JPS6225714B2 - - Google Patents
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- Publication number
- JPS6225714B2 JPS6225714B2 JP59146274A JP14627484A JPS6225714B2 JP S6225714 B2 JPS6225714 B2 JP S6225714B2 JP 59146274 A JP59146274 A JP 59146274A JP 14627484 A JP14627484 A JP 14627484A JP S6225714 B2 JPS6225714 B2 JP S6225714B2
- Authority
- JP
- Japan
- Prior art keywords
- phosphor
- ppm
- europium
- less
- brightness
- 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 46
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 6
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052693 Europium Inorganic materials 0.000 description 24
- -1 europium-activated yttrium oxysulfide Chemical class 0.000 description 22
- 239000000243 solution Substances 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000012535 impurity Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 229910001940 europium oxide Inorganic materials 0.000 description 4
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000012190 activator Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 3
- LHBNLZDGIPPZLL-UHFFFAOYSA-K praseodymium(iii) chloride Chemical compound Cl[Pr](Cl)Cl LHBNLZDGIPPZLL-UHFFFAOYSA-K 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000000638 stimulation Effects 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 2
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 description 1
- MBXOOYPCIDHXGH-UHFFFAOYSA-N 3-butylpentane-2,4-dione Chemical compound CCCCC(C(C)=O)C(C)=O MBXOOYPCIDHXGH-UHFFFAOYSA-N 0.000 description 1
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000003213 activating effect Effects 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- UHTYDNCIXKPJDA-UHFFFAOYSA-H oxalate;praseodymium(3+) Chemical class [Pr+3].[Pr+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O UHTYDNCIXKPJDA-UHFFFAOYSA-H 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
Description
【発明の詳細な説明】
Ａ 産業上の利用分野
本発明は、主として、カラーブラウン管、デイ
スプレイ用ブラウン管等に使用される赤色蛍光体
であるユーロピウム付活酸硫化イツトリウム
（Y2O2S：Eu）蛍光体の改良に係り、特に、電子
線刺激の場合に付いて従来のユーロピウム付活酸
硫化イツトリウム（Y2O2S：Eu）蛍光体よりも
優れた特性を有するユーロピウム付活酸硫化イツ
トリウム蛍光体に関する。[Detailed Description of the Invention] A. Field of Industrial Application The present invention mainly relates to europium-activated yttrium oxysulfide (Y 2 O 2 S: Eu), which is a red phosphor used in color cathode ray tubes, display cathode ray tubes, etc. Regarding the improvement of phosphors, in particular, europium-activated yttrium oxysulfide phosphors have better properties than conventional europium-activated yttrium oxysulfide (Y 2 O 2 S: Eu) phosphors in the case of electron beam stimulation. Regarding the body.
本明細書に於て、電流飽和特性とは、電子線の
加速電圧を一定とし、蛍光体の電流密度を増加し
た場合に、電流密度に比例して蛍光体り輝度が上
昇すれば飽和は生じないが、もし輝度が電流密度
に比例すべき値に達せず、その値より低い値とな
れば、飽和が生じるという意味である。 In this specification, the current saturation characteristic means that when the acceleration voltage of the electron beam is kept constant and the current density of the phosphor is increased, saturation occurs if the luminance of the phosphor increases in proportion to the current density. However, if the brightness does not reach the value that should be proportional to the current density and becomes lower than that value, saturation occurs.
Ｂ 従来の技術
ユーロピウム付活酸硫化イツトリウム
（Y2O2S：Eu）蛍光体は米国R.C.A社の特公昭43
―21859（登録第0537954号）に示されている。こ
の特許が公表されて以後、この蛍光体の特性の改
善について種種の提案が行われている。例えば、
輝度などを向上させる手段として、微量（数
10ppm）のテルビウム（Tb）の添加する技術
（特公昭47―13243）、或は、少量（10分の数％）
のサマリウム（Sm）を導入する方法（特公昭57
―354，登録第1161508号）が知られている。B. Conventional technology Europium-activated yttrium oxysulfide (Y 2 O 2 S: Eu) phosphor was manufactured by RCA Corporation in the United States in 1972.
