US3666666A - Ferroelectric ceramic materials - Google Patents

Ferroelectric ceramic materials Download PDF

Info

Publication number
US3666666A
US3666666A US885789A US3666666DA US3666666A US 3666666 A US3666666 A US 3666666A US 885789 A US885789 A US 885789A US 3666666D A US3666666D A US 3666666DA US 3666666 A US3666666 A US 3666666A
Authority
US
United States
Prior art keywords
polarization
zero
ferroelectric
electrooptic
materials
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US885789A
Other languages
English (en)
Inventor
Gene H Haertling
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
US Atomic Energy Commission (AEC)
Original Assignee
US Atomic Energy Commission (AEC)
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by US Atomic Energy Commission (AEC) filed Critical US Atomic Energy Commission (AEC)
Application granted granted Critical
Publication of US3666666A publication Critical patent/US3666666A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G7/00—Capacitors in which the capacitance is varied by non-mechanical means; Processes of their manufacture
    • H01G7/02—Electrets, i.e. having a permanently-polarised dielectric
    • H01G7/025—Electrets, i.e. having a permanently-polarised dielectric having an inorganic dielectric
    • H01G7/026—Electrets, i.e. having a permanently-polarised dielectric having an inorganic dielectric with ceramic dielectric
    • 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
    • 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
    • C04B35/48—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 zirconium or hafnium oxides, zirconates, zircon or hafnates
    • 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
    • C04B35/50—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
    • 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
    • C04B35/51—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on compounds of actinides
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/0009—Materials therefor
    • G02F1/0018—Electro-optical materials
    • G02F1/0027—Ferro-electric materials

