WO2015172585A1 - Pyroelectric relaxor ferroelectric infrared detector - Google Patents

Pyroelectric relaxor ferroelectric infrared detector Download PDF

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WO2015172585A1
WO2015172585A1 PCT/CN2015/071792 CN2015071792W WO2015172585A1 WO 2015172585 A1 WO2015172585 A1 WO 2015172585A1 CN 2015071792 W CN2015071792 W CN 2015071792W WO 2015172585 A1 WO2015172585 A1 WO 2015172585A1
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electrode
pyroelectric
single crystal
sensitive element
relaxation ferroelectric
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PCT/CN2015/071792
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French (fr)
Chinese (zh)
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罗豪甦
许晴
赵祥永
狄文宁
焦杰
李龙
杨林荣
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上海硅酸盐研究所中试基地
中国科学院上海硅酸盐研究所
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides
    • C30B29/22—Complex oxides
    • C30B29/30—Niobates; Vanadates; Tantalates
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides
    • C30B29/22—Complex oxides
    • C30B29/32—Titanates; Germanates; Molybdates; Tungstates
    • 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

Definitions

  • the invention relates to the field of microelectronic chips, and in particular to a pyroelectric relaxation ferroelectric infrared detector.
  • Infrared detectors are mainly divided into photon type infrared detectors and thermal infrared detectors.
  • the common photon-type infrared detector mainly uses a narrow band gap semiconductor material represented by mercury cadmium telluride and an optoelectronic semiconductor material represented by gallium arsenide.
  • semiconductor infrared devices generally require low-temperature refrigeration, which is bulky, costly, and consumes a lot of power.
  • the pyroelectric relaxation ferroelectric infrared detector developed by the pyroelectric effect of the material has a flat spectral response in the ultraviolet, visible, and infrared bands, and has no need for refrigeration, low power consumption, and low noise bandwidth.
  • the compact structure, portability and low cost have become one of the most eye-catching focuses in the field of infrared technology.
  • pyroelectric relaxation ferroelectric infrared detectors are rapidly expanding from the military market to the civilian market, especially in human body detection. Fire warning, gas analysis, infrared spectrometer and infrared thermal imaging have played an important role, while reflecting huge market potential.
  • the materials currently used for pyroelectric relaxation ferroelectric infrared detectors mainly include lead zirconate titanate (PZT), barium titanate (BST) and lead citrate (PST), etc., for pyroelectric unit detectors.
  • the materials are mainly limited to lithium tantalate (LiTaO3), triglyceride sulfate (TGS) and the like.
  • these traditional materials have the disadvantages of low pyroelectric coefficient, large dielectric loss and unstable physical properties, and it is difficult to meet the application requirements of high-performance pyroelectric relaxation ferroelectric infrared detectors and their extended products.
  • the detection level of the more mature commercial LiTaO3 infrared detector is only 1 ⁇ 108cmHz1/2/W to 4 ⁇ 108. CmHz1/2/W. Therefore, at the same time, overcoming the shortcomings of the above materials, exploring new pyroelectric materials with high detection value has become an urgent need for the development of uncooled infrared devices.
  • Mn-doped PMNT single crystal in which the composition is Mn-doped PMN-0.26PT single crystal, pyroelectric
  • Mn Mn-doped PMN-0.26PT single crystal
  • pyroelectric pyroelectric
  • the processing method of the infrared detecting sensitive element of the material is different from the conventional pyroelectric material, especially when the thinning process is performed to improve the infrared detecting performance, the introduced size effect and surface damage effect cause single crystal reduction.
  • the performance of the post-thinness is seriously degraded, and the problem has not been solved so far, making the new pyroelectric material difficult to be practically used in an infrared device (Paper Literature 1).
  • the PMN single crystal has a low Curie temperature and has certain application limitations.
  • chemical composition control is used to prepare a high-Curie temperature ternary system of bismuth indium magnesium titanate (1).
  • -xy)Pb(In1/2Nb1/2)O3-yPb(Mg1/3Nb2/3)O3-xPbTiO3 (referred to as PIMNT or PIN-PMN-PT) single crystal has been paid attention by researchers, but due to ternary system single crystal
  • the composition of the complex, high thermal and electrical properties, high Curie temperature and low dielectric constant of the composition of the difficulty of regulation, so the performance optimization of the crystal has not yet clear research results and public reports (paper 2).
  • the sensitive components of the traditional pyroelectric relaxation ferroelectric infrared detector are generally full electrodes, and the area is fixed. It is not easy to reduce the electrode area to regulate the electrical parameters of the sensitive components for other purposes. This is achieved, and therefore improvements in the adjustment of the electrode structure are also required.
  • Patent literature
  • Patent Document 1 Chinese patent CN 1080777C;
  • Patent Document 2 Chinese Patent CN100429334C.
  • the conventional pyroelectric infrared sensor usually adopts a full-electrode configuration on the sensitive element chip.
  • FIG. 1 it is a conventional electrode structure in the prior art, and its area is fixed. If it is desired to reduce the electrode area to regulate the sensitive element, The electrical parameters of the sensitive components are not easily achievable for other uses. In addition, especially for very thin sensitive components, the dielectric noise of the device prepared is too high, and the detector's specific detection rate is low.
  • the present invention provides a novel pyroelectric relaxation ferroelectric infrared detector, thereby solving the problems in the prior art.
  • the invention discloses a pyroelectric relaxation ferroelectric infrared detector, the detector comprising: a base of the pin; a package with one or more windows that is packaged with the base to form a receiving space; one or more pyroelectric relaxations that are polarized in the receiving space a sensitive elementary chip composed of a single crystal sensitive element of a ferroelectric ferroelectric; an electrode respectively disposed on an upper surface and a lower surface of the pyroelectric relaxation ferroelectric single crystal sensitive element; covering the pyroelectric relaxation ferroelectric single crystal An absorbing layer on the upper surface of the sensitive element; a support for supporting the pyroelectric relaxation ferroelectric single crystal sensitive element; and an amplifying circuit using a voltage mode or a current mode, wherein the upper electrode disposed on the upper surface is The single electrode, the lower electrode disposed on the lower surface includes left and right electrodes separated from each other, and the left and right electrodes are not connected to each other to form the lower electrode into a divided electrode.
  • the distance between the left electrode and the right electrode is between 0.5 mm and 1 mm.
  • the distance between the left electrode and the right electrode is 0.5 mm.
  • the upper electrode is circular; the left and right electrodes are rectangular.
  • the spacing between the rectangular left electrode and the right electrode is equal.
  • the left and right electrodes are symmetric with a diameter of the circular upper electrode.
  • the material of the pyroelectric relaxation ferroelectric single crystal sensitive element is one or more of the following materials:
  • the hexagonal phase Mn is doped with (1-x)Pb(Mg1/3Nb2/3)O3-xPbTiO3 single crystal, wherein 0.26 ⁇ x ⁇ 0.29 and the crystallographic direction is [111],
  • the hexagonal phase Mn is doped with (1-xy)Pb(In1/2Nb1/2)O3-yPb(Mg1/3Nb2/3)O3-xPbTiO3, where 0.15 ⁇ 1-xy ⁇ 0.38, 0.36 ⁇ y ⁇ 0.57,0.26 ⁇ x ⁇ 0.30, and the crystallographic direction is [111];
  • the absorbing layer is formulated by multi-walled carbon nanotubes, nano-ferric oxide or a mixture of nano-carbon powder and alcohol, and covers the upper surface by intermittent multiple spraying, the absorbing layer
  • the infrared absorption rate is ⁇ 90%; the stent adopts a fine, low thermal conductivity alumina ceramic support, which is supported at the center of the pyroelectric relaxation ferroelectric single crystal sensitive element to achieve infrared detection sensitivity The heat of the component is suspended.
  • the matching resistance RG of the voltage mode amplifying circuit is reduced to be much smaller than 100 G
  • the feedback capacitance Cf of the current mode amplifying circuit is ⁇ 10 pF
  • the feedback resistance Rf is reduced to be much smaller than 100 G.
  • Pyroelectric relaxation ferroelectric infrared detector has ultra-high response rate, low noise and high ratio detection rate
  • the dielectric noise of the device prepared by the sensitive element is reduced, and the specific detection rate of the detector prepared by the sensitive element chip is improved;
  • the split electrode can be polarized at high temperature.
  • FIG. 1 is a schematic structural view of a conventional electrode on a sensitive element chip in the prior art
  • FIG. 2 is a schematic structural view of an electrode on a sensitive element chip according to an embodiment of the present invention
  • FIG. 3 is a schematic view showing a comparison of pyroelectric coefficients when the left electrode and the right electrode are at different intervals in the present invention
  • FIG. 4 is a schematic view showing a comparison of capacitance and dielectric loss when the left electrode and the right electrode are at different intervals in the present invention
  • FIG. 5 is a schematic view showing a comparison of response rates of different electrode structures of the present invention and the prior art
  • Fig. 6 is a schematic view showing the comparison of the detection ratios of the electrode structures of the present invention and the prior art.
