U.S. patent application number 10/879364 was filed with the patent office on 2004-11-25 for batio3-pbtio3 series single crystal and method of manufacturing the same, piezoelectric type actuator and liquid discharge head using such piezoelectric type actuator.
This patent application is currently assigned to Canon Kabushiki Kaisha. Invention is credited to Aoto, Hiroshi, Fukui, Tetsuro, Ikesue, Akio, Unno, Akira.
Application Number | 20040231581 10/879364 |
Document ID | / |
Family ID | 18849501 |
Filed Date | 2004-11-25 |
United States Patent
Application |
20040231581 |
Kind Code |
A1 |
Aoto, Hiroshi ; et
al. |
November 25, 2004 |
BaTiO3-PbTiO3 series single crystal and method of manufacturing the
same, piezoelectric type actuator and liquid discharge head using
such piezoelectric type actuator
Abstract
BaTiO.sub.3--PbTiO.sub.3 series single crystal is
single-crystallized by heating BaTiO.sub.3--PbTiO.sub.3 compact
powder member or sintered member having a smaller Pb-containing mol
number than Ba-containing mol number, while keeping the powder or
substance in non-molten condition. In this way, this single crystal
can be manufactured at a crystal growing speed faster still and
stabilized more, significantly contributing to improving the
dielectric loss and electromechanical coupling coefficient for the
provision of excellent BaTiO.sub.3--PbTiO.sub.3 series single
crystal in various properties, as well as for the provision of
piezoelectric material having a small ratio of lead content, which
is particularly excellent in piezoelectric property and
productivity.
Inventors: |
Aoto, Hiroshi; (Kanagawa,
JP) ; Unno, Akira; (Kanagawa, JP) ; Fukui,
Tetsuro; (Kanagawa, JP) ; Ikesue, Akio;
(Aichi, JP) |
Correspondence
Address: |
FITZPATRICK CELLA HARPER & SCINTO
30 ROCKEFELLER PLAZA
NEW YORK
NY
10112
US
|
Assignee: |
Canon Kabushiki Kaisha
Tokyo
JP
|
Family ID: |
18849501 |
Appl. No.: |
10/879364 |
Filed: |
June 30, 2004 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10879364 |
Jun 30, 2004 |
|
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10014355 |
Dec 14, 2001 |
|
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6783588 |
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Current U.S.
Class: |
117/2 |
Current CPC
Class: |
C30B 1/00 20130101; H01L
41/39 20130101; H01L 41/1871 20130101; C04B 35/4684 20130101; C30B
29/32 20130101 |
Class at
Publication: |
117/002 |
International
Class: |
C30B 001/00 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 15, 2000 |
JP |
2000-381522 |
Claims
1. BaTiO.sub.3--PbTiO.sub.3 series single crystal
single-crystallized by heating BaTiO.sub.3--PbTiO.sub.3 compact
powder member or sintered member having a smaller Pb-containing mol
number than Ba-containing mol number, while keeping said powder or
member in non-molten condition.
2. BaTiO.sub.3--PbTiO.sub.3 series single crystal according to
claim 1, wherein the rearrangement density is 10.sup.2
pieces/cm.sup.2 or more and 10.sup.6 pieces/cm.sup.2 or less, and
the ratio of pore content is within a range of 1 volume ppm or more
and 5 volume % or less.
3. BaTiO.sub.3--PbTiO.sub.3 series single crystal according to
claim 1, wherein the ratio of PbTiO.sub.3 content is 45 mol % or
less.
4. BaTiO.sub.3--PbTiO.sub.3 series single crystal according to
claim 3, wherein the ratio of PbTiO.sub.3 content is 30 mol % or
less.
5. BaTiO.sub.3--PbTiO.sub.3 series single crystal according to
claim 4, wherein the ratio of PbTiO.sub.3 content is 25 mol % or
less.
6. BaTiO.sub.3--PbTiO.sub.3 series single crystal according to
claim 1, wherein the volume of said single crystal is 1 mm.sup.3 or
more.
7. A piezoelectric type actuator comprising: a layer formed by
BaTiO.sub.3--PbTiO.sub.3 series single crystal according to claim
1.
8. A liquid discharge head comprising: the piezoelectric type
actuator according to claim 7.
9. BaTiO.sub.3--PbTiO.sub.3 series single crystal having the
rearrangement density of 10.sup.2 pieces/cm.sup.2 or more and
10.sup.6 pieces/cm.sup.2 or less, and the ratio of pore content
being within in a range of 1 volume ppm or more and 5 volume % or
less.
10. BaTiO.sub.3--PbTiO.sub.3 series single crystal according to
claim 9, wherein the ratio of PbTiO.sub.3 content is 45 mol % or
less.
11. A piezoelectric type actuator comprising: a layer formed by
BaTiO.sub.3--PbTiO.sub.3 series single crystal according to claim
9.
12. A liquid discharge head comprising: the piezoelectric type
actuator according to claim 11.
13-24. (Cancelled)
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to the
BaTiO.sub.3--PbTiO.sub.3 series single crystal that can be utilized
as a piezoelectric element, for example, and also, relates to the
method of manufacturing the same. Further, the invention relates to
a piezoelectric type actuator formed by the
BaTiO.sub.3--PbTiO.sub.3 series single crystal, and the liquid
discharge head that uses such piezoelectric type actuator as
well.
[0003] 2. Related Background Art
[0004] The BaTiO.sub.3 series single crystal is a nonlinear optical
crystal utilized for optical communications, information
processing, or the like, and having a great marketability, which is
not only used as a phase conjugate wave generating medium for a
high resolution image processing, a real-time hologram, or a laser
resonator, but also, used as a highly capable piezoelectric
material if the crystallization thereof can be implemented at lower
costs.
[0005] Now, obviously, the composition of the BaTiO.sub.3 makes it
difficult to obtain single crystal directly from the BaTiO.sub.3
solution when BaTiO.sub.3 series single crystal is manufactured.
Therefore, only the flux growth that uses solution (flux) having
fluoride and chloride as main component or the method, in which the
BaTiO.sub.3 series single crystal of low-temperature component is
picked up directly by making the composition of the solution
TiO.sub.2 rich (the so-called top seeded solution growth (TSSG
method)), is applicable to the growth thereof. With the flux
growth, the obtainable size is only 1 mm.sup.3 or less
approximately. Also, for the TSSG method, not only an expensive
noble metal crucible, such as a platinum crucible, is needed, but
the growing speed is slow to make the manufacturing costs extremely
high.
[0006] Conventionally, it has been attempted to provide a method
for manufacturing larger BaTiO.sub.3 series single crystal more
effectively and easily with the improvement of the aspects that
present the problems as described above.
[0007] For example, there are experiments carried out in
manufacturing BaTiO.sub.3 series single crystal efficiently by
sintering method. In the specifications of Japanese Patent
Application Laid-Open Nos. 4-300296, 5-155696 and 5-155697, a
method for manufacturing BaTiO.sub.3 series single crystal is
disclosed, in which the BaTiO.sub.3 series single crystal serving
as the seed crystal is coupled with the BaTiO.sub.3 polycrystal,
and heated to mono-crystalize such polycrystal by means of
solid-phase reaction. In the specification of Japanese Patent
Application Laid-Open No. 9-263496, a method for manufacturing
BaTiO.sub.3 series single crystal is disclosed, in which a
temperature gradient is given to the BaTiO.sub.3 micro-crystal
granular aggregate, the mol ratio of Ti/Ba of which is 1.0 or more
and 1.1 or less, for the execution of single crystallization
thereof. With these methods, however, the mono-crystalline growth
rate greatly varies to make it impossible to grow any bulky single
crystal with good reproducibility. Also, the rearrangement density
is high, and the crystallinity of the BaTiO.sub.3 series single
crystal thus obtained is inferior to the one obtained by the
conventional TSSG method and the flux method. There are also the
examples of solid-phase methods other than the sintering method. In
the specification of Japanese Patent Application Laid-Open No.
59-3091, there is the disclosure of a method for manufacturing the
oxide single crystal, in which a crystal oxide, such as
PbTiO.sub.3, BaTiO.sub.3, SrTiO.sub.3, CaTiO.sub.3, is quenched and
solidified after molten to make it amorphous, and then,
re-crystallized under a temperature gradient. This method makes the
manufacturing apparatus and process complicated, because there is a
need for a process to melt the crystal oxide. Also, the single
crystal thus obtained has inferior crystallization properties, and
only the crystal that has a high ratio of pore content is
obtainable eventually.
[0008] Also, improvement studies have been made on the TSSG method
and the flux method. In the specification of Japanese Patent
Application Laid-Open No. 6-321698, there is disclosed, as the flux
method, a method for manufacturing BaTiO.sub.3 using a mixed
substance of BaF.sub.2, NaF, Li.sub.2MoO.sub.4, or the like as
flux. In this method, the solubility of BaTiO.sub.3 is enhanced for
the purpose of obtaining bulky BaTiO.sub.3 series single crystal
with a long-time crystal growth. However, this method is not fully
satisfactory in terms of the time required for manufacturing and
costs. In the specification of Japanese Patent Application
Laid-Open No. 9-59096, there is disclosed BaTiO.sub.3 series single
crystal having the doping of fine quantities of Mg and Fe. This
material aims at obtaining a high photo-refractivity in the near
infrared range, but Mg, Fe, or some other element, which may exert
unfavorable influence on the piezoelectric property, is contained
in that material. As a result, it is not preferable to use this as
a piezoelectric material. Also, for the utilization at the
industrial level, it is not satisfactory in terms of the time
required for manufacture and costs.
[0009] As described above, the TSSG or flux method for
manufacturing BaTiO.sub.3 series single crystal makes it extremely
difficult to improve problems related to manufacturing efficiency,
such as the time required for manufacturing and costs, among some
others. Here, although the sintering method is anticipated to
enhance the manufacturing efficiency, the variation of growing
speed of BaTiO.sub.3 series single crystal makes it impossible to
obtain any satisfactory result, and also, the crystallinity of the
BaTiO.sub.3 series single crystal thus obtained is inferior to the
one obtainable by means of TSSG or flux method. In other words, it
has been difficult to implement the manufacture of BaTiO.sub.3
series single crystal having excellent crystallinity and property
in a shorter period of time at lower costs.
SUMMARY OF THE INVENTION
[0010] For the formation of BaTiO.sub.3 series single crystal by
sintering method, the inventors hereof have attempted to make the
enhancement of the reproducibility of single crystal growth
compatible with the enhancement of crystallinity and other
substances by adding other component to BaTiO.sub.3 itself. With
this in view, the inventors hereof have studied assiduously, with
the result that a system, in which PbTiO.sub.3 is added to
BaTiO.sub.3, is found to enable a crystallization growth to occur
with an extremely fine reproducibility, satisfied only with a
predetermined condition. Therefore, the studies have been made
further in detail on the BaTiO.sub.3--PbTiO.sub.3 system to design
the present invention completely.
[0011] The inventors hereof have measured the crystallinity of the
BaTiO.sub.3--PbTiO.sub.3 series single crystal obtained in
accordance with the present invention. As a result, it is found
that the BaTiO.sub.3--PbTiO.sub.3 of the present invention is
extremely fine in the crystallinity thereof. It is also confirmed
by the X-ray diffraction and electron beam diffraction that the
crystal orientation of the single crystal is completely coincident.
Also, by the observation of etch pit, which will be described
later, it is confirmed that the rearrangement density of the
crystal is low, and that from this observation, the excellent
crystal has a small amount of lattice defect. The ratio of pore
content is also extremely small.
[0012] Following this, the other properties of the
BaTiO.sub.3--PbTiO.sub.- 3 series single crystal, such as
permittivity, piezoelectric property, and pyroelectric property,
among some others, are examined. As a result, it is found that the
piezoelectric property is excellent in particular, which is far
superior to the property of PZT (Pb (Ti, Zr) O.sub.3) polycrystal
currently used as standards, or that of BaTiO.sub.3 series single
crystal manufactured by means of the TSSG method, not to mention
that of BaTiO.sub.3 polycrystal.
