JPS6136798B2 - - Google Patents
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- Publication number
- JPS6136798B2 JPS6136798B2 JP13455579A JP13455579A JPS6136798B2 JP S6136798 B2 JPS6136798 B2 JP S6136798B2 JP 13455579 A JP13455579 A JP 13455579A JP 13455579 A JP13455579 A JP 13455579A JP S6136798 B2 JPS6136798 B2 JP S6136798B2
- Authority
- JP
- Japan
- Prior art keywords
- phosphor
- mol
- diffraction pattern
- luminescence intensity
- calcined
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims 1
- 238000004020 luminiscence type Methods 0.000 description 11
- 238000010894 electron beam technology Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 2
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- 229910020203 CeO Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001785 cerium compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Luminescent Compositions (AREA)
Description
【発明の詳細な説明】
本発明は新規な螢光体、すなわち、セリウムで
付活したランタニウムチオガレート螢光体に関す
るものである。本発明による螢光体は電子線およ
び紫外線励起で、緑色発光を示す短残光螢光体で
あり、特に、フライングスポツト管、インデツク
ス管への応用に適するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel fluorophore, a cerium-activated lanthanium thiogallate fluorophore. The phosphor according to the present invention is a short afterglow phosphor that emits green light when excited by electron beams or ultraviolet light, and is particularly suitable for application to flying spot tubes and index tubes.
アンヌ・マリー、ロワロー・ロザツチユ等の論
文（Mat.Res.Bull.vol.12、PP881−886、1977）
によれば、La2S3−Ga2S3系にはLa6Ga10/3S14
と、LaGaS3の２つの化合物が存在し、前者はヘ
キサゴナル（格子定数ａ＝10.15Å、ｃ＝6.08
Å）、後者は不明の構造を有すると報告されてい
る。一方、これらの化合物を発光中心を形成する
イオンで付活した螢光体に関する報告は全くな
く、これらと似たLa2S3・3Ga2S3をホロミウムで
付活したガラス質螢光体に関する報告があるのみ
である（J.Luminesence、vol 18／19Part
PP253−2561979）。 Paper by Anne-Marie, Roileau Rosatuille et al. (Mat.Res.Bull.vol.12, PP881-886, 1977)
According to La 2 S 3 −Ga 2 S 3 system, La 6 Ga 10/3 S 14
There are two compounds, LaGaS 3 and
), the latter is reported to have an unknown structure. On the other hand, there are no reports on phosphors in which these compounds are activated with ions that form luminescent centers, and there are no reports on glassy phosphors in which similar La 2 S 3 and 3Ga 2 S 3 are activated with holmium. There are only reports (J. Luminesence, vol 18/19 Part
PP253−2561979).
本発明者はLa2S3とGa2S3をモル比でほぼ１対
１で混合し、付活剤としてセリウム化合物を加え
た混合系を、800℃乃至950℃でH2S中等の硫化雰
囲気中で焼成して得られた螢光体が電子線および
紫外線励起で効率のよい緑色発光を示し、且つ、
約20ナノ秒の短い発光減衰時間（τ1/e）を示す
ことを見出した。本発明の螢光体の合成に際して
は出発原料として硫化物を用いることは勿論、
La2O3、Ga2O3、CeO2の如き酸化物を用い、800
℃乃至950℃でH2S中等の硫化雰囲気中で行なう
ことも可能である。さらに、実施例でも述べる如
く、La2S3とGa2S3の混合モル比は必ずしも１対
１である必要はなく、これよりGa2S3を若干過剰
に加えることにより、さらに発光特性を向上させ
ることが可能である。 The present inventor prepared a mixed system in which La 2 S 3 and Ga 2 S 3 were mixed at a molar ratio of approximately 1:1, and a cerium compound was added as an activator. The phosphor obtained by firing in an atmosphere exhibits efficient green light emission when excited with electron beams and ultraviolet rays, and
It was found that the luminescence decay time (τ 1/e ) was short, about 20 nanoseconds. In the synthesis of the phosphor of the present invention, sulfide can of course be used as a starting material.
Using oxides such as La 2 O 3 , Ga 2 O 3 and CeO 2 , 800
It is also possible to carry out in a sulfiding atmosphere such as H 2 S at a temperature of 0.degree. C. to 950.degree. Furthermore, as described in the examples, the mixing molar ratio of La 2 S 3 and Ga 2 S 3 does not necessarily have to be 1:1, and by adding a slight excess of Ga 2 S 3 , the luminescent properties can be further improved. It is possible to improve.
