JPH03200891A - Plzt phosphor - Google Patents
Plzt phosphorInfo
- Publication number
- JPH03200891A JPH03200891A JP1338086A JP33808689A JPH03200891A JP H03200891 A JPH03200891 A JP H03200891A JP 1338086 A JP1338086 A JP 1338086A JP 33808689 A JP33808689 A JP 33808689A JP H03200891 A JPH03200891 A JP H03200891A
- Authority
- JP
- Japan
- Prior art keywords
- plzt
- lanthanoids
- phosphor
- phosphors
- powder
- 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.)
- Pending
Links
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 15
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 15
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 4
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 4
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 3
- 229910052691 Erbium Inorganic materials 0.000 claims description 3
- 229910052689 Holmium Inorganic materials 0.000 claims description 3
- 229910052771 Terbium Inorganic materials 0.000 claims description 3
- 229910052775 Thulium Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000005693 optoelectronics Effects 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- 229910003077 Ti−O Inorganic materials 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910052693 Europium Inorganic materials 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000001272 pressureless sintering Methods 0.000 description 3
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000007569 slipcasting Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000009694 cold isostatic pressing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical group [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Luminescent Compositions (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
Abstract
Description
【発明の詳細な説明】 且豆立韮盟見互 本！［は、ＰＬＺＴ系蛍光体に間する。[Detailed description of the invention] And Mutate Nitai Mei Mutual Book! [ is between PLZT-based phosphors.
１」ｂ久盗遣」Ｌａ
従来より発光体、螢光体材料としては■−Ｖ族、ＩＩ−
ＶＩ族を中心とする化合物半導体、ＺｎＳを中心とする
ＥＬ材料、ランタン族をドープしたガーネット系固体レ
ーザ用材料など様々な材料が実用化されてきた。1"b Kutazai" La Conventionally, the materials for luminous bodies and phosphors are ■-V group, II-
Various materials have been put into practical use, including compound semiconductors mainly based on VI group, EL materials mainly based on ZnS, and materials for garnet-based solid-state lasers doped with lanthanum group.
また、ＰＬＺＴはこのような発光体や螢光体としてでな
く、２次の電気光学効果が大きいことを利用した光制御
用デバイス材料として光シヤツター、光偏向器等に応用
研究が進められてきた。In addition, PLZT has been researched not only as a light emitter or phosphor, but also as a device material for light control that takes advantage of its large second-order electro-optic effect, such as in optical shutters and optical deflectors. .
従って、従来、ＰＬＺＴが発光体、螢光体として報告さ
れた例はなかった。Therefore, there have been no reports of PLZT as a light-emitting or fluorescent material.
しかしながら、発明者等がＰＬＺＴを研究した結果、Ｐ
ＬＺＴのＬａの一部もしくは全部を他の一部のランタノ
イドに置き換えると蛍光特性を示すことを確認した。However, as a result of the inventors' research on PLZT, P
It was confirmed that when part or all of La in LZT is replaced with some other lanthanoids, it exhibits fluorescent properties.
五里皇璽底
本発明は、（１）（Ｐ ｂｗ Ｌ ａｘ）（Ｚ ｒｙ
Ｔ ｉ ｚ）Ｏ。The present invention consists of (1) (P bw La ax) (Z ry
T i z) O.
（但し、ｗ＋ｘ＝１ ｙ＋ｚ＝１）において、Ｌａの一
部又は全部を他の一種類又は複数種のランタノイドに置
き換えたことを特徴とするＰＬＺＴ系蛍光体、及び（２
）ランクメイドの種類が、Ｐｒ、Ｎｄ。(However, w + x = 1 y + z = 1), a PLZT-based phosphor characterized in that part or all of La is replaced with one or more other types of lanthanoid, and (2
) The type of rank maid is Pr, Nd.
Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ％Ｄｙ％Ｈｏ、Ｅｒ。Sm, Eu, Gd, Tb%Dy%Ho, Er.
Ｔｍ、Ｙｂであることを特徴とする上記（１）に記載の
ＰＬＺＴ系蛍光体、並びに（３）ｘの範囲がＯより大で
あり、かつ０．２よりも小なることを特徴とする上記（
１）記載のＰＬＺＴ系蛍光体に関する。PLZT-based phosphor according to (1) above, characterized in that Tm, Yb; and (3) above, characterized in that the range of x is larger than O and smaller than 0.2. (
1) Regarding the PLZT-based phosphor described above.
