WO2016009698A1 - 強誘電体セラミックス及びその製造方法 - Google Patents
強誘電体セラミックス及びその製造方法 Download PDFInfo
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- WO2016009698A1 WO2016009698A1 PCT/JP2015/062647 JP2015062647W WO2016009698A1 WO 2016009698 A1 WO2016009698 A1 WO 2016009698A1 JP 2015062647 W JP2015062647 W JP 2015062647W WO 2016009698 A1 WO2016009698 A1 WO 2016009698A1
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- 239000000919 ceramic Substances 0.000 title claims abstract description 33
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
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Definitions
- the present invention relates to a ferroelectric ceramic and a manufacturing method thereof.
- PZT Pb (Zr, Ti) O 3
- a 300 nm thick SiO 2 film is formed on a 4-inch Si wafer, and a 5 nm thick TiO x film is formed on the SiO 2 film.
- a Pt film having a film thickness of, for example, (111) is formed on the TiO X film, and a PZT sol-gel solution is spin-coated on the Pt film by a spin coater.
- the spin condition at this time is a condition for rotating for 30 seconds at a rotational speed of 1500 rpm and for 10 seconds at a rotational speed of 4000 rpm.
- the applied PZT sol-gel solution is heated and held on a hot plate at 250 ° C. for 30 seconds to dry, and after removing moisture, further heated and held on a hot plate held at a high temperature of 500 ° C. for 60 seconds. And pre-baking. By repeating this several times, a 150 nm thick PZT amorphous film is generated.
- PZT crystallization is performed on the PZT amorphous film by performing an annealing treatment at 700 ° C. using a pressure type lamp annealing apparatus (RTA: “rapidly” thermal annealing).
- RTA pressure type lamp annealing apparatus
- the PZT film thus crystallized has a perovskite structure (see, for example, Patent Document 1).
- An object of one embodiment of the present invention is to improve piezoelectric characteristics.
- Pb (Zr 1-A Ti A ) O 3 film, A Pb (Zr 1-x Ti x ) O 3 film formed on the Pb (Zr 1-A Ti A ) O 3 film, A and x satisfy the following formulas 1 to 3, respectively. 0 ⁇ A ⁇ 0.1 Formula 1 0.1 ⁇ x ⁇ 1 Formula 2 A ⁇ x Equation 3 Note that the Pb (Zr 1-x Ti x ) O 3 film is oriented to (001).
- A is 0,
- a ferroelectric ceramic wherein the Pb (Zr 1-A Ti A ) O 3 is a PbZrO 3 film. Note that the Pb (Zr 1-x Ti x ) O 3 film is oriented to (001).
- the oxide film is preferably an oxide having a perovskite structure.
- the Sr (Ti, Ru) O 3 film is preferably a Sr (Ti 1-x Ru x ) O 3 film, and x satisfies the following formula 4. 0.01 ⁇ x ⁇ 0.4 Formula 4
- a ferroelectric ceramic wherein the Pb (Zr 1-A Ti A ) O 3 film is formed on an electrode film.
- the oxide may be a Sr (Ti 1-x Ru x ) O 3 film, where x satisfies the following formula 4. 0.01 ⁇ x ⁇ 0.4 Formula 4
- y Ferroelectric ceramics characterized in that the electrode film is formed on a ZrO 2 film.
- the ZrO 2 film is oriented to (100).
- a ferroelectric ceramic characterized in that the electrode film is formed on a Si substrate. Note that the Si substrate is oriented to (100).
- a method for producing a ferroelectric ceramic in which a Pb (Zr 1-x Ti x ) O 3 film is formed on a Pb (Zr 1-A Ti A ) O 3 film A method for producing a ferroelectric ceramic, wherein A and x satisfy the following formulas 1 to 3. 0 ⁇ A ⁇ 0.1 Formula 1 0.1 ⁇ x ⁇ 1 Formula 2 A ⁇ x Equation 3 Note that the Pb (Zr 1-x Ti x ) O 3 film is oriented to (001).
- a method for producing a ferroelectric ceramic wherein the Pb (Zr 1-A Ti A ) O 3 film is a PbZrO 3 film. Note that the Pb (Zr 1-x Ti x ) O 3 film is oriented to (001).
