JPH0228282A - Fluorescent material excitable with low-speed electron ray - Google Patents
Fluorescent material excitable with low-speed electron rayInfo
- Publication number
- JPH0228282A JPH0228282A JP14753389A JP14753389A JPH0228282A JP H0228282 A JPH0228282 A JP H0228282A JP 14753389 A JP14753389 A JP 14753389A JP 14753389 A JP14753389 A JP 14753389A JP H0228282 A JPH0228282 A JP H0228282A
- Authority
- JP
- Japan
- Prior art keywords
- phosphor
- fluorescent material
- fluorescent
- electron beam
- low
- 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.)
- Granted
Links
- 239000000463 material Substances 0.000 title abstract description 12
- 229910052709 silver Inorganic materials 0.000 claims abstract description 11
- 229910052737 gold Inorganic materials 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 61
- 230000005284 excitation Effects 0.000 abstract description 11
- 229910052744 lithium Inorganic materials 0.000 abstract description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- -1 AgCl Chemical class 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 3
- 239000000843 powder Substances 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 3
- 229910000366 copper(II) sulfate Inorganic materials 0.000 abstract description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 229910004042 HAuCl4 Inorganic materials 0.000 abstract 1
- 229910021607 Silver chloride Inorganic materials 0.000 abstract 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract 1
- 101000604097 Xenopus laevis Homeobox protein notochord Proteins 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- 230000018044 dehydration Effects 0.000 abstract 1
- 238000006297 dehydration reaction Methods 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 abstract 1
- UQMZPFKLYHOJDL-UHFFFAOYSA-N zinc;cadmium(2+);disulfide Chemical compound [S-2].[S-2].[Zn+2].[Cd+2] UQMZPFKLYHOJDL-UHFFFAOYSA-N 0.000 abstract 1
- 238000010894 electron beam technology Methods 0.000 description 22
- 239000011701 zinc Substances 0.000 description 9
- 239000005083 Zinc sulfide Substances 0.000 description 8
- 229910052984 zinc sulfide Inorganic materials 0.000 description 8
- 229910003002 lithium salt Inorganic materials 0.000 description 6
- 159000000002 lithium salts Chemical class 0.000 description 6
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 4
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 108091006629 SLC13A2 Proteins 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Luminescent Compositions (AREA)
- Cathode-Ray Tubes And Fluorescent Screens For Display (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は低速電子線励起下において高輝度の発光を示す
螢光体に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a phosphor that emits high-intensity light when excited by a slow electron beam.
（従来の技術）
従来、加速電圧がＩＫＶ以下、特に１００ Ｖ以下の低
速電子線の励起によって高輝度に発光する螢光体として
亜鉛付活酸化亜鉛螢光体（ＺｎＯ：Ｚｎ）がよく知られ
ている。このＺｎＯ：Ｚｎ螢光体は低速電子線で励起し
た場合に高輝度の緑白色発光を示し、低速電子線励起螢
光表示管の螢光膜として実用されている。(Prior Art) Zinc-activated zinc oxide phosphor (ZnO:Zn) has been well known as a phosphor that emits high-intensity light when excited by a slow electron beam with an accelerating voltage of IKV or less, especially 100 V or less. ing. This ZnO:Zn phosphor exhibits high-intensity green-white light emission when excited by a slow electron beam, and is put into practical use as a fluorescent film for a fluorescent display tube excited by a slow electron beam.
低速電子線励起螢光表示管（以下「螢光表示管」と略称
する）は基本的には片面に螢光膜を有する陽極プレート
と、この螢光膜に対向するように設けられた陰極とを、
その内部が真空である容器内に封入したものであり、陰
極から放射される低速電子線（一般に加速電圧がｔｏｏ
ｖ以下の低速電子線）によって陽極プレート上の螢光
膜を励起して発光せしめるものである。上記ＺｎＯ：
Ｚｎ螢光体からなる螢光膜を有する螢光表示管は卓上計
算器、各種計測機器等の表示素子として広く利用されて
いる。A low-speed electron beam-excited fluorescent display tube (hereinafter abbreviated as a "fluorescent display tube") basically consists of an anode plate with a fluorescent film on one side, and a cathode opposite the fluorescent film. of,
It is sealed in a container with a vacuum inside, and a low-velocity electron beam (generally the accelerating voltage is too high) is emitted from the cathode.
The fluorescent film on the anode plate is excited by a low-velocity electron beam (low-velocity electron beam of less than V) to emit light. Above ZnO:
Fluorescent display tubes having a fluorescent film made of Zn fluorescent material are widely used as display elements for desktop calculators, various measuring instruments, and the like.
