JP2004043893A - Ceramic film deposition method, and ceramic film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for depositing a ceramic filmm having highly crystalline, and to provide the ceramic film. <P>SOLUTION: In the ceramic film depositing method for growing a film on a substrate by spraying aerosol containing ceramic powder on the substrate to collide the ceramic powder on the substrate, the ceramic film is deposited by using the highly crystalline ceramic powder in which the half-width of the highest intensity diffraction ray peak of the X-ray diffraction ray when C-Kα ray is used is below 0.3°. The highly crystalline ceramic powder is manufactured by pulverizing ceramic sintered body, or by the hydrothermal synthesis. <P>COPYRIGHT: (C)2004,JPO

Description

【００１４】
仮焼温度を上げることでセラミックス粉体の結晶性を改善することができる。
また、緻密化したセラミックス焼結体を粉砕してセラミックス粉体を作製することで、波長１．５４１ÅのＸ線を使用して測定したときのＸ線回折パターンの（１１０）のピークの半値幅が０．３°未満である、高い結晶性のセラミックス粉体を作製することができる。
【００１５】
また、波長１．５４１ÅのＸ線を使用したときのＸ線回折パターンの（１１０）のピークの半値幅が０．３°未満である高い結晶性のセラミックス粉体は緻密化したセラミックス焼結体を粉砕する方法以外にセラミックス粉体の前駆体を用いた水熱合成法によっても作製することができる。
【００１６】
表１の作製したセラミックス粉体１、２および３をガスと攪拌してエアロゾルを作製し、エアロゾル中のセラミックス粉体を基板上に衝突させることで基板上に膜を成長させるセラミックス膜の形成装置内にそれぞれ設置し、Ｓｉ基板上に大きさ４ｍｍ×６ｍｍ、厚さ４０μｍのＰｂ（Ｎｉ、Ｎｂ）Ｏ_３−ＰｂＺｒＯ_３―ＰｂＴｉＯ_３のセラミックス膜１、２および３を形成した。形成したセラミックス膜１、２および３の表面のＸ線回折パターンを波長１．５４１ÅのＸ線を使用して測定した。Ｘ線回折パターンを図１に示す。また、Ｘ線回折パターンの（１１０）のピークの半値幅を算出した結果を表２に示す。
【００１７】
【表２】

【００１８】
セラミックス膜のＸ線回折パターンの（１１０）のピークの半値幅はセラミックス粉体のＸ線回折パターンの（１１０）のピークの半値幅に比べて大きくなっている。セラミックス粉体が基板に衝突することによって、結晶粒子に歪みが導入され結晶性が低下していることが判る。しかし、高い結晶性のセラミックス粉体３を用いて形成したセラミックス膜３のＸ線回折パターン膜のピークはセラミックス膜１および２に比べて、シャープであり、ピークの半値幅は小さくなっている。Ｘ線回折パターンの（１１０）のピークの半値幅が０．３°未満であるセラミックス粉体３を用いて形成したセラミックス膜３は高い結晶性を示している。
【００１９】
形成したＳｉ基板上のＰｂ（Ｎｉ、Ｎｂ）Ｏ_３−ＰｂＺｒＯ_３―ＰｂＴｉＯ_３のセラミックス膜１、２および３を８００℃、１時間、大気中で熱処理し、熱処理後セラミックス膜１、２および３を作製した。作製した熱処理後セラミックス膜１、２および３の表面のＸ線回折パターンを波長１．５４１ÅのＸ線を使用して測定し、（１１０）のピークの半値幅を算出した。結果を表３に示す。
【００２０】
【表３】

【００２１】
波長１．５４１ÅのＸ線を使用したときのＸ線回折パターンの（１１０）のピークの半値幅が０．３°未満である高い結晶性のセラミックス粉体３を用いて形成したセラミックス膜は８００℃の低い温度の熱処理でＸ線回折パターンの（１１０）のピークの半値幅が０．２°未満となる高い結晶性のセラミックス膜となる。
【００２２】
熱処理後セラミックス膜１、２および３をＳｉ基板から剥離し、熱処理後セラミックス膜の上下面にＣｒ／Ａｕ電極を蒸着した。試料を２ｍｍ×０．３ｍｍの大きさに切断後、試料の片側を固定して、自立型カンチレーバー１、２および３を作製した。自立型カンチレーバー１、２および３に電界を印加して、電界に対して垂直方向の変位を測定し、熱処理後セラミックス膜１、２および３の圧電歪定数（−ｄ_３１）を算出した。結果を表４に示す。
【００２３】
【表４】

