JPH0411687A - Green phosphor for color cathode ray tube - Google Patents
Green phosphor for color cathode ray tubeInfo
- Publication number
- JPH0411687A JPH0411687A JP11449190A JP11449190A JPH0411687A JP H0411687 A JPH0411687 A JP H0411687A JP 11449190 A JP11449190 A JP 11449190A JP 11449190 A JP11449190 A JP 11449190A JP H0411687 A JPH0411687 A JP H0411687A
- Authority
- JP
- Japan
- Prior art keywords
- zns
- phosphor
- mol
- green phosphor
- cathode ray
- 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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000012190 activator Substances 0.000 claims abstract description 22
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 238000010894 electron beam technology Methods 0.000 abstract description 7
- 239000010949 copper Substances 0.000 description 38
- 229910052984 zinc sulfide Inorganic materials 0.000 description 28
- 230000005284 excitation Effects 0.000 description 12
- 238000010304 firing Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- 238000004020 luminiscence type Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- PFNQVRZLDWYSCW-UHFFFAOYSA-N (fluoren-9-ylideneamino) n-naphthalen-1-ylcarbamate Chemical compound C12=CC=CC=C2C2=CC=CC=C2C1=NOC(=O)NC1=CC=CC2=CC=CC=C12 PFNQVRZLDWYSCW-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052950 sphalerite Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Luminescent Compositions (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は例えばカラーＴＶ特に高輝度ＴＶ等のカラー表
示装置におけるカラー陰極線管用緑色蛍光体に係わる。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a green phosphor for a color cathode ray tube in a color display device such as a color TV, particularly a high-intensity TV.
［発明の概要］
本発明はＺ ｎ Ｓ ： Ｃｕ ＋ ＡＩよりなるカラ
ー陰極線管用緑色蛍光体において、付活剤Ｃｕが７．５
Ｘ１０−４〜１．５Ｘ １０− ”モル１モルＺｎＳに
選定され、各付活剤ＣｕのＡＩに対する比［Ｃｕ］ ／
［ＡＺ］ （モル比）を１〜１／１０とすることによ
り、電流−輝度特性の高電流領域における線形性の向上
をはかり、かつ高電子線励起に強い蛍光体を従供するも
のである。[Summary of the Invention] The present invention provides a green phosphor for color cathode ray tubes made of ZnS: Cu + AI, in which the activator Cu is 7.5
X10-4 to 1.5X10-'' mol 1 mol ZnS was selected, and the ratio of each activator Cu to AI [Cu]/
[AZ] (molar ratio) is set to 1 to 1/10 to improve the linearity of current-brightness characteristics in a high current region, and to provide a phosphor that is resistant to high electron beam excitation.
（従来の技術〕
近年、プロジェクタすなわち投射型ＴＶ（テレビ）の高
輝度化、高精細度カラーＣＲＴ （陰極線管）やカラー
大型ＴＶの普及に伴う輝度特性の向上が課題となってい
る。例えば、カラー大型ＴＶにおいては高励起対応の含
浸型カソードを有する電子銃が開発され、そのスポット
径の縮小化すなわち単位面積当たりの通電電流が増大化
されており、また高精細度カラーＣＲＴについてもその
画素ピンチの縮小化に伴ったスポット径の縮小化をはか
った電子銃の改良がなされている。このため、高電流に
対しても輝度が線形性を保持するような輝度特性、さら
にこのような高電流すなわち高輝度における長寿命化が
望まれている。(Prior Art) In recent years, it has become a challenge to increase the brightness of projectors, that is, projection TVs, and to improve brightness characteristics with the spread of high-definition color CRTs (cathode ray tubes) and large color TVs.For example, Electron guns with impregnated cathodes capable of high excitation have been developed for large-format color TVs, and the spot diameter has been reduced, which means the current per unit area has been increased.Also, for high-definition color CRTs, the pixels Electron guns have been improved by reducing the spot diameter in line with the reduction of the pinch.This has led to improvements in brightness characteristics that maintain linear brightness even at high currents, and Longer life is desired at higher currents, that is, higher brightness.
