WO2016104243A1 - 光電面、光電変換管、イメージインテンシファイア、及び光電子増倍管 - Google Patents
光電面、光電変換管、イメージインテンシファイア、及び光電子増倍管 Download PDFInfo
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- WO2016104243A1 WO2016104243A1 PCT/JP2015/085037 JP2015085037W WO2016104243A1 WO 2016104243 A1 WO2016104243 A1 WO 2016104243A1 JP 2015085037 W JP2015085037 W JP 2015085037W WO 2016104243 A1 WO2016104243 A1 WO 2016104243A1
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- photocathode
- photoelectric conversion
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 53
- 239000000463 material Substances 0.000 claims abstract description 46
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims abstract description 4
- 239000010936 titanium Substances 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000010453 quartz Substances 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 229910052714 tellurium Inorganic materials 0.000 claims description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 4
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 19
- 239000010408 film Substances 0.000 description 192
- 238000001514 detection method Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 11
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 238000002834 transmittance Methods 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 6
- 239000002585 base Substances 0.000 description 4
- 239000002041 carbon nanotube Substances 0.000 description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 4
- 229910004261 CaF 2 Inorganic materials 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 3
- 150000002222 fluorine compounds Chemical class 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J1/00—Details of electrodes, of magnetic control means, of screens, or of the mounting or spacing thereof, common to two or more basic types of discharge tubes or lamps
- H01J1/02—Main electrodes
- H01J1/34—Photo-emissive cathodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J1/00—Details of electrodes, of magnetic control means, of screens, or of the mounting or spacing thereof, common to two or more basic types of discharge tubes or lamps
- H01J1/54—Screens on or from which an image or pattern is formed, picked-up, converted, or stored; Luminescent coatings on vessels
- H01J1/78—Photoelectric screens; Charge-storage screens
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J29/00—Details of cathode-ray tubes or of electron-beam tubes of the types covered by group H01J31/00
- H01J29/02—Electrodes; Screens; Mounting, supporting, spacing or insulating thereof
- H01J29/10—Screens on or from which an image or pattern is formed, picked up, converted or stored
- H01J29/36—Photoelectric screens; Charge-storage screens
- H01J29/38—Photoelectric screens; Charge-storage screens not using charge storage, e.g. photo-emissive screen, extended cathode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J31/00—Cathode ray tubes; Electron beam tubes
- H01J31/08—Cathode ray tubes; Electron beam tubes having a screen on or from which an image or pattern is formed, picked up, converted, or stored
- H01J31/50—Image-conversion or image-amplification tubes, i.e. having optical, X-ray, or analogous input, and optical output
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J31/00—Cathode ray tubes; Electron beam tubes
- H01J31/08—Cathode ray tubes; Electron beam tubes having a screen on or from which an image or pattern is formed, picked up, converted, or stored
- H01J31/50—Image-conversion or image-amplification tubes, i.e. having optical, X-ray, or analogous input, and optical output
- H01J31/506—Image-conversion or image-amplification tubes, i.e. having optical, X-ray, or analogous input, and optical output tubes using secondary emission effect
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J40/00—Photoelectric discharge tubes not involving the ionisation of a gas
- H01J40/02—Details
- H01J40/04—Electrodes
- H01J40/06—Photo-emissive cathodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J40/00—Photoelectric discharge tubes not involving the ionisation of a gas
- H01J40/16—Photoelectric discharge tubes not involving the ionisation of a gas having photo- emissive cathode, e.g. alkaline photoelectric cell
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/0272—Selenium or tellurium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
- H01L31/03925—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate including AIIBVI compound materials, e.g. CdTe, CdS
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- H—ELECTRICITY
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- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J2201/00—Electrodes common to discharge tubes
- H01J2201/34—Photoemissive electrodes
- H01J2201/342—Cathodes
- H01J2201/3421—Composition of the emitting surface
- H01J2201/3423—Semiconductors, e.g. GaAs, NEA emitters
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- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
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- H01J2201/34—Photoemissive electrodes
- H01J2201/342—Cathodes
- H01J2201/3421—Composition of the emitting surface
- H01J2201/3426—Alkaline metal compounds, e.g. Na-K-Sb
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- H—ELECTRICITY
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- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J2231/00—Cathode ray tubes or electron beam tubes
- H01J2231/50—Imaging and conversion tubes
- H01J2231/50005—Imaging and conversion tubes characterised by form of illumination
- H01J2231/5001—Photons
- H01J2231/50015—Light
- H01J2231/50021—Ultraviolet
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J31/00—Cathode ray tubes; Electron beam tubes
- H01J31/08—Cathode ray tubes; Electron beam tubes having a screen on or from which an image or pattern is formed, picked up, converted, or stored
- H01J31/49—Pick-up adapted for an input of electromagnetic radiation other than visible light and having an electric output, e.g. for an input of X-rays, for an input of infrared radiation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Definitions
- the present invention relates to a photocathode, a photoelectric conversion tube having the photocathode, an image intensifier (IMAGE INTENSIFIER), and a photomultiplier tube.