Definitions

  • ABSTRACT An electrooptic ferroelectric ceramic material of a lead lanthanum zirconate titanate solid solution having about 5 to 25 atom percent lanthanum with the ratio of zirconium to titanium varying from about 5/95 to about 95/5, hot-pressed, having an optical transmittance throughout the visible spectrum of about 100 percent for optically polished plates about 0.25 millimeters thick, with an effective birefringence of from about 0.003 to 0.03 at saturation remanence polarization to near zero as the remanent polarization is switched to electrical zero, and an effective electrooptic coefficient at saturation remanence from about 1 X 10 to 5 X 10 m /C, and for memory applications a coercive field from about 2 to l0kV/cm.
  • Electrooptic materials which exhibit non-volatile memory capabilities i.e., materials which may be switched from one birefringence value to another and retain the new birefringence when the switching field is removed, are required for optical memories and controlled persistence displays. Also, for memories and controlled persistence displays, it is important that large numbers of small discrete areas be switchable independently in order to achieve a high density of storage sites in a given piece of electrooptic material.
  • Birefringent, optically uniaxial materials are characterized by two refractive indexes: n,, the refractive index parallel to the optic axis, and n the refractive index perpendicular to the optic axis.
  • the birefringence of these materials is defined as the difference, rt -n of the two refractive indexes.
  • the propagation velocity of light in birefringent materials depends on the orientation of the optical electric vector, i.e., on the light polarization condition.
  • incident light which is linearly polarized parallel to the optic axis propagates with a velocity chi
  • incident light which is linearly polarized perpendicular to the optic axis propagates with a different velocity c/n
  • Linearly polarized light with its plane of polarization at some angle other that or 90 to the optic axis is resolved into two perpendicular linearly polarized components when it enters the birefringent material.
  • the polarization plane of one compound is parallel to the optic axis; the plane of the other component is perpendicular to the optic axis.
  • the retardation I The total phase difference of the components as they emerge from the material is called the retardation I.
  • the retardation obviously depends on the birefringence rt -n, (which determines the difference in component velocities) and the material thickness t:
  • the polarization condition of the light emerging from the material depends on the retardation. As the two phase-displaced components emerge, they recombine (interfere) to produce elliptically polarized light.
  • the elliptical polarization may vary from circular to linear depending on the retardation. Assuming the incident'linearly polarized light is monochromatic with wavelength A (in air), light emerging from the op posite surface of the material is circularly polarized if F is an odd multiple of )t/4, and the emerging light is linearly polarized if T is an even multiple of )t/4. If I is an integral multiple of A, the polarization planes of the incident and emergent light are parallel. If 1" is an odd multiple of M2 the polarization plane of the emergent light is rotated with respect to that of the incident light by an angle 2p, where p is the angle between the polarization plane of the incident light and the optic axis.
  • Electrooptic materials commonly used in the past have been ferroelectric single crystals. These materials exhibit the conventional Pockels or Kerr electrooptic effects.
  • single crystals do not exhibit non-volatile optical memory capabilities.
  • the exceptions, gadolinium molybdate and bismuth titanate have only binary memory capabilities.
  • single crystals have poor localized switching capabilities. When switched in small localized areas, the locally switched areas are surrounded by wide partially switched fringes thus preventing high density localized switching.
  • Other limitations on single crystal electrooptic materials are high cost and difficulties in growing large homogeneous crystals.
  • ferroelectric single crystals in electrooptic applications have been overcome by the discovery of the electrooptic properties of fine-grained, hotpressed lead zirconate-lead titanate ferroelectric ceramics (Land and Thacher, Proc. IEEE, Vol. 57, No. 5, pp. 75l-768, May 1969).
  • these materials become uniaxially birefringent on a macroscopic scale when they are electrically poled (polarized by an external field).
  • their effective birefringence is electrically variable by either applying an external biasing field (the conventional electrooptic effect) or by partially switching the ferroelectric polarization. Variation of the effective birefringence by partial or incremental switching is a property unique to ferroelectric ceramics.
  • Locally switched domains in ceramics remain in their switched orientation after the switching field is removed and the locally switched areas can be erased by switching them back to their original orientation.
  • Locally switched areas have narrow fringes, usually only 5 to 10 grain diameters in width, which permits a high density of storage sites on a ceramic plate.
  • Ferroelectric ceramics may be hot-pressed in virtually any size and shape and are relatively inexpensive compared to single crystals.
  • the optic axis orientation in ferroelectric ceramics depends on the direction of the electric poling or switching field, hence it can be switched in any direction. This is not possible in single crystals.
