US20040061990A1 - Temperature-compensated ferroelectric capacitor device, and its fabrication - Google Patents

Temperature-compensated ferroelectric capacitor device, and its fabrication Download PDF

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Publication number
US20040061990A1
US20040061990A1 US10/256,446 US25644602A US2004061990A1 US 20040061990 A1 US20040061990 A1 US 20040061990A1 US 25644602 A US25644602 A US 25644602A US 2004061990 A1 US2004061990 A1 US 2004061990A1
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Prior art keywords
temperature
ferroelectric
negative
layer
capacitor
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Abandoned
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US10/256,446
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English (en)
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T. Dougherty
John Drab
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Raytheon Co
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Raytheon Co
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Priority to US10/256,446 priority Critical patent/US20040061990A1/en
Assigned to RAYTHEON COMPANY reassignment RAYTHEON COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DOUGHERTY, T. KIRK, DRAB, JOHN J.
Priority to JP2004540141A priority patent/JP4638232B2/ja
Priority to PCT/US2003/029709 priority patent/WO2004030100A1/en
Priority to KR1020057005250A priority patent/KR100807518B1/ko
Priority to TW092126675A priority patent/TWI239541B/zh
Publication of US20040061990A1 publication Critical patent/US20040061990A1/en
Priority to US11/207,925 priority patent/US8053251B2/en
Abandoned legal-status Critical Current

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10B—ELECTRONIC MEMORY DEVICES
    • H10B53/00—Ferroelectric RAM [FeRAM] devices comprising ferroelectric memory capacitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
    • H01L27/04—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being a semiconductor body
    • H01L27/08—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being a semiconductor body including only semiconductor components of a single kind
    • H01L27/0805—Capacitors only
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L28/00—Passive two-terminal components without a potential-jump or surface barrier for integrated circuits; Details thereof; Multistep manufacturing processes therefor
    • H01L28/40—Capacitors
    • H01L28/55—Capacitors with a dielectric comprising a perovskite structure material
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10B—ELECTRONIC MEMORY DEVICES
    • H10B53/00—Ferroelectric RAM [FeRAM] devices comprising ferroelectric memory capacitors
    • H10B53/30—Ferroelectric RAM [FeRAM] devices comprising ferroelectric memory capacitors characterised by the memory core region

