JPS59105074A - Fluophor - Google Patents

Abstract

PURPOSE:To provide an alkaline earth chalcogenite fluophor having excellent resistance to water and acid, prepared by forming two layers of specified metal oxides on the surface. CONSTITUTION:A layer of an alkaline earth metal oxide contained in fluophor (A) and a layer of a water-resistant metal oxide, such as silicon oxide, aluminum oxide or lead oxide, are formed on the surface of an alkaline earth chalcogenide fluophor (A), such as CaS, StS or MgTe, in that order. For example, CaS fluophor particle 1 containing Ce and Na is heated to about 750 deg.C in an oxygen atmosphere to form a CaO layer 2 on the surface. The particles are immediately dispersed in a silicone oil diluted with a non-aqueous solvent, dried and heated to form an SiO2 layer on the layer 2 to obtain the alkaline earth fluophor covered with a surface protective layer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a phosphor, which is an alkaline earth chalcoke formed according to Table 1.

Alkaline earth chalconides (also referred to as alkaline earth metals), which are compounds of Group IA and Group VIA, are particularly known as first-grade calcium (hereinafter referred to as CaS). It is expressed as follows.I1C) Bunoruko (The same is indicated for boot 9) (-i high (・'! et al.) Since it is well known to indicate self-efficiency, it is a log material.

5(11) has low water resistance and acid resistance, and is currently used in the G process because it does not dye 11. I've been left with a crab 5. During this time, I wanted to make 1 and 2 holes for BL!Q point (te,
So far, several improved methods have been developed.

The main ones are surface protection law and clothing + it' + reform q], law and power. Surface protection methods include micro-casing
Those who use leeches 1'F (Sho 60-26782,!
Shinto J-Ru Nobu method (・rke 11; 1989-12948)
No. 1, Tohoku] etc. 75; I know (・ru. The trench surface modification method involves alkali ± LN treatment (+i・++4 (
How to form a humanoid (U, S, P, ,!, 61
7332, Festin Quinius Co., Ltd., 1973
5-123675, Tohoku), a method for forming Ibo 11 se salt, and 1 dog salt. All of these surface modification methods cause chemical reactions on the chalcogenide surface,
Chalcogenide is changed into a more stable alkali compound. However, none of the above-mentioned improved methods have yet been put into practical use. The present inventors investigated the reasons for this and found that (1) it is technically difficult to completely cover the body particles thinly and uniformly with the deep protective film formed by the above-mentioned surface protection method; (11) It was found that the phosphor surface layer improved by the above surface modification method was still chemically unstable. If we carefully and carefully use the frugal feeding method, in order to completely cover the alkaline soil-grown chalcogenide surface with a uniform, dense thin film, we can make the cations or group 1 ions common, but the child bonds on the surface. It was confirmed that it is very effective to form the entire area.

In the process of film formation by the above-mentioned protection method, a part of the alkali metal carbide shown in Table 1/J1 is an alkali metal hydroxide or sulfate.

It is converted into carbonate, etc., and the molecular bond that makes both cations and anions 110 is not formed over the entire surface between the protective film and the chalcogenide.

For this reason, the average intensity of the taste:'-'J llt' becomes a non-luminous component, and it is presumed that it cannot be put to practical use.

The purpose of the present invention is to eliminate such drawbacks of the prior art and to provide an alkali +m chalcocenide coated with a homogeneous and stable R-protection layer.

In order to achieve the above-mentioned advantages, in the present invention, as shown in Figure 1, an alkaline earth metal chalcogenide phosphor 10 is coated with a thin oxide layer (n
active oxide 1 ayer) 2'r
: Shape (shape, nucleus?') A stable water-resistant oxide layer 3 was formed on the 1st slope 2. That is, from the center 1- to 21- as shown in the figure.
The three layers may be formed in order, starting from the one formed in the -th treatment step to the chemical or material 111! It also sinks when a three-layer groove is formed as a result of manual treatment. Thin film layer 2 has very low water resistance, but it is different from alkaline earth chalcogenide 1.
The chemical bonding force is strong to equalize the hot water ions,
Further, since the anions (oxygen ions) are equal to the water-resistant oxidation auxiliary layer 3, the chemical bond strength is low. That is,
Thin 1μ layer 2 is chalcogenide 1 for alkaline earth and water resistance β
! It acts as a binder with layer 3 of '11171.

As a result, a lurical earth chalcocenide compound is obtained which exhibits excellent water resistance.