  • Ferroelectric ceramics may be prepared by sintering at atmospheric pressure as well as by sintering at high pressures (i.e., pressure sintering or hot-pressing). Materials sintered at atmospheric pressure, regardless of material composition and sintering parameters, are inhomogeneous and have relatively high porosity (2 to 6 percent) and, as such, are incapable of use aselectrooptic elements or devices due to large and uncontrolled intemal light scattering caused by inhomogeneity and porosity. Many ferroelectric ceramics sintered at atmospheric pressure have a generally yellowish, opaque appearance regardless of size and plate thickness.
  • optical transmittance of these materials may be typically less than one percent (neglecting reflection losses) for plates 0.05 mm thick and any light which is transmitted will generally be completely depolarized due to internal scattering.
  • This depolarization and low optical transmittance is inherent in all commonly available atmospheric-pressure sintered ferroelectric ceramics, including lead zirconate-lead titanate compositions previously known in the art and including those having rare earth element additives of any amount such as those having 10 atom percent or less.
  • Ferroelectric ceramics produced by high pressure sintering techniques may have significantly increased homogeneity and decreased porosity (essentially zero) from that of ferroelectric ceramics sintered at atmospheric pressure.
  • l-lot pressed ferroelectric ceramics may exhibit higher optical transmittance as well as the additional capabilities of non-volatile optical memory, high density localized switching and the like as previously described for finegrained, hot-pressed lead zirconate-lead titanate ceramics (Land and Thacher, lEEE Proc., Vol. 57 No. 5, pp. 751-768, May 1969).
  • optical transmittance may be defined as the ratio of light intensity transmitted by an optical material or device into a specific detector, to the light intensity incident on the optical material or device measured by the same detector. This ratio is always expressed as a percentage in this application.
  • the birefringence of fine-grained, hot-pressed lead zirconate-lead titanate solid solutions may be about -0.02 at saturation remanence and it may vary to about 0.0l at zero remanent polarization. This means that the birefringence may be varied over a range of about 50 percent of its value at saturation remanence by partial or incremental switching of the remanent polarization. It is highly desirable for optical memory and controlled persistence display applications that the range of birefringence variation as a function of remanent polarization be increased.
  • the effective electrooptic coefficients (r l'yT may be about l X lO m /C and the coercive field (field at which the polarization can be switched from saturation remanence to zero) may be about l2kV/cm.
  • the invention comprises a hot-pressed ferroelectric ceramic solid solution composed of lead lanthanum zirconate titanate with about to 25 atom percent lanthanum substituted for the lead and with the zirconium to titanium ratio varying from about 5/95 to about 95/5.
  • FIG. 1 is a perspective and somewhat schematic view of a ferroelectric ceramic optical system
  • FIG. 2 is a partial phase diagram of the lead lanthum zirconate titanate solid solution system
  • FIGS. 3a and 3b are graphs of polarization versus applied electric field for ferroelectric ceramic materials of this invention.
  • FIG. 4 is a graph of effective birefringence versus remanent polarization for different grain sizes of a ferroelectric material of this invention with a hysteresis loop as shown in FIG. 3a;
  • FIG. 5a is a graph of effective birefringence versus electric field for different grain sizes of the material used in FIG. 4;
  • FIG. 5a is a graph of effective birefringence versus electric field for ferroelectric material as shown in FIG. 3b;
  • FIGS. 6a and 6b are graphs of typical transmittance versus wavelength for materials of this invention.
  • Electrooptical device 10 may include a ferroelectric ceramic plate or member 12 composed of the material of this invention and prepared as described below.
  • Plate 12 may have any convenient electrode arrangement or pattern to provide a desired optical output, such as those described in the Land and Thacher article referred to hereinabove, for example, a pair of electrodes 14 and 16. Electrodes 14 and 16 may be disposed on a surface of plate 12 on opposite sides of a polarization area or information location 18. An electric field may be produced between electrodes 14 and 16 in location 18 of plate 12 by an appropriate power source or pulse generator 20. Pulse generator 20 may be any appropriate electrical pulse source which may produce pulses of a desired polarity and amplitude and switch domains of plate 12 disposed between electrodes 14 and 16 at location 18 in one or more directions.
  • a source of light 21 may be positioned near plate 12 so as to impinge light, such as shown by arrow 22, against location 18 and through plate 12.
  • the light source may be any conventional ordinary or white light source, such as an incandescent or mercury arc lamp, or for certain applications a monochromatic or narrow band light source, such as a laser or filtered light source, which is capable of projecting a desired beam of light against location 18.
  • the light source may also include standard collimating means including special lens or fiber optic systems.
  • the light source preferably includes a linear polarizer element 23 between the light source and location 18 so as to polarize the light impinging on location 18 some prescribed direction.
  • a linear analyzer 25 and a suitable photosensitive device 26 may be aligned with the light beam emerging from plate 12, such as shown by arrow 24, to sense the amplitude of the light beam emerging from plate 12 and polarized in the direction of the linear analyzer.
  • Linear analyzer 25 is generally positioned so as to have its polarization axis at right angles to that of linear polarizer 23.
