighed in the same molar ratio, and 0.15 mol% of Eu and 0.015 mol% of Ce are added to each mol of the mixture in the form of an oxide, and the amount of BaCO ₃ of Table 2 is added thereto. The mixed sample is kept at 1300 ° C for 10 hours to obtain an oxide. This oxide was maintained at 1200 ° C. for 3 hours in an H ₂ S. atmosphere to obtain Ca0.5-x / 2Sr0.5-x / 2 BaxS: Eu, Ce phosphors colored in red.

For comparison, phosphors were similarly prepared without adding Ba at all.

The relative energy efficiency (based on the absence of Ba) of luminescence observed when each phosphor was excited with an electron beam of 10 kV (current density 1 × 10 ⁻⁶ A) was measured at room temperature, and Ba actually contained in each phosphor. Table 2 shows the concentrations together. As shown in the table, the significant increase and decrease of Ba can be seen. In addition, the emission spectrum of each phosphor is the same, and shows a single peak at 643 mm as shown in FIG.

TABLE 2

[Examples 16-20]

0.08 mol% of Eu ₂ O ₃ , 0.01 mol% of CeO ₂ , and BaCO ₃ in the amounts shown in Table ₃ were respectively mixed with respect to 1 mol of CaCO ₃ , and the resulting oxide was maintained at 1300 ° C. for 10 hours to obtain H ₂ S and H _2. The mixture was kept at 1200 DEG C for 4 hours to obtain a phosphor having Ca _1-x BaxS: Eu, Ce colored in red. This structure was confirmed by X-ray diffraction. For comparison, phosphors were similarly formed by using a sample without mixing Ba.

Each phosphor was excited using an electron beam of 10 kV (current density 1 × 10 ⁻⁶ A) at room temperature, and its emission spectrum and emission intensity were measured. Each phosphor has the same emission spectrum and shows red emission with a single peak at 652 mm as shown in FIG. Ba concentration and relative energy efficiency (based on not containing Ba) are shown in Table 3.

TABLE 3

[Examples 21-25]

SrCO ₃ was used in place of CaCO ₃ of Examples 16 to 20 to carry out the same treatment to obtain phosphors of Sr _1-x BaxS Eu, Ce colored orange. The results are shown in Table 4. The emission spectrum of each phosphor is orange light emission showing a single peak at 613 mm as shown in FIG.

TABLE 4

[Examples 26-32]

0.15 mol% of CeO ₂ and BaCO ₃ in the amounts shown in Table 5 were respectively mixed with respect to 1 mol of CaCO ₃ , and the resultant oxide was maintained at 1400 ° C. for 5 hours, and the obtained oxide was maintained at 1200 ° C. for 3 hours in an H ₂ S atmosphere. _A phosphor having _1-x BaxS: Ce was obtained. This structure was confirmed by X-ray diffraction. For comparison, the same treatment was performed using a sample in which BaCO ₃ was not mixed to obtain a phosphor. The emission spectrum of each of these phosphors was as shown in Fig. 8 and showed green light emission having a main emission peak at 520 mm and a total of 580 mm.

TABLE 5

[Examples 33-40]

0.1 mol% of Eu ₂ O ₃ , 0.01 mol% of CeO ₂ and BaCO ₃ in the amounts shown in Table 6 were respectively mixed with CaCO ₃ and calcined in air at 1300 ° C. for 4 hours to obtain an oxide obtained in an H ₂ S atmosphere. Sulfurized at 1200 ° C. for 2 hours, and heated at 1200 ° C. for 30 minutes in a mixed gas of Ar 0.5 atmosphere and H ₂ S 0.5 atmosphere containing 5 mol% of PCl ₃ , and colored Ca _1-x BaxS: A phosphor of Eu, Ce, P, Cl was obtained. For comparison, a phosphor containing no Ba was obtained without adding BaCO ₃ and setting the baking time in air to 5 hours. Table 6 shows the results of measuring the relative energy efficiency (based on not containing Ba) by irradiating 10 kV, 1 × 10 ⁻⁶ A electron beams under vacuum of 2 × 10 ⁻⁶ Torr. In addition, the emission spectrum of each sample was about the same as that of the phosphor which does not contain P and Cl.