の
通常ＰＬＺＴは（Ｐ ｂｗ Ｌ ａｘ） （Ｚ ｒｙ
Ｔ １ｚ）Ｏｌ（但し、ｗ＋ｘｌ ｙ＋ｚ＝１）で表わ
すことのできる組成を有するペロブスカイト型複合酸化
物である。The normal PLZT of (P bw L ax) (Z ry
It is a perovskite-type composite oxide having a composition that can be expressed as T 1z)Ol (where w+xl y+z=1).
ＰＬＺＴの粉体合成にあたっては一般的に酸化物混合法
のような乾式合成法や、共沈法、アルコキシド法、シュ
ウ酸法等種々の湿式法が提案されている。しかし、ＰＬ
ＺＴを螢光体として取り扱うにはこれらの粉体合成プロ
セスにおいて、Ｌａの一部又は全部をＬａ以外のランタ
ノイドに置き換えることが適当である。For powder synthesis of PLZT, various dry synthesis methods such as an oxide mixing method, and various wet methods such as a coprecipitation method, an alkoxide method, and an oxalic acid method have generally been proposed. However, P.L.
In order to treat ZT as a fluorescent material, it is appropriate to replace part or all of La with a lanthanoid other than La in these powder synthesis processes.
本発明において上記ランタノイドのうち、より好ましい
ものとしては、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ％Ｔｂ％
Ｄｙ、Ｈｏ、Ｅｒ％Ｔｍ、Ｙｏである。他のランタノイ
ドは、好ましい蛍光をもたらさなかったためである。ま
たＸは、 Ｏより大であり、０．２よりも小なることが
より好ましい。In the present invention, among the above lanthanoids, Pr, Nd, Sm, Eu, Gd%Tb%
Dy, Ho, Er%Tm, and Yo. This is because other lanthanoids did not provide favorable fluorescence. Moreover, it is more preferable that X is larger than O and smaller than 0.2.
常誘電性であると他の機能例えば、電気光学効果を期待
できなくなり、シャッター機能等をもたらせすらいため
である。This is because if it is paraelectric, other functions such as electro-optical effects cannot be expected, and it cannot even provide a shutter function.
Ｌａの一部又は全部を他のランタノイドに置き換えて合
成された粉体（以下ＰＬＺＴ系粉体と略す）から、続く
成形、焼結工程を経て定形され、焼結体を得る。A powder synthesized by replacing part or all of La with other lanthanoids (hereinafter abbreviated as PLZT-based powder) is shaped through subsequent molding and sintering steps to obtain a sintered body.
成形はＰＬＺＴ系粉体を一軸加圧プレス、ＣＩＰ、スリ
ップキャスト、ドクターブレード等種々の方法にて行う
。Molding is performed using various methods such as uniaxial pressure pressing, CIP, slip casting, doctor blade, etc. using PLZT powder.
焼結は成形が終了したＰＬＺＴ系粉体の成形体をホット
プレス法、常圧焼結法などで行う。ホットプレス法では
１０００〜１３００℃、５０〜ａｏｏｋｇ／−の条件に
て５〜２０時間の焼結を行うことで、緻密質なＰＬＺＴ
系焼結体を得ることができ、−軸加圧プレス、ＣＩＰ、
スリップキャスト等で得られた円柱状又は角柱状の成形
体の焼結に適している。Sintering is performed by hot pressing, pressureless sintering, or the like on the PLZT-based powder compact that has been formed. In the hot press method, dense PLZT is produced by sintering for 5 to 20 hours at 1000 to 1300°C and 50 to aookg/-.
A system sintered body can be obtained by -axial pressure pressing, CIP,
Suitable for sintering cylindrical or prismatic molded bodies obtained by slip casting or the like.
常圧焼結法では、１０００〜１３００℃ｐｂｏ含有酸素
雰囲気中にて１０−１００時間の焼結を行うことで緻密
質なＰＬＺＴ系焼結体を得ることができた。In the pressureless sintering method, a dense PLZT-based sintered body could be obtained by performing sintering for 10 to 100 hours at 1000 to 1300° C. in a pbo-containing oxygen atmosphere.
この焼結方法は成形体の形状および寸法に比較的制約が
少ないので、種々の形状の焼結体を得るのに好ましい方
法といえる。Since this sintering method has relatively few restrictions on the shape and dimensions of the compact, it can be said to be a preferred method for obtaining sintered compacts of various shapes.