近年、螢光表示管の利用分野が拡大されるにつれて螢光
表示管の発光色の多様化が望まれるようになり、低速電
子線励起下で緑色以外の発光を示す螢光体の開発が盛ん
に進められてきた。その結果、低速電子線励起下で緑色
以外の発光を示す螢光体がいくつか見出されたが、それ
らのうちの１種にその組成式が
（Ｚｎ＋−ｘ ＋ Ｃｄｘ ）Ｓ ： Ａｇで表わさ
れる螢光体を１例とする（ Ｚ ｎ １−ｘ ＋ＣｄＸ
）Ｓ系螢光体がある。In recent years, as the field of use of fluorescent display tubes has expanded, it has become desirable to diversify the emission colors of fluorescent display tubes, and the development of phosphors that emit light other than green under slow electron beam excitation has been active. has been advanced. As a result, several phosphors were found that emitted light in colors other than green under excitation with slow electron beams, and one of them had a compositional formula of (Zn+-x+Cdx)S:Ag. Let us take as an example the phosphor (Z n 1-x +CdX
) There is an S-based phosphor.
このような（Ｚｎ＋−ｘ＋ ＣｄＸ）Ｓ系螢光体の製
造においてはＨ，Ｗ、Ｌｅｖｅｒｅｎｚ著「＾ｎ ！ｎ
ｔｒｏｄｕｃｔｉ。In the production of such (Zn+-x+ CdX)S-based phosphors, the method described by H.W.
troducti.
ｎ Ｔｏ Ｌｕｎ＋１ｎｅｓｅｅｎｃｅ Ｏｆ’ ５ｏ
ｌｉｄｓ Ｊ １９８〜１９９ページ、Ｊｏｈｎ Ｗｌ
ｌｅｙ ＆ ５ｏｎｓ、Ｉｎｃ、、１９５０年、特開昭
５５−１２９４８０号および特開昭５７−１６７３８１
号に開示されているようにＮａＣＪＩを用いることが従
来知られている。n To Lun + 1necession Of' 5o
lids J pages 198-199, John Wl.
ley & 5ons, Inc., 1950, JP-A-55-129480 and JP-A-57-167381
It is conventionally known to use NaCJI as disclosed in No.
また、例えば上記の（Ｚｎｌ−ｘ 、Ｃｄｘ ） Ｓ
：Ａｇ螢光体を用いた螢光表示管を高輝度化するたため
の手段として、螢光体のＡｇ含有量を多くすることが上
記特開昭５７−１１３７３８１号に開示されており、一
方、特公昭５９−３３１５３号等にはこの目的を達成す
るために小さな粒子径を有するＩｎ２Ｏ３等の導電性物
質と螢光体とを混合してなる発光組成物を用いることが
開示されている。Also, for example, the above (Znl-x, Cdx) S
:As a means for increasing the brightness of a fluorescent display tube using an Ag phosphor, increasing the Ag content of the phosphor is disclosed in the above-mentioned JP-A-57-1137381; Japanese Patent Publication No. 59-33153 discloses the use of a luminescent composition comprising a phosphor mixed with a conductive substance such as In2O3 having a small particle size in order to achieve this purpose.
しかしながら、螢光表示管のカラー化およびその利用分
野の拡大に伴って低速電子線励起下すなわち低電圧、低
電力の使用時における螢光表示管の発光をさらに高輝度
化することが要望されている。However, as fluorescent display tubes become more colored and their fields of use expand, there is a need to further increase the luminance of fluorescent display tubes under low-speed electron beam excitation, that is, when using low voltage and low power. There is.
（発明の目的）
本発明は上記要望に鑑みて加速電圧がＩＫＶ以下、特に
１００Ｖ以下の低速電子線励起下で高輝度の発光を示す
螢光体を提供することを目的とするものである。(Object of the Invention) In view of the above-mentioned needs, the object of the present invention is to provide a phosphor that emits light with high brightness under slow electron beam excitation at an accelerating voltage of IKV or less, particularly 100V or less.
