U.S. patent application number 14/576780 was filed with the patent office on 2015-07-02 for method for producing ferroelectric thin film.
The applicant listed for this patent is MITSUBISHI MATERIALS CORPORATION. Invention is credited to Toshihiro Doi, Hideaki Sakurai, Nobuyuki Soyama, Toshiaki Watanabe.
Application Number | 20150187569 14/576780 |
Document ID | / |
Family ID | 46208299 |
Filed Date | 2015-07-02 |
United States Patent
Application |
20150187569 |
Kind Code |
A1 |
Watanabe; Toshiaki ; et
al. |
July 2, 2015 |
METHOD FOR PRODUCING FERROELECTRIC THIN FILM
Abstract
A method for producing a ferroelectric thin film comprising:
coating a composition for forming a ferroelectric thin film on a
base electrode of a substrate having a substrate body and the base
electrode that has crystal faces oriented in the (111) direction,
calcining the coated composition, and subsequently performing
firing the coated composition to crystallize the coated
composition, and thereby forming a ferroelectric thin film on the
base electrode, wherein the method includes formation of a
orientation controlling layer b coating the composition on the base
electrode, calcining the coated composition, and firing the coated
composition, where an amount of the composition coated on the base
electrode is controlled such that a thickness of the orientation
controlling layer after crystallization is in a range of 35 nm to
150 nm, and thereby controlling the preferential crystal
orientation of the orientation controlling layer in the (100)
plane.
Inventors: |
Watanabe; Toshiaki;
(Sanda-shi, JP) ; Sakurai; Hideaki; (Naka-gun,
JP) ; Soyama; Nobuyuki; (Naka-gun, JP) ; Doi;
Toshihiro; (Naka-gun, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
MITSUBISHI MATERIALS CORPORATION |
Tokyo |
|
JP |
|
|
Family ID: |
46208299 |
Appl. No.: |
14/576780 |
Filed: |
December 19, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
13471796 |
May 15, 2012 |
8956689 |
|
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14576780 |
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Current U.S.
Class: |
428/336 ;
427/58 |
Current CPC
Class: |
H01L 28/75 20130101;
H01L 28/65 20130101; Y10T 428/265 20150115; Y10T 428/249921
20150401; B05D 5/00 20130101; H01L 21/02197 20130101; H01L 41/0815
20130101; H01L 29/40111 20190801; B05D 3/0254 20130101; H01L 28/55
20130101; Y10T 428/26 20150115; H01L 41/319 20130101; H01L 21/02282
20130101; Y10T 428/25 20150115; H01L 21/022 20130101 |
International
Class: |
H01L 21/02 20060101
H01L021/02; H01L 21/28 20060101 H01L021/28; H01L 49/02 20060101
H01L049/02; H01L 41/319 20060101 H01L041/319; B05D 3/02 20060101
B05D003/02; B05D 5/00 20060101 B05D005/00 |
Foreign Application Data
Date |
Code |
Application Number |
May 17, 2011 |
JP |
2011-110680 |
Mar 28, 2012 |
JP |
2012-073402 |
Claims
1-13. (canceled)
14. A ferroelectric thin film that has preferred crystal
orientation in the (100) plane that is produced by a method
comprising: coating a composition for forming a ferroelectric thin
film on a base electrode of a substrate having a substrate body and
the base electrode that has crystal faces oriented in the (111)
direction, performing calcination of the coated composition, and
subsequently performing firing of the coated composition to
crystallize the coated composition, and thereby forming a
ferroelectric thin film on the base electrode, wherein the method
includes performing formation of a orientation controlling layer by
a process including coating the composition for forming a
ferroelectric thin film on the base electrode, performing
calcination of the coated composition, and performing firing of the
coated composition, where an amount of the composition for forming
a ferroelectric thin film coated on the base electrode is
controlled such that a thickness of the orientation controlling
layer after crystallization is in a range of 35 nm to 150 nm, and
thereby controlling the preferred orientation of crystals of the
orientation controlling layer in the (100) plane.
15. A composite electronic part of a device selected from a
thin-film capacitor, a capacitor, an IPD, a condenser for a DRAM
memory, a stacked capacitor, a gate insulator of a transistor, a
non-volatile memory, a pyloelectric infrared sensor, a
piezoelectric element, an electro-optic element, an actuator, a
resonator, an ultrasonic motor, and a LC noise filer, wherein the
composite electronic part includes a ferroelectric thin film
according to claim 14.
16. The ferroelectric thin film according to claim 14, wherein the
method further comprises forming a crystal diameter controlling
layer on the base electrode before forming the orientation
controlling layer, wherein the orientation controlling layer is
formed on the crystal diameter controlling layer and the crystal
diameter of the orientation controlling layer is equal to the
crystal diameter of the crystal diameter controlling layer as a
result.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a method for producing a
ferroelectric thin film that is controlled to have preferential
crystal orientation in the (100) plane with a simple process.
[0003] Priority is claimed on Japanese Patent Application No.
2011-110680 filed on May 17, 2011 and Japanese Patent Application
No. 2012-073402 filed on Mar. 28, 2012, the content of which is
incorporated herein by reference.
[0004] 2. Description of Related Art
[0005] In recent years, ferroelectric thin films utilized as
capacitors and piezoelectric elements are widely developed so as to
satisfy requirements for downsizing electronic elements.
[0006] Lead zirconate titanate (PZT) is a ferroelectric material
that has a perovskite structure and exhibits excellent
ferroelectric properties. Using a chemical solution deposition
(CSD) method utilizing sol-gel solution, it is possible to achieve
homogeneous film composition in the plane of a substrate with
inexpensive film-forming process. Therefore, the CSD method is
known as a method of obtaining film-capacitors utilizing the PZT as
a material for ferroelectric thin films.
[0007] Where the ferroelectric film is formed by the CSD method
utilizing sol-gel solution, platinum or iridium having crystal
faces oriented in the (111) direction may be formed as a base
electrode on a substrate. By forming the ferroelectric thin film on
the base electrode formed on the substrate, it has been possible to
obtain ferroelectric thin films having crystals with preferred
orientation in the (111) plane depending on the (111) orientation
of the base substrate.
[0008] Such ferroelectric thin films having a (111)-preferred
orientation are appropriately utilized in an IPD (Integrated
Passive Device), a non-volatile memory or the like because of their
high withstand voltage and life-time reliability.
[0009] On the other hand, conventional methods known to form a film
having preferred crystal orientation in (100) plane or (110) plane
on the base electrode oriented in the (111) direction include using
a seed layer composed of a material different from the
ferroelectric thin film and introducing a buffer layer composed of
a material different from the ferroelectric thin film so as to
suppress the structural influence of the bottom electrode.
Ferroelectric thin films having a preferred orientation in (100)
plane are appropriately used in the application such as actuators
because of a large e.sub.31 piezoelectric constant. Ferroelectric
thin films having a preferred orientation in (110) plane are
appropriately used in the application such as capacitors because of
the large dielectric constant.
[0010] A method for producing a ferroelectric film including
introduction of a buffer layer is disclosed, for example, in
Japanese Unexamined Patent Application First Publication No.