-21859 (Registration No. 0537954). Since this patent was published, various proposals have been made to improve the characteristics of this phosphor. for example,
As a means to improve brightness etc., a trace amount (a few
Technology to add terbium (Tb) (10ppm) (Special Publication No. 47-13243) or a small amount (several tenths of a percent)
How to introduce samarium (Sm)
-354, Registration No. 1161508) is known.
更に、ユーロピウム（Eu）と共にプラセオジ
ム（Pr）を共存させるユーロピウム付活酸硫化
イツトリウム（Y2O2S：Eu）蛍光体も開発され
ている。（特公昭48―31830号）
この特公昭48―31830号公報に示されるユーロ
ピウム付活酸硫化イツトリウム（Y2O2S：Eu）
蛍光体は、Euの付活量が２×10-4〜0.2モルに調
整され、これにPrを10〜50ppm共存させて輝度
を20〜30向上させる技術が開示されている。 Furthermore, a europium-activated yttrium oxysulfide (Y 2 O 2 S:Eu) phosphor in which praseodymium (Pr) coexists with europium (Eu) has also been developed. (Special Publication No. 48-31830) Europium activated yttrium oxysulfide (Y 2 O 2 S: Eu) shown in this Japanese Patent Publication No. 48-31830
A technique has been disclosed in which the activation amount of Eu is adjusted to 2 x 10 -4 to 0.2 mole in the phosphor, and 10 to 50 ppm of Pr is added thereto to improve the luminance by 20 to 30 times.
Ｃ 当該発明が解決しようとする問題点
ところで、近年ブラウン管はカラー受像管の他
に、カラーデイスプレイ管、投写管等の需要が高
まり、これらの管に於ては刺激する電子線の電流
密度は従来の0.5μＡ／cm2よりも更に上昇し最大
５μＡ／cm2程度の高電流密度で刺激する場合が多
くなつた。このため蛍光体の輝度に飽和現象が生
じブラウン管の色調などに色ずれが起こりやすく
なつた。蛍光体側としてはこの飽和現象について
解決をせまられており、本発明はこれらの特性に
付いて改善をつくつたものである。C Problems to be Solved by the Invention Incidentally, in recent years, demand for cathode ray tubes, such as color display tubes and projection tubes, has increased in addition to color picture tubes, and in these tubes, the current density of the stimulating electron beam is lower than that of conventional ones. The current density increased further than the current density of 0.5 μA/cm 2 , and stimulation was often performed at a high current density of about 5 μA/cm 2 . This caused a saturation phenomenon in the brightness of the phosphor, making color shifts more likely to occur in the color tone of the cathode ray tube. On the phosphor side, there is a need to solve this saturation phenomenon, and the present invention is an attempt to improve these characteristics.
本発明は、ユーロピウム付活酸硫化イツトリウ
ム（Y2O2S：Eu）蛍光体の付活剤に、Euと共
に、極めて限定された範囲内でPrを共存させる
ことによつて、ユーロピウム付活酸硫化イツトリ
ウム（Y2O2S：Eu）蛍光体の輝度の現象を改善
することを目的としている。 The present invention enables europium-activated yttrium oxysulfide (Y 2 O 2 S: Eu) phosphor to be activated by coexisting Pr in a very limited range with Eu in the activator of the europium-activated yttrium oxysulfide (Y 2 O 2 S: Eu) phosphor. The aim is to improve the brightness phenomenon of yttrium sulfide (Y 2 O 2 S: Eu) phosphors.
Ｄ 問題点を解決する為の手段
本発明は、母体となるユーロピウム付活酸硫化
イツトリウム蛍光体に、Euの共付活剤として、
2ppm以上10ppm未満と超微量のPrを使用してい
る。又、一般式ユーロピウム付活酸硫化イツトリ
ウムＹ(2―a)EuaO2Sに於て、Euの付活量、即ち
ａの値は、0.0002≦ａ≦0.2に特定している。D. Means for Solving the Problems The present invention provides a base material, europium-activated yttrium oxysulfide phosphor, containing Eu as a co-activator.
