WO2007125664A1 - 焦電性磁器組成物、及び焦電素子、並びに赤外線検出器 - Google Patents
焦電性磁器組成物、及び焦電素子、並びに赤外線検出器 Download PDFInfo
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- WO2007125664A1 WO2007125664A1 PCT/JP2007/052349 JP2007052349W WO2007125664A1 WO 2007125664 A1 WO2007125664 A1 WO 2007125664A1 JP 2007052349 W JP2007052349 W JP 2007052349W WO 2007125664 A1 WO2007125664 A1 WO 2007125664A1
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- pyroelectric
- pyroelectric element
- infrared detector
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- 239000000203 mixture Substances 0.000 title claims abstract description 51
- 239000000919 ceramic Substances 0.000 title abstract description 12
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 18
- 229910052573 porcelain Inorganic materials 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 23
- 230000003287 optical effect Effects 0.000 claims description 15
- 238000001514 detection method Methods 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 4
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- 238000000034 method Methods 0.000 description 9
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- 238000012545 processing Methods 0.000 description 7
- ORQBXQOJMQIAOY-UHFFFAOYSA-N nobelium Chemical compound [No] ORQBXQOJMQIAOY-UHFFFAOYSA-N 0.000 description 6
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- 230000007423 decrease Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
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- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 241000234435 Lilium Species 0.000 description 1
- 229910018054 Ni-Cu Inorganic materials 0.000 description 1
- 229910018481 Ni—Cu Inorganic materials 0.000 description 1
- 229910018605 Ni—Zn Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000011805 ball Substances 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
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Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J5/00—Radiation pyrometry, e.g. infrared or optical thermometry
- G01J5/10—Radiation pyrometry, e.g. infrared or optical thermometry using electric radiation detectors
- G01J5/34—Radiation pyrometry, e.g. infrared or optical thermometry using electric radiation detectors using capacitors, e.g. pyroelectric capacitors
-
- 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
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N15/00—Thermoelectric devices without a junction of dissimilar materials; Thermomagnetic devices, e.g. using the Nernst-Ettingshausen effect
- H10N15/10—Thermoelectric devices using thermal change of the dielectric constant, e.g. working above and below the Curie point
- H10N15/15—Thermoelectric active materials
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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
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
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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
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3251—Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof
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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
- C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
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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
- C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3279—Nickel oxides, nickalates, or oxide-forming salts thereof
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/76—Crystal structural characteristics, e.g. symmetry
- C04B2235/768—Perovskite structure ABO3
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- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/79—Non-stoichiometric products, e.g. perovskites (ABO3) with an A/B-ratio other than 1
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase
- C04B2235/81—Materials characterised by the absence of phases other than the main phase, i.e. single phase materials
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase
- C04B2235/85—Intergranular or grain boundary phases
Definitions
- the present invention relates to a pyroelectric porcelain composition, a pyroelectric element formed of the pyroelectric porcelain composition, and an infrared detector including the pyroelectric element.
- a pyroelectric porcelain composition absorbs infrared radiant energy and undergoes a temperature change, whereby a charge is formed on the surface due to a change in spontaneous polarization.
- pyroelectric porcelain compositions are widely used in infrared detectors as pyroelectric elements for pyroelectric elements.
- This type of pyroelectric porcelain composition is required to have a large change in spontaneous polarization with respect to a temperature change of the pyroelectric material, that is, a large pyroelectric property. Also, if the relative permittivity of the pyroelectric material is too small, it will be affected by the stray capacitance of the external circuit of the infrared detector, and large noise will be generated immediately. On the other hand, if the relative dielectric constant is too large, the surface charge (pyroelectric charge) generated on the surface of the pyroelectric element is accumulated in the element itself and the detection sensitivity is lowered. For this reason, the pyroelectric porcelain composition is required to have an appropriate relative dielectric constant.
- Patent Document 1 the general formula: (Pb Ca) ⁇ (Ni Nb)
- Ti l-y 3 as shown by Ti ⁇ 0 (Sheet, x, y are 0.25 ⁇ x ⁇ 0.35, 0.01 ⁇ y ⁇ 0.06)
- Patent Document 1 the ⁇ site component of the perovskite crystal structure (general formula ⁇ )
- Patent Document 1 A part of Pb is replaced with Ca in the range of 25 to 35 mol%, thereby obtaining the desired optimum relative dielectric constant. Furthermore, in Patent Document 1, a part of Ti, which is a B site component, is replaced with (Ni Nb).