以下、実施例にしたがつて、本発明による螢光
体の詳細を述べる。 Hereinafter, details of the phosphor according to the present invention will be described according to Examples.
実施例 １
La2S3対Ga2S3のモル比が、0.8対0.2、0.643対
0.357、0.6対0.4、0.55対0.45、0.5対0.5、0.45対
0.55、0.4対0.6、0.357痴0.643、0.3対0.7、0.2対
0.8で、且つ、Ce濃度がLaに対し１原子％になる
ようにCe2（CO3）3を加えた混合物10種を準備
し、石英ボート上で、850℃４時間H2S中で焼成
し、冷却粉砕後、900℃で４時間同じ条件で再焼
成した。Example 1 The molar ratio of La 2 S 3 to Ga 2 S 3 is 0.8 to 0.2, 0.643 to
0.357, 0.6 vs. 0.4, 0.55 vs. 0.45, 0.5 vs. 0.5, 0.45 vs.
0.55, 0.4 vs. 0.6, 0.357 vs. 0.643, 0.3 vs. 0.7, 0.2 vs.
0.8 and Ce 2 (CO 3 ) 3 added so that the Ce concentration was 1 atomic % relative to La were prepared and calcined in H 2 S at 850°C for 4 hours on a quartz boat. After cooling and pulverizing, the product was recalcined at 900°C for 4 hours under the same conditions.
第１図ａ〜ｅに、La2S3対Ga2S3が0.643対
0.357、0.55対0.45、0.5対0.5、0.45対0.55の焼成
物およびGa2S3の粉末Ｘ線回折パターンの一部を
示す。La2S3：Ga2S3＝0.643：0.357は
La6Ga10/3S14に対する化学量論比であり、得ら
れた回折パターンは上記のアンヌ・マリー ロワ
ロー・ロザツチユ等の論文中の格子定数を用いて
解析した結果とよい一致を示すことから、第１図
ａのパターンはLa6Ga10/3S14によるものと同定
される。La2S3：Ga2S3＝0.8：0.2では
La6Ga10/3S14に加え、La2S3の回折パターンが観
測され、一方、La2S3：Ga2S3＝0.6：0.4、0.55：
0.45では、例えば第１図ｂの如く、
La6Ga10/3S14に加え、未同定の相による回折パ
ターンが強く観測される。La2S3：Ga2S3＝0.5：
0.5ではLa6Ga10/3S14の回折パターンはほぼ完全
に消失したと見做され、上記の未同定の相による
回折パターンのみとなる（第１図ｃ）。Ga2S3の
量がさらに増大し、La2S3：Ga2S3＝0.45：0.55に
なると、未同定の相に加えGa2S3による回折パタ
ーンが観測される（第１図ｄ）。以上の結果か
ら、第１図ｃに示された回折パターンは上記論文
中の構造不明のLaGaS3と同一相によるものと推
定される。 In Figure 1 a to e, La 2 S 3 to Ga 2 S 3 is 0.643 pair.
0.357, 0.55 vs. 0.45, 0.5 vs. 0.5, 0.45 vs. 0.55 calcined products and part of the powder X-ray diffraction patterns of Ga 2 S 3 are shown. La 2 S 3 : Ga 2 S 3 = 0.643: 0.357 is
This is the stoichiometric ratio to La 6 Ga 10/3 S 14 , and the obtained diffraction pattern shows good agreement with the results of the analysis using the lattice constant in the paper by Anne-Marie Loileau-Rosatuille et al. , the pattern in Figure 1a is identified as La 6 Ga 10/3 S 14 . At La 2 S 3 :Ga 2 S 3 =0.8:0.2
In addition to La 6 Ga 10/3 S 14 , a diffraction pattern of La 2 S 3 was observed, while La 2 S 3 :Ga 2 S 3 =0.6:0.4, 0.55:
At 0.45, for example, as shown in Figure 1b,
In addition to La 6 Ga 10/3 S 14 , a strong diffraction pattern due to an unidentified phase is observed. La 2 S 3 : Ga 2 S 3 =0.5:
At 0.5, the diffraction pattern of La 6 Ga 10/3 S 14 is considered to have almost completely disappeared, leaving only the diffraction pattern due to the above-mentioned unidentified phase (Fig. 1c). When the amount of Ga 2 S 3 increases further to La 2 S 3 :Ga 2 S 3 =0.45:0.55, a diffraction pattern due to Ga 2 S 3 is observed in addition to an unidentified phase (Figure 1d). . From the above results, it is estimated that the diffraction pattern shown in FIG. 1c is due to the same phase as LaGaS 3 , whose structure is unknown in the above paper.