Ultra-trace amounts of Pr are used, ranging from 2ppm to less than 10ppm. Furthermore, in the general formula europium-activated yttrium oxysulfide Y (2 - a) Eu a O 2 S, the activation amount of Eu, that is, the value of a, is specified to be 0.0002≦a≦0.2.
Ｅ 作用
超微量のPrは、Euと共にユーロピウム付活酸
硫化イツトリウムに付活されてユーロピウム付活
酸硫化イツトリウム（Y2O2S：Eu）蛍光体の高
電流密度領域に於ける輝度飽和現象を改善する。E Effect A very small amount of Pr is activated by europium-activated yttrium oxysulfide together with Eu, and causes the brightness saturation phenomenon in the high current density region of europium-activated yttrium oxysulfide (Y 2 O 2 S:Eu) phosphor. Improve.
Ｆ 実験例
ユーロピウム付活酸硫化イツトリウム
（Y2O2S：Eu）蛍光体の製造に於て、母体となる
ユーロピウム付活酸硫化イツトリウムの原料とし
て使用するY2O3には、含まれる希土類不純物が
それぞれの化合物について2ppm以下である高純
度のものを使用した。即ち、Y2O3には、CeO2が
1ppm以下、Pr6O11が0.5ppm以下、Nd2O3が
1ppm以下、Sm2O3が2ppm以下、Tb4O7が1ppm
以下、Dy2O3が2ppm以下、Ho2O3が2ppm以下、
Eu2O3が2ppm以下、Tm2O3が1ppm以下、Yb2O3
が1ppm以下の原料を使用した。F Experimental example In the production of europium-activated yttrium oxysulfide (Y 2 O 2 S: Eu) phosphor, Y 2 O 3 used as a raw material for the parent europium-activated yttrium oxysulfide contains rare earth elements. Highly purified products with impurities of 2 ppm or less for each compound were used. That is, Y 2 O 3 contains CeO 2
1ppm or less, Pr 6 O 11 0.5ppm or less, Nd 2 O 3
1ppm or less, Sm 2 O 3 2ppm or less, Tb 4 O 7 1ppm
Below, Dy 2 O 3 is 2 ppm or less, Ho 2 O 3 is 2 ppm or less,
Eu 2 O 3 2ppm or less, Tm 2 O 3 1ppm or less, Yb 2 O 3
We used raw materials with a content of 1ppm or less.
ただ、Y2O3には、不純物濃度範囲以外のも
の、例えば、各不純物が5ppm以下の原料も使用
できる。 However, for Y 2 O 3 , materials outside the impurity concentration range, for example, raw materials containing each impurity of 5 ppm or less can also be used.
また付活剤原料として使用する酸化ユーロピウ
ム（Eu2O3）については、Y2O2S：EuにおけるEu
の含量が数％（重量）程度で、10％未満の導入で
あるから、希土類不純物は各々10ppm未満であ
れば、ユーロピウム付活酸硫化イツトリウム
（Y2O2S：Eu）中では各々1ppm以下となるの
で、このような純度のものを使用した。 Regarding europium oxide (Eu 2 O 3 ) used as an activator raw material, Y 2 O 2 S: Eu
Since the content of rare earth impurities is about a few percent (by weight) and less than 10%, if each rare earth impurity is less than 10 ppm, it is less than 1 ppm each in europium-activated yttrium oxysulfide (Y 2 O 2 S: Eu). Therefore, a product with such purity was used.
本発明者等は、種種の希土類を微量、Euと共
存させるユーロピウム付活酸硫化イツトリウム
（Y2O2S：Eu）蛍光体を試作した。その結果、超
微量のPrをEu共存させたユーロピウム付活酸硫
化イツトリウム（Y2O2S：Eu）蛍光体のみが、
電流飽和特性について優れた特性を示すことを見
いだした。 The present inventors prototyped a europium-activated yttrium oxysulfide (Y 2 O 2 S:Eu) phosphor in which trace amounts of various rare earths coexist with Eu. As a result, only the europium-activated yttrium oxysulfide (Y 2 O 2 S:Eu) phosphor, in which an ultra-trace amount of Pr coexists with Eu,
It was found that the current saturation characteristics were excellent.