- the pyroelectric characteristics are improved, and by adding a predetermined amount of Mn as a subcomponent, the sinterability is improved.
- Patent Document 1 Japanese Patent Laid-Open No. 1 261876
- the pyroelectric porcelain composition of Patent Document 1 has a high insulation resistance, when a pyroelectric element using the pyroelectric porcelain composition is used for an infrared detector, the pyroelectric element As a result, the pyroelectric current output from the sensor becomes small, and stable sensor characteristics against temperature changes could not be obtained.
- the pyroelectric element 102 changes in magnitude of polarization according to the amount of infrared rays.
- a pyroelectric current proportional to the magnitude is output.
- This pyroelectric current is converted into a voltage by impedance conversion via the load resistor 101, and a voltage signal corresponding to the pyroelectric current is input to the gate terminal 104 of a field effect transistor (hereinafter referred to as “FET”) 103.
- FET field effect transistor
- the A power supply voltage is applied to the drain terminal 105 of the FET 103, and the source terminal 106 and the ground terminal 107 are connected via a source resistor (not shown). Then, the bias voltage divided by the resistance value between the drain terminal 105 and the source terminal 106 and the resistance value of the source resistance (not shown) and the voltage signal input to the gate terminal 104 are superimposed, and the source signal is superimposed. Terminal 106 Force A voltage signal is output.
- Patent Document 1 the A site component of the perovskite crystal structure (general formula ABO)
- the Curie temperature Tc (e.g., 260 ° or C) can be obtained It is said that.
- the present invention has been made in view of such circumstances, and has a pyroelectric property that provides a good pyroelectric property while having a reasonably low insulation resistance and a high temperature and a Curie temperature Tc. It is an object of the present invention to provide a porous ceramic composition, a pyroelectric element using the pyroelectric ceramic composition, and an infrared detector equipped with the pyroelectric element.
- the present inventors have conducted intensive research. As a result, the molar ratio of the A-site component of the lead titanate-based compound having a perovskato-type crystal structure (general formula AB0).
- the present invention has been made on the basis of such knowledge, and the pyroelectric porcelain composition according to the present invention has a general formula (Pb Ca) ⁇ (Ni Nb) Ti ⁇ 0 (where x
- lx x (1 + a) 1/3 2/3 y (1- y) 3, y, a are 0. 20 ⁇ x ⁇ 0.27, 0. 01 ⁇ y ⁇ 0.06, 0. 001 ⁇ a ⁇ 0.02) is the main component, and 0.3 to 2.5 mol of Mn is contained per 100 mol of the main component.
- the present inventors conducted further diligent research. As a result, the segregation product containing Ni, Ti, and Mn. In the sintered body, 1. Insulation resistance is reduced when Ovol% or less. I understood That is, in the pyroelectric porcelain composition of the present invention, the segregated material containing Ni, Ti and Mn is 1. Ovol% or less (including Ovol%) in the sintered body. It is characterized by.
- the pyroelectric element according to the present invention is a pyroelectric element having a pyroelectric body and an electrode formed on a surface of the pyroelectric body, wherein the pyroelectric body is the pyroelectric porcelain. It is formed from a composition, and is specially characterized as being made.
- the pyroelectric element Furthermore, by using the pyroelectric element, stable sensor characteristics can be obtained in which the fluctuation of the bias voltage Vs is small with respect to temperature changes, and the pyroelectric characteristics are good even after reflow processing. An infrared detector can be obtained.
- an infrared detector according to the present invention is characterized by including the above pyroelectric element.
- an infrared detector is a surface-mounting infrared including the pyroelectric element, a package that houses the pyroelectric element, and an optical filter that transmits infrared light of a predetermined wavelength.
- a line detector wherein the package is formed in a box shape having an opening on one surface, and a wiring pattern electrically connected to the pyroelectric element is disposed inside the package.
- the optical filter has a function of causing the pyroelectric element to receive the infrared light and a function as a lid for sealing the opening, and is disposed so as to cover the entire opening of the package. It is characterized by that.