- the Pb (Zr 1-A Ti A ) O 3 film is formed by applying a precursor solution of Pb (Zr 1-A Ti A ) O 3 on a substrate and oxygen at 5 atm or higher (preferably 7.5 atm or higher).
- a method for producing a ferroelectric ceramic characterized by being formed by crystallization in an atmosphere.
- C a specific C
- B a specific B
- C is formed above (or below) a specific B
- C is formed
- C is directly formed on (or below) B
- the present invention is not limited to above (or below) B as long as the effect of the embodiment of the present invention is not inhibited.
- C is formed via another (C is formed) is also included.
- the piezoelectric characteristics can be improved by applying one embodiment of the present invention.
- FIGS. 5A to 5C are cross-sectional views for explaining a method for manufacturing a sample according to Example 1.
- FIGS. 4 is an XRD (X-Ray-Diffraction) chart of a sample formed up to a Pt film 13 shown in FIG. It is a chart which shows the XRD diffraction result of the sample shown to FIG. 3 (A). It is a chart which shows the XRD diffraction result of the sample shown in FIG.3 (C).
- FIG. 6 is a cross-sectional view for explaining a method for producing a sample according to Example 2.
- FIG. It is sectional drawing for demonstrating the manufacturing method of the sample by a comparative example. It is an XRD chart of Sample 4 (Example). It is an XRD chart of Sample 6 (Example). It is an XRD chart of sample 9 (comparative example). It is an XRD chart of Sample 1 (Example). It is an XRD chart of Sample 2 (Example). It is an XRD chart of Sample 3 (Example).
- FIG. 1 is a schematic cross-sectional view illustrating a method for manufacturing a ferroelectric ceramic according to one embodiment of the present invention.
- a substrate (not shown).
- various substrates can be used.
- a single crystal substrate such as a Si single crystal or a sapphire single crystal, a single crystal substrate with a metal oxide film formed on the surface, a polysilicon film or a silicide film on the surface
- a Si substrate oriented in (100) is used.
- a ZrO 2 film (not shown) is formed on a Si substrate (not shown) at a temperature of 550 ° C. or lower (preferably a temperature of 500 ° C.) by vapor deposition.
- This ZrO 2 film is oriented to (100).
- the ZrO 2 film is formed by vapor deposition at 750 ° C. or higher, the ZrO 2 film is not oriented in (100).
- orientation to (100), the orientation to (200) and the orientation to (400) are substantially the same, and the orientation to (001) and the orientation to (002). And orientation to (004) are substantially the same.
- the lower electrode 103 is formed on the ZrO 2 film.
- the lower electrode 103 is formed of an electrode film made of metal or oxide.
- a Pt film or an Ir film is used as the electrode film made of metal.
- An electrode film made of an oxide is, for example, a Sr (Ti 1-x Ru x ) O 3 film, where x satisfies the following formula 4. 0.01 ⁇ x ⁇ 0.4 Formula 4
- the Pt film 103 by epitaxial growth is formed as a lower electrode by sputtering at a temperature of 550 ° C. or lower (preferably a temperature of 400 ° C.) on the ZrO 2 film.
- This Pt film 103 is oriented to (200).
- a PbZrO 3 film (hereinafter also referred to as “PZO film”) 104 is formed on the lower electrode 103.
- the PZO film 104 can be formed by various methods, for example, a sol-gel method, a CVD method, or a sputtering method.
- a PZO precursor solution is applied on a substrate and crystallized in an oxygen atmosphere of 5 atm or more (preferably 7.5 atm or more).
- the a-axis length is about twice the average perovskite (ap ⁇ 4 angstroms), the c-axis length is c ⁇ ( ⁇ 2) ap, and the b-axis length is b ⁇ 2c.
- This change in the lattice constant of PZO is basically the rotation of the perovskite octahedral crystal and the distortion of the octahedron to which the period in the b-axis direction is doubled.
- PZO is orthorhombic as shown in FIG. For this reason, PZO has an apparently large lattice constant.
- the perovskite is rotated about 45 ° in the vertical direction, and the rotated crystal is treated like a large crystal, surrounding the periphery like a dotted line portion.
- the orthorhombic practice is to treat the a, b, and c axes as if they appear to be very long.