（発明の構成）
本発明者は上記目的を達成するべく、低速電子線励起下
で発光を示す螢光体（以下「低速電子線励起螢光体」と
称す）のうち特に前述の（Ｚｎ＋−ｘ 、Ｃｄｘ ）Ｓ
系螢光体について鋭意研究を重ねた結果、リチウム（Ｌ
ｉ）を含有する（Ｚｎ、−ｘ 、Ｃｄｘ ）Ｓ系螢光体
は高速電子線励起下においては従来の（Ｌｉを含有しな
い）螢光体と同等もしくはそれ以下の輝度の発光を示す
に過ぎないにも拘らず、低速電子線励起下におけるその
発光は従来のものよりもはるかに向上されることを発見
し、本発明を完成するに至った。この発見はリチウムの
添加が従来とは根本的に異なる特性を付与することを示
す点で極めて重要なものと考えられる。(Structure of the Invention) In order to achieve the above-mentioned object, the present inventor has specifically developed the above-mentioned (Zn+- x, Cdx)S
As a result of intensive research on fluorescent materials, lithium (L
(Zn, -x, Cdx) S-based phosphors containing i) only emit light with a brightness equal to or lower than that of conventional phosphors (not containing Li) under high-speed electron beam excitation. Despite this, the inventors discovered that the light emission under slow electron beam excitation is much improved compared to conventional ones, leading to the completion of the present invention. This discovery is considered extremely important in that it shows that the addition of lithium imparts properties that are fundamentally different from conventional ones.
このような発見に基づく本発明の低速電子線励起螢光体
は一般式
％式％
（但し、式中０≦Ｘ≦１．Ｑ＜ａ＜１ｘｌＯ−２ｇ／ｇ
。Based on this discovery, the low-speed electron beam-excited phosphor of the present invention has the general formula % (where 0≦X≦1.Q<a<1xlO-2g/g
.
ｂ＞Ｑ、ｃ＞０であり、Ｍｌはｘ−０の時、Ａｇおよび
Ａｕの中の少なくとも１種の元素であり、Ｘ≠０の時、
Ａｇ、ＡｕおよびＣｕの中の少なくとも１種の元素、Ｘ
はＡｌ１． ＣＪＩ、 Ｂｒおよび■の中の少なく
とも１種の元素である。）で表わされるものであり、Ｌ
ｉを含有することを特徴とする（Ｚｎｌ−Ｘ＋ Ｃｄ
ｘ）Ｓ系螢光体である。b>Q, c>0, Ml is at least one element among Ag and Au when x-0, and when X≠0,
At least one element among Ag, Au and Cu, X
is Al1. At least one element among CJI, Br and ■. ), and L
(Znl-X+ Cd
x) It is an S-based phosphor.
本発明の螢光体においてはＬｉの含有量が現在の分析技
術における検出限界程度の微量なもの（１ｐｐｍ以下）
であっても所望の輝度向上の得られることが判明した。The phosphor of the present invention has a trace amount of Li (1 ppm or less), which is at the detection limit of current analytical technology.
It has been found that the desired brightness improvement can be obtained even if
使用されるリチウム塩の種類および組合せ数は任意に調
節することができる。The type and number of combinations of lithium salts used can be adjusted as desired.
また、Ｌｉ含有量の上限は現在の製造技術から１０’
ｇ／ｇ（１００００ｐｐｍ）と定められた。In addition, the upper limit of Li content is 10' from current manufacturing technology.
g/g (10000 ppm).
Ｌｉは該螢光体母体に対してその含有量を１ｐｐＩ１１
〜７１００ｐｐＩＩの範囲とすることが好ましく、より
好ましくはその含有量を３５ｐｐｍ〜５０００ｐｐｍの
範囲とする。The content of Li is 1ppI11 for the phosphor matrix.
The content is preferably in the range of 7100 ppm to 7100 ppm, more preferably 35 ppm to 5000 ppm.
本発明の螢光体は一般に以下に述べるような方法によっ
て製造される。すなわち硫化亜鉛（ＺｎＳ）粉と硫化カ
ドミウム（Ｃｄ Ｓ）粉とをＣｄＳ粉Ｘモルに対してＺ
ｎＳ粉が（１−ｘ）モルとなるような割合で混合してな
る混合硫化物粉に例えば、ＡｇＣＪ、ＨＡｕＣＪ４ 、
ＣｕＳＯ４等の、付活剤となるＡｇ、ＡｕおよびＣｕの
中の少なくとも１種の化合物と、Ａｊ！ （ＮＯ３）
３．ＮａＣ１等の、共付活剤となる元素（Ｘ）を含む化
合物を所定量添加混合し、さらにリチウム供給源として
Ｌｉ、単体のみならず、例えば塩化リチウム、硫酸リチ
ウム、燐酸リチウム等のＬＬのハロゲン化物、酸素酸塩
等、任意の種類および数のリチウム塩を適当量添加し、
硫化水素雰囲気、硫黄雰囲気等の硫化性雰囲気中で５０
０乃至１２００℃で０．２時間乃至５時間焼成した後、
水等の溶媒により充分洗浄し、脱水し、乾燥することに
よって得られる。The phosphor of the present invention is generally manufactured by the method described below. In other words, zinc sulfide (ZnS) powder and cadmium sulfide (CdS) powder are
For example, AgCJ, HAuCJ4,
At least one compound selected from Ag, Au and Cu as an activator, such as CuSO4, and Aj! (NO3)
3. A predetermined amount of a compound containing the element (X) that serves as a co-activator, such as NaC1, is added and mixed, and Li is used as a lithium supply source. Adding an appropriate amount of any type and number of lithium salts such as oxides, oxyacids, etc.