  • the electrooptical device 10 may thus effectively control the color or intensity of light from a white light source or intensity of light from a monochromatic source as the emerging beam impinges upon photosensitive device 26.
  • Plate 12 is an optically uniaxial ferroelectric material having a multiplicity of grains with uniform nominal grain diameters typically about 10 microns or less, a relative density greater than about 99 percent theoretical, and maximum homogeneity, light transmittance, surface smoothness.
  • the grain diameter needed to achieve the desired electrically controlled opti cal properties may be dependent upon the particular ferroelectric composition and the hot-pressing parameters used. It has been found that in order to achieve these properties, the ferroelectric material must be prepared by hot-pressing or pressure sintering techniques.
  • An optically uniaxial ferroelectric ceramic for purposes of this invention is one in which the poled or polarized ceramic is effectively optically uniaxial, i.e., it exhibits the macroscopic symmetry properties of an optically uniaxial, birefringent crystal.
  • the individual grains or crystallites of an optically uniaxial ceramic may exhibit either uniaxial (tetragonal, rhombohedral and hexagonal) symmetry or the generally biaxial (orthrhombic, monoclinic, and triclinic) symmetry.
  • a poled ferroelectric ceramic is generally optically birefringent. With the individual crystallites exhibiting negative birefringence, the electrical polar direction is the fast axis of the ceramic.
  • the effective birefringence in a ferroelectric ceramic plate depends upon the degree or magnitude of electrical poling in a given direction, i.e., whether the ceramic is fully or only partially poled in a particular direction.
  • the orientation of the optic axis depends upon the direction of electrical poling in the ceramic. It has been found that electric control of the light transmission properties of device 10 may be effected by varying the magnitude of the ferroelectric polarization at location 18 in plate 12 by the application of an external electric field by pulse generator 20.
  • the pulse amplitude and pulse width may be adjusted to produce partial or incremental switching of the ceramic polarization.
  • the pulse amplitude is adjusted to produce the required switching speed; the pulse width is adjusted to produce the desired change in polarization.
  • Typical pulse widths and pulse amplitudes may vary from about 0.1 microsecond to 100 microseconds and about to about 30 kilovolts per centimeter depending on the electrode separation distance, plate thickness and composition.
  • Ferroelectric ceramic plate 12 in accordance with this invention, is a ferroelectric ceramic Pb La (Zr, Ti O where x is between about and about 25 atom percent with a ratio of y/z from about 5/95 to about 95/5.
  • This compositional series is a lead lanthanum zirconate titanate (hereinafter referred to as PLZT) solid solution having lanthanum substituted for lead in the prescribed amounts.
  • Compositions may also be prepared according to an alternate formula; i.e., Pb, 2 La (Zr, Ti,) 0 However, where this formula is used, an additional quantity of lead oxide, ranging from 0.1 to 8 weight percent, must be added to the original batch weight.
  • compositions or solid solutions covered by this invention are included within the rectangular area ABCD.
  • Compositions which are ferroelectric tetragonal phase and fall within the area EFG may exhibit good memory material characteristics while those which fall within the area FBHG may exhibit good hard (high coercivity) conventional electrooptic material characteristics.
  • Paraelectric cubic phase as well as mixed paraelectric-ferroelectric compositions (having a coercive field of about 0) falling in the remaining area, AEI-ICD, and principally those in area AEHCI may exhibit good Kerr effect characteristics. As the lanthanum substituent increases, the magnitude of the Kerr effect may decrease.
  • ferroelectric ceramic material prepared in accordance with this invention having a Zr/T i ratio of 65/35 and having a lanthanum substitute-of from about 5 to 8 atom percent may exhibit a polarization hysteresis curve similar to that shown in FIG. 3a while a material having lanthanum substituted at greater than about 9 atom percent may have a polarization hysteresis curve similar to that shown in FIG. 312.
  • the hysteresis curve of FIG. 3a becomes more slanted with respect to the polarization axis and becomes narrower until reaching the condition shown in FIG. 3b.
  • the materials having lanthanum substituted up to about 8 atom percent exhibit a plurality of stable, polarization states between the remanent polarization states 27 and 28. These states are shown by way of example as 30, 32 and 34, 32 being at zero polarization. Many materials may exhibit 10 or more stable polarization states between saturation remanent and zero polarization. As the lanthanum substitute is increased, the saturation remanent polarization decreases in amplitude and approaches zero polarization.
  • the group of materials having a hysteresis characteristic similar to that shown in FIG. 30 may have coercive fields varying from about 2 to 10 kilovolts per centimeter.
  • Ferroelectric ceramic material prepared in accordance with this invention having a Zr/T i ratio of from 55/45 to 5/95 and having a lanthanum substitute of from 12 to atom percent respectively (within the area FBHG of FIG. 2), may exhibit a polarization hysteresis loop curve similar to that shown in FIG.
  • the above materials may exhibit effective birefringences varying from O to as much as about 0.003 to 0.03 (depending upon composition and hot-pressing parameters), the latter birefringence being at saturation remanence polarization with the former being at zero polarization.
  • the variation of effective birefringence with varying remanent polarization is illustrated in a typical example in FIG. 4 for the composition PLZT 8/65/35 (where 8/65/35 designates atom percents of La, Zr and Ti respectively).
