WO2011096012A1 - Détecteur de rayons infrarouges - Google Patents

Détecteur de rayons infrarouges Download PDF

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WO2011096012A1
WO2011096012A1 PCT/JP2010/000638 JP2010000638W WO2011096012A1 WO 2011096012 A1 WO2011096012 A1 WO 2011096012A1 JP 2010000638 W JP2010000638 W JP 2010000638W WO 2011096012 A1 WO2011096012 A1 WO 2011096012A1
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Prior art keywords
crystal
glass material
resistance
glass
resistivity
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PCT/JP2010/000638
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English (en)
Japanese (ja)
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宮田素之
内藤孝
山本浩貴
藤枝正
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株式会社日立製作所
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Priority to JP2011552578A priority Critical patent/JP5444376B2/ja
Priority to PCT/JP2010/000638 priority patent/WO2011096012A1/fr
Publication of WO2011096012A1 publication Critical patent/WO2011096012A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • 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
    • G01J5/02—Constructional details
    • 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
    • G01J5/02—Constructional details
    • G01J5/0225—Shape of the cavity itself or of elements contained in or suspended over the cavity
    • G01J5/024—Special manufacturing steps or sacrificial layers or layer structures
    • 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
    • G01J5/02—Constructional details
    • G01J5/04—Casings
    • 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
    • G01J5/02—Constructional details
    • G01J5/04—Casings
    • G01J5/046—Materials; Selection of thermal materials
    • 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
    • G01J5/20—Radiation pyrometry, e.g. infrared or optical thermometry using electric radiation detectors using resistors, thermistors or semiconductors sensitive to radiation, e.g. photoconductive devices

Definitions

  • the present invention relates to a glass material used for an infrared sensor.
  • Vanadium-based glass containing vanadium pentoxide as a main component is known to be a glass semiconductor that conducts electricity, and studies are underway to use it for thermistors and the like.
  • Patent Document 1 discloses a glass-like resistance material for a heat-sensitive resistance element, which contains 50 mol% or more of vanadium pentoxide, and in which cerium oxide, tin oxide, and lead oxide are added to a glass composition composed of phosphorus pentoxide and barium oxide. It is disclosed.
  • Patent Document 2 discloses a thermistor made of glass obtained by adding 13 mol% or less of copper oxide to glass containing vanadium pentoxide 70 mol% or more and phosphorus pentoxide 5 to 15 mol%.
  • Patent Document 3 discloses that an electrical resistance at room temperature is obtained by heating an oxide glass composition containing vanadium, barium, and iron at a temperature not lower than the glass transition temperature and not higher than the crystallization temperature, thereby reducing the distortion of the glass skeleton.
  • a vanadate glass that is a glass semiconductor of 10 1 to 10 4 ⁇ ⁇ cm is disclosed.
  • Patent Document 4 discloses an oxide thin film for bolometer in which a part of V in vanadium oxide (VO X ) is substituted with at least one of Cr, Al, Fe, Mn, Nb, Ta, and Ti, and an infrared ray using the same. A sensor is disclosed.
  • V in vanadium oxide VO X
  • Patent Document 6 discloses a method for forming a vanadium oxide thin film in which a thin film made of vanadium oxide (VOx: 2.25 ⁇ x ⁇ 2.5) is heat-treated at a predetermined temperature in a reducing atmosphere.
  • VOx vanadium oxide
  • Patent Document 7 discloses a vanadium oxide thin film obtained by reducing a vanadium pentoxide thin film prepared by a sputtering method or a sol-gel method and heat-treated in air with an argon-hydrogen mixed gas, and this vanadium oxide is expressed as VOx. Vanadium oxide thin film satisfying the range of 1.875 ⁇ x ⁇ 2.0 is disclosed.