この実験に於て、Prの最適含量は次通りの方
法で特定した。高純度Y2O3には、特にPrの含量
が0.5ppm以下の高品質のものを選び、これを476
ｇ秤量する。Eu2O324.0ｇと共に濃塩酸に溶解
し、次に純水で希釈して３リツトルの容量とす
る。ついで１ミリリツトル中に0.1mgのPrを含有
する塩化プラセオジム（PrCl3）溶液を作り、これ
を前記の塩化イツトリウム（YCl3）および塩化ユ
ーロピウム（EuCl3）の混合溶液に添加した。塩
化プラセオジムの添加量を、Ｏミリリツトル、10
ミリリツトル、15ミリリツトル、20ミリリツト
ル、30ミリリツトル、40ミリリツトル、50ミリリ
ツトル、60ミリリツトルとして８種の混合溶液を
つくつた。次に各々の濃度の混合溶液にしゆう酸
溶液（純水３リツトルにしゆう酸二水和物1200ｇ
を溶解）を添加してＹ，Eu，Prのしゆう酸塩を
共沈させる。ろ過後800℃に熱処理してこれを酸
化物にかえる。以下Ｓ，Na2CO3等を使用して焼
成し蛍光体を得る方法は以下の実施例の通りとし
た。このようにして得られた蛍光体の８種の試料
はこれを一般式で示すと（Y1.938Eu0.062）O2S：
Pr（1ppm以下〜12ppm）であり、Prの10ppm
は、上式のEu0.0062の表わし方をすればPr0.000008
程度になつて非常に微量である。 In this experiment, the optimum content of Pr was determined by the following method. For high-purity Y 2 O 3 , choose a high quality one with a Pr content of 0.5 ppm or less, and add it to 476
Weigh g. Dissolve in concentrated hydrochloric acid with 24.0 g of Eu 2 O 3 and then dilute with pure water to a volume of 3 liters. Then, a praseodymium chloride (PrCl 3 ) solution containing 0.1 mg of Pr in 1 ml was prepared and added to the above-mentioned mixed solution of yttrium chloride (YCl 3 ) and europium chloride (EuCl 3 ). The amount of praseodymium chloride added is O milliliter, 10
Eight types of mixed solutions were prepared in milliliters, 15 milliliters, 20 milliliters, 30 milliliters, 40 milliliters, 50 milliliters, and 60 milliliters. Next, add oxalic acid solution to the mixed solution of each concentration (1200 g of oxalic acid dihydrate to 3 liters of pure water)
(dissolved) to coprecipitate the oxalates of Y, Eu, and Pr. After filtration, it is heat-treated at 800°C to convert it into an oxide. The method for obtaining the phosphor by firing using S, Na 2 CO 3 , etc. was as described in the following example. The eight types of phosphor samples obtained in this way have the general formula (Y 1 . 938 Eu 0 . 062 ) O 2 S:
Pr (1ppm or less ~ 12ppm), 10ppm of Pr
If we express Eu 0.0062 in the above formula, we get Pr 0.000008 .
The amount is extremely small.
これら試料について刺激電圧27KV（一定）、電
流密度0.05μＡ／cm2，0.1μＡ／cm2，0.5μＡ／
cm2，1.0μＡ／cm2，5.0μＡ／cm2の各々の条件で測
定した数値をプロツトすると第１図の電流に対す
る輝度飽和曲線が得られた。 For these samples, stimulation voltage was 27KV (constant), current density was 0.05μA/cm 2 , 0.1μA/cm 2 , 0.5μA/
By plotting the values measured under the conditions of cm 2 , 1.0 μA/cm 2 and 5.0 μA/cm 2 , the brightness saturation curve versus current shown in FIG. 1 was obtained.