  • the maximum effective birefringence at a given polarization increases with decreasing lanthanum substitute.
  • FIG. 5a The dependence of the effective birefringence of the three samples of FIG. 4 on bias electric field E is shown in FIG. 5a.
  • the ceramic plates were first poled to saturation remanent polarization (+1.0 of FIG. 4), and then the bias field was applied in the saturation (positive) direction. It is apparent that the birefringence increases with increasing bias field and to fields as high as IOkV/cm the increase is approximately a linear function of the applied field.
  • the electrooptic coefficients (r /e are all larger than any previously measured for fine-grained lead zirconate-lead titanate solid solutions.
  • Curve A of FIG. 5b is a plot of effective birefringence vs. bias electric field for the composition PLZT-9/65/35; curve B is a similar plot for the composition PLZT-l 1/65/35. Note that the composition PLZT-9/65/35 falls on the FE tetragonal-PE cubic phase boundary of FIG. 2. For this reason, one would expect the birefringence variation with electric field to be greater for this material than for the PLZT-l l'/65/35 composition which falls well inside the PE cubic phase of FIG. 2.
  • a ferroelectric ceramic plate made of a material within the above compositional ranges may exhibit an optical transmittance throughout the visible spectrum of about 100 percent (after correcting for reflection losses) with optically polished surfaces and a plate of about 0.25 millimeters or less. As the thickness of the plate increases the transmittance may decrease, for example, with a plate 1.5 millimeters thick the transmittance may be about 50 percent. Some materials may exhibit a 100 percent transmittance with plates slightly greater or less than 0.25 millimeters thick, depending upon the composition and hot-pressing parameters, however, this variation in transmittance with plate thickness may be minimal.
  • FIGS. 6a and 6b illustrate the transmittance of a typical ferroelectric ceramic (PLZT 8/65/35) within the compositional range noted above over the visible light spectrum and infrared spectrums respectively.
  • ferroelectric ceramic compositions may be prepared by 1 weighing lead oxide, zirconia, titania and lanthana powders, (2) wet mixing the powders in a suitable liquid medium such as distilled water, (3) drying the wet mixed powders, (4) calcining the dried powder mixture at a temperature of about 900 C. for about 1 hour, (5) granulating or wet ball milling of the calcine to break down the partially sintered particle aggregates, (6) drying the wet milled calcine, and (7) compressing the resulting powder into a slug.
  • a suitable liquid medium such as distilled water
  • the grain size may be controlled by selecting raw materials oxide powders which are of high chemical purity (generally greater than about 99.2 percent) and by the proper selection of hot-pressing conditions of temperature, time and pressure. After hot-pressing, it is desirable that the finished slug be sliced into thin wafers or plates and the major surfaces polished to an optical quality finish. The plates may then be annealed at from about 500 to 700 C. for about minutes, cooled to room temperature, electrodes positioned or plated thereon and the plate polarized to a desired uniform initial polarization.
  • Ferroelectric ceramic materials thus formed and within the compositional ranges noted above exhibit the high optical transmittance, wide range of variable effective birefringence, high effective electrooptic coefficients and low coercive fields desired in electrooptic devices.
  • the properties exhibited by these materials may be orders of magnitude better than any previously known ferroelectric ceramic electrooptical material.
  • the uniform optical transmittance over the visible spectrum and the wide range of effective birefringence permits use of such ferroelectric material in optical displays requiring the production of color over the entire visible spectrum. This latter feature is further enhanced by the high level of optical transmittance with plate thicknesses many orders of magnitude greater than previous materials.
  • oxide raw materials having chemical purity as noted above may commonly include iron in quantities greater than 500 parts per million. It has been discovered that the optical clarity of the hot-pressed ferroelectric ceramic materials may be improved by insuring that the iron content of the raw material oxides is below about 300 parts per million.
  • Examples of typical hot-pressed lead lanthanum zirconate titanate materials prepared in accordance with this invention are listed in the following table illustrating some of their electrical and optical characteristics. All materials listed exhibited about 100 percent optical transmittance except PLZT 2/65/35 which exhibited about 25 percent transmittance for samples 0.25 millimeters thick.
  • portion of the visible s ctrum of about percent after correction for reflection osses with material about 0.25 millimeters thick.
  • the material of claim 1 having about 100 percent transmittance after correction for reflection losses in the electromagnetic spectrum from about 0.7 to about 7 microns.
  • the material of claim 1 having an effective birefringence of from about 0.003 to 0.03 at saturation remanence polarization varying to near zero as remanent polarization is switched to electrical zero and having an effective electrooptic coefficient at saturation remanence from about l X 10 to about 5 X 10 m /C.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Nonlinear Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Plasma & Fusion (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Inorganic Insulating Materials (AREA)
US885789A 1969-12-17 1969-12-17 Ferroelectric ceramic materials Expired - Lifetime US3666666A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US88578969A 1969-12-17 1969-12-17