- the infrared detector of the present invention is characterized in that a load resistance is not provided in parallel with the pyroelectric element.
- ⁇ (However, x, y, and a are 0.20 ⁇ x ⁇ 0.27, 01.01 ⁇ y ⁇ 0.06, and 0.001 ⁇ a, respectively.
- Mn 0.3-2 for 100 mol of the main component.
- the insulation resistance is moderately low, and it has a high Curie temperature Tc (eg, 260 ° C or higher) that can withstand reflow treatment, but it can obtain good pyroelectric characteristics. I'll do it.
- Tc Curie temperature
- the segregated material containing Ni, Ti and Mn is 1. Ovol% or less (including Ovol%) in the sintered body. , Effect the insulation resistance to the desired value Can be reduced.
- the pyroelectric material is formed from the pyroelectric porcelain composition, the insulation resistance is moderately low and the Curie temperature Tc is high. A pyroelectric element having good pyroelectric characteristics can be obtained.
- the infrared detector of the present invention includes the pyroelectric element formed of the above pyroelectric porcelain composition, a stable sensor in which the fluctuation of the bias voltage Vs is small with respect to the temperature change. Characteristics can be detected.
- an infrared detector includes the pyroelectric element, a package in which the pyroelectric element is accommodated, and an optical filter that transmits infrared light having a predetermined wavelength.
- the package has an opening on one surface.
- a wiring pattern electrically connected to the pyroelectric element is disposed inside the package, and the optical filter causes the pyroelectric element to receive the infrared line. Since it has a function and a function as a lid for sealing the opening, and is disposed so as to cover the entire opening of the package, the above-described effects can be easily achieved.
- the infrared detector can obtain stable sensor characteristics without providing a load resistance in parallel with the pyroelectric element, thereby enabling infrared detection with a small size, a low profile, and a low cost.
- the design of the vessel can be realized.
- the Curie temperature of the pyroelectric porcelain composition is high, a surface-mountable infrared detector having good pyroelectric properties even after reflow treatment can be obtained.
- FIG. 1 is a cross-sectional view schematically showing one embodiment of a pyroelectric element according to the present invention.
- FIG. 2 is a cross-sectional view showing an embodiment of an infrared detector incorporating the pyroelectric element.
- FIG. 3 is a basic circuit diagram of the infrared detector of FIG.
- FIG. 4 is a diagram showing the change with time of the source voltage in Sample No. 2 and Sample No. 3 together with the temperature change.
- FIG. 5 is a basic circuit diagram of a conventional infrared detector.
- the pyroelectric porcelain composition according to an embodiment of the present invention is composed of a PNN-PT-based compound having a perovskite crystal structure (general formula ABO) as a main component, and 100 mol of the main component.
- Mn is contained in the range of 0.3-3 to 2.5 mol.
- the main component is represented by the following general formula ( ⁇ ).
- the molar ratio x of Ca in the A site the molar ratio y of (Ni Nb), the A site component
- the molar ratio a of the B site component satisfies the following mathematical formulas (1) to (3).
- the segregated material containing Ni, Ti, and Mn is 1. Ovol% (including 0 vol%) or less in the sintered body. It is comprised so that.
- the pyroelectric porcelain composition is composed of the above-described composition components, the insulation resistance is appropriately low, and the pyroelectric ceramic composition does not have a high Curie temperature Tc that can withstand a reflow process of 260 ° C or higher. However, good pyroelectric characteristics can be obtained.
- the relative permittivity ⁇ r and key The lily temperature Tc can be controlled to a value suitable for an infrared detector.
- the molar ratio X of Ca in the A site is less than 0.20, the sinterability decreases and a dense sintered body cannot be obtained.
- the molar ratio X is more than 0.27, the Curie temperature Tc is lowered to less than 260 ° C. and heat resistance sufficient to withstand the reflow treatment cannot be obtained.
- the content molar ratio X is adjusted to be 0.20 ⁇ x ⁇ 0.27.
- Ni compounds and Nb compounds that can no longer be deposited will precipitate at the grain boundaries, making it impossible to obtain a dense sintered body.