50 in a sulfidic atmosphere such as a hydrogen sulfide atmosphere or a sulfur atmosphere
After baking at 0 to 1200°C for 0.2 to 5 hours,
It is obtained by thoroughly washing with a solvent such as water, dehydrating, and drying.
なお、この時、上記螢光体原料中に融剤としてＮａ、
Ｋ、 ＲｂおよびＣｓの中の少なくとも１種のアルカリ
金属ハロゲン化物を添加して焼成しても良い。At this time, Na, Na,
At least one alkali metal halide among K, Rb and Cs may be added and fired.
第１図はこのようにして得た本発明の低速電子線励起螢
光体の１例である（ Ｚ ｎ ｏ、 ｂｓ、 Ｃｄ ０
．３りＳ：Ｌｉ、Ａｇ、ＣＩ！螢光体を使用した螢光膜
を有する螢光表示管におけるこの螢光体のＬｉ含有量と
特性値の関係を示すグラフである。FIG. 1 shows an example of the slow electron beam-excited phosphor of the present invention obtained in this manner (Z no, bs, Cd 0
．． 3ri S: Li, Ag, CI! 2 is a graph showing the relationship between Li content of a phosphor and characteristic values in a fluorescent display tube having a phosphor film using a phosphor.
本図面において曲線ａ１ ＊ ｂｌ ｒ ’１はリ
チウム塩としてＬｉＣｊｊを添加して製造した上記螢光
体に対応し、曲線ａ２ ｒ ｂｌ ＋ Ｃ２はリチ
ウム塩として等モル量のＬｉＣＪｉ、Ｌｉｚ ＳＯ４・
Ｈ２０およびＬｉ３ＰＯ４・□Ｈ２０を添加し更に、こ
れにこれらリチウム塩と等モル量のＮａＣ１を添加して
製造した上記螢光体に対応する。そして、曲線ａ１＋
８２は発光開始電圧（すなわち０．１ｃｄ ／Ｔｄの
輝度を得るために必要な印加電圧）のＬｉ含有量による
変化を示すものであり、一方、曲線ｂ１＋ ｂｌは印
加電圧５０Ｖの時（低速電子線励起下）のＬｉ含有量に
よる輝度変化、曲線ｃｌ。In this drawing, the curve a1 * bl r '1 corresponds to the above-mentioned phosphor manufactured by adding LiCjj as a lithium salt, and the curve a2 r bl + C2 corresponds to the phosphor produced by adding LiCJj as a lithium salt, and the curve a2 r bl + C2 corresponds to the phosphor produced by adding LiCJi and Liz SO4 in equimolar amounts as a lithium salt.
This corresponds to the above-mentioned phosphor produced by adding H20 and Li3PO4.□H20 and further adding NaCl in an equimolar amount to these lithium salts. And curve a1+
82 shows the change in the luminescence starting voltage (that is, the applied voltage necessary to obtain a luminance of 0.1 cd/Td) depending on the Li content, while the curve b1 + bl shows the change when the applied voltage is 50 V (low-speed electron beam). Brightness change with Li content under excitation), curve cl.
Ｃ２は印加電圧１２ＫＶの時（高速電子線励起下）のＬ
ｉ含有量による輝度変化をそれぞれ示すものである。ま
た、本図面における各曲線においてＬｉ含有量０として
表わされる値はＬＬを含有しない従来の螢光体を用いて
得られた螢光表示管について測定した値である。本図面
に示すように、螢光体にＬｉを添加することにより発光
開始電圧の低下および低速電子線励起下における発光輝
度の著しい向上が認められた。C2 is L when the applied voltage is 12KV (under high-speed electron beam excitation)
The graphs each show a change in brightness depending on the i content. Further, in each curve in this figure, the value expressed as Li content 0 is a value measured for a fluorescent display tube obtained using a conventional phosphor not containing LL. As shown in this figure, by adding Li to the phosphor, it was observed that the emission starting voltage was lowered and the emission brightness was significantly improved under slow electron beam excitation.