- Patent Documents 1, 2, and 3 describe photocathodes having a laminated structure.
- the photoelectric surface of Patent Document 1 has a stacked structure in which a substrate, a base film, an intermediate film, and a photoelectric conversion film are stacked in this order.
- the photoelectric surface of Patent Documents 2 and 3 has a laminated structure in which a window material, a base film, and a photoelectric emission film are laminated in this order.
- the photocathode described in Patent Documents 1, 2, and 3 may be used for detecting a flame.
- the flame has a characteristic spectrum in a wavelength region of 300 nm or less.
- sunlight reaching the ground has an extremely small spectrum in the ultraviolet band of 300 nm or less due to absorption of the ozone layer.
- This band where the spectrum of sunlight becomes extremely small is also called a solar blind band. If the photocathode exhibits good sensitivity in this solar blind band, good light detection characteristics in which the influence of sunlight is suppressed can be expected.
- One embodiment of the present invention is a photocathode having a stacked structure, a window material that transmits ultraviolet light, a conductive film formed on the window material, and a conductive film formed on the conductive film, and a compound of magnesium and fluorine. And a photoelectric conversion film formed on the intermediate film and containing tellurium and an alkali metal.
- the wavelength band detected by the photocathode can be an ultraviolet band including the solar blind band.
- An intermediate film containing magnesium and a fluorine compound is formed between the photoelectric conversion film and the conductive film. Since the intermediate film containing the compound of magnesium and fluorine has a relatively large band gap, a film having a large band gap is disposed on the surface of the photoelectric conversion film on the window material side. Then, the band is bent, and the photoelectron extraction efficiency is improved. Therefore, according to this photocathode, the sensitivity in the ultraviolet band can be improved.
- the compound may be magnesium fluoride, and the alkali metal may be cesium. According to these configurations, since the lattice mismatch that may occur between the photoelectric conversion film and the intermediate film tends to be suppressed, it is possible to suppress a decrease in crystallinity of the photoelectric conversion film. Therefore, the sensitivity of the photocathode can be further improved.
- the conductive film may contain titanium. According to this configuration, photoelectrons generated in the photoelectric conversion film can be taken out efficiently.
- the window material may contain quartz. According to this configuration, the attenuation of light that occurs when passing through the window material is suppressed, so that the sensitivity of the photocathode can be further improved.
- another embodiment of the present invention is a photoelectric conversion tube including a vacuum vessel provided with the above-described photocathode. Since this photoelectric conversion tube includes the above-described photocathode, sensitivity in the ultraviolet band can be improved.
- Still another embodiment of the present invention provides a vacuum vessel provided with the above-described photocathode, an electron multiplying unit for multiplying electrons emitted from the photoelectric conversion film contained in the vacuum vessel, and an electron multiplying unit.
- the image intensifier includes: a fluorescent screen that receives the electrons multiplied by the electron multiplier and converts the electrons multiplied by the electron multiplying means into light. Since this image intensifier includes the above-described photocathode, sensitivity in the ultraviolet band can be improved.
