WO2009126199A2 - New class of pure piezoeletric materials - Google Patents

New class of pure piezoeletric materials Download PDF

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Publication number
WO2009126199A2
WO2009126199A2 PCT/US2009/001548 US2009001548W WO2009126199A2 WO 2009126199 A2 WO2009126199 A2 WO 2009126199A2 US 2009001548 W US2009001548 W US 2009001548W WO 2009126199 A2 WO2009126199 A2 WO 2009126199A2
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materials
phase
tio
piezoelectric
thin film
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PCT/US2009/001548
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English (en)
French (fr)
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WO2009126199A3 (en
Inventor
Ronald Cohen
Ganesh Panchapakesan
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Carnegie Institution of Washington
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Carnegie Institution of Washington
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Priority to CA2717350A priority patent/CA2717350A1/en
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Publication of WO2009126199A3 publication Critical patent/WO2009126199A3/en
Anticipated expiration legal-status Critical
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/003—Titanates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C04B35/472—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on lead titanates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
    • H01B3/12—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances ceramics
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/80—Constructional details
    • H10N30/85—Piezoelectric or electrostrictive active materials
    • H10N30/853—Ceramic compositions
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/80—Constructional details
    • H10N30/85—Piezoelectric or electrostrictive active materials
    • H10N30/853—Ceramic compositions
    • H10N30/8548—Lead-based oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
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    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2006/40—Electric properties
    • C—CHEMISTRY; METALLURGY
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3287—Germanium oxides, germanates or oxide forming salts thereof, e.g. copper germanate
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3293—Tin oxides, stannates or oxide forming salts thereof, e.g. indium tin oxide [ITO]
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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    • C04B2235/74—Physical characteristics
    • C04B2235/76—Crystal structural characteristics, e.g. symmetry
    • C04B2235/768—Perovskite structure ABO3

