WO2003023338A1 - Element de conversion visible par infrarouge et detecteur de rayonnement infrarouge - Google Patents

Element de conversion visible par infrarouge et detecteur de rayonnement infrarouge Download PDF

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Publication number
WO2003023338A1
WO2003023338A1 PCT/JP2002/009232 JP0209232W WO03023338A1 WO 2003023338 A1 WO2003023338 A1 WO 2003023338A1 JP 0209232 W JP0209232 W JP 0209232W WO 03023338 A1 WO03023338 A1 WO 03023338A1
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WO
WIPO (PCT)
Prior art keywords
infrared
light
visible
visible light
phosphor layer
Prior art date
Application number
PCT/JP2002/009232
Other languages
English (en)
Japanese (ja)
Inventor
Itaru Mizuno
Minoru Kondo
Atsushi Onoda
Kyozo Mizutani
Original Assignee
Hamamatsu Photonics K.K.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hamamatsu Photonics K.K. filed Critical Hamamatsu Photonics K.K.
Publication of WO2003023338A1 publication Critical patent/WO2003023338A1/fr

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J1/00—Photometry, e.g. photographic exposure meter
    • G01J1/58—Photometry, e.g. photographic exposure meter using luminescence generated by light
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2/00—Demodulating light; Transferring the modulation of modulated light; Frequency-changing of light
    • G02F2/02—Frequency-changing of light, e.g. by quantum counters
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components 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
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures
    • H01L27/14665—Imagers using a photoconductor layer
    • H01L27/14669—Infrared imagers

Definitions

  • the present invention relates to an infrared-visible conversion member and an infrared detector, and more particularly, to an infrared-visible conversion member that converts infrared light into visible light using a phosphor, and an infrared detection device using the member. Things.
  • an inorganic material containing a specific rare earth element has the property of converting infrared light into ultraviolet light by multiphoton excitation of rare earth ions, and is relatively inexpensive.
  • Japanese Unexamined Patent Application Publication No. Hei 6 — 256661 Japanese Unexamined Patent Application Publication No. 6_1-25050, Japanese Unexamined Patent Application Publication No. 6-247 741, Japanese Unexamined Patent Application Publication No. — No. 2 9 8 1 9 and Tokuhei Hei 8 — 6 9 0 25).
  • the present invention has been made in view of the above-mentioned problems of the related art, and has a sufficiently high visible light emission intensity and a high resolution when converting infrared light into visible light, and is an inexpensive infrared-visual conversion member. It is an object of the present invention to provide a sensitive and inexpensive infrared detector.
  • a first infrared-visible conversion member of the present invention comprises: an infrared-visible conversion member disposed on a light receiving surface of a photodetector having sensitivity to visible light; A substrate which is disposed on a surface and has transparency to visible light; and an upcoming phosphor which is disposed on the substrate and converts infrared light into visible light and has a film thickness of 5 to 12 And a phosphor layer having a thickness of 0 ⁇ m.
  • the first infrared-visible conversion member of the present invention when the phosphor layer is irradiated with infrared light, infrared rays are absorbed by an infrared exci- table phosphor (IEP) and visible light is re-emitted. .
  • IEP infrared exci- table phosphor
  • the film thickness of the phosphor layer to 5 to 120 tm, it is possible to achieve both a high level of visible light emission intensity and high resolution. Therefore, by arranging the first infrared-visible conversion member such that the side closer to the light receiving surface of the photodetector is the substrate and the far side is the phosphor layer, the visible light converted from the infrared light is converted to the substrate. Since the image is transmitted to the light receiving surface of the photodetector via the optical sensor and the image of the visible light is detected with high sensitivity and high resolution, an excellent infrared detecting element can be realized.
  • the first infrared-visible conversion member of the present invention preferably further includes a visible light shielding layer that transmits infrared light and reflects or absorbs visible light, on the phosphor layer. This prevents visible light from entering the phosphor layer and allows infrared light to selectively enter the phosphor layer. As a result, the phosphor layer Since the visible light is substantially only the visible light emitted from the up-conversion phosphor, the resolution of the image detected by the photodetector can be improved.
  • the first infrared-visible conversion member of the present invention is formed by integrating the substrate in a state where a plurality of optical fibers are bundled, and a plurality of cores for transmitting visible light incident from the phosphor layer.