TABLE 6

Examples 41 to 43

0.066 mol%, 0.132 mol%, and 0.264 mol% of MgCO ₃ was added to the same raw material as in Example 37, and the same treatment was performed to synthesize a phosphor having Ca _1-xy BaxMg _y S: Eu, Ce, P, Cl. It was. The relative energy efficiency of these phosphors is shown in Table 7. When the Ca lattice point is replaced with Ba ion as in the phosphor described in Example 37, the ion radius (1.43A) of Ba ion is larger than that of Ca ion (1.06A), and thus lattice distortion occurs due to substitution. It is trying to compensate with Mg ion (0.78A) which has smaller ion radius than ion. That is, in Example 42, Mg ions were mixed at a ratio such that the lattice distortion caused by the mixing of Ba ions was canceled by calculation, and the energy efficiency was higher than that of the amount of Mg ions. Too much Mg results in lower energy efficiency than only Ba. The emission spectrum was almost the same as that showing a single peak at 653 mm and containing no Mg, P, or Cl.

TABLE 7

Example 44

0.1 mole% Eu ₂ O ₃ , 0.01 mole% CeO ₂ , 0.1 mole% CeO ₂ and 0.1 mole% BaCO ₃ were mixed with SrCO ₃ to bring the temperature of sulfide to 1000 ° C. and a concentration of 3 moles of PCl ₃ . It processed similarly to Examples 33-40 except having made into%. The obtained phosphor was pulverized and again maintained at 1050 ° C. for 2 hours in a mixed gas of Ar 0.5 atm and H ₂ S 0.5 atm. This phosphor was represented by the formula Sr 1-x Ba x S: Eu, Ce, P, Cl, and the relative energy efficiency was improved by 12.5% compared with that obtained by the same treatment without mixing BaCO ₃ for comparison. The emission spectrum showed a single peak at 612 mm and was almost the same as not containing P and Cl.

Example 45

The same treatment was performed with CeO ₂ as 0.15 mol% without mixing Eu ₂ O ₃ in the case of Example 44, to obtain a phosphor having Sr _1-x Ba _x S: Ce, P, Cl. The relative energy efficiency of this phosphor was 22% higher than that obtained by the same treatment without mixing BaCO ₃ for comparison. As shown in Fig. 9, the emission spectrum was a compound peak of 506 and 560 mm, which was the same as no addition of Ba.

Example 46

0.15 mol% of CeO _{2 and} 0.1 mol% of BaCO _{3 are} mixed with a mixture of 50 mol% of CaCO _{3 and} 50 mol% of SrCO3, and maintained at 1300 ° C in air for 4 hours, and the obtained oxide is maintained at 1150 ° C in H ₂ S atmosphere for 2 hours. maintaining the sulfide _{and, Ca0.5 -x /2Sr0.5 -x / 2 BaxS} : Ce phosphor was obtained. When the phosphor was irradiated with an electron beam of 10 kV and 1 × 10 ^-6 A in a vacuum, a light emission spectrum having a main peak at 514 mm and a bulk peak at 578 mm was obtained, and the relative energy efficiency was prepared without adding Ba for comparison. 14% better than that.