第１図の電流に対する輝度飽和特性は、各電流
域に於て、輝度飽和を起こさない理想の蛍光体、
即ち、輝度が電流密度に比例して増加する蛍光体
を100％とし、これに対して輝度が低下する率を
％で表わしている。 The brightness saturation characteristics with respect to the current shown in Figure 1 show that an ideal phosphor that does not cause brightness saturation in each current range,
That is, the phosphor whose brightness increases in proportion to the current density is defined as 100%, and the rate at which the brightness decreases is expressed in %.
従つて、理想の蛍光体は、第１図において、電
流密度を問わず100％水平となる。 Therefore, the ideal phosphor is 100% horizontal in FIG. 1 regardless of the current density.
第１図に於て、曲線ＡはPrの含有量が不純物
濃度以下、即ち、0.5ppm以下、曲線ＢはPrの含
有量が2ppm、曲線ＣはPrの含有量が3ppm又は
4ppm、曲線ＤはPrの含有量が6ppm又は5ppm、
曲線ＥはPrの含有量が8ppm，10ppm，12ppm
で、Y1.938Eu0.062O2S：Pr蛍光体の輝度飽和曲線
を示す。 In Figure 1, curve A shows that the Pr content is below the impurity concentration, that is, 0.5 ppm or less, curve B shows that the Pr content is 2 ppm, and curve C shows that the Pr content is 3 ppm or less.
4ppm, curve D has a Pr content of 6ppm or 5ppm,
Curve E shows Pr content of 8ppm, 10ppm, and 12ppm.
shows the brightness saturation curve of Y 1 . 938 Eu 0 . 062 O 2 S:Pr phosphor.
この図から明らかなように、５μＡ／cm2の場合
には、Prを添加しない蛍光体、即ち、Prの含有
量が0.5ppm以下のユーロピウム付活酸硫化イツ
トリウム（Y2O2S：Eu）蛍光体は、輝度飽和を
起こさない理想の蛍光体に比べて輝度が30％も低
下した。これに対し、Prを2ppm含む本発明の蛍
光体は、輝度低下が16％と減少し、更に3ppm〜
12ppmのPrを含む蛍光体は、輝低下が10〜７％
程度となり、輝度飽和現象が減少している。そし
てPr含有量8ppm〜12ppmでは輝度飽和度の減少
は向上せず、殆ど等しい数値を示す。 As is clear from this figure, in the case of 5 μA/cm 2 , a phosphor without Pr added, that is, europium-activated yttrium oxysulfide (Y 2 O 2 S: Eu) with a Pr content of 0.5 ppm or less The luminance of the phosphor was 30% lower than that of an ideal phosphor that would not cause brightness saturation. On the other hand, the phosphor of the present invention containing 2 ppm of Pr showed a reduction in brightness of 16%, and an additional 3 ppm~
Phosphor containing 12ppm Pr has a brightness reduction of 10-7%.
The brightness saturation phenomenon is reduced. When the Pr content ranges from 8 ppm to 12 ppm, the decrease in brightness saturation does not improve, and the values are almost the same.
一方Prの含有量は蛍光体の輝度に影響を及ぼ
す。即ち、輝度飽和を起こさない低電流密度領域
における輝度は、含有量に影響を受け、Prの添
加量が増加すると輝度は５〜10％程度減少して行
く傾向がある。この状態を第２図に示す。輝度の
落下点はPr含量8ppm付近より始まる。従つて電
流飽和、輝度の両面から考察するとPrの添加の
範囲は2ppm以上10ppm未満、好ましくは4ppm
〜8ppm付近が最良の範囲となる。何れにしても
Prの含有量は非常に狭い範囲に於て蛍光体の特
性が改善されるという事実を見いだすことができ
た。 On the other hand, the content of Pr affects the brightness of the phosphor. That is, the brightness in a low current density region where brightness saturation does not occur is affected by the content, and as the amount of Pr added increases, the brightness tends to decrease by about 5 to 10%. This state is shown in FIG. The falling point of brightness begins around the Pr content of 8 ppm. Therefore, considering both current saturation and brightness, the range of Pr addition is 2 ppm or more and less than 10 ppm, preferably 4 ppm.