  • a pyroelectric relaxation ferroelectric infrared detector comprising: a base provided with a pin; a package with one or more windows encased with the base to form a receiving space; disposed in the receiving space a sensitive element chip composed of one or more pyroelectric relaxation ferroelectric single crystal sensitive elements subjected to polarization treatment; respectively disposed on the upper surface and the lower surface of the pyroelectric relaxation ferroelectric single crystal sensitive element An electrode; an absorption layer covering the upper surface of the pyroelectric relaxation ferroelectric single crystal sensitive element; a support for supporting the pyroelectric relaxation ferroelectric single crystal sensitive element; and adopting a voltage mode or a current mode Amplifying circuit.
  • the sensitive element chip comprises one or more pyroelectric relaxation ferroelectric single crystal sensitive elements, and the upper and lower surfaces are respectively provided with electrodes.
  • the electrodes disposed on the upper and lower surfaces are all electrodes, and in the present invention, the upper electrode disposed on the upper surface is a single electrode, and the electrode structure disposed on the lower surface is changed from the entire electrode to each other.
  • the separated left and right electrodes as the name suggests, the left and right electrodes are two separate electrodes arranged at two places on the lower surface, which are separated from each other and are not electrically connected or connected, so that the lower electrode on the lower surface is formed. It is a divided electrode.
  • FIG. 4 are schematic diagrams showing the comparison of the pyroelectric coefficient when the left electrode and the right electrode are at different intervals, and the capacitance and dielectric loss when the left electrode and the right electrode are at different intervals.
  • the abscissa is the distance l between the left and right electrodes
  • the ordinate is the pyroelectric coefficient p. It can be clearly seen from the graph shown in the experiment that the distance between the left electrode and the right electrode is 0.5 mm.
  • the pyroelectric coefficient p When the distance is 1mm, the pyroelectric coefficient p is about 14 ⁇ 10 -4 C/m 2 K, and when the spacing l is 0.1 mm, the pyroelectric coefficient is about 6 ⁇ 10 -4 C/m 2 K, and the spacing is l. At 1.5 mm, the pyroelectric coefficient is about 8 ⁇ 10 -4 C/m 2 K, so that the distance l between the left electrode and the right electrode is significantly higher than the pitch l at 0-0.5 mm and 1 between 0.5 mm and 1 mm. When the pyroelectric coefficient p is between -1.5 mm, it is preferable that the pyroelectric coefficient is large when the pitch l is between 0.5 mm and 1 mm, and the polarization of the left and right electrodes is relatively complete.
  • the abscissa is still the spacing l
  • the left ordinate represents the sensitive element capacitance
  • the right ordinate represents the dielectric loss
  • the square point coordinates in Figure 3 represent the sensitive element capacitance
  • the dot coordinates represent the dielectric loss.
  • the pitch l is 0.5 mm
  • the sensitive element capacitance is only about 200 pF
  • the dielectric loss is about 5 ⁇ 10 -4 , which is other values such as 0.1 mm compared to the pitch l.
  • the product of the sensitive element capacitance and the dielectric loss is the smallest, that is, the dielectric noise is the smallest. Therefore, most preferably, the distance between the left electrode and the right electrode is 0.5 mm.
  • the structure of the upper electrode is circular, while the left and right electrodes are rectangular, and the left and right electrodes are the same size.
  • the upper surface does not need to be taken out of the upper electrode, and all of them can be used for absorbing infrared light, which increases the absorption efficiency of infrared light, and reduces the capacitance of the sensitive element, which is greatly shortened, while the pyroelectric coefficient remains unchanged.
  • the response time of the detector provided with the sensitive element chip.
  • the pitch of the left and right electrodes of the rectangle is constant, that is, one side of the left and right electrodes of the rectangle is parallel, or the left and right electrodes are symmetric with respect to a diameter of a circular upper electrode, and the regular and symmetrical structure can ensure the polarization effect. Easy to assemble and manufacture.
  • FIG. 5 and FIG. 6, respectively, the schematic diagrams of the comparison of the response rate and the specific detection rate under different electrode structures of the present invention and the prior art are shown.
  • the abscissa represents the frequency f
  • the ordinate represents the response rate R v
  • the square point coordinates represent the response rate R v of the conventional electrode structure in the prior art
  • the dot coordinates represent the distributed electrode structure in the present invention.
  • the response rate R v it is apparent that the distributed electrode structure is nearly four times more efficient than the prior art detectors at the same frequency f. It is precisely because of the use of the split structure that the relative dielectric constant is greatly reduced, resulting in an effect. Referring again to FIG.
  • the abscissa represents the frequency f
  • the ordinate represents the specific detection rate D *
  • the square point coordinates represent the specific detection rate D * of the conventional motor structure in the prior art
  • the dot coordinates represent the distributed electrode of the present invention.
  • the specific detection rate D * under the structure from the detection ratio, the detection ratio of the detector using the distributed electrode structure is about 1.5 times higher than that of the conventional detector of the prior art at 10 Hz, and As the frequency continues to increase, the difference between the two is greater than the detection rate, and the detection ratio of the detector under the distributed electrode structure is always at a high level. It is precisely because of the use of the split structure, the dielectric noise is greatly reduced, and the effect is brought about.
  • the dielectric properties of the materials involved in the examples were measured using an Agilent Model 4294A Impedance Analyzer (Agilent Technologies, Inc.) and approximated from a plate capacitor; The pyroelectric coefficient after single crystal polarization is measured by a dynamic pyroelectric coefficient measurement system.
  • the AC drive temperature range is 1 ° C and the frequency is 45 mHz;
  • the single crystal sensitive element chip is first deposited by magnetron sputtering; then the single crystal sensitive element is polarized; the response rate of the pyroelectric detector is measured by the black body infrared response test system, device noise
  • the Agilent 35670 A Dynamic Signal Analyzer (Agilent Technologies, Inc.) measured the detection rate based on the theoretical formula of the blackbody detection rate, calculated from the measured response rate and noise.
  • a 1 mol% Mn doped 0.71 Pb (Mg 1/3 Nb 2/3 ) O 3 -0.29 PbTiO 3 single crystal sensitive element was prepared with a crystallographic orientation ⁇ 111>, a size of 20 ⁇ 20 mm 2 and a thickness of 20 ⁇ . 1m.
  • the properties of the sputtered heterogeneous electrode after polarization are as follows: the Curie temperature is 135 ° C, the tripartite-tetragonal phase transition temperature is 108 ° C, the dielectric constant r ⁇ 750, and the pyroelectric coefficient p ⁇ 12.0 ⁇ 10 -4 C / m 2 K.
  • the 0.71Pb (Mg 1/3 Nb 2/3 )O 3 -0.29PbTiO 3 pyroelectric relaxation ferroelectric single crystal sensitive element was subjected to chemical mechanical thinning polishing technology to reduce the relaxation ferroelectric single crystal.
  • a large-size (20 ⁇ 20mm 2 ) single crystal sensitive element is prepared, and the thickness of the single crystal sensitive element can be controlled below 20m, and then cut into small pieces by using a dicing machine as needed to prepare a pyroelectric detector sensitive element chip. . Due to the action of chemical mechanical polishing, the surface stress and damage layer are introduced.
  • the detection performance of the single crystal detector therefore, through the post-treatment process technology adopted by the present invention, while obtaining extremely thin single crystal sensitive elements, it also minimizes surface damage and defects on the pyroelectric and dielectric properties of the single crystal sensitive element.
  • the effect of performance enables the preparation of high performance, high quality single crystal sensitive elements.
  • a HF:NH 4 F:H 2 O corrosion inhibitor with a ratio of 8.3:33:58.7 was used to wet-etch the surface of the prepared Mn-doped PMNT single crystal sensitive element. It can be concluded that the corrosion rate of the etchant in the ratio to the Mn-doped PMNT single crystal is about 20.8 nm/min.
  • the pyroelectric coefficient increases with the increase of corrosion time, then gradually increases, and then the plateau tends to be stable; the dielectric loss increases first and then increases with the increase of corrosion time. This shows that wet etching can optimize the pyroelectric coefficient of the material to some extent, and the corrosion time is controlled to 15-20 minutes to effectively reduce the dielectric loss of the material.
  • the etched single crystal sensitive element is annealed to further remove residual mechanical stress on the surface and internal defects of the single crystal.
  • the annealing temperature was 500 ° C
  • the annealing atmosphere was oxygen (oxygen-rich atmosphere)
  • the annealing time was 10 hours.
  • the treated 1 mol% Mn doped 0.71 Pb (Mg 1/3 Nb 2/3 ) O 3 -0.29 PbTiO 3 single crystal sensitive element was placed in an electrode mask, and the distributed electrode was magnetron sputtered, and the lower surface was splashed.