このようなカラー陰極線管においてはその画像の三原色
として赤、青及び緑の蛍光体を用いておリ、例えば特開
昭６３−１５０３７２号公報（資料１）においては上述
したような投射形ＴＶ等において輝度特性の良好な、す
なわち高電流高輝度においても充分長時間発光が可能な
青色蛍光体を提案している。In such a color cathode ray tube, red, blue and green phosphors are used as the three primary colors of the image. proposed a blue phosphor that has good luminance characteristics, that is, can emit light for a sufficiently long time even under high current and high brightness.
また緑色蛍光体としては一般にＣｕ、、 ＡＩ等の付活
剤を添加した硫化亜鉛ＺｎＳ：Ｃｕ，Ａｌが用いられて
おり、このような緑色蛍光体に対してジャパニーズ・ジ
ャーナル・オブ・アプライド・フィジックス（Ｊａｐａ
ｎｅｓｅ Ｊｏｕｒｎａｌ ｏｆ Ａｐｐｌｉｅｄ
Ｐｈｙｓｉｃｓ） Ｖｏｌ。In addition, zinc sulfide ZnS:Cu,Al to which activators such as Cu and AI are added is generally used as a green phosphor. (Japa
nese Journal of Applied
Physics) Vol.
１３、Ｎｏ、１０，０ｃｔｏｂｅｒ、１９７４ （資料
２）においては、一定の電流値に対して付活剤Ｃｕ、
ＡＩの各濃度変化に対する発光強度変化についての報告
がなされている。しかしながら上述したような高電流下
の輝度特性についての考察及び改善はなされていない。13, No. 10,0ctober, 1974 (Document 2), the activator Cu,
There have been reports on changes in luminescence intensity with respect to changes in AI concentration. However, no consideration or improvement has been made regarding the brightness characteristics under high current as described above.
一方ではこのような高電流下の励起による劣化によって
緑色蛍光体ＺｎＳ：Ｃｕ，Ａｌの短寿命化も問題となっ
てきており、また特に緑色蛍光体の電流輝度特性の線形
性の悪化すなわち飽和特性の発生によっていわゆるマゼ
ンタリングが発生し易くなるという問題もあった。On the other hand, shortening of the lifetime of the green phosphor ZnS:Cu,Al due to deterioration due to excitation under such high current has also become a problem, and in particular, deterioration of the linearity of the current luminance characteristic of the green phosphor, that is, saturation characteristic. There is also a problem in that so-called magentaring tends to occur due to the occurrence of .
（発明が解決しようとする課題］
本発明は、上述したようなＺｎＳ：Ｃｕ、ＡＩよりなる
緑色蛍光体において電流−輝度特性の向上をはかる。(Problems to be Solved by the Invention) The present invention aims to improve current-luminance characteristics in a green phosphor made of ZnS:Cu, AI as described above.
本発明はＺｎＳ：Ｃｕ、ＡＩよりなるカラー陰極線管用
緑色蛍光体において、付活剤Ｃｕが７．５Ｘ１０−４〜
１．５ＸＩＯ−３モル１モルＺｎＳに選定され、各付活
剤ＣｕのＡＩに対する比［Ｃｕ］ ／ ［Ａｆ ］ （
モル比）を１〜１／１０とする。The present invention provides a green phosphor for color cathode ray tubes made of ZnS:Cu, AI, in which the activator Cu is 7.5X10-4~
1.5XIO-3 mol 1 mol ZnS was selected and the ratio of each activator Cu to AI [Cu] / [Af]
molar ratio) is set to 1 to 1/10.
上述した本発明によるカラー陰極線管用緑色蛍光体を用
いたときの電子線励起下における励起電流密度（Ｉｋ）
−輝度（Ｂ）特性を第１図に示す。Excitation current density (Ik) under electron beam excitation when using the above-described green phosphor for color cathode ray tubes according to the present invention
-The brightness (B) characteristics are shown in FIG.