Publications (1)

Publication Number Publication Date
US3666666A true US3666666A (en) 1972-05-30

Family

ID=25387702

Family Applications (1)

Application Number Title Priority Date Filing Date
US885789A Expired - Lifetime US3666666A (en) 1969-12-17 1969-12-17 Ferroelectric ceramic materials

Country Status (6)

Country Link
US (1) US3666666A (fr)
JP (1) JPS4842318B1 (fr)
CA (1) CA926607A (fr)
DE (1) DE2061447C3 (fr)
FR (1) FR2070895B1 (fr)
GB (1) GB1280808A (fr)

Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3740118A (en) * 1971-12-01 1973-06-19 Atomic Energy Commission Self strain biased ferroelectricelectrooptics
US3741627A (en) * 1971-12-01 1973-06-26 Atomic Energy Commission Strain biased ferroelectric electro-optics
US3744875A (en) * 1971-12-01 1973-07-10 Atomic Energy Commission Ferroelectric electrooptic devices
JPS4933200A (fr) * 1972-07-31 1974-03-27
JPS4940753A (fr) * 1972-08-23 1974-04-16
US3855004A (en) * 1973-11-01 1974-12-17 Us Army Method of producing current with ceramic ferroelectric device
US3871745A (en) * 1972-03-27 1975-03-18 Nippon Telegraph & Telephone Visual information storage and display device
US3955190A (en) * 1972-09-11 1976-05-04 Kabushiki Kaisha Suwa Seikosha Electro-optical digital display
US3963630A (en) * 1974-11-21 1976-06-15 Nippon Electric Company Limited Lead zirconate-titanate powder of particle sizes between 0.02 and 0.2 micron, process for producing same, and high-density piezoelectric ceramics made of powder
US3997690A (en) * 1975-05-27 1976-12-14 Honeywell Inc. Method of adjusting refractive index of PLZT optical coating on optical element
US4152280A (en) * 1978-04-17 1979-05-01 General Electric Company Molten salt synthesis of modified lead zirconate titanate solid solution powder
US4158201A (en) * 1977-10-18 1979-06-12 The Singer Company Flat electro optic display panel and method of using same
US4185266A (en) * 1976-06-28 1980-01-22 Nippondenso Co., Ltd. Display apparatus for motor vehicle
US4201450A (en) * 1978-04-03 1980-05-06 Polaroid Corporation Rigid electro-optic device using a transparent ferroelectric ceramic element
US4312004A (en) * 1979-05-07 1982-01-19 Bell & Howell Company Methods and apparatus for recording electric signals
DE3121743A1 (de) 1980-06-04 1982-02-11 Hitachi Ltd Transparentes keramikmaterial fuer optische anwendungen
US4621903A (en) * 1983-01-14 1986-11-11 Sony Corporation Electro-optic light shutter
EP0381524A2 (fr) * 1989-02-02 1990-08-08 Sumitomo Special Metals Company Limited Procédé pour la production de matériau céramique transparent à densité élevée
US5139689A (en) * 1990-02-26 1992-08-18 Ube Industries, Ltd. Method for preparing plzt transparent ceramic
US5308462A (en) * 1986-03-04 1994-05-03 Matsushita Electric Industrial Co., Ltd. Process for producing a ferroelectric film device
US6331234B1 (en) 1999-06-02 2001-12-18 Honeywell International Inc. Copper sputtering target assembly and method of making same
US20020112791A1 (en) * 1999-06-02 2002-08-22 Kardokus Janine K. Methods of forming copper-containing sputtering targets
US6451222B1 (en) * 1999-12-16 2002-09-17 Honeywell International Inc. Ferroelectric composition, ferroelectric vapor deposition target and method of making a ferroelectric vapor deposition target
US6746618B2 (en) 2002-05-21 2004-06-08 Corning Incorporated Electro-optic ceramic material and device
US20040145006A1 (en) * 2003-01-28 2004-07-29 Chih-Wei Hung Flash memory cell structure and operating method thereof
US6890874B1 (en) 2002-05-06 2005-05-10 Corning Incorporated Electro-optic ceramic material and device
US20060043844A1 (en) * 2003-06-10 2006-03-02 Marianne Hammer-Altmann Method for production of pzt-based ceramics having a slow sintering temperature
US20070039817A1 (en) * 2003-08-21 2007-02-22 Daniels Brian J Copper-containing pvd targets and methods for their manufacture
US20070285763A1 (en) * 2006-06-09 2007-12-13 Kewen Kevin Li Electro-optic gain ceramic and lossless devices
US20080074723A1 (en) * 2006-09-07 2008-03-27 U.S.A. As Represented By The Administrator Of The National Aeronautics And Space Administration Ferroelectric Light Control Device
US20080151358A1 (en) * 2006-06-09 2008-06-26 Hua Jiang Transparent electro-optic gain ceramics and devices

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5315628B2 (fr) * 1973-04-06 1978-05-26
GB1516408A (en) * 1975-06-09 1978-07-05 Mullard Ltd Ferroelectric ceramic materials
JPS56131979A (en) * 1980-03-19 1981-10-15 Hitachi Ltd Piezoelectric material for transparent vibrator and transparent vibrator