The best range is around ~8ppm. In any case
It was found that the properties of the phosphor were improved within a very narrow range of Pr content.
本発明の蛍光体は、合成された最終の蛍光体に
おいて、Pr含量が2ppm以上10ppm未満に特定さ
れていることを特徴とする。従つて、蛍光体を製
造する原料に含有されるPr量を調整し、或はPr
含量が一定範囲の原料を使用し、製造された蛍光
体が2ppm〜10ppm未満のPrを含むユーロピウム
付活酸硫化イツトリウム（Y2O2S：Eu）蛍光体
とすることも可能である。 The phosphor of the present invention is characterized in that the final synthesized phosphor has a Pr content of 2 ppm or more and less than 10 ppm. Therefore, it is necessary to adjust the amount of Pr contained in the raw material for manufacturing the phosphor, or
It is also possible to use raw materials with a certain range of content so that the produced phosphor is a europium-activated yttrium oxysulfide (Y 2 O 2 S:Eu) phosphor containing 2 ppm to less than 10 ppm of Pr.
以下、本発明の実施例を具体的に説明する。 Examples of the present invention will be specifically described below.
実施例 １
酸化ユーロピウム24.0ｇおよびPrを0.5ppm以
下含む高純度酸化イツトリウム476.0ｇを濃塩酸
に溶解し、これを純水で希釈して約３リツトルに
する。次に１ミリリツトル中に0.1mgのPrを含有
する塩化プラセオジム溶液を調整し、この溶液25
ミリリツトルを上記イツトリウム、ユーロピウム
を含有する塩酸溶液に添加してよく混合し、次に
60℃に加熱する。一方シユウ酸２水加物1200ｇを
純水３リツトルに溶解したシユウ酸水溶液を80℃
に加熱し、これをかき混ぜながら、上記60℃に加
熱した塩酸溶液に添加し、添加終了後10分間撹は
んする。かくして前記混合溶液中にはイツトリウ
ム、ユーロピウム、プラセオジムのシユウ酸塩が
生成し共沈する。次に係る沈澱を含む溶液を放冷
後、デカンテーシヨンにより純水で５回洗浄を繰
り返し、沈澱を吸引ろ過する。この沈澱を800℃
で３時間加熱分解してシユウ酸塩を酸化物とす
る。このようにして得られた希土類酸化物200ｇ
にイオウ59ｇ炭酸ナトリウム63ｇを配合し、よく
混合したのち密閉したアルミナルツボで1100℃に
おいて３時間焼成後、かかる焼結体をボールミル
で粉砕し、水でよく洗浄してから150℃で乾燥す
る。ここで製造された蛍光体は、一般式がY1.
938Eu0.062O2Sで約5ppmのプラセオジムを含有し
た。Example 1 24.0 g of europium oxide and 476.0 g of high-purity yttrium oxide containing 0.5 ppm or less of Pr are dissolved in concentrated hydrochloric acid and diluted with pure water to make about 3 liters. Next, prepare a praseodymium chloride solution containing 0.1 mg of Pr in 1 milliliter, and this solution
Add milliliter to the above hydrochloric acid solution containing yttrium and europium, mix well, and then
Heat to 60℃. On the other hand, an oxalic acid aqueous solution prepared by dissolving 1200 g of oxalic acid dihydrate in 3 liters of pure water was heated to 80°C.
While stirring, add this to the hydrochloric acid solution heated to 60°C, and stir for 10 minutes after the addition is complete. In this way, yttrium, europium, and praseodymium oxalates are produced and coprecipitated in the mixed solution. Next, the solution containing the precipitate is left to cool, and then washed five times with pure water by decantation, and the precipitate is suction-filtered. This precipitate was heated to 800℃.
The mixture is thermally decomposed for 3 hours to convert the oxalate into an oxide. 200g of rare earth oxide thus obtained
59 g of sulfur and 63 g of sodium carbonate were blended, mixed well, and fired at 1100°C for 3 hours in a sealed alumina crucible.The sintered body was ground in a ball mill, thoroughly washed with water, and then dried at 150°C. The phosphor produced here has a general formula of Y 1 .