- Actual PZO is a solid crystal, which is a normal perovskite crystal.
- the PZT film 105 is a Pb (Zr 1-x Ti x ) O 3 film, and x satisfies the following formula 2.
- the Pb (Zr 1-x Ti x ) O 3 film is oriented to (001). 0 ⁇ x ⁇ 1 Formula 2 ′
- the “PZT film” includes an element containing an impurity in Pb (Zr, Ti) O 3 , as long as the function of the piezoelectric body of the PZT film is not eliminated even if the impurity is included. Various things may be included.
- sol-gel solution for forming a PZT film an E1 solution having a concentration of 10% by weight, to which 70% to 90% of lead with butanol as a solvent was added, was used.
- the above-mentioned solution was used to spin-form a PZT amorphous film.
- the spin coater was performed using MS-A200 manufactured by Mikasa Corporation. First, after rotating at 800 rpm for 5 seconds and 1500 rpm for 10 seconds, gradually increasing the rotation to 3000 rpm in 10 seconds, and then 5 minutes on a 150 ° C. hot plate (AHS One Co., Ltd. ceramic hot plate AHS-300), After being left in the air, it was left in the air for 10 minutes on a 300 ° C. hot plate (AHS-300), and then cooled to room temperature. By repeating this five times, a PZT amorphous film having a desired film thickness of 200 nm was formed on the PZO film 104. A plurality of these were produced.
- the PZT amorphous film is formed on the PZO film 104 by heat-treating the PZT amorphous film in a pressurized oxygen atmosphere to crystallize the PZT amorphous film.
- An example of the lattice constant of PZT is 0.401 nm.
- the PZT film 105 may be subjected to a polling process.
- the PZT film 105 is formed by the sol-gel method, but the PZT film may be formed by a sputtering method.
- PZO film 104 is an initial nucleus layer (that is, a buffer layer) of the PZT film 105, the piezoelectric characteristics of the PZT film 105 can be improved.
- PbZrO 3 is an antiferroelectric material when the Ti ratio is 0 (zero) in the phase diagram of Pb (Zr 1-x Ti x ) O 3 (PZT). Since the c-axis length is the longest among (Zr 1-x Ti x ) O 3 , PZO works in the direction of extending the c-axis length of all PZTs, making it easy to obtain the maximum piezoelectric performance that the structure can take. be able to.
- the entire PZT is affected by the crystal axis of the PZO initial nucleus, and the c crystal axis is easily extended in the entire PZT film, that is, is easily polarized, and piezoelectricity is easily extracted. It becomes possible.
- a PZO film 104 having a Ti ratio of 0 in the phase diagram of Pb (Zr, Ti) O 3 is formed on the lower electrode 103, and Pb (Zr 1-x Ti) is formed on the PZO film 104.
- x ) O 3 film 105 (0 ⁇ x ⁇ 1 Formula 2 ′) is formed, but Pb (Zr 1 ⁇ x 1 ⁇ x on the Pb (Zr 1 ⁇ A Ti A ) O 3 film having a very small Ti ratio.
- a Ti x ) O 3 film may be formed. However, A and x satisfy the following formulas 1 to 3.
- the Pb (Zr 1-x Ti x ) O 3 film is oriented to (001).
- the Pb (Zr 1-A Ti A ) O 3 film used as the initial nucleus is PZT of antiferroelectric orthorhombic phase (that is, Pb ( In the phase diagram of Zr, Ti) O 3 , it becomes PZT in the orthorhombic region (ortho region), and Pb (Zr 1-A Ti A ) O 3 becomes all Pb (Zr 1-x Ti x ) O 3 ( PZT) works in the direction of extending the c-axis length, and the same effect as in the above embodiment can be obtained.
- FIG. 2 is a schematic cross-sectional view for explaining a method of manufacturing a ferroelectric ceramic according to one aspect of the present invention, and the same reference numerals are given to the same portions as those in FIG.
- the Si substrate (not shown), the ZrO 2 film (not shown), and the lower electrode 103 are formed by the same method as in the first embodiment, description thereof is omitted.
- the oxide film 106 may be an oxide having a perovskite structure, for example, a Sr (Ti, Ru) O 3 film.
- This Sr (Ti, Ru) O 3 film is a Sr (Ti 1-x Ru x ) O 3 film, and x satisfies the following formula 4 and is formed by sputtering.