- the content molar ratio y is adjusted to be 0.01 ⁇ y ⁇ 0.06.
- Insulation resistance can be reduced by making the molar ratio a of the A site and B site in the main component a more A site than the stoichiometric composition, and good pyroelectric characteristics even after reflow treatment Can be obtained.
- the blending molar ratio a is less than 0.001
- the segregated material containing Ni, Ti, and Mn exceeds 1.0 vol% in the fired sintered body, and the insulation resistance is sufficient.
- the temperature The force and the pyroelectric characteristics after reflow processing are also degraded.
- the blending molar ratio a exceeds 0.02
- the insulation resistance is excessively lowered and the polarization treatment becomes difficult.
- the blending molar ratio a is adjusted to 0.001 ⁇ a ⁇ 0.02.
- the molar amount of Mn is less than 0.3 moles with respect to 100 moles of the main component, the sinterability is lowered and a dense sintered body cannot be obtained.
- the molar amount of Mn is 100 mol
- the amount exceeds 2.5 mol segregation of Mn, which cannot be completely dissolved in the crystal grains, to the crystal grain boundary becomes remarkable, and the pyroelectric characteristics deteriorate.
- the molar amount of Mn is 0.3-2 with respect to 100 mol of the main component.
- the present pyroelectric ceramic composition Ni as described above, segregants containing Ti and Mn, a sintered body in which has been made baked 1. 0 ⁇ ⁇ 1. /. (Including 0 ⁇ 1%)
- the segregated material can be lowered to the extent that the insulation resistance does not become excessively low by further reducing the volume content within the range of 1. Ovol% or less. .
- the volume content of the segregated material can be controlled by adjusting the composition and the firing temperature.
- FIG. 1 is a cross-sectional view schematically showing an embodiment of a pyroelectric element.
- the pyroelectric element 1 is a pyroelectric body obtained by using the pyroelectric porcelain composition. 2 and an upper electrode 3a and a lower electrode 3b formed on both main surfaces of the pyroelectric body 2, and polarization treatment is performed in the direction of arrow A.
- the pyroelectric element 1 can be manufactured as follows, for example.
- Pb compounds such as PbO, CaCO, etc.
- Ni compounds such as NiO
- Nb compounds such as NbO
- Ti compounds such as TiO
- Zirconia Put into a ball mill with a grinding medium such as balls and water and mix, and wet pulverize. Thereafter, dehydration and drying are performed, and then a predetermined temperature (for example, 800 to 95).
- a predetermined temperature for example, 800 to 95.
- Calcination is performed for a predetermined time at about 0 ° C. to obtain a calcined product.
- an organic binder, a dispersant, and water are mixed with this calcination product together with a pulverizing medium in a ball mill, wet pulverized again, dehydrated and dried, and then pressed to obtain a predetermined shape.
- a molded ceramic molded body is obtained.
- the ceramic molded body is subjected to a binder removal treatment at a temperature of about 400 to 600 ° C, and then contained in a sealed sheath, and segregated containing Ni, Ti, and Mn. 1.
- a sintered body is produced.
- both main surfaces of the sintered body are subjected to polishing treatment to produce pyroelectric body 2, and thereafter, a thin film forming method such as a sputtering method or a vacuum evaporation method, a plating method, or an electrode paste baking process, etc.
- a thin film forming method such as a sputtering method or a vacuum evaporation method, a plating method, or an electrode paste baking process, etc.
- the upper electrode 3a and the lower electrode 3b are formed on both main surfaces of the pyroelectric body 2, respectively.
- the pyroelectric element 1 can be manufactured by applying a predetermined electric field in silicone oil heated to a predetermined temperature to perform a polarization treatment.
- the segregated material containing Ni, Ti, and Mn is 1. Ovol% or less. .
- the pyroelectric element 1 having an insulation resistance that is moderately small and that has a high Curie temperature Tc that can withstand a reflow process and that has good pyroelectric characteristics.
- the pyroelectric element 1 when the pyroelectric element 1 is incorporated in an infrared detector, good pyroelectric characteristics can be ensured even after reflow processing, and therefore, it is suitable for surface mounting.
- FIG. 2 is a cross-sectional view schematically showing an embodiment of an infrared detector in which the pyroelectric element 1 is incorporated.