  • the Ni-Cr/Au electrode was deposited, the electrode area was 0.5 ⁇ 2 mm 2 , the pitch was 0.1 mm, 0.5 mm, 1 mm and 1.5 mm, respectively; the upper surface Ni-Cr electrode was a ⁇ 2.5 mm round electrode.
  • the electrodes at both ends of the sensitive element are polarized at 1.25kV/mm and -1.25kV/mm, respectively, forming reverse polarization, including: infrared absorption black layer, Ni-Cr electrode, pyroelectric material, Ni-Cr/Au electrode , P represents the polarization orientation.
  • the two sensitive electrodes of the sensitive element are led out by the gold wire, and the voltage mode amplifying circuit composed of the field effect transistor and the 20G ⁇ resistor is packaged in the TO39 pipe socket (Shanghai Kefa Precision Alloy Material Sales Co., Ltd.).
  • a multi-walled carbon nanotube and an alcohol mixture are sprayed on the surface of the above sensitive element chip to prepare an absorption layer, thereby obtaining a high-frequency pyroelectric relaxation ferroelectric infrared detector.
  • the performance of the detector was characterized by a black body infrared response test system.
  • Figure 8 shows the frequency response of the 20m high-frequency pyroelectric relaxation ferroelectric infrared detector based on the detection rate in the voltage mode prepared by the electrode structure. The specific detection rate at the electrode spacing of 0.5mm and 10Hz It is 1.49 ⁇ 10 9 cm Hz 1/2 /W.
  • the detection performance is better than the 20m Mn doped PMNT single crystal sensitive element detector in the above voltage mode, and maintains a high specific detection rate in the case of high frequency (100Hz), and is significantly better than the current commercial LiTaO 3 infrared. Detectors to meet the needs of higher frequency use.
  • the upper surface of the sensitive element of the pyroelectric detector of the structure does not need to take out the electrode, and all of them can be used for absorbing infrared light, thereby increasing the absorption efficiency of the infrared light; in addition, the structure is greatly maintained under the condition that the pyroelectric coefficient remains substantially unchanged.
  • the capacitance of the sensitive element is reduced, that is, the equivalent dielectric constant of the sensitive element is reduced, so that the dielectric noise is one order of magnitude smaller than the resistance noise, and the advantage of relaxing the high pyroelectric coefficient of the ferroelectric single crystal is simultaneously reduced.
  • the disadvantage of its high dielectric constant is reduced, and the specific detection rate of the detector is improved to some extent, and the higher specific detection rate is maintained at a higher frequency.
  • the structure provides a new pyroelectric detector structure that is easy to miniaturize and integrate, meeting the requirements of modern detectors with low cost, low power consumption, and compatibility with integrated circuits.

Abstract

Provided is a pyroelectric relaxor ferroelectric infrared detector. The detector comprises: a base provided with a pin; a casing having one or a plurality of windows, the casing being packaged together with the base to form an accommodating space; a sensitive element chip arranged within the accommodating space; electrodes respectively arranged on an upper surface and a lower surface of a pyroelectric relaxor ferroelectric single crystal sensitive element; an absorption layer covering the upper surface of the single crystal sensitive element; a frame supporting the single crystal sensitive element; an amplification circuit using a voltage mode or a current mode. An upper electrode arranged on the upper surface is a single electrode, and a lower electrode arranged on the lower surface comprises a left electrode and a right electrode separated from one another. The left electrode and the right electrode are not connected to one another to form the lower electrode as a divided electrode. Therefore, dielectric noise of device preparation is reduced, and the response rate and specific detectivity of the detector is increased.

Description

一种热释电弛豫铁电红外探测器Pyroelectric relaxation ferroelectric infrared detector 技术领域Technical field
本发明涉及微电子芯片领域，尤其涉及一种热释电弛豫铁电红外探测器。The invention relates to the field of microelectronic chips, and in particular to a pyroelectric relaxation ferroelectric infrared detector.
背景技术Background technique
当今世界各国竞相发展红外探测和成像技术，其应用遍及军事、航天、科研、医疗、工业等众多领域。红外探测器主要分为光子型红外探测器和热型红外探测器两大类。目前常见的光子型红外探测器主要采用以碲镉汞为代表的窄禁带半导体材料和以砷化镓为代表的光电子半导体材料。但半导体红外器件一般需要低温致冷工作，体积大、成本高、功耗大。In the world today, countries are competing to develop infrared detection and imaging technology, which is used in many fields such as military, aerospace, scientific research, medical, industrial and so on. Infrared detectors are mainly divided into photon type infrared detectors and thermal infrared detectors. At present, the common photon-type infrared detector mainly uses a narrow band gap semiconductor material represented by mercury cadmium telluride and an optoelectronic semiconductor material represented by gallium arsenide. However, semiconductor infrared devices generally require low-temperature refrigeration, which is bulky, costly, and consumes a lot of power.
而利用材料热释电效应研制的热释电弛豫铁电红外探测器由于其在紫外波段、可见波段、红外波段具有平坦的光谱响应，同时具有无需致冷、功耗低、噪声带宽小、结构紧凑、便于携带、成本低等优点，已经成为当前红外技术领域中最引人瞩目的焦点之一。随着热释电弛豫铁电红外探测器向低成本、低功耗及小型化发展，热释电弛豫铁电红外探测器正从军用市场向民用市场快速拓展，尤其是在人体探测、火灾预警、气体分析、红外光谱仪以及红外热成像等领域发挥了重要作用，同时体现了巨大的市场潜力。The pyroelectric relaxation ferroelectric infrared detector developed by the pyroelectric effect of the material has a flat spectral response in the ultraviolet, visible, and infrared bands, and has no need for refrigeration, low power consumption, and low noise bandwidth. The compact structure, portability and low cost have become one of the most eye-catching focuses in the field of infrared technology. With the development of pyroelectric relaxation ferroelectric infrared detectors for low cost, low power consumption and miniaturization, pyroelectric relaxation ferroelectric infrared detectors are rapidly expanding from the military market to the civilian market, especially in human body detection. Fire warning, gas analysis, infrared spectrometer and infrared thermal imaging have played an important role, while reflecting huge market potential.
目前用于热释电弛豫铁电红外探测器的材料主要包括锆钛酸铅(PZT)，钛酸锶钡(BST)和钽钪酸铅(PST)等，用于热释电单元探测器件的材料主要局限于钽酸锂(LiTaO3)、硫酸三甘酞(TGS)等。但是，这些传统材料有着热释电系数低、介电损耗大以及物理性能不稳定等缺点，很难满足高性能热释电弛豫铁电红外探测器及其延伸产品的应用要求。例如，比较成熟的商用LiTaO3红外探测器的探测率水平仅为1×108cmHz1/2/W至4×108 cmHz1/2/W。因此同时克服以上材料的缺点，探索获得高探测优值的新型热释电材料成为目前发展非制冷红外器件的迫切需求。The materials currently used for pyroelectric relaxation ferroelectric infrared detectors mainly include lead zirconate titanate (PZT), barium titanate (BST) and lead citrate (PST), etc., for pyroelectric unit detectors. The materials are mainly limited to lithium tantalate (LiTaO3), triglyceride sulfate (TGS) and the like. However, these traditional materials have the disadvantages of low pyroelectric coefficient, large dielectric loss and unstable physical properties, and it is difficult to meet the application requirements of high-performance pyroelectric relaxation ferroelectric infrared detectors and their extended products. For example, the detection level of the more mature commercial LiTaO3 infrared detector is only 1×108cmHz1/2/W to 4×108. CmHz1/2/W. Therefore, at the same time, overcoming the shortcomings of the above materials, exploring new pyroelectric materials with high detection value has become an urgent need for the development of uncooled infrared devices.
从1996年开始，罗豪甦等人率先用改进的布里奇曼(Bridgman)方法成功生长出大尺寸高质量的弛豫铁电单晶，如(1-x)Pb(Mg1/3Nb2/3)O3-xPbTiO3铌镁钛酸铅(简称PMNT或PMN-PT)，并成功实现了高质量PMNT单晶的批量生产(专利文献1)。Since 1996, Luo Haosu and others have pioneered the successful growth of large-sized high-quality relaxed ferroelectric single crystals using the improved Bridgman method, such as (1-x)Pb(Mg1/3Nb2/3)O3. -xPbTiO3 bismuth magnesium titanate (referred to as PMNT or PMN-PT), and mass production of high quality PMNT single crystals has been successfully achieved (Patent Document 1).