第１図において線ａは本発明によるカラー陰極線管用緑
色蛍光体における特性を示し、線すは従来のカラー陰極
線管用緑色蛍光体における特性を示す。第１図かられか
るように、本発明による場合は従来の緑色蛍光体に比し
て高い電流値に対しても輝度が線形性を保持しており、
これによって良好な画質を保持してプロジェクタＴＶ等
における高輝度化をはかることができる。In FIG. 1, line a shows the characteristics of the green phosphor for color cathode ray tubes according to the present invention, and line a shows the characteristics of the conventional green phosphor for color cathode ray tubes. As can be seen from FIG. 1, in the case of the present invention, the luminance maintains linearity even at high current values compared to the conventional green phosphor.
This makes it possible to maintain good image quality and increase the brightness of a projector TV or the like.
これは、ＺｎＳ：Ｃｕ、ＡＩよりなる緑色蛍光体の付活
剤Ｃｕを７．５Ｘ１０−’モル１モルＺｎＳ以上に選定
したことにより、従来に比して各付活剤Ｃｕ、 ＡＺの
濃度が大となり、高電流においてもこの付活剤による発
光センターが増大するため、電流−輝度特性における線
形性の改善をはかることができるものと思われる。しか
しながらこの場合Ｃｕの濃度を１．５×１０−３モル１
モルＺｎＳ以上に設定するとＺｎに置換されないＣｕが
格子間に入り込み、エネルギー準位の変化等を伴うため
、発光強度が低下する。ここに本発明においては付活剤
Ｃｕを７．５Ｘ１０−’ 〜１．５Ｘ１０−’モル５モ
ルＺｎＳに選定した理由がある。This is because the activator Cu of the green phosphor consisting of ZnS:Cu, AI is selected to be 7.5 x 10-' mol 1 mol ZnS or more, and the concentration of each activator Cu and AZ is lower than before. Since the number of luminescent centers caused by this activator increases even at high currents, it is thought that it is possible to improve the linearity of current-luminance characteristics. However, in this case, the concentration of Cu is 1.5 x 10-3 mol 1
If the amount is set to be more than mol ZnS, Cu that is not substituted by Zn will enter the interstitial space, causing a change in energy level, etc., resulting in a decrease in emission intensity. This is the reason why in the present invention, the activator Cu was selected to be 7.5X10-' to 1.5X10-' moles and 5 moles of ZnS.
また本発明においては各付活剤ＣｕのＡＩに対する比［
Ｃｕ］ ／ ［ＡＺ ’ｌ （モル比）を１−１／１０
としたが、この妥当性は第２図に示した前記資料２に記
載のＺｎＳ中の付活剤Ｃｕ、 ＡＺの濃度を変化させた
ときの発光強度の変化をみることによって理解される。Furthermore, in the present invention, the ratio of each activator Cu to AI [
Cu]/[AZ'l (molar ratio) 1-1/10
However, the validity of this can be understood by looking at the changes in the luminescence intensity when the concentrations of the activators Cu and AZ in ZnS are changed as shown in Figure 2 and shown in Document 2 above.
第２図において実線ＣはＣｕのＡｌに対するモル比［Ｃ
ｕｌ／［八！１を１７２に固定してＣｕ及びＡＩの濃度
を変化させた場合、鎖線ｄはＣｕの濃度を１．５ＸＩＯ
−’モル１モルＺｎＳに固定してＡｌの濃度を変化させ
た場合、破線ｅはＡｌの濃度を３ＸＩＯ−’モル１モル
ＺｎＳに固定してＣｕの濃度を変化させた場合を示す。In FIG. 2, the solid line C indicates the molar ratio of Cu to Al [C
ul/[eight! 1 is fixed at 172 and the concentrations of Cu and AI are varied, the chain line d indicates the concentration of Cu at 1.5XIO
-' When the Al concentration is fixed at 1 mol ZnS, the broken line e shows the case where the Al concentration is fixed at 3XIO-' mol 1 mol ZnS and the Cu concentration is varied.