Example 47

An aqueous solution containing 0.01% Eu ²⁺ was mixed with 6 g of CaCO ₃ and the concentration of Eu ^{2+ in} the mixture was 0.1 mol% relative to CaCO ₃ . The mixture was kept at 1400 ° C. in air for 4 hours to obtain 3.4 g of Eu-added CaO calcined product. The oxide to a bisecting after grinding, by filling the one side in a quartz vessel into a quartz reaction bundle, to a 1150 ℃ flows through the H ₂ S gas at a rate of 100cc per minute sulfide was 3 hours. Let this sample be a. On the other hand, 1.7 g of the remaining calcined product was similarly sulfided, but at this time, the first two hours were flowed only with H ₂ S, the next 30 minutes with Ar containing 10 ^-3 mol% of PCl ₃ , and the last 30 minutes were again H _2. Only S was passed to obtain a sulfide (preferred as sample b). Apart from these, Eu is mixed in the same manner as in the above using CaCO ₃ containing 0.1 mol% of BaCO ₃ , and the same treatment as in the case of Sample b is carried out, and the phosphor is Ca _1-x Ba _x S: Eu, P, Cl Was obtained (sample c). The p concentration contained in samples b and c was 200 ppm, and the Ba concentration contained in sample c was 200 m. The emission spectrum obtained when each sample was broken with a 10 kV electron beam under a vacuum of 5 × 10 ⁻⁶ Torr has the same peak with a single peak at 652 mm, but the relative energy efficiency is set to sample a with 1, sample b with 1.18, and sample. c was 1.34.

[Examples 48-53]

To ₂ g of CaCO ₃ and 2.95 g of SrCO ₃ , 0.05 mol% of Eu ₂ O ₃ and 0.01 mol% of CeO ₂ were mixed with respect to the carbonate, and a mixture of BaCO ₃ in the amounts shown in Table 8 was further prepared. It was also prepared not to mix BaCO ₃ for fertilizers. Each of these was calcined at 1300 ° C. for 4 hours in air, and then the fired product was filled in a quartz vessel, respectively, placed in a quartz reaction tube, and heated to 1200 ° C. to flow H ₂ S gas. 1.5 hours later, the Ar containing 0.001 mol of PCl _3% to flow for 30 minutes flow rate, such as H ₂ S gas and passes only 30 minutes H ₂ S gas thereon. Thus, phosphors Ca _{0.5-x / 2} Sr _{0.5-x / 2} Ba _x S: Eu, Ce, P, Cl and phosphors containing no Ba for comparison were obtained. The emission spectra of the electron beams of these phosphors were the same as those having a single peak at 640 mm. However, when the emission intensity was compared with the relative energy efficiency, the effect of adding Ba was recognized.

TABLE 8

Example 54

Using CaCO ₃ and SrCO ₃ as raw materials, 0.1 mol% of Eu ₂ O ₃ and 0.01 mol% of CeO ₂ are added and mixed well, and Eu, Ce is applied while maintaining at 1300 ° C. for 4 hours in air. One Ca _x Sr _1-x O (0 ≦ _X ≦ 1) was made.

Each sample corresponding to X = 1,0.9,0.8,0.75,0.7,0.6,0.5,0.1,0 was kept at 1200 ° C for 3 hours in a hydrogen sulfide atmosphere to obtain a sulfide coated with Eu and Ce. Next, 3 mol% of CaF ₂ and SrF ₂ mixed with these groups of sulfides at a ratio corresponding to the mixing ratio X, and ₂ mol% of NH ₄ H ₂ PO ₄ were added to each other, and again at 1200 ° C in a hydrogen sulfide atmosphere. Hold for 3 hours. The obtained FP-added alkaline earth metal sulfide phosphor exhibited much better water resistance compared to the same kind of matrix to which F was not added. That is, each phosphor was immersed in water, the immersion time was 5 minutes and 1 hour, after a predetermined time, washed with ethyl alcohol and dried in a dryer to determine the electron beam emission characteristics of the sample. In contrast to the sample sulfided with FP free for 6 hours, the luminance variation of each sample of X = 0.5, 1 is investigated as shown in FIG. However, the electron beam acceleration voltage was 10 kV and the measurement was performed at room temperature. Curves 1,2,3 and 4 show the case of X = 1 (FP addition), X = 0.5 (dong), X = 1 (no addition) and X = 0.5 (dong) respectively.