第２図に、これらの螢光体を10KVの電子線で
励起した時の発光強度を示すが、La2S3対Ga2S3
が0.55対0.45乃至0.3対0.7の範囲で実用的な発光
強度を有する螢光体が得られ、0.4対0.6の付近で
発光強度が最大になる。図から明らかな如く、
Ce付活La6Ga10/3S14は螢光体として実用に供し
得ない。 Figure 2 shows the luminescence intensity when these phosphors are excited with a 10KV electron beam, and it shows the luminescence intensity of La 2 S 3 vs. Ga 2 S 3
A phosphor having a practical luminescence intensity can be obtained in the range of 0.55 to 0.45 to 0.3 to 0.7, and the luminescence intensity reaches a maximum around 0.4 to 0.6. As is clear from the figure,
Ce-activated La 6 Ga 10/3 S 14 cannot be put to practical use as a phosphor.
第３図に、La2S3：Ga2S3＝１：１の試料にお
ける発光スペクトルを示す。発光のピーク波長は
約500mmであり、緑色を呈する。 FIG. 3 shows the emission spectrum of a sample with La 2 S 3 :Ga 2 S 3 =1:1. The peak wavelength of light emission is approximately 500 mm, and the color is green.
実施例 ２
La2S31モル、Ce2（CO3）3Xモル、Ga2S31モル
の割合の混合物を900℃で４時間H2S中で焼成し
た。ただし、ｘ＝0.003、0.005、0.01、0.03、
0.05、0.07および0.15であつた。第４図に発光強
度のCe濃度依存性を示すが、ｘが0.01乃至0.07
（１乃至７原子％）で最も強い発光が得られる。Example 2 A mixture of 1 mol of La 2 S 3 , X mol of Ce 2 (CO 3 ) 3 , and 1 mol of Ga 2 S 3 was calcined in H 2 S at 900° C. for 4 hours. However, x=0.003, 0.005, 0.01, 0.03,
They were 0.05, 0.07 and 0.15. Figure 4 shows the dependence of luminescence intensity on Ce concentration, where x is 0.01 to 0.07.
(1 to 7 atomic %) gives the strongest luminescence.
実施例 ３
実施例２における混合物のうち、ｘ＝0.03（３
原子％）の混合物を石英ボートにのせ、800℃で
４時間、950℃で４時間２回焼成をH2S中で行な
つた。10KVの電子線で励起し、シリコンPINダ
イオード（松下電子工業PN303）で光出力を検出
したところ、市販のP16螢光体（化成オプトニク
ス製）に比べ、約2.3倍の出力が得られた。さら
に、パルス幅20ナノ秒の電子線パルスで励起し
１／ｅ減衰時間を測定したところ、τ1/e〜21ナ
ノ秒が得られた。この値はP16螢光体に関して報
告されている値の約1/4であり、螢光体が短残光
螢光体として非常にすぐれた特性を示すことが明
らかになつた。電子線衝撃に対する発光強度低下
（劣化）も、P16螢光体に比べきわめてすぐれて
おり、同条件で測定した場合、P16螢光体の発光
強度が約50％低下する間に本螢光体では約８％し
か発光強度が低下しなかつた。Example 3 Among the mixtures in Example 2, x=0.03(3
%) was placed on a quartz boat and calcined twice at 800° C. for 4 hours and at 950° C. for 4 hours in H 2 S. When excited with a 10 KV electron beam and detecting the optical output with a silicon PIN diode (Matsushita Electronics PN303), the output was approximately 2.3 times that of a commercially available P16 phosphor (manufactured by Kasei Optonics). Further, when excited with an electron beam pulse having a pulse width of 20 nanoseconds and measuring the 1/e decay time, τ 1/e ~21 nanoseconds was obtained. This value is about 1/4 of the value reported for the P16 phosphor, and it has become clear that the phosphor exhibits excellent properties as a short afterglow phosphor. The reduction (deterioration) in luminescence intensity due to electron beam impact is also extremely superior to that of P16 phosphor.When measured under the same conditions, while the luminescence intensity of P16 phosphor decreased by approximately 50%, this phosphor decreased by approximately 50%. The luminescence intensity decreased by only about 8%.