（発明の効果）
以上述べた様に本発明め低速電子線励起螢光体は（Ｚ
ｎ １−ｘ 、 Ｃｄｚ ） Ｓ系螢光体にＬｉを添
加することによって、加速電圧がＩＫＶ以下、特に１０
０ｖ以下の低速電子線励起下において著しく高い発光輝
度を呈し、この螢光体単独又はこれと導電性物質との混
合物からなる発光組成物となり螢光表示管用として有用
であり、その工業的利用価値は極めて大きなものである
。(Effect of the invention) As described above, the low-speed electron beam-excited phosphor of the present invention has (Z
n 1-x , Cdz ) By adding Li to the S-based phosphor, the acceleration voltage can be lowered to IKV or less, especially 10
It exhibits extremely high luminance under low-speed electron beam excitation of 0V or less, and is a luminescent composition composed of this phosphor alone or a mixture of it and a conductive substance, and is useful for fluorescent display tubes, and its industrial utility value is extremely large.
（実 施 例） 次に実施例によって本発明を説明する。(Example) Next, the present invention will be explained by examples.
実施例１
硫化亜鉛（ＸｎＳ）試薬螢光体グレード品 １３７．５
９硫化力Ｆｉ’）ム（ＣｄＳ）試薬螢光体グレード品
８７．５ ｇ銀２０００ｐｐｍを含有するＣｄＳ
２５ ９塩化リチウム（ＬｉＣ１ｌ）試薬特
級 ２．５ｇをよく混合し、石英ルツボに入
れて電気Ｐ中において８００℃で２時間焼成し、水篩を
行なった後、上澄液の電導度が３μｓ ／ ｃｒｎとな
るまで水洗を行ない、脱水し、乾燥することにより、Ｌ
ｉ含有量が（Ｚｎｏ、６ｓ、 Ｃｄｏ、３ｓ） Ｓ ：
Ａｇ、 ＣＪ １ ｇｌ：対して８．５ｐｐｍである
（Ｚｎｏ、Ｃ６，Ｃｄｏ、３ｓ） Ｓ ：ＬＬ、Ａｇ、
ＣＪｌ螢光体を得た。Example 1 Zinc sulfide (XnS) reagent phosphor grade product 137.5
9 Sulfurization power Fi') Mu (CdS) reagent phosphor grade product
87.5 g CdS containing 2000 ppm silver
25 9 Lithium chloride (LiC1l) reagent special grade 2.5g was mixed well, placed in a quartz crucible, fired at 800°C for 2 hours in electric P, and after sieving with water, the conductivity of the supernatant liquid was 3 μs / By washing with water until crn, dehydrating, and drying, L
i content is (Zno, 6s, Cdo, 3s) S:
Ag, CJ 1 gl: 8.5 ppm (Zno, C6, Cdo, 3s) S: LL, Ag,
A CJl phosphor was obtained.
この螢光体をエチルセルロースとカルピトールとからな
る結合剤中に混合してインク状とし、２５０メツシニの
シルクスクリーンを用いてプレート上に塗布し、４５０
℃で３０分間加熱し、さらに１００℃で３０分間乾燥し
て（Ｚｎｏ、６ｓ＋ Ｃｄｏ、３ｓ）ＳＥＬＬ、Ａｇ
、Ｃ，ｅ螢光体からなる螢光膜を形成した。This phosphor was mixed in a binder consisting of ethyl cellulose and calpitol to form an ink, and the mixture was applied onto a plate using a 250 mesh silk screen.
℃ for 30 minutes and further dried at 100℃ for 30 minutes (Zno, 6s + Cdo, 3s) to produce SELL, Ag.
, C, and e phosphors were formed.
一方、これとは別にＬｉを含有しない従来の（Ｚｎｏ、
６ｓ＋ Ｃｄｏ、ｉｓ） Ｓ ： Ａｇ、 Ｃ４！螢
光体を得、上記螢光膜の作製と同様にして（Ｚｎ、、６
ｇ＋Ｃｄｏ、ｉｓ） Ｓ ： Ａｇ、 ＣＪＩ螢光体か
らなる螢光膜を形成した。On the other hand, apart from this, conventional (Zno,
6s+ Cdo, is) S: Ag, C4! A phosphor was obtained, and a phosphor (Zn, 6
g+Cdo, is) S: Ag, A fluorescent film consisting of a CJI phosphor was formed.