2011-29399 (Claim 7, paragraphs [0003], [0022] to [0026], [0039]
and FIG. 1). This method for producing a ferroelectric film
includes: a step of forming a base film oriented to a predetermined
crystal plane on a surface of a substrate; a step of forming a
carbon film on the base film; a step of forming an amorphous thin
film containing ferroelectric material on the carbon film; and a
step of forming a ferroelectric film on the base film by heating
and thereby crystallizing the amorphous thin film. The
ferroelectric film formed by this method is oriented to a crystal
plane different from the predetermined crystal plane, and the
ferroelectric material is composed of at least one of five types of
materials, a first type material composed of perovskite structure
and bismuth layered-structure oxide, a second type material
composed of superconducting oxide, a third type material composed
of tungsten-bronze structure oxide, a fourth type material composed
of at least one selected from a group consisting of CaO, BaO, PbO,
ZnO, MgO, B.sub.2O.sub.3, Al.sub.2O.sub.3, Y.sub.2O.sub.3,
La.sub.2O.sub.3, Cr.sub.2O.sub.3, Bi.sub.2O.sub.3, Ga.sub.2O.sub.3,
ZrO.sub.2, TiO.sub.2, HfO.sub.2, NbO.sub.2, MoO.sub.3, WO.sub.3,
and V.sub.2O.sub.3, a fifth type material containing the fourth
type material and SiO.sub.2, and a sixth type material containing
the fourth type material, SiO.sub.2, and GeO.sub.2. In Japanese
Unexamined Patent Application First Publication No. 2011-29399
(hereafter referred to as Patent Reference 1), the crystal
orientation of the ferroelectric film formed on the carbon film is
controlled by controlling a thickness of the carbon film formed as
a buffer layer. In the practical embodiment described in Patent
Reference 1, the orientation of the PZT is controlled to have a
(111) plane+(001) plane orientation where a thickness x of the
diamond like carbon (DLC) film formed as the carbon film is in the
range of 0 nm<x<10 nm, the PZT is controlled to have a (001)
plane orientation where the thickness x of the DLC film is 10 nm,
the PZT is controlled to have a (001) plane+(110) plane orientation
where the thickness x of the diamond like DLC film is in the range
of 10 nm<x<100 nm, the PZT is controlled to have a (110)
plane orientation where the thickness x of the DLC film is 100 nm,
and orientation of the PZT is controlled to have weak (110)
orientation where the thickness x of the DLC film is larger than
100 nm.
[0011] The Patent Reference 1 also describes constituting a buffer
layer by stacking LaNiO.sub.3 strongly self-oriented in the (001)
direction on the base electrode having (111) orientation, and
forming a PZT film on the LaNiO3 buffer layer, and thereby
achieving a PZT film having (001) orientation.
[0012] However, the method described in the above-described Patent
Reference 1 requires complicated processes including introduction
of the seed layer and the buffer layer. In addition, the presence
of such a seed layer and a buffer layer may cause deterioration of
properties of the ferroelectric thin film and may cause
contamination or the like.
[0013] As a method for controlling crystal orientation of
ferroelectric thin film, for example, Japanese Unexamined Patent
Application, First Publication No. H06-116095 (hereafter referred
to as Patent Reference 2) discloses a method including: coating a
precursor solution of PZT or PLZT on a platinum substrate having
crystal faces oriented in (111) direction, and heating the
substrate to form a ferroelectric thin film, wherein the substrate
being coated with the precursor solution is firstly subjected to a
heat treatment at a temperature of 150 to 550.degree. C. to achieve
a designated crystal orientation, and is subsequently subjected to
firing at a temperature of 550 to 800.degree. C. to crystallize the
precursor, thereby selectively orienting the crystal plane of the
thin film to a specific direction depending on the heat treatment
temperature (Claims 1 to 4, paragraphs [0005], [0006], FIG. 1).
[0014] In Patent Reference 2, crystal orientation of ferroelectric
thin film is controlled depending on the temperature range of heat
treatment corresponding to preliminary firing, thereby forming a
ferroelectric film having controlled crystal orientation on the
base electrode directly without interposing a seed layer or a
buffer layer. Specifically, Patent Reference 2 describes that the
crystal orientation is controlled such that preferred orientation
in the (111) plane is achieved by the heat treatment at 150 to
250.degree. C., preferred orientation in the (111) plane and (100)
plane is achieved by a heat treatment at 250 to 350.degree. C., and
preferred orientation in the (100) plane and (200) plane is
achieved by a heat treatment at 450 to 550.degree. C.
[0015] However, applicability of the above-described method of
Patent Reference 2 is limited or performance of the film is
insufficient in a practical application since the achieved
preferred orientation includes plural orientations, for example,
(111) plane and (100) plane, or (100) plane and (200) plane.
[0016] When the Pb-containing perovskite type ferroelectric film
has thin thickness, there is a case that crystal nuclei cannot be
generated in sufficient density, resulting in anomalous growth of
large crystals, and making it difficult to control the grain
diameters of crystals. The ferroelectric film with such anomalously
grown crystals is sometimes inferior in insulation property,
thereby including problems in its quality.
[0017] An object of the present invention is to provide a method
for producing ferroelectric thin film that enables achievement of a
ferroelectric thin film that is controlled to have preferred
crystal orientation in the (100) plane with a simple process
without forming a seed layer or a buffer layer.
[0018] The other object of the present invention is to provide a
method for producing a ferroelectric thin film by which the
thickness of a ferroelectric film having preferred crystal
orientation in the (100) plane can be arbitrary adjusted depending
on its intended use.
[0019] Still another object of the present invention is to provide
a method of producing a ferroelectric thin film that enables
control of crystal diameters of a ferroelectric thin film having a
preferred crystal orientation in the (100) plane.
SUMMARY OF THE INVENTION
[0020] Based on the extensive research by the inventors for
ferroelectric thin film having controlled crystal orientation, it
was found that a ferroelectric thin film controlled to have
preferred crystal orientation in (100) plane being independent of
the (111) direction of the base electrode could be achieved simply
without forming a seed layer or a buffer layer by controlling a
thickness of a ferroelectric thin film when the ferroelectric thin
film was formed by the following sol-gel method including: coating
a composition for forming a ferroelectric thin film on a base
electrode of a substrate having the base electrode having crystal
faces oriented in (111) direction; drying and preliminarily firing
the coated composition to form a gel film; and firing and
crystallizing the gel film. It is also found that where the thus
achieved ferroelectric thin film controlled to have preferred
orientation in the (100) plane is used as a base layer, and a
ferroelectric thin film is further formed on the base layer, a
ferroelectric thin film having crystal orientation similar to the
base layer could be obtained irrespective of the thickness of the
ferroelectric film. It is also found that ferroelectric thin film
controlled to have preferred crystal orientation in the (100) plane
can be achieved with fine-grained crystal texture by introducing a
crystal grain size controlling layer to increase nucleation density
before forming the ferroelectric film having a crystal orientation
in the (100) plane. The present invention has been developed based
on the above-described findings.
[0021] A first aspect of the present invention is a method for
producing a ferroelectric thin film including: coating a
composition for forming a ferroelectric thin film on a base
electrode of a substrate having a substrate body and the base
electrode that has crystal faces oriented in the (111) direction,
performing calcination of the coated composition, and subsequently
performing firing of the coated composition to crystallize the
coated composition, and thereby forming a ferroelectric thin film
on the base electrode, wherein the method includes performing
formation of a orientation controlling layer by a process including
coating the composition for forming a ferroelectric thin film on
the base electrode, performing calcination of the coated
composition, and performing firing of the coated composition, where
an amount of the composition for forming a ferroelectric thin film
coated on the base electrode is controlled such that a thickness of
the orientation controlling layer after crystallization is in a
range of 35 nm to 150 nm, and thereby controlling preferred
orientation of crystals of the orientation controlling layer to be
in the (100) plane.
[0022] In the above-described first aspect, since the crystal faces
are oriented in the (111) direction, the surface of the base
electrode is substantially normal (perpendicular) to the (111) axis
of the crystals. The orientation controlling layer formed on the
base electrode is controlled to have (100)-preferred
orientation.
[0023] In the above-described first aspect, the orientation
controlling layer may be formed by repeated coating and calcination
of the composition for forming a ferroelectric thin film for a
plurality of times, and subsequently firing the coated
composition.
[0024] In the above-described first aspect, the substrate body may
be a silicon substrate or a sapphire substrate. The base electrode
may be made of at least one metal selected from Pt, Ir, and Ru.
[0025] A second aspect of the present invention is a method for
producing ferroelectric thin film according to the first aspect,
wherein the calcination for forming the orientation controlling
layer is performed at a temperature in a range of 150.degree. C. to
200.degree. C. or in a range of 285.degree. C. to 315.degree.
C.
[0026] A third aspect of the present invention is a method for
producing a ferroelectric thin film according to the first aspect
or the second aspect, further including forming a crystal diameter
controlling layer on the base electrode before forming the
orientation controlling layer, wherein the orientation controlling
layer is formed on the grain size controlling layer. In the
above-described third aspect, the crystal diameter controlling
layer may be made of a compound selected from at least one of lead
titanate, lead titanate zirconate, and lead zirconate.