- a sintered body of Sr (Ti 1-x Ru x ) O 3 is used as a sputtering target at this time.
- x satisfies the following formula 4. 0.01 ⁇ x ⁇ 0.4 (preferably 0.05 ⁇ x ⁇ 0.2) Formula 4
- x in the Sr (Ti 1-x Ru x ) O 3 film is 0.4 or less. If x exceeds 0.4, the Sr (Ti 1-x Ru x ) O 3 film becomes powder. Because it cannot be hardened sufficiently.
- the Sr (Ti 1-x Ru x ) O 3 film is crystallized by RTA (Rapid Thermal Anneal) in a pressurized oxygen atmosphere.
- the Sr (Ti 1-x Ru x ) O 3 film is a compound having a perovskite structure, which is a composite oxide of strontium, titanium, and ruthenium.
- the PZO film 104 is formed on the oxide film 106 by the same method as in the first embodiment.
- the PZT film 105 is formed on the PZO film 104 by the same method as in the first embodiment.
- the PZT film 105 is oriented to (001).
- the PZO film 104 is formed on the oxide film 106, and the PZT 105 is formed on the PZO film 104.
- a Pb (Zr 1-x Ti x ) O 3 film may be formed on the Pb (Zr 1-A Ti A ) O 3 film having a very small Ti ratio.
- a and x satisfy the following formulas 1 to 3.
- the Pb (Zr 1-x Ti x ) O 3 film is oriented to (001). 0 ⁇ A ⁇ 0.1 Formula 1 0.1 ⁇ x ⁇ 1 Formula 2 A ⁇ x Equation 3
- the same effect as that of the first embodiment can be obtained.
- 3A to 3C are cross-sectional views for explaining a sample manufacturing method according to the first embodiment.
- a ZrO 2 film 12 was formed on a 6-inch Si substrate 11 having a (100) crystal plane by reactive vapor deposition.
- the vapor deposition conditions at this time are as shown in Table 1.
- This ZrO 2 film 12 was oriented to (100).
- a Pt film 13 having a thickness of 100 nm was formed on the ZrO 2 film 12 by sputtering.
- the film forming conditions at this time are as shown in Table 1. This Pt film 13 was oriented to (200).
- the XRD pattern at this time is shown in FIG.
- the vertical axis represents intensity
- the horizontal axis represents 2 ⁇ .
- PZO film a PbZrO 3 film
- PZT film a Pb (Zr 0.55 Ti 0.45 ) O 3 film
- a laminated film 15 was formed.
- a PZO film having a thickness of 250 nm was applied on the Pt film 13 by a sol-gel method.
- the conditions at this time are as follows. 1.4 mol / kg 1.3PbZrO 3 formation MOD solution (Lot.00050667-1 manufactured by Toshima Seisakusho), ethanol, and 2n butoxyethanol are combined to make 1000 ml (each mixed at a ratio of 1: 1: 1).
- a PZT film having a thickness of 2500 nm was formed on the PZO film by a sputtering method.
- the sputtering conditions at this time are the same as in Example 2.
- the XRD pattern at this time is shown in FIG.
- the vertical axis represents intensity
- the horizontal axis represents 2 ⁇ .
- FIG. 7 is a chart showing XRD diffraction results of a sample of a PZT film as a comparative example in which (400) orientation and (004) orientation are mixed.
- the PZO film as the initial nucleus layer (that is, the buffer layer) of the PZT film, a PZT film unidirectionally oriented on the (001) c-axis can be obtained, and the piezoelectric characteristics of the PZT film Can be improved.
- PZO PbZrO 3
- PZT PbZrO 3
- PZT PbZrO 3
- the c-axis length is the longest in O 3
- PZO works in the direction of extending the c-axis length of all PZTs, thereby making it easy to polarize. As a result, the piezoelectricity can be easily taken out.
- FIG. 8 is a cross-sectional view for explaining the sample manufacturing method according to the second embodiment.
- the Si substrate 11, the ZrO 2 film 12, and the Pt film 13 of the sample shown in FIG. 8 were produced by the same method as the sample according to Example 1 shown in FIG.