上述のようにして得られた各々の螢光膜を真空容器中に
入れ、５０Ｖの低速電子線で励起すると（Ｚｎｏ６５＋
Ｃｄｏ、ｇｓ） Ｓ ： Ｌ ｉ、 Ａｇ、 ＣＪＩ
螢光体からなる螢光膜は（Ｚ ｎ ｏ、 ｂ、、 Ｃ
ｄ ０．３５） ＳＡｇ、ＣＪ２螢光体からなる螢光膜
の約３０倍の相対発光輝度を示した。When each of the fluorescent films obtained as described above was placed in a vacuum container and excited with a 50V slow electron beam (Zno65+
Cdo, gs) S: Li, Ag, CJI
The fluorescent film made of phosphors is (Z no, b,, C
d 0.35) The relative luminance was about 30 times that of the fluorescent film made of SAg and CJ2 phosphors.
実施例２
螢光体原料中に等モル量のＬｉｃｌとＬｉ２ＳＯ４・Ｈ
２ＯとＬ ｉ３ ＰＯ４・−Ｈ２０を添加して焼成する
以外は従来の（Ｚｎ０．９．ＣｄｏＩ）Ｓ ： Ａｕ＋
ＡＩ螢光体と同様にして、Ｌｉ含有量が（Ｚｎｏ９．
Ｃｄｏ、＋ ）Ｓ ： Ａｕ、Ａ１１ｇに対してｔｏｏ
ｏｐｐＩＩである（Ｚｎ０．９１ Ｃｄｏ、、 ）
Ｓ ： Ｌｉ、 Ａｕ、 ＡＪ螢光体を得た。一方、比
較のためにＬｉを含有しない従来の（Ｚｎｏ、、＋Ｃｄ
ｏ、＋ ）Ｓ ： Ａｕ、ＡＪｊ螢光体を得た。これら
の螢光体を用いて実施例１と同様の方法で螢光膜を形成
し、真空容器中に入れ、５０Ｖの低速電子線で励起する
と（Ｚｎｏ、＋ Ｃｄｏ、＋ ）Ｓ ： Ｌ ｔ。Example 2 Equimolar amounts of LiCl and Li2SO4.H in phosphor raw material
Conventional (Zn0.9.CdoI)S: Au+ except for adding 2O and Li3PO4・-H20 and firing
Similarly to the AI phosphor, the Li content (Zno9.
Cdo, +) S: too for Au, A11g
oppII (Zn0.91 Cdo, )
S: Li, Au, AJ phosphors were obtained. On the other hand, for comparison, conventional (Zno, +Cd) containing no Li
o, +) S: Au, AJj phosphor was obtained. A fluorescent film was formed using these phosphors in the same manner as in Example 1, placed in a vacuum container, and excited with a 50V slow electron beam (Zno, +Cdo, +)S: L t.
Ａｕ、ＡＪ２螢光体からなる螢光膜は（Ｚｎｏ、ｓ＋＋
Ｃｄｏ、＋ ）Ｓ ： Ａｕ、ＡＪ！螢光体からなる螢
光膜の３．５倍の発光輝度を示した。The fluorescent film consisting of Au and AJ2 phosphors is (Zno, s++
Cdo, +) S: Au, AJ! The luminance was 3.5 times higher than that of a fluorescent film made of fluorescent material.
実施例３
螢光体原料中に等モル量のＬｉＣＪとＬｉｚｓｏ、−ａ
２ｏとＬ ｉ３ ＰＯａ ” Ｈ２０およびＮａ
Ｃ１を添加して焼成する以外は従来の（Ｚ ｎＱ、？
＋ Ｃｄｏ、３） Ｓ ： Ａｇ、ＡＪ螢光体と同様
にして、Ｌｉ含有量が（Ｚｎｏｙ７．Ｃｄｏ３）Ｓ ：
Ａｇ、Ａ１１ｇ１．：、対しテ４ｏｏｐｐｌｉテあり
、Ｎａ含有量が７ ｐｐｎ＋である（Ｚｎｏ７．Ｃｄｏ
３）Ｓ 二Ｌｉ、Ｎａ、Ａｇ、ＡＪ！螢光体を得た。一
方、比較のためにＬｉを含有しない従来の（ＺｎＱ、７
゜Ｃｄｏ、３） Ｓ ： Ａｇ、 ＡＪ！螢光体を得た
。これらの螢光体を用いて実施例１と同様の方法で螢光
膜を形成し、真空容器中に入れ、５０Ｖの低速電子線で
励起すると（Ｚｎｏ、ｔ 、 Ｃｄｏ、ｉ ） Ｓ
： Ｌ ｔ。Example 3 Equimolar amounts of LiCJ and Lizso, -a in phosphor raw material
2o and L i3 POa ” H20 and Na
Except for adding C1 and firing, the conventional method (Z nQ,?