  • Japanese Patent Publication No.42-24785 Japanese Examined Patent Publication No. 39-9140 Japanese Patent No. 3854985 JP 2000-143243 A JP 2001-247958 A JP 2000-321124 A JP-A-9-257565
  • An object of the present invention is to provide a vanadium oxide glass material having a low resistivity and a large absolute value of resistance temperature coefficient, and an infrared sensor using the glass material for a bolometer.
  • the glass material of the present invention includes a crystal phase and an amorphous phase, and the crystal phase includes at least M x V 2 O 5 crystal and V 2 O 5 crystal, where M is Li, Na, K , Cu, Ag, Au, Ga, and In, and the amorphous phase contains vanadium, phosphorus, and oxygen.
  • an infrared sensor having a bolometer with a low resistivity and a large absolute value of resistance temperature coefficient.
  • the present invention relates to a temperature-sensitive resistance material (glass material) whose resistance value varies with temperature and a bolometer-type infrared sensor using the same.
  • the glass material includes a crystal phase and an amorphous phase, and the crystal phase includes at least M x V 2 O 5 crystal and V 2 O 5 crystal, and M is Li, Na, K, Cu, Ag. , Au, Ga, and In, and the amorphous phase contains vanadium, phosphorus, and oxygen.
  • x 0.28 to 0.76.
  • the crystal phase ratio is 60 to 99% by volume.
  • the ratio of M x V 2 O 5 crystals in the crystal phase is 60 to 99% by weight.
  • the crystallite size of the M x V 2 O 5 crystal is 50 nm or more.
  • the crystallite size of the V 2 O 5 crystal is 30 nm or less.
  • the composition in terms of oxide is such that V 2 O 5 is 62 to 92% by weight, P 2 O 5 is 5 to 20% by weight, Li 2 O, Na 2 O, K 2 O, One or more selected from the group consisting of Cu 2 O, Ag 2 O, Ga 2 O and In 2 O is 1 to 15% by weight, WO 3 , MoO 3 , Fe 2 O 3 , MnO 2 , BaO, One or more selected from the group consisting of Sb 2 O 3 and Bi 2 O 3 is 0 to 20% by weight.
  • the glass material has a resistivity of 10 ⁇ ⁇ cm or less and an absolute value of a resistance temperature coefficient of 3% / ° C. or more.
  • the glass material can be applied to an infrared sensor and an infrared imaging device.
  • FIG. 1 is a schematic diagram showing an infrared sensor of an example.
  • a bolometer thin film 1 (also simply referred to as a bolometer) is installed on a substrate 2 so as to be covered with protective films 5 and 6 and supported by a conductive film 3 which is also covered with protective films 5 and 6. ing.
  • the bolometer thin film 1 and the protective films 5 and 6 constitute a diaphragm 8, and a space 7 is provided between the diaphragm 8 and the substrate 2.
  • the space 7 is for reducing the amount of heat transfer between the diaphragm 8 and the substrate 2.
  • a reflective film 4 is provided on the surface of the substrate 2 facing the space 7.
  • the reflective film 4 is for reflecting the infrared ray 9 that has passed through the diaphragm 8 and allowing the diaphragm 8 to absorb as much energy of the infrared ray 9 as possible.
  • the bolometer thin film 1 is a temperature-sensitive resistance material (glass material) whose resistance changes due to a temperature change accompanying absorption of infrared rays 9. Infrared light is detected by processing the change in resistance as a change in electrical signal by the substrate 2 (signal circuit).
  • an image can be formed by arranging the sensors two-dimensionally.
  • the sensor is usually manufactured using MEMS technology.
  • the glass material of the present embodiment is formed on the substrate 2 such as Si, Si 3 N 4 , or SiC using a sputtering method, a coating pyrolysis method, a screen printing method, an aerosol deposition method, or the like. Can do. In particular, the latter two methods (screen printing method and aerosol deposition method) can be reduced in cost compared to the sputtering method.
  • vanadium oxide (VO 2 ) undergoes a metal-semiconductor transition at about 70 ° C., it cannot be used in a temperature range higher than that.