Definitions

  • This invention relates to ferroelectric capacitors and, more particularly, to a ferroelectric capacitor device which is temperature compensated to reduce its variation of ferroelectric properties with temperature.
  • Ferroelectric materials are used in a variety of applications.
  • One such application is a ferroelectric capacitor used in a nonvolatile, random access memory whose information is retained even after a power loss.
  • a ferroelectric material is one whose physical state changes upon the application of an electrical field, in a manner analogous with the change undergone by ferromagnetic materials to which a magnetic field is applied.
  • a memory cell may be constructed based upon the hysteresis effects associated with the physical state change.
  • the ferroelectric material has the advantages that its physical state is controlled by the application of a voltage rather than a magnetic field, a measurable state is retained after a power loss, and small-size memory elements may be constructed by microelectronics fabrication techniques, resulting in memory elements that consume little power.
  • ferroelectric nonvolatile memory One difficulty with using ferroelectric materials in some applications of interest, such as ferroelectric nonvolatile memory, is that some of the material properties such as permittivity change substantially over relatively narrow temperature ranges. These properties change so greatly, in some cases more than 100 percent over a temperature range of less than 100° C., that the associate read/write electronics can be quite difficult to design and implement.
  • Ferroelectric materials such as barium titanate, strontium titanate, calcium titanate, calcium stannate, and calcium zirconate are also used to produce discrete ceramic capacitors.
  • the material composition is varied to provide a relatively high permittivity over a specified temperature range. While these devices are optimized to provide a relatively constant capacitance value over a specified temperature range, they are not useful to non-volatile memory applications due to their lack of a remnant polarization component which can be used for information storage.
  • the present invention provides a temperature-compensated capacitor device having ferroelectric properties, but in which the ferroelectric properties of the capacitor device have a reduced dependence upon the ambient temperature.
  • the temperature compensation is built into the temperature-compensated capacitor device, and does not require the use of separate compensation devices. It may be fabricated with a relatively minor modification to the fabrication procedure.
  • a temperature-compensated capacitor device having ferroelectric properties comprises a ferroelectric capacitor comprising a ferroelectric material, a negative-temperature-variable capacitor comprising a negative-temperature-coefficient-of-capacitance material, and an electrical series interconnection between the negative-temperature-variable capacitor and the ferroelectric capacitor.
  • the negative-temperature-coefficient-of-capacitance material, and thence the negative-temperature-variable capacitor exhibits decreased capacitance with increasing temperature over an operational temperature range.
  • the electrical series connection may comprise a direct physical contact between the ferroelectric capacitor and the negative-temperature-variable capacitor.
  • the ferroelectric material comprises a ferroelectric layer
  • the negative-temperature-coefficient of capacitance material comprises another layer in direct, facing contact with the ferroelectric layer.
  • the ferroelectric capacitor and the negative-temperature-variable capacitor are fabricated as an integral unit.
  • the electrical series connection may instead comprise a discrete electrical connection extending between the ferroelectric capacitor and the negative-temperature-variable capacitor.
  • the ferroelectric capacitor and the negative-temperature-variable capacitor are fabricated separately and then linked in series with the electrical connection.
  • the ferroelectric material is preferably a metal oxide ferroelectric material, such as lead titanate, lead zirconate titanate, lead lanthanum zirconate titanate, barium titanate, strontium bismuth tantalate, strontium bismuth niobate, strontium bismuth tantalate niobate, or bismuth lead titanate.
  • the presently most-preferred ferroelectric material is strontium bismuth tantalate niobate.
  • the negative-temperature-coefficient of capacitance material is preferably a paraelectric material.
  • One such negative-temperature-coefficient-of-capacitance material is a metal oxide negative-temperature-coefficient-of-capacitance material, such as strontium titanate or barium strontium titanate.
  • the presently most-preferred negative-temperature-coefficient-of-capacitance material is barium strontium titanate.
  • an integrated temperature-compensated capacitor device has ferroelectric properties and comprises a ferroelectric capacitor comprising a first electrode layer, and a ferroelectric layer of a ferroelectric material in direct physical contact with the first electrode layer.
  • a negative-temperature-variable capacitor comprises a negative-temperature-variable layer of a negative-temperature-coefficient-of-capacitance material, such as a paraelectric material, in direct physical contact with the ferroelectric layer, and a second electrode layer in direct physical contact with the temperature-variable layer.
  • Such an integrated structure may be fabricated by providing a first electrode layer, depositing a ferroelectric precursor layer of a ferroelectric precursor material on the first electrode layer, reacting the ferroelectric precursor layer to produce a ferroelectric layer, depositing a temperature-variable precursor layer of a negative-temperature-coefficient-of-capacitance material on the ferroelectric layer, reacting the temperature-variable precursor layer to form a paraelectric layer, and placing a second electrode layer on the paraelectric layer.
  • Compatible features discussed elsewhere herein may be used in relation to this fabrication procedure.