第２図がられかるように、ＣｕのＡｆに対するモル比ｆ
ｃｕｌ／［Ａｒ１を１７２に固定した場合は線Ｃに示す
ようにほぼ一定の発光強度となる。これに対してＣｕの
Ａｌに対するモル比［Ｃｕｌ ／ （Ａｌ ｌが１より
大、すなわち線ｄにおいてＡｌの濃度が１．５Ｘ１０−
’モル１モルＺｎＳ以下の場合と、線ｅにおいてＣｕの
濃度が３Ｘ１０−’モル１モルＺｎＳ以上の場合とでは
著しく発光強度が低下しており、ＣｕのＡＩに対するモ
ル比［Ｃｕ］／［Ａｌ］は１以下とするとよいことがわ
かる。As shown in Figure 2, the molar ratio f of Cu to Af
When cul/[Ar1 is fixed at 172, the luminescence intensity is approximately constant as shown by line C. On the other hand, the molar ratio of Cu to Al [Cul / (Al l is greater than 1, that is, the concentration of Al at line d is 1.5
The emission intensity is significantly lower when the concentration of Cu is less than 1 mol ZnS and when the concentration of Cu is 3X10-' mol 1 mol ZnS or more in line e, and the molar ratio of Cu to AI [Cu]/[Al ] is preferably 1 or less.
なお、この比［Ｃｕ］／［Ａｌ］が１／１０未満すなわ
ちＡＩが１０倍を超える場合はＺｎＳの結晶構造に影響
を及ぼすため発光強度が低下する。Note that if this ratio [Cu]/[Al] is less than 1/10, that is, if AI exceeds 10 times, the crystal structure of ZnS is affected and the emission intensity decreases.
従って、各付活剤ＣｕのＡＩに対する比［Ｃｕ］／［Ａ
Ｚ］を１〜１／１０とすることにより、良好な発光強度
が得られ、これら付活剤の濃度および濃度比の選定によ
って高電流における輝度特性の向上をはかることができ
る。Therefore, the ratio of each activator Cu to AI [Cu]/[A
By setting Z] to 1 to 1/10, good emission intensity can be obtained, and by selecting the concentration and concentration ratio of these activators, it is possible to improve the brightness characteristics at high current.
以下本発明によるカラー陰極線管用緑色蛍光体の例を詳
細に説明する。この場合各側ともに次の方法によって緑
色蛍光体を合成した。Examples of the green phosphor for color cathode ray tubes according to the present invention will be described in detail below. In this case, green phosphors were synthesized on each side by the following method.
まず市販の高純度（ルミネッセンス級）の硫化亜鉛Ｚｎ
Ｓ、９９．９９％の硫酸銅ＣｕＳＯ４及び硫酸アルミニ
ウムＡｌ ｔ （ＳＯａ） ３を所定の割合で秤量して
水溶液にし、更に所定量の塩化マグネシウムＭｇＣ１□
を添加してロータリー・エバポレータにて乾燥させる。First, commercially available high purity (luminescence grade) zinc sulfide Zn.
S, 99.99% copper sulfate CuSO4 and aluminum sulfate Al t (SOa) 3 are weighed in a predetermined ratio to make an aqueous solution, and further a predetermined amount of magnesium chloride MgC1□
was added and dried in a rotary evaporator.
次に調合した原料に９９．９９９％の硫黄Ｓを１０重量
％加えてから石英製或いはアルミナ製のルツボに充填し
、内蓋をしてその上に粒状活性炭を２５重量％載せて外
蓋をする。Next, add 10% by weight of 99.999% sulfur S to the prepared raw material, then fill it into a quartz or alumina crucible, cover with an inner lid, place 25% by weight of granular activated carbon on top, and cover with an outer lid. do.
焼成は毎時２００°Ｃで所定の温度まで昇温し、所定時
間この場合各側とも４時間保持して行う。この焼成の後
、炉から取り出して温水洗浄を充分行い、残留ＭｇＣ１
□を取り除く。Firing is carried out by raising the temperature to a predetermined temperature at 200° C./hour and holding it for a predetermined time, in this case 4 hours on each side. After this firing, it is taken out from the furnace, thoroughly washed with hot water, and the residual MgC1
Remove □.