- Still another embodiment of the present invention provides a vacuum vessel provided with the above-described photocathode, an electron multiplying means for multiplying electrons emitted from the photoelectric conversion film contained in the vacuum vessel, and the interior of the vacuum vessel And an anode to which electrons multiplied by the electron multiplying means are incident. Since this photomultiplier tube is provided with the above-described photocathode, the sensitivity in the ultraviolet band can be improved.
- the photoelectric conversion tube, the image intensifier, and the photomultiplier tube according to another embodiment, the sensitivity in the ultraviolet band can be improved.
- 10 is a graph showing the relationship between the detection wavelength of the photocathode and the quantum efficiency according to Comparative Example 1. It is a graph which shows the relationship between the detection wavelength of the photocathode which concerns on the comparative example 2, and quantum efficiency. It is a graph which shows the relationship between a band gap and quantum efficiency.
- the photocathode 1 shown in FIG. 1 detects light L in the ultraviolet band.
- the wavelength band of the light L detected by the photocathode 1 (hereinafter also referred to as “detection band”) is set to a wavelength band included in the ultraviolet band.
- the detection band may be set to 200 nm to 350 nm included in the near ultraviolet band, and may be set to 260 nm to 300 nm.
- the detection band may be set to a band centered on 280 nm.
- a band having a wavelength of 280 nm or less is a so-called solar blind band in which the spectrum of sunlight is extremely small. As shown in FIG.
- the spectrum of sunlight (see graph G2a) is extremely small in the region where the wavelength is about 280 nm or less (see band A1). Therefore, when the detection band (see graph G2b) is set to 280 nm or less, the photocathode 1 can be used for engine flare analysis or the like in a sunlight environment.
- the photocathode 1 has a laminated structure.
- the photocathode 1 includes a window material 2, a conductive film 3, an intermediate film 4, and a photoelectric conversion film 6, which are stacked in this order. Therefore, the light L incident on the window material 2 reaches the photoelectric conversion film 6 after passing through the window material 2, the conductive film 3 and the intermediate film 4.
- the window material 2 forms a substrate of the photocathode 1.
- the window material 2 has an incident surface 2a on which the light L is incident and a back surface 2b on the opposite side of the incident surface 2a.
- the window material 2 has good transparency to light in the detection band of the photocathode 1. Therefore, the window material 2 is made of a material that can transmit ultraviolet rays.
- the permeable material with ultraviolet light include silica (SiO 2) is.
- the conductive film 3 is formed on the back surface 2 b of the window material 2.
- the conductive film 3 has a surface 3a in contact with the window material 2 and a back surface 3b on the opposite side of the surface 3a.
- the conductive film 3 is a base film of the photoelectric conversion film 6 for the window material 2.
- the conductive film 3 transmits the light L incident on the window material 2 and supplies photoelectrons emitted from the photoelectric conversion film 6.
- Examples of the material forming the conductive film 3 include a conductive metal material such as titanium (Ti).
- the film thickness may be 2 nm or more and 10 nm or less. In other words, the film thickness may be 20 to 100 mm.
- the film thickness may be 0.1 nm or more and 2 nm or less. In other words, the film thickness may be 1 to 20 mm.
- the intermediate film 4 is formed on the back surface 3 b of the conductive film 3.
- the intermediate film 4 has a surface 4a in contact with the conductive film 3 and an interface 4b on the opposite side of the surface 4a.
- the intermediate film 4 is a base film of the photoelectric conversion film 6 for the conductive film 3. Further, the intermediate film 4 transmits the light L incident on the window material 2 and forms a high band gap region on the surface 6 a side of the photoelectric conversion film 6.
- the intermediate film 4 is composed of magnesium fluoride (MgF 2 ) which is a compound of magnesium (Mg) and fluorine (F).
- the band gap of MgF 2 is 11.4 eV.
- the film thickness of the intermediate film 4 is 0.5 nm or more and 5 nm or less.
- the film thickness of the intermediate film 4 is 5 to 50 mm.