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2911370A (en) * 1959-11-03 Time after polarization
US2915407A (en) * 1957-03-11 1959-12-01 Gulton Ind Inc Ceramic electrical bodies
US3434122A (en) * 1964-03-13 1969-03-18 Atomic Energy Commission Multiremanence ferroelectric ceramic memory element

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2911370A (en) * 1959-11-03 Time after polarization
US2915407A (en) * 1957-03-11 1959-12-01 Gulton Ind Inc Ceramic electrical bodies
US3434122A (en) * 1964-03-13 1969-03-18 Atomic Energy Commission Multiremanence ferroelectric ceramic memory element

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Haertling, Am. Ceram. Soc. Bull., Vol. 47, P. 389 (1968) *

Cited By (42)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3741627A (en) * 1971-12-01 1973-06-26 Atomic Energy Commission Strain biased ferroelectric electro-optics
US3744875A (en) * 1971-12-01 1973-07-10 Atomic Energy Commission Ferroelectric electrooptic devices
US3740118A (en) * 1971-12-01 1973-06-19 Atomic Energy Commission Self strain biased ferroelectricelectrooptics
US3871745A (en) * 1972-03-27 1975-03-18 Nippon Telegraph & Telephone Visual information storage and display device
JPS552852B2 (fr) * 1972-07-31 1980-01-22
JPS4933200A (fr) * 1972-07-31 1974-03-27
JPS4940753A (fr) * 1972-08-23 1974-04-16
US3955190A (en) * 1972-09-11 1976-05-04 Kabushiki Kaisha Suwa Seikosha Electro-optical digital display
US3855004A (en) * 1973-11-01 1974-12-17 Us Army Method of producing current with ceramic ferroelectric device
US3963630A (en) * 1974-11-21 1976-06-15 Nippon Electric Company Limited Lead zirconate-titanate powder of particle sizes between 0.02 and 0.2 micron, process for producing same, and high-density piezoelectric ceramics made of powder
US3997690A (en) * 1975-05-27 1976-12-14 Honeywell Inc. Method of adjusting refractive index of PLZT optical coating on optical element
US4185266A (en) * 1976-06-28 1980-01-22 Nippondenso Co., Ltd. Display apparatus for motor vehicle
US4158201A (en) * 1977-10-18 1979-06-12 The Singer Company Flat electro optic display panel and method of using same
US4201450A (en) * 1978-04-03 1980-05-06 Polaroid Corporation Rigid electro-optic device using a transparent ferroelectric ceramic element
US4152280A (en) * 1978-04-17 1979-05-01 General Electric Company Molten salt synthesis of modified lead zirconate titanate solid solution powder
US4312004A (en) * 1979-05-07 1982-01-19 Bell & Howell Company Methods and apparatus for recording electric signals
DE3121743A1 (de) 1980-06-04 1982-02-11 Hitachi Ltd Transparentes keramikmaterial fuer optische anwendungen
US4621903A (en) * 1983-01-14 1986-11-11 Sony Corporation Electro-optic light shutter
US5308462A (en) * 1986-03-04 1994-05-03 Matsushita Electric Industrial Co., Ltd. Process for producing a ferroelectric film device
US5032304A (en) * 1989-02-02 1991-07-16 Sumitomo Special Metal Co. Ltd. Method of manufacturing transparent high density ceramic material
EP0381524A2 (fr) * 1989-02-02 1990-08-08 Sumitomo Special Metals Company Limited Procédé pour la production de matériau céramique transparent à densité élevée
EP0381524A3 (fr) * 1989-02-02 1991-04-10 Sumitomo Special Metals Company Limited Procédé pour la production de matériau céramique transparent à densité élevée
US5139689A (en) * 1990-02-26 1992-08-18 Ube Industries, Ltd. Method for preparing plzt transparent ceramic
US6331234B1 (en) 1999-06-02 2001-12-18 Honeywell International Inc. Copper sputtering target assembly and method of making same
US20020112791A1 (en) * 1999-06-02 2002-08-22 Kardokus Janine K. Methods of forming copper-containing sputtering targets
US6645427B1 (en) 1999-06-02 2003-11-11 Honeywell International Inc. Copper sputtering target assembly and method of making same
US6849139B2 (en) 1999-06-02 2005-02-01 Honeywell International Inc. Methods of forming copper-containing sputtering targets
US6451222B1 (en) * 1999-12-16 2002-09-17 Honeywell International Inc. Ferroelectric composition, ferroelectric vapor deposition target and method of making a ferroelectric vapor deposition target
US6579467B2 (en) 1999-12-16 2003-06-17 Honeywell International Inc. Ferroelectric composition, ferroelectric vapor deposition target and method of making a ferroelectric vapor deposition target
US6746619B2 (en) 1999-12-16 2004-06-08 Honeywell International Inc. Ferroelectric vapor deposition targets
US6890874B1 (en) 2002-05-06 2005-05-10 Corning Incorporated Electro-optic ceramic material and device
US6746618B2 (en) 2002-05-21 2004-06-08 Corning Incorporated Electro-optic ceramic material and device
US20040145006A1 (en) * 2003-01-28 2004-07-29 Chih-Wei Hung Flash memory cell structure and operating method thereof
US20060043844A1 (en) * 2003-06-10 2006-03-02 Marianne Hammer-Altmann Method for production of pzt-based ceramics having a slow sintering temperature
US7678290B2 (en) * 2003-06-10 2010-03-16 Robert Bosch Gmbh Method for production of PZT-based ceramics having a slow sintering temperature
US20070039817A1 (en) * 2003-08-21 2007-02-22 Daniels Brian J Copper-containing pvd targets and methods for their manufacture
US20070285763A1 (en) * 2006-06-09 2007-12-13 Kewen Kevin Li Electro-optic gain ceramic and lossless devices
US20080151358A1 (en) * 2006-06-09 2008-06-26 Hua Jiang Transparent electro-optic gain ceramics and devices
US20090168150A1 (en) * 2006-06-09 2009-07-02 Kewen Kevin Li Electro-optic gain ceramic and lossless devices
US7791791B2 (en) 2006-06-09 2010-09-07 Boston Applied Technologies, Incorporated Transparent electro-optic gain ceramics and devices
US20080074723A1 (en) * 2006-09-07 2008-03-27 U.S.A. As Represented By The Administrator Of The National Aeronautics And Space Administration Ferroelectric Light Control Device
US7379231B2 (en) * 2006-09-07 2008-05-27 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Ferroelectric Light Control Device