Definitions

  • the present invention relates to a novel class of piezoelectric and ferroelectric materials.
  • PZT-based ceramics have been the primary material used in piezoelectric devices over the past several decades, especially in piezoelectric devices such as ultrasound medical probes, hydrophones and sonar for underwater imaging and communications, multi-layer actuators for fuel injection, piezoelectric printers etc.
  • compositions near a phase transition are chosen.
  • the invention contemplates a novel class of piezoelectrics and ferroelectrics based on the use of chemical pressure to shift the high-pressure extremely high coupling transition recently found in PbTiO 3 , to lower pressures.
  • a particularly preferred compound within this group is Pb 1Z2 Sn 1Z2 TiO 3 (referred to elsewhere herein for convenience as PSnT). This new compound is considered to have giant piezoelectric coefficients, significantly higher than any currently known materials.
  • the class of ferroelectric and piezoelectric materials constituting the present invention is based on the concept of applying "chemical pressure” to tune (shift) the morphotropic phase boundary of pure PbTiO 3 [1 ,2] to lower pressures.
  • Application of "chemical pressure” was performed by substituting the 'A' site of PbTiO 3 perovskite by smaller-atoms with similar ionic charge, e.g. Sn, Ge or the like.
  • Examples of the compounds thus obtainable are Pb 1Z2 Sn 1Z2 TiO 3 , Pb 1/2 Ge 1/2 Ti0 3 and Sn 1/2 Ge 1/2 TiO 3 .
  • These compounds represent a class of materials having superior electromechanical properties compared to previously available piezoelectric materials (Fig 1 and Fig 2).
  • Fig. 1 illustrates the structure of Pb. /2 Sn /2 TiO 3 (also referred to herein as PbSnT);
  • Fig. 2 illustrates the pattern of two other compounds according to the invention.
  • Fig. 3 Illustrates the Electric Enthalpy difference (meV) versus E z (mV/Angstrom) between the phases of PSnT. The intersection with the zero axis shows the required field to rotate the polarization between the phases, The Cm to P4mm transition rotates the polarization and has a large strain, giving a giant electromechanical coupling d 33 - 2100pC/N . The results show that this transition is highly non-linear.
  • the Polarization (P), as computed by the Berry's phase method, in the P4mm phase is (0, 0, 1.2) C/m 2 and in its ground state Pmm2 phase is (1.1 , 0, 0) C/m 2 .
  • the large predicted polarization implies a large Curie temperature T c .
  • the orthorhombic and the monoclinic phases are found to be dynamically stable.
  • One can define an electric enthalpy H U - P.E, where 1 U 1 is the total energy and 'P' and 1 E 1 are the polarization and electric field.
  • Fig 3 shows the enthalpy versus electric field along 'z' direction for the Cm phase with respect to the ground state and the P4mm phase with respect to the Cm phase.
  • the zero crossing of the curves show that the critical field is very high to go from the Pmm2 phase to the Cm phase, but to rotate the polarization from the Cm to the P4mm phase one needs an electric field of only about ⁇ 500 kV/cm.
  • the ground state of PSnT ordered along (001 ) is considered to be orthorhombic, and does not have giant piezoelectric coefficients. Rather the monoclinic Cm phase is believed to have giant coupling.
  • the Cm phase is stabilized by growing PSnT epitaxially on SrTiO 3 .
  • Pb I z 2 Sn 1Z2 TiO 3 has a lattice parameter a -7.44 a.u., very close to the lattice parameter of SrTiO 3 (a - 7.40 a.u ), so that it can be grown epitaxially using conventional MBE methods over SrTiO 3 and make it the ground state.
  • Pb 1/2 Ge 1/2 TiO 3 and Sn 1/2 Ge 1/2 Ti0 3 both have a rhombohedral ground state in the rock salt pattern (space group R3m) with the tetragonal phase (space group 14mm) higher up in energy by 10.1 meV/at and 17.7 meV/at respectively.
  • Their polarizations in the P4mm phase are (0, 0, 1.3) C/m 2 and (0, 0, 1.5) C/m 2 respectively.
  • the materials of the invention there are many uses for the materials of the invention.
  • one application of thin films of PSnT grown on SrTiO 3 is the wings of artificial insects, which can be used for surveillance, monitoring of hazardous environments such as in reactors or other high radiation areas, or in toxic locations.
  • Another use of the present materials is as micropumps in medical applications. Numerous other applications in MEMS exist. Bulk samples can be used as high performance piezoelectrics wherever PZT or relaxor ferroelectrics are currently used.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Inorganic Insulating Materials (AREA)
PCT/US2009/001548 2008-03-11 2009-03-11 New class of pure piezoeletric materials Ceased WO2009126199A2 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2010550689A JP5509103B2 (ja) 2008-03-11 2009-03-11 新しい種類の純粋圧電物質
CA2717350A CA2717350A1 (en) 2008-03-11 2009-03-11 New class of pure piezoeletric materials

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US6455008P 2008-03-11 2008-03-11
US61/064,550 2008-03-11

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WO2009126199A2 true WO2009126199A2 (en) 2009-10-15
WO2009126199A3 WO2009126199A3 (en) 2009-12-30

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JP (1) JP5509103B2 (https=)
KR (1) KR101557784B1 (https=)
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8039131B2 (en) * 2008-03-11 2011-10-18 Carnegie Institution Of Washington Class of pure piezoelectric materials
EP3564188A1 (en) * 2018-05-04 2019-11-06 Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. Sntio3 material, method of preparation thereof, use thereof as ferroelectric material and device comprising a ferroelectric material
US11819702B2 (en) * 2020-03-04 2023-11-21 North Carolina State University Perovskite materials and methods of making and use thereof

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Also Published As

Publication number Publication date
JP2011513191A (ja) 2011-04-28
US20090291324A1 (en) 2009-11-26
CA2717350A1 (en) 2009-10-15
US8679652B2 (en) 2014-03-25
JP5509103B2 (ja) 2014-06-04
US20120009361A1 (en) 2012-01-12
WO2009126199A3 (en) 2009-12-30
KR20100131485A (ko) 2010-12-15
US8039131B2 (en) 2011-10-18
KR101557784B1 (ko) 2015-10-06

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