- the film thickness of the intermediate film 4 may be set to 0.5 nm or more and 5 nm or less. In other words, the film thickness of the intermediate film 4 may be set to 5 mm or more and 50 mm or less.
- the intermediate film 4 is formed by vapor deposition or sputtering.
- the photoelectric conversion film 6 is formed on the interface 4b of the intermediate film 4.
- the photoelectric conversion film 6 has a surface 6 a in contact with the intermediate film 4.
- the photoelectric conversion film 6 generates photoelectrons by the incident light L.
- the photoelectric conversion film 6 is made of a compound of tellurium (Te) and an alkali metal such as cesium-tellurium (CsTe).
- the detection wavelength can be set to the ultraviolet band including the solar blind band.
- An intermediate film 4 made of MgF 2 is formed between the photoelectric conversion film 6 and the conductive film 3. Since the intermediate film 4 has a relatively large band gap, a film having a large band gap is disposed on the surface of the photoelectric conversion film 6 on the window material 2 side. Then, the band is bent, and the photoelectron extraction efficiency is improved. Therefore, according to the photocathode 1, the sensitivity in the ultraviolet band can be improved.
- the intermediate film 4 is MgF 2 and the photoelectric conversion film 6 is CsTe. According to these configurations, lattice mismatch that may occur between the photoelectric conversion film 6 and the intermediate film 4 can be suppressed, and a decrease in crystallinity of the photoelectric conversion film 6 can be suppressed. Therefore, the sensitivity of the photocathode 1 can be further improved.
- the conductive film 3 is titanium. According to this configuration, photoelectrons generated in the photoelectric conversion film 6 can be taken out efficiently.
- Window material 2 is quartz. According to this configuration, since the attenuation of the light L generated when passing through the window material 2 is suppressed, the sensitivity of the photocathode 1 can be further improved.
- the photocathode 1 described above is used in the image intensifier 11 shown in FIG.
- FIG. 3 shows the structure of the image intensifier 11 with the photocathode 1.
- the proximity type image intensifier 11 includes a photoelectric surface 1, a vacuum container 12, a microchannel plate 13, a fluorescent screen 14, and an exit window member 16.
- the photocathode 1 is provided on one end side of the vacuum vessel 12.
- a microchannel plate 13 serving as an electron multiplying unit is provided behind the photocathode 1 in the vacuum vessel 12.
- a fluorescent screen 14 is provided further behind the microchannel plate 13.
- the electrons multiplied by the microchannel plate 13 enter the phosphor screen 14.
- the fluorescent screen 14 converts incident electrons into light. The converted light is emitted to the outside through the emission window member 16.
- the image intensifier 11 includes the photocathode 1 described above, sensitivity in the ultraviolet band can be improved.
- Example 1 In Example 1, the sensitivity of the photocathode 1 was confirmed. As the sensitivity of the photocathode 1, quantum efficiency was adopted. The quantum efficiency is the ratio of the number of photoelectrons to the number of photons incident on the photocathode 1. The quantum efficiency is measured by, for example, a spectral sensitivity measuring device.
- the spectral sensitivity measuring instrument has a light source, a spectroscope that monochromatically measures light to be measured, and a standardized photodetector (for example, a silicon photodiode).
- the photocathode 1 according to Example 1 has the following configuration.
- Example 1 a plurality of photocathodes 1 having the following configuration were produced, and the quantum efficiency of each photocathode 1 was measured.
- Window material Quartz (film thickness 5.94mm)
- Conductive film Ti (0.5 nm film thickness)
- Intermediate film MgF 2 (film thickness 5 nm)
- Photoelectric conversion film CsTe (film thickness 10 nm)
- FIG. 4 shows the relationship between the detection wavelength of the photocathode 1 and the quantum efficiency. The horizontal axis indicates the wavelength, and the vertical axis indicates the quantum efficiency.
- a plurality of graphs G4 show the quantum efficiency of each photocathode 1. As shown in FIG.
