JPS6038433B2 - Rare earth oxysulfide phosphor - Google Patents
Rare earth oxysulfide phosphorInfo
- Publication number
- JPS6038433B2 JPS6038433B2 JP8500176A JP8500176A JPS6038433B2 JP S6038433 B2 JPS6038433 B2 JP S6038433B2 JP 8500176 A JP8500176 A JP 8500176A JP 8500176 A JP8500176 A JP 8500176A JP S6038433 B2 JPS6038433 B2 JP S6038433B2
- Authority
- JP
- Japan
- Prior art keywords
- crab
- light
- luminous efficiency
- rare earth
- improved
- 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
Links
Landscapes
- Conversion Of X-Rays Into Visible Images (AREA)
- Measurement Of Radiation (AREA)
- Luminescent Compositions (AREA)
Description
【発明の詳細な説明】
本発明はTb(テレビウム)付活希士類オキシサルフア
ィド蟹光体に関し、特に発光効率が高く、燐光度(長残
光成分)の低い、希士類オキシサルフアィド化合物に関
する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a Tb (terevitium)-activated rare oxysulfide phosphor, which has particularly high luminous efficiency and low phosphorescence (long afterglow component). Regarding ide compounds.
Tb付活の希士類オキシサルフアイド蟹光体は、X線励
起により効率良く発光するため、増感紙などのX線蟹光
面に使用され、従釆のCaW04(タングステン酸カル
シウム)などの蟹光体にとって代りつつある。Tb-activated rare oxysulfide photons emit light efficiently upon X-ray excitation, so they are used for X-ray light surfaces such as intensifying screens, and they It is gradually replacing the crab light body.
この蟹光体において、蟹光体の1モル当りのTb濃度は
5×105〜3×10‐2モルであり、この濃度範囲に
おいて発光輝度の高い実用的な蟹光体となる。またこれ
等の蟹光体は陰極線管の蟹光面や、後光ランプにも使用
されるものである。本発明は従来のTb付活希士類オキ
シサルフアィド蟹光体にYb(イッテルビウム)を入れ
ることにより、発光効率が向上し、又燐光が弱くなる実
験事実によりなされたものである。In this crab photon, the Tb concentration per 1 mol of the crab photon is 5 x 105 to 3 x 10-2 mol, and in this concentration range, the crab photon becomes a practical crab photon with high luminance. These crab light bodies are also used for the crab light surface of cathode ray tubes and backlight lamps. The present invention was made based on experimental findings that by adding Yb (ytterbium) to a conventional Tb-activated rare oxysulfide phosphor, luminous efficiency was improved and phosphorescence was weakened.
すなわち、本発明の希士類オキシサルフアィド総光体は
以下の組成式で表わされる。Ln2(1−p−q)02
S/TQPYb幻た)、しp、qの範囲は1×10‐4
≦p≦3×10‐2、1×10‐6≦q≦0.075p
、ここでLnはY、い、W、Luのうちの少くとも一種
類を表わす。That is, the rare group oxysulfide phosphor of the present invention is represented by the following compositional formula. Ln2(1-p-q)02
The range of S/TQPYb), p, and q is 1×10-4
≦p≦3×10-2, 1×10-6≦q≦0.075p
, where Ln represents at least one of Y, I, W, and Lu.