- This infrared detector includes a package 4 corresponding to surface mounting in which the pyroelectric element 1 is accommodated, and an optical filter 5 that transmits infrared light of a predetermined wavelength.
- the pyroelectric element 1 is of a so-called dual type.
- two upper electrodes (light receiving electrodes) 3a, 3a arranged on the surface of pyroelectric body 2 are connected in series and in reverse polarity, when infrared rays are simultaneously incident on these upper electrodes 3a, 3a, the external temperature
- the system is designed to eliminate external noise caused by changes.
- the package 4 has a box shape in which an opening 4a is formed on the top surface and a hole is formed on the bottom surface.
- a metal material such as 42Ni, phosphor bronze, brass, Cu_Ni-Zn alloy, iron, etc. It is formed with.
- An insulating member 6 made of glass, LCP (liquid crystal polyester) resin or the like is attached to the inner surface of the package 4. Further, the wiring pattern 10 and the FET 12 are disposed at predetermined positions on the inner bottom surface of the insulating member 6, and are configured to be electrically connected to electrodes and wiring (not shown).
- a support member 11 is disposed at a suitable position on the inner bottom surface of the insulating member 6, and the pyroelectric element 1 is placed on the support member 11. That is, the pyroelectric element 1 is connected to the above through the lower electrode 3b. It is supported by the support member 11.
- an external connection terminal 7 is provided on the lower surface of the wiring pattern 10, and an insulator 8 such as glass is interposed between the external connection terminal 7 and the package 4, so that the package 4 and the external connection terminal are provided. 7 is configured to be electrically insulated. As a result, the pyroelectric element 1 is electrically connected to an external device via the wiring pattern disposed in the package 4 or the external connection terminal 7.
- an optical filter 5 is provided in the opening 4 a of the package 4.
- the optical filter 5 has a function of causing the pyroelectric element 1 to receive infrared light of a predetermined wavelength and a function as a lid for sealing the opening 4a of the package 4.
- the optical filter 5 is formed using a single crystal silicon that transmits infrared rays having a predetermined wavelength as a filter base material. Then, the optical filter 5 is bonded to the package 4 via a conductive adhesive 9 so as to cover the entire opening 4a of the package 4, whereby the optical filter 5 and the package 4 are electrically connected. Has been.
- the optical filter 5 is not partially shielded, and thus is configured so that the entire surface transmits infrared rays. This makes it possible to widen the infrared light receiving region, and to improve detection accuracy. A high infrared detector can be obtained.
- FIG. 3 is a basic circuit diagram of the infrared detector shown in FIG.
- the upper electrode 3a of the pyroelectric element 1 is connected to the ground terminal 15, and the lower electrode 3b is connected to the gate terminal 12a of the FET 12.
- a power supply voltage is applied to the drain terminal 12b of the FET 12, and a source resistance (not shown) is interposed between the source terminal and the ground terminal 15.
- the pyroelectric element 1 responds to the amount of infrared rays.
- the magnitude of the polarization changes, and a pyroelectric current proportional to the magnitude is output, and a voltage signal corresponding to the pyroelectric current is input to the gate terminal 12a.
- the bias voltage divided by the resistance value between the drain terminal 12b and the source terminal 12c and the resistance value of the source resistance and the voltage signal input to the gate terminal 12a are superimposed to generate a voltage from the source terminal 12c.
- a signal is output.
- the bias voltage Vs can be controlled against the temperature change without providing a load resistance in parallel to the pyroelectric element 1. Stable sensor characteristics with small fluctuations can be detected. In other words, it is not necessary to incorporate a load resistance in parallel with the pyroelectric element 1, and it is possible to save cost and labor. It is possible to prevent complication of the internal structure of the element, thereby reducing the size of the infrared detector. Can be realized. In addition, since the Curie temperature Tc is high, good pyroelectric characteristics can be secured even after surface mounting by reflow treatment. Therefore, it is possible to realize a surface-mount type infrared detector having the pyroelectric element 1 with a thin layer size.
- the present invention is not limited to the above-described embodiment.
- the pyroelectric element 1 may be of a type having an electrode force, or an infrared detector having a plurality of pyroelectric elements 1 connected in series. Needless to say, it can be applied.