[0013] From the viewpoint of the BaTiO.sub.3--PbTiO.sub.3 series
single crystal as a piezoelectric material, it has such advantages
as the wide range of temperatures at which it can be used, and the
lower amount of lead content that it has attained, as well as the
excellent piezoelectric property that it can provide. The curie
temperature of BaTiO.sub.3 series single crystal is approximately
120.degree. C. (T.sub.c). Any element that uses the BaTiO.sub.3
series single crystal has a narrow usable temperature range due to
low T.sub.c as practical drawbacks. The BaTiO.sub.3--PbTiO.sub.3
series single crystal of the present invention has a higher curie
temperature (T.sub.c) than the aforesaid BaTiO.sub.3 polycrystal to
make it possible to make the range of usable temperature
larger.
[0014] Also, in order to reduce the load to the environment on
earth, it is required to reduce the amount of lead to be used for
any industrial product in recent years. As compared with the PZT
polycrystal, which presents the main current of piezoelectric
material at present, the BaTiO.sub.3--PbTiO.sub.3 series single
crystal of the present invention is found to be able to reduce the
use amount of lead significantly owing to the composition that is
different therefrom, and further, to enhance the piezoelectric
property conspicuously. Also, it has been found that the use amount
of piezoelectric material itself, which is needed for producing the
same effect, is reduced significantly. At present, it is considered
to use BaTiO.sub.3 polycrystal, Bi.sub.0.5Na.sub.0.5TiO.sub.3
series single crystal (Na.sub.0.5K.sub.0.5) NbO.sub.3 polycrystal
as a promising material for substitution of PZT for the purpose of
reducing the lead use amount. However, against the PZT
piezoelectric constant d.sub.33=300 to 400 (.times.10.sup.-12 C/N)
and electromechanical coupling coefficient k.sub.33=0.6 to 0.7, the
BaTiO.sub.3 polycrystal has the piezoelectric constant d.sub.33=120
(.times.10.sup.-12 C/N) and electromechanical coupling coefficient
k.sub.33=0.4 to 0.5, and the Bi.sub.0.5Na.sub.0.5TiO.sub.3 has the
piezoelectric constant d.sub.33=110 (.times.10.sup.-12 C/N) and
electromechanical coupling coefficient k.sub.33=0.4 to 0.6.
Therefore, the piezoelectric property is not satisfactory.
[0015] Also, the piezoelectric property of the
BaTiO.sub.3--PbTiO.sub.3 polycrystal is far inferior in terms of a
piezoelectric material to that of the PZT polycrystal or the
BaTiO.sub.3--PbTiO.sub.3 series single crystal, and there is no way
fundamentally to enhance the piezoelectric property as single
crystal. It is also considered more difficult to manufacture
BaTiO.sub.3--PbTiO.sub.3 series single crystal by the method other
than the one designed by the present invention, such as the flux
method, the TSSG method, or any other melt-solidification method
than to manufacture BaTiO.sub.3 series single crystal. There is no
value that can be found in these methods. As described earlier,
regarding the BaTiO.sub.3 series single crystal, only the small
one, the size of which is approximately 1 mm.sup.3 or less, is
obtainable by means of the flux method. Also, for the TSSG method,
an expensive noble crucible, such a platinum crucible, is needed.
In addition, the growing speed is only 0.1 to 0.2 mm/h
approximately, leading to an extremely high cost of manufacture.
Further, the material loss is great, and there is a drawback that
it is difficult to obtain bulky crystal. Such an extremely high
cost of manufacture is inevitable to make the field of utilization
thereof extremely limited. It has been pointed out that this is
valueless as a material of industrial use. On the functional
aspect, too, impurities tend to be mixed during the single crystal
growing process. There are often the cases where the anticipated
performance cannot be demonstrated after all. It is also
anticipated that there is the same problem regarding the
BaTiO.sub.3--PbTiO.sub.3 series single crystal if it should be
manufactured using the melt-solidification method.
[0016] As the example of a method for manufacturing perovskite
oxide single crystal, there is the discloser in the specification
of Japanese Patent Application Laid-Open No. 9-188597, in which a
process is provided for enabling the perovskite sintered member of
Pb {(Mg.sub.1/3Nb.sub.2/3)- .sub.1-xTi.sub.x} O.sub.3 (in the
aforesaid composition formula, 0.ltoreq.x.ltoreq.0.55. Pb of 10 mol
% or less may be replaced with Ba, Sr, Ca, or the like) to be in
contact with seed crystal, and heated at a temperature of 1,000 to
1,450.degree. C. in the closed container in the lead atmosphere.
However, there is no disclosure of the BaTiO.sub.3--PbTiO.sub.3
series single crystal having a smaller mol number of Pb than that
of Ba. There is also no disclosure as to the effect thereof as a
matter of course. Also, when the ratio between the A site and B
site of the aforesaid perovskite sintered member is 1.00>A/B,
the crystallization speed is remarkably slow. This is the tendency
that differs from the present invention as described later.
[0017] It is an object of the present invention to improve the
dielectric loss and electromechanical coupling coefficient, and
provide excellent BaTiO.sub.3--PbTiO.sub.3 series single crystal in
various properties, such as permittivity, piezoelectric property,
pyroelectric property, and also, to provide
BaTiO.sub.3--PbTiO.sub.3 series single crystal as the piezoelectric
material having a small ratio of lead content, which is
particularly excellent in piezoelectric property and productivity.
It is another object of the invention to provide a method for
manufacturing BaTiO.sub.3--PbTiO.sub.3 series single crystal
capable of manufacturing BaTiO.sub.3--PbTiO.sub.3 series single
crystal efficiently, not by means of the single crystal growth
using the melt-solidification method. It is still another object of
the invention to provide a piezoelectric type actuator using the
BaTiO.sub.3--PbTiO.sub.3 series single crystal, and a liquid
discharge head as well.
[0018] The BaTiO.sub.3--PbTiO.sub.3 series single crystal of the
present invention is single-crystallized by heating
BaTiO.sub.3--PbTiO.sub.3 compact powder member or sintered member
having a smaller Pb-containing mol number than Ba-containing mol
number, while keeping the powder or member in non-molten condition.
The inventors hereof have found that it becomes possible for the
conventional manufacture of BaTiO.sub.3 series single crystal by
means of the sintering method, which is unable to grow single
crystal with good reproducibility, to perform a stable single
crystal growth by adding PbTiO.sub.3 to BaTiO.sub.3 so that the
Pb-containing mol number is made smaller than the Ba-containing mol
number, hence designing the present invention completely.
[0019] It is preferable for the BaTiO.sub.3--PbTiO.sub.3 series
single crystal of the invention that the rearrangement density is
10.sup.2 pieces/cm.sup.2 or more and 10.sup.6 pieces/ m.sup.2 or
less, and the ratio of pore content is within a range of 1 volume
ppm or more and 5 volume % or less. In this way, the
BaTiO.sub.3--PbTiO.sub.3 series single crystal of the invention
makes the dielectric loss smaller, and the electromechanical
coupling coefficient larger. For example, the dielectric loss is 1%
or less, and the electromechanical coupling coefficients exceeds
85%.
[0020] It is preferable for the BaTiO.sub.3--PbTiO.sub.3 series
single crystal of the invention that the ratio of PbTiO.sub.3
content is 45 mol % or less in the BaTiO.sub.3--PbTiO.sub.3 series
single crystal. When the ratio of PbTiO.sub.3 content in the
BaTiO.sub.3--PbTiO.sub.3 compact powder member or sintered member,
which serves as the starting substance, is arranged to be 45 mol %
or less, the single crystal growing speed is promoted more to make
it possible to manufacture the single crystal substance more
stably. Then, the resultant ratio of PbTiO.sub.3 content in the
BaTiO.sub.3--PbTiO.sub.3 series single crystal is the same as the
ratio of PbTiO.sub.3 content in the starting substance. It is
preferable for the BaTiO.sub.3--PbTiO.sub.3 series single crystal
of the invention that the ratio of PbTiO.sub.3 content is 30 mol %
or less, and more preferably, it is 25 mol % or less. If the ratio
of PbTiO.sub.3 content is too much, the evaporation of Pb becomes
conspicuous, and composition changes from the target one, while the
single crystal thus obtained tends to become porous. In order to
suppress the Pb evaporation, it is imperative that a pressurized
container be utilized, presenting a disadvantage that the
manufacturing costs become higher. Also, the minimum amount of
PbTiO.sub.3 content in the BaTiO.sub.3--PbTiO.sub.3 series single
crystal of the invention should preferably be 0.01 mol % or more,
and more preferably, it is 0.02 mol % or more.
[0021] It is preferable for the BaTiO.sub.3--PbTiO.sub.3 series
single crystal of the invention that the volume of the single
crystal is 1 mm.sup.3 or more. The volume of the
BaTiO.sub.3--PbTiO.sub.3 series single crystal of the invention can
easily be made 1 mm.sup.3 or more with the stable crystal growth.
With the volume of 1 mm.sup.3 or more, the single crystal makes it
possible to favorably deal with many devices in various sizes due
to the area that can be made larger. Also, according to another
mode of the present invention, the BaTiO.sub.3--PbTiO.sub.3 series
single crystal is characterized in that the rearrangement density
of 10.sup.2 pieces/cm.sup.2 or more and 10.sup.6 pieces/cm.sup.2 or
less, and the ratio of pore content being within in a range of 1
volume ppm or more and 5 volume % or less. More preferably, the
ratio of PbTiO.sub.3 content is 45 mol % or less for the
BaTiO.sub.3--PbTiO.sub.3 series single crystal of the invention. In
this way, the BaTiO.sub.3--PbTiO.sub.- 3 series single crystal of
the invention makes the dielectric loss smaller, and the
electromechanical coupling coefficient larger.
[0022] Also, the method of the present invention t,or manufacturing
BaTiO.sub.3--PbTiO.sub.3 series single crystal comprises the step
of single-crystallizing BaTiO.sub.3--PbTiO.sub.3 compact powder
member or sintered member having a smaller Pb-containing mol number
than Ba-containing mol number by defining the range of the mol
ratio of elements contained therein to be
0.9800<(Ba+Pb)/Ti<1.0000, and by heating, while keeping the
powder or substance in non-molten condition. More preferably, the
range of the mol ratio of elements contained in the compact powder
member or sintered member is defined to be
0.9900<(Ba+Pb)/Ti<1.0000. Still more preferably, the range of
the mol ratio of elements contained in the compact powder member or
sintered member is defined to be
0.9950.ltoreq.(Ba+Pb)/Ti.ltoreq.0.9999. By heating the
BaTiO.sub.3--PbTiO.sub.3 compact powder member or sintered member
having a smaller Pb-containing mol number than Ba-containing mol
number, while keeping it in non-molten condition, the
reproducibility of single crystal growth is enhanced as compared
with the same process of only the BaTiO.sub.3 compact powder member
or sintered member that does not contain PbTiO.sub.3, thus making
it possible to manufacture the stable BaTiO.sub.3--PbTiO.sub.3
series single crystal. Further, by defining the mol ratio of
elements contained in the BaTiO.sub.3--PbTiO.sub.3 series single
crystal within a specific range, the crystal growing speed of
BaTiO.sub.3--PbTiO.sub.3 series single crystal becomes faster.
[0023] It is preferable for the method of the present invention for
manufacturing BaTiO.sub.3--PbTiO.sub.3 series single crystal that
the ratio of PbTiO.sub.3 content is 45 mol % or less in the
BaTiO.sub.3--PbTiO.sub.3 compact powder member or sintered member.