  • the heat resistance is improved by improving the sputtering film forming conditions (Patent Document 7), but the temperature is about 150 ° C. at most.
  • the glass material of the present example is stable up to the glass transition point (around 300 ° C.) and contributes to the improvement of heat resistance and reliability.
  • the glass material of the present example shows a characteristic that the resistivity decreases as the temperature rises
  • the infrared detection characteristics in a higher temperature region than the glass material used in the conventional infrared sensor should be improved. Can do.
  • the glass material of the present embodiment can reduce the resistivity by generating and dispersing conductive M x V 2 O 5 crystals and V 2 O 5 crystals in the amorphous phase. .
  • the conventional glass material has a smaller absolute value of resistance temperature coefficient as the resistivity decreases.
  • the glass material of the present embodiment is made of at least two types of crystals having different resistivity, such as a relatively low resistance M x V 2 O 5 crystal and a relatively high resistance V 2 O 5 crystal.
  • the ratio of the crystal phase is 60 to 99% by volume, and more preferably the ratio of the crystal phase is 70 to 99% by volume. This is because when the proportion of the crystal phase is less than 60% by volume, the resistance value is larger than the desired range, and when it exceeds 99% by volume, the temperature coefficient of resistance is smaller than the desired range.
  • the proportion of M x V 2 O 5 crystals in the crystal phase is preferably 60 to 99% by weight, and more preferably 70 to 99% by weight. This is because when the ratio of M x V 2 O 5 crystals is less than 60% by weight, the resistance value becomes larger than the desired range, and when it exceeds 99% by weight, the temperature coefficient of resistance becomes smaller than the desired range.
  • FIG. 2 shows a structural model of the crystal of V 2 O 5 .
  • FIG. 3 shows a structural model of the crystal of M x V 2 O 5 .
  • the VO 5 pyramid 101 is covalently bonded in a two-dimensional direction via an oxygen atom to form a layered structure.
  • the crystal of M x V 2 O 5 has a cylindrical structure in which cations (M) are regularly bonded between layers of the vanadium oxide layered structure. Therefore, the crystal of this example is superior in chemical stability compared to V 2 O 5 laminated by electrostatic interaction.
  • M in the M x V 2 O 5 crystallite is at least one element selected from the group consisting of monovalent cations Li, Na, K, Cu, Ag, Au, Ga, and In, More preferably, it is at least one element selected from the group consisting of Li, Na, K, Cu and Ag.
  • the size of the M x V 2 O 5 crystallite is preferably 50 nm or more in the direction of the (111) plane or the (11-1) plane, and more preferably 100 nm or more. This is because the resistance of the glass material decreases as the size of the M x V 2 O 5 crystallite increases, but if the size of the M x V 2 O 5 crystallite is smaller than 50 nm, it does not contribute to the decrease in resistance. Note that the larger the size of the M x V 2 O 5 crystallite, the smaller the temperature coefficient of resistance. Therefore, the size of the M x V 2 O 5 crystallite is preferably 500 nm or less.
  • the size of the V 2 O 5 crystallite is preferably 30 nm or less in the (001) plane direction, and more preferably 20 nm or less. This is because, when dispersed together with M x V 2 O 5 crystals, the resistance of the glass material decreases as the size of the V 2 O 5 crystallites decreases, but if it exceeds 30 nm, it does not contribute to the decrease in resistance. . In addition, since the temperature coefficient of resistance decreases as the size of the V 2 O 5 crystallite decreases, the size of the V 2 O 5 crystallite is preferably 5 nm or more.
  • the amorphous phase of this example includes at least one selected from the group consisting of vanadium oxide, phosphorus oxide, tungsten oxide, molybdenum oxide, iron oxide, manganese oxide, barium oxide, antimony oxide, and bismuth oxide.