- the infrared detector of the present invention does not hinder the incorporation of a load resistance. If there is no restriction of downsizing, low profile, and low cost, the load is parallel to the pyroelectric element 1. You can incorporate resistance.
- the calcined product after drying is sized using a 40 mesh sieve, and the obtained powder is press-molded at a pressure of 8.6 X 10 7 Pa, length 25 mm, width 40 mm, thickness 1 A 2 mm plate-like molded body was produced.
- the plate-shaped molded body is accommodated in an alumina sheath, subjected to binder removal treatment at a temperature of about 500 ° C, and then fired at a temperature of 1100 to 1200 ° C for 2 hours.
- a sintered body of sample numbers:! -29 was obtained.
- the power of whether or not there is a pixel having an X-ray intensity more than twice the average X-ray intensity of the entire image (in 250 X 250 pixels) is determined.
- the positive case that is, when it exists, it is assumed that there is a segregated material of Mn at the image position.
- the X-ray intensity is at least twice the average X-ray intensity of the entire image, at the same coordinate position as the image position where the segregated matter of Mn is present. If the result is affirmative, Ni and Ti segregated materials are present at the image position, and the position of segregated materials containing Ni, Ti and Mn is thereby determined. Identified.
- the area ratio of the abundance (number of pixels) of the segregated matter in the entire image (250 X 250 pixels) was calculated, and this was defined as the abundance ratio (vol%) of the segregated matter.
- the capacitance of each sample was obtained using an impedance analyzer (HP4294A manufactured by Agilent Technologies), and the relative dielectric constant ⁇ r was calculated from the capacitance and the sample dimensions.
- the temperature characteristic of the relative permittivity ⁇ r was measured, and the maximum temperature of the relative permittivity ⁇ r was calculated to be the queue temperature Tc.
- each of these samples is put into a container capable of changing the temperature at a constant rate, and the temperature is changed from 10 ° C to 70 ° C with a temperature change rate of 0.5 ° C / s.
- the pyroelectric current 1 (A) was measured while changing the temperature within the range, and the pyroelectric coefficient Tp (C / m 2 'K) was calculated based on Equation (4).
- S is the area (m 2 ) of the main surface, and the diameter of the sample was measured using a micrometer and calculated from the diameter. At represents the temperature change per unit time.
- Table 1 shows the compositions of the sample numbers:! To 29 and the measurement results.
- Sample Nos. 1 to 25 were fired at 1150 ° C.
- Sample No. 1 has a molar ratio a of A site to B site of -0.005, and the B site is excessive, so the log p force becomes 5 and exceeds 12.0. The insulation resistance could not be reduced.
- Sample No. 2 has a mixing molar ratio a of A site to B site of 0.000 and a stoichiometric ratio, so the log p force is 2.3 and exceeds 12.0. The insulation resistance could not be reduced.
- Sample No. 17 does not contain (Ni Nb) at all, so the pyroelectric coefficient Tp is 2.27.
- Sample No. 20 had a (Ni Nb) content molar ratio y of 0.10 and exceeded 0.06.
- NiO or Nb O that cannot be completely dissolved in the crystal grains in the form of (Ni Nb)
- Sample No. 21 has a small Mn content of 0.2 moles with respect to 100 moles of the main component, so a dense sintered body cannot be obtained at a firing temperature of 1150 ° C, and the sinterability It was found that this would lead to a decrease in
- the molar amount of Mn is an excess of 3.0 moles with respect to 100 moles of the main component, which makes it difficult to form a solid solution of Mn in the crystal grains, and the prayer to the grain boundaries. Becomes noticeable The electrical property deteriorated and the polarization process became difficult.
- Sample No. 25 had a molar ratio X of 0.32 and exceeded 0.27, and the compounding molar ratio a was 0.000 and less than 0.001, so the Curie temperature Tc decreased to 225 ° C, pyroelectric coefficient Tp after reflow treatment became 0.07, and pyroelectricity was almost burned out.