【００２４】
波長１．５４１ÅのＸ線を使用したときのＸ線回折パターンの（１１０）のピークの半値幅が０．３°未満である高い結晶性のセラミックス粉体３を用いて形成したセラミックス膜３は８００℃の低い温度の熱処理で高い結晶性を示し、熱処理後セラミックス膜３は圧電歪定数（−ｄ_３１）が１００（ｐｍ／Ｖ）以上の高い変位特性を示す。
【００２５】
【発明の効果】
以上説明したように、本発明によれば、波長１．５４１ÅのＸ線を使用したときのＸ線回折パターンの（１１０）のピークの半値幅が０．３°未満である高い結晶性のセラミックス粉体を用いて、セラミックス膜を形成することにより、結晶性の高いセラミックス膜を形成することができる。また、ジルコン酸鉛およびチタン酸鉛を含む高い結晶性のセラミックス粉体を用いて、圧電セラミックス膜を形成した場合、低い熱処理温度で高い圧電歪定数を示す圧電セラミックス膜を提供することができる。
【図面の簡単な説明】
【図１】本発明と比較例のセラミックス膜の表面のＸ線回折パターン。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for forming a ceramic film for growing a film on a substrate by spraying an aerosol containing the ceramic powder on the substrate and causing the ceramic powder to collide with the substrate, and to a ceramic film.
[0002]
[Prior art]
Conventionally, the gas deposition method is, for example, a film formation method using ultrafine particles described in Japanese Patent No. 1660799, in which a metal heating source and a vacuum vessel are arranged in the same manner as in a vacuum evaporation method, and a metal vapor is formed. This is a method of forming ultrafine particles and forming a film composed of the ultrafine particles.
[0003]
On the other hand, formation of ceramic films using ceramic powders as ultrafine particles has also been performed. A method for forming a ceramic film by such a method is described in, for example, Jpn. J. Appl. Phys. 36 (1997) 1159. The results show that lead zirconate titanate (PZT) powder aerosolized on a Si substrate provided with a Pt film was made to impinge on the PZT film. The characteristics were confirmed, and it was shown that the film functions as a piezoelectric film.
[0004]
[Problems to be solved by the invention]
However, when a ceramic film is formed using ceramic powder, the aerosolized ceramic powder must collide with the substrate to form the ceramic film, and the impact due to the collision causes the ceramic crystal particles to be distorted. Was introduced, and the crystallinity of the ceramic film was lowered. For this reason, the formed ceramics film could obtain only lower characteristics than those of the bulk sintered body obtained by sintering the ceramic powder after molding.
[0005]
For example, when a piezoelectric ceramic film is formed using ceramic powder containing lead zirconate titanate (PZT) as a main component, the crystallinity of the piezoelectric ceramic film is reduced due to collision with the substrate due to film formation. In addition, in order to obtain high piezoelectric characteristics, it is necessary to perform heat treatment to recover the reduced crystallinity. However, heat treatment must be performed at a low temperature of 800 ° C. or less in order to prevent deterioration of the substrate such as Si forming the ceramic film. In order to obtain extremely high piezoelectric characteristics, the heat treatment temperature must be higher than 800 ° C., and for example, it cannot be applied to applications requiring a high piezoelectric strain constant (−d ₃₁ ) such as a microactuator. As the piezoelectric distortion constant _{(-d 31)} is in the micro-actuator and the like applications, 100 (pm / V) or more values are required. An object of the present invention is to solve the above problems of the conventional ceramic film forming method and ceramic film, and an object of the present invention is to provide a ceramic film having high crystallinity and a method of forming the ceramic film.
[0006]
[Means for Solving the Problems]
[1] In the method of forming a ceramic film according to the present invention, in order to achieve the above object, the half-width of the peak of the highest intensity diffraction line of the X-ray diffraction pattern when Cu-Kα radiation is used is less than 0.3 °. The film is formed using such a highly crystalline ceramic powder. That is, a method of forming a ceramic film in which a ceramic powder is stirred with a gas to produce an aerosol, and the ceramic powder in the aerosol collides with the substrate to grow the film on the substrate. Wherein the half-width of the peak of the highest intensity diffraction line of the X-ray diffraction pattern of the ceramic powder when using is less than 0.3 °. Thus, even if the aerosolized ceramic powder collides with the substrate and strains the ceramic particles, and the crystallinity of the formed ceramic film is lower than that of the ceramic powder used for forming the ceramic film, Since the crystallinity of the ceramic powder used for forming the ceramic film is sufficiently high, a ceramic film having higher crystallinity can be formed as compared with a case where a conventional ceramic powder is used. Here, the Cu-Kα ray is a characteristic X-ray of copper and corresponds to an X-ray having a wavelength near 1.54 ° (0.154 nm). The X-ray diffraction pattern corresponds to a graph showing the relationship between 2θ (horizontal axis) and X-ray intensity (vertical axis) obtained by X-ray diffraction. The peak having the maximum X-ray intensity in the curve of the graph is referred to as the highest intensity diffraction line peak, and its half-value width is the same as the horizontal axis 2θ, and is expressed in (°).
[0007]
[2] In the method of forming a ceramic film according to the present invention, the ceramic powder used for forming the ceramic film, that is, half of the peak of the highest intensity diffraction line of the X-ray diffraction pattern when Cu-Kα rays are used. As a highly crystalline ceramic powder with a value range of less than 0.3 °, a dense ceramic sintered body obtained by compacting and sintering ceramic powder used for forming a conventional ceramic film And then use the ceramic powder produced by grinding the powder. Alternatively, a ceramic powder is produced by a hydrothermal synthesis method using a ceramic precursor used for forming a ceramic film. By these methods, a ceramic powder having high crystallinity can be produced, and by forming a ceramic film using this ceramic powder, a higher ceramic powder can be obtained as compared with the case where a conventional ceramic powder is used. A ceramic film having crystallinity can be formed.
[0008]
[3] The ceramic film of the present invention uses a highly crystalline ceramic powder in which the half-width of the peak of the highest intensity diffraction line of the X-ray diffraction pattern when Cu-Kα rays is used is less than 0.3 °. The formed highly crystalline ceramic film is used.
[0009]
[4] The ceramic film according to the present invention is the ceramic film according to [3], wherein the half-value width of the peak of the highest intensity diffraction line of the X-ray diffraction pattern when Cu-Kα radiation is used is less than 0.2 °. This is a certain ceramic film.
[0010]
[5] The ceramic film of the present invention is the ceramic film according to [4], which is a ceramic film having high crystallinity that has been heat-treated at a temperature of 800 ° C. or lower.
[0011]
[6] The ceramic film of the present invention is a ceramic film having high crystallinity according to [5], and is a piezoelectric ceramic film formed using a ceramic powder containing lead zirconate and lead titanate, The ceramic film has a piezoelectric strain constant (−d ₃₁ ) of 100 pm / V or more.
[0012]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, specific examples of the present invention will be described. However, the present invention is not limited by these examples.
After mixing five kinds of raw materials of PbO, NiO, Nb ₂ O ₅ , ZrO ₂ and TiO ₂ , they are calcined and pulverized at 850 ° C., and the composition is Pb (Ni, Nb) O ₃ —PbZrO ₃ —PbTiO ₃ . A ceramic powder 1 containing lead zirconate (PbZrO ₃ ) and lead titanate (PbTiO ₃ ) was produced. Also, after mixing the same five kinds of oxide raw materials, the mixture was calcined and pulverized at 1000 ° C. to produce ceramic powder 2 having the same composition. Further, after the ceramic powder 1 was compacted, it was sintered at 1200 ° C. to obtain a dense ceramic sintered body. This ceramic sintered body was pulverized to produce a ceramic powder 3 having the same composition as the two types of ceramic powders 1 and 2. The X-ray diffraction patterns of the produced ceramic powders 1, 2, and 3 were measured, and the half width of the peak of (110), which was the highest intensity diffraction line, was calculated. Table 1 shows the results. X-rays having a wavelength of 1.541 ° were used for the measurement.
[0013]
[Table 1]