  • the temperature-compensated capacitor device takes advantage of the different temperature dependencies in ferroelectric and paraelectric materials so that the changes in permittivity and coercive voltage with temperature are greatly diminished, as compared with a conventional ferroelectric capacitor.
  • the voltage across the temperature-compensated capacitor is divided across the ferroelectric capacitor and the negative-temperature-variable capacitor, in either the discrete or integrated embodiments as discussed herein.
  • the paraelectric (negative-temperature-variable) capacitor has a relatively high capacitance at the lower temperatures in the range of operation. Most of the voltage drop is therefore across the ferroelectric capacitor, and a normal ferroelectric hysteresis loop is observed. At higher temperatures within the operating temperature range, the paraelectric material has a lower permittivity so that the voltage drop is greater across the negative-temperature-variable capacitor relative to the ferroelectric capacitor. For small signal capacitance, the temperature-compensated capacitor device exhibits less variation over a selected temperature range than does the ferroelectric capacitor taken by itself. Regarding the hysteresis loop, the increased voltage across the paraelectric material at high temperature serves to compensate the decrease in coercive voltage for the ferroelectric material. Consequently, the change in performance as a function of temperature is less for the temperature-compensated capacitor device than for a conventional ferroelectric capacitor.
  • the present approach provides a capacitor device having ferroelectric properties which have a smaller dependence upon temperature than conventional ferroelectric capacitors. It may be used in any circuitry that requires a ferroelectric capacitor, such as those described in U.S. Pat. No. 5,729,488, U.S. Pat. No. 5,487,030, and U.S. Pat. No. 4,853,893, whose disclosures are incorporated by reference, and particularly those which are expected to experience variations in the operating temperature during their service lives. The need for associated temperature-compensation electronics is reduced, and in some cases eliminated.
  • FIG. 1 is a schematic representation of a temperature-compensated ferroelectric capacitor device using discrete components
  • FIG. 2 is a schematic representation of an integrated temperature-compensated ferroelectric capacitor device
  • FIG. 3 is a graph of the relative permittivity change with temperature for ferroelectric and paraelectric materials
  • FIG. 4 presents calculated capacitor performance curves of an uncompensated and a compensated ferroelectric capacitor device
  • FIG. 5 is a block diagram of a preferred approach for fabricating the temperature-compensated ferroelectric capacitor device.
  • FIG. 1 depicts one preferred embodiment of a temperature-compensated capacitor device 20 having ferroelectric properties.
  • the temperature-compensated capacitor device 20 comprises a ferroelectric capacitor 22 , a negative-temperature-variable capacitor 24 , and an electrical series connection 26 between the negative-temperature-variable capacitor 24 and the ferroelectric capacitor 22 .
  • the ferroelectric capacitor 22 includes a ferroelectric layer 28 of a ferroelectric material, with electrodes 30 on either side of and contacting the ferroelectric layer 28 .
  • the negative-temperature-variable capacitor 24 includes a paraelectric layer 32 of a negative-temperature-coefficient-of-capacitance material, with electrodes 34 on either side of and contacting the paraelectric layer 32 .
  • the electrical series connection 26 extends between one of the electrodes 30 and one of the electrodes 34 .
  • the temperature-compensated capacitor device 20 of FIG. 1 utilizes discrete capacitors 22 and 24 , with the electrical series connection 26 in the form of a discrete electrical connection extending between the ferroelectric capacitor 22 and the negative-temperature-variable capacitor 24 .
  • FIG. 2 An integrated embodiment is illustrated in FIG. 2, where the ferroelectric capacitor 22 and the negative-temperature-variable capacitor 24 are integrated into a single structure that forms the temperature-compensated capacitor device 20 .
  • the integrated embodiment of FIG. 2 is preferred to the discrete embodiment of FIG. 1 because of its compact structure, for those cases where the integrated embodiment of FIG. 2 may be manufactured.
  • the ferroelectric material comprises the ferroelectric layer 28
  • the negative-temperature-coefficient of capacitance material comprises the paraelectric layer 32 in direct, facing contact with the ferroelectric layer 28 . That is, the direct, facing contact serves as the electrical series connection 26 .
  • a first electrode 38 and a second electrode 40 have the ferroelectric layer 28 and the contacting paraelectric layer 32 sandwiched therebetween.
  • the ferroelectric layer 28 is from about 500 Angstroms to about 4000 Angstroms thick
  • the paraelectric layer 32 is from about 75 Angstroms to about 3000 Angstroms thick.
  • the electrodes 30 , 38 and 40 may be made of a metal such as platinum, iridium, ruthenium, or palladium, or an electrically conductive nonmetal such as iridium oxide or ruthenium oxide.
  • the ferroelectric material of the ferroelectric layer 28 is preferably a metal oxide ferroelectric material such as lead titanate, lead zirconate titanate, lead lanthanum zirconate titanate, barium titanate, strontium bismuth tantalate, strontium bismuth niobate, strontium bismuth tantalate niobate, or bismuth lead titanate. Most preferably, the ferroelectric material is strontium bismuth tantalate niobate.
  • FIG. 3 illustrates properties of typical ferroelectric and paraelectric materials.
  • the relative permittivity k of the ferroelectric materials typically increases strongly with temperature, and the relatively permittivity of the paraelectric materials typically decreases with increasing temperature.
  • the negative-temperature-variable capacitor 24 therefore desirably exhibits decreased capacitance with increasing temperature over an operational temperature range.