[0027] A fourth aspect of the present invention is a method for
producing a ferroelectric thin film according to any one of the
above-described first aspect to third aspect, further including,
after forming the orientation controlling layer, forming a
thickness adjusting layer having crystal orientation that is the
same as the crystal orientation of the orientation controlling
layer by coating the composition for forming a ferroelectric thin
film on the orientation controlling layer, performing calcination
of the coated composition, and performing firing of the coated
composition.
[0028] In the above-described fourth aspect, each of coating of the
coating of the composition, calcination, and firing may be
performed for a plurality of times. For example, the firing may be
performed after repeating coating of the composition and
calcination of the coated composition for a plurality of times. The
process including firing after a repeated coating and calcination
may be repeated a plurality of times. The composition used in the
formation of the thickness adjusting layer may be the same
composition used in the formation of the orientation controlling
layer. Alternatively, concentration of a component to be
crystallized may be different between a composition (a first
composition) used in the formation of the orientation controlling
layer and a composition (a second composition) used in the
formation of the thickness adjusting layer.
[0029] A fifth aspect of the present invention is a method for
producing a ferroelectric thin film according to the fourth aspect,
wherein the calcination for forming the thickness adjusting layer
is performed at a temperature in a range of 200.degree. C. to
450.degree. C.
[0030] A sixth aspect of the present invention is a method for
producing a ferroelectric thin film according to any one of the
first to fifth aspect, wherein the ferroelectric thin film includes
Pb-containing perovskite type oxide, and the composition for
forming the ferroelectric thin film includes .beta.-diketone and
polyhydric alcohol.
[0031] A seventh aspect of the present invention is a method for
producing ferroelectric thin film according to the sixth aspect,
wherein the .beta.-diketone group is acetylacetone and the
polyhydric alcohol is propylene glycol.
[0032] An eighth aspect of the present invention is a ferroelectric
thin film that is produced by a method according to any one of the
first to seventh aspects and has preferred crystal orientation in
the (100) plane.
[0033] A ninth aspect of the present invention is a composite
electronic part of a device selected from a thin-film capacitor, a
capacitor, an IPD, a condenser for a DRAM memory, a stacked
capacitor, a gate insulator of a transistor, a non-volatile memory,
a pyloelectric infrared sensor, a piezoelectric element, an
electro-optic element, an actuator, a resonator, an ultrasonic
motor, and a LC noise filer, wherein the composite electronic part
includes a ferroelectric thin film according to the eighth
aspect.
[0034] According to the first aspect of the present invention, the
method for producing a ferroelectric thin film includes coating a
composition for forming a ferroelectric thin film on a base
electrode of a substrate having the base electrode in which
crystals are oriented in the (111) direction, heating the coated
composition to crystallize the coated composition, wherein the
ferroelectric thin film includes a orientation controlling layer
having crystal orientation controlled to preferred orientation in
the (100) plane, and a thickness of the orientation controlling
layer after crystallization is controlled to be in a range of 35 nm
to 150 nm By thus controlling the thickness of the orientation
controlling layer after the crystallization in the above-described
range, it is possible to achieve a ferroelectric thin film having
crystal orientation controlled to have a preferred orientation in
the (100) plane simply without forming a seed layer or a buffer
layer.
[0035] According to the second aspect of the present invention,
calcination temperature for forming the orientation controlling
layer is controlled to be in a range of 150.degree. C. to
200.degree. C. or in a range of 285.degree. C. to 315.degree. C. By
this constitution, it is possible to form the ferroelectric thin
film controlled to have a preferred orientation in the (100) plane
more stably.
[0036] According to the third aspect of the present invention,
crystal diameter controlling layer is formed on the base layer
before forming the orientation controlling layer, thereby
suppressing anomalous grain growth in the orientation controlling
layer. As a result, it is possible to achieve an orientation
controlling layer having preferred orientation in the (100) plane
with fine-grained crystal texture.
[0037] According to the fourth aspect of the present invention,
after forming the orientation controlling layer, a thickness
adjusting layer is formed on the orientation controlling layer by
coating a composition for forming a ferroelectric film on the
orientation controlling layer, calcining (calcinating) and firing
the coated composition, thereby forming a thickness adjusting layer
having the same crystal orientation as the crystal orientation of
the orientation controlling layer. Therefore, it is possible to
achieve a thickness adjusting layer which is controlled to have
preferred crystal orientation in the (100) plane. By this
constitution, it is possible to control a thickness of the
ferroelectric thin film having preferred orientation in the (100)
plane arbitrarily depending on the use of the ferroelectric thin
film.
[0038] According to the fifth aspect of the present invention, when
the thickness adjusting layer is formed, temperature of the
calcination after coating a composition for forming a ferroelectric
thin film is controlled within a range of 200.degree. C. to
450.degree. C. By this constitution, it is possible to form a
ferroelectric thin film controlled to have preferred orientation in
the (100) plane more stably depending on the crystal orientation of
the thickness adjusting layer further stably.
BRIEF DESCRIPTION OF THE DRAWINGS
[0039] FIG. 1 is a schematic cross sectional drawing for explaining
production method according to a first aspect of the present
invention.
[0040] FIG. 2 is a schematic cross sectional drawing for explaining
a production method according to a second aspect of the present
invention.
[0041] FIG. 3 shows XRD patterns of Examples 1, 2, 5, 6, 9, 11, 12,
13, 15, 16, 19, and 20.
[0042] FIG. 4 shows XRD patterns of Comparative Examples 1, 2, and
3.
[0043] FIG. 5 shows a surface SEM image (10000 times magnification)
of Example 9.
[0044] FIG. 6 shows a surface SEM image (50000 times magnification)
of Example 13.
DETAILED DESCRIPTION OF THE INVENTION
[0045] Embodiments of the present invention are explained with
reference to drawings.
[0046] The present invention improves a method for producing
ferroelectric material including: coating a composition for forming
a ferroelectric thin film on a base electrode of a substrate that
has the base electrode having crystal faces oriented in the (111)
direction, heating the coated composition, and thereby
crystallizing the coated composition.
[0047] In the present invention, the ferroelectric thin film
includes a orientation controlling layer (first ferroelectric
layer). Formation process of the orientation controlling layer
includes: performing formation of a coated film by coating a
composition for forming a ferroelectric thin film on the base
electrode directly or interposing a crystal diameter controlling
layer therebetween; performing calcination (drying and preliminary
firing) of the coated film to form a gel film; and performing
firing (main firing) of the gel film to crystallize the gel film.
The amount of the composition for forming a ferroelectric thin film
is controlled such that a thickness of the orientation controlling
layer after crystallization is controlled to be in the range of 35
nm to 150 nm By this constitution, it is possible to control the
crystals of the orientation controlling layer formed as a
polycrystalline film to have a preferred orientation in the (100)
plane. The state that "crystals of a layer have a preferred
orientation in the (100) plane" denotes a state that (100) planes
of the crystals are preferentially oriented substantially parallel
to the surface (interface) of the layer. In other words, the state
may be described that the layer has (100)-preferred
orientation.
[0048] For example, where crystal orientation of the orientation
controlling layer is analyzed by X-ray diffraction, diffraction
intensity of (100) plane shows maximum value in diffraction
intensities of crystal planes of constituent crystals of the
orientation controlling layer. The ferroelectric thin film may be
constituted of the above-described orientation controlling layer.
On the other hand, the ferroelectric thin film may further includes
a thickness adjusting layer formed on the orientation controlling
layer. Formation process of the thickness adjusting layer includes:
performing coating of a composition for forming a ferroelectric
thin film on the orientation controlling layer to form a coated
film; performing calcination of the coated film to form a gel film;
and performing firing of the gel film to crystallize the gel film.
Since the orientation controlling layer is formed as a base layer,
the thickness adjusting layer (second ferroelectric layer) formed
on the orientation controlling layer is formed as a polycrystalline
film that is controlled to have preferred crystal orientation in
the (100) plane.
[0049] Where the crystal diameter controlling layer is formed, a
gel film (having a thickness of about 1 to 10 nm) is formed as the
crystal diameter controlling layer on the base electrode, and the
orientation controlling layer is formed on the crystal diameter
controlling layer. Formation process of the crystal diameter
controlling layer includes: coating a composition for the crystal
diameter controlling layer on the base electrode to forma a coated
film; and calcining the coated film to form a gel film.