  • the glass material of this example has a resistivity at room temperature (25 ° C.) of 10 ⁇ ⁇ cm or less, a resistance temperature coefficient at 20 to 40 ° C. of ⁇ 3% / ° C. or less (the absolute value of the resistance temperature coefficient is 3% / ° C or higher).
  • the resistivity and the temperature coefficient of resistance show a contradictory relationship, but in the glass material of this example, the glass structure should be optimized, such as the composition of the glass material, the proportion of the crystal phase, and the size of the crystallite. Thus, it is possible to keep the resistivity and the temperature coefficient of resistance within the optimum ranges.
  • the composition of the glass composition is 62 to 92% by weight of V 2 O 5 and 5 to 20% by weight of P 2 O 5 in terms of oxide, Li 2 O, Na 2 O, K 2 O, Cu 2 O and Any one of Ag 2 O is 1 to 15% by weight, and any one or more of WO 3 , MoO 3 , Fe 2 O 3 , MnO 2 , BaO, Sb 2 O 3 and Bi 2 O 3 is 0 to 20% by weight. It is.
  • a more preferable composition of the glass composition is, in terms of oxide, V 2 O 5 of 70 to 80 wt%, P 2 O 5 of 8 to 14 wt%, Li 2 O, Na 2 O and K 2 O. Is 1 to 5 wt%, and one or more selected from the group consisting of WO 3 , MoO 3 , Fe 2 O 3 , MnO 2 , BaO, Sb 2 O 3 and Bi 2 O 3 is 0 to 20 wt% or less is there.
  • Vanadium pentoxide and phosphorus pentoxide are substances that form the skeleton of the glass material (glass composition) of this example.
  • This type of glass material is composed of VO 5 pentahedron units centered on vanadium atoms and having oxygen atoms as vertices, and the units are covalently bonded in a two-dimensional direction via oxygen atoms to form a layered structure. It is vitrified by bonding PO 4 tetrahedrons between these layers.
  • V 2 O 5 When V 2 O 5 is less than 62% by weight, there are few crystals that precipitate, and the resistance value does not decrease. Further, if V 2 O 5 exceeds 92 wt%, the ratio of V 2 O 5 crystal phase is more than 90 wt% is not preferable.
  • Li 2 O, Na 2 O, K 2 O, Cu 2 O, and Ag 2 O are components for producing monoclinic crystals by firing. Even if the amount is less than 1% by weight or more than 15% by weight, it is not preferable because monoclinic crystals are hardly precipitated.
  • the metal element that is stable in the state of a monovalent cation Li, Na, and K, which are alkali metals that have a low electronegativity and are easy to vitrify stably, are preferable.
  • WO 3 , MoO 3 , Fe 2 O 3 , MnO 2 , BaO, Sb 2 O 3 and Bi 2 O 3 are glass modifying components. It is a component that adjusts the characteristics of the glass amorphous phase, such as water resistance, thermal expansion, and characteristic temperature, and can be added as appropriate. The water resistance improves as the amount added increases. However, if it exceeds 25% by weight, the proportion of monoclinic crystals in the conductive material decreases, which is not preferable. In addition, since a material with low water resistance easily absorbs moisture, it becomes unstable under the influence of moisture. Therefore, it readily available, and the safety is added WO 3 and 10 wt% combined WO 3 and Fe 2 O 3 at least one of Fe 2 O 3 ⁇ 20% by weight is high material preferable.
  • the glass composition of this example has a transition temperature of 300 ° C. or lower and a crystallization (start) temperature of 400 ° C. or lower, and can be crystallized by heat treatment at a temperature of the crystallization (start) temperature or higher. Since the crystal phase is generated in two stages, that is, the generation of crystal nuclei and the growth of crystals, the crystal states generated under the heat treatment conditions are different. In order to reduce the size of the crystallite (also referred to as crystallite size or crystallite diameter), the crystallite is kept long at the crystal nucleation temperature, and crystal nuclei are sufficiently precipitated and then grown.