  • the fiber optic plate has a lower refractive index than the core, and has a cladding covering each outer peripheral portion of the core.
  • the average particle size of the gap-compared phosphor is 1 Z 2 or less of the distance between adjacent cores. It is preferred that As a result, when the visible light from the up-conversion phosphor enters a predetermined core, the visible light is more reliably prevented from being incident on another core adjacent to the core. The sensitivity at the time of detection with a detector can be improved.
  • the first infrared detection device of the present invention includes a photodetector having sensitivity to visible light, and the first infrared-visible conversion device of the present invention arranged on a light receiving surface of the photodetector. And a member.
  • the first infrared detection device of the present invention by arranging the first infrared-visible conversion member of the present invention on the light-receiving surface of the photodetector, the first infrared-visible conversion member of the present invention can be used to convert infrared light into visible light. Both the light emission intensity and the resolution are compatible at a high level, and it is possible to detect an image by the converted visible light with high sensitivity and high resolution.
  • the second infrared-visible conversion member of the present invention includes a substrate having transparency to infrared light, and an up-conversion member disposed on the substrate for converting infrared light into visible light.
  • the second infrared-visible conversion member of the present invention by setting the thickness of the phosphor layer containing the up-compensation phosphor to 5 to 120 ⁇ , both the visible light emission intensity and the resolution are improved. It is the same as the first infrared-visible conversion member described above in that the compatibility can be achieved at a high level. Furthermore, the second infrared-visible conversion member is arranged such that the side closer to the light receiving surface of the photodetector is the phosphor layer and the far side is the substrate, so that the infrared light transmitted through the substrate is converted into visible light by the phosphor layer.
  • the light After being converted to the light, the light is directly transmitted to the light receiving surface of the photodetector, so that deterioration of the image due to visible light can be sufficiently prevented. Further, since the substrate prevents the phosphor layer from being damaged, the above-mentioned excellent characteristics can be stably obtained over a long period of time.
  • the infrared-visible conversion member of the present invention preferably further includes, on the phosphor layer, a visible light shielding layer that transmits infrared light and reflects or absorbs visible light. This prevents visible light from entering the phosphor layer and allows infrared light to selectively enter the phosphor layer.
  • the visible light from the phosphor layer is substantially only the visible light emitted from the up-compared phosphor, so that the resolution of the image detected by the photodetector can be improved.
  • the infrared detection device of the present invention comprises: a light detector having sensitivity to visible light;
  • the infrared detector of the present invention by arranging the second infrared-visible conversion member of the present invention on the light receiving surface of the light detector, the visible light emission intensity and the infrared light conversion at the time of conversion from infrared light to visible light are improved. Both resolutions are compatible at a high level and can be converted It is possible to detect an image by visual light with high sensitivity and high resolution.
  • FIG. 1 is a schematic configuration diagram showing an infrared detector according to the first embodiment.
  • FIG. 2 is a graph showing the correlation between the thickness of the phosphor layer and the light intensity.
  • FIG. 3 is a graph showing the correlation between the thickness of the phosphor layer and the resolution.
  • FIG. 4 is a graph showing the correlation between the thickness of the phosphor layer and the relative luminance.
  • Fig. 5 is a graph showing the infrared absorption spectrum of water glass.
  • FIG. 6 is a schematic sectional view showing an example of a fiber optic plate.
  • FIG. 7 is a schematic configuration diagram showing an infrared detector according to the second embodiment.
  • FIG. 8 is a schematic sectional view showing an infrared-visible conversion member according to the third embodiment.
  • FIG. 1 is a schematic configuration diagram showing a first embodiment according to the infrared-visible conversion member of the present invention.
  • Fig. 1 shows an infrared detector equipped with a CCD image sensor as an image sensor.
  • An infrared-visible conversion member 2 a is arranged on the light receiving surface of the light of the CCD image sensor 1.
  • the driver 5 is electrically connected to the CCD image sensor 1.
  • the infrared-visible conversion member 2 a is obtained by laminating a phosphor layer 3 containing an upcomparation phosphor on a fiber optic plate (FOP) 4.
  • the thickness of the phosphor layer 3 is set in the range of 5 to 12.
  • the phosphor layer 3 is disposed farther from the light receiving surface of the CCD image sensor 1 and the FOP 4 is disposed closer to the light receiving surface.