  • the negative-temperature-coefficient of capacitance material of the layer 32 is desirably a paraelectric material whose relative permittivity decreases with increasing temperature.
  • the negative-temperature-coefficient of capacitance material is preferably a metal oxide negative-temperature-coefficient-of-capacitance material such as strontium titanate or barium strontium titanate, and is most preferably barium strontium titanate.
  • FIG. 4 depicts the calculated capacitance of a conventional, uncompensated ferroelectric capacitor made of strontium bismuth tantalate niobate (SBTN), whose total capacitance increases sharply with temperature. Also shown in FIG. 4 are the similarly calculated properties of the temperature-compensated capacitance device 20 of the present invention, utilizing an SBTN ferroelectric layer 28 and a Ba 05 Sr 05 TiO 3 (BST) paraelectric layer 32 .
  • the temperature-compensated capacitance device 20 exhibits some temperature dependence of the total capacitance, but substantially less than that of the uncompensated ferroelectric capacitor. If only the small signal capacitance is of interest, the total capacitance of the temperature-compensated capacitor device 20 may be made to be nearly temperature invariant.
  • FIG. 5 illustrates a preferred approach for practicing the invention to make the preferred embodiment of the temperature-compensated capacitance device 20 shown in FIG. 2.
  • the first electrode 38 in the form of the first electrode layer is provided, step 60 .
  • the first electrode 38 may be of any operable material, and may be provided by any operable approach.
  • the first electrode 38 is desirably a platinum electrode deposited upon a substrate by vacuum evaporation of the platinum, and then thermally annealed at a temperature of about 700° C. to stabilize the first electrode 38 .
  • a ferroelectric precursor layer of a ferroelectric precursor material is deposited on the first electrode layer, step 62 .
  • a liquid solution of the metal oxide ferroelectric precursor material is prepared and then spun onto the first electrode layer.
  • the metal-2-ethylhexanoate salts of strontium, bismuth, tantalum, and niobium are dissolved in a solvent of xylene and n-butylacetate.
  • the atomic ratio of strontium:bismuth:tantalum:niobium is 0.9:2.18:1.5:0.5.
  • the resulting ferroelectric precursor solution is spun onto the first electrode layer in one or more steps to achieve the desired thickness, with drying between each spin-on step.
  • the ferroelectric precursor layer is reacted, step 64 , by crystallizing in a rapid thermal processor and then sintering in a tube furnace to form the ferroelectric material of the ferroelectric layer 28 .
  • the crystallizing is performed at a temperature of about 725° C.
  • the sintering is performed at a temperature of about 700° C.
  • a negative-temperature-variable precursor layer of a negative-temperature-coefficient of capacitance material is deposited on the ferroelectric layer 28 , step 66 .
  • the temperature-precursor material is a mixture of the metal-2-ethylhexanoate salts of strontium, barium, and titanium, dissolved in the solvent of xylene and n-butylacetate.
  • the atomic ratio of strontium:barium:titanium is 0.5:0.5:1.05.
  • the resulting temperature-variable precursor solution is spun onto the ferroelectric layer 28 in one or more steps to achieve the desired thickness, with drying between each spin-on step.
  • the temperature-variable precursor layer is reacted, step 68 , by crystallizing in a rapid thermal processor and thereafter sintering in a tube furnace to form the ferroelectric material of the paraelectric layer 32 .
  • the crystallizing is performed at a temperature of about 725° C.
  • the sintering is performed at a temperature of 700° C.
  • the second electrode 40 in the form of a second electrode layer is placed on the paraelectric layer 32 , step 70 .
  • the second electrode 40 is preferably deposited in the manner described for the first electrode 38 .
  • a temperature-compensated capacitor device 20 as discussed above in the form illustrated in relation to FIG. 2 was prepared as described in relation to FIG. 5.
  • the resulting temperature-compensated capacitor device functioned as described above.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
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  • Microelectronics & Electronic Packaging (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
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Application Number Priority Date Filing Date Title
US10/256,446 US20040061990A1 (en) 2002-09-26 2002-09-26 Temperature-compensated ferroelectric capacitor device, and its fabrication
JP2004540141A JP4638232B2 (ja) 2002-09-26 2003-09-19 温度補償された強誘電キャパシタ装置およびその製造方法
PCT/US2003/029709 WO2004030100A1 (en) 2002-09-26 2003-09-19 Temperature-compensated ferroelectric capacitor device, and its fabrication
KR1020057005250A KR100807518B1 (ko) 2002-09-26 2003-09-19 온도 보상형 강유전성 커패시터 장치 및 그 제조
TW092126675A TWI239541B (en) 2002-09-26 2003-09-25 Temperature-compensated ferroelectric capacitor device, and its fabrication
US11/207,925 US8053251B2 (en) 2002-09-26 2005-08-19 Temperature-compensated ferroelectric capacitor device, and its fabrication

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US20180138902A1 (en) * 2016-11-14 2018-05-17 Ford Global Technologies, Llc Sensorless temperature compensation for power switching devices
CN113314346A (zh) * 2021-06-07 2021-08-27 通号(北京)轨道工业集团有限公司轨道交通技术研究院 一种变容电容器
US20230094616A1 (en) * 2021-09-30 2023-03-30 Tdk Corporation Thin film capacitor, power source module, and electronic device

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JP5259940B2 (ja) * 2005-09-05 2013-08-07 日東電工株式会社 粘着剤組成物、粘着シートおよび表面保護フィルム
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CN101842970A (zh) * 2007-12-06 2010-09-22 英特赛尔美国股份有限公司 用于改进dc/dc调压器的电感器电流检测准确度的系统和方法
JP5766011B2 (ja) * 2011-05-06 2015-08-19 京セラ株式会社 静電容量素子
US10139288B2 (en) 2013-09-25 2018-11-27 3M Innovative Properties Company Compositions, apparatus and methods for capacitive temperature sensing
WO2022230432A1 (ja) * 2021-04-28 2022-11-03 パナソニックＩｐマネジメント株式会社 誘電体、キャパシタ、電気回路、回路基板、及び機器
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