- STRO film 14 an Sr (Ti 0.8 Ru 0.2 ) O 3 film (hereinafter referred to as “STRO film”) 14 was formed on the Pt film 13 by sputtering.
- the sputtering conditions at this time are as follows.
- the STRO film 14 is crystallized by RTA in a pressurized oxygen atmosphere.
- the RTA conditions at this time are as follows.
- Annealing temperature 600 °C Introduced gas: Oxygen gas Pressure: 9kg / cm 2 Temperature increase rate: 100 ° C / sec Annealing time: 5 minutes
- a PZO film 16 having a thickness of 50 to 400 nm is formed on the STRO film 14 by spin coating.
- the film forming conditions at this time are as follows (1) to (3).
- PZT film 17 a Pb (Zr 0.55 Ti 0.45 ) O 3 film having a thickness of 1000 to 4000 nm was formed on the PZO film 16 by sputtering.
- the sputtering conditions at this time are as follows.
- FIG. 9 is a cross-sectional view for explaining a sample manufacturing method according to a comparative example, and the same reference numerals are given to the same portions as those in FIG.
- the sample shown in FIG. 9 is obtained by removing the PZO film 16 from the sample shown in FIG. 8, and has the same film structure as the sample shown in FIG. 8 except for the PZO film 16, and the formation method of each film is also the same. .
- Samples 1 to 6 shown in Table 2 are samples according to Example 2, and have a film structure shown in FIG.
- Samples 7 to 9 shown in Table 2 are samples according to comparative examples, and have a film structure shown in FIG.
- the film thicknesses of the PZO films 16 of the samples 1 to 6 and the film thicknesses of the PZT films 17 of the samples 1 to 9 are as follows.
- 10 is an XRD chart of Sample 4 (Example)
- FIG. 11 is an XRD chart of Sample 6 (Example)
- FIG. 12 is an XRD chart of Sample 9 (Comparative Example). 10 to 12 each show a range of 15 ° ⁇ 2 ⁇ ⁇ 50 °.
- the samples 4, 6 and 9 show almost no difference in crystallinity in the range of 2 ⁇ ⁇ 50 °, and all are good PZT crystal films.
- FIG. 13 is an XRD chart of Sample 1 (Example)
- FIG. 14 is an XRD chart of Sample 2 (Example)
- FIG. 15 is an XRD chart of Sample 3 (Example).
- Each of FIGS. 13 to 15 shows a range of 90 ° ⁇ 2 ⁇ ⁇ 110 °.
- FIGS. 16 to 18 shows a range of 90 ° ⁇ 2 ⁇ ⁇ 110 °.
- 20 is an XRD chart of sample 7 (comparative example)
- FIG. 21 is an XRD chart of sample 8 (comparative example)
- FIG. 22 is an XRD chart of sample 9 (comparative example). 20 to 22 each show a range of 90 ° ⁇ 2 ⁇ ⁇ 110 °.
- the PZT (004) peak intensity was very good with a crystallinity of 175000 cps or more per 1000 nm thickness. Further, as shown in Table 2, in Samples 4 to 6 (Examples), the PZT (004) / Pt (400) peak intensity ratio was (004) / (400)> 60%. Further, as shown in Table 2, in samples 4 to 6 (examples), the 2 ⁇ difference in ac axis length of
- the full width at half maximum FWHM that is, the so-called half width
- FWHM full width at half maximum
- the PZO film as the initial nucleus layer (that is, the buffer layer) of the PZT film, a PZT film unidirectionally oriented on the (001) c-axis can be obtained, and the piezoelectric characteristics of the PZT film Can be improved.
- the Si substrate, the ZrO 2 film, and the Pt film were produced by the same method as the sample according to Example 1. Then, a PZO precursor solution (the same solution as in Examples 1 and 2) was applied onto the Pt film by a spin coating method with a thickness of 40 nm under a rotation condition of 5000 rpm to 10 seconds. Thereafter, crystallization was performed at a heating rate of 10 ° C./sec, a sintering environment of O 2 , 10 atm and a sintering temperature of 650 ° C. for 1 min. Thereafter, when XRD diffraction evaluation was performed, a PZO film having a thickness of 40 nm and (001) orientation was obtained as shown in FIG.