[0014]
By increasing the calcination temperature, the crystallinity of the ceramic powder can be improved.
Further, by crushing the densified ceramic sintered body to produce a ceramic powder, the half width of the (110) peak of the X-ray diffraction pattern measured using X-rays having a wavelength of 1.541 °. Is less than 0.3 °, a highly crystalline ceramic powder can be produced.
[0015]
A highly crystalline ceramic powder having a half-width of the peak of (110) of the X-ray diffraction pattern when the X-ray having a wavelength of 1.541 ° is less than 0.3 ° is a dense ceramic sintered body. Can be prepared by a hydrothermal synthesis method using a precursor of ceramic powder in addition to the method of pulverizing the powder.
[0016]
An aerosol is produced by agitating the produced ceramic powders 1, 2 and 3 of Table 1 with a gas, and the ceramic powder in the aerosol is caused to collide with the substrate to grow a film on the substrate. each was placed within, to form a Si size 4 mm × 6 mm on a substrate, a thickness of _{40μm Pb (Ni, Nb) O} 3 -PbZrO 3 ceramic film 1, 2 and 3 of -PbTiO _3. The X-ray diffraction patterns on the surfaces of the formed ceramic films 1, 2, and 3 were measured using X-rays having a wavelength of 1.541 °. The X-ray diffraction pattern is shown in FIG. Table 2 shows the results of calculating the half width of the (110) peak in the X-ray diffraction pattern.
[0017]
[Table 2]