When the ratio of PbTiO.sub.3 content in the
BaTiO.sub.3--PbTiO.sub.3 compact powder member or sintered member,
which serves as the starting substance, is arranged to be 45 mol %
or less, the single crystal growing speed is promoted more to make
it possible to manufacture the single crystal substance more
stably. It is preferable for the method of the invention for
manufacturing BaTiO.sub.3--PbTiO.sub.3 series single crystal that
the ratio of PbTiO.sub.3 content in the BaTiO.sub.3--PbTiO.sub.3
series single crystal compact powder or sintered member is 30 mol %
or less, and more preferably, it is 25 mol % or less. If the ratio
of PbTiO.sub.3 content is too much, the evaporation of Pb becomes
conspicuous, and composition changes from the target one, while the
single crystal thus obtained tends to become porous. In order to
suppress the Pb evaporation, it is imperative that a pressurized
container be utilized, presenting a disadvantage that the
manufacturing costs become higher. Also, in the method for
manufacturing BaTiO.sub.3--PbTiO.sub.3 series single crystal, the
minimum amount of PbTiO.sub.3 content in the
BaTiO.sub.3--PbTiO.sub.3 compact powder member or sintered member
should preferably be 0.01 mol % or more, and more preferably, it is
0.02 mol % or more.
[0024] It is preferable for the method of the present invention for
manufacturing BaTiO.sub.3--PbTiO.sub.3 series single crystal to
comprise the step of single-crystallizing by heating the
BaTiO.sub.3--PbTiO.sub.3 compact powder member or sintered member
within a temperature range of 1,200.degree. C. or more and
1,400.degree. C. or less. By heating the BaTiO.sub.3--PbTiO.sub.3
compact powder member or sintered member within a range of
designated temperatures, the crystal growing speed of
BaTiO.sub.3--PbTiO.sub.3 series single crystal becomes faster.
[0025] Further, the method of the present invention for
manufacturing BaTiO.sub.3--PbTiO.sub.3 series single crystal
comprises the steps of preparing BaTiO.sub.3 series single crystal
or BaTiO.sub.3--PbTiO.sub.3 series single crystal as seed crystal;
coupling BaTiO.sub.3--PbTiO.sub.3 series sintered member composed
of crystal grain of average granular diameter of 20 .mu.m or less,
having the relative density of 95% or more, with the {100} plane,
{110} plane, or {111} plane of the seed crystal; and
single-crystallizing by heating, while keeping the coupled
substance in non-molten condition. More preferably, the mol ratio
of elements contained in the BaTiO.sub.3--PbTiO.sub.3 compact
powder member or sintered member is within a range of
0.9950.ltoreq.(Ba+Pb)/Ti.ltoreq.0.99- 99. In the method of the
invention for manufacturing BaTiO.sub.3--PbTiO.sub.3 series single
crystal, the single crystallization takes place stably form the
coupling portion between the compact powder member or sintered
member and the seed crystal by use of the BaTiO.sub.3--PbTiO.sub.3
compact powder member or sintered member coupled with the seed
crystal in the aforesaid condition, and the reproducibility of
single crystal growth is enhanced. Also, if the mol ratio of
elements contained in the aforesaid compact powder or sintered
member is within the designated range, the crystal growing speed of
BaTiO.sub.3--PbTiO.sub.3 series single crystal becomes faster
still.
[0026] It is preferable for the method of the present invention for
manufacturing BaTiO.sub.3--PbTiO.sub.3 series single crystal to
comprise the step of single-crystallizing by heating, while keeping
the compact powder member or sintered member in the lead atmosphere
and in non-molten condition. As one of the methods for forming the
lead atmosphere, it is possible to evaporate lead or lead oxide
form the lead-contained compound by enabling the lead-contained
compound to coexist in the environment in which the
BaTiO.sub.3--PbTiO.sub.3 compact powder member or sintered member
is heated, while being kept in non-molten condition. By heating the
BaTiO.sub.3--PbTiO.sub.3 compact powder member or sintered member
in the lead atmosphere, it becomes possible to prevent lead, lead
oxide, or the like from being evaporated from the
BaTiO.sub.3--PbTiO.sub.3 compact powder member or sintered member
or the BaTiO.sub.3--PbTiO.sub.3, series single crystal. In this
way, the increase of rearrangement density and the ratio of pore
content in the BaTiO.sub.3--PbTiO.sub.3 series single crystal can
be suppressed, thus making it possible to manufacture high quality
BaTiO.sub.3--PbTiO.sub.3 series single crystal.
[0027] Further, the piezoelectric type actuator of the present
invention comprises a layer formed by BaTiO.sub.3--PbTiO.sub.3
series single crystal described earlier. Also, the liquid discharge
head of the present invention comprises the aforesaid piezoelectric
type actuator. Here, the piezoelectric type actuator and liquid
discharge head of the present invention use the
BaTiO.sub.3--PbTiO.sub.3 series single crystal that has high
electromechanical coupling coefficient, high piezoelectric
constant, and high curie temperature altogether as the
piezoelectric material. Thus, the piezoelectric actuator and liquid
discharge head can be materialized to provide high output with a
wide range of usable temperatures. Also, from the viewpoint of the
environmental improvement on earth, it is preferable to use the
aforesaid actuator and head, because the amount of lead contented
in them is small.
[0028] The BaTiO.sub.3--PbTiO.sub.3 series single crystal of the
present invention is single-crystallized by heating
BaTiO.sub.3--PbTiO.sub.3 compact powder member or sintered member
having a smaller Pb-containing mol number than Ba-containing mol
number, while keeping the powder or substance in non-molten
condition. The effect of the reproducibility of the crystal growth
of the present invention cannot be demonstrated even if the method
of manufacture thereof is applied to the compact powder member or
sintered member composed of only BaTiO.sub.3. Although the
mechanism thereof has not been confirmed as yet, it is inferred as
given below. When the BaTiO.sub.3--PbTiO.sub.3 compact powder
member or sintered member is heated, while kept in non-molten
condition, lead or lead compound is evaporated from the surface of
the powder or signatured substance, and externally dispersed, and
the deficiency of lead ensues on the surface of the compact powder
member or sintered member. Thus, lead shifts from the inside of the
compact powder member or sintered member to the surface to
compensate for the deficiency thereof. At this juncture, the
granular interface in the inside the compact powder member or
sintered member tends to move easily, hence enabling the crystal
growth to occur stably.
[0029] The BaTiO.sub.3--PbTiO.sub.3 series single crystal of the
present invention can be manufactured at a crystal growing speed
faster still by preparing the BaTiO.sub.3--PbTiO.sub.3 compact
powder member or sintered member, which serves as starting
substance, with a designated composition as described earlier or by
heating it within a designated range of temperatures. The
BaTiO.sub.3--PbTiO.sub.3 series single crystal of the present
invention can be manufactured with a crystal growing speed
stabilized more by coupling a designated single crystal as a seed
crystal with the BaTiO.sub.3--PbTiO.sub.3 compact powder member or
sintered member, which serves as starting substance. FIGS. 2A to 2D
are views that illustrate the state of the crystal growth when the
BaTiO.sub.3--PbTiO.sub.3 series single crystal of the present
invention is manufactured, in which the designated single crystal
22 is coupled with the BaTiO.sub.3--PbTiO.sub.3 compact powder
member or sintered member 24, and heated in non-molten condition.
As shown in FIG. 2B, it is understandable that on the coupling
portion of the BaTiO.sub.3--PbTiO.sub.3 compact powder member or
sintered member with the seed crystal, particularly on the
circumferential area thereof, the crystal growth occurs
conspicuously. Conceivably, this is because the shift of lead
occurs intensively particularly on the aforesaid circumferential
area, and also, conceivably, this is the phenomenon that supports
the aforesaid mechanism of crystal growth. Typically, in FIG. 2C, a
reference numeral 26 designates the single-crystallized portion,
and 28, the polycrystal portion.
[0030] In accordance with the present invention, it is possible to
provide the BaTiO.sub.3--PbTiO.sub.3 series single crystal having
the property comparable to the PZT material already made available
as a Pb-less, piezoelectric material that serves the purpose of
reducing the harmful substance, such as Pb in PZT, among some
others. Also, along with the increased amount of Pb-containing, the
curie temperature becomes higher, but it is possible to select the
curie temperature up to approximately 300.degree. C. appropriately,
thus presenting no problem as to the curie temperature. Also, the
BaTiO.sub.3--PbTiO.sub.3 series single crystal manufactured by the
sintering method has a smaller dielectric loss, and the amount of
inductive distortion increases at the time of electric field
application due to significant rising of electromechanical coupling
coefficient along with the extinction of granular boundaries of the
largely oblique-angled ones, hence presenting extremely favorable
piezoelectric property.
[0031] Further, in accordance with the method of manufacture of the
present invention, it is possible to obtain high quality
BaTiO.sub.3--PbTiO.sub.3 series single crystal by preparing the
seed crystal having bulky grain formed by sintering compact powder
member, the specific composition range of which is (Ba+Pb)/Ti
ratio, or by preparing the seed crystal by means of the
conventional melt-solidification method, and also, producing the
BaTiO.sub.3--PbTiO.sub.3 series sintered member, which is given the
same composition adjustment, and then, by giving heat treatment
subsequent to the coupling of the seed crystal and the sintered
member. The growing speed of single crystal by means of this
sintering method is comparable to that of the Melt-Growth method or
superior thereto, and the property of this single crystal is far
superior to that of the PZT sintered member currently
available.
[0032] Also, it is possible to process many numbers of samples by
sintering method at a time, thus not only contributing to reducing
the production cost significantly, but also, making the
productivity and the maintenance of property compatible so as to
keep the rearrangement density in crystal in an extremely small
amount, and attain the high quality thereof.
BRIEF DESCRIPTION OF THE DRAWINGS
[0033] FIG. 1A is a perspective view that shows a liquid discharge
head in accordance with the present invention. FIG. 1B is a
cross-sectional view taken along line 1B-1B in FIG. 1A.
[0034] FIGS. 2A, 2B, 2C and 2D are the views of process flow that
illustrate one example of the method for manufacturing
BaTiO.sub.3--PbTiO.sub.3 series single crystal in accordance with
the present invention.
[0035] FIG. 3 is a view that shows the X-ray diffraction pattern of
the BaTiO.sub.3--PbTiO.sub.3 series single crystal of the present
invention after single crystallization by coupling seed crystals in
accordance with an eleventh embodiment.
[0036] FIG. 4 is a view that shows the X-ray diffraction pattern of
the BaTiO.sub.3--PbTiO.sub.3 series single crystal of the present
invention after single crystallization by coupling seed crystals in
accordance with the eleventh embodiment.
[0037] FIG. 5 is a view that shows the electron diffraction pattern
of the BaTiO.sub.3--PbTiO.sub.3 series single crystal of the
present invention after single crystallization using seed crystals
in accordance with the eleventh embodiment.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0038] The BaTiO.sub.3--PbTiO.sub.3 series single crystal of the
present invention is such that the BaTiO.sub.3--PbTiO.sub.3 compact
powder member or sintered member, the mol number of Pb-containing
of which is smaller than that of Ba, is heated and retained in
non-molten condition for the single crystallization. Further, it is
preferable for the BaTiO.sub.3--PbTiO.sub.3 series single crystal
of the present invention to mono-crystallize the
BaTiO.sub.3--PbTiO.sub.3 compact powder member or sintered member
by heating and retaining in the non-molten condition, with the mol
ratio of elements contained in them being arranged to be within a
range of 0.9800<(Ba+Pb)/Ti<1.0000. It is more preferable to
keep the mol ratio of elements contained in the compact power or
sintered member within a range of 0.9900<(Ba+Pb)/Ti<1.0000.
Still more preferably, the ratio should be kept within a range of
0.9950.ltoreq.(Ba+Pb)/Ti.ltoreq.0.9999.