特に本発明の蟹光体はX線増感紙用として優れた特性を
有する。本発明の1つである(Y、Gb)20ぶ/Tb
,Ybは従来使用されている。CaW04に比べ輝度が
2.5〜3.ぴ苦、X線吸収率が約30%高く、増感紙
にした場合、高感度、低量子ノイズの優れた特性を示す
。これ等希±頚オキシサルフアド蟹光体は以下のように
して作る。希±類を硝酸で溶解する。この溶液にシュウ
酸(又はシュウ酸ジメチル)を加え希±頚シュウ酸塩と
する。これを熱分解して酸化物としてからこれにィオウ
粉末、及びフラックスとしてK3P04、NをC03を
加えて1100〜130000で焼成する。このように
して得れらた(Y、Gd)20ぶ/Th、YbはYbが
1×10‐6以上であってTb濃度の0.07母音以下
の範囲で発光効率が向上し、技高で約20%輝度向上す
る。Yb濃度がTb濃度の0.075倍を超えると発光
強度は極端に減少する。第1図はYb濃度と発光強度の
関係を示す図である。又従来の蟹光体(Y、Gd)20
2S/ThはX線励起停止後長い残光(燐光)が見られ
るがYbが1×10‐4mol′RE以上添加されると
長残光が約1桁減少する。第2図はこの関係を示す図で
ある。他の希±類を母体とした場合でもほゞ同様の傾向
が見られ、Yb量が1×10‐5mol′REの微少量
から長残光成分が減少される。第3図はLa202S、
Gd202S、Y2Cぶ母体とするTb付活蟹光体のY
b添加による増感作用を示す図である。ところで増感紙
用蟹光体として用いられている蟹光体(Y、仇)20交
/TbはTbが1×10‐3モル/REの前後で青色か
ら緑色領域に強い発光を示し、従来使用されている標準
フィルム感度に合った発光特性を示す。感度はCaW0
4に比べ2.5〜3倍と高い。ところがこのTb濃度の
範囲ではX線励起停止後長残光成分が強いため写真の画
像がぼやけたり、前に撮影した像が重なって写るなどの
欠点が生じた。しかし本発明のYb添加により長残光成
分をなくした(Y、Gd)202S/Tb,Ybを用い
ると上記の欠点は解決され、且つ発光効率の向上により
増感紙感度を高めることができる。又緑色発光の受光体
La202S/Tb、Gd202S/T℃を添加して発
光強度を高めたものは蟹光ランプに使用して優れた特性
を示した。さらにオシロスコープなどのディスプレー用
陰極線管に使用すると従来使用されているZnS母体の
後光体に比べ電流密度による輝度飽和が少ないため電流
特性が大中に改善される。実施例 1Y203113夕
、Gd203181夕、Tb4070.374夕、YQ
030.0118夕を硝酸に溶解する。In particular, the crab photoreceptor of the present invention has excellent properties for use in X-ray intensifying screens. One of the present invention (Y, Gb) 20bu/Tb
, Yb are conventionally used. Brightness is 2.5-3. compared to CaW04. The X-ray absorption rate is approximately 30% higher, and when used as an intensifying screen, it exhibits excellent characteristics of high sensitivity and low quantum noise. These rare ±cervical oxysulfado crab photons are prepared as follows. Dissolve rare species with nitric acid. Add oxalic acid (or dimethyl oxalate) to this solution to obtain dilute oxalate. This is thermally decomposed to form an oxide, and then sulfur powder and K3P04, N and C03 are added as a flux and fired at 1,100 to 130,000. The thus obtained (Y, Gd) 20b/Th, Yb has improved luminous efficiency in the range where Yb is 1 x 10-6 or more and the Tb concentration is 0.07 vowels or less, and the luminous efficiency is improved. The brightness will be improved by about 20%. When the Yb concentration exceeds 0.075 times the Tb concentration, the emission intensity decreases extremely. FIG. 1 is a diagram showing the relationship between Yb concentration and luminescence intensity. Also, the conventional crab light body (Y, Gd) 20
In 2S/Th, a long afterglow (phosphorescence) is observed after X-ray excitation is stopped, but when Yb is added in an amount of 1×10-4 mol'RE or more, the long afterglow decreases by about one order of magnitude. FIG. 2 is a diagram showing this relationship. Almost the same tendency is observed when other rare species are used as the matrix, and the long afterglow component is reduced from a very small amount of Yb of 1 x 10-5 mol'RE. Figure 3 shows La202S,
Gd202S, Y of the Tb-activated crab photoreceptor as the parent body of Y2C
It is a figure showing the sensitization effect by addition of b. By the way, the crab photo substance (Y, 20)/Tb used as the crab photo substance for intensifying screens exhibits strong luminescence in the blue to green region when Tb is around 1 x 10-3 mol/RE, which is different from the conventional one. Displays luminescent characteristics that match the standard film speed used. Sensitivity is CaW0
It is 2.5 to 3 times higher than 4. However, in this Tb concentration range, the long afterglow component after the X-ray excitation stops is strong, resulting in drawbacks such as blurred photographic images and overlapping of previously taken images. However, by using (Y,Gd)202S/Tb,Yb which eliminates the long afterglow component by adding Yb of the present invention, the above-mentioned drawbacks can be solved and the sensitivity of the intensifying screen can be increased by improving the luminous efficiency. In addition, green-emitting photoreceptors La202S/Tb and Gd202S/T° C. were added to increase the luminous intensity and showed excellent characteristics when used in crab light lamps. Furthermore, when used in cathode ray tubes for displays such as oscilloscopes, the current characteristics are greatly improved because brightness saturation due to current density is less than in conventional ZnS matrix backlights. Example 1Y203113 evening, Gd203181 evening, Tb4070.374 evening, YQ
Dissolve 030.0118 in nitric acid.