上述の方法により行った各実施例及び比較例を以下に示
す。Examples and comparative examples carried out by the above-mentioned method are shown below.
実施例ｌ
ＺｎＳを１モル、ＣｕＳＯ４及びＡ／ｚ（ＳＯａ）３を
７．５ Ｘ １０−’モル、ＭｇＣ１□をＩ Ｘｌ０−
”モルとして、焼成温度を９００°Ｃとして合成した。Example l 1 mol of ZnS, 7.5 X 10-' mol of CuSO4 and A/z(SOa)3, I Xl0-' of MgC1□
"It was synthesized as a molar at a calcination temperature of 900°C.
実施例２
ＺｎＳを１モル、Ｃｕ５Ｏａ及びＡｌ ２ （５０４）
３を１．５Ｘ１０−３モル、ＭｇＣｌ□をｌＸｌ０−
３モルとして、焼成温度を９００°Ｃとして合成した。Example 2 1 mol of ZnS, Cu5Oa and Al 2 (504)
3 to 1.5X10-3 mol, MgCl□ to lXl0-
Synthesis was carried out using 3 moles and a calcination temperature of 900°C.
実施例３
ＺｎＳを１モル、ＣｕＳＯ４及びＡｌ ２ （ＳＯ４）
３を７．５Ｘ１０−’モル、ＭｇＣ１ｚをｌＸｌ０−
’モルとして、更にＺｎ５ｅ（セレン化亜鉛）を０．０
３モル１モルＺｎＳすなわちこ、の場合０．０３モルを
添加して焼成温度を１２００°Ｃとして合成した。Example 3 1 mol of ZnS, CuSO4 and Al 2 (SO4)
3 to 7.5X10-' mol, MgC1z to lXl0-
'Additionally 0.0 mol of Zn5e (zinc selenide)
Synthesis was carried out by adding 3 moles and 1 mole of ZnS, that is, 0.03 moles in this case, and setting the firing temperature to 1200°C.
比較例１
ＺｎＳを１モル、Ｃｕ５Ｏ，及びＡｌ ｚ （Ｓ０４）
３を１．５ Ｘ １０−’モル、ＭｇＣ１ｔをｌＸｌ
０−’モルとして、焼成温度を９００°Ｃとして合成し
た。Comparative Example 1 1 mol of ZnS, Cu5O, and Al z (S04)
3 to 1.5 X 10-' mol, MgClt to 1Xl
Synthesis was carried out at a calcination temperature of 900°C and a 0-' mol.
このようにして合成した各蛍光体の特性評価を行うため
、第１図に示したような励起電流密度に対する輝度の飽
和度の目安として、励起電流密度を０．４〜４０μＡ／
ｃ１ｉＩと変化させたときの輝度の傾きをγ値とし、比
較例１におけるγ値を１として相対評価した。この結果
を表１に示す。In order to evaluate the characteristics of each phosphor synthesized in this way, the excitation current density was set at 0.4 to 40 μA/
The slope of the luminance when changing c1iI was taken as the γ value, and the γ value in Comparative Example 1 was set as 1 for relative evaluation. The results are shown in Table 1.
表 １ 同等の発光特性を有する。Table 1 They have the same luminescent properties.
表１かられかるように、従来の発光特性に対して実施例
１による蛍光体はγ値が８％改善された。As can be seen from Table 1, the γ value of the phosphor according to Example 1 was improved by 8% compared to the conventional light emitting characteristics.
また実施例２による蛍光体では１５％、実施例３による
蛍光体では１８％もγ値が改善された。Further, the γ value was improved by 15% in the phosphor according to Example 2, and by 18% in the phosphor according to Example 3.