[0039] For the BaTiO.sub.3--PbTiO.sub.3 series single crystal of
the present invention, it is preferable to arrange the content
ratio of PbTiO.sub.3 of the BaTiO.sub.3--PbTiO.sub.3 compact powder
member or sintered member, which is the starting substance thereof,
to be 45 mol % or less. When the ratio of PbTiO.sub.3 content of
the aforesaid compact powder member or sintered member is arranged
to be 45 mol % or less, the growing speed of single crystal is
promoted, while the single crystal substance is produced more
stably. The resultant composition of BaTiO.sub.3--PbTiO.sub.3
series single crystal thus obtained is almost the same as that of
the starting BaTiO.sub.3--PbTiO.sub.3 compact powder member or
sintered member. Here, it is more preferable to arrange the amount
of PbTiO.sub.3 content to be 30 mol % or less or still more
preferable to arrange it to be 25 mol % or less. If the amount of
PbTiO.sub.3 content is too much, the evaporation of lead becomes
conspicuous from the BaTiO.sub.3--PbTiO.sub.3 compact powder
member, sintered member, or single crystal. Consequently, the
obtainable composition of the BaTiO.sub.3--PbTiO.sub.3 series
single crystal is caused to change, and deviated from the target
composition. Further, the obtained BaTiO.sub.3--PbTiO.sub.3 series
single crystal becomes porous easily. In order to suppress the lead
evaporation, it is imperative that a pressurized container be used,
which leads to such an unfavorable problem of increased cost of
manufacture. Also, the minimum amount of PbTiO.sub.3 content of the
BaTiO.sub.3--PbTiO.sub.3 compact powder member or sintered member
should preferably be 0.01 mol % or more or, more preferably, 0.02
mol % or more. The BaTiO.sub.3--PbTiO.sub.3 series single crystal
of the present invention is single-crystallized by heating the
BaTiO.sub.3--PbTiO.sub.3 compact powder member or sintered member
within a preferable temperature range of 1,200.degree. C. or more
and 1,400.degree. C. or less. The BaTiO.sub.3--PbTiO.sub.3 series
single crystal of the present invention may also be
single-crystallized by preparing another single crystal, such as
BaTiO.sub.3 series single crystal or BaTiO.sub.3--PbTiO.sub.3
series single crystal as seed crystal, and coupling this seed with
the BaTiO.sub.3--PbTiO.sub.3 compact powder member or sintered
member, which is heated and retained. (If the crystal construction
is coincident, it is preferable that a lattice constant and a
thermal expansion coefficient of the polycrystal member and seed
crystal is within .+-.15%.) When using such seed crystal, it
becomes possible to match the crystal orientation of the
BaTiO.sub.3--PbTiO.sub.3 series single crystal with that of the
seed crystal. Further, the BaTiO.sub.3--PbTiO.sub.3 series single
crystal of the present invention is composed of the crystalline
particles, the average granular diameter of which is 20 .mu.m or
less, with the BaTiO.sub.3 series single crystal or
BaTiO.sub.3--PbTiO.sub.3 series single crystal as seed crystal, and
may be single-crystallized by coupling the BaTiO.sub.3--PbTiO.sub.3
series sintered member having a relative density of 95% or more
with the {100}, {110}, or {111} surface of the aforesaid seed
crystal, which is heated and retained in non-molten condition.
Here, the BaTiO.sub.3 series single crystal or
BaTiO.sub.3--PbTiO.sub.3 series single crystal used as the seed
crystal is manufactured by the method for manufacturing the
BaTiO.sub.3--PbTiO.sub.3 series single crystal of the present
invention or may be manufactured either by the general sintering
method or by the flux or TSSG method. Here, although the reasons
are not clear, it is possible to manufacture excellent
BaTiO.sub.3--PbTiO.sub.3 series single crystal in a better quality
when using the single crystal that has been manufactured by the
method of the present invention for manufacturing
BaTiO.sub.3--PbTiO.sub.3 series single crystal as the seed crystal
than the single crystal manufactured by the flux or TSSG method.
The method of the present invention for manufacturing
BaTiO.sub.3--PbTiO.sub.3 series single crystal includes a process
in which BaTiO.sub.3--PbTiO.sub.3 compact powder member or sintered
member is single-crystallized by heating it preferably in the lead
atmosphere, and retained in non-molten condition. As a method for
forming the lead atmosphere, a lead-contained compound, such as PZT
or PbTiO.sub.3, is arranged to be coexistent in the environment
where the BaTiO.sub.3--PbTiO.sub.3 compact powder member or
sintered member is heated, and then, lead or lead oxide is
evaporated from the aforesaid lead-contained compound. In this way,
the composition changes of the BaTiO.sub.3--PbTiO.sub.3 series
single crystal in the growing process (particularly, the lead
evaporation from the BaTiO.sub.3--PbTiO.sub.3 series single
crystal) can be suppressed, thus making it possible to increase the
crystallization speed more.
[0040] However, when manufacturing the BaTiO.sub.3--PbTiO.sub.3
series single crystal the ratio of PbTiO.sub.3 content of which
exceeds 30 mol %, the lead evaporation becomes particularly
conspicuous to make it easier to change the composition from the
target one. Further, the ratio of pore content of the obtained
single crystal tends to become higher. In order to suppress the
lead evaporation, there are often the cases where only the
execution of the heating process under the lead atmosphere as
described earlier is not good enough. For example, it is preferable
to execute the heating process in a pressurized container under a
pressure of more than one atmosphere. There is a need for a
comparatively long period of heating process (10 hours or more)
when a single crystal synthesis is executed by the sintering method
using such a pressurized container as HIP. As compared with the
precess under the normal pressure, this is unfavorable in terms of
the productivity and costs. For the BaTiO.sub.3--PbTiO.sub.3 series
single crystal of the present invention, it is desirable to provide
the rearrangement density of 10.sup.2 pieces/cm.sup.2 or more and
10.sup.6 pieces/cm.sup.2 or less, and the ratio of pore content of
1 volume ppm or more and 5 volume % or less. In this way, the
single crystal of the present invention presents a small dielectric
loss, and a large electromechanical coupling coefficient. For
example, the dielectric loss is 1 % or less, and the
electromechanical coupling coefficient exceeds 85 %.
[0041] Also, it is desirable for the BaTiO.sub.3--PbTiO.sub.3
series single crystal of the present invention to provide a volume
of 1 mm.sup.3 or more. With the volume of 1 mm.sup.3 or more, the
crystal can be utilized for the various sizes of many kinds of
devices with the provision of a large area thereof, among some
other means. Also, for the method of manufacture of the present
invention, the material powder used for manufacturing the
BaTiO.sub.3--PbTiO.sub.3 compact powder member or sintered member
is not particularly limited, and the following may be usable. In a
case of using the solid-phase reaction, the following can be
used:
[0042] 1) BaTiO.sub.3 powder is produced by preliminarily sintering
a mixture of BaO (obtainable by thermal decomposition from
BaCO.sub.3 or barium oxalate) and TiO.sub.2, and PbTiO.sub.3 powder
is produced by preliminarily sintering a mixture of PbO and
TiO.sub.2; and further,
[0043] 2) The BaTiO.sub.3--PbTiO.sub.3 powder or the like, which is
directly produced from BaO, PbO, and TiO.sub.2 powder.
[0044] Also, it is possible to use the mixture of BaTiO.sub.3 and
PbTiO.sub.3, which are obtainable by the wet or hydrothermal
method, such as coprecipitation or oxalic acid method, and also,
BaTiO.sub.3--PbTiO.sub.3 powder or the like, which is obtainable by
the wet, hydrothermal method, such as coprecipitation or oxalic
acid method, among some others. For the material powder, it is
desirable to keep the average granular diameter of the primary
grain to be within a range of 0.055 .mu.m. Also, as described
earlier, it is preferable to adjust the material powder so that the
mol ratio of the elements contained in the BaTiO.sub.3--PbTiO.sub.3
compact powder member or sintered member, which is obtained from
such material power to become the starting substance, should be
0.9800<(Ba+Pb)/Ti<1.0000. Also, more preferably, the material
powder is adjusted so that the mol ratio of the elements contained
in the BaTiO.sub.3--PbTiO.sub.3 compact powder member or sintered
member should be 0.9900<(Ba+Pb)/Ti<1.0000. Still more
preferably, it should be 0.9950.ltoreq.(Ba+Pb)/Ti<0.9999. The
composition-adjusted powder is made to be the compact powder member
after the general formation by means of a uniaxial press or a cold
press using hydrostatic pressure. The compact powder member, thus
obtained may be made a sintered member by sintering under the
normal condition. The compact powder member or sintered member is
heated in the non-molten condition to obtain the bulky crystal
grain of the BaTiO.sub.3--PbTiO.sub.3 series single crystal having
the average granular diameter of 1 mm or more. The heating in the
non-molten condition is given more preferably within a temperature
range of 1,200.degree. C. or more and 1,400.degree. C. or less.
Further, using the single crystal thus obtained by the aforesaid
method as seed crystal it may become comparatively easy to make
large BaTiO.sub.3--PbTiO.sub.3 series single crystal.
[0045] As described above, in order to make larger
BaTiO.sub.3--PbTiO.sub.- 3 series single crystal with ease, it is
preferable to use some other single crystal as seed crystal. The
seed crystal and the starting BaTiO.sub.3--PbTiO.sub.3 compact
powder member or sintered member are coupled, which is heated and
retained for crystallization. As a preferred seed crystal,
BaTiO.sub.3 series single crystal or BaTiO.sub.3--PbTiO.sub.3
series single crystal is usable here. As a preferred method for
preparing the seed crystal, the method of the present invention for
manufacturing BaTiO.sub.3--PbTiO.sub.3 series single crystal, a
general sintering method, or a melt solidification method, such as
TSSG or flux method, is applicable here. Particularly, it is
preferable to use the single crystal prepared by the method of the,
present invention for manufacturing BaTiO.sub.3--PbTiO.sub.3 series
single crystal as the seed crystal, because the crystalline defect
can be suppressed more for the BaTiO.sub.3--PbTiO.sub.3 series
single crystal thus obtained. The {100}, {110}, or {111} surface is
cut out and polished to be the coupling surface of the seed
crystal.
[0046] Also, when the single crystallization is executed using the
seed crystal, the mol ratio of the elements contained in the
BaTiO.sub.3--PbTiO.sub.3 series sintered member to be
single-crystallized should preferably be adjusted to be
0.9800<(Ba+Pb)/Ti<1.0000. More preferably, the mol ratio
should be adjusted to be 0.9900<(Ba+Pb)/Ti<1.0000. Still more
preferably, it should become
0.9950.ltoreq.(Ba+Pb)/Ti.ltoreq.0.9999. Further, the sintered
member is sintered so that the average granular diameter of the
crystalline grain should be 20 .mu.m or less, and the relative
density should be 95% or more. The sintering method is not
particularly limited, and the normally pressurized sintering, the
hot press, the HIP (hot isostatic press), or the like is applicable
here. In this respect, if the ratio of pore content of the sintered
member exceed 5 volume %, the ratio of pore content in the single
crystal obtained by the crystal growth is also increased, which
unfavorably lowers the mechanical strength thereof. With the
composition having a large amount of lead in particular, the ratio
of pore content tends to become greater due to the lead evaporation
during the growth of single crystal. In this case, therefore, it is
preferable to keep the ratio of pore content in the sintered member
to be less than 5 volume %. It is also preferable to precisely
polish the coupling surface of the sintered member and seed crystal
to be the surface roughness Ra=1.0 nm or less, and the flatness
.lambda. (.lambda.=633 nm) or less, respectively. The polished
surfaces of the sintered member and seed crystal may be in contact
directly or may be in contact after coating the organic or
inorganic acid that contains Ba, Pb, Ti component. The seed crystal
and sintered member, the polished surfaces of which are in contact
with each other, should preferably be coupled by heating for a
specific time with self-weight or a load of approximately 9.8 MPa
or less. Further, it is more preferable to execute the coupling in
the lead atmosphere in order to suppress the lead evaporation from
neat the surface of sample in the coupling process.