自2003年开始，罗豪甦等人又首先发现了弛豫铁电单晶(如PMNT)的优异热释电性能，并开展了大量的相关热释电性能优化和材料工艺研究，例如，当材料组成为x处于0.24-0.30之间，晶体学方向沿自发极化方向时，制备得到高热释电性能的PMNT单晶材料(专利文献2)。Since 2003, Luo Haosu and others have first discovered the excellent pyroelectric properties of relaxed ferroelectric single crystals (such as PMNT), and carried out a large number of related pyroelectric performance optimization and material process research, for example, when the composition of materials When x is in the range of 0.24 to 0.30 and the crystallographic direction is in the direction of spontaneous polarization, a PMNT single crystal material having high pyroelectricity is prepared (Patent Document 2).
为了进一步降低材料的介电损耗，提高器件的探测率，研究人员生长了Mn掺杂PMNT单晶(简称Mn:PMNT)，其中组分为Mn掺杂PMN-0.26PT的单晶，热释电系数达到17.2×10-4C/m2K，介电损耗降到0.05％。尽管该材料性能优异，但由于对该材料的红外探测灵敏元件加工工艺不同于传统热释电材料，尤其是为提高红外探测性能进行减薄工艺时，引入的尺寸效应和表面损伤效应引起单晶体减薄后性能的严重劣化，该问题至今尚未解决，使得该新型热释电材料难以在红外器件中的实际应用(论文文献1)。In order to further reduce the dielectric loss of the material and improve the detection rate of the device, the researchers have grown Mn-doped PMNT single crystal (abbreviated as Mn: PMNT), in which the composition is Mn-doped PMN-0.26PT single crystal, pyroelectric The coefficient reached 17.2 x 10-4 C/m2K and the dielectric loss dropped to 0.05%. Although the material has excellent performance, since the processing method of the infrared detecting sensitive element of the material is different from the conventional pyroelectric material, especially when the thinning process is performed to improve the infrared detecting performance, the introduced size effect and surface damage effect cause single crystal reduction. The performance of the post-thinness is seriously degraded, and the problem has not been solved so far, making the new pyroelectric material difficult to be practically used in an infrared device (Paper Literature 1).
另外，PMNT单晶居里温度偏低，具有一定的应用限制性，为提高应用范围及其温度稳定性，采用化学组分调控，制备高居里温度的三元体系铌铟镁钛酸铅(1-x-y)Pb(In1/2Nb1/2)O3-yPb(Mg1/3Nb2/3)O3-xPbTiO3(简称PIMNT或PIN-PMN-PT)单晶得到了研究人员的重视，但由于三元体系单晶的组分复杂，兼顾高热释电性能、高居里温度和低介电常数的组分调控难度较高，因此对该晶体的性能优化尚未有明确研究结果和公开报道(论文文献2)。In addition, the PMN single crystal has a low Curie temperature and has certain application limitations. In order to improve the application range and temperature stability, chemical composition control is used to prepare a high-Curie temperature ternary system of bismuth indium magnesium titanate (1). -xy)Pb(In1/2Nb1/2)O3-yPb(Mg1/3Nb2/3)O3-xPbTiO3 (referred to as PIMNT or PIN-PMN-PT) single crystal has been paid attention by researchers, but due to ternary system single crystal The composition of the complex, high thermal and electrical properties, high Curie temperature and low dielectric constant of the composition of the difficulty of regulation, so the performance optimization of the crystal has not yet clear research results and public reports (paper 2).
另外，传统热释电弛豫铁电红外探测器的敏感元件一般为全电极，面积固定，若想减小电极面积以调控敏感元件的电学参数用于其它用途则不容易 实现，因此也需要在电极结构的调整方面进行改进。In addition, the sensitive components of the traditional pyroelectric relaxation ferroelectric infrared detector are generally full electrodes, and the area is fixed. It is not easy to reduce the electrode area to regulate the electrical parameters of the sensitive components for other purposes. This is achieved, and therefore improvements in the adjustment of the electrode structure are also required.
迄今为止，本领域尚未开发出一种克服了上述现有技术缺陷的高性能热释电弛豫铁电红外探测器。To date, a high performance pyroelectric relaxation ferroelectric infrared detector that overcomes the above-mentioned drawbacks of the prior art has not been developed in the art.
专利文献：Patent literature:
专利文献1：中国专利CN 1080777C；Patent Document 1: Chinese patent CN 1080777C;
专利文献2：中国专利CN100429334C。Patent Document 2: Chinese Patent CN100429334C.
论文文献：Papers:
论文文献1：L.H.Liu,X.B.Li,X.Wu,Y.J.Wang,W.N.Di,D.Lin,X.Y.Zhao,H.S.Luo,N.Neumann,Appl.Phys.Lett.95(2009)192903；Papers 1: L.H. Liu, X.B. Li, X. Wu, Y.J. Wang, W.N. Di, D. Lin, X.Y. Zhao, H.S. Luo, N. Neumann, Appl. Phys. Lett. 95 (2009) 192903;
论文文献2：P.Yu,F.F.Wang,D.Zhou,W.W.Ge,X.Y.Zhao,H.S.Luo,J.L.Sun,X.J.Meng,J.H.Chu,Appl.Phys.Lett.92(2008)252907。Paper 2: P. Yu, F. F. Wang, D. Zhou, W. W. Ge, X. Y. Zhao, H. S. Luo, J. L. Sun, X. J. Meng, J. H. Chu, Appl. Phys. Lett. 92 (2008) 252907.
此外，传统的热释电红外传感器的灵敏元芯片上通常采用全电极的配置，参图1，为现有技术中传统的电极结构，其面积固定，若想要减小电极面积以调控灵敏元的敏感元件的电学参数用于其他用途则不容易实现。另外，尤其对于极薄的灵敏元件而言，其所制备器件的介电噪声过高，探测器的比探测率较低。In addition, the conventional pyroelectric infrared sensor usually adopts a full-electrode configuration on the sensitive element chip. Referring to FIG. 1, it is a conventional electrode structure in the prior art, and its area is fixed. If it is desired to reduce the electrode area to regulate the sensitive element, The electrical parameters of the sensitive components are not easily achievable for other uses. In addition, especially for very thin sensitive components, the dielectric noise of the device prepared is too high, and the detector's specific detection rate is low.
因此，需要一种新型的热释电弛豫铁电红外探测器，其介电噪声和介电损耗降低。Therefore, there is a need for a novel pyroelectric relaxation ferroelectric infrared detector with reduced dielectric noise and dielectric loss.
发明内容Summary of the invention
为了克服上述技术缺陷，本发明提供了一种新颖的热释电弛豫铁电红外探测器，从而解决了现有技术中存在的问题。In order to overcome the above technical deficiencies, the present invention provides a novel pyroelectric relaxation ferroelectric infrared detector, thereby solving the problems in the prior art.
本发明公开了一种热释电弛豫铁电红外探测器，所述探测器包括：设有 引脚的底座；与所述底座封装在一起以形成容纳空间的带有一个或多个窗口的管壳；设置于所述容纳空间中的由经过极化处理的一个或多个热释电弛豫铁电单晶敏感元构成的灵敏元芯片；分别设置于所述热释电弛豫铁电单晶敏感元的上表面和下表面的电极；覆盖所述热释电弛豫铁电单晶敏感元上表面的吸收层；对所述的热释电弛豫铁电单晶敏感元进行支撑的支架；以及采用了电压模式或电流模式的放大电路，设于所述上表面的上电极为单电极，设于所述下表面的下电极包括互相分离的左电极及右电极，所述左电极和右电极互不连通将所述下电极成型为一分割电极。The invention discloses a pyroelectric relaxation ferroelectric infrared detector, the detector comprising: a base of the pin; a package with one or more windows that is packaged with the base to form a receiving space; one or more pyroelectric relaxations that are polarized in the receiving space a sensitive elementary chip composed of a single crystal sensitive element of a ferroelectric ferroelectric; an electrode respectively disposed on an upper surface and a lower surface of the pyroelectric relaxation ferroelectric single crystal sensitive element; covering the pyroelectric relaxation ferroelectric single crystal An absorbing layer on the upper surface of the sensitive element; a support for supporting the pyroelectric relaxation ferroelectric single crystal sensitive element; and an amplifying circuit using a voltage mode or a current mode, wherein the upper electrode disposed on the upper surface is The single electrode, the lower electrode disposed on the lower surface includes left and right electrodes separated from each other, and the left and right electrodes are not connected to each other to form the lower electrode into a divided electrode.
优选地，所述左电极及右电极的间距为0.5mm-1mm间。Preferably, the distance between the left electrode and the right electrode is between 0.5 mm and 1 mm.
优选地，所述左电极及右电极的间距为0.5mm。Preferably, the distance between the left electrode and the right electrode is 0.5 mm.
优选地，所述上电极呈圆形；所述左电极及右电极呈矩形。Preferably, the upper electrode is circular; the left and right electrodes are rectangular.
优选地，所述矩形左电极及右电极的间距处处相等。Preferably, the spacing between the rectangular left electrode and the right electrode is equal.