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Abstract
Description
[1]Pb(Zr1-ATiA)O3膜と、
前記Pb(Zr1-ATiA)O3膜上に形成されたPb(Zr1-xTix)O3膜と、を具備し、
前記A及び前記xは下記式1~式3を満たすことを特徴とする強誘電体セラミックス。
0≦A≦0.1 ・・・式1
0.1<x<1 ・・・式2
A<x ・・・式3
なお、Pb(Zr1-xTix)O3膜は(001)に配向する。
前記Aが0であり、
前記Pb(Zr1-ATiA)O3がPbZrO3膜であることを特徴とする強誘電体セラミックス。
なお、Pb(Zr1-xTix)O3膜は(001)に配向する。
前記Pb(Zr1-ATiA)O3膜は酸化膜上に形成されていることを特徴とする強誘電体セラミックス。
なお、前記酸化膜は、ペロブスカイト構造の酸化物であることが好ましい。
前記酸化膜はSr(Ti,Ru)O3膜であることを特徴とする強誘電体セラミックス。
なお、前記Sr(Ti,Ru)O3膜は、Sr(Ti1-xRux)O3膜であることが好ましく、前記xは下記式4を満たす。
0.01≦x≦0.4 ・・・式4
前記Pb(Zr1-ATiA)O3膜は電極膜上に形成されていることを特徴とする強誘電体セラミックス。
前記電極膜は酸化物または金属からなることを特徴とする強誘電体セラミックス。
なお、前記酸化物はSr(Ti1-xRux)O3膜であってもよく、前記xは下記式4を満たす。
0.01≦x≦0.4 ・・・式4
前記電極膜はPt膜またはIr膜であることを特徴とする強誘電体セラミックス。
なお、Pt膜は(100)に配向する。
y 前記電極膜はZrO2膜上に形成されていることを特徴とする強誘電体セラミックス。
なお、ZrO2膜は(100)に配向する。
前記電極膜はSi基板上に形成されていることを特徴とする強誘電体セラミックス。
なお、Si基板は(100)に配向している。
前記A及び前記xは下記式1~式3を満たすことを特徴とする強誘電体セラミックスの製造方法。
0≦A≦0.1 ・・・式1
0.1<x<1 ・・・式2
A<x ・・・式3
なお、Pb(Zr1-xTix)O3膜は(001)に配向する。
前記Aが0であり、
前記Pb(Zr1-ATiA)O3膜がPbZrO3膜であることを特徴とする強誘電体セラミックスの製造方法。
なお、Pb(Zr1-xTix)O3膜は(001)に配向する。
[12]上記[10]または[11]において、
前記Pb(Zr1-ATiA)O3膜は、Pb(Zr1-ATiA)O3の前駆体溶液を基板上に塗布し、5atm以上(好ましくは7.5気圧以上)の酸素雰囲気で結晶化を行うことで形成されることを特徴とする強誘電体セラミックスの製造方法。
図1は、本発明の一態様に係る強誘電体セラミックスの製造方法を説明する模式的な断面図である。
0.01≦x≦0.4 ・・・式4
PZOは図23に示すように斜方晶である。このため、PZOは見かけ上格子定数が大きくなっている。それは、ペロブスカイトが縦に45°程度回転していて、あたかも回転した結晶を点線部分のように周囲を取り囲んで、大きな結晶のように取り扱っているためである。つまり、見かけ上、a,b,c軸の長さがとても長くなっているように取り扱うのが斜方晶の慣例である。実際のPZOは実線のような結晶で、通常のペロブスカイト結晶である。
0<x<1 ・・・式2'
PZT膜形成用ゾルゲル溶液としては、ブタノールを溶媒とする鉛が70%~90%不足した量添加された、濃度10重量%濃度のE1溶液を用いた。
0≦A≦0.1 ・・・式1
0.1<x<1 ・・・式2
A<x ・・・式3
上記式1を満たすこと、つまりTi比率を10%以下とすることで、初期核として用いるPb(Zr1-ATiA)O3膜が反強誘電性斜方晶相のPZT(つまりPb(Zr,Ti)O3の相図中、斜方晶領域(ortho領域)のPZT)となり、Pb(Zr1-ATiA)O3が全てのPb(Zr1-xTix)O3(PZT)のc軸長を伸ばす方向に働き、上記実施形態と同様の効果を得ることができる。
図2は、本発明の一態様に係る強誘電体セラミックスの製造方法を説明する模式的な断面図であり、図1と同一部分には同一符号を付す。
0.01≦x≦0.4(好ましくは0.05≦x≦0.2) ・・・式4
0≦A≦0.1 ・・・式1
0.1<x<1 ・・・式2