938 Eu 0 . 062 O 2 S and contained approximately 5 ppm praseodymium.
この蛍光体は、電流密度が５μＡ／cm2のときの
輝度が、0.05μＡ／cm2のときに比べると−9.0％
の低下に留まつた。 The luminance of this phosphor is -9.0% when the current density is 5 μA/cm 2 compared to when it is 0.05 μA/cm 2
remained at a decline.
実施例 ２
酸化ユーロピウム32.7ｇおよびPrを0.5ppm以
下含む前記高純度酸化イツトリウム467.3ｇを濃
硝酸に溶解し、これを純水で希釈して約３リツト
ルにする。次に１ミリリツトル中に0.1mgのPrを
含有する硝酸プラセオジム溶液を調整しこの溶液
10ミリリツトルを上記希土類元素を含む硝酸溶液
に添加してよく混合し、次に60℃に加熱する。以
下の操作は上記実施例１と全く同様にしてPr入
りEu付活ユーロピウム付活酸硫化イツトリウム
Y2O2S蛍光体を得た。かくして得られた蛍光体
は、一般式がY1.914Eu0.086O2Sで約2ppmのPrを
含有していた。Example 2 32.7 g of europium oxide and 467.3 g of the high-purity yttrium oxide containing 0.5 ppm or less of Pr are dissolved in concentrated nitric acid, and this is diluted with pure water to make about 3 liters. Next, prepare a praseodymium nitrate solution containing 0.1 mg of Pr in 1 milliliter, and this solution
Add 10 milliliters to the rare earth element-containing nitric acid solution, mix well, and then heat to 60°C. The following operations were carried out in exactly the same manner as in Example 1 above to prepare Pr-containing Eu-activated europium-activated yttrium oxysulfide.
A Y 2 O 2 S phosphor was obtained. The thus obtained phosphor had a general formula of Y 1 . 914 Eu 0 . 086 O 2 S and contained about 2 ppm of Pr.
この蛍光体は、電流密度が５μＡ／cm2のときの
輝度が、0.05μＡ／cm2のときに比べると−16％の
低下に留まつた。 The luminance of this phosphor when the current density was 5 μA/cm 2 was only -16% lower than when the current density was 0.05 μA/cm 2 .
実施例 ３
酸化ユーロピウム23.0ｇおよびPrを0.5ppm以
下含む前記高純度酸化イツトリウム477ｇを濃硝
酸に溶解し、これを純水で希釈して約３リツトル
にする。次に１ミリリツトル中に0.1mgのPrを含
有する硝酸プラセオジム溶液を調整し、この溶液
40ミリリツトルを上記希土類元素を含む硝酸溶液
に添加してよく混合し、次に60℃に加熱する。以
下の操作は上記実施例１と全く同様にしてPr入
りEu付活ユーロピウム付活酸硫化イツトリウム
Y2O2S蛍光体を得た。かくして得られた蛍光体
は、Y1.940Eu0.060O2Sで約8ppmのPrを含有して
いた。Example 3 23.0 g of europium oxide and 477 g of the high-purity yttrium oxide containing 0.5 ppm or less of Pr are dissolved in concentrated nitric acid and diluted with pure water to make about 3 liters. Next, prepare a praseodymium nitrate solution containing 0.1 mg of Pr in 1 milliliter, and this solution
Add 40 milliliters to the rare earth element-containing nitric acid solution, mix well, and then heat to 60°C. The following operations were carried out in exactly the same manner as in Example 1 above to prepare Pr-containing Eu-activated europium-activated yttrium oxysulfide.
A Y 2 O 2 S phosphor was obtained. The thus obtained phosphor was Y 1 .940 Eu 0 .060 O 2 S and contained about 8 ppm Pr.
この蛍光体は、電流密度が５μＡ／cm2のときの
輝度が、0.05μＡ／cm2のときに比べると−7.5％
の低下に留まつた。 The luminance of this phosphor is -7.5% when the current density is 5 μA/cm 2 compared to when it is 0.05 μA/cm 2
remained at a decline.