优选地，所述左电极及右电极以所述圆形上电极的一直径对称。Preferably, the left and right electrodes are symmetric with a diameter of the circular upper electrode.
优选地，所述热释电弛豫铁电单晶敏感元的材料为如下材料中的一种或多种：Preferably, the material of the pyroelectric relaxation ferroelectric single crystal sensitive element is one or more of the following materials:
三方相Mn掺杂(1-x)Pb(Mg1/3Nb2/3)O3-xPbTiO3单晶，其中，0.26≤x≤0.29、且晶体学方向为[111]，The hexagonal phase Mn is doped with (1-x)Pb(Mg1/3Nb2/3)O3-xPbTiO3 single crystal, wherein 0.26≤x≤0.29 and the crystallographic direction is [111],
四方相Mn掺杂(1-x)Pb(Mg1/3Nb2/3)O3-xPbTiO3单晶，其中，0.35≤x≤0.40、且晶体学方向为[001]；a tetragonal phase Mn doped (1-x)Pb(Mg1/3Nb2/3)O3-xPbTiO3 single crystal, wherein 0.35≤x≤0.40 and the crystallographic direction is [001];
三方相Mn掺杂(1-x-y)Pb(In1/2Nb1/2)O3-yPb(Mg1/3Nb2/3)O3-xPbTiO3,其中0.15≤1-x-y≤0.38,0.36≤y≤0.57,0.26≤x≤0.30，且晶体学方向为[111]；The hexagonal phase Mn is doped with (1-xy)Pb(In1/2Nb1/2)O3-yPb(Mg1/3Nb2/3)O3-xPbTiO3, where 0.15≤1-xy≤0.38, 0.36≤y≤0.57,0.26≤x ≤0.30, and the crystallographic direction is [111];
四方相Mn掺杂(1-x-y)Pb(In1/2Nb1/2)O3-yPb(Mg1/3Nb2/3)O3-xPbTiO3,其中0.20≤1-x-y≤0.29、0.30≤y≤0.45、0.35≤x≤0.42，且晶体学方向为[001]。 Tetragonal phase Mn doped (1-xy)Pb(In1/2Nb1/2)O3-yPb(Mg1/3Nb2/3)O3-xPbTiO3, where 0.20≤1-xy≤0.29, 0.30≤y≤0.45, 0.35≤x ≤ 0.42, and the crystallographic direction is [001].
优选地，所述吸收层的配方为多壁碳纳米管、纳米四氧化三铁或纳米碳粉和酒精的混合液，并以间歇多次式喷涂的方式覆盖所述上表面，所述吸收层的红外吸收率≥90％；所述支架采用细的、低热导率的氧化铝陶瓷支架，其在所述热释电弛豫铁电单晶敏感元的中心位置进行支撑，以实现红外探测灵敏元件的热悬空。Preferably, the absorbing layer is formulated by multi-walled carbon nanotubes, nano-ferric oxide or a mixture of nano-carbon powder and alcohol, and covers the upper surface by intermittent multiple spraying, the absorbing layer The infrared absorption rate is ≥90%; the stent adopts a fine, low thermal conductivity alumina ceramic support, which is supported at the center of the pyroelectric relaxation ferroelectric single crystal sensitive element to achieve infrared detection sensitivity The heat of the component is suspended.
优选地，所述电压模式放大电路的匹配电阻RG降至远小于100G，所述电流模式放大电路的反馈电容Cf≤10pF，反馈电阻Rf降至远小于100G。Preferably, the matching resistance RG of the voltage mode amplifying circuit is reduced to be much smaller than 100 G, the feedback capacitance Cf of the current mode amplifying circuit is ≤ 10 pF, and the feedback resistance Rf is reduced to be much smaller than 100 G.
采用了上述技术方案后，与现有技术相比，具有以下有益效果：After adopting the above technical solution, compared with the prior art, the following beneficial effects are obtained:
1.热释电弛豫铁电红外探测器具有超高响应率、低噪声和高比探测率；1. Pyroelectric relaxation ferroelectric infrared detector has ultra-high response rate, low noise and high ratio detection rate;
2.灵敏元所制备器件的介电噪声降低，由该灵敏元芯片制备的探测器的比探测率提高；2. The dielectric noise of the device prepared by the sensitive element is reduced, and the specific detection rate of the detector prepared by the sensitive element chip is improved;
3.特别适用于高介电常数的热释电材料及高介电损耗的热释电材料；3. Particularly suitable for pyroelectric materials with high dielectric constant and pyroelectric materials with high dielectric loss;
4.分割电极可高温极化。4. The split electrode can be polarized at high temperature.
附图说明DRAWINGS
图1为现有技术中灵敏元芯片上传统电极的结构示意图；1 is a schematic structural view of a conventional electrode on a sensitive element chip in the prior art;
图2为本发明一实施例中灵敏元芯片上电极的结构示意图；2 is a schematic structural view of an electrode on a sensitive element chip according to an embodiment of the present invention;
图3为本发明中左电极与右电极不同间距时热释电系数对比的示意图；3 is a schematic view showing a comparison of pyroelectric coefficients when the left electrode and the right electrode are at different intervals in the present invention;
图4为本发明中左电极与右电极不同间距时电容与介电损耗对比的示意图；4 is a schematic view showing a comparison of capacitance and dielectric loss when the left electrode and the right electrode are at different intervals in the present invention;
图5为本发明与现有技术不同电极结构下响应率对比的示意图；5 is a schematic view showing a comparison of response rates of different electrode structures of the present invention and the prior art;
图6为本发明与现有技术不同电极结构下比探测率对比的示意图。 Fig. 6 is a schematic view showing the comparison of the detection ratios of the electrode structures of the present invention and the prior art.
具体实施方式detailed description
以下结合附图与具体实施例进一步阐述本发明的优点。Advantages of the present invention are further explained below in conjunction with the accompanying drawings and specific embodiments.
参阅图2，为本发明中灵敏元芯片上电极的结构示意图。热释电弛豫铁电红外探测器包括：设有引脚的底座；与所述底座封装在一起以形成容纳空间的带有一个或多个窗口的管壳；设置于所述容纳空间中的由经过极化处理的一个或多个热释电弛豫铁电单晶敏感元构成的灵敏元芯片；分别设置于所述热释电弛豫铁电单晶敏感元的上表面和下表面的电极；覆盖所述热释电弛豫铁电单晶敏感元上表面的吸收层；对所述的热释电弛豫铁电单晶敏感元进行支撑的支架；以及采用了电压模式或电流模式的放大电路。灵敏元芯片包括有一个或多个热释电弛豫铁电单晶敏感元，其上下表面分别设有电极。如前所述的，现有技术中，设置在上下表面的电极均为全电极，而本发明中，设置在上表面的上电极为单电极，设置在下表面的电极结构由全电极变更为互相分离的左电极及右电极，顾名思义，左电极和右电极为分设的两个电极，排设在下表面的两处，两者互相分开，且不电连接或连通，使得位于下表面的下电极成型为一分割电极。2 is a schematic structural view of an electrode on a sensitive element chip of the present invention. a pyroelectric relaxation ferroelectric infrared detector comprising: a base provided with a pin; a package with one or more windows encased with the base to form a receiving space; disposed in the receiving space a sensitive element chip composed of one or more pyroelectric relaxation ferroelectric single crystal sensitive elements subjected to polarization treatment; respectively disposed on the upper surface and the lower surface of the pyroelectric relaxation ferroelectric single crystal sensitive element An electrode; an absorption layer covering the upper surface of the pyroelectric relaxation ferroelectric single crystal sensitive element; a support for supporting the pyroelectric relaxation ferroelectric single crystal sensitive element; and adopting a voltage mode or a current mode Amplifying circuit. The sensitive element chip comprises one or more pyroelectric relaxation ferroelectric single crystal sensitive elements, and the upper and lower surfaces are respectively provided with electrodes. As described above, in the prior art, the electrodes disposed on the upper and lower surfaces are all electrodes, and in the present invention, the upper electrode disposed on the upper surface is a single electrode, and the electrode structure disposed on the lower surface is changed from the entire electrode to each other. The separated left and right electrodes, as the name suggests, the left and right electrodes are two separate electrodes arranged at two places on the lower surface, which are separated from each other and are not electrically connected or connected, so that the lower electrode on the lower surface is formed. It is a divided electrode.