[0018]
The half width of the (110) peak of the X-ray diffraction pattern of the ceramic film is larger than the half width of the (110) peak of the X-ray diffraction pattern of the ceramic powder. It can be seen that when the ceramic powder collides with the substrate, strain is introduced into the crystal particles and the crystallinity is reduced. However, the peak of the X-ray diffraction pattern film of the ceramic film 3 formed using the highly crystalline ceramic powder 3 is sharper than the ceramic films 1 and 2, and the half width of the peak is smaller. The ceramic film 3 formed by using the ceramic powder 3 in which the half width of the (110) peak of the X-ray diffraction pattern is less than 0.3 ° shows high crystallinity.
[0019]
The formed Si _Pb (Ni, _Nb) on the substrate _O 3 -PbZrO 3 -PbTiO ₃ of the ceramic film 1, 2 and 3 of 800 ° C., 1 hour, and heat treated in the atmosphere, the heat treatment after the ceramic film 1, 2 and 3 Was prepared. After the heat treatment, the X-ray diffraction patterns on the surfaces of the ceramic films 1, 2, and 3 were measured using X-rays having a wavelength of 1.541 °, and the half width of the peak of (110) was calculated. Table 3 shows the results.
[0020]
[Table 3]

[0021]
The ceramic film formed by using the highly crystalline ceramic powder 3 having a half width of the peak of (110) of the X-ray diffraction pattern when the X-ray having a wavelength of 1.541 ° is less than 0.3 ° is 800. The heat treatment at a low temperature of ° C. results in a highly crystalline ceramic film in which the half value width of the (110) peak of the X-ray diffraction pattern is less than 0.2 °.
[0022]
After the heat treatment, the ceramic films 1, 2, and 3 were separated from the Si substrate, and after the heat treatment, Cr / Au electrodes were deposited on the upper and lower surfaces of the ceramic film. After the sample was cut into a size of 2 mm × 0.3 mm, one side of the sample was fixed to produce self-supporting cantilevers 1, 2 and 3. By applying an electric field to the free-standing cantilever Leber 1, 2 and 3, to measure the displacement of the direction perpendicular to the electric field was calculated piezoelectric distortion constant of the heat treatment after the ceramic film 1, 2 and 3 (-d _31). Table 4 shows the results.
[0023]
[Table 4]

[0024]
The ceramic film 3 formed by using the highly crystalline ceramic powder 3 having a half-width of the (110) peak of the X-ray diffraction pattern of less than 0.3 ° when the X-ray having a wavelength of 1.541 ° is used. The ceramic film 3 exhibits high crystallinity by a heat treatment at a low temperature of 800 ° C., and the ceramic film 3 after the heat treatment exhibits a high displacement characteristic with a piezoelectric strain constant (−d ₃₁ ) of 100 (pm / V) or more.
[0025]
【The invention's effect】
As described above, according to the present invention, a highly crystalline ceramic in which the half-width of the (110) peak of the X-ray diffraction pattern when using X-rays having a wavelength of 1.541 ° is less than 0.3 °. By forming a ceramic film using powder, a ceramic film with high crystallinity can be formed. In addition, when a piezoelectric ceramic film is formed using a highly crystalline ceramic powder containing lead zirconate and lead titanate, a piezoelectric ceramic film exhibiting a high piezoelectric strain constant at a low heat treatment temperature can be provided.
[Brief description of the drawings]
FIG. 1 is an X-ray diffraction pattern of the surface of a ceramic film of the present invention and a comparative example.

Claims (6)

A method of forming a ceramic film in which a ceramic powder is stirred with a gas to produce an aerosol, and the ceramic powder in the aerosol collides with the substrate to grow the film on the substrate, using Cu-Kα rays. A method of forming a ceramic film, wherein the half-width of the peak of the highest intensity diffraction line of the X-ray diffraction pattern of the ceramic powder obtained is less than 0.3 °. The method for forming a ceramic film according to claim 1, wherein the ceramic powder used for forming the ceramic film is a ceramic powder produced by grinding a ceramic sintered body or by a hydrothermal synthesis method. Method for forming a ceramic film. A ceramic film formed on a substrate by agitating the ceramic powder with a gas to produce an aerosol, and colliding the ceramic powder in the aerosol on the substrate. A ceramic film formed using a ceramic powder having a half-width of a peak of the highest intensity diffraction line of a diffraction pattern of less than 0.3 °. The ceramic film according to claim 3, wherein a half-width of a peak of the highest intensity diffraction line of an X-ray diffraction pattern when Cu-Kα rays is used is less than 0.2 °. The ceramic film according to claim 4, wherein after being formed on the substrate, a heat treatment is performed in a temperature range of 800C or less. The ceramic film according to claim 5, wherein the ceramic film is a piezoelectric ceramic film formed using a ceramic powder containing lead zirconate and lead titanate, and has a piezoelectric strain constant (−d _{31) of the} piezoelectric ceramic film. ) Is 100 pm / V or more.

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