  • the up-conversion phosphor contained in the phosphor layer 3 absorbs infrared light and re-emits visible light. This conversion from infrared light to visible light does not require pre-excitation.
  • Such up-conversion phosphors include, for example, rare earth elements or compounds thereof, more specifically, erbium (Er), yttrium (Y), ytterbium (Yb), and dysprosium.
  • Dr thulium
  • Sm samarium
  • inorganic materials containing these halides fluoride, chloride.
  • infrared light of a specific wavelength eg, 1.5 m
  • visible light of a specific wavelength eg, 550 nm, 660 nm.
  • One of the above up-conversion phosphors may be used alone, or two or more may be used in combination.
  • the correlation between the thickness of the phosphor layer 3 and the visible light emission intensity is shown in Fig. 2
  • the correlation between the thickness of the phosphor layer 3 and the resolution is shown in Fig. 3
  • the correlation between the thickness of the phosphor layer 3 and the relative luminance is shown.
  • the correlation is shown in FIG.
  • the visible light emission intensity and the resolution show different dependencies on the thickness of the phosphor layer 3.
  • both the visible light emission intensity and the resolution can be compatible at a high level.
  • a sufficiently high relative luminance can be achieved as shown in FIG.
  • the thickness of the phosphor layer 3 exceeds 120 ⁇ m, at least one of the visible light emission intensity and the resolution becomes insufficient, while the thickness of the phosphor layer 3 is less than 5 ⁇ m In the case of (1), it becomes difficult to form a uniform phosphor layer, and in any case, the above effects cannot be obtained.
  • the phosphor layer 3 can be formed by, for example, a centrifugal sedimentation method.
  • a predetermined amount of the fine particles of the up-conversion phosphor corresponding to the thickness of the phosphor layer 3 is added to a water glass solution to form a suspension, and this suspension is placed on a predetermined surface of the FOP 4. Apply. Sedimentation of the up-conversion phosphor in the suspension After being deposited on the FOP 4, the phosphor layer 3 is obtained by sucking and drying the water glass solution by suction or the like.
  • the phosphor layer 3 thus obtained may contain water glass.
  • Figure 5 shows the infrared absorption spectrum of water glass. As shown in the figure, water glass shows almost no absorptivity to infrared light, so that it can be used as a binder for binding the up-compensation phosphor.
  • the binder of the phosphor layer 3 is not particularly limited as long as it transmits infrared light, and an organic binder or the like may be used in addition to the water glass.
  • the visible light from the phosphor layer 3 is transmitted to the CCD image sensor 1 by the FOP4.
  • FIG. 6 is a cross-sectional view of the FOP 4 perpendicular to the optical path direction.
  • the FOP 4 includes a plurality of cores 11 made of a core glass having a high refractive index, a clad 12 made of a clad glass having a lower refractive index than the core glass, and covering each outer peripheral portion of the core 11, An absorber 13 made of an absorber glass exhibiting absorptivity to visible light and disposed between the cores 11.
  • the visible light that has entered the FOP 4 repeats total reflection within the core 11 and is transmitted from the light receiving surface to the emission surface. At this time, light (stray light) leaking from the core 11 without total reflection may be generated. However, such stray light is absorbed by the absorber 13 to prevent the stray light from entering the other cores 2. Thus, the FOP 4 allows the visible light from the phosphor layer 3 to be transmitted to the CCD image sensor 1 with a sufficiently high resolution.
  • the average particle diameter of the up-compensation phosphor contained in the phosphor layer 3 is not more than ⁇ of the distance d between the adjacent cores 11.
  • the average particle size of the up-conversion phosphor is preferably 3 ⁇ m or less (more preferably, 2 ⁇ m or less).
  • the average particle size of the upcomparation phosphor is If it exceeds 1/2, when visible light from the upcoming phosphor enters the predetermined core, the visible light is also likely to enter other cores adjacent to the core, and the CCD image sensor The resolution of the image detected in step 1 tends to decrease.
  • the up-conversion phosphor absorbs infrared light and becomes visible. When light is re-emitted, both visible light emission intensity and resolution can be compatible at a high level. Further, by transmitting the visible light from the infrared-visible conversion member 2a to the CCD image sensor 1 by the FOP 4, the resolution of the image by the visible light is maintained at a high level. Can be detected with high sensitivity.