- the photocathode 1 has a quantum efficiency of about 2% to 26% in the band A2 from 280 nm to 315 nm. Moreover, it was confirmed that the photocathode 1 has a quantum efficiency of about 20% to 32% in the band A3 from 200 nm to 280 nm. Moreover, it was confirmed that the photocathode has a quantum efficiency of about 20% to 26% at a wavelength of 280 nm.
- Example 2 the influence of the film thickness of the intermediate film 4 on the quantum efficiency was confirmed. Specifically, a plurality of photocathodes 1 that differ only in the film thickness of the intermediate film 4 were produced, and the quantum efficiency of each photocathode 1 was measured.
- the photocathode 1 according to Example 2 has the following configuration.
- Window material Quartz (film thickness 5.94mm)
- Intermediate film MgF 2 (film thickness 50 nm, 10 nm, 5 nm, in other words, film thickness 500 mm, 100 mm, 50 mm)
- Photoelectric conversion film CsTe (film thickness 10 nm)
- Graph G5 is a quantum efficiency of the photocathode 1 in which the thickness of the intermediate film 4 is 50 nm.
- Graph G5b is the quantum efficiency of the photocathode 1 in which the film thickness of the intermediate film 4 is 10 nm.
- Graph G5c is the quantum efficiency of the photocathode 1 in which the film thickness of the intermediate film 4 is 5 nm. According to the graphs G5a, G5b, and G5c, it was found that the magnitude relationship of the quantum efficiency changes depending on the film thickness of the intermediate film 4 in the wavelength band from 200 nm to 280 nm.
- the film thickness of the intermediate film 4 thinner (see plot P5a).
- the thin film thickness is, for example, 5 nm. In other words, the thin film thickness is, for example, 50 mm.
- the thicker film thickness is, for example, 50 nm. In other words, the thick film thickness is, for example, 500 mm.
- Example 3 the influence of the configuration of the conductive film 3 on the quantum efficiency was confirmed. Specifically, a plurality of photocathodes 1 having different materials or structures of the conductive film 3 were produced, and the quantum efficiency of each photocathode 1 was measured.
- the photocathode 1 according to Example 3 has the following configuration.
- Window material Quartz (film thickness 5.94mm)
- Conductive film Ti (film thickness 0.5 nm), Ti (film thickness 2.5 nm), carbon nanotube (film thickness 1 nm), graphene (film thickness 0.335 nm), stripe electrode (film thickness 2.5 nm)
- Intermediate film MgF 2 (film thickness 5 nm)
- Photoelectric conversion film CsTe (film thickness 10 nm)
- FIG. 6 shows the quantum efficiency of the photocathode 1 for a wavelength of 280 nm.
- the vertical axis represents the quantum efficiency of the photocathode 1.
- the horizontal axis indicates the transmittance of the conductive film 3.
- the transmissivity shown on the horizontal axis in FIG. 6 is the measured transmissivity of a test piece in which various conductive films are formed on the window member 2 that is a quartz face plate. This transmittance is measured by measuring with a spectrophotometer or by measuring the transmittance with a spectrophotometer provided with a light source, a spectroscope, and a photodetector.
- a plot P6a is the quantum conversion efficiency when the conductive film 3 is graphene.
- the plot P6b is the quantum conversion efficiency when the conductive film 3 has a stripe electrode structure.
- the plot P6c is the quantum conversion efficiency when the conductive film 3 is Ti (film thickness: 0.5 nm).
- the plot P6d is the quantum conversion efficiency when the conductive film 3 is Ti (film thickness 2.5 nm).
- the plot P6e is the quantum conversion efficiency when the conductive film 3 is a carbon nanotube. As shown in the plots P6a, P6b, P6c, P6d, and P6e, it was found that the quantum efficiency increases as the transmittance of the conductive film 3 increases. In particular, it was found that when the conductive film 3 is graphene, a stripe electrode, or Ti having a film thickness of 0.5 nm, the quantum efficiency at a wavelength of 280 nm can be 20% or more.