- Sample Nos. 3 to 7, 10, 11, 18, 19, 22, and 23 all have x, y, a, and Mn-containing moles within the scope of the present invention. Since the segregated substance present in the aggregate is also 1.0 vol% or less, it was found that the log p force was:! ⁇ 11.8 and the insulation resistance could be reduced appropriately. Also force, pyroelectric coefficient Tp is 3.46 to 4. Clearly Clearly Clearly Clearly 81 X 10- 8 C / cm 2 'K can maintain good pyroelectric properties, also the Curie temperature Tc or higher 260 ° C I was able to secure it. Furthermore, it was found that the relative dielectric constant ⁇ r was 161 to 226 and could be maintained at an appropriate value.
- Sample Nos. 26 and 27 have the same composition as Sample No. 1, and the firing temperature is 1100 ° C or
- Sample Nos. 28 and 29 have the same composition as Sample No. 3, and the firing temperature is 1175 ° C or
- the ratio of segregated materials containing Ni, Ti and Mn in the sintered body can be made smaller than 1.0 vol%, and log p is also 11.5, 11. 4 and / J, the power that can be drilled.
- the segregated material containing Ni, Ti and Mn in the sintered body is 1.0 vol% or less, and log p is 12. Decrease below 0.
- the volume content of the segregated material can be reduced as the firing temperature is increased, and as the volume content of the segregated material is lowered, the insulation resistance also increases. It turned out to be lower.
- each pyroelectric element of sample number 2 outside the scope of the present invention and sample number 3 within the scope of the present invention was installed in the infrared detector shown in Fig. 2, and the temperature range from 25 ° C to 60 ° C was changed by 1 reciprocation at 1 ° CZ, and the fluctuation of the bias voltage Vs from the source terminal was measured.
- Fig. 4 is a graph showing the change over time in the output voltage together with the temperature change, and the solid line indicates the sample number 3
- the broken line indicates sample number 2 and the two-dot chain line indicates temperature.
- the pyroelectric element of sample number 3 within the scope of the present invention has low insulation resistance (log p: 11.
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JP2007531507A JP4085289B2 (ja) | 2006-04-28 | 2007-02-09 | 焦電性磁器組成物、及び焦電素子、並びに赤外線検出器 |
EP07714005.1A EP2017239B1 (en) | 2006-04-28 | 2007-02-09 | Pyroelectric ceramic composition, pyroelectric element, and infrared detector |
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JP2014187193A (ja) * | 2013-03-22 | 2014-10-02 | Seiko Epson Corp | 赤外線センサー及び熱電変換素子 |
US9274006B2 (en) | 2012-08-08 | 2016-03-01 | Nec Tokin Corporation | Infrared sensor |
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CN102104010B (zh) * | 2009-12-22 | 2012-07-11 | 陈志恭 | 一种能提升绝缘电压VISO又能降低结壳热阻Rthjc的模块结构件 |
JP2012122785A (ja) * | 2010-12-07 | 2012-06-28 | Sony Corp | 赤外線検出素子、赤外線撮像装置 |
CN103493231B (zh) * | 2011-02-24 | 2015-02-25 | 日本碍子株式会社 | 热电元件 |
CN104204951B (zh) * | 2012-03-20 | 2017-03-01 | Asml荷兰有限公司 | 光刻设备、传感器以及方法 |
US8324783B1 (en) | 2012-04-24 | 2012-12-04 | UltraSolar Technology, Inc. | Non-decaying electric power generation from pyroelectric materials |
JP2016076591A (ja) * | 2014-10-06 | 2016-05-12 | セイコーエプソン株式会社 | 焦電体、焦電体の製造方法、焦電素子、焦電素子の製造方法、熱電変換素子、熱電変換素子の製造方法、熱型光検出器、熱型光検出器の製造方法および電子機器 |
EP3268706B1 (en) * | 2015-03-12 | 2020-10-28 | Laser Components GmbH | Differential circuit for pyroelectric infrared detector |
CN114133239B (zh) * | 2021-10-29 | 2022-09-06 | 湖北大学 | 一种无铅热释电陶瓷材料及其制备方法 |
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US7897921B2 (en) | 2011-03-01 |
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JP4085289B2 (ja) | 2008-05-14 |
EP2017239B1 (en) | 2013-04-10 |
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CN101437777B (zh) | 2013-09-11 |
CN101437777A (zh) | 2009-05-20 |
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