[0050] Preferably, the ferroelectric thin film constituted of the
orientation controlling layer or of the orientation controlling
layer and the thickness adjusting layer may be made of at least one
Pb-containing perovskite type oxide selected from PZT, PLZT, PMnZT,
and PNbZT. The crystal diameter controlling layer may be made of at
least one compound selected from lead titanate, lead titanate
zirconate, and lead zirconate. Each of the composition for forming
a ferroelectric thin film and the composition for forming a crystal
diameter controlling layer may be a composition that includes
organic solvent and organic metal compound dissolved in the organic
solvent.
[0051] The calcination and firing in the above-explained formation
process of the orientation controlling layer and the thickness
adjusting layer, and calcination in the above-explained formation
process of the crystal diameter controlling layer may be performed
by heat treatment of a substrate after forming the coated film at a
predetermined temperature in a predetermined atmosphere.
[0052] Hereafter, embodiments of the present invention is explained
with reference to the drawings.
[0053] FIG. 1 shows a schematic cross sectional view of a
constitution formed by the method according to a first embodiment
of the invention. As shown in FIG. 1, in a first embodiment, a base
electrode 11 having crystal faces oriented in the (111) direction
is formed on a substrate body 10, and a ferroelectric thin film is
formed on the base electrode 11. In the present invention, the
ferroelectric thin film includes a orientation controlling layer
(first ferroelectric layer) 13 that is controlled to have preferred
crystal orientation in the (100) plane, and thickness of the
orientation controlling layer 13 after the crystallization is
controlled to be in the range of 35 nm to 150 nm By the thus
controlling the thickness of the orientation controlling layer 13
after the crystallization to be in the range of 35 nm to 150 nm, it
is possible to achieve a ferroelectric thin film that is controlled
to have preferred crystal orientation in the (100) plane simply
without forming a seed layer or a buffer layer. It is considered
that, where a thickness of the orientation controlling layer after
the crystallization is controlled to be in the above-described
range, crystals of the orientation controlling layer is
spontaneously oriented so as to minimize the surface energy,
resulting in preferred crystal orientation in the (100) plane. A
thickness of the orientation controlling layer 13 after the
crystallization is in the range of 35 nm to 150 nm Where the
thickness is less than 35 nm, it is not preferable since the layer
is oriented to different direction such as (110) orientation.
Because of the same reason, a thickness exceeding 150 nm is not
preferable. In the thickness exceeding 150 nm, the layer has
crystal orientation different from (100) plane. More preferably,
thickness of the orientation controlling layer after the
crystallization is in the range of 45 nm to 90 nm Where the
thickness is less than 45 nm, it is difficult to achieve
(100)-orientation stably since the optimum temperature for
calcination must be controlled in a narrow range. Similarly,
optimum temperature range for calcination is narrowed where the
thickness exceeds 90 nm.
[0054] A refractory (heat-resisting) substrate such as silicon
substrate, sapphire substrate or the like is used as the substrate
body 10 for producing a ferroelectric thin film. A base electrode
11 having crystal faces oriented in the (111) direction is formed
on the substrate 10. The base electrode is made of a material that
has electro-conductivity and that is not reacted with the
ferroelectric thin film. For example, the base electrode may be
made of at least one metal selected from Pt, Ir, and Ru. In the
above and in the following description, the base electrode having
crystal faces oriented in the (111) direction denotes a state that
faces of the crystals exposed on the surface of the base electrode
is substantially normal to the (111) axis. The above-explained base
electrode may be formed on the substrate body using a sputtering
method or the like. Preferably, the ferroelectric thin film is made
of Pb-containing perovskite type oxide (Pb-containing oxide having
perovskite structure). For example, the ferroelectric thin film may
be made of at least one composite oxide selected from PZT (lead
zirconate titanate), PLZT (lead lanthanum zirconate ritanate),
PMnZT, and PNbZT. A composition for forming a ferroelectric thin
film is made of a solution in which organic metal compound is
dissolved in organic solvent such that materials for constituting
the composite oxide provides designated atomic ratio. As a raw
material for the composite oxide, it is preferable to use chemical
compound in which organic group is connected to respective metallic
element such as Pb, La, Zr, and Ti via a oxygen or nitrogen atom of
the organic group. For example, the raw material may be selected
from one or two or more compounds selected from metal alkoxide,
metal diol complex, metal triol complex, metal carbonate, metal
.beta.-diketonate complex, metal .beta.-diketoester complex, metal
.beta.-iminoketo complex, and metal amino complex. Especially,
metal alkoxide, hydrolysate of the metal alkoxide, or organic salt
are preferred. For example, lead acetate (Pb(OAc).sub.2 or lead
diisopropoxide (Pb(OiPr).sub.2) may be used as a lead compound.
Lanthanum acetate (La(OAc).sub.3) or lanthanum triisopropoxide:
La(OiPr).sub.3 may be used as a lanthanum compound. Titanium
alkoxide such as titanium tetraethoxide: Ti(OEt).sub.4, titanium
tetraisopropoxide: Ti(OiPr).sub.4, titanium tetra-n-butoxide:
Ti(OnBu)4, titanium tetra-iso-butoxite: Ti(OiBu).sub.4, titanium
tetra-t-butoxide: Ti(OtBu)4, and titanium dimetoxy-di-isopropoxide:
Ti(OMe).sub.2(OiPr).sub.2 may be used as a titanium compound. Like
as the above-described titanium compound, zirconium compound may be
selected from zirconium olkoxides such as zirconium methoxide:
Zr(OEt).sub.4, zirconium tetraisopropoxide: Zr(OiPr).sub.4,
zirconium tetra-n-butoxide: Zr(OnBu).sub.4, zirconium
tetra-iso-butoxite: Zr(OiBu).sub.4, zirconium tetra-t-butoxide:
Zr(OtBu)4, and zirconium dimetoxy-di-isopropoxide:
Zr(OMe).sub.2(OiPr).sub.2. The above-described metal alkoxide may
be used as it is. Alternatively, hydrolysate of the metal alkoxide
may be used so as to enhance decomposition. In the preparation
process of the composition for forming a ferroelectric material,
the above-explained raw materials are dissolved at a ratio
corresponding to the chemical composition of designated
ferroelectric thin film in an appropriate solvent thereby
controlling the concentration to a value that is appropriate for
coating.
[0055] As a typical example, precursor solution as the composition
for forming a ferroelectric thin film can be obtained by
below-described flow of solution synthesis. Zr source (for example,
zirconium tetra-n-butoxide) and Ti source (for example, titanium
isopropoxide), and stabilizing agent (for example, acetylacetone)
are contained in a reaction vessel and are refluxed in nitrogen
atmosphere. Next, chemical compound after the refluxing is added
with Pb source (for example, lead acetate trihydrate) and solvent
(for example, propylene glycol), and is refluxed in nitrogen
atmosphere to obtain a solution. After removing byproducts from the
solution by vacuum distillation, concentration of the solution is
modified by adding propylene glycol. Further, n-butanol is added to
the solution. As a result, a composition for forming a
ferroelectric thin film is obtained.
[0056] The solvent used in the preparation of the composition for
forming ferroelectric thin film may be selected depending on the
source materials for the ferroelectric thin film. In general case,
calboxylic acid, alcohol (for example, propylene glycol as a
polyhydric alcohol), ester, ketones (for example, acetone, methyl
ethyl ketone), ethers (for example, dimethyl ether, diethyl ether),
cycloalkanes (for example, cyclohexane), cycloalkanol (for example,
cyclohexanol), aromatic solvents (for example, benzene, toluene,
xylene), tetrahydrofuran or the like may be used as the solvent.
One solvent selected from the above-described solvents or a mixture
of two or more solvents selected from the above-described solvents
may be used. Preferably, the carboxylic acid may be selected from
the group consisting of n-butyric acid, .alpha.-methylbutyric acid,
i-valeric acid, 2-ethylbutyric acid, 2,2-dimethylbutyric acid,
3,3-dimethyl butyric acid, 2,3-dimetyl butyric acid,
3-methylpentanoic acid, 4-methylpentanoic acid, 2-ethylpentanoic
acid, 3-ethylpentanoic acid, 2,2-dimethylpentanoic acid,
2-ethylhexanoic acid, and 3-ethylhexanoic acid.