  • a method is generally used in which crystal nucleation temperature is passed quickly and crystals are grown while maintaining the number of crystal nuclei at a high temperature.
  • the firing method is not particularly limited as long as it is an apparatus capable of heating amorphous glass at a temperature higher than the crystallization temperature, such as heater heating, laser annealing, induction heating and the like.
  • 300 g of mixed powder in which raw material compounds are blended and mixed so as to have a predetermined composition is placed in a platinum crucible and heated to 1100 ° C. at a temperature rising rate of 5 to 10 ° C./min (° C./min) using an electric furnace. Hold for 2 hours. During holding, stirring was performed to obtain a uniform glass. Next, the platinum crucible was taken out from the electric furnace and poured onto a stainless steel plate heated to 200 to 300 ° C. in advance.
  • Table 1 shows the glass composition and properties produced and studied.
  • the characteristic temperature of the glass was determined from the peak temperature by differential thermal analysis (DTA) using glass powder.
  • the measurement sample was pulverized using a stamp mill to prepare a glass composition powder.
  • the obtained glass composition was processed into a size of 10 ⁇ 10 ⁇ 4 mm to obtain a sample piece, and this sample piece was placed on an alumina substrate and heated at a temperature 50 ° C. or more higher than the crystallization start temperature for 50 hours.
  • the produced conductive material was produced.
  • the glass composition containing the crystal phase after firing is pulverized into a powder form, and using a wide-angle X-ray diffractometer (manufactured by Rigaku Corporation, RINT 2500HL), the crystal identification, the crystal ratio, and the crystallite diameter Measurements were made.
  • the crystal identification and crystal ratio measurement conditions are as follows.
  • the X-ray source was Cu, and its output was set to 50 kV and 250 mA.
  • a divergence slit of 0.5 deg, a receiving slit of 0.15 mm, and a scattering slit of 0.5 deg were selected.
  • the scanning axis of X-ray diffraction was a 2 ⁇ / ⁇ interlocking type, and measurement was performed in a range of 5 ⁇ 2 ⁇ ⁇ 100 deg by continuous scanning under conditions of a scanning speed of 1.0 deg / min and sampling of 0.01 deg.
  • ICDD data which is a collection of X-ray diffraction standard data was used to identify crystals precipitated in the material.
  • the crystal ratio was calculated from the ratio between the diffraction peak due to crystal and the halo due to amorphous in the obtained diffraction pattern.
  • the crystallite diameter is the diffraction peak having the highest peak intensity among the diffraction peaks originating from the identified crystal, and in the case of a Li 0.3 V 2 O 5 crystal, the (11-1) plane, V 2 O Five crystals used the (001) plane, and the crystallite diameter was calculated therefrom.
  • the following is a method for measuring the crystallite diameter.
  • ⁇ Detailed measurement was performed by narrow scan at an angle near the detected main peak.
  • the narrow scan was measured by using integrated scanning as the scanning method and narrowing the scanning range to the vicinity of the detected main peak.
  • the crystallite diameter was calculated from the half width of the detected main peak obtained by narrow scan by the Scherrer equation.
  • the measurement method used here cannot measure a crystallite diameter of 100 nm or more, the crystallite diameter was confirmed by SEM (scanning electron microscope) observation or TEM (transmission electron microscope) observation for samples exceeding the measurement limit. .
  • the oxide powder was used for vanadium pentoxide, phosphorus pentoxide, iron oxide, antimony trioxide, tungsten trioxide, etc., which are raw materials for each component. Moreover, about sodium, potassium, and lithium, sodium carbonate, potassium carbonate, and lithium carbonate were used, respectively.
  • samples described as “Examples” are “V 2 O 5 is 63 wt% to 88.8 wt%”, “P 2 O 5 ” with respect to the composition of the glass composition before firing shown in Table 1.
  • At least one of 2 and Bi 2 O 3 satisfies the condition “0 wt% to 20 wt%”.