[0047] For the purpose of promotion of crystal growth, a fine
quantity of additives which is not replaceable or very difficult to
be replaced with A and B sites is added to the
BaTiO.sub.3--PbTiO.sub.3 series single crystal of the present
invention, the A site or B site of perovskite ABO.sub.3 structure
is replaced with some other element, or a third component of other
perovskite structure may be given solid solution for the purpose of
site exchange. The quantity thereof is not particularly limited,
but preferably, it is 10 weight percent or less for the fine amount
of additives; 10 mol percent or less for each cyto as the element
to be replaced with the A cyto or B cyto; or 10 mol percent or less
for all the components as the third component to be given solid
solution. The kind of the component is not particularly limited,
but preferably, it is such element (ion) as Na, K, Ca, Cr, Co, Bi,
Sr, La, Zr, Sn, Mg, Mn, Zn, Nb, Ta, Ni or the oxide or compound
oxide that contains these elements. An extreme part of impurity
components for promoting crystal growth resides in the single
crystal as impurities in association with movement of the crystal
growth border. However, there is no practical problem since most of
the components move to a distal end of the grown crystal.
[0048] Now, the element analysis of Ba, Pb, Ti, or the like for the
compact powder member, sintered member, or single crystal can be
made by use of an analyzer dedicated therefor in accordance with
the analytical method, such as fluorescent X-ray analysis, ICP
(emission plasma) analysis, or ICP-MASS (emission plasma-mass)
analysis, among some others. Also, the crystallinity and
orientation of single crystal can be confirmed by means of such
method as etch-pit image observation, the in-plane measurement and
out-of-plane measurement of X-ray diffraction, or electron
diffraction measurement, among some others, which are used for the
measurement of rearrangement density to be described later.
[0049] Regarding the ratio of pore content in the sintered member
and the grown single crystal, the porous amount (porous area)
exposed on the surface of a sample after the mirror surface
polishing is measured by use of a reflection microscope, SEM
(scanning electron microscope), or the like if the value thereof is
approximately 0.1 volume % or more, and then, the ratio of pore
content is worked out by the ratio of such amount to the measured
area. Also, if the value is approximately less than 0.1 volume %,
this method is not good enough in terms of precision. Therefore, a
thin piece of approximately several tens .mu.m thick is prepared,
and the size of pore and the number thereof, which exist in the
observable sight of a transmission microscope, are measured, and
the ratio of pore content is worked out by the ratio thereof to the
observed volume.
[0050] Also, the rearrangement in single crystal can be observed
using a microscope or the like as etch pit (=rearangement) by
corroding the crystalline surface of the single crystal with
HCl--HF solution or the like. In detail, the number of
rearrangement (etch pit) generated in several hundreds to thousand
.mu.m.sup.2 is counted and the counted number is changed to per 1
cm.sup.2 in order to determine the rearrangement density.
[0051] Hereinafter, the present invention will be described further
in detail in accordance with the specific embodiments. It is to be
understood, however, the present invention is not limited to such
embodiments.
First Embodiment
[0052] TiO.sub.2 (26.7557 g), PbO (0.7440 g), and BaCO.sub.3
(65.1209 g) are wet blended, and after dried, tentatively burned at
1,100.degree. C. for five hours, and, while being crushed, formed
into a disk (of 16 mm diameter). For the compact powder member thus
formed, the mol ratio of contained elements is (Ba+Pb)/Ti=0.9950.
This powder is sintered at 1,360.degree. C. for 10 hours to obtain
the sintered member. The sintered member thus obtained is composed
of bulky crystal grain of average granular diameter of
approximately 2.0 mm. The composition of the sintered member is:
BaTiO.sub.3 of 99.0 mol %-PbTiO.sub.3 of 1.0 mol %. From this
sintered member, the bulky crystal grain is drawn out as seed
crystal, and the (100) plane of the crystal grain is cut out and
finished with the surface roughness Ra=0.2 nm and the flatness
.lambda./2. On the other hand, the same compound is formed into a
disc of 10 mm diameter.times.15 mm thick, and sintered at
1,280.degree. C. for three hours to obtain the sintered member of
BaTiO.sub.3 of 99.0 mol %-PbTiO.sub.3 of 1.0 mol % in the relative
density of 97.3%. The average granular diameter of the crystal
grain that constitutes this sintered member is approximately 10
.mu.m. The composition thereof is (Ba+Pb)/Ti=0.9950. The end face
of this sintered member is likewise mirror finished to be the
surface roughness Ra=0.2 nm and the flatness .lambda./2. The
polished surfaces of both seed crystal and sintered member are
rinsed using acetone for mechanical coupling, and retained in the
oxygen atmosphere at 1,360.degree. C. for 40 hours, while keeping
this state in the non-molten condition, for the execution of single
crystallization. In the process of the single crystal growth, a
magnesia crucible is covered over the sample to suppress the Pb
evaporation. After the growing process, the single crystallization
takes place from the surface coupled with the single crystal to
approximately 12 mm.
[0053] From this result, it has been found that the growing speed
is 0.3 mm/h, and that the growth is possible at a speed much faster
than the growing speed of the conventional melt solidification
method. Also, the ratio of pore content is 0.9 volume % in the
single crystal of BaTiO.sub.3 of 99.0 mol %-PbTiO.sub.3 of 1.0 mol
%, which is obtained by the sintering method using the seed
crystal, and the rearrangement density is found to be
1.times.10.sup.3/cm.sup.2 when examined by etching it in the
HCl--HF solution.
Second Embodiment
[0054] TiO.sub.2 (26.64868 g), PbO (5.2080 g), and BaCO.sub.3
(61.1742 g) are wet blended, and after dried, tentatively burned at
1,150.degree. C. for five hours, and, while being crushed, formed
into a disc (of 20 mm diameter). For the compact powder member thus
formed, the mol ratio of contained elements is (Ba+Pb)/Ti=0.9990.
This powder is sintered at 1,350.degree. C. for 10 hours to obtain
the sintered member. The sintered member thus obtained is composed
of bulky crystal grain of average granular diameter of
approximately 3.0 mm. The composition of the sintered member is:
BaTiO.sub.3 of 93.0 mol %-PbTiO.sub.3 of 7.0 mol %. From this
sintered member, the bulky crystal grain is drawn out as seed
crystal, and the (110) plane of the crystal grain is cut out and
finished with the surface roughness Ra=0.3 nm and the flatness
.lambda./4. On the other hand, the same compound is formed into a
disc of 10 mm diameter.times.20 mm thick, and sintered at
1,250.degree. C. for three hours to obtain the sintered member of
BaTiO.sub.3 of 93.0 mol %-PbTiO.sub.3 of 7.0 mol % in the relative
density of 99.1%. The average granular diameter of the crystal
grain that constitutes this sintered member is approximately 8
.mu.m. The composition thereof is (Ba+Pb)/Ti=0.9990. The end face
of this sintered member is likewise mirror finished to be the
surface roughness Ra=0.2 nm and the flatness .lambda./2. The
polished surfaces of both seed crystal and sintered member are
rinsed using acetone for coupling by coating a mixed solution of
BaCl.sub.3 and TiOCl.sub.2 (mixing ratio thereof=1:0.5) on the
coupling interface, and retained in the oxygen atmosphere at
1,370.degree. C. for 50 hours, while keeping this state in the
non-molten condition, for the execution of single crystallization.
After the growing process, the single crystallization takes place
from the surface coupled with the seed crystal to approximately 18
mm.
[0055] From this result, it has been found that the growing speed
is 0.36 mm/h, and that the growth is possible at a speed much
faster than the growing speed of the conventional melt
solidification method. Also, the ratio of pore content is 0.8
volume % in the single crystal of BaTiO.sub.3 of 93.0 mol
%-PbTiO.sub.3 of 7.0 mol %, which is obtained by the sintering
method using the seed crystal, and the rearrangement density is
found to be 5.times.10.sup.2/cm.sup.2 when examined by etching it
in the HCl--HF solution.
Third Embodiment
[0056] The BaTiO.sub.3 series single crystal, which is manufactured
by the TSSG method and made available on the market, is cut
5.times.5.times.0.5 mm on the orientation plane (100), and this
plane is polished to be the surface roughness Ra=0.4 nm and the
flatness .lambda./6. On the other hand, the BaTiO.sub.3
(Ba/Ti=0.9996) powder, which is manufactured by the hydrothermal
method, and the PbTiO.sub.3 (Pb/Ti=1.0000) powder, which is
manufactured by the solid-phase method, are blended in the ratio of
99.8 mol:0.2 mol. While being crushed by means of pot mill, this
powder is formed into a disc (of 16 mm diameter), and sintered at
1,280.degree. C. for three hours to produce the sintered member
having relative density of 98.9%. The mol percent of the elements
contained in the sintered member thus obtained, with BaTiO.sub.3 of
99.8 mol %-PbTiO.sub.3 of 0.2 mol %, is (Ba+Pb)/Ti=0.9996, and the
average granular diameter of the crystal grain that constitutes
this sintered member, having BaTiO.sub.3 of 99.8 mol %-PbTiO.sub.3
of 0.2 mol %, is approximately 12 .mu.m. The end face of this
sintered member is mirror finished to be the surface roughness
Ra=0.4 nm and the flatness .lambda./6. The polished surfaces of
both seed crystal and sintered member are rinsed using acetone for
mechanical coupling, and retained in the oxygen atmosphere at
1,380.degree. C. for 30 hours, while keeping this state in the
non-molten condition, for the execution of single crystallization.
After the growing process, the single crystallization takes place
from the surface coupled with the seed crystal to approximately 11
mm.
[0057] From this result, it has been found that the growing speed
is 0.37 mm/h, and that the growth is possible at a speed much
faster than the growing speed of the conventional melt
solidification method. Also, the ratio of pore content is 0.7
volume % in the single crystal of BaTiO.sub.3 of 99.8 mol
%-PbTiO.sub.3 of 0.2 mol %, which is obtained by the sintering
method using the seed crystal, and the rearrangement density is
found to be 5.times.10.sup.3/cm.sup.2 when examined by etching it
in the HCl--HF solution.
Fourth Embodiment
[0058] Single crystal growth is executed by the sintering method in
the same condition as that of the second embodiment. However, for
the present embodiment, an electric furnace having an effective
volume of 150.times.150.times.150 mm, which is provided with
molybdenum silicide heat generating member, is used. Then, 30
samples and 6 PZT sintered elements of 20 mm diameter each are
inserted into the furnace for growing in the atmosphere of 100%
oxygen. After this process, all of the samples are
single-crystallized up to almost 18 mm in length. The production
speed is roughly estimated to be 108 cm.sup.3/furnace, because 30
samples of 16 mm diameter.times.18 mm long each (volume, 3.6
cm.sup.3) are produced. The time required for the growth is 50
hours, which is 2.16 cm.sup.3 per hour. Therefore, the productivity
is extremely high.
Fifth Embodiment
[0059] The BaTiO.sub.3 (Ba/Ti=0.9973) powder, which is obtained by
the solid-phase method with 5-hour, provisional burning at
1,150.degree. C. and crushing, and the PbTiO.sub.3 (Pb/Ti=1.0000)
powder, which is prepared by wet method, are blended in a ratio of
75.0 mol and 25.0 mol, and formed into a disc (of 30 mm diameter).
The mol ratio of elements contained in the compact power thus
formed is (Ba+Pb)/Ti=0.9998. This compact powder member is sintered
at 1,320.degree. C. for 50 hours to obtain the sintered member. The
sintered member is composed of bulky crystal grain of approximately
1.10 mm diameter, and the composition of the sintered member is
BaTiO.sub.3 of 75.0 mol %-PbTiO.sub.3 of 25.0 mol %. From this
sintered member, the bulky crystal grain (single crystal) of
BaTiO.sub.3 of 75.0 mol %-PbTiO.sub.3 of 25.0 mol % is drawn
out.