Also Published As

Publication number Publication date
CA926607A (en) 1973-05-22
DE2061447A1 (de) 1971-06-24
FR2070895B1 (fr) 1973-02-02
JPS4842318B1 (fr) 1973-12-12
DE2061447B2 (de) 1981-07-09
GB1280808A (en) 1972-07-05
DE2061447C3 (de) 1982-05-13
FR2070895A1 (fr) 1971-09-17

Similar Documents

Publication Publication Date Title
US3666666A (en) Ferroelectric ceramic materials
Haertling Electro-optic ceramics and devices
US3531182A (en) Multiremanent ferroelectric ceramic optical devices
Carl et al. Dielectric and optical properties of a quasi-ferroelectric PLZT ceramic
Yokomizo et al. Ferroelectric properties of Pb (Zn1/3Nb2/3) O3
US3512864A (en) Ferroelectric ceramic optical retardation devices
US3923379A (en) Light control element having a wide viewing angle
US6700694B2 (en) Ferro-electric azimuth rotator
Wu et al. Domain structure and polarization reversal in films of ferroelectric bismuth titanate
US3744875A (en) Ferroelectric electrooptic devices
US3702724A (en) Ferroelectric ceramic plate electrooptical light scattering device and method
Barkley et al. Control and application of domain wall motion in gadolinium molybdate
Thacher et al. Ferroelectric electrooptic ceramics with reduced scattering
US3439974A (en) Tunable light filter
US3602904A (en) Ferroelectric gadolinium molybdate bistable light gate-memory cell
US3418036A (en) Magneto-optical rotation device with europium chalcogenide magneto-optical elements
US3586415A (en) Light modulator element
Cummins et al. A new method of optically reading domains in bismuth titanate for display and memory applications
US3936146A (en) Irregular ferroelectric element for controllable single domain
US3612656A (en) Liquid crystal device with lower means located behind the liquid crystal cell
US3701585A (en) Optical line scanner using the polarization properties of ferroelectric-ferroelastic crystals
US3614754A (en) Ferroelectric gadolinium molybdate compensation type bistable light gate and logic cell having memory
Schmid et al. Review of ferroelectric materials usable for passive electro-optic alphanumeric display devices
US3453561A (en) Devices utilizing crystals of pb3mgnb2o9
US3667828A (en) Digital light deflector