  • a sample that does not satisfy the above composition range was described as “Comparative Example”.
  • sample number 1-01 in Table 1 corresponds to sample number 2-01 in Table 2.
  • the precipitated main crystals (mainly precipitated crystals) were Li 0.3 V 2 O 5 , Na 0.287 V 2 O 5 , Na 0.76 V 2 O 5 , and K 0, respectively. .33 V 2 O 5 , Cu 0.261 (V 2 O 5 ), Ag 0.333 (V 2 O 5 ).
  • This crystal is a compound of a monovalent cation (M) and V 2 O 5 and is a crystal represented by M x V 2 O 5 .
  • x is 0.28 to 0.76.
  • the crystal ratio is 62% by volume or more, and the crystallite diameter is 50 nm or more.
  • the conductive materials obtained from these compositions exhibited good conductivity with a conductivity of 10 ⁇ ⁇ cm or less.
  • the precipitated main crystal is V 2 O 5 or Li 0.97 V 3 O 8
  • a crystal of Li 0.3 V 2 O 5 is precipitated.
  • the crystal ratio is less than 60% by volume.
  • the resistance value after the crystallization treatment was also larger than 10 ⁇ ⁇ cm.
  • the ratio of the crystal phase to be generated and the crystallite size vary depending on the glass composition and heat treatment conditions.
  • FIG. 4 is a graph showing the relationship between the ratio of crystal phase, resistivity, and temperature coefficient of resistance.
  • the horizontal axis represents the crystal phase ratio
  • the left vertical axis represents resistivity
  • the right vertical axis represents resistance temperature coefficient
  • the glass material used as a sample is 1-11 in Table 1.
  • the resistivity decreases as the proportion of the crystal phase increases, and when the proportion of the crystal phase is 60% by volume or more, the resistivity shows a value of 10 ⁇ ⁇ cm or less.
  • the temperature coefficient of resistance shows a negative value, but its absolute value decreases with an increase in the ratio of the crystal phase.
  • the absolute value of the resistance temperature coefficient Indicates a value of 3.2% / ° C. or lower (resistance temperature coefficient is ⁇ 3.2% / ° C. or higher).
  • FIG. 5 is a graph showing the relationship between the amount of M x V 2 O 5 in the crystal phase, the resistivity, and the temperature coefficient of resistance.
  • the horizontal axis represents the amount of M x V 2 O 5
  • the left vertical axis represents the resistivity
  • the right vertical axis represents the temperature coefficient of resistance.
  • the amount of M x V 2 O 5 is the ratio of Li 0.3 V 2 O 5 crystal, which is one of the main precipitated crystals shown in Table 2-11.
  • the resistivity is reduced with an increase in the proportion of M x V 2 O 5 amount i.e. Li 0.3 V 2 O 5 crystal, M x V 2 O 5 amount is more than 60 wt% In this case, the value is 10 ⁇ ⁇ cm or less.
  • the resistance temperature coefficient shows a negative value, its absolute value decreases with an increase in the proportion of the crystal phase (Li 0.3 V 2 O 5 crystal), and the amount of M x V 2 O 5 decreases.
  • the absolute value of the resistance temperature coefficient is 3.2% / ° C. or less (the resistance temperature coefficient is ⁇ 3.2% / ° C. or more).
  • FIG. 6 is a graph showing the relationship between the size of M x V 2 O 5 crystallites and the resistivity.
  • M x V 2 O 5 is Li 0.3 V 2 O 5 which is one of the main precipitated crystals shown in 2-10 of Table 2, and the size of the M x V 2 O 5 crystallite Is the size of the Li 0.3 V 2 O 5 crystallite.
  • the resistivity decreases as the size of the M x V 2 O 5 crystallite increases, and shows a value of 10 ⁇ ⁇ cm or less at 50 nm or more.