[0060] The ratio of pore content is 3.2 volume % in the single
crystal of the BaTiO.sub.3 of 75.0 mol %-PbTiO.sub.3 of 25.0 mol %.
Also, the rearrangement density thereof is examined by etching it
in the HCl--HF solution, with the result of
1.times.10.sup.2/cm.sup.2, thus making the crystal defect
small.
Sixth Embodiment
[0061] The BaTiO.sub.3 (Ba/Ti=0.9973) powder and the PbTiO.sub.3
(Pb/Ti=1.0000) powder, which are prepared by the same method as the
fifth embodiment, are blended by wet method in a ratio of 75.0 mol
and 25.0 mol, and formed into a disc (of 20 mm diameter). The mol
ratio of elements contained in the compact power thus formed is
(Ba+Pb)/Ti=0.9998. This compact powder member is sintered at
1,190.degree. C. for five hours to obtain the sintered member. The
composition of this sintered member is BaTiO.sub.3 of 75.0 mol
%-PbTiO.sub.3 of 25.0 mol %, and the relative density is 97.8%.
This sintered member is composed of crystal grain the average
granular diameter of which is approximately 10 .mu.m. End face of
this sintered member is processed to be the surface roughness
Ra=0.2 nm, and the flatness .lambda./6. Then, the end face (100) of
the BaTiO.sub.3 series single crystal, which is prepared by the
melt solidification method for use of seed crystal, is processed in
the same precision. Both polished faces of the sintered member and
seed crystal are in contact and coupled at 1,200.degree. C. for 1
hour under a pressure of 9.8 MPa. With the sample thus coupled, the
sintered member of BaTiO.sub.3 of 30.0 mol %-PbTiO.sub.3 of 70.0
mol % is placed on a setter. With an MgO crucible being covered,
the lead atmosphere is formed, and the single crystallization is
executed at 1,280.degree. C. for 30 hours. After the growing
process, the single crystallization is effectuated from the surface
coupled with the seed crystal to approximately 14 mm.
[0062] From this result, it has been found that the growing speed
is 0.47 mm/h, and that the growth is possible at a speed much
faster than the growing speed of the conventional melt
solidification method. Also, the ratio of pore content is 2.1
volume % in the single crystal of BaTiO.sub.3 of 75.0 mol
%-PbTiO.sub.3 of 25.0 mol %, which is obtained by the sintering
method, and the rearrangement density is found to be
5.times.10.sup.2/cm.sup.2 when examined by etching it in the
HCl--HF solution, thus making crystal defect small.
Seventh Embodiment
[0063] TiO.sub.2 (26.6753 g), PbO (5.2080 g), and BaCO.sub.3
(61.1742 g) are wet blended, and after dried, tentatively burned at
1,150.degree. C. for five hours, and, while being crushed, formed
into a disc (of 20 mm diameter). For the compact powder member thus
formed, the mol ratio of contained elements is (Ba+Pb)/Ti=0.9980.
This powder is sintered at 1,350.degree. C. for 10 hours to obtain
the sintered member. The sintered member thus obtained is composed
of bulky crystal grain of average granular diameter of
approximately 3.0 mm. The composition of the sintered member is
BaTiO.sub.3 of 93.0 mol %-PbTiO.sub.3 of 7.0 mol %. From this
sintered member, the bulky crystal grain is drawn out as seed
crystal, and the (110) plane of the crystal grain is cut out and
finished with the surface roughness Ra=0.3 nm and the flatness
.lambda./4. On the other hand, the same compound is formed into a
disc of 10 mm diameter.times.20 mm thick, and sintered at
1,250.degree. C. for three hours to obtain the sintered member of
BaTiO.sub.3 of 93.0 mol %-PbTiO.sub.3 of 7.0 mol % in the relative
density of 99.1%. The average granular diameter of the crystal
grain that constitutes this sintered member is approximately 7
.mu.m. The composition thereof is (Ba+Pb)/Ti=0.9980. The end face
of this sintered member is mirror finished to be the surface
roughness Ra=0.2 nm and the flatness .lambda./2. The polished
surfaces of both seed crystal and sintered member are rinsed using
acetone for coupling by coating a mixed solution of BaCl.sub.3 and
TiOCl.sub.2 (mixing ratio thereof=1:0.5) on the coupling interface.
Each one of sample and PZT sintered member are placed on a setter,
and further, covered with an MgO crucible to form the atmosphere
that contains Pb. While maintaining this state, these are retained
at 1,370.degree. C. for 20 hours in the non-molten condition for
the execution of single crystallization. After the growing process,
the single crystallization takes place from the surface coupled
with the single crystal to approximately 18 mm.
[0064] From this result, it has been found that the growing speed
is 0.90 mm/h, and that the growth is possible at a speed faster
than the growing speed indicated in the second embodiment. Also,
the Pb density of the surface layer of the sample of the single
crystal of BaTiO.sub.3 of 93.0 mol %-PbTiO.sub.3 of 7.0 mol %,
which is obtained by the sintering method, has almost no difference
with the Pb density in the central portion, and it has been found
that the simple is composed uniformly as a whole. The ratio of pore
content is 0.4 volume % in the single crystal of BaTiO.sub.3 of
93.0 mol %-PbTiO.sub.3 of 7.0 mol %, using the seed crystal, and
the rearrangement density is found to be 5.times.10.sup.2/cm.sup.2
when examined by etching it in the HCl--HF solution.
Eighth Embodiment
[0065] The BaTiO.sub.3 series single crystal, which is manufactured
by the TSSG method and made available on the market as in the case
of the third embodiment, is cut 5.times.5.times.0.5 mm on the
orientation plane (111), and this plane is polished to be the
surface roughness Ra=0.3 nm and the flatness .lambda./4 to make it
seed crystal. On the other hand, the BaTiO.sub.3 (Ba/Ti=0.9993)
powder, which is manufactured by the oxalate method, and the
PbTiO.sub.3 (Pb/Ti=0.9960) powder, which is prepared by the
solid-phase method are blended in the ratio of 93.2 mol:6.8 mol.
While being crushed by means of pot mill, this powder is formed
into a disc (of 16 mm diameter), and sintered by means of hot press
at 1,200.degree. C. for 1 hour to produce the sintered member
having relative density of 99.4%. The composition of the sintered
member thus obtained is BaTiO.sub.3 of 93.2 mol %-PbTiO.sub.3 6.8
mol %. The mol percent of the elements contained in the sintered
member is (Ba+Pb)/Ti=0.9991. The sintered member is composed of the
crystal grain the average granular diameter of which is,
approximately 2 .mu.m. The end face of this sintered member is
mirror finished to be the surface roughness Ra=0.3 nm and the
flatness .lambda./4. The polished surfaces of both seed crystal and
sintered member are rinsed using acetone for mechanical coupling.
Each one of PZT sintered member coupled with the sample is placed
on a setter, and further, covered by an MgO crucible to form the
atmosphere that contains Pb, and then, retained in the oxygen
atmosphere at 1,370.degree. C. for 20 hours, while keeping this
state in the non-molten condition, for the execution of single
crystallization. After the growing process, the single
crystallization takes place from the surface coupled with the seed
crystal to approximately 14 mm.
[0066] From this result, it has been found that the growing speed
is 0.70 mm/h, and that the growth is possible at a speed much
faster than the growing speed of the conventional melt
solidification method. Also, the ratio of pore content is 0.2
volume % in the single crystal of BaTiO.sub.3 of 93.2 mol
%-PbTiO.sub.3 of 6.8 mol %, which is obtained by the sintering
method using the seed crystal, and the rearrangement density is
found to be 1 10.sup.3/cm.sup.2 when examined by etching it in the
HCl--HF solution.
Ninth Embodiment
[0067] The BaTiO.sub.3 series single crystal, which is manufactured
by the TSSG method and made available on the market as in the third
embodiment, is cut 5.times.5.times.0.5 mm on the orientation plane
(100), and this plane is polished to be the surface roughness
Ra=0.3 nm and the flatness .lambda./4 to make it seed crystal. On
the other hand, the BaTiO.sub.3 (Ba/Ti=0.9990) powder, which is
manufactured by the oxalate method, and the PbTiO.sub.3
(Pb/Ti=0.9980) powder, which is manufactured by the solid-phase
method, are blended in the ratio of 90.7 mol:9.3 mol. While being
crushed by means of pot mill, this powder is formed into a disc (of
16 mm diameter), and sintered at 1,200.degree. C. for 1 hour
O.sup.2--HIP (atmosphere: 20% O.sup.2 and pressure: 98 MPa) to
produce the sintered member of BaTiO.sub.3 of 90.7 mol
%-PbTiO.sub.3 of 9.3 mol %, the relative density of which is
99.96%. The sintered member thus obtained is composed of crystal
grain of average diameter of approximately 1 .mu.m. The mol ratio
of elements contained in this sintered member is (Ba+Pb)/Ti=0.9989.
The end face of this sintered member is mirror finished to be the
surface roughness Ra=0.3 nm and the flatness .lambda./4. The
polished surfaces of both seed crystal and sintered member are
rinsed using acetone for mechanical coupling. Each one of PZT
sintered member coupled with the sample is placed on a setter, and
further, covered by an MgO crucible to form the atmosphere that
contains Pb, and then, retained in the oxygen atmosphere at
1,370.degree. C. for 19 hours, while keeping this state in the
non-molten condition, for the execution of single crystallization.
After the growing process, the single crystallization takes place
from the surface coupled with the seed crystal to approximately 18
mm.
[0068] From this result, it has been found that the growing speed
is 0.95 mm/h, and that the growth is possible at a speed much
faster than the growing speed of the conventional melt
solidification method. Also, the ratio of pore content is 0.0003
volume % in BaTiO.sub.3--PbTiO.sub.3 series single crystal, which
is obtained by the sintering method using the seed crystal, and the
rearrangement density is found to be 1.times.10.sup.3/cm.sup.2 when
examined by etching it in the HCl--HF solution.
Tenth Embodiment
[0069] The BaTiO.sub.3 series single crystal, which is manufactured
by the TSSG method and made available on the market as in the third
embodiment, is cut 5.times.5.times.0.5 mm on the orientation plane
(100), and this plane is polished to be the surface roughness
Ra=0.3 nm and the flatness .lambda./4 to make it seed crystal. On
the other hand, the BaTiO.sub.3 (Ba/Ti=0.9945) powder, which is
manufactured by the oxalate method, and the PbTiO.sub.3
(Pb/Ti=0.9952) powder, which is manufactured by the solid-phase
method, are blended in the ratio of 55.0 mol:45.0 mol. While being
crushed by means of pot mill, this powder is formed into a disc (of
16 mm diameter), and sintered at 1,200.degree. C. for 1 hour
O.sup.2,--HIP (atmosphere: 20% O.sup.2 and pressure: 98 MPa) to
produce the sintered member of BaTiO.sub.3 of 55.0 mol
%-PbTiO.sub.3 of 45.0 mol %, the relative density of which is
99.96%. The sintered member thus obtained is composed of crystal
grain of average diameter of approximately 4 .mu.m. The mol ratio
of elements contained in this sintered member is (Ba+Pb)/Ti=0.9948.
The end face of this sintered member is mirror finished to be the
surface roughness Ra=0.3 nm and the flatness .lambda./4. The
polished surfaces of both seed crystal and sintered member are
rinsed using acetone for mechanical coupling. Each one of PZT
sintered member coupled with the sample is placed on a setter, and
further, covered by an MgO crucible to form the atmosphere that
contains Pb, and then, retained in the oxygen atmosphere at
1,360.degree. C. for 20 hours, while keeping this state in the
non-molten condition, for the execution of single crystallization.
After the growing process, the single crystallization takes place
from the surface coupled with the seed crystal to approximately 13
mm. However, the ratio of pore content in the single crystal thus
formed is 8.9 volume %, which is in a condition of being too porous
to be utilizable.