これにシュウ酸ジメチル425夕を加え8000に加熱
後放置すると、シュウ酸塩の共枕が得られる。この共次
を1100qCI時間焼成酸化物とする。得られた希土
類酸化物100のこ対しィオウ粉末25夕、K3P04
14タ Na2C0325夕を加えて混合する。Add 425 grams of dimethyl oxalate to the mixture, heat to 8,000 ℃, and leave to stand to obtain an oxalate compound. Let this co-order be an oxide fired for 1100 qCI hours. Obtained rare earth oxide 100 sulfur powder to 25 sulfur powder, K3P04
14 Add Na2C0325 and mix.
この混合物をルゾボに詰め、1200ooで4時間窒素
雰囲気中で焼成すると(Y、Gd),.母80ぶ/mo
.oのYb側oの6の組成の蟹光体が得られる。この蟹
光体は従釆の(Y、Gd),.99802S/Tち.o
o2に比べ発光効率が約20%向上し第2図に示す如く
残光が弱くなった。又この蟹光体を用いて試作した増感
紙は従来品に比べ感度が25%向上し、コントラストが
10%向上した。When this mixture is packed in a Ruzobo and fired at 1200 oo for 4 hours in a nitrogen atmosphere, (Y, Gd). Mother 80bu/mo
.. A crab photon having a composition of 6 on the Yb side of o is obtained. This crab light body has subordinate columns (Y, Gd), . 99802S/Tchi. o
The luminous efficiency was improved by about 20% compared to o2, and the afterglow became weaker as shown in FIG. In addition, the intensifying screen prototyped using this crab photon showed a 25% improvement in sensitivity and a 10% improvement in contrast compared to conventional products.
実施例 2
La203326タ Tq072.617# Yb20
330.0079夕を実施例1と同様にしてLa,.9
9鏡02S/ThO.o,4Ybo.ooの2をつくる
。Example 2 La203326ta Tq072.617# Yb20
330.0079 in the same manner as in Example 1, La, . 9
9 mirror 02S/ThO. o, 4Ybo. Make 2 of oo.
こうして得られた蟹光体は従来のい202S/Tbに比
べ発光効率が約15%向上した。この蟹光体を用いて蟹
光ランプを試作すると、従来により使用されている縁色
蟹光ランプに比べ発光効率が10%向上した。又い20
2S/Tbを用いた蟹光ランプに比べ約18%向上した
。実施例 3
GQO夕 362.5タ Tb4071.495タ Y
Q030.0079タ 実施例 1 同機 に し て
GdM9202S /ThO.雌Ybo.ooの4なる
蟹光体をつくる。The thus obtained crab luminous material had luminous efficiency improved by about 15% compared to the conventional 202S/Tb. When a crab light lamp was prototyped using this crab light body, the luminous efficiency was improved by 10% compared to the conventionally used edge-colored crab light lamp. Matai 20
This is an improvement of about 18% compared to the crab light lamp using 2S/Tb. Example 3 GQO evening 362.5 ta Tb 4071.495 ta Y
Q030.0079 Example 1 The same aircraft as GdM9202S/ThO. Female Ybo. Create a crab light body named oo.