+ Cdo, 3) S: Same as Ag, AJ phosphor, Li content is (Znoy7.Cdo3) S:
Ag, A11g1. :, whereas there is 4oopplite, and the Na content is 7 ppn+ (Zno7.Cdo
3) S two Li, Na, Ag, AJ! I got a phosphor. On the other hand, for comparison, conventional (ZnQ, 7
゜Cdo, 3) S: Ag, AJ! I got a phosphor. A phosphor film was formed using these phosphors in the same manner as in Example 1, placed in a vacuum container, and excited with a 50 V slow electron beam (Zno, t, Cdo, i) S.
: Lt.
Ａｇ、Ａ、［螢光体からなる螢光膜は（Ｚｎｏ、７゜Ｃ
ｄｏ、ｉ ） Ｓ ： Ａｇ、 ＡＪ！螢光体からなる
螢光膜の４倍の発光輝度を示した。The fluorescent film consisting of Ag, A, [fluorescent material is (Zno, 7°C
do, i) S: Ag, AJ! The luminance was four times higher than that of a fluorescent film made of fluorescent material.
実施例４
螢光体原料中に等モル量のＬｉＣＪとＬｉ２を添加して
焼成する以外は従来の（Ｚｎｏ、９．＋ Ｃｄｏ、ｏ、
） Ｓ ： Ｃｕ、 Ａｊ！螢光体と同様にして、Ｌｉ
含有量がｔｏｏｏｐｐｍである（Ｚｎｏ、９ｇ、 Ｃ
ｄｏ、ｏ、）Ｓ：Ｌｉ、Ｃｕ、Ａ１螢光体を得た。一方
、比較のためにＬｉを含有しない従来の（Ｚ ｎ Ｏ，
９５，Ｃｄｏ、ｏ５） Ｓ ； Ｃｕ、 Ａ ｆｌ螢光
体を得り。コレラノ螢光体を用いて実施例１と同様の方
法で螢光膜を形成し、真空容器中に入れ、５０Ｖの低速
電子線で励起すると（Ｚｎｏ、、５． Ｃｄｏ、ｏ、
） Ｓ ： Ｌ ｉ、 Ｃｕ、ＡＪ！螢光体からなる螢
光膜は（Ｚｎｏ９５＋ Ｃｄｏ、ｏ、） Ｓ ： Ｃ
ｕ、 Ａ ｌｌ螢光体カラナル螢光膜ノ３倍の発光輝度
を示した。Example 4 The conventional method (Zno, 9.+Cdo, o,
) S: Cu, Aj! In the same way as the phosphor, Li
The content is tooppm (Zno, 9g, C
do, o,) S:Li, Cu, A1 phosphor was obtained. On the other hand, for comparison, conventional (Z n O,
95, Cdo, o5) S; Cu, A fl phosphor was obtained. A fluorescent film was formed using the Cholerano phosphor in the same manner as in Example 1, placed in a vacuum container, and excited with a 50 V slow electron beam (Zno, 5. Cdo, o,
) S: L i, Cu, AJ! The fluorescent film made of fluorescent material is (Zno95+ Cdo, o,) S: C
The luminance was three times higher than that of the u, All phosphor caranal phosphor film.
実施例５
螢光体原料中にＬｉＣＪ！を添加して焼成する以外は従
来のＺｎＳ：Ａｇ、Ａ１螢光体と同様にして、Ｌｉ含有
量が３００ｐｐＩｍであるＺｎＳ：Ｌｉ、Ａｇ、ＡＩ螢
光体を得た。一方、比較のためにＬｉを含有しない従来
のＺｎＳ：Ａｇ、Ａｉ螢光体を得た。これらの螢光体を
用いて実施例１と同様の方法で螢光膜を形成し、真空容
器中に入れ、５０Ｖの低速電子線で励起するとＺｎＳ
： Ｌ ｔ、 Ａｇ。Example 5 LiCJ in the phosphor raw material! A ZnS:Li,Ag,AI phosphor having a Li content of 300 ppIm was obtained in the same manner as the conventional ZnS:Ag,A1 phosphor except that it was added and fired. On the other hand, for comparison, a conventional ZnS:Ag, Al phosphor containing no Li was obtained. A fluorescent film was formed using these phosphors in the same manner as in Example 1, placed in a vacuum container, and excited with a 50V slow electron beam to form ZnS.