Next, the luminance of each sample (FP addition) of X = 1,0.9,0.8,0.75,0.7,0.6,0.5,0.1,0 after immersion in water for 1 hour is expressed as a relative value with respect to the brightness before water immersion. That is FIG. Curve 11 adds F-P and curve 12 adds no. In all cases, the water resistance of the F-P-added sample was markedly improved. However, it was found that the water resistance was lowered as Sr became an excess component even when F was added. In the above example, the effect of adding F6 mol% and P2 mol% to the mother was shown. However, the water resistance is mainly in the addition concentration of F in the range of 0.5-10 mol% and F of 0.05-10 mol%. Therefore, it was found to improve. In the above example, F and P were added as a solid, but it was found that the same water resistance effect can be obtained even when PF5 gas is added together with hydrogen sulfide in the pacing. The addition of F-P improved the luminous efficiency as well as improving the water resistance, as described in other examples. In addition, the water resistance improvement by F-P addition was observed not only in said CaxSr1-xS but also in other alkaline earth metal sulfides, such as CaxMg1-xS and Ba1-xS, for example.

[Examples 55-56]

Red phosphor Ca obtained by alkaline earth metal sulfide salts, rare earth or metal sulfides and BaS as a raw material, calcined at 1150 ° C. for 8 hours in a hydrogen sulfide atmosphere _0.85 Mg _0.15 S: Eu (0.008%), Ba (0.1%), green Phosphor Ca _0.5 Mg _0.5 S: Ce (0.1%), Ba (0.1%), Blue phosphor CaS: Cu (0.1%), Na (0.1%), Ba (0.1%) are 10kV electronic wave controllers, respectively 15%, 23 It showed high energy efficiency of% and 18%. This efficiency exhibited an excellent characteristic that no change was observed even when each phosphor was heated up to 200 ° C. and the current density was increased up to 150 mA / cm 2. The color sound line tube having the screen applied by separating the phosphors of Examples 1 to 56 by a so-called black stripe produces no luminance saturation at all even if the current density is increased by two or more digits. Could be implemented.

[Examples 57-71]

Compounds containing Ca, Sr, Ba or Mg carbonates or sulfates and elements of the active agent (Cu and Ag are sulfides, Au is metal powder, Mn and Pb are oxides), and M is Ca or Mg Is maintained at 1100 ° C., Sr is 1000 ° C., and Ba is 700 ° C. in H ₂ S atmosphere. The powder obtained is mixed again and then maintained in an H 2 S atmosphere for 4 hours at a temperature higher than the temperature. Electron light emission characteristics of the obtained phosphor are as follows.

The result of apply | coating the fluorescent substance demonstrated above to the inner surface of a cathode ray tube face plate is demonstrated.

Fig. 12 curve 21 shows the relationship between the stimulation current and the luminance of a cathode ray tube with a phosphor of Ca _-1-x Ba _x S: Ce, P, and Cl, with almost no luminance saturation (acceleration voltage: 10 kV). , Same as in Fig. 12 below room temperature). On the other hand, in the cathode ray tube with ZnS: Cu, Al, which is a conventional green light-emitting phosphor, as shown in curve 22, the luminance decreases as the current increases. The cathode ray tube with the phosphor of Gd ₂ O ₂ S: Tb, which is currently used in projection TVs, does not show luminance saturation as shown by curve 23, but has a low relative luminance. Moreover, there exists a tendency for brightness to fall with temperature rise.

13 is a diagram showing the temperature and luminance characteristics of the green phosphor. Curves 21 'and 23' are characteristic curves of the phosphor as used for curves 21 and 23 in Fig. 12, respectively. Curves 24 and 25 are characteristic curves of phosphors of Y ₂ O ₃ S: Tb and Zn ₂ SiO ₂ : Mn, respectively. Fig. 14 shows the deviation of chromaticity coordinates according to the temperature rise of the green light-emitting phosphor. Curves 21 ", 23 " and 25 " are characteristics of phosphors such as curves 21, 23, 24 and 25 of FIGS. 12 and 13, respectively.

Claims (1)

P is added in the range of 100 to 10000 ppm in the presence of a halogen element to an alkaline earth metal sulfide activated by at least one element selected from the group consisting of lanthanide series and Mn, Cu, Ag, Pb and Au. Phosphor composition made into.

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