  • FIG. 7 is a graph showing the relationship between the size of the V 2 O 5 crystallite and the resistivity.
  • V 2 O 5 is the main precipitated crystals shown in 2-11 of Table 2.
  • the resistivity decreases with a decrease in the size of the V 2 O 5 crystallite, and shows a value of 10 ⁇ ⁇ cm or less at 30 nm or less.
  • the glass material of the present embodiment and the infrared sensor and infrared imaging device using the glass material can improve long-term stability and reliability, and can reduce costs.
  • the glass material of the present invention and the infrared sensor and infrared imaging device using the glass material can be applied to products used in general households, offices, factories, vehicles, ships and the like.

Abstract

La présente invention concerne, d'une part une substance à base de verre contenant à l'oxyde de vanadium présentant une faible résistivité et une importante valeur absolue de coefficient thermique de résistivité, et d'autre part un détecteur de rayons infrarouges dans lequel cette substance à base de verre sert de bolomètre. Cette substance à base de verre comprend une phase cristalline et une phase amorphe. La phase cristalline comprend au moins des cristaux de MxV2O5 et des cristaux de V2O5, le M de la formule représentant au moins un élément choisi dans le groupe constitué de Li, Na, K, Cu, Ag, Au, Ga et In, la phase amorphe contenant du vanadium, du phosphore et de l'oxygène.
PCT/JP2010/000638 2010-02-03 2010-02-03 Détecteur de rayons infrarouges WO2011096012A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2468693A3 (fr) * 2010-12-24 2012-08-22 Hitachi Ltd. Matériau de conversion thermoélectrique
CN103359932A (zh) * 2012-03-30 2013-10-23 株式会社日立制作所 表面具有精细结构的玻璃基材
WO2021018856A1 (fr) * 2019-07-30 2021-02-04 Commissariat à l'Energie Atomique et aux Energies Alternatives Procede de fabrication d'un microbolometre comportant un materiau sensible a base d'oxyde de vanadium

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JPS61111935A (ja) * 1984-11-02 1986-05-30 Hitachi Ltd ガラス組成物
JP2007320823A (ja) * 2006-06-02 2007-12-13 Hitachi Ltd 導電部材とその製造方法、画像表示装置及びガラススペーサ
JP2009298687A (ja) * 2008-05-16 2009-12-24 Nagaoka Univ Of Technology 結晶化ガラスおよびその製造方法

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Publication number Priority date Publication date Assignee Title
JPS6136135A (ja) * 1984-07-27 1986-02-20 Hitachi Ltd 磁気ヘツド用充填ガラス
JPS61111935A (ja) * 1984-11-02 1986-05-30 Hitachi Ltd ガラス組成物
JP2007320823A (ja) * 2006-06-02 2007-12-13 Hitachi Ltd 導電部材とその製造方法、画像表示装置及びガラススペーサ
JP2009298687A (ja) * 2008-05-16 2009-12-24 Nagaoka Univ Of Technology 結晶化ガラスおよびその製造方法

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Publication number Priority date Publication date Assignee Title
EP2468693A3 (fr) * 2010-12-24 2012-08-22 Hitachi Ltd. Matériau de conversion thermoélectrique
US8802963B2 (en) 2010-12-24 2014-08-12 Hitachi, Ltd. Thermoelectric conversion material
CN103359932A (zh) * 2012-03-30 2013-10-23 株式会社日立制作所 表面具有精细结构的玻璃基材
WO2021018856A1 (fr) * 2019-07-30 2021-02-04 Commissariat à l'Energie Atomique et aux Energies Alternatives Procede de fabrication d'un microbolometre comportant un materiau sensible a base d'oxyde de vanadium
FR3099573A1 (fr) * 2019-07-30 2021-02-05 Commissariat A L'energie Atomique Et Aux Energies Alternatives Procédé de fabrication d’un microbolomètre comportant un matériau sensible à base d’oxyde de vanadium

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