このようにして得られた蟹光体は従来のW,.9920
2S/Tbo.。The crab photons thus obtained are conventional W, . 9920
2S/Tbo. .
偽に比べ発光効率が約25%向上した。この蟹光体を使
用してシク。スコープ用オシロ管をつくると従来のP−
31蟹光面(ZnS/Cu後光体)に比べ電流特性が大
中によくなり高電流密度領域で輝度が40%向上した。
又、Gd,.99202S/Tb側ぽ蟹光面に比べ30
%輝度向上した。実施例 4
Y203225.8タ Tb4070.374タ Y
QOの.の395を実施例1同様にしてY,.$802
S/Tb肌舵Ybo.oの。The luminous efficiency was improved by about 25% compared to the fake one. Sik using this crab light body. When making an oscilloscope tube, the conventional P-
Compared to No. 31 Crab light surface (ZnS/Cu backlight), the current characteristics were much better, and the brightness was improved by 40% in the high current density region.
Also, Gd,. 99202S/Tb side 30 compared to light side
% brightness improved. Example 4 Y203225.8ta Tb4070.374ta Y
QO's. 395 in the same manner as in Example 1, Y, . $802
S/Tb skin rudder Ybo. o's.
2なる麹光体をつくる。Create the second Kojiko body.
この鰭光体は従来のY,.99802S/Tbo.oの
に比べ発光効率が15%向上した。This fin light body is the conventional Y, . 99802S/Tbo. The luminous efficiency was improved by 15% compared to that of
実施例 5
L均033班タ TLO?0.3錠紙タ Yb2030
.0118夕を実施例1と同機に し てLu…980
2S/ThO.側Ybo.o側6なる蟹光体をつくる。Example 5 L average 033 group TLO? 0.3 tablet paper Yb2030
.. Lu...980 on the evening of 0118 with the same aircraft as Example 1
2S/ThO. Side Ybo. Create a crab light body called 6 on the o side.
この蟹光体は従釆のLu,.9凶02S/Tho.oo
2に比べ発光効率が20%向上した。以上実施例に述べ
た如く本発明により従来のTbで活性化した希土類のオ
キシサルフアィド姿光体の発光効率が数十%向上し、又
従来X線で励起したとき(Y、Gd)202S/Tdな
どに見られた最残光の成分をなくすことができた。This crab light body is subordinate to Lu, . 9Kyou02S/Tho. oo
The luminous efficiency was improved by 20% compared to 2. As described in the examples above, the present invention improves the luminous efficiency of the conventional rare earth oxysulfide photomaterial activated with Tb by several tens of percent, and when excited with conventional X-rays (Y, Gd) 202S /Td etc. was able to eliminate the afterglow component.
これ等の蟹光体はX線蟹光面、陰極線管後光面、姿光ラ
ンプに使用し従来のものに比べ効率向上ができる。These light beams can be used in X-ray light surfaces, cathode ray tube rear light surfaces, and full-body light lamps to improve efficiency compared to conventional ones.
【図面の簡単な説明】
第1図は(Y、Gb)…笹○交/T広.oo2姿光体に
Ybを添加した場合の発光効率の変化を表わす図、第2
図はこの蟹光体にYbを加した場合の残光強度の経時変
化を示す図、第3図はLa202S、Gら○ぶ、Y20
2Sの各々の母体のYb添加の発光効率変化を表わす図
である。
第1図
第2図
第3図[Brief explanation of the drawings] Figure 1 shows (Y, Gb)...Sasa○ko/T Hiroshi. Figure 2 showing the change in luminous efficiency when Yb is added to the oo2 phosphor.