また実施例３においては焼成温度を１２００°Ｃとして
蛍光体を合成したため、その結晶構造は六方晶系となる
。実施例１による蛍光体と実施例３による蛍光体につい
て、強制劣化率を測定した結果を表２に示す。ここで強
制劣化率の測定は、それぞれ励起電流密度を５００μＡ
／ｃ＋ｆｌとして１０００時間通電したのち１日冷却し
、励起電流密度を２５０μＡ／Ｃ１１ｌとしてその発光
強度の変化（劣化）を測定したものである。Furthermore, in Example 3, the phosphor was synthesized at a firing temperature of 1200°C, so its crystal structure was hexagonal. Table 2 shows the results of measuring forced deterioration rates for the phosphor according to Example 1 and the phosphor according to Example 3. Here, the forced deterioration rate was measured using an excitation current density of 500 μA.
/c+fl was applied for 1000 hours, then cooled for one day, and the change (deterioration) in luminescence intensity was measured at an excitation current density of 250 μA/C11l.
表２
比較例１による蛍光体は、従来のカラーＴＶ市販品に用
いていたＺｎＳ：Ｃｕ、Ａ７と同等の組成とした場合で
、従来のカラーＴＶ市販品の緑色蛍光体と表２かられか
るように、実施例１による立方晶系の蛍光体は初期輝度
からの低下率が３８％であるに比して実施例３による六
方晶系の蛍光体は１５％しか低下しておらず、結晶性が
著しく安定化し、長寿命化することがわかる。Table 2 The phosphor according to Comparative Example 1 has the same composition as ZnS:Cu, A7 used in conventional color TV commercial products, and is compared with the green phosphor of conventional color TV commercial products from Table 2. As shown, the cubic crystal system phosphor according to Example 1 had a decrease rate of 38% from the initial brightness, while the hexagonal system system phosphor according to Example 3 had a decrease of only 15%, and the luminance decreased by only 15%. It can be seen that the properties are significantly stabilized and the lifespan is extended.
緑色蛍光体においてはその結晶構造が六方晶系となると
発光スペクトルが約１４０人短波長側ヘシフトしてしま
うのでバンドギャップの小さいＺｎ５ｅやＣｄＳ、 Ｚ
ｎ５ｅを２〜５モル％添加して、或いはＣｕや八！の他
に更にＡｕ（金）を添加することにより色度を調整する
ことが必要となる。実施例３においてはＺｎ５ｅを３モ
ル％添加して蛍光体を合成したことにより良好な緑色ス
ペクトルを得ることができた。For green phosphors, when the crystal structure becomes hexagonal, the emission spectrum shifts to the shorter wavelength side by approximately 140 nm, so Zn5e, CdS, and Z, which have small band gaps, are used.
Add 2 to 5 mol% of n5e, or add Cu or 8! In addition, it is necessary to adjust the chromaticity by further adding Au (gold). In Example 3, a good green spectrum could be obtained by synthesizing the phosphor by adding 3 mol % of Zn5e.
なお、上述した各実施例においては付活剤ＣｕのＡｆに
対する比［Ｃｔ＋＋／［ＡＺ］を１７２として行ったが
、この比は上述した１〜１／１０の間であればよい。ま
た上述したように焼成温度を変化させかつ添加剤を加え
る等種々の変更をとり得る。In each of the above-mentioned Examples, the ratio [Ct++/[AZ] of activator Cu to Af was set to 172, but this ratio may be between 1 and 1/10 as described above. Further, as mentioned above, various changes can be made such as changing the firing temperature and adding additives.
上述したように本発明によるＺｎＳ：Ｃｕ、Ａｆよりな
るカラー陰極線管用緑色蛍光体は、付活剤Ｃｕが７．５
ｘｌＯ−’ 〜１．５ｘｌＯ−’モル１モルＺｎＳに選
定され、各付活剤ＣｕのＡＩに対する比［Ｃｕｌ ／
［ＡＺ］ Ｃモル比）を１〜１／１０とすることにより
、電流−輝度特性、特に高電流領域における特性の改善
すなわち線形性の向上をはかることができ、第１図中線
ａで示すように電子線励起の良好な蛍光体を得ることが
できる。As mentioned above, the green phosphor for color cathode ray tubes made of ZnS:Cu, Af according to the present invention has an activator Cu of 7.5
xlO-' ~ 1.5xlO-' mol 1 mol ZnS was selected, and the ratio of each activator Cu to AI [Cul/
[AZ] By setting the C molar ratio) to 1 to 1/10, it is possible to improve the current-luminance characteristics, particularly in the high current region, that is, improve the linearity, as shown by the line a in Figure 1. Thus, a phosphor with good electron beam excitation can be obtained.