[0057] Preferably, the ester used as the solvent may be selected
from the group consisting of ethyl acetate, propyl acetate, n-butyl
acetate, sec-butyl acetate, tert-butyl acetate, isobutyl acetate,
n-amyl acetate, sec-amyl acetate, tert-amyl acetate, and isoamyl
acetate. Preferably, alcohol used as the solvent may be selected
from the group consisting of 1-propanl, 2-propanol, 1-butanol,
2-butanol, isobutyl alcohol, 1-pentanol, 2-pentanpl,
2-methyl-2-pentanol, and 2-methoxy ethanol.
[0058] Total concentration of the organic metal compound in the
organic metal compound solution as a composition for forming a
ferroelectric thin film is preferably controlled in the range of
0.1 to 20% by mass in converted amount where the amount of the
organic metal compound is converted to the amount of metal
oxide.
[0059] Where necessary, stabilizing agent may be added to the
organic metal compound solution in an amount such that (number of
molecules of the stabilizing agent)/(number of metal atoms) is 0.2
to 3. The stabilizing agent may be selected from the group
consisting of .beta.-diketones (for example, acetyl acetone,
heptafluoro butanoyl pivaloyl methane, dipivaloyl methane,
trifluoroacetylacetone, benzoylacetone or the like), .beta.-ketonic
acids (for example, acetoacetic acid, propionyl acetic acid,
benzoyl acetic acid or the like), .beta.-keto esters (for example,
lower alkyl esters such as methyl, propyl, or butyl of the
above-described ketonic acids), oxyacids (for example, lactic acid,
glycol acid, .alpha.-oxybutyric acid, salicylic acid or the like),
lower alkyl esters of the above-described oxyacids, oxyketones,
diacetone alcohol, acetoin, or the like), diol, triol, higher
carboxylic acid, alkanol amines (for example, diethanolamine,
triethanolamine, monoethanolamine), and polyamine or the like.
[0060] Preferably, the compositions for forming a ferroelectric
thin film includes .beta.-diketone and polyhydric alcohol. More
preferably, the composition includes acetyl acetone as the
.beta.-diketone and propylene glycol as the polyhydric alcohol.
[0061] Preferably, number of particles contained in the organic
metal compound solution is controlled such that numbers of
particles of 0.5 .mu.m or more (more preferably, 0.3 .mu.m or more,
and more preferably, 0.2 .mu.m or more) in diameter is 50 or less
per 1 mL of the solution by removing the particles by filtering or
the like. Where the number of particles of 0.5 .mu.m or more in
diameter in the organic metal compound solution exceeds 50/mL, the
solution cannot be preserved stably for a long time. In the organic
metal compound solution, it is preferable to reduce the number of
particles of 0.5 .mu.m or more in diameter to be as small as
possible, preferably to 30/ml or less.
[0062] A treatment for controlling the number of particles to the
above-described range is not particularly limited. For example, the
following methods can be applied. In a first method, a commercially
available membrane filter having a pore size of 0.2 .mu.m is used
for filtering, and the solution is sent to the filter under
pressure by a syringe. A second method is a pressurized filtering
using a commercially available membrane filter having a pore size
of 0.2 .mu.m and a pressurizing tank. A third method is a
circulation filtering using the filter used in the second method
and a solution circulating bath.
[0063] In any of the method, ratio of capturing the particles by
the filter is different depending on the pressure for sending the
solution. It is generally known that the ratio of capturing is
increased as the pressure is decreased. Specifically in the first
and the second method, it is preferable to filtrate the solution
very slowly with low pressure so as to realize the conditions such
that number of particles of 0.5 .mu.m or more in diameter in the
solution is 50/mL or less.
[0064] The composition for forming a ferroelectric thin film may be
used in the formation of a ferroelectric layer as a constituent of
a ferroelectric thin film. The ferroelectric layer may be obtained
by coating the above-described composition on the base electrode
oriented to (111) direction by spin coating, dip coating, LSMCD
(Liquid Source Misted Chemical Deposition) or the like, performing
drying and preliminary firing of the coated composition using a hot
plate or the like and thereby forming a gel layer, and performing
firing of the gel layer using a hot plate or the like.
[0065] In the formation of the ferroelectric layer, the formation
of the gel layer by coating, drying, and preliminary firing the
composition may be repeated for a plurality of times, and the
stacked gel layers may be fired in the same time. By this method,
it is possible to form a ferroelectric thin film of desired
thickness. In the first embodiment shown in FIG. 1, a orientation
controlling layer (first ferroelectric layer) is formed directly on
the surface of the base electrode 11 by the above-described
method.
[0066] Drying and preliminary firing are performed so as to remove
the solvent from the coated composition, and to convert the organic
metal compound to composite oxide by thermal decomposition or by
hydrolysis of the organic metal compound. Therefore, the heat
treatment (calcination) for drying and preliminary firing is
performed under the air atmosphere, oxidizing atmosphere, or water
vapor containing atmosphere. Even in the air atmosphere, humidity
in the air provides sufficient water component required for the
hydrolysis. The heat treatment may be performed by two step heating
including low-temperature hearting for removing the solvent and
high-temperature heating for decomposing the organic metal
compound.
[0067] Firing (main firing, second firing) is performed so as to
heat a thin film obtained by the drying and preliminary firing at a
temperature of not lower than crystallizing temperature, thereby
crystallizing the thin film. By this treatment, a ferroelectric
thin film is obtained. As an atmosphere for the crystallizing
process, it is preferable to use an atmosphere of one gas selected
from O.sub.2, N.sub.2, Ar, N.sub.2O, and H.sub.2 or the like or a
mixed gas of two or more selected from those gases.
[0068] Drying and preliminary firing may be performed at a
temperature of 150 to 550.degree. C. for 1 to 10 minutes.
[0069] In the above-described temperature range, it is preferable
to use a range of 150.degree. C. to 200.degree. C. or a range of
285.degree. C. to 315.degree. C. where the grain diameter
controlling layer is not introduced into the ferroelectric thin
film. In this case, heating temperature around 250.degree. C. is
not appropriate for forming primary nuclei having (100) orientation
are not generated in the interface between the substrate and the
film. On the other hand, where a grain diameter controlling layer
is introduced into the ferroelectric thin film as in the
below-described second embodiment, it is preferable to control the
heating temperature to be in the range of 175.degree. C. to
315.degree. C. As a result of introduction of crystal diameter
controlling layer having low-crystallizing temperature, primary
nuclei having (100) orientation are formed at a temperature of
175.degree. C. to 315.degree. C.
[0070] Main firing is performed at a temperature of 450 to
800.degree. C. for 1 to 60 minutes. The main firing may be
performed by rapid thermal annealing (RTA treatment). When the main
firing is performed by RTA treatment, it is preferable to control
the temperature-increasing rate to 10 to 100.degree. C./second.
[0071] FIG. 2 is a schematic cross sectional view showing a
constitution of the second embodiment of the present invention. As
shown in FIG. 2, it is preferable to form a crystal diameter
controlling layer 12 on the base electrode 11 of the substrate 10
before forming the orientation controlling layer 13, and to form
the orientation controlling layer 13 on the crystal diameter
controlling layer 12. By the thus forming the crystal diameter
controlling layer 12, it is possible to increase density of
generated nuclei, thereby suppressing anomalous growth of crystals
of the orientation controlling layer 13. As a result, it is
possible to obtain the orientation controlling layer 13 having a
preferred orientation in the (100) plane with fine crystal
texture.
[0072] As a material of crystal diameter controlling layer 12, it
is possible to use lead titanate, lead titanate zirconate, lead
zirconate or the like. Preferably, thickness of the crystal
diameter controlling layer is 1 nm to 10 nm. If the thickness of
the crystal diameter controlling layer exceeds 10 nm, effect of
enhancing generation density of nuclei cannot be obtained. As a
result, it is impossible to achieve a fine crystal texture.
Therefore, thickness of the crystal diameter controlling layer is
controlled in the above-describe range.