このようにして得られた焼結体に２００〜３５０ｎｍの
紫外光を照射すると第１表に示すような種々の波長での
蛍光を示す。When the sintered body thus obtained is irradiated with ultraviolet light of 200 to 350 nm, it exhibits fluorescence at various wavelengths as shown in Table 1.
以下余白
去」１４Ｌ
ＰｂＯ，Ｌａ、Ｏ，、ＺｒＯ，、Ｔ ｉ Ｏ，およびＥ
ｕ、Ｏ，の粉体をそれぞれ（Ｐｂ＊、ｓ Ｌａ−、ａｓ
Ｅｕ＊、ｅ＋）（Ｚｒ、、 ａｓ Ｔｉｅ、 ｓｍ）
Ｏｓ組成となるように秤量し、ボールミルにてアルコー
ル湿式混合した後、９００℃、２時間の仮焼を行い、そ
の後、ボールミルにてアルコール湿式粉砕にて所定の上
記組成を有する粉体を得た。14L PbO, La, O,, ZrO,, T i O, and E
Powders of u and O, respectively (Pb*, s La-, as
Eu*, e+) (Zr,, as Tie, sm)
The powder was weighed so as to have the Os composition, mixed with alcohol wet in a ball mill, calcined for 2 hours at 900°C, and then wet-milled with alcohol in a ball mill to obtain a powder having the above-determined composition. .
前記粉体６０ｇを直径４０ＩＩＩＩ１１の金型にて一軸
加圧プレス後、ＣＩＰにて等方的に加圧した成形体を得
た。60 g of the powder was uniaxially pressed using a mold with a diameter of 40III11, and then isotropically pressed using CIP to obtain a molded body.
次に、前記成形体をＰｂＯ含有酸素雰囲気中にて１２０
０℃、５０時間の常圧焼結を行った。Next, the molded body was placed in an oxygen atmosphere containing PbO for 120 minutes.
Pressureless sintering was performed at 0° C. for 50 hours.
更に得られた焼結体より厚さ０．３ｍｍのウェハを切り
出し、両面研磨機により両面鏡面状態のウェハを作製し
た。Further, a wafer with a thickness of 0.3 mm was cut from the obtained sintered body, and a wafer having mirror surfaces on both sides was produced using a double-sided polisher.
このように作製したウェハを蛍光分光光度計にて、紫外
光（２００〜３００ｎｍ）を照射し、蛍光スペクトルを
測定したときの最強線とそのピークの波長位置を第２図
に示した。The wafer thus prepared was irradiated with ultraviolet light (200 to 300 nm) using a fluorescence spectrophotometer, and the fluorescence spectrum was measured. The strongest line and the wavelength position of its peak are shown in FIG.
１」０連１
Ｐｂ０％Ｌａ、Ｏ，、ＺｒＯ，、Ｔｉｅ、およびＮｄ、
Ｏ，、Ｅｕ、Ｏ，の粉末をそれぞれＣＰｂ＊、＠ Ｌａ
ｍ、＠ＩＩ Ｎｄ０．ｍ＊＊ Ｅｕ＠、Ｉｌｌ、）（ｚ
ｒ＠、＠Ｉｔ Ｔｌｓ、ａｍ）Ｏｓ組成となるように秤
量し、ボールミルにて２０時間のアルコール湿式混合、
９００℃、２時間の仮焼、更にボールミルにてアルコー
ル湿式粉砕を行い、上記組成の粉末を得た。1” 0 series 1 Pb0%La, O,, ZrO,, Tie, and Nd,
The powders of O,, Eu, and O are respectively CPb* and @La
m, @II Nd0. m** Eu@, Ill, )(z
r@, @It Tls, am) Weighed so as to have the Os composition, and wet-mixed with alcohol in a ball mill for 20 hours.
Calcination was performed at 900° C. for 2 hours, followed by alcohol wet pulverization in a ball mill to obtain a powder having the above composition.
この粉体６０ｇを円柱状に一軸加圧プレス、ＣＩＰ成形
し、ＰｂＯ含有酸素雰囲気中にて１２００℃、５０時間
の常圧焼結を行った。60 g of this powder was subjected to uniaxial pressure pressing and CIP molding into a cylindrical shape, and normal pressure sintering was performed at 1200° C. for 50 hours in a PbO-containing oxygen atmosphere.