[0070] Based upon this result, the growing atmosphere is arranged
with 20% O.sup.2--80% Ar composition under 50 atmospheric pressure,
and the aforesaid coupled sample of seed crystal--sintered member
is retained at, 1,350.degree. C. for twenty-four hours for the heat
treatment in the non-molten condition. The sample, which has been
processed under pressure, is single-crystallized from the surface
coupled with the seed crystal to approximately 15 mm, and the
growing speed is 0.63 mm/h. Thus, it has been found that the growth
is possible at a speed much faster than the growing speed of the
conventional melt solidification method. Also, the ratio of pore
content is reduced to 5.1 volume % in the single crystal of
BaTiO.sub.3 of 55.0 mol %-PbTiO.sub.3 of 45.0 mol %, which is
obtained by the sintering method using the seed crystal, and the
rearrangement density is also found to be 1.times.10.sup.4/cm.sup.2
when examined by etching it in the HCl--HF solution.
Eleventh Embodiment
[0071] TiO.sub.2 (26.7288 g), PbO (0.3720 g), and BaCO.sub.3
(65.4498 g) are wet blended, and after dried, tentatively burned at
1,100.degree. C. for five hours, and, while being crushed, formed
into a disc (of 20 mm diameter). For the compact powder member thus
formed, the mol ratio of contained elements is (Ba+Pb)/Ti=0.9960.
This powder is sintered at 1,330.degree. C. for 10 hours to obtain
the sintered member. The sintered member thus obtained is composed
of bulky crystal grain of average granular diameter of
approximately 2.6 mm. The composition of the sintered member is
BaTiO.sub.3 of 99.5 mol %-PbTiO.sub.3 of 0.5 mol %. From this
sintered member, the bulky crystal grain is drawn out as seed
crystal, and the (001) plane of the crystal grain is cut out and
finished with the surface roughness Ra=0.2 nm and the flatness
.lambda./2. The electron beam diffraction image of this bulky
crystal grain is measured. It is then confirmed that the single
crystal has the crystalline orientation of extremely uniform. FIG.
5 shows this electron beam diffraction image. On the other hand,
the same compound is formed into a disc of 10 mm diameter.times.20
mm thick, and sintered at 1,250.degree. C. for three hours to
obtain the sintered member of BaTiO.sub.3 of 99.5 mol %-PbTiO.sub.3
of 0.5 mol % in the relative density of 96.8%. The average granular
diameter of the crystal grain that constitutes this sintered member
is approximately 6 .mu.m. The mol ratio of elements contained in
this sintered member is (Ba+Pb)/Ti=0.9960. The end face of this
sintered member is likewise mirror finished to be the surface
roughness Ra=0.2 nm and the flatness .lambda./2. The polished
surfaces of both seed crystal and sintered member are rinsed using
acetone for coupling by coating a mixed solution of BaCl.sub.3 and
TiOCl.sub.2 (mixing ratio thereof=1:0.5) on the coupling interface,
and retained in the oxygen atmosphere at 1,300.degree. C. for 30
hours, while keeping this state in the non-molten condition, for
the execution of single crystallization. After the growing process,
the single crystallization takes place from the surface coupled
with the seed crystal to approximately 14 mm.
[0072] From this result, it has been found that the growing speed
is 0.47 mm/h, and that the growth is possible at a speed much
faster than the growing speed of the conventional melt
solidification method. Also, the ratio of pore content is 0.8
volume % in the single crystal of BaTiO.sub.3 of 99.5 mol
%-PbTiO.sub.3 of 0.5 mol %, which is obtained by the sintering
method using the seed crystal, and the rearrangement density is
found to be 2.times.10.sup.2/cm.sup.2 when examined by etching it
in the HCl--HF solution. FIG. 3 shows the result of measurement of
the sample by means of X-ray diffraction (before single
crystallization), and FIG. 4 shows the result thereof (after single
crystallization). (In FIG. 4, two peeks are observable in the
vicinity of 2.theta.=45.degree.. This is because the X-ray of
target own is separated into K.alpha..sub.1 and
K.alpha..sub.2.)
Twelfth Embodiment
[0073] The BaTiO.sub.3 series single crystal, which is manufactured
by the TSSG method and made available on the market as in the third
embodiment, is cut 5.times.5.times.0.5 mm on the orientation plane
(001), and this plane is polished to be the surface roughness
Ra=0.3 nm and the flatness .lambda./4 to make it seed crystal. On
the other hand, the BaTiO.sub.3 (Ba/Ti=0.9945) powder, which is
manufactured by the oxalate method, and the PbTiO.sub.3
(Pb/Ti=0.9952) powder, which is manufactured by the solid-phase
method, are blended in the ratio of 70.0 mol:30.0 mol. While being
crushed by means of pot mill, this powder is formed into a disc (of
16 mm diameter), and sintered at 1,200.degree. C. for 1 hour
O.sup.2--HIP (atmosphere: 20% O.sup.2 and pressure: 98 MPa) to
produce the sintered member of BaTiO.sub.3 of 70.0 mol
%-PbTiO.sub.3 of 30.0 mol %, the relative density of which is
99.96%. The sintered member thus obtained is composed of crystal
grain of average diameter of approximately 4 .mu.m. The mol ratio
of elements contained in this sintered member is (Ba+Pb)/Ti=0.9947.
The end face of this sintered member is mirror finished to be the
surface roughness Ra=0.3 nm and the flatness .lambda./4. The
polished surfaces of both seed crystal and sintered member are
rinsed using acetone for mechanical coupling. Each one of PZT
sintered member coupled with the sample is placed on a setter, and
further, covered by an MgO crucible to form the atmosphere that
contains Pb, and then, retained in the oxygen atmosphere at
1,330.degree. C. for 20 hours, while keeping this state in the
non-molten condition, for the execution of single crystallization.
After the growing process, the single crystallization takes place
from the surface coupled with the seed crystal to approximately 12
mm. The ratio of pore content is 3.8 volume % in the single crystal
thus formed. The rearrangement density is found to be
7.times.10.sup.3/cm.sup.2 when examined by etching the sample in
the HCl--HF solution.
Thirteenth Embodiment
[0074] TiO.sub.2 (26.6246 g), PbO (3.7200 g), and BaCO.sub.3
(62.4898 g) are wet blended, and after dried, tentatively burned at
1,100.degree. C. for five hours, and, while being crushed, formed
into a disc (of 20 mm diameter). For the compact powder member thus
formed, the mol ratio of contained elements is (Ba+Pb)/Ti=0.9999.
This powder is sintered at 1,300.degree. C. for 10 hours to obtain
the sintered member. The sintered member thus obtained is composed
of bulky crystal grain of average granular diameter of
approximately 2.2 mm. The composition of the sintered member is
BaTiO.sub.3 of 95.0 mol %-PbTiO.sub.3 of 5.0 mol %. From this
sintered member, the bulky crystal grain is drawn out as seed
crystal, and the (111) plane of the crystal grain is cut out and
finished with the surface roughness Ra=0.3 nm and the flatness
.lambda./4. On the other hand, the same compound is formed into a
disc of 10 mm diameter.times.20 mm thick, and sintered at
1,250.degree. C. for three hours to obtain the sintered member of
BaTiO.sub.3 of 95.0 mol %-PbTiO.sub.3 of 5.0 mol % in the relative
density of 98.4%. The average granular diameter of the crystal
grain that constitutes this sintered member is approximately 5
.mu.m. The mol ratio of elements contained in this sintered member
is (Ba+Pb)/Ti=0.9999. The end face of this sintered member is
mirror finished to be the surface roughness Ra=0.3 nm and the
flatness .lambda./4. The polished surfaces of both seed crystal and
sintered member are rinsed using acetone for coupling by coating a
mixed solution of BaCl.sub.3 and TiOCl.sub.2 (mixing ratio
thereof=1:0.5) on the coupling interface. While maintaining this
state, these are retained at 1,350.degree. C. for 20 hours in the
non-molten condition for the execution of single crystallization.
After the growing process, the single crystallization takes place
from the surface coupled with the single crystal to approximately
12 mm.
[0075] From this result, it has been found that the growing speed
is 0.60 mm/h, and that the growth is possible at a speed faster
than the growing speed of the conventional melt-solidification
method. Also, the ratio of pore content is 0.5 volume % in the
single crystal of BaTiO.sub.3 of 95.0 mol %-PbTiO.sub.3 of 5.0 mol
%, which is obtained by the sintered method using the seed crystal,
and the rearrangement density is found to be
5.times.10.sup.2/cm.sup.2 when examined by etching it in the
HCl--HF solution.
Fourteenth Embodiment
[0076] TiO.sub.2 (26.8908 g), PbO (3.7200 g), and BaCO.sub.3
(62.4898 g) are wet blended, and after dried, tentatively burned at
1,100.degree. C. for five hours, and, while being crushed, formed
into a disc (of 20 mm diameter). For the compact powder member thus
formed, the mol ratio of contained elements is (Ba+Pb)/Ti=0.9990.
This powder is sintered at 1,300.degree. C. for 10 hours to obtain
the sintered member. The sintered member thus obtained is composed
of bulky crystal grain of average granular diameter of
approximately 2.8 mm. The composition of the sintered member is
BaTiO.sub.3 of 95.0 mol %-PbTiO.sub.3 of 5.0 mol %. From this
sintered member, the bulky crystal grain is drawn out as seed
crystal, and the (001) plane of the crystal grain is cut out and
finished with the surface roughness Ra=0.3 nm and the flatness
.lambda./4. On the other hand, the same compound is formed into a
disc of 10 mm diameter.times.20 mm thick, and sintered at
1,250.degree. C. for three hours to obtain the sintered member of
BaTiO.sub.3 of 95.0 mol %-PbTiO.sub.3 of 5.0 mol % in the relative
density of 98.7%. The average granular diameter of the crystal
grain that constitutes this sintered member is approximately 6
.mu.m. The mol ratio of elements contained in this sintered member
is (Ba+Pb)/Ti=0.9990. The end face of this sintered member is
mirror finished to be the surface roughness Ra=0.3 nm and the
flatness .lambda./4. The polished surfaces of both seed crystal and
sintered member are rinsed using acetone for coupling by coating a
mixed solution of BaCl.sub.3 and TiOCl.sub.2 (mixing ratio
thereof=1:0.5) on the coupling interface. While maintaining this
state, these are retained at 1,350.degree. C. for 30 hours in the
non-molten condition for the execution of single crystallization.
After the growing process, the single crystallization takes place
from the surface coupled with the single crystal to approximately 7
mm.
[0077] From this result, it has been found that the growing speed
is 0.23 mm/h, and that the growth is possible at a speed faster
than the growing speed of the conventional melt-solidification
method. Also, the ratio of pore content is 0.6 volume % in the
single crystal of BaTiO.sub.3 of 95.0 mol %-PbTiO.sub.3 of 5.0 mol
%, which is obtained by the sintered method using the seed crystal,
and the rearrangement density is found to be
1.times.10.sup.4/cm.sup.2 when examined by etching it in the
HCl--HF solution.