Hereinafter, the present invention will be described in detail with reference to Examples. As is well known, cerium (Ce)-activated CaS can still produce original light effects*'i/buzz green phosphor, 0 carbon RF salts and oxides by negative one-sided stimulation. 1, and convert this to (↓4e
CaS gold was synthesized by attacking 0.1 mot % of Co and 2 mot % of sodium (Na). The obtained phosphor is a light green particle with a diameter of 5 to 8 microns (μm), and when stimulated with ultraviolet light,
06 nun: peak, 555 nm I/Cf
A green color of a light starch with a thin beak was observed. When this firefly was heated to about 750'C in a 7JI+ atmosphere, , last time 1
Completed calcium (Cab) Itl 2 is formed.

The thickness of Ca,01t
~03 microns. This was immediately dispersed in Inazawa (Recon oil) using a non-aqueous latent medium, taken out for a while, dried, and added.
06 (15-(1,1 miku o y no + 92 conversion soli'
7 (SiO)4) layer 3 was completely formed. CaS ni
t bilayer dislocation + 5j CaO.

5tO2 is so thick that the light is so low that it can be seen as a gruesome line or a hindrance to ultraviolet stimulation. 10 F(V
, -Next flow 10 -L (J 1 Orukono 3'l'j 11'♀Scanning Fluorescent Body (5i02./'CnO/
CnS:Ce, Na) is relatively light in the first year of high school, and the key is 1.1 times. 254 n
Even if the ice line tφ of m is crossed, the maximum iQ+l ft! : Below was not recognized.

-Power, 1jiij water ih K+・;L Seven significant improvements were seen.1. Ta. Do not use a broken transverse membrane.・Firefly 1. Boku (Akashina Ha)
Is it the three-layer 4 that expands? Ji blue 9ε) can be done, (shrub) B ノ, fu yohi CaS J second, use the above process to form c1 Wataru T/'H8102 kan and get 7.
1 direct no'l = body (trial MC) noso #t ('tL10.
P etJl,)r'Z L,,! Old 3.0 (This, Ran 1 sparrow!! i3i acidic water bath so IQ is dispersed in the inside)
, about IL) If you leave it for 30 minutes (1 with shi vL (51 umbrellas, Morisashi I Ebisujima degree)
) 11 plus. Table 1 shows the ratio of weak tβ to 7x bath and S i1 (relative value to the fineness of taro (IOKV, when primary flow 10 = A).R'r1 table.・44 1 Table ttc top,・”＼No゛
2. 1. et al. 41 Expressed as a prediction for the initial feather 11η. Of course, the three-layer grooved phosphor C body of the present invention is better compared to J@@ (sample C) coated only with water-resistant oxide 810211Mo3, as well as without any cross-covering. (Sample B)
It can be seen that it shows excellent water resistance. This γ
The binder Is (CaOrI suspension) formed between the CaS fluorescent light 1 and 51021j13 acts effectively, and as a result, the water-resistant 5in2 film 3 is uniformly exposed to CaS.
I think this is because I & Mitsuki completely collapsed.

above) I: iA! For i t<l, water-resistant oxide layer 3
Although S i02 was used as an oxide, any oxide that is transparent to the radiation from the fluorescent particles 1 and has a certain degree of water resistance will basically work. The present invention can be applied to the three-layered three-layer structure band body without any restrictions. For example, the case where 5n02 is used as a water-resistant oxide is shown.

CaS, SrS with 0.05 rnot% of Eu activated by a well-known method using charcoal 1 Yahanawa and oxidized Nabu as the material.
1Mg5.

Each BaS was prepared separately. When cathode ray stimulation light is fkl, the peak wavelength is CaS 652 nm,
5rS612 nm, MgS 591 nm,
BaS changed to 572 nm.

A part of each of these fireflies) YS bodies is heat-treated for a short time in a dry atmosphere as described in J.G.
A layer 2 was formed. The processing temperature is CaS 750
℃.

SrS 750”C, Mg8500℃, BaS 4
The temperature was 50°C. Next, Sn was electrolessly plated on the surfaces of these samples.

The liquid was heated to 45°C for 1 hour, and then adjusted to 2 to 40 degrees Celsius.By optimizing the treatment time, the surface of each sample was white-gray with a thickness of 0.2-0.3. Micron Sn was broken almost uniformly. After washing with water and drying, these samples were heat treated again in a dry oxygen atmosphere. Heat treatment temperature is 850
'C.

It was a short time. In this gross process, the Sn thin film is a transparent 5n0
Changed to 21 and 3. The breaking force of each of the above 4 +iAI phosphors is excellent, and at 600'C,
@, Immediately after heating, it was rapidly cooled, and no C<Mff was observed at all.

1iiJ Note 11pHf 6. OK 4・'l 'N
A water resistance test was conducted in a liquid containing F, (, 5ff ["i2 water"), but there was almost no increase in pH even after 8 hours.
1! <4 It was confirmed that the alkaline earth sulfide phosphor cup 1 was stably coated. In addition, it was found that the brightness reduction due to oxide coating of these 31 (14+M fireworks) YS bodies was within 10% when exposed to 10 KV l polar radiation stimulation, and there was no change at all even after the surface 1 water test.