- Comparative Example 1 In Comparative Example 1, the influence of the constituent material of the intermediate film 4 on the quantum efficiency was confirmed. Specifically, photocathodes having intermediate films containing oxides were produced, and the quantum efficiency of each photocathode was measured.
- the photocathode according to Comparative Example 1 has the following configuration.
- Window material Quartz (film thickness 5.94mm) Conductive film: Ti (film thickness 2.5 nm), Pt (film thickness 2.5 nm)
- Intermediate film two-layer structure (a first layer: Al 2 O 3, a second layer: ZnO), Al 2 O 3 conductive film is Ti, TiO 2, Al 2 O 3 conductive film is Pt
- Graph G7a shows the quantum efficiency of the photocathode having an interlayer film with a two-layer structure.
- the intermediate film has a first layer made of Al 2 O 3 and a second layer made of ZnO.
- Graph G7b shows the quantum efficiency of the photocathode in which the conductive film is Ti and the intermediate film is Al 2 O 3 .
- Graph G7c shows the quantum efficiency of the photocathode in which the conductive film is Pt and the intermediate film is TiO 2 .
- Graph G7d shows the quantum efficiency of the photocathode in which the conductive film is Pt and the intermediate film is Al 2 O 3 .
- Graph G7e shows intermediate film 4 is the quantum efficiency of the photocathode 1 is MgF 2. As shown in FIG. 7, it was found that the graph G7e shows the highest quantum efficiency in a band extending from 200 nm to 350 nm. Therefore, it was found that the material constituting the intermediate film 4 is preferably fluoride rather than oxide.
- Comparative Example 2 In Comparative Example 2, the influence of the constituent material of the intermediate film 4 on the quantum efficiency was confirmed. Specifically, photocathodes having an intermediate film formed of a fluoride different from MgF 2 were prepared, and the quantum efficiency of each photocathode was measured. Lithium fluoride (LiF) and calcium fluoride (CaF 2 ) were used as fluorides different from MgF 2 . Each photocathode according to Comparative Example 2 has the following configuration.
- FIG. 8 is a graph comparing the quantum efficiency of the photocathode in Comparative Example 2 with the quantum efficiency of the photocathode 1.
- Graph G8a shows the quantum efficiency of photocathode 1 whose intermediate film 4 is LiF.
- Graph G8b shows intermediate film 4 is the quantum efficiency of the photocathode 1 is CaF 2.
- Graph G8c shows intermediate film 4 is the quantum efficiency of the photocathode 1 is MgF 2.
- the graph G8c shows the highest quantum efficiency in a band extending from 200 nm to 350 nm. Therefore, it was found that the intermediate film 4 is most preferably composed of MgF 2 among the fluorides.
- the intermediate film 4 forms a region having a high band gap in the vicinity of the photoelectric conversion film 6. Then, it seems that the quantum efficiency of the photocathode 1 becomes higher as the band gap of the intermediate film 4 is higher.
- the band gap of each material used as the material of the intermediate film 4 and the band gap of MgF 2 used as the material of the intermediate film 4 are as follows.
- FIG. 9 shows the relationship between the band gap and the quantum efficiency.
- the quantum efficiency in FIG. 9 is a value when the detection wavelength is 280 nm.
- the following plots P9a, P9b, P9c, P9d, and P9e correspond to the plots P9a, P9b, P9c, P9d, and P9e in FIG.
- calcium fluoride (CaF) or magnesium fluoride (MgF 2 ) may be used as the material constituting the window material 2.
- a carbon-based material such as graphene and carbon nanotube (CNT) may be used.
- the conductive film 3 may have a stripe structure or a mesh structure, paying attention to light transmittance.
- sodium (Ni), potassium (K), or rubidium (Rb) may be used as the alkali metal contained in the photoelectric conversion film 6.
- the photocathode is provided in the image intensifier.
- the photocathode may be used in an optical device other than the image intensifier.
- the photocathode 1 shown in the above embodiment is provided inside the vacuum vessel, and a dynode or microchannel plate serving as a multiplication unit for multiplying electrons is provided behind the photocathode 1.