Fifteenth Embodiment
[0078] BaTiO.sub.3 (Ba/Ti=0.9954) powder, PbTiO.sub.3
(Pb/Ti=1.0000) powder, and CaTiO.sub.3 (Ca/Ti=1.0000) powder, which
are manufactured by wet method, are wet blended in a mol ration of
70.0:29.0:1.0 in that order, and formed into a disc (of 20 mm
diameter). For the compact powder member thus formed, the mol ratio
of contained elements is (Ba+Pb)/Ti=0.9868. This powder is sintered
at 1,350.degree. C. for 10 hours to obtain the sintered member. The
sintered member thus obtained is composed of bulky crystal grain of
average granular diameter of approximately 3.3 mm. The composition
of the sintered member is BaTiO.sub.3 of 70.0 mol %-PbTiO.sub.3 of
29.0 mol %-CaTiO.sub.3 of 1.0 mol %. From this sintered member, the
bulky crystal grain is drawn out as seed crystal, and the (001)
plane of the crystal grain is cut out and finished with the surface
roughness Ra=0.3 nm and the flatness .lambda./4. On the other hand,
the same compound is formed into a disc of 10 mm diameter.times.20
mm thick, and sintered at 1,250.degree. C. for three hours to
obtain the sintered member of BaTiO.sub.3 of 70.0 mol %-PbTiO.sub.3
of 29.0 mol %-CaTiO.sub.3 of 1.0 mol % in the relative density of
98.9%. The average granular diameter of the crystal grain that
constitutes this sintered member is approximately 6 .mu.m. The mol
ratio of elements contained in this sintered member is
(Ba+Pb)/Ti=0.9868. The end face of this sintered member is mirror
finished to be the surface roughness Ra=0.3 nm and the flatness
.lambda./4. The polished surfaces of both seed crystal and sintered
member are rinsed using acetone, and then, coupled at 1,200.degree.
C. for one hour under a pressure of 9.8 MPa. The PZT sintered
member is placed on a setter together with the coupled sample, and
covered with an MgO crucible to form the lead atmosphere for the
single crystallization at 1,350.degree. C. for 50 hours. After the
growing process, the single crystallization takes place from the
surface coupled with the single crystal to approximately 11 mm.
[0079] From this result, it has been found that the growing speed
is 0.22 mm/h. The ratio of pore content is 4.1 volume % in the
single crystal of BaTiO.sub.3 of 70.0 mol %-PbTiO.sub.3 of 29.0 mol
%-CaTiO.sub.3 of 1.0 mol' % which is obtained by the sintered
method. Also, the rearrangement density is found to be
1.times.10.sup.4/cm.sup.2 when examined by etching it in the
HCl--HF solution.
FIRST COMPARATIVE EXAMPLE
[0080] TiO.sub.2 (27.1652 g), PbO (3.7200 g), and BaCO.sub.3
(62.4898 g) are wet blended, and after dried, tentatively burned at
1,110.degree. C. for five hours, and, while being crushed, formed
into a disc (of 16 mm diameter). For the compact powder member thus
formed, the mol ratio of contained elements is (Ba+Pb)/Ti=0.9800.
This powder is sintered at 1,350.degree. C. for 30 hours to obtain
the sintered member of BaTiO.sub.3 of 95.0 mol %-PbTiO.sub.3 of 5.0
mol %. The sintered member thus obtained is composed of crystal
grain of average granular diameter of only 50 .mu.m. Therefore, the
same process as the third embodiment is given to the (100) plane of
the BaTiO.sub.3 series single crystal, which is grown by the TSSG
method and made available on the market, to make it the seed
crystal. On the other hand, the same compound is formed into a disc
of 10 mm diameter.times.10 mm thick, and sintered at 1,250.degree.
C. for three hours to obtain the sintered member of BaTiO.sub.3 of
95.0 mol %-PbTiO.sub.3 of 5.0 mol % in the relative density of
98.1%. The average granular diameter of the crystal grain that
constitutes this sintered member is approximately 12 .mu.m. The mol
ratio of elements contained in this sintered member is
(Ba+Pb)/Ti=0.9800. The end face of this sintered member is mirror
finished to be the surface roughness Ra=0.4 nm and the flatness
.lambda./6 as in the third embodiment. The polished surfaces of
both seed crystal and sintered member are rinsed using acetone for
coupling by coating a solution of HNO.sub.3 of 2N on the coupling
interface. While maintaining this state, these are retained at
1,370.degree. C. for 50 hours in the non-molten condition for the
execution of single crystallization.
[0081] After the single crystal growing process, the single
crystallization takes place from the surface coupled with the
single crystal only to 100 .mu.m. It is found from this result that
the growing speed is 2.times.10.sup.-3 mm/h, that almost no single
crystallization has advanced.
SECOND COMPARATIVE EXAMPLE
[0082] BaTiO.sub.3 (Ba/Ti=1.0000) and PbTiO.sub.3 (Pb/Ti=1.0100)
powder is prepared by the coprecipitation method, and blended in a
ration of 90.0 mol:10.0 mol. While being crashed by means of hot
mill, this blended powder is formed into a disc (of 16 mm
diameter). For the compact powder member thus formed, the mol ratio
of contained elements is (Ba+Pb)/Ti=1.0010. This powder is sintered
at 1,350.degree. C. for 10 hours to obtain the sintered member of
BaTiO.sub.3 of 90.0 mol %-PbTiO.sub.3 of 10.0 mol %. The sintered
member thus obtained is composed of minute crystal grain of average
granular diameter of approximately 3 .mu.m, thus making it
impossible to obtain the single crystal in a size sufficient enough
to be used as seed crystal. Therefore, as in the case of the first
comparative example, the BaTiO.sub.3 series single crystal, which
is grown by means of the TSSG method and made available on the
market, is used as the seed crystal. On the other hand the same
compound is formed into a disc of 10 mm diameter.times.15 mm thick,
and sintered at 1,250.degree. C. for three hours to obtain the
sintered member of BaTiO.sub.3 of 90.0 mol %-PbTiO.sub.3 of 10.0
mol % in the relative density of 97.8%. The mol ratio of elements
contained in this sintered member is (Ba+Pb)/Ti=1.0010. The end
face of this sintered member is mirror finished to be the surface
roughness Ra=0.4 nm and the flatness .lambda./6 as in the first
comparative example. The polished surfaces of both seed crystal and
sintered member are rinsed using acetone for coupling by coating a
mixed solution of BaCl.sub.3 and TiOCl.sub.2 (mixing ratio: 1:1) on
the coupling interface. While maintaining this state, these are
retained at 1,390.degree. C. for 30 hours in the non-molten
condition for the execution of single crystallization. After this
growing process, it is found that almost no single crystallization
has taken place, but only in a width of approximately 1 to 2 grain
(approximately 5 to 10 .mu.m) from the surface coupled with the
seed crystal.
THIRD COMPARATIVE EXAMPLE
[0083] BaTiO.sub.3--PbTiO.sub.3 series single crystal is grown by
means of the TSSG method. As the material of solution, the
BaTiO.sub.3 powder, TiO.sub.2 powder, and PbTiO.sub.3 powder, which
are available on the market, are used. The sintered member is
prepared using the material powder in a mol ratio of
BaTiO.sub.3:TiO.sub.2:PbTiO.sub.3=1:0.5:0.01. This sintered member
is placed in a platinum crucible to melt the material by means of
high-frequency induction heating. The growing temperature is
1,440.degree. C. The BaTiO.sub.3 seed crystal of <100>
orientation, which is fixed to the platinum holer, is immersed in
this solution, and the temperature is decreased at 0.4.degree. C./h
along with the rotation of 30 rpm, and the crystallization is
performed by a speed of 0.1 mm/h. After approximately 200 hours,
the drawing-up terminates when the temperature reaches
1,330.degree. C. (eutectoid temperature). The crystal thus obtained
is 25 mm diameter and 16 mm long (volume: 7.9 cm.sup.3). the inside
of the crystal is of porous structure (the ratio of pore content: 8
volume %) having many numbers of voids of several .mu.m to several
tens of .mu.m created along with the Pb evaporation on the way of
growth. With a microscope, the occurrence of many inclusions other
than perovskite phase is observed. The rearrangement density in the
crystal is 2.times.10.sup.6/cm.sup.2. It is larger than the
rearrangement density of the BaTiO.sub.3--PbTiO.sub.3 series single
crystal of the present invention. Also, the productivity is only
0.04 cm.sup.3/h, which is approximately {fraction (1/100)} as
compared with the productivity of the BaTiO.sub.3--PbTiO.sub.3
series single crystal of the present invention.
[0084] As regards each of the embodiments described above, the
Table 1 shows the various piezoelectric properties of the
BaTiO.sub.3--PbTiO.sub.- 3 series single crystal manufactured
particularly in the first, second, and six embodiments, the general
PZT sintered member, the BaTiO.sub.3 sintered member and
BaTiO.sub.3 series single crystal grown by means of the TSSG
method, respectively.
1TABLE 1 Comparison of Specific Characteristics between the Present
Invention and the Conventional Art Fist Second Sixth Comperative
Comperative Embodiment Embodiment Embodiment Example Example
BaTiO.sub.3 of 99.0 BaTiO.sub.3 of 93.0 BaTiO.sub.3 of 75.0
Comperative BaTiO.sub.3 BaTiO.sub.3 mol %-PbTiO.sub.3 of mol
%-PbTiO.sub.3 of mol %-PbTiO.sub.3 Example Series Series 1.0 mol %
Single 7.0 mol % Single of 25.0 mol % PZT Sintered Sintered Single
Sample Crystal Crystal Single Crystal Member Member Crystal Curie
Temperature (.degree. C.) 125 155 246 290 120 120 Permittivity
after Polarization 3900 2700 1500 300 3000 4700 Dielectric Loss (%)
0.30 0.28 0.19 1.9 2.5 0.25 Coupling Coefficient k.sub.33 (%) 86 89
91 71 48 85 Piezoelectric Constant d.sub.33 (pC/N) 520 580 620 290
118 500 Amount of Induced Distortion (%) 0.92 1.25 1.69 0.11 0.06
0.90 Field 30 (kV .multidot. cm)
[0085] Next, with reference to FIGS. 1A and 1B, the description
will be made of a piezoelectric type actuator (piezoelectric
oscillator) using the BaTiO.sub.3--PbTiO.sub.3 series single
crystal of the present invention, and a liquid discharge head using
such piezoelectric type actuator. The liquid discharge head 11
shown in FIG. 1A and FIG. 1B is provided with a plurality of
discharge ports 12; the liquid chamber 13 which is arranged
corresponding to each discharge port 12; and the piezoelectric type
actuator 19 which is arranged for each liquid chamber 13,
respectively. The piezoelectric type actuator 19 comprises the
piezoelectric member 14 that includes at least the layer formed by
BaTiO.sub.3--PbTiO.sub.3 series single crystal; electrodes (not
shown) of Pt, Au, Al, or the like formed on the surface of the
piezoelectric member 14; and the oscillating plate 17 that is
bonded with the piezoelectric member 14, thus forming a
piezoelectric oscillator. Each liquid discharge port 12 for the
liquid discharge head 11 is formed for a nozzle plate 15 at
specific intervals. Each liquid chamber 13 is formed on the base
plate portion 16 in parallel to each liquid discharge port 12
correspondingly. Each of the liquid discharge ports 12 and the
corresponding liquid chamber 13 are connected through the liquid
flow path 16a formed for the base plate portion 16, respectively.
Also, on the upper face of the base plate portion 16, each opening
portion 16b is formed corresponding to each of the liquid chambers
13, and on the upper face of base plate portion 16, the oscillating
plate 17 is formed to cover each opening portion 16b. On this
oscillating plate 17, the piezoelectric member 14 is arranged to be
positioned corresponding to each liquid chamber 13.
[0086] For the liquid discharge head 11 structured described above,
the piezoelectric type actuator 19 is driven to press liquid in the
corresponding liquid chamber 13 when driving signals are applied
from outside to the piezoelectric type actuator 19, and liquid is
discharged as liquid droplet from the liquid discharge port 12
communicated with the liquid chamber 13.
[0087] With the BaTiO.sub.3--PbTiO.sub.3 series single crystal,
which is a piezoelectric material having a small amount of lead
content therein, and used as the piezoelectric member
(piezoelectric oscillator) that constitutes such piezoelectric type
actuator, it becomes possible to obtain excellent piezoelectric
properties at lower costs in much better condition than the PZT
properties conventionally available. Further, it becomes possible
to manufacture the environment-friendly piezoelectric type actuator
(piezoelectric oscillator), and the liquid discharge head as
well.
* * * * *