The figure shows the change in afterglow intensity over time when Yb is added to this crab photon.
FIG. 2 is a diagram showing changes in luminous efficiency due to addition of Yb to each base material of 2S. Figure 1 Figure 2 Figure 3
Claims (1)
フアイド螢光体。 Ln_2(1−p−q)O_2S/Tb_2pYb_2
q ただし、p、qの範囲は1×10^−^4≦p≦3
×10^−^2、1×10^−^6≦q≦0.075p
、ここでLnはY、La、Gd、Luのうち少なくとも
一種類を表わす。[Scope of Claims] 1. A Tb-activated rare earth oxysulfide phosphor represented by the following compositional formula. Ln_2(1-p-q)O_2S/Tb_2pYb_2
q However, the range of p and q is 1×10^-^4≦p≦3
×10^-^2, 1×10^-^6≦q≦0.075p
, where Ln represents at least one of Y, La, Gd, and Lu.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8500176A JPS6038433B2 (en) | 1976-07-19 | 1976-07-19 | Rare earth oxysulfide phosphor |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8500176A JPS6038433B2 (en) | 1976-07-19 | 1976-07-19 | Rare earth oxysulfide phosphor |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5311178A JPS5311178A (en) | 1978-02-01 |
JPS6038433B2 true JPS6038433B2 (en) | 1985-08-31 |
Family
ID=13846415
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP8500176A Expired JPS6038433B2 (en) | 1976-07-19 | 1976-07-19 | Rare earth oxysulfide phosphor |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6038433B2 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5312560A (en) * | 1992-03-19 | 1994-05-17 | Nichia Chemical Industries, Ltd. | Rare earth phosphor |
JP2776445B2 (en) * | 1992-03-19 | 1998-07-16 | 日亜化学工業株式会社 | Rare earth phosphor |
-
1976
- 1976-07-19 JP JP8500176A patent/JPS6038433B2/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
JPS5311178A (en) | 1978-02-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP2001139942A (en) | GREEN LIGHT-EMITTING SrAl12019 LUMINESCENT MATERIAL ACTIVATED WITH Mn2+ | |
JP3918051B2 (en) | Mechanoluminescence material and method for producing the same | |
JP4507862B2 (en) | Phosphor and apparatus using the same | |
US3758413A (en) | Terbium activated yttrium silicate phosphors | |
JPS6038433B2 (en) | Rare earth oxysulfide phosphor | |
JP3263991B2 (en) | Blue light emitting phosphor | |
US4068129A (en) | Bismuth activated rare earth oxybromide phosphors and X-ray image converters utilizing said phosphors | |
JP2006335967A (en) | Phosphor for displaying device and electric field-emission type displaying device | |
US3868533A (en) | Cathode-ray tube for image display | |
JP3790854B2 (en) | Strontium titanate phosphor | |
JP2001335777A (en) | Vacuum ultraviolet ray-excited fluorophor and light emitting device using the same | |
JP2000026855A (en) | Phosphor paste composition and vacuum-ultraviolet- excited light-emitting element | |
JP3391356B2 (en) | Blue light emitting phosphor | |
JP3440301B2 (en) | Phosphor | |
JP4711588B2 (en) | Thin film electroluminescence emitter | |
JP3232540B2 (en) | Rare earth phosphor for monochrome CRT | |
JPS643920B2 (en) | ||
JPH0629421B2 (en) | Blue light emitting phosphor and blue light emitting cathode ray tube for color projection type image device using the same | |
JP3705765B2 (en) | Red light emitting phosphor and color display device using the same | |
JP2004263068A (en) | Green light emitting fluorescent substance for low voltage/high current density use, and field emission type display unit using the same | |
KR930003388B1 (en) | Blue-luminous materials | |
JPH0726098B2 (en) | Phosphor for cathode ray tube and cathode ray tube | |
JP2776445B2 (en) | Rare earth phosphor | |
JPS60147490A (en) | Fluorescent substance of sulfide | |
JPH0570775A (en) | Red emitting phosphor |