: Lt, Ag.
Ａ１螢光体からなる螢光膜はＺｎＳ：Ａｇ、Ａ１螢光体
からなる螢光膜の２倍の発光輝度を示した。The phosphor film made of A1 phosphor exhibited twice the luminance of the phosphor film made of ZnS:Ag and A1 phosphor.
【図面の簡単な説明】
第１図は本発明の低速電子線励起螢光体の１例である（
Ｚｎｏ、６．＋ Ｃｄｏ、ｉｓ） Ｓ ： Ｌ ｉ＋
Ａｇ＋０１螢光体を使用した螢光膜を有する螢光表示
管におけるこの螢光体中のＬｉ含有量と発光輝度および
発光開始電圧の変化との関係を示すグラフである。[Brief Description of the Drawings] Figure 1 is an example of the low-speed electron beam-excited phosphor of the present invention (
Zno, 6. + Cdo, is) S: L i+
2 is a graph showing the relationship between the Li content in the phosphor and changes in luminance and luminescence starting voltage in a fluorescent display tube having a phosphor film using an Ag+01 phosphor.
Claims (2)
，ｃＸ（但し、式中０≦ｘ≦１、０＜ａ＜１×１０＾−
＾２ｇ／ｇ、ｂ＞０、ｃ＞０であり、Ｍ＾１はｘ＝０の
時、ＡｇおよびＡｕの中の少なくとも１種の元素であり
、ｘ≠０の時、Ａｇ、ＡｕおよびＣｕの中の少なくとも
１種の元素、ＸはＡｌ、Ｃｌ、ＢｒおよびＩの中の少な
くとも１種の元素である）で表わされる低速電子線励起
螢光体。(1) General formula (Zn_1_-_x, Cd_x) S: aLi, bM^1
, cX (where 0≦x≦1, 0<a<1×10^-
^2g/g, b>0, c>0, and when x=0, M^1 is at least one element among Ag and Au, and when x≠0, it is Ag, Au and Cu. X is at least one element selected from Al, Cl, Br and I).
Ｃｌであることを特徴とする特許請求の範囲第１項記載
の低速電子線励起螢光体。(2) The slow electron beam-excited phosphor according to claim 1, wherein in the general formula, M^I is Ag and X is Cl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14753389A JPH0662946B2 (en) | 1989-06-09 | 1989-06-09 | Slow electron beam excited phosphor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14753389A JPH0662946B2 (en) | 1989-06-09 | 1989-06-09 | Slow electron beam excited phosphor |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59266816A Division JPS61145277A (en) | 1984-12-18 | 1984-12-18 | Low-speed electron beam excitation phosphor, light-emitting composition and fluorescent display tube |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0228282A true JPH0228282A (en) | 1990-01-30 |
| JPH0662946B2 JPH0662946B2 (en) | 1994-08-17 |
Family
ID=15432465
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14753389A Expired - Fee Related JPH0662946B2 (en) | 1989-06-09 | 1989-06-09 | Slow electron beam excited phosphor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0662946B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03275791A (en) * | 1990-03-27 | 1991-12-06 | Kasei Optonix Co Ltd | Sulfide-based fluorescent material |
| WO2007086310A1 (en) * | 2006-01-27 | 2007-08-02 | Semiconductor Energy Laboratory Co., Ltd. | Light emitting material, light emitting device, and electronic device |
| WO2007086311A1 (en) * | 2006-01-27 | 2007-08-02 | Semiconductor Energy Laboratory Co., Ltd. | Light-emitting material, light-emitting element, light-emitting device, and electronic appliance |
-
1989
- 1989-06-09 JP JP14753389A patent/JPH0662946B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03275791A (en) * | 1990-03-27 | 1991-12-06 | Kasei Optonix Co Ltd | Sulfide-based fluorescent material |
| WO2007086310A1 (en) * | 2006-01-27 | 2007-08-02 | Semiconductor Energy Laboratory Co., Ltd. | Light emitting material, light emitting device, and electronic device |
| WO2007086311A1 (en) * | 2006-01-27 | 2007-08-02 | Semiconductor Energy Laboratory Co., Ltd. | Light-emitting material, light-emitting element, light-emitting device, and electronic appliance |
| US7560749B2 (en) | 2006-01-27 | 2009-07-14 | Semiconductor Energy Laboratory Co., Ltd. | Light emitting material, light emitting device, and electronic device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0662946B2 (en) | 1994-08-17 |
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