- the anode (anode) is provided in a state of being accommodated in the vacuum vessel.
- a predetermined bias voltage is applied to the anode via the lead pin to the photocathode, the electron multiplier, and the anode.
- An output signal from the anode is output to the outside via the lead pin.
- SYMBOLS 1 Photoelectric surface, 2 ... Window material, 3 ... Conductive film, 4 ... Intermediate film, 6 ... Photoelectric conversion film, 11 ... Image intensifier, 12 ... Vacuum container, 13 ... Microchannel plate (electron multiplication means), 14 ... phosphor screen, 16 ... exit window material.
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Abstract
Description
実施例1では、光電面1の感度を確認した。光電面1の感度として、量子効率を採用した。量子効率は、光電面1に入射した光子数に対する光電子の数の比である。量子効率は、例えば、分光感度測定器により測定する。分光感度測定器は、光源と、測定対象光を単色化する分光器と、値付けされた標準の光検出器(例えばシリコンフォトダイオード)とを有する。実施例1に係る光電面1は、下記の構成を有する。実施例1では、下記の構成を有する光電面1を複数作製し、それぞれの光電面1の量子効率を測定した。
窓材 :石英 (膜厚5.94mm)
導電膜 :Ti (膜厚0.5nm)
中間膜 :MgF2(膜厚5nm)
光電変換膜:CsTe(膜厚10nm)
図4は、上記光電面1の検出波長と量子効率との関係を示す。横軸は、波長を示し、縦軸は量子効率を示す。複数のグラフG4は、各光電面1の量子効率を示す。図4に示されるように、光電面1は、280nmから315nmまでの帯域A2において2%から26%程度の量子効率を有することが確認できた。また、光電面1は、200nmから280nmまでの帯域A3において、20%から32%程度の量子効率を有することが確認できた。また、光電面は、280nmの波長において、20%から26%程度の量子効率を有することが確認できた。
実施例2では、量子効率に対する中間膜4の膜厚の影響を確認した。具体的には、中間膜4の膜厚のみが異なる複数の光電面1を作製し、それぞれの光電面1が有する量子効率を測定した。実施例2に係る光電面1は、下記の構成を有する。
窓材 :石英 (膜厚5.94mm)
導電膜 :Ti (膜厚0.5nm)
中間膜 :MgF2(膜厚50nm、10nm、5nm、換言すると膜厚500Å、100Å、50Å)
光電変換膜:CsTe(膜厚10nm)
実施例3では、量子効率に対する導電膜3の構成の影響を確認した。具体的には、導電膜3の材料又は構造が互いに異なる複数の光電面1を作製し、それぞれの光電面1が有する量子効率を測定した。実施例3に係る光電面1は、下記の構成を有する。
窓材 :石英(膜厚5.94mm)
導電膜 :Ti(膜厚0.5nm)、Ti(膜厚2.5nm)、カーボンナノチューブ(膜厚1nm)、グラフェン(膜厚0.335nm)、ストライプ電極(膜厚2.5nm)
中間膜 :MgF2(膜厚5nm)
光電変換膜:CsTe(膜厚10nm)
比較例1では、量子効率に対する中間膜4の構成材料の影響について確認した。具体的には、酸化物を含む中間膜を有する光電面を作製し、それぞれの光電面が有する量子効率を測定した。比較例1に係る光電面は、下記の構成を有する。
窓材 :石英(膜厚5.94mm)
導電膜 :Ti(膜厚2.5nm)、Pt(膜厚2.5nm)
中間膜 :二層構造(第1の層:Al2O3、第2の層:ZnO)、導電膜がTiであるAl2O3、TiO2、導電膜がPtであるAl2O3
光電変換膜:CsTe(膜厚10nm)