[0073] As like as the formation of the above-described orientation
controlling layer, the crystal diameter controlling layer 12 may be
formed by coating a composition for crystal diameter controlling
layer on the base electrode oriented in the (111) direction by spin
coating, dip coating, LSMCD (Liquid Source Misted Chemical
Deposition) or the like, performing drying and preliminary firing
of the coated composition using a hot plate or the like at a
temperature of 150 to 550.degree. C. for 1 to 10 minutes. The
process of coating, drying, and preliminary firing of the substrate
may be repeated for a plurality of times so as to achieve a gel
film (gel layer) of desired thickness. Where the crystal diameter
controlling layer 12 is formed, the orientation controlling layer
13 is formed on the crystal diameter controlling layer 12. The gel
film of the crystal diameter controlling layer 12 is crystallized
in the time of main firing for forming the orientation controlling
layer 12. Composition for the size may be prepared in the same
manner as the above-explained preparation of the composition for
forming a ferroelectric thin film, where concentration of the
organic metal compound dissolved in the organic solvent is
controlled depending on the designated thickness. For example,
where a composition for forming a ferroelectric thin film has
concentration of 5 to 12% by mass in conversion to the amount of
metal oxide, the composition for the crystal diameter controlling
layer may has a concentration of 1 to 2% by mass in conversion to
the amount of metal oxide.
[0074] Both in the first embodiment and the second embodiment, it
is preferable to form a thickness adjusting layer 14 on the
orientation controlling layer 13 utilizing the orientation
controlling layer 13 as a base layer such that the thickness
adjusting layer 14 has the same crystal orientation as the base
layer (orientation controlling layer 13). By forming the thickness
adjusting layer 14 on the base layer, preferred orientation of
crystal plane of the thickness adjusting layer 14 is formed similar
to that of the orientation controlling layer 13 depending on the
preferred orientation of the orientation controlling layer 13. By
the thus forming a thickness adjusting layer 14, a thickness of
ferroelectric thin film having a preferred orientation controlled
to (10) plane by the presence of the orientation controlling layer
can be adjusted arbitrarily depending on the intended use of the
film.
[0075] The thickness adjusting layer 14 is a film made of the same
Pb-containing perovskite type oxide as the orientation controlling
layer 14. Preferably, thickness of the thickness adjusting layer 14
is smaller than 5000 nm. When a thickness of the thickness
adjusting layer is 5000 nm or more, long processing time is
required, and dependence of orientation of the thickness adjusting
layer on the preferred orientation of the orientation controlling
layer is deteriorated resulting in small degree of preferred
orientation in the (100) plane.
[0076] Formation of the thickness adjusting layer 14 may be
performed in the similar manner as the above-described formation of
the orientation controlling layer 13. Composition for thickness
adjusting layer is coated on the orientation controlling layer 13
by spin coating, dip coating, LSMCD (Liquid Source Misted Chemical
Deposition) or the like. The coated composition is dried and
preliminarily fired using a hot plate or the like at 150 to
550.degree. C. for 1 to 10 minutes in the air atmosphere. After
repeating the process from coating to drying and preliminary firing
of the composition to form a gel film of designated thickness, the
gel film is subjected to main firing in at 450 to 800.degree. C.
for 1 to 60 minutes in the oxygen atmosphere. The above-explained
composition for forming a ferroelectric thin film can be used as
the composition for the thickness adjusting layer as well as the
composition for the orientation controlling layer. The orientation
controlling layer 13 and the thickness adjusting layer 14 may be
formed using the same composition for forming a ferroelectric thin
film. Alternatively, the composition used in the formation of the
orientation controlling layer 13 and the composition used in the
formation of the thickness adjusting layer 14 may be selected from
two compositions for forming ferroelectric thin films having
different concentration of oxide component.
[0077] The thus produced ferroelectric thin film of the present
invention is controlled to have preferred orientation in the (100)
plane, and has large piezoelectric constant e.sub.31.
[0078] For example, where I.sub.100, I.sub.110, and I.sub.111
respectively denote diffraction intensity of (100) plane, (110)
plane, and (111) plane of ferroelectric crystals determined by
X-ray diffraction of the ferroelectric thin film produced by the
above-described method, degree of orientation defined by
I.sub.100/(I.sub.100+I.sub.110+I.sub.111) is 0.86 or more where the
ferroelectric thin film is composed of the orientation controlling
layer and is 0.78 or more (for example, 0.78 to 0.91) where the
ferroelectric thin film is composed of the orientation controlling
layer and the thickness adjusting layer.
[0079] The ferroelectric thin film of the present invention may be
used as a member of a composite electronic part of a device
selected from a thin-film capacitor, a capacitor, an IPD, a
condenser for a DRAM memory, a stacked capacitor, a gate insulator
of a transistor, a non-volatile memory, a pyloelectric infrared
sensor, a piezoelectric element, an electro-optic element, an
actuator, a resonator, an ultrasonic motor, and a LC noise
filer,
EXAMPLES
[0080] Next examples of the present invention and comparative
examples are explained in detail.
Preparation of Composition for Crystal Diameter Controlling Layer,
Composition for Orientation Controlling Layer, and Composition for
Thickness Adjusting Layer
[0081] As a typical process, the compositions were prepared by the
following flows of solution synthesis.
[0082] Firstly, zirconium tetra-n-butoxide (Zr source), titanium
isopropoxide (Ti source), and acetyl acetone (stabilizing agent)
were contained in a reaction vessel and were refluxed in nitrogen
atmosphere. Next, the above-described chemical compound after the
refluxing was added with lead acetate trihydrate (Pb source), and
propylene glycol (solvent), and was refluxed in nitrogen
atmosphere. After removing byproducts from the thus formed solution
by vacuum distillation, concentration of the solution was
controlled by adding propylene glycol. Further, n-butanol was added
to the solution. As a result, the composition was obtained as a
precursor solution.
[0083] Practically, synthesis of respective compositions were
performed in accordance with the below-described process.
[0084] Firstly, titanium isopropoxide (Ti source), and acetyl
acetone (stabilizing agent) were contained in a reaction vessel and
were refluxed in nitrogen atmosphere. Next, the above-described
chemical compound after the refluxing was added with lead acetate
trihydrate (Pb source), and propylene glycol (solvent), and
wasrefluxed in nitrogen atmosphere. After removing byproducts from
the thus formed solution by vacuum distillation, concentration of
the solution was controlled by adding propylene glycol. Further,
diluted alcohol was added to the solution thereby controlling the
concentration of metallic compound in the solution, thereby
obtaining a composition for crystal diameter controlling layer. By
the above-described method, ratio of metals in the ratio in
converted oxide was controlled to Pb/Ti=125/100. As shown in Table
1 and Table 2, two types of compositions for respectively
containing metal compound of 1% by mass and 2% by mass in
concentration of converted lead titanate (PT) component were
prepared.
[0085] Firstly, zirconium tetra-n-butoxide (Zr source), titanium
isopropoxide (Ti source), and acetyl acetone (stabilizing agent)
were contained in a reaction vessel and were refluxed in nitrogen
atmosphere. Next, the above-described chemical compound after the
refluxing was added with lead acetate trihydrate (Pb source), and
propylene glycol (solvent), and was refluxed in nitrogen
atmosphere. After removing byproducts from the thus formed solution
by vacuum distillation, concentration of the solution was
controlled by adding propylene glycol. Further, diluted alcohol was
added to the solution thereby controlling the concentration of
metallic compound in the solution, thereby obtaining a composition
for forming a ferroelectric layer. By the above-described method,
ratio of metals in the ratio in converted oxide was controlled to
be Pb/Zr/Ti=110/52/48. As shown in Table 1 and Table 2, four types
of compositions for respectively containing metal compound of 5% by
mass, 10% by mass, 11% by mass, and 12% by mass in concentration of
converted PZT component and were used as the composition for the
orientation controlling layer and the composition for the thickness
adjusting layer.
[0086] The above-described organic metal compound solution
constituting the composition for crystal diameter controlling
layer, composition for orientation controlling layer, and
composition for thickness adjusting layer were filtrated by sending
each solution under pressure by a syringe to a commercial membrane
filter having pore diameter of 0.2 .mu.m. As a result, number of
particles of 0.5 .mu.m or more in diameter was 1/mL, 2/mL, and 1/mL
respectively.