A<x ・・・式3
上記式1を満たすことで第1の実施形態と同様の効果を得ることができる。
1.4mol/kg濃度の1.3PbZrO3形成用MOD溶液(豊島製作所製Lot.00050667-1),エタノール,2nブトキシエタノールを合わせて1000ml(それぞれ1:1:1の割合で混合)とし、その中に、ポリビニルピロリドン(日本触媒K-30)という白色粉末を20g添加し、撹拌溶解したものをPZO250nmの原料溶液とした、この溶液3mlを6inウェハ上に滴下し、3000rpmで10sec回転塗布した後、150℃ホットプレート上に30sec保持、次に250℃ホットプレート上に90sec保持した後、1atm-O2雰囲気中で600℃,3min焼結した。
図8に示すサンプルのSi基板11、ZrO2膜12及びPt膜13は、図3(A)に示す実施例1によるサンプルと同様の方法で作製された。
プロセス :RF-スパッタリング
ターゲット :Sr(Ti0.8Ru0.2)O3
RFパワー :400W/13.56MHz
プロセス圧力 :4Pa
ガス流量 Ar/O2(sccm):30/10
基板温度 :600℃
プロセス時間 :20sec
膜厚:50nm
アニール温度:600℃
導入ガス :酸素ガス
圧力 :9kg/cm2
昇温レート :100℃/sec
アニール時間:5分
(1)1.4mol/kg濃度の1.3PbZrO3形成用MOD溶液(豊島製作所製Lot.00050667-1),エタノール,2nブトキシエタノールを合わせて1000ml(それぞれ1:1:1の割合で混合)とし、その中に、ポリビニルピロリドン(日本触媒K-30)という白色粉末を10g添加し、撹拌溶解したものをPZO-50nmの原料溶液とした、この溶液3mlを6inウェハ上に滴下し、5000rpmで10sec回転塗布した後、150℃ホットプレート上に30sec保持、次に250℃ホットプレート上に90sec保持した後、1atm-O2雰囲気中で600℃,3min焼結し、厚さ50nmのPZO膜を形成した。
(2)1.4mol/kg濃度の1.3PbZrO3形成用MOD溶液(豊島製作所製Lot.00050667-1),エタノール,2nブトキシエタノールを合わせて1000ml(それぞれ1:1:1の割合で混合)とし、その中に、ポリビニルピロリドン(日本触媒K-30)という白色粉末を20g添加し、撹拌溶解したものをPZO-250nmの原料溶液とした、この溶液3mlを6inウェハ上に滴下し、3000rpmで10sec回転塗布した後、150℃ホットプレート上に30sec保持、次に250℃ホットプレート上に90sec保持した後、1atm-O2雰囲気中で600℃,3min焼結し、厚さ250nmのPZO膜を形成した。
(3)1.4mol/kg濃度の1.3PbZrO3形成用MOD溶液(豊島製作所製Lot.00050667-1),エタノール,2nブトキシエタノールを合わせて1000ml(それぞれ1:1:1の割合で混合)とし、その中に、ポリビニルピロリドン(日本触媒K-30)という白色粉末を20g添加し、撹拌溶解したものをPZO-400nmの原料溶液とした、この溶液3mlを6inウェハ上に滴下し、1000rpmで10sec回転塗布した後、150℃ホットプレート上に30sec保持、次に250℃ホットプレート上に90sec保持した後、1atm-O2雰囲気中で600℃,3min焼結し、厚さ400nmのPZO膜を形成した。
装置 : RFマグネトロンスパッタリング装置
パワー : 1500W
ガス : Ar/O2
圧力 : 0.14Pa
温度 : 600℃
成膜速度 : 0.63nm/秒
成膜時間 : 1.3分
サンプル1(実施例): 50nm なし
サンプル2(実施例): 250nm なし
サンプル3(実施例): 400nm なし
サンプル4(実施例): 50nm 1000nm(総膜厚1050nm)
サンプル5(実施例):250nm 2500nm(総膜厚2750nm)
サンプル6(実施例):400nm 4000nm(総膜厚4400nm)
サンプル7(比較例): なし 1000nm
サンプル8(比較例): なし 2500nm
サンプル9(比較例): なし 4000nm
12 ZrO2膜
13 Pt膜
14 Sr(Ti0.8Ru0.2)O3膜(STRO膜)
15 PbZrO3膜(PZO膜)とPb(Zr0.55Ti0.45)O3膜(PZT膜)を順に積層した積層膜