図7は、比較例1における光電面の量子効率を、光電面1の量子効率と比較したグラフである。グラフG7aは、二層構造の中間膜を有する光電面の量子効率を示す。中間膜は、Al2O3により構成された第1の層と、ZnOにより構成された第2の層とを有する。グラフG7bは、導電膜がTiであり、中間膜がAl2O3である光電面の量子効率を示す。グラフG7cは、導電膜がPtであり、中間膜がTiO2である光電面の量子効率を示す。グラフG7dは、導電膜がPtであり、中間膜がAl2O3である光電面の量子効率を示す。グラフG7eは、中間膜4がMgF2である光電面1の量子効率を示す。図7に示されるように、200nm以上350nm以下に亘る帯域においてグラフG7eが最も高い量子効率を示すことがわかった。従って、中間膜4を構成する材料は、酸化物よりもフッ化物が好ましいことがわかった。
比較例2では、量子効率に対する中間膜4の構成材料の影響について確認した。具体的には、MgF2とは異なるフッ化物により形成された中間膜を有する光電面を作製し、それぞれの光電面が有する量子効率を測定した。MgF2とは異なるフッ化物として、フッ化リチウム(LiF)、フッ化カルシウム(CaF2)を用いた。比較例2に係る各光電面は、下記の構成を有する。
窓材 :石英(膜厚5.94mm)
導電膜 :Ti(膜厚2.5nm)
中間膜 :LiF(膜厚5nm)、CaF2(膜厚5nm)
光電変換膜:CsTe(膜厚10nm)
図8は、比較例2における光電面の量子効率を、光電面1の量子効率と比較したグラフである。グラフG8aは、中間膜4がLiFである光電面1の量子効率を示す。グラフG8bは、中間膜4がCaF2である光電面1の量子効率を示す。グラフG8cは、中間膜4がMgF2である光電面1の量子効率を示す。図8に示されるように、グラフG8cが200nm以上350nm以下に亘る帯域において最も高い量子効率を示すことがわかった。従って、中間膜4は、フッ化物のうちMgF2により構成することが最も好ましいことがわかった。
MgF2(プロットP9a):11.4eV
LiF(プロットP9b):13.8eV
CaF2(プロットP9c):11.0eV
Al2O3(プロットP9d):7.5eV
TiO2(プロットP9e):3.2eV
Claims (8)
- 積層構造を有する光電面であって、
紫外線を透過する窓材と、
前記窓材に形成され、導電性を有する導電膜と、
前記導電膜に形成され、マグネシウム及びフッ素の化合物を含む中間膜と、
前記中間膜に形成され、テルル及びアルカリ金属を含む光電変換膜と、を備える光電面。 - 前記化合物は、フッ化マグネシウムである、請求項1に記載の光電面。
- 前記アルカリ金属は、セシウムである、請求項1又は2に記載の光電面。
- 前記導電膜は、チタンを含む、請求項1~3の何れか一項に記載の光電面。
- 前記窓材は、石英を含む、請求項1~4の何れか一項に記載の光電面。
- 請求項1~5の何れか一項に記載の光電面が設けられた真空容器を備える光電変換管。
- 請求項1~5の何れか一項に記載の光電面が設けられた真空容器と、
前記真空容器に収容され前記光電変換膜から放出された電子を増倍する電子増倍手段と、
前記電子増倍手段で増倍された電子が入射され、前記電子増倍手段で増倍された前記電子を光に変換する蛍光面と、を備えるイメージインテンシファイア。 - 請求項1~5の何れか一項に記載の光電面が設けられた真空容器と、
前記真空容器に収容され前記光電変換膜から放出された電子を増倍する電子増倍手段と、
前記真空容器の内部に収容され、前記電子増倍手段で増倍された前記電子が入射されるアノードと、を備える光電子増倍管。
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CN201580070708.7A CN107112175B (zh) | 2014-12-26 | 2015-12-15 | 光电面、光电转换管、图像增强器和光电子倍增管 |
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KR1020177019010A KR102582084B1 (ko) | 2014-12-26 | 2015-12-15 | 광전면, 광전 변환관, 이미지 인텐시파이어 및 광전자 증배관 |
US15/538,693 US10559445B2 (en) | 2014-12-26 | 2015-12-15 | Photoelectric surface, photoelectric conversion tube, image intensifier, and photomultiplier tube |
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