由于左右电极互相分离，两者间必然具有间距。参阅图3至图4，分别为本发明中左电极与右电极不同间距时热释电系数对比的示意图，及左电极与右电极不同间距时电容与介电损耗对比的示意图。首先参阅图3，其横坐标为左电极与右电极的间距l，纵坐标为热释电系数p，由实验所表示的图表中可明显看出，左电极与右电极的间距l在0.5mm至1mm间时，热释电系数p约为14×10-4C/m2K，而间距l在0.1mm时，热释电系数约为6×10-4C/m2K，间距l在1.5mm时，热释电系数约为8×10-4C/m2K，从而左电极与右电极的间距l在0.5mm至1mm间时明显高于间距l在0-0.5mm和1-1.5mm间时的热释电系数p，则优选的是，间距l在0.5mm-1mm间时，热释电系数较大，左右电极极化较完全。再参阅图4，其横坐标仍为间距l，左纵坐标表示敏感元电容，右纵坐标表示介电损耗，且图3中方点坐标表示敏感元电容，圆点 坐标表示介电损耗。从图4中也可明显看出，当间距l为0.5mm时，敏感元电容仅约为200pF，且介电损耗约为5×10-4，则相比于间距l为其他数值如0.1mm、1.0mm和1.5mm的实施例，敏感元电容与介电损耗的乘积最小，也就是说介电噪声最小。因此，最优选地，左电极和右电极的间距为0.5mm。Since the left and right electrodes are separated from each other, there must be a gap between the two. 3 to FIG. 4 are schematic diagrams showing the comparison of the pyroelectric coefficient when the left electrode and the right electrode are at different intervals, and the capacitance and dielectric loss when the left electrode and the right electrode are at different intervals. Referring first to Figure 3, the abscissa is the distance l between the left and right electrodes, and the ordinate is the pyroelectric coefficient p. It can be clearly seen from the graph shown in the experiment that the distance between the left electrode and the right electrode is 0.5 mm. When the distance is 1mm, the pyroelectric coefficient p is about 14×10 -4 C/m 2 K, and when the spacing l is 0.1 mm, the pyroelectric coefficient is about 6×10 -4 C/m 2 K, and the spacing is l. At 1.5 mm, the pyroelectric coefficient is about 8×10 -4 C/m 2 K, so that the distance l between the left electrode and the right electrode is significantly higher than the pitch l at 0-0.5 mm and 1 between 0.5 mm and 1 mm. When the pyroelectric coefficient p is between -1.5 mm, it is preferable that the pyroelectric coefficient is large when the pitch l is between 0.5 mm and 1 mm, and the polarization of the left and right electrodes is relatively complete. Referring again to Figure 4, the abscissa is still the spacing l, the left ordinate represents the sensitive element capacitance, the right ordinate represents the dielectric loss, and the square point coordinates in Figure 3 represent the sensitive element capacitance, and the dot coordinates represent the dielectric loss. It is also apparent from Fig. 4 that when the pitch l is 0.5 mm, the sensitive element capacitance is only about 200 pF, and the dielectric loss is about 5 × 10 -4 , which is other values such as 0.1 mm compared to the pitch l. In the 1.0mm and 1.5mm embodiments, the product of the sensitive element capacitance and the dielectric loss is the smallest, that is, the dielectric noise is the smallest. Therefore, most preferably, the distance between the left electrode and the right electrode is 0.5 mm.
一实施例中，上电极的结构呈圆形，而左电极和右电极呈矩形，且左电极和右电极的大小相同。上述配置下，上表面无需引出上电极，可全部用于吸收红外光，增加了红外光的吸收效率，且在热释电系数保持不变的情况下，降低了灵敏元的电容，极大地缩短了设置有该灵敏元芯片的探测器的响应时间。更优选地，矩形左右电极的间距恒等，即矩形左右电极的一条边平行，或是左右电极以圆形上电极的一条直径为对称轴对称，规则、对称的结构可保证极化效果，也方便装配制造。In one embodiment, the structure of the upper electrode is circular, while the left and right electrodes are rectangular, and the left and right electrodes are the same size. In the above configuration, the upper surface does not need to be taken out of the upper electrode, and all of them can be used for absorbing infrared light, which increases the absorption efficiency of infrared light, and reduces the capacitance of the sensitive element, which is greatly shortened, while the pyroelectric coefficient remains unchanged. The response time of the detector provided with the sensitive element chip. More preferably, the pitch of the left and right electrodes of the rectangle is constant, that is, one side of the left and right electrodes of the rectangle is parallel, or the left and right electrodes are symmetric with respect to a diameter of a circular upper electrode, and the regular and symmetrical structure can ensure the polarization effect. Easy to assemble and manufacture.
参阅图5及图6，分别为本发明与现有技术不同电极结构下响应率对比和比探测率对比的示意图。首先参阅图5，横坐标表示频率f，纵坐标表示响应率Rv，其中方点坐标表示现有技术中传统电极结构的响应率Rv，而圆点坐标表示本发明中分布式电极结构下的响应率Rv，可明显看出，在频率f相同的情况下，分布式电极结构比现有技术的探测器响应率提高了近4倍。正是由于采用了分割的结构后，相对介电常数大大降低，带来的效果。再参阅图6，横坐标表示频率f，纵坐标表示比探测率D*，其中方点坐标表示现有技术中传统电机结构的比探测率D*，而圆点坐标表示本发明中分布式电极结构下的比探测率D*，从比探测率来看，采用分布式电极结构的探测器比探测率相比于现有技术传统探测器的比探测率在10Hz处提高了约1.5倍，且随着频率的继续升高，两者比探测率的差越来越大，分布式电极结构下的探测器的比探测率始终保持在较高的水平。正是由于采用了分割的结构后，介电噪声大大降低，带来的效果。Referring to FIG. 5 and FIG. 6, respectively, the schematic diagrams of the comparison of the response rate and the specific detection rate under different electrode structures of the present invention and the prior art are shown. Referring first to Fig. 5, the abscissa represents the frequency f, and the ordinate represents the response rate R v , wherein the square point coordinates represent the response rate R v of the conventional electrode structure in the prior art, and the dot coordinates represent the distributed electrode structure in the present invention. The response rate R v , it is apparent that the distributed electrode structure is nearly four times more efficient than the prior art detectors at the same frequency f. It is precisely because of the use of the split structure that the relative dielectric constant is greatly reduced, resulting in an effect. Referring again to FIG. 6, the abscissa represents the frequency f, and the ordinate represents the specific detection rate D * , wherein the square point coordinates represent the specific detection rate D * of the conventional motor structure in the prior art, and the dot coordinates represent the distributed electrode of the present invention. The specific detection rate D * under the structure, from the detection ratio, the detection ratio of the detector using the distributed electrode structure is about 1.5 times higher than that of the conventional detector of the prior art at 10 Hz, and As the frequency continues to increase, the difference between the two is greater than the detection rate, and the detection ratio of the detector under the distributed electrode structure is always at a high level. It is precisely because of the use of the split structure, the dielectric noise is greatly reduced, and the effect is brought about.
实施例中涉及的材料介电性能测试是用Agilent 4294A型阻抗分析仪(安捷伦科技有限公司)测得样品电容，根据平板电容器近似计算得到的； 单晶极化后的热释电系数是通过动态法热释电系数测量***测得的，其中将单晶沿自发极化方向升温极化后，交流驱动温度幅度为1℃，频率为45mHz；单晶灵敏元芯片上是先通过磁控溅射沉积电极；再对单晶敏感元进行极化处理得到的；热释电探测器的响应率是通过黑体红外响应测试***测得的，器件噪声通过Agilent 35670 A动态信号分析仪(安捷伦科技有限公司)测得，探测率是根据黑体探测率的理论公式，由测得的响应率和噪声计算得到。The dielectric properties of the materials involved in the examples were measured using an Agilent Model 4294A Impedance Analyzer (Agilent Technologies, Inc.) and approximated from a plate capacitor; The pyroelectric coefficient after single crystal polarization is measured by a dynamic pyroelectric coefficient measurement system. After the single crystal is heated and polarized in the direction of spontaneous polarization, the AC drive temperature range is 1 ° C and the frequency is 45 mHz; The single crystal sensitive element chip is first deposited by magnetron sputtering; then the single crystal sensitive element is polarized; the response rate of the pyroelectric detector is measured by the black body infrared response test system, device noise The Agilent 35670 A Dynamic Signal Analyzer (Agilent Technologies, Inc.) measured the detection rate based on the theoretical formula of the blackbody detection rate, calculated from the measured response rate and noise.
敏感元的制备：Preparation of sensitive elements:
制备一种1mol％Mn掺杂的0.71Pb(Mg1/3Nb2/3)O3-0.29PbTiO3单晶敏感元，晶体学取向<111>，尺寸为20×20mm2，厚度为20±1m。溅射异构电极并极化后的性能如下：居里温度为135℃，三方-四方相变温度为108℃，介电常数r≤750，热释电系数p≥12.0×10-4C/m2K。A 1 mol% Mn doped 0.71 Pb (Mg 1/3 Nb 2/3 ) O 3 -0.29 PbTiO 3 single crystal sensitive element was prepared with a crystallographic orientation <111>, a size of 20×20 mm 2 and a thickness of 20±. 1m. The properties of the sputtered heterogeneous electrode after polarization are as follows: the Curie temperature is 135 ° C, the tripartite-tetragonal phase transition temperature is 108 ° C, the dielectric constant r ≤ 750, and the pyroelectric coefficient p ≥ 12.0 × 10 -4 C / m 2 K.