  • the infrared detector of the first embodiment when the thickness of the phosphor layer 3 is 5 ⁇ , and infrared light having an intensity of 156.7 W is incident thereon, a peak of 797 counts is obtained. Was detected (gamma value: 1.4). This result indicates that the infrared detector has sufficient sensitivity for detecting the position of the laser beam.
  • the apparatus shown in FIG. 1 has a CCD image sensor 1 as an image sensor, but a MOS image sensor may be used instead of the CCD image sensor 1. Thereby, an image with visible light from the infrared-visible detection member 2 can be detected with high sensitivity.
  • FIG. 7 is a schematic configuration diagram showing a second embodiment according to the present invention.
  • Figure 7 shows an infrared detector equipped with a Si photodiode as a photodetector.
  • the phosphor layer 3 is placed on the light receiving surface of the Si photodiode 6 and a glass plate 7 that transmits infrared light.
  • the infrared-visible conversion member 2b is formed by laminating in order, and the thickness of the phosphor layer 3 is set within a range of 5 to 120 ⁇ .
  • the up-conversion phosphor absorbs infrared light and re-emits visible light.
  • both the visible light emission intensity and the resolution can be compatible at a high level, and the visible light can be detected with high sensitivity by the S 1 photodiode 6.
  • the infrared light transmitted through the glass plate 7 is After being converted into visible light by the light source, the light is directly transmitted to the light receiving surface of the Si photodiode 6, so that light attenuation can be sufficiently prevented.
  • the glass plate 7 prevents the phosphor layer 3 from being damaged, the above-mentioned excellent characteristics can be stably obtained over a long period of time.
  • the second embodiment is not limited to this.
  • a CCD image sensor or a MOS type image sensor may be used as an image pickup device instead of the Si photodiode 6 which is a photodetector.
  • the deterioration of the resolution can be prevented by disposing the phosphor layer 3 on the light receiving surface of the image sensor, whereby the image by the visible light from the infrared-visible conversion member 2 can be highly sensitive. Can be detected.
  • FIG. 8 is a schematic configuration diagram showing a second embodiment according to the present invention.
  • a phosphor layer 3 having a thickness of 5 to 12 ⁇ m and a visible light shielding layer 8 are laminated in this order on the FOP 4 to constitute an infrared-visible conversion member 2.
  • Visible light blocking layer 8 is composed of a S i O 2 layer and T i 0 2 layers are stacked in a plurality alternately on the planarization layer 9 formed on the phosphor layer 3 dielectric multilayer reflection film, a fluorescent Approximately 90% of infrared light incident on the body layer 3 is transmitted, while 90% or more of visible light incident on the phosphor layer 3 is reflected.
  • a dielectric multilayer reflective film formed on a flat substrate that absorbs visible light and transmits infrared light may be bonded to the phosphor layer 3.
  • the up-compensation phosphor absorbs infrared light and regenerates visible light. It is the same as in the first and second embodiments that both the emission intensity of visible light and the resolution can be compatible at a high level when emitting.
  • a visible light shielding layer 8 is further provided on the phosphor layer 3 to suppress the incidence of visible light on the phosphor layer and to select infrared light for the phosphor layer 3. Since it is possible to make the incident light incident, the resolution of the image by the visible light converted from the infrared light can be further improved.
  • the third embodiment is not limited to this.
  • the visible light shielding layer 8 only needs to reflect or absorb visible light and transmit infrared light.
  • the visible light shielding layer 8 absorbs visible light and transmits infrared light.
  • An Si substrate can also be used.
  • the infrared-visible conversion member 2 is subjected to force coupling so that the surface on the FOP 4 side is on the light receiving surface of the image sensor. By doing so, an infrared detector can be obtained.
  • any of a CCD image sensor, a MOS image sensor, and a Si photodiode may be used as such an image sensor.
  • Industrial applicability As described above, according to the infrared-visible conversion member of the present invention, by setting the thickness of the phosphor layer to 5 to 120 m, both the visible light emission intensity and the resolution can be achieved at a high level. Becomes possible.
  • the infrared-visible conversion member of the present invention on the light-receiving surface of a photodetector having sensitivity to visible light, an image formed by the visible light converted from the infrared light has high sensitivity and high resolution Therefore, an excellent infrared detecting element can be realized.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Photometry And Measurement Of Optical Pulse Characteristics (AREA)
  • Optical Modulation, Optical Deflection, Nonlinear Optics, Optical Demