JPH02167893A - Production of single crystal of lead titanate - Google Patents
Production of single crystal of lead titanateInfo
- Publication number
- JPH02167893A JPH02167893A JP32178288A JP32178288A JPH02167893A JP H02167893 A JPH02167893 A JP H02167893A JP 32178288 A JP32178288 A JP 32178288A JP 32178288 A JP32178288 A JP 32178288A JP H02167893 A JPH02167893 A JP H02167893A
- Authority
- JP
- Japan
- Prior art keywords
- single crystal
- melt
- crystal
- mol
- lead titanate
- 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
- 239000013078 crystal Substances 0.000 title claims abstract description 51
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000000155 melt Substances 0.000 claims abstract description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910000464 lead oxide Inorganic materials 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims abstract 3
- 238000001816 cooling Methods 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 229910003781 PbTiO3 Inorganic materials 0.000 abstract description 12
- 239000008710 crystal-8 Substances 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 2
- 230000001376 precipitating effect Effects 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 7
- 230000004907 flux Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 239000013081 microcrystal Substances 0.000 description 4
- 238000007716 flux method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 239000012212 insulator Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000006854 communication Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- FPHIOHCCQGUGKU-UHFFFAOYSA-L difluorolead Chemical compound F[Pb]F FPHIOHCCQGUGKU-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000048 melt cooling Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は、純度の高い大型単結晶を得る標準的な手段
として、目的とする結晶を同一組成の融液から種子結晶
によって引き上げるチョクラルスキー法を原型とするチ
タン酸鉛単結晶の製造方法に関するものである。[Detailed Description of the Invention] [Industrial Application Field] This invention is a standard method for obtaining large single crystals with high purity. The present invention relates to a method for manufacturing lead titanate single crystals using the method as a prototype.
ＰｂＴｉＯ３（チタン酸鉛）は４９０ｔｌ：１７）高い
キュリー点を示す強誘電物質であり、高温まで使用でき
る圧電材料として、また、比誘電率が小さく高周波用に
も適している等の特徴を持っている。PbTiO3 (lead titanate) is a ferroelectric material that exhibits a high Curie point of 490 tl: 17), and has the characteristics of being a piezoelectric material that can be used up to high temperatures, and that it has a small dielectric constant and is suitable for high frequency applications. There is.
ところで、ＰｂＴｉ０．は焼結が困難であり、抗電界が
非常に大きいため分極が難しく実用材料として開発が遅
れており、良質の大型単結晶を得ることが期待されてい
る。By the way, PbTi0. It is difficult to sinter, and its coercive electric field is extremely large, making it difficult to polarize, so its development as a practical material has been delayed, and it is hoped that it will be able to produce high-quality, large-sized single crystals.
このようにＰ ｂ Ｔ ｉ Ｏｓの単分域の良質な単結
晶が得られていない理由の一つとして、ＰｂＴｉＯ３が
１２８５℃という高温で融解するため、有毒なＰｂＯの
蒸発が激しく、そのまま融解してから単結晶を育成する
方法が困難であることがあげられる。そのため、融剤を
用いて結晶育成温度を低くするフラックス法が、この単
結晶の育成に専ら用いられており、融剤の種類も多数報
告されているが、育成されている単結晶の大きさは５ｍ
ｍ角程度にすぎないという問題点があった。［Ｊ、Ｐ。One of the reasons why high-quality single crystals of PbTiOs in a single domain have not been obtained is that PbTiO3 melts at a high temperature of 1285°C, which causes rapid evaporation of toxic PbO. One problem is that it is difficult to grow single crystals after this process. Therefore, the flux method, which uses a flux to lower the crystal growth temperature, is exclusively used to grow this single crystal, and although many types of flux have been reported, the size of the single crystal grown is 5m
There was a problem that it was only about m square. [J, P.