Ｇ 効果
本発明のユーロピウム付活酸硫化イツトリウム
Y2O2S：Eu蛍光体は、第１図に示すようにEuと
ともに超微量のPrで付活することにより、高電
流密度領域における輝度飽和現象を著しく改善出
来、投写管やカラーデスプレイ管等に便利に利用
出来る。又、添加されるPr量が超微量であるた
め、原料コストは従来の蛍光体とほとんど同一
で、しかもPr添加による蛍光体自体の輝度低下
現象は殆どない等、数々の卓効を実現する。G Effect Europium-activated yttrium oxysulfide of the present invention
As shown in Figure 1, Y 2 O 2 S: Eu phosphor can significantly improve the brightness saturation phenomenon in high current density regions by activating Eu with an ultra-trace amount of Pr, making it suitable for projection tubes and color display tubes. It can be conveniently used. In addition, since the amount of Pr added is extremely small, the raw material cost is almost the same as that of conventional phosphors, and there is almost no reduction in the brightness of the phosphor itself due to the addition of Pr, achieving a number of excellent effects.
第１図は電流密度に対する輝度の変化を示すグ
ラフ、第２図はプラセオジム混合量に対する輝度
の変化を示すグラフである。
FIG. 1 is a graph showing changes in brightness with respect to current density, and FIG. 2 is a graph showing changes in brightness with respect to the amount of praseodymium mixed.
Claims (1)
おいてａは0.0002≦ａ≦0.2であり、かつ、プラ
セオジム（Pr）が2ppm以上10ppm未満の範囲で
含有されていることを特徴とする蛍光体。 ２ プラセオジム（Pr）の含有量が4ppm〜
8ppmである特許請求の範囲第１項記載の蛍光
体。[Claims] 1 In the phosphor represented by the general formula Y (2 - a) Eu a O 2 S, a is 0.0002≦a≦0.2, and praseodymium (Pr) is in the range of 2 ppm or more and less than 10 ppm. A phosphor characterized by containing. 2 Praseodymium (Pr) content is 4ppm ~
The phosphor according to claim 1, which has a concentration of 8 ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14627484A JPS6126689A (en) | 1984-07-14 | 1984-07-14 | Fluorescent material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14627484A JPS6126689A (en) | 1984-07-14 | 1984-07-14 | Fluorescent material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6126689A JPS6126689A (en) | 1986-02-05 |
| JPS6225714B2 true JPS6225714B2 (en) | 1987-06-04 |
Family
ID=15404024
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14627484A Granted JPS6126689A (en) | 1984-07-14 | 1984-07-14 | Fluorescent material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6126689A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6669867B2 (en) | 2001-11-15 | 2003-12-30 | Georgia Tech Research Corporation | Oxide-based quantum cutter method and phosphor system |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3418246A (en) * | 1965-03-24 | 1968-12-24 | Rca Corp | Rare earth activated yttrium and gadolinium oxy-chalcogenide phosphors |
| JPS4831830A (en) * | 1971-08-20 | 1973-04-26 | ||
| JPS57158283A (en) * | 1981-03-26 | 1982-09-30 | Toshiba Corp | Fluorescent substance |
| JPS5817189A (en) * | 1981-07-23 | 1983-02-01 | Kasei Optonix Co Ltd | Fluorescent material for current modulation type multicolor cathode ray tube |
-
1984
- 1984-07-14 JP JP14627484A patent/JPS6126689A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3418246A (en) * | 1965-03-24 | 1968-12-24 | Rca Corp | Rare earth activated yttrium and gadolinium oxy-chalcogenide phosphors |
| JPS4831830A (en) * | 1971-08-20 | 1973-04-26 | ||
| JPS57158283A (en) * | 1981-03-26 | 1982-09-30 | Toshiba Corp | Fluorescent substance |
| JPS5817189A (en) * | 1981-07-23 | 1983-02-01 | Kasei Optonix Co Ltd | Fluorescent material for current modulation type multicolor cathode ray tube |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6126689A (en) | 1986-02-05 |
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