この焼結体より厚さ０．３ｗｕｎのウェハを切り出し、
両面を鏡面研磨した後、実施例Ｉと同様に蛍光分光光度
計にて紫外光（２００〜３００ｎｍ）を照射し、蛍光ス
ペクトルを測定した。A wafer with a thickness of 0.3 wun was cut out from this sintered body,
After mirror-polishing both sides, as in Example I, ultraviolet light (200 to 300 nm) was irradiated using a fluorescence spectrophotometer to measure the fluorescence spectrum.
この結果、６１０．９１０．１０６０％＋３４０ｎｍの
発光ピークが認められ、複数のランタノイドの混合物か
らの蛍光も効果的であることが判明した。As a result, an emission peak of 610.910.1060%+340 nm was observed, indicating that fluorescence from a mixture of multiple lanthanoids is also effective.
且里皇羞呈
（１） Ｐ Ｌ Ｚ Ｔ製造工程に若干の変更を加え
るだけで比較的透明なＰＬＺＴ系蛍光体を提供すること
ができる。Relatively transparent PLZT-based phosphor can be provided by simply making some changes to the PLZT manufacturing process.
（２） 添加するランタノイドの種類を変更すること
により、種々の波長の蛍光体を容易に得ることができる
。(2) By changing the type of lanthanoid added, phosphors with various wavelengths can be easily obtained.
（３） 複数のランタノイドを添加することにより、
複数の発光ピークを有する蛍光体を得ることができる。(3) By adding multiple lanthanoids,
A phosphor having multiple emission peaks can be obtained.
（４） Ｐ Ｌ Ｚ Ｔの電気光学効果を利用し、光
制御が可能な複合的機能をもった蛍光体を得ることがで
きる。(4) By utilizing the electro-optical effect of PLZT, it is possible to obtain a phosphor with multiple functions that can be controlled by light.
第１図は、Ｅｕを添加したＰＬＺＴの発光特性の一例を
示す。
第２図は、蛍光スペクトルを測定したときの最強線とそ
のピークの波長位置を示した一例である。FIG. 1 shows an example of the luminescent characteristics of PLZT doped with Eu. FIG. 2 is an example showing the strongest line and the wavelength position of its peak when a fluorescence spectrum is measured.
Claims (2)
ｘ＝１ ｙ＋ｚ＝１）において、Ｌａの一部又は全部を
他の一種類又は複数種のランタノイドに置き換えたこと
を特徴とするＰＬＺＴ系蛍光体。(1) Compositional formula of PLZT (PbwLax) (ZryTiz)O_3 (however, w+
x=1 y+z=1), a PLZT-based phosphor characterized in that part or all of La is replaced with one or more other types of lanthanoids.
、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｏであるこ
とを特徴とする特許請求の範囲第１項に記載のＰＬＺＴ
系蛍光体。（３）ｘの範囲が０より大であり、かつ０．
２よりも小なることを特徴とする特許請求の範囲第１項
に記載のＰＬＺＴ系蛍光体。(2) Types of lanthanoids are Pr, Nd, Sm, Eu
, Gd, Tb, Dy, Ho, Er, Tm, Yo.
system phosphor. (3) The range of x is greater than 0, and 0.
2. The PLZT-based phosphor according to claim 1, wherein the PLZT-based phosphor is smaller than 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1338086A JPH03200891A (en) | 1989-12-28 | 1989-12-28 | Plzt phosphor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1338086A JPH03200891A (en) | 1989-12-28 | 1989-12-28 | Plzt phosphor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03200891A true JPH03200891A (en) | 1991-09-02 |
Family
ID=18314774
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1338086A Pending JPH03200891A (en) | 1989-12-28 | 1989-12-28 | Plzt phosphor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03200891A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010110156A1 (en) * | 2009-03-23 | 2010-09-30 | 株式会社ノリタケカンパニーリミテド | Fluorescent zirconia material |
-
1989
- 1989-12-28 JP JP1338086A patent/JPH03200891A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010110156A1 (en) * | 2009-03-23 | 2010-09-30 | 株式会社ノリタケカンパニーリミテド | Fluorescent zirconia material |
| JP2010222466A (en) * | 2009-03-23 | 2010-10-07 | Noritake Co Ltd | Fluorescent zirconia material |
| US8685278B2 (en) | 2009-03-23 | 2014-04-01 | Noritake Co., Limited | Fluorescent zirconia material |
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