随后对前述0.71Pb(Mg1/3Nb2/3)O3-0.29PbTiO3热释电弛豫铁电单晶敏感元，采用了化学机械减薄抛光技术对弛豫铁电单晶进行减薄抛光，化学抛光液为酸性(pH＝3-4)硅溶胶，硅溶胶的粒径一般为50-80nm。制备了大尺寸(20×20mm2)单晶敏感元，单晶敏感元厚度可控制在20m以下，然后根据需要使用划片机将之划切为小片，以制备热释电探测器灵敏元芯片。由于化学机械抛光的作用，会引入表面应力和损伤层，当单晶敏感元厚度减小至微米级别时，该表面效应的作用更加凸显，使得单晶芯片的整体介电损耗明显增大，影响单晶探测器的探测性能，因此通过本发明所采取的后处理工艺技术，在获得极薄单晶敏感元的同时，也尽可能降低表面损伤及缺陷对单晶敏感元热释电、介电性能的影响，实现高性能高质量单晶敏感元的制备。Subsequently, the 0.71Pb (Mg 1/3 Nb 2/3 )O 3 -0.29PbTiO 3 pyroelectric relaxation ferroelectric single crystal sensitive element was subjected to chemical mechanical thinning polishing technology to reduce the relaxation ferroelectric single crystal. Thin polishing, chemical polishing solution is acidic (pH = 3-4) silica sol, the particle size of silica sol is generally 50-80nm. A large-size (20×20mm 2 ) single crystal sensitive element is prepared, and the thickness of the single crystal sensitive element can be controlled below 20m, and then cut into small pieces by using a dicing machine as needed to prepare a pyroelectric detector sensitive element chip. . Due to the action of chemical mechanical polishing, the surface stress and damage layer are introduced. When the thickness of the single crystal sensitive element is reduced to the micron level, the surface effect is more prominent, and the overall dielectric loss of the single crystal chip is significantly increased. The detection performance of the single crystal detector, therefore, through the post-treatment process technology adopted by the present invention, while obtaining extremely thin single crystal sensitive elements, it also minimizes surface damage and defects on the pyroelectric and dielectric properties of the single crystal sensitive element. The effect of performance enables the preparation of high performance, high quality single crystal sensitive elements.
首先采用了配比(重量比)为8.3:33:58.7的HF:NH4F:H2O缓蚀液，对制备的Mn掺杂PMNT单晶敏感元表面进行湿法腐蚀。可以得出该配比下的腐 蚀液对Mn掺杂PMNT单晶的腐蚀速率约为20.8nm/min。热释电系数随腐蚀时间的增加，先逐渐增大，然后趋于平稳；介电损耗则随腐蚀时间的增加，先降低后增大。这说明湿法腐蚀可在一定程度上优化材料的热释电系数，且腐蚀时间控制在15-20分钟能有效降低材料的介电损耗。First, a HF:NH 4 F:H 2 O corrosion inhibitor with a ratio of 8.3:33:58.7 was used to wet-etch the surface of the prepared Mn-doped PMNT single crystal sensitive element. It can be concluded that the corrosion rate of the etchant in the ratio to the Mn-doped PMNT single crystal is about 20.8 nm/min. The pyroelectric coefficient increases with the increase of corrosion time, then gradually increases, and then the plateau tends to be stable; the dielectric loss increases first and then increases with the increase of corrosion time. This shows that wet etching can optimize the pyroelectric coefficient of the material to some extent, and the corrosion time is controlled to 15-20 minutes to effectively reduce the dielectric loss of the material.
其后，对腐蚀后的单晶敏感元进行退火处理，以进一步去除表面残余的机械应力以及单晶的内部缺陷。退火温度为500℃，退火气氛为氧气(富氧氛围)，退火时间为10小时。单晶敏感元在减薄抛光至微米尺度时，相比于体材料，其介电损耗明显增大，但是通过湿法腐蚀和氧气退火后，单晶敏感元的介电损耗得到有效改善。Thereafter, the etched single crystal sensitive element is annealed to further remove residual mechanical stress on the surface and internal defects of the single crystal. The annealing temperature was 500 ° C, the annealing atmosphere was oxygen (oxygen-rich atmosphere), and the annealing time was 10 hours. When the single crystal sensitive element is thinned and polished to the micron scale, the dielectric loss is significantly increased compared to the bulk material, but the dielectric loss of the single crystal sensitive element is effectively improved by wet etching and oxygen annealing.
探测器的制备：Preparation of the detector:
将处理后的1mol％Mn掺杂0.71Pb(Mg1/3Nb2/3)O3-0.29PbTiO3单晶敏感元放入电极掩模板中，并磁控溅射分布式电极，下表面溅射沉积Ni-Cr/Au电极，电极面积为0.5×2mm2,间距分别为0.1mm、0.5mm、1mm和1.5mm；上表面Ni-Cr电极为Φ2.5mm圆型电极。The treated 1 mol% Mn doped 0.71 Pb (Mg 1/3 Nb 2/3 ) O 3 -0.29 PbTiO 3 single crystal sensitive element was placed in an electrode mask, and the distributed electrode was magnetron sputtered, and the lower surface was splashed. The Ni-Cr/Au electrode was deposited, the electrode area was 0.5×2 mm 2 , the pitch was 0.1 mm, 0.5 mm, 1 mm and 1.5 mm, respectively; the upper surface Ni-Cr electrode was a Φ 2.5 mm round electrode.
灵敏元两端电极分别在1.25kV/mm和-1.25kV/mm下极化，形成反向极化，包括：红外吸收黑层，Ni-Cr电极，热释电材料，Ni-Cr/Au电极，P代表极化取向。灵敏元两下电极通过金线引出信号，与场效应管和20GΩ电阻组成电压模式放大电路封装于TO39管座(上海科发精密合金材料销售有限公司)中。将多壁碳纳米管与酒精混合液喷涂在上述灵敏元芯片表面制备吸收层，从而得到高频用热释电弛豫铁电红外探测器。采用黑体红外响应测试***测对探测器进行性能表征。图8给出了基于该电极结构所制备的电压模式下20m高频用热释电弛豫铁电红外探测器比探测率的频率响应关系，在电极间距为0.5mm、10Hz下的比探测率为1.49×109cm Hz1/2/W。探测性能优于上述电压模式下的20m Mn掺杂PMNT单晶敏感元探测器，并在频率 较高的情况(100Hz)下仍保持较高的比探测率，且明显优于目前商用LiTaO3红外探测器，满足较高频使用的需求。The electrodes at both ends of the sensitive element are polarized at 1.25kV/mm and -1.25kV/mm, respectively, forming reverse polarization, including: infrared absorption black layer, Ni-Cr electrode, pyroelectric material, Ni-Cr/Au electrode , P represents the polarization orientation. The two sensitive electrodes of the sensitive element are led out by the gold wire, and the voltage mode amplifying circuit composed of the field effect transistor and the 20GΩ resistor is packaged in the TO39 pipe socket (Shanghai Kefa Precision Alloy Material Sales Co., Ltd.). A multi-walled carbon nanotube and an alcohol mixture are sprayed on the surface of the above sensitive element chip to prepare an absorption layer, thereby obtaining a high-frequency pyroelectric relaxation ferroelectric infrared detector. The performance of the detector was characterized by a black body infrared response test system. Figure 8 shows the frequency response of the 20m high-frequency pyroelectric relaxation ferroelectric infrared detector based on the detection rate in the voltage mode prepared by the electrode structure. The specific detection rate at the electrode spacing of 0.5mm and 10Hz It is 1.49 × 10 9 cm Hz 1/2 /W. The detection performance is better than the 20m Mn doped PMNT single crystal sensitive element detector in the above voltage mode, and maintains a high specific detection rate in the case of high frequency (100Hz), and is significantly better than the current commercial LiTaO 3 infrared. Detectors to meet the needs of higher frequency use.