16 PZO膜
17 Pb(Zr0.55Ti0.45)O3膜(PZT膜)
103 下部電極
104 PbZrO3膜(PZO膜)
105 PZT膜
106 酸化膜
Claims (12)
- Pb(Zr1-ATiA)O3膜と、
前記Pb(Zr1-ATiA)O3膜上に形成されたPb(Zr1-xTix)O3膜と、
を具備し、
前記A及び前記xは下記式1~式3を満たすことを特徴とする強誘電体セラミックス。
0≦A≦0.1 ・・・式1
0.1<x<1 ・・・式2
A<x ・・・式3 - 請求項1において、
前記Aが0であり、
前記Pb(Zr1-ATiA)O3がPbZrO3膜であることを特徴とする強誘電体セラミックス。 - 請求項1または2において、
前記Pb(Zr1-ATiA)O3膜は酸化膜上に形成されていることを特徴とする強誘電体セラミックス。 - 請求項3において、
前記酸化膜はSr(Ti,Ru)O3膜であることを特徴とする強誘電体セラミックス。 - 請求項1乃至4のいずれか一項において、
前記Pb(Zr1-ATiA)O3膜は電極膜上に形成されていることを特徴とする強誘電体セラミックス。 - 請求項5において、
前記電極膜は酸化物または金属からなることを特徴とする強誘電体セラミックス。 - 請求項5または6において、
前記電極膜はPt膜またはIr膜であることを特徴とする強誘電体セラミックス。 - 請求項5乃至7のいずれか一項において、
y 前記電極膜はZrO2膜上に形成されていることを特徴とする強誘電体セラミックス。 - 請求項5乃至8のいずれか一項において、
前記電極膜はSi基板上に形成されていることを特徴とする強誘電体セラミックス。 - Pb(Zr1-ATiA)O3膜上にPb(Zr1-xTix)O3膜を形成する強誘電体セラミックスの製造方法であり、
前記A及び前記xは下記式1~式3を満たすことを特徴とする強誘電体セラミックスの製造方法。
0≦A≦0.1 ・・・式1
0.1<x<1 ・・・式2
A<x ・・・式3 - 請求項10において、
前記Aが0であり、
前記Pb(Zr1-ATiA)O3膜がPbZrO3膜であることを特徴とする強誘電体セラミックスの製造方法。 - 請求項10または11において、
前記Pb(Zr1-ATiA)O3膜は、Pb(Zr1-ATiA)O3の前駆体溶液を基板上に塗布し、5atm以上の酸素雰囲気で結晶化を行うことで形成されることを特徴とする強誘電体セラミックスの製造方法。
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WO2019093471A1 (ja) | 2017-11-13 | 2019-05-16 | アドバンストマテリアルテクノロジーズ株式会社 | 膜構造体及びその製造方法 |
JPWO2018216225A1 (ja) * | 2017-05-26 | 2020-05-21 | アドバンストマテリアルテクノロジーズ株式会社 | 膜構造体及びその製造方法 |
US11527706B2 (en) | 2017-07-07 | 2022-12-13 | Krystal Inc. | Film structure body and method for manufacturing the same |
US11758817B2 (en) | 2016-06-21 | 2023-09-12 | Krystal Inc. | Film structure and method for manufacturing the same |
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JP6677076B2 (ja) * | 2016-05-24 | 2020-04-08 | Tdk株式会社 | 積層膜、電子デバイス基板、電子デバイス及び積層膜の製造方法 |
WO2023122250A2 (en) * | 2021-12-22 | 2023-06-29 | University Of Maryland, College Park | Vapor deposition systems and methods, and nanomaterials formed by vapor deposition |
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