Ｒｅｍｅｉｋａ ａｎｄ Ａ、Ｍ、Ｇｌａｓｓ
Ｍａｔ、Ｒｅｓ、Ｂｕｌｌ、Ｖｏｌ、５Ｐ、３７ （１
９７０）参照］
従来のフラックス法では［小林托三、ＰｂＴｉＯ３およ
びＣａ２ Ｓ ｒ （Ｃ２Ｏ５ＣＯ２）ａの結晶成長１
日本物理学会誌２０巻３号２０３頁参照コ、Ｐｋ）Ｏ，
ＫＦ、ＰｂＦ２ 、Ｖ２０ｓ等の融剤にＰｂＴｉＯ３を
混入し、結晶育成後に融剤だけを薬品で取り去るか、徐
冷中にるつぼを炉から取り出して固化していない融剤だ
けを捨て去ってＰｂＴｉＯ３単結晶を取り出してきた。Remeika and A, M, Glass
Mat, Res, Bull, Vol, 5P, 37 (1
970)] Conventional flux method [Takuzo Kobayashi, Crystal growth of PbTiO3 and Ca2S r (C2O5CO2)a 1
See Journal of the Physical Society of Japan, Vol. 20, No. 3, p. 203, Pk) O,
PbTiO3 is mixed into a flux such as KF, PbF2, V20s, etc., and only the flux is removed with chemicals after crystal growth, or the crucible is removed from the furnace during slow cooling, only the unsolidified flux is discarded, and the PbTiO3 single crystal is taken out. It's here.
このように薬品を用いて長い時間を要したり、危険な操
作をしないと融液の固化物とＰ ｂ Ｔ ｉ Ｏ３単結
晶の分離はできないという問題点があった。As described above, there was a problem that the solidified product of the melt and the P b T i O3 single crystal could not be separated without using chemicals, taking a long time, or performing dangerous operations.
この発明は、上記のような問題点を解決するためになさ
れたもので、ｐｂｏ （酸化鉛）とＴｉＯ２（酸化チタ
ン）とを混合し、その融液中に析出してくるＰｂＴｉＯ
３微結晶を種子結晶上に結晶化させてＰ ｂ Ｔ ｉ
Ｏｓ単結晶を製造するチタン酸鉛単結晶の製造方法を得
ることを目的とする。This invention was made in order to solve the above-mentioned problems.Pbo (lead oxide) and TiO2 (titanium oxide) are mixed, and the PbTiO precipitated in the melt is
3. Crystallize the microcrystals on the seed crystal to form P b T i
The object of the present invention is to obtain a method for producing a lead titanate single crystal for producing an Os single crystal.
この発明に係るチタン酸鉛単結晶の製造方法は、酸化鉛
を８８．０〜７５．０モル％、酸化チタンを１２．０〜
２５．０モル％の範囲の組成に混合した原料を１１５０
〜８３８℃において加熱融解した後に、その融液を降温
させることによりチタン酸鉛単結晶を析出させ、種子結
晶に育成させて引き上げるものである。The method for producing a lead titanate single crystal according to the present invention includes 88.0 to 75.0 mol% of lead oxide and 12.0 to 75.0 mol% of titanium oxide.
1150% of raw materials mixed with a composition in the range of 25.0 mol%
After heating and melting at ~838°C, the temperature of the melt is lowered to precipitate a lead titanate single crystal, which is then grown into a seed crystal and pulled up.
〔作用）
この発明において、目的物であるＰ ｂ Ｔ ｉ Ｏ３
を析出させ得る組成範囲内にｐｂｏとＴ ｉ ０２を混
合し、その融液を降温させることにより融液中に析出し
てくるＰｂＴｉＯ３微結晶を融液に接触させた種子結晶
上に結晶化させ、これを溶液引き上げ法によってＰｂＴ
ｉＯ３単結晶を製造する方法である。[Operation] In this invention, the target product P b T i O3
By mixing pbo and T i 02 within a composition range that can precipitate the melt and lowering the temperature of the melt, the PbTiO3 microcrystals precipitated in the melt are crystallized on the seed crystals in contact with the melt. , this was made into PbT using the solution pulling method.
This is a method for producing iO3 single crystal.
（実施例）
まず、この発明の原理について説明する。第１図はＰ
ｂ Ｏ−Ｔ ｉ Ｏ２系の相平衡図である［Ｄ、Ｅ。(Example) First, the principle of this invention will be explained. Figure 1 is P
b Phase equilibrium diagram of the O-T i O2 system [D,E.