5nQ2b2thickness1]t1 has a high phosphor density, and therefore the fully coated three-layer tIi phosphor 7e can also be used as a phosphor for low-speed electron beams.

Separately, 3g of P2+18 and 23g of Ce were respectively added to CaS and CaSe, which were synthesized separately by a well-known method, and the two were mixed and heated in vacuum for 9 minutes to obtain BuO, 05mol1%.
r Ce0.005moAchi activation Ca5o, 6Seo,
4. The mixed crystal phosphor was fired. This phosphor emits cathodostimulated light, which peaks at 632 nm, and exhibits high brightness as a red phosphor. This phosphor is briefly dispersed in hot water at 50'C, dried, and then heated to 500C in air to form a CaOrW film 2 on the surface. It was immediately stored in an A2 container and subjected to the well-known glass-ma CVD. By dropping C> CaSO,6SeO,4 little by little without giving a finger motion and passing it through a mixed plasma of r'l12, alkino, and aluminum, h2ox (2<x<3) A thin film 3 was formed.

Also, for comparison, Eu in which CaO has not been completely formed,
At20 directly on Ce-activated CaSO,6Se 0.4
x 'i'A What happened to the detective? The Al2Ox tl flaw thickness is very wide and is 1 based on the εSCA tall constant results.
It was estimated to be about 10 nm. One of the two three-layer borrowed fireflies was heated to 450° C. in dry oxygen to stabilize the At20x film (At20x-+At203). A
The same effect can be obtained even if tz03 is directly coated.

No oxide film + ti qi Eu, Ce phrase 18 Ca
Samples D, E, and F are respectively 5o, 6seo, and 4 phosphors having a three-layer structure of 96 brightness, and a phosphor in which 1G contact with ht203 is formed on sulfur selenide-H. Parts of samples E and F were dispersed in the above-mentioned water resistance test solution (pH 6,0), and after 107 J, they were taken out and dried. Original c by cathode ray stimulation before and after water resistance test
When comparing the luminances of , a result not shown in Table 2 was obtained.

Last month/li! +1 1j If the same thin film layer 2 is omitted and directly Table 2 IMI water test results A12031ji 3 is formed (sample F), A
It is determined that the 12o3 range is unevenly distributed, and the N intensity is also non-luminous. Therefore, the water resistance was also insufficient. However, the 3I☆1 ((4) photoluminescent material (sample E) described in the present invention had good +mJ aqueous properties and 7F, indicating that the desired goal was achieved.

The water-resistance effect of the two-layered pharyngeal membrane of Shizuoka was also the same with CaTe and Mg5e. Therefore, due to the nature of alkaline earth chalcogenides, the same effect can be seen with other compounds and mixtures of these compounds and their respective forms. It is obvious that this effect can be obtained.In this patent, 5t02 is used as an example of water-resistant oxide.
, 5n02, and At203, but the f
lt(At20x (however, X)3), TiOx +
The same effect was observed with Y20x + Ta20x, In2O3, and ZnO.

Furthermore, as is clear from these Examples, it is obvious that the present invention can be extended to other water-resistant oxides.

The water resistance and chemical stability of alkaline earth chalcogenide phosphors have been significantly improved by the present invention, and it has become possible to realize highly practical phosphors that take advantage of their original excellent phosphor properties.

[Brief explanation of the drawing]

FIG. 1 is a cross-sectional view schematically showing an 11-1 structure of a three-layer phosphor having six brightnesses. In the figure, 1 is an alkaline earth chalcogenide phosphor, 2 is a monomer compound layer that shares an alkaline earth metal ion with 1, and 3 is a water-resistant oxide layer.

Claims (1)

[Scope of Claims] (1) An oxidized 4'vJ layer of the alkaline earth metal in contact with the surface of the alkali-chalcokenide phosphor, which is 1' agglomerated with the alkaline earth metal! In contact with the 1277 layer, a water resistant layer was formed in this order. , Ba
S, MgS, Ca5eSrSe, Ba5
e, MgSe, CaTe, 5rTe, B
aTe. The phosphor is selected from the group consisting of MgTe and a mixture of nine mixed crystals thereof. 3. Claims 1 (4! Water resistance described in 1)
The temporary layer is S 1Ox (1<, x<2), A
t20x(2(x≦3), Ti0xSnOx(1<X<
2) + In2O3+ Ga2σ3 + “203
A phosphor comprising a layer of at least one m-oxide selected from the group consisting of +5b2o5ZnO and PIoO.