Formation of Ferroelectric Thin Film
[0087] Twenty three substrates having a Si substrate body and a Pt
base electrode were prepared. Each substrate was prepared by
forming the Pt base electrode by sputtering method on a Si
substrate of 6 inches in diameter. Ferroelectric thin films of
Examples 1 to 30 and Comparative Examples 1 to 3 were respectively
formed on the Pt base electrode of the substrate using the
compositions formed by the above-explained preparation process
under different film formation conditions. Film formation
conditions of ferroelectric thin films of Examples 1 to 30 and
Comparative Examples 1 to 3 are shown in Tables 1 and 2. Coating of
the composition was performed using a spin coater. In Tables,
"repetition" shows a number of repeated coating and calcination the
composition, rotation rate and time respectively show rotation rate
of the spin coater and time of rotation at that rate. In each of
the coating conditions, the spin coater was rotated at a rate of
500 rpm for 3 seconds in the starting of coating, and subsequently
rotated at a rate shown in the Tables. Calcination (drying and
preliminary firing) was performed using a hot plane in the air
atmosphere. In each case, formation process of the orientation
controlling layer and formation process of the thickness adjusting
layer each included main firing, where the main firing was
performed by heating the substrate to 700.degree. C. at heating
rate of 10.degree. C./second and annealing the substrate at
700.degree. C. for 1 minute in oxygen atmosphere, thereby
crystallizing the film after the calcination. Frequency of firing
in the Tables shows number of repetition of the process including
coating, drying, and preliminary firing of the composition, and
subsequent firing (main firing). Examples of detailed formation
processes of the orientation controlling layer, thickness adjusting
layer, and the crystal diameter controlling layer are described in
the below described explanation of Examples 1, 4, and 12.
Example 1
[0088] A substrate having a Pt base electrode was prepared by
forming the Pt base layer on a silicon substrate by sputtering
method. Composition for orientation controlling layer which had
been prepared as described-above was coated on the Pt base
electrode by spin coating method, where the spin coating was
performed firstly with a rotation rate of 500 rpm for 3 seconds,
and subsequently with a rotation rate of 3500 rpm for 15 seconds.
Next, the coated composition was dried and preliminarily fired by
heating the substrate using a hot-plate at 300.degree. C. for 5
minutes in the air atmosphere. After performing the coating and
calcination of the composition for one time the coated composition
was subjected to firing (main firing) by heating the substrate to
700.degree. C. with heating rate of 10.degree. C./second and
annealing the substrate at 700.degree. C. for 1 minute in oxygen
atmosphere. By this process, the coated composition was
crystallized, and a orientation controlling layer of 35 nm in
thickness was obtained. Ferroelectric thin film of Example 1 was
constituted of the orientation controlling layer.
Examples 2, 3, 6 and 7
[0089] In Examples 2, 3, 6, and 7, a ferroelectric thin film was
formed on Pt base electrode of each substrate under conditions
shown in Table 1, and the ferroelectric thin film was obtained as
an orientation controlling layer having a thickness shown in Table
3.
TABLE-US-00001 TABLE 1 Example Number 1 2 3 4 5 6 7 8 9 10 11
Orientation Concentration (mass %) 10 12 12 10 12 5 12 12 12 12 12
controlling layer Frequency of coating 1 1 1 2 1 3 1 1 1 1 1
Rotation rate (rpm) 3500 2000 3000 3000 2000 2000 2000 2000 2000
2000 2000 Time of rotation (second) 15 20 15 15 15 15 20 20 20 20
20 Calcination temperature .sup.(.degree. C.) 300 150 175 175 175
175 200 200 200 315 175 Time of calcination (minute) 5 5 5 5 5 5 5
5 5 5 5 Frequency of firing 1 1 1 1 1 1 1 1 1 1 1 Thickness
Concentration (mass %) 10 10 5 12 10 10 adjusting layer Frequency
of coating 6 6 1 4 6 6 Rotation rate (rpm) 3000 2000 2000 2000 3000
3000 Time of rotation (second) 15 15 20 20 15 15 Calcination
temperature .sup.(.degree. C.) 175 175 300 300 300 300 Time of
calcination (minute) 5 5 5 5 5 5 Frequency of firing 1 1 1 1 1
1
TABLE-US-00002 TABLE 2 Comparative Example Example Number 12 13 14
15 16 17 18 19 20 1 2 3 Crystal diameter Concentration (mass %) 1 1
2 1 1 1 1 1 1 1 controlling layer Frequency of coating 1 1 1 1 1 1
1 1 1 1 Rotation rate (rpm) 2000 2000 2000 2000 2000 3000 3000 3000
3000 2000 Time (second) 20 20 20 20 20 20 20 15 15 20 Calcination
temperature (.degree. C.) 175 200 200 200 200 200 200 250 250 200
Time of calcination 5 5 5 5 5 5 5 5 5 5 Controlled Concentration
(mass %) 12 12 12 12 12 10 10 12 12 5 11 10 orientation layer
Frequency of coating 1 1 1 2 1 1 2 1 1 2 3 6 Rotation rate (rpm)
2000 2000 2000 2000 2000 3000 3000 3000 3000 2000 3000 3000 Time of
rotation (second) 20 20 20 20 20 20 20 20 20 20 20 20 Calcination
temperature .sup.(.degree. C.) 175 200 300 200 200 200 200 250 250
200 200 200 Time of calcination (minute) 5 5 5 5 5 5 5 5 5 5 5 5
Frequency of firing 1 1 1 1 1 1 1 1 1 1 1 1 Thickness adjusting
Concentration (mass %) 12 12 12 12 10 10 12 layer Frequency of
coating 4 4 4 4 6 6 4 Rotation rate (rpm) 2000 2000 2000 2000 3000
3000 2000 Time of rotation (second) 20 20 20 20 20 20 20
Calcination temperature .sup.(.degree. C.) 300 300 300 300 300 300
300 Time of calcination (minute) 5 5 5 5 5 5 5 Frequency of firing
1 1 1 10 1 1
Examples 4, 5, 8, 9, 10, 11
[0090] In Example 4, orientation controlling layer of 90 nm in
thickness was formed on the Pt base electrode of a substrate using
conditions shown in Table 1. After that, composition for a
thickness adjusting layer was coated on the substrate by spin
coating method. The composition which was prepared as described
above had a concentration of 10% by mass. The spin coating was
performed firstly at a rotation rate of 500 rpm for 3 seconds, and
subsequently at a rotation rate of 3000 rpm for 15 seconds. Next,
using a hot plate, the coated composition was dried and preliminary
fired at a temperature of 175.degree. C. for five minutes. The
above-described step of coating and subsequent calcination of the
composition for thickness adjusting layer was repeated for 6 times.
After that, the coated composition was crystallized by main firing,
thereby obtaining a thickness adjusting layer of 270 nm in
thickness. The thus produced orientation controlling layer and the
thickness adjusting layer constitute a ferroelectric thin film of
Example 4.
[0091] In each of Examples 5, 8, 9, 10, and 11, a orientation
controlling layer was formed on the Pt base electrode, and a
thickness adjusting layer was formed on the orientation controlling
layer, thereby obtaining a ferroelectric thin film. Film formation
conditions are shown in Table 1, and thickness of the orientation
controlling layer and thickness of the thickness adjusting layer
are shown in Tables 3 and 4.
Examples 12, 19, 20
[0092] In Example 12, composition for crystal diameter controlling
layer which had been prepared as described-above to have a
concentration of 1% by mass was coated on the Pt base electrode of
the substrate by spin coating method, where the spin coating was
performed firstly with a rotation rate of 500 rpm for 3 seconds,
and subsequently with a rotation rate of 2000 rpm for 20 seconds.
Next, the coated composition was dried and preliminarily fired by
heating the substrate using a hot-plate at 175.degree. C. for 5
minutes in the air atmosphere, thereby obtaining a crystal diameter
controlling layer of 2 nm in thickness. Next, an orientation
controlling layer of 60 nm in thickness was formed on the crystal
diameter controlling layer using conditions shown in Table 2, to
constitute a ferroelectric thin film.