Ｒａ５ｅ （１９６３） ｐａｒｓｏｎａｌ ｃｏｍｍ
ｕｎｉｃａｔｉｏｎ Ｂ、Ｊａｆｆｅ。Ra5e (1963) personal comm
unication B, Jaffe.
Ｗ、Ｒ，Ｃｏｏｋ Ｊｒ ａｎｄ ＨＪａｆｆｅ Ｐｉ
ｅｚｏｅｌｅｃｔｒｉｃ Ｃｅｒａｍ−ｉｃｓ Ｐ、１
１７ Ａｃａｄｅｍｉｃ Ｐｒｅｓｓ Ｌｏｎｄｏｎ
＆ Ｎｅｗ Ｙｏｒｋ（１９７１）参照］。W, R, Cook Jr and HJaffe Pi
ezoelectric Ceram-ics P, 1
17 Academic Press London
& New York (1971)].
この図において、ＰｂＯが過剰の８６．０〜５０．１モ
ル％、ＴｉＯ２が１４．０〜４９．９モル％の組成に混
合した原料を１２８５〜８３８℃に加熱融解したのち、
融液を徐々に降温させると過飽和溶液となりＰ ｂ Ｔ
ｉ Ｏ３が固相となって析出してくることを示してい
る。この発明はこれを利用し、ｐｂｏの蒸発の障害が事
実上問題とならないｐｂｏが８８．０〜７５．０モル％
、ＴｉＯ２が１２．０〜２５．０モル％の組成範囲の融
液から種子結晶上に析出してきたＰ ｂ Ｔ ｉ Ｏ３
微結晶を育成させて引き上げる方法をとったものである
。In this figure, after heating and melting a raw material containing an excess of 86.0 to 50.1 mol% of PbO and a composition of 14.0 to 49.9 mol% of TiO2 at 1285 to 838°C,
When the temperature of the melt is gradually lowered, it becomes a supersaturated solution and P b T
This shows that i O3 becomes a solid phase and precipitates. This invention takes advantage of this, and the pbo concentration is 88.0 to 75.0 mol%, in which impediment to pbo evaporation is virtually no problem.
, P b Ti O3 precipitated on seed crystals from a melt with a composition range of 12.0 to 25.0 mol % TiO2.
This method involves growing microcrystals and pulling them up.
第２図はこの発明を実施するためのＰｂＴｉＯ３の製造
装置を示す構成図である。なお、この製造装置は有毒の
ｐｂｏ蒸気を製造者からＶＦＡｉｌｉｆｆするための結
晶育成観察窓付の容器に入っている。FIG. 2 is a block diagram showing a PbTiO3 manufacturing apparatus for carrying out the present invention. Note that this production equipment is housed in a container with a crystal growth observation window for VFAiliffing toxic PBO vapor from the manufacturer.
この図で、１は水冷シャフト、２は白金シャフト、３は
保温材、４は高周波加熱コイル、５は熱電対 ６はる
つぼ支持物、７は種子結晶、８はＰ ｂＴ ｉ Ｏ３単
結晶、９は出発原料、１０は白金るつぼである。In this figure, 1 is a water cooling shaft, 2 is a platinum shaft, 3 is a heat insulator, 4 is a high frequency heating coil, 5 is a thermocouple, 6 is a crucible support, 7 is a seed crystal, 8 is a P bT i O3 single crystal, 9 is the starting material, and 10 is the platinum crucible.
次に製造方法について説明する。Next, the manufacturing method will be explained.