実施例 ４
La2O31モル、Ce2（CO3）30.01モル、Ga2O31モ
ルの割合の混合物を石英ボートにのせ800℃で４
時間、900℃で４時間の２回焼成をH2S中で行な
つた。焼成物のＸ線回折パターンは第１図ｃと同
じであり、明かるい緑色発光が観測された。Example 4 A mixture of 1 mol of La 2 O 3 , 0.01 mol of Ce 2 (CO 3 ) 3 , and 1 mol of Ga 2 O 3 was placed on a quartz boat and heated at 800°C.
Two calcinations of 4 hours at 900° C. were carried out in H 2 S. The X-ray diffraction pattern of the fired product was the same as that in Figure 1c, and bright green light emission was observed.
実施例 ５
La2S31モル、Ga2S31モル、Ce2（CO3）30.01モ
ル、NH4Cl 0.2モルの割合で混合し、800℃で10
時間H2S中で焼成した。焼成物のＸ線回折パター
ンは第１図ｃと同じであり、明かるい緑色発光が
観測された。Example 5 1 mol of La 2 S 3 , 1 mol of Ga 2 S 3 , 0.01 mol of Ce 2 (CO 3 ) 3 and 0.2 mol of NH 4 Cl were mixed and heated at 800°C for 10 min.
Calcined in H2S for an hour. The X-ray diffraction pattern of the fired product was the same as that in Figure 1c, and bright green light emission was observed.
このように本発明はすぐれた発光特性を示す新
規な螢光体を提供するものである。 As described above, the present invention provides a novel phosphor exhibiting excellent luminescent properties.
第１図ａ，ｂ，ｃ，ｄ，ｅは各々La2S3：
Ga2S3＝0.643：0.357、0.55：0.45、0.5：0.5、
0.45：0.55の混合物から得た焼成体およびGa2S3
のＸ線回折パターンを示す図、第２図はLa2S3対
Ga2S3のモル比と発光強度の関係を示す図、第３
図は本発明の一実施例の螢光体の発光スペクトル
を示す図、第４図はCe濃度と発光強度の関係を
示す図である。
Figure 1 a, b, c, d, e are each La 2 S 3 :
Ga 2 S 3 = 0.643: 0.357, 0.55: 0.45, 0.5: 0.5,
Calcined body obtained from a 0.45:0.55 mixture and Ga 2 S 3
Figure 2 shows the X-ray diffraction pattern of La 2 S 3 pairs.
Diagram showing the relationship between Ga 2 S 3 molar ratio and luminescence intensity, 3rd
The figure is a diagram showing the emission spectrum of a phosphor according to an example of the present invention, and FIG. 4 is a diagram showing the relationship between Ce concentration and emission intensity.
Claims (1)
割合が0.55対0.45乃至0.3対0.7の範囲にあり、か
つ発光中心Ceの添加量がLaに対し１乃至７原子
％であるセリウム付活ランタニウムチオガレート
よりなる螢光体。1 Cerium activation in which the ratio of the number of La and Ga atoms in the mixture of starting materials is in the range of 0.55:0.45 to 0.3:0.7, and the amount of luminescent center Ce added is 1 to 7 at% to La. A phosphor made of lanthanium thiogallate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13455579A JPS5657877A (en) | 1979-10-17 | 1979-10-17 | Fluorescent material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13455579A JPS5657877A (en) | 1979-10-17 | 1979-10-17 | Fluorescent material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5657877A JPS5657877A (en) | 1981-05-20 |
| JPS6136798B2 true JPS6136798B2 (en) | 1986-08-20 |
Family
ID=15131053
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13455579A Granted JPS5657877A (en) | 1979-10-17 | 1979-10-17 | Fluorescent material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5657877A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104178166A (en) * | 2013-05-22 | 2014-12-03 | 海洋王照明科技股份有限公司 | Praseodymium-doped sulfo lanthanum gallate up-conversion luminescent materials, and preparing method and applications thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5309070A (en) * | 1991-03-12 | 1994-05-03 | Sun Sey Shing | AC TFEL device having blue light emitting thiogallate phosphor |
| GB9907730D0 (en) * | 1999-04-01 | 1999-05-26 | Innovation Tk Limited | Cathode ray tubes |
| JP3472236B2 (en) | 2000-04-17 | 2003-12-02 | Ｔｄｋ株式会社 | Phosphor thin film, manufacturing method thereof and EL panel |
-
1979
- 1979-10-17 JP JP13455579A patent/JPS5657877A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104178166A (en) * | 2013-05-22 | 2014-12-03 | 海洋王照明科技股份有限公司 | Praseodymium-doped sulfo lanthanum gallate up-conversion luminescent materials, and preparing method and applications thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5657877A (en) | 1981-05-20 |
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