该结构的热释电探测器灵敏元上表面无需引出电极，可全部用于吸收红外光，增加了红外光的吸收效率；另外，该结构在热释电系数基本保持不变的情况下，大大降低了灵敏元的电容，也即降低了灵敏元的等效介电常数，使介电噪声相比电阻噪声小了一个数量级，发挥了弛豫铁电单晶高热释电系数的优势，同时减小了其高介电常数的劣势，在一定程度上提高了探测器的比探测率，并在较高频率下仍然保持较高的比探测率。该结构提供了一种新的热释电探测器的结构，易于小型化和集成化，满足现代探测器低成本，低功耗，易于与集成电路相兼容的要求。The upper surface of the sensitive element of the pyroelectric detector of the structure does not need to take out the electrode, and all of them can be used for absorbing infrared light, thereby increasing the absorption efficiency of the infrared light; in addition, the structure is greatly maintained under the condition that the pyroelectric coefficient remains substantially unchanged. The capacitance of the sensitive element is reduced, that is, the equivalent dielectric constant of the sensitive element is reduced, so that the dielectric noise is one order of magnitude smaller than the resistance noise, and the advantage of relaxing the high pyroelectric coefficient of the ferroelectric single crystal is simultaneously reduced. The disadvantage of its high dielectric constant is reduced, and the specific detection rate of the detector is improved to some extent, and the higher specific detection rate is maintained at a higher frequency. The structure provides a new pyroelectric detector structure that is easy to miniaturize and integrate, meeting the requirements of modern detectors with low cost, low power consumption, and compatibility with integrated circuits.
应当注意的是，本发明的实施例有较佳的实施性，且并非对本发明作任何形式的限制，任何熟悉该领域的技术人员可能利用上述揭示的技术内容变更或修饰为等同的有效实施例，但凡未脱离本发明技术方案的内容，依据本发明的技术实质对以上实施例所作的任何修改或等同变化及修饰，均仍属于本发明技术方案的范围内。 It should be noted that the embodiments of the present invention are preferred embodiments, and are not intended to limit the scope of the present invention. Any one skilled in the art may use the above-disclosed technical contents to change or modify the equivalent embodiments. Any modification or equivalent changes and modifications of the above embodiments in accordance with the technical spirit of the present invention are still within the scope of the technical solutions of the present invention.

Claims (9)

  1. 一种热释电弛豫铁电红外探测器，所述探测器包括：A pyroelectric relaxation ferroelectric infrared detector, the detector comprising:
    设有引脚的底座；a base with a pin;
    与所述底座封装在一起以形成容纳空间的带有一个或多个窗口的管壳；a package with one or more windows that is packaged with the base to form a receiving space;
    设置于所述容纳空间中的由经过极化处理的一个或多个热释电弛豫铁电单晶敏感元构成的灵敏元芯片；a sensitive element chip composed of one or more pyroelectric relaxation ferroelectric single crystal sensitive elements disposed in the accommodating space;
    分别设置于所述热释电弛豫铁电单晶敏感元的上表面和下表面的电极；Electrodes respectively disposed on the upper surface and the lower surface of the pyroelectric relaxation ferroelectric single crystal sensitive element;
    覆盖所述热释电弛豫铁电单晶敏感元上表面的吸收层；Covering an absorbing layer on the upper surface of the pyroelectric relaxation ferroelectric single crystal sensitive element;
    对所述的热释电弛豫铁电单晶敏感元进行支撑的支架；以及采用了电压模式或电流模式的放大电路，其特征在于，a support for supporting the pyroelectric relaxation ferroelectric single crystal sensitive element; and an amplifying circuit using a voltage mode or a current mode, characterized in that
    设于所述上表面的上电极为单电极，设于所述下表面的下电极包括互相分离的左电极及右电极，所述左电极和右电极互不连通将所述下电极成型为一分割电极。The upper electrode disposed on the upper surface is a single electrode, and the lower electrode disposed on the lower surface includes left and right electrodes separated from each other, and the left and right electrodes are not connected to each other to form the lower electrode into one Divide the electrodes.
  2. 如权利要求1所述的热释电弛豫铁电红外探测器，其特征在于，The pyroelectric relaxation ferroelectric infrared detector according to claim 1, wherein
    所述左电极及右电极的间距为0.5mm-1mm间。The distance between the left electrode and the right electrode is between 0.5 mm and 1 mm.
  3. 如权利要求2所述的热释电弛豫铁电红外探测器，其特征在于，The pyroelectric relaxation ferroelectric infrared detector according to claim 2, wherein
    所述左电极及右电极的间距为0.5mm。The distance between the left electrode and the right electrode is 0.5 mm.
  4. 如权利要求1所述的热释电弛豫铁电红外探测器，其特征在于， The pyroelectric relaxation ferroelectric infrared detector according to claim 1, wherein
    所述上电极呈圆形；所述左电极及右电极呈矩形。The upper electrode has a circular shape; the left and right electrodes have a rectangular shape.
  5. 如权利要求4所述的热释电弛豫铁电红外探测器，其特征在于，The pyroelectric relaxation ferroelectric infrared detector according to claim 4, wherein
    所述矩形左电极及右电极的间距处处相等。The spacing between the rectangular left electrode and the right electrode is equal.
  6. 如权利要求4或5所述的热释电弛豫铁电红外探测器，其特征在于，A pyroelectric relaxation ferroelectric infrared detector according to claim 4 or 5, wherein
    所述左电极及右电极以所述圆形上电极的一直径对称。The left electrode and the right electrode are symmetric with a diameter of the circular upper electrode.
  7. 如权利要求1所述的热释电弛豫铁电红外探测器，其特征在于，The pyroelectric relaxation ferroelectric infrared detector according to claim 1, wherein
    所述热释电弛豫铁电单晶敏感元的材料为如下材料中的一种或多种：The material of the pyroelectric relaxation ferroelectric single crystal sensitive element is one or more of the following materials:
    三方相Mn掺杂(1-x)Pb(Mg1/3Nb2/3)O3-xPbTiO3单晶，其中，0.26≤x≤0.29、且晶体学方向为[111]，The hexagonal phase Mn is doped with (1-x)Pb(Mg1/3Nb2/3)O3-xPbTiO3 single crystal, wherein 0.26≤x≤0.29 and the crystallographic direction is [111],
    四方相Mn掺杂(1-x)Pb(Mg1/3Nb2/3)O3-xPbTiO3单晶，其中，0.35≤x≤0.40、且晶体学方向为[001]；a tetragonal phase Mn doped (1-x)Pb(Mg1/3Nb2/3)O3-xPbTiO3 single crystal, wherein 0.35≤x≤0.40 and the crystallographic direction is [001];
    三方相Mn掺杂(1-x-y)Pb(In1/2Nb1/2)O3-yPb(Mg1/3Nb2/3)O3-xPbTiO3,其中0.15≤1-x-y≤0.38,0.36≤y≤0.57,0.26≤x≤0.30，且晶体学方向为[111]；The hexagonal phase Mn is doped with (1-xy)Pb(In1/2Nb1/2)O3-yPb(Mg1/3Nb2/3)O3-xPbTiO3, where 0.15≤1-xy≤0.38, 0.36≤y≤0.57,0.26≤x ≤0.30, and the crystallographic direction is [111];
    四方相Mn掺杂(1-x-y)Pb(In1/2Nb1/2)O3-yPb(Mg1/3Nb2/3)O3-xPbTiO3,其中0.20≤1-x-y≤0.29、0.30≤y≤0.45、0.35≤x≤0.42，且晶体学方向为[001]。Tetragonal phase Mn doped (1-xy)Pb(In1/2Nb1/2)O3-yPb(Mg1/3Nb2/3)O3-xPbTiO3, where 0.20≤1-xy≤0.29, 0.30≤y≤0.45, 0.35≤x ≤ 0.42, and the crystallographic direction is [001].
  8. 如权利要求7所述的热释电弛豫铁电红外探测器，其特征在于，The pyroelectric relaxation ferroelectric infrared detector according to claim 7, wherein
    所述吸收层的配方为多壁碳纳米管、纳米四氧化三铁或纳米碳粉和酒精的混合液，并以间歇多次式喷涂的方式覆盖所述上表面，所述吸收层的红外吸收率≥90％；所述支架采用细的、低热导率的氧化铝陶瓷支架，其在所述热释电弛豫铁电单晶敏感元的中心位置进行支撑，以实现红外探测灵 敏元件的热悬空。The absorbing layer is formulated by multi-walled carbon nanotubes, nano-ferric trioxide or a mixture of nano-carbon powder and alcohol, and covers the upper surface by intermittent multiple spraying, and the infrared absorption of the absorbing layer The rate is ≥90%; the stent adopts a fine, low thermal conductivity alumina ceramic support, which is supported at the center of the pyroelectric relaxation ferroelectric single crystal sensitive element to realize infrared detection The thermal element of the sensitive element is suspended.
  9. 如权利要求7所述的热释电弛豫铁电红外探测器，其特征在于，The pyroelectric relaxation ferroelectric infrared detector according to claim 7, wherein
    所述电压模式放大电路的匹配电阻RG降至远小于100G，所述电流模式放大电路的反馈电容Cf≤10pF，反馈电阻Rf降至远小于100G。 The matching resistance RG of the voltage mode amplifying circuit is reduced to be much smaller than 100G, the feedback capacitance Cf ≤ 10pF of the current mode amplifying circuit, and the feedback resistance Rf is reduced to be much smaller than 100G.
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