出発原料９は、−例としてＰｂＯを８５モル％、ＴｉＯ
２を１５モル％の組成に混合し、第２図に示す口径５５
ｍｍ、高さ４０ｍｍの発熱体を兼ねた白金るつぼ１０に
４００ｇ入れ、高周波加熱コイル４による誘電加熱方式
により〜９００℃まで加熱して融解させた後、種子結晶
７を融液表面に接触させる。融液を徐々に降温させると
、融液中で最も温度の低い種子結晶７と接触している融
液の界面にＰｂＴｉＯ３の微結晶が少しずつ析出してき
て種子結晶７上に結晶化する。このようにして成長した
Ｐ ｂ Ｔ ｉ ０３単結晶８を融液から徐々に引き上
げる。すなわち、融液を降温しながら育成されたＰｂＴ
ｉＯ３単結晶８の引き上げを同時に行っていくのである
。このときの製造条件としては、Ｐ ｂ Ｔ ｉ Ｏ３
！＃拮晶８の引き上げ速度は０ 、 ２〜１ ｍ ｍ
／ ｈ 、融液降温速度１〜ｂｈ５結晶回転数３０〜５
０ｒｐｍ、雰囲気は空気中である。また、ＰｂＴｉＯ３
単結晶８の育成を完了するまでに要する時間は、１４Ｘ
１４Ｘ６ｍｍの大きさで約７ｇの単結晶を得るのに１１
時間要しただけであった。結晶は黄褐色をしており、四
角い品位の表われたものが得られた。有毒なｐｂｏの蒸
発は約１２ｇであった。Starting material 9 contains - for example 85 mol% PbO, TiO
2 to a composition of 15 mol%, and the diameter 55 shown in FIG.
400 g is placed in a platinum crucible 10 having a height of 40 mm and serving as a heating element, and is heated to ~900° C. by a dielectric heating method using a high frequency heating coil 4 to melt it, and then a seed crystal 7 is brought into contact with the surface of the melt. When the temperature of the melt is gradually lowered, microcrystals of PbTiO3 gradually precipitate at the interface of the melt that is in contact with the seed crystal 7, which has the lowest temperature in the melt, and are crystallized on the seed crystal 7. The P b T i 03 single crystal 8 grown in this way is gradually pulled out of the melt. In other words, PbT grown while cooling the melt
The iO3 single crystal 8 is pulled at the same time. The manufacturing conditions at this time are P b T i O3
! #The pulling speed of the crystal 8 is 0, 2~1 mm
/ h, melt cooling rate 1~bh5 crystal rotation number 30~5
0 rpm, the atmosphere is air. Also, PbTiO3
The time required to complete the growth of single crystal 8 is 14X
11 to obtain a single crystal of about 7 g with a size of 14 x 6 mm.
It just took time. The crystals were yellowish-brown in color and square in shape, showing good quality. Evaporation of toxic pbo was approximately 12 g.
なお、第１図ではｐｂｏが８８モル％、ＴｉＯ２が１２
モル％の組成ではＰｂＯが析出し、ＰｂＴｉＯ３が析出
しないことが示されているが、同組成で上記と同じ条件
、操作によりＰｂＴ ｉ Ｏ３単結晶８を育成すること
ができた。また、ｐｂｏが８０モル％、ＴｉＯ２が２０
モル％までの組成については同じ条件、操作によりｐｂ
Ｔｉｅ、単結晶８を育成できることを確かめた。In addition, in Figure 1, pbo is 88 mol% and TiO2 is 12 mol%.
Although it has been shown that PbO precipitates and PbTiO3 does not precipitate with a composition of mol %, PbT i O3 single crystal 8 was able to be grown with the same composition and under the same conditions and operations as above. In addition, pbo is 80 mol%, TiO2 is 20
Regarding the composition up to mol%, pb
Tie confirmed that single crystal 8 can be grown.
ｐｂｏが８８モル％以下、ＴｉＯ□が１２モル％以上と
第１図において、ＴｉＯ２の組成比が増える組成の融液
はど結晶育成温度が上昇し、ｐｂ。In Fig. 1, when pbo is 88 mol% or less and TiO□ is 12 mol% or more, the crystal growth temperature of the melt increases as the composition ratio of TiO2 increases, and pb.
の蒸発が激しくなり、結晶育成が困難になってくると思
われる。It is thought that evaporation of the crystals will become more intense and crystal growth will become difficult.