また更に例えば上述の電子線励起の良好な蛍光体におい
て、焼成温度を高温化してその結晶構造を六方晶系とし
、かつＺｎ５ｅを添加して発光スペクトルのずれを回避
したことにより、高温安定型で長寿命の緑色蛍光体を得
ることができる。Furthermore, for example, in the above-mentioned phosphor with good electron beam excitation, the firing temperature is raised to make the crystal structure hexagonal, and Zn5e is added to avoid deviations in the emission spectrum, making it stable at high temperatures. A long-life green phosphor can be obtained.
第１図は本発明によるカラー陰極線管用緑色蛍光体を用
いたときの電子線励起下における励起電流密度（ｔｈ）
−輝度（Ｂ）特性を示す図、第２図はカラー陰極線管用
緑色蛍光体のＺｎＳ中の付活剤Ｃｕ、Ａｌの濃度を変化
させたときの発光強度の変化を示す図である。Figure 1 shows the excitation current density (th) under electron beam excitation when using the green phosphor for color cathode ray tubes according to the present invention.
- A diagram showing brightness (B) characteristics. FIG. 2 is a diagram showing changes in emission intensity when the concentrations of activators Cu and Al in ZnS of a green phosphor for a color cathode ray tube are changed.
Claims (1)
光体において、 付活剤Ｃｕが７．５×１０＾−＾４〜１．５×１０＾−
＾３モル／モルＺｎＳに選定され、各付活剤ＣｕのＡｌ
に対する比［Ｃｕ］／［Ａｌ］（モル比）が１〜１／１
０とされたこと を特徴とするカラー陰極線管用緑色蛍光体。[Claims] In a green phosphor for color cathode ray tubes made of ZnS:Cu, Al, the activator Cu is 7.5×10^-^4 to 1.5×10^-
^3 mol/mol ZnS was selected, and the Al of each activator Cu
The ratio [Cu]/[Al] (molar ratio) is 1 to 1/1
A green phosphor for a color cathode ray tube, characterized in that the phosphor is 0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11449190A JP2956123B2 (en) | 1990-04-27 | 1990-04-27 | Green phosphor for color cathode ray tubes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11449190A JP2956123B2 (en) | 1990-04-27 | 1990-04-27 | Green phosphor for color cathode ray tubes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0411687A true JPH0411687A (en) | 1992-01-16 |
| JP2956123B2 JP2956123B2 (en) | 1999-10-04 |
Family
ID=14639088
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11449190A Expired - Fee Related JP2956123B2 (en) | 1990-04-27 | 1990-04-27 | Green phosphor for color cathode ray tubes |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2956123B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5558817A (en) * | 1992-05-15 | 1996-09-24 | U.S. Philips Corporation | Green-luminescing zinc sulphide and cathode ray tube provided with this zinc sulphide |
| US6808829B2 (en) | 2001-01-30 | 2004-10-26 | Hitachi, Ltd. | Image-display device |
| EP2067433A1 (en) | 2007-12-03 | 2009-06-10 | Olympus Medical Systems Corporation | Medical appliance, endoscope overtube and endoscope apparatus |
-
1990
- 1990-04-27 JP JP11449190A patent/JP2956123B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5558817A (en) * | 1992-05-15 | 1996-09-24 | U.S. Philips Corporation | Green-luminescing zinc sulphide and cathode ray tube provided with this zinc sulphide |
| US6808829B2 (en) | 2001-01-30 | 2004-10-26 | Hitachi, Ltd. | Image-display device |
| EP2067433A1 (en) | 2007-12-03 | 2009-06-10 | Olympus Medical Systems Corporation | Medical appliance, endoscope overtube and endoscope apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2956123B2 (en) | 1999-10-04 |
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