[0093] In each of Examples 19 and 20, ferroelectric thin film was
obtained by forming a orientation controlling layer on a crystal
diameter controlling layer after forming the crystal diameter
controlling layer on the Pt base layer of the substrate, where film
formation conditions were controlled as shown in Table 2, and
resultant crystal diameter controlling layer and orientation
controlling layer had thicknesses as shown in Table 4.
Examples 13 to 18
[0094] In each of Examples 13 to 18, a ferroelectric thin film was
obtained by forming a crystal diameter controlling layer on a Pt
base layer of a substrate, forming a orientation controlling layer
on the crystal diameter controlling layer, and forming a thickness
adjusting layer on the orientation controlling layer. In Example
16, a step constituted of one time firing after 4 times repetition
of coating and calcination of composition for thickness adjusting
layer was repeated for 10 times, thereby obtaining a thickness
adjusting layer of 3000 nm in thickness. Film formation conditions
of each layer are shown in Table 2, and thickness of each layer is
shown in Table 4.
Comparative Examples 1 to 3
[0095] In Comparative Example 1, a ferroelectric thin film was
obtained by forming a crystal diameter controlling layer on a Pt
base electrode of a substrate, forming a orientation controlling
layer on the crystal diameter controlling layer, and forming a
thickness adjusting layer on the orientation controlling layer
using film formation conditions shown in Table 2. In each of
Comparative Examples 2 and 3, a ferroelectric thin film was formed
by forming a orientation controlling layer on a Pt base substrate.
Film formation conditions are shown in Table 2, and thicknesses of
the layers are shown in Table 4.
Comparing Experiment
[0096] Thickness of each layer, crystal plane of preferred
orientation, degree of the preferred orientation, and average grain
diameter of each of ferroelectric thin films obtained in Examples 1
to 20 and Comparative Examples 1 to 3 were determined as shown in
Tables 3 and 4. XRD patterns of Examples 1, 2, 5, 6, 9, 11, 12, 13,
15, 16, 19, and 20 are shown in FIG. 3. XRD patterns of Comparative
Examples 1 to 3 are shown in FIG. 4. A surface SEM image (10000
times magnification) of a ferroelectric thin film of Example 5 is
shown FIG. 5. A surface SEM image (5000 times magnification) of a
ferroelectric thin film of Example 6 is shown FIG. 6.
1. Measurement of Layer (Film) Thickness
[0097] Thickness of each layer was determined by the following
procedure. Firstly, each ferroelectric thin film was measured using
a spectroscopic ellipsometer (J.A. Woollam Co., Inc.: M-2000),
thereby determining a total thickness of a crystal diameter
controlling layer and a orientation controlling layer, a thickness
of the orientation controlling layer, and a thickness of a
thickness adjusting layer. Thickness of the crystal diameter
controlling layer was determined by subtracting a thickness of the
orientation controlling layer from the total thickness of the
crystal diameter controlling layer and the orientation controlling
layer.
2. Plane of Preferred Orientation
[0098] Preferentially oriented crystal plane was determine by
measurement of each ferroelectric thin film using a X-ray
diffraction apparatus (XRD: Bruker Corporation: MXP18HF). A plane
of highest diffraction intensity selected from the planes of
ferroelectric crystal detected in the XRD chart was regarded as a
plane of preferred orientation (preferentially oriented crystal
plane).
3. Degree of Orientation
[0099] Degree of (100) preferred orientation was determined using
diffraction intensities obtained in the above-described
measurement, and was defined to be I.sub.100/(I.sub.100+I.sub.110)
where I.sub.100 was the diffraction intensity of (100) plane and
I.sub.110 was the diffraction intensity of (110) plane of
ferroelectric crystals.
4. Average Grain Diameter
[0100] SEM image of a surface of each ferroelectric thin film was
obtained by scanning electron microscope (SEM; HITACHI,
Ltd.:S-900). 90 crystal grains were arbitrarily selected from the
SEM photograph (surface image) and diameter (longest diameter and
shortest diameter) of each crystal was measured using a vernier
caliper. The average diameter of the crystals was calculated from
the results of the measurements.
TABLE-US-00003 TABLE 3 Thickness of crystal Thickness of Thickness
of diameter orientation thickness Degree of Average controlling
controlling adjusting Preferentially preferred grain layer layer
layer oriented orientation in diameter [nm] [nm] [nm] plane (100)
plane [.mu.m] Example 1 0 35 0 (100) 0.87 1.88 Example 2 0 60 0
(100) 0.85 1.89 Example 3 0 75 0 (100) 0.91 1.67 Example 4 0 90 270
(100) 0.89 0.98 Example 5 0 75 270 (100) 0.84 1.53 Example 6 0 60 0
(100) 0.86 1.75 Example 7 0 75 0 (100) 0.87 1.55 Example 8 0 75 20
(100) 0.88 1.61 Example 9 0 75 300 (100) 0.88 1.49 Example 10 0 75
270 (100) 0.91 1.43
TABLE-US-00004 TABLE 4 Thickness Thickness of crystal of Thickness
diameter orientation of thickness Degree of Average controlling
controlling adjusting Preferentially preferred grain layer layer
layer oriented orientation in diameter [nm] [nm] [nm] plane (100)
plane [.mu.m] Example 11 0 60 270 (100) 0.96 1.12 Example 12 2 60 0
(100) 0.89 0.11 Example 13 2 75 300 (100) 0.82 0.11 Example 14 2 75
300 (100) 0.8 0.14 Example 15 2 150 300 (100) 0.78 0.13 Example 16
2 75 3000 (100) 0.91 0.11 Example 17 2 45 270 (100) 0.85 0.12
Example 18 2 90 270 (100) 0.86 0.11 Example 19 2 60 0 (100) 0.89
0.1 Example 20 2 60 0 (100) 0.86 0.12 Comparative1 2 20 300 (110)
0.04 2.13 Comparative 2 0 170 0 (111) 0.03 0.13 Comparative 3 0 270
0 (111) 0.03 0.12
[0101] As it is obvious from Table 3, Table 4, FIG. 3, and FIG. 4,
ferroelectric thin films having high degree of preferential
orientation in the (100) plane in the range of 0.78 to 0.96 were
obtained in Examples 1 to 20 in which thickness of the orientation
controlling layer was controlled in the range of 30 nm to 150 nm.
Since Examples 4, 5, 8 to 11, and 13 to 18 each having a thickness
adjusting layer formed on a orientation controlling layer
respectively showed preferred orientation in the (100) plane, it
was confirmed that the same preferred orientation of the
orientation controlling layer was maintained in crystal plane
orientation of the thickness adjusting layer, and that the
thickness of a ferroelectric thin film preferentially oriented in
the (100) plane could be controlled arbitrarily by the presence of
the thickness adjusting layer.
[0102] On the other hand, each of Comparative Example 1 having a
orientation controlling layer of 20 nm in thickness, Comparative
Example 2 having a orientation controlling layer of 170 nm in
thickness, and Comparative Example 3 having a orientation
controlling layer of 270 nm in thickness respectively showed
preferred orientation other than (100) plane such that (110) plane
was preferentially oriented in Comparative Example 1, and (111)
plane was preferentially oriented in Comparative Example 2 and
Comparative Example 3.
[0103] As it is obvious from FIG. 5 and FIG. 6, compared to
ferroelectric thin films of Examples 2 to 12 formed without
introducing crystal diameter controlling layer, ferroelectric thin
films of Examples 13 to 20 formed on the crystal diameter
controlling layer had crystal had very fine grain diameter in the
outermost layers of the films.
[0104] According to the production method of the present invention,
it is possible to achieve a ferroelectric thin film having
preferred crystal orientation in the (100) plane can be obtained
with a simple process without using a seed layer or a buffer layer.
In addition, the obtained Pb-containing perovskite type
ferroelectric thin film such as PZT film having (100)-preferred
orientation has large e31 piezoelectric constant, and is applicable
in actuator, censor, gyro, ink-jet head, and MEMS application such
as auto-focusing system.
[0105] While preferred embodiments of the invention have been
described and illustrated above, it should be understood that these
are exemplary of the invention and are not to be considered as
limiting. Additions, omissions, substitutions, and other
modifications can be made without departing from the scope of the
present invention. Accordingly, the invention is not to be
considered as being limited by the foregoing description, and is
only limited by the scope of the appended claims.
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