以上説明したようにこの発明は、酸化鉛を８８．０〜７
５．０モル％、酸化チタンを１２．０〜２５．０モル％
の範囲の組成に混合した原料を１１５０〜８３８℃にお
いて加熱融解した後に、その融液を降温させることによ
りチタン酸鉛単結晶を析出させ、種子結晶に育成させて
ひきあげるようにしたので、従来のフラックス法で育成
された単結晶が５ｍｍ角程度の大きさであるのと比較す
ると、１４Ｘ１４Ｘ６ｍｍの大きさの単結晶が種子結晶
により良質で望みの方向に成長したものが固化した融剤
の除去操作なしに得られるという利点を有する。As explained above, this invention uses lead oxide of 88.0 to 7
5.0 mol%, titanium oxide 12.0-25.0 mol%
After heating and melting a raw material mixed with a composition in the range of 1150 to 838 degrees Celsius, the temperature of the melt is lowered to precipitate a lead titanate single crystal, grow it into a seed crystal, and pull it up. Compared to the size of a single crystal grown by the flux method, which is about 5 mm square, a single crystal with a size of 14 x 14 x 6 mm grows in good quality and in the desired direction using seed crystals.The flux removal operation solidifies the single crystal. It has the advantage that it can be obtained without
第１図はこの発明の詳細な説明するためのｐｂＯ−Ｔｉ
０２系の平衡図、第２図はこの発明を実施するためのＰ
ｂ Ｔ ｉ Ｏｓ単結晶の製造装置の構成図である。
図中、１は水冷シャフト、２は白金シャフト、３は保温
材、４は高周波加熱コイル、５は熱電対、６はるつぼ支
持物、７は種子結晶、８はｐｂＴｉＯａ−ｌ結晶、９は
出発原料、１０は白金るつぼである。
□ＢβＢ８８８８呉委奈β□案
第
図
ト
フに冷シャフト
１０二
白金すつは−Figure 1 shows pbO-Ti for detailed explanation of this invention.
The equilibrium diagram of the 02 system, Figure 2 is the P for implementing this invention.
b It is a block diagram of the manufacturing apparatus of a TiOs single crystal. In the figure, 1 is a water cooling shaft, 2 is a platinum shaft, 3 is a heat insulator, 4 is a high frequency heating coil, 5 is a thermocouple, 6 is a crucible support, 7 is a seed crystal, 8 is a pbTiOa-l crystal, and 9 is a starting point. The raw material 10 is a platinum crucible. □BβB8888 Kure Konnaβ □Draft diagram Toph and cold shaft 10 two platinum Tsuha-
Claims (1)
．０〜２５．０モル％の範囲の組成に混合した原料を１
１５０〜８３８℃において加熱融解した後に、その融液
を降温させることによりチタン酸鉛単結晶を析出させ、
種子結晶に育成させて引き上げることを特徴とするチタ
ン酸鉛単結晶の製造方法。88.0 to 75.0 mol% lead oxide, 12% titanium oxide
．． 1 raw material mixed with a composition in the range of 0 to 25.0 mol%
After heating and melting at 150 to 838°C, lead titanate single crystal is precipitated by cooling the melt,
A method for producing a lead titanate single crystal, which is characterized by growing a seed crystal and pulling it.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32178288A JPH02167893A (en) | 1988-12-20 | 1988-12-20 | Production of single crystal of lead titanate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32178288A JPH02167893A (en) | 1988-12-20 | 1988-12-20 | Production of single crystal of lead titanate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02167893A true JPH02167893A (en) | 1990-06-28 |
| JPH0478595B2 JPH0478595B2 (en) | 1992-12-11 |
Family
ID=18136364
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32178288A Granted JPH02167893A (en) | 1988-12-20 | 1988-12-20 | Production of single crystal of lead titanate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02167893A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6479923B1 (en) * | 1998-05-29 | 2002-11-12 | Murata Manufacturing Co., Ltd. | Piezoelectric ceramic, method for producing piezoelectric ceramic, and piezoelectric oscillator |
-
1988
- 1988-12-20 JP JP32178288A patent/JPH02167893A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6479923B1 (en) * | 1998-05-29 | 2002-11-12 | Murata Manufacturing Co., Ltd. | Piezoelectric ceramic, method for producing piezoelectric ceramic, and piezoelectric oscillator |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0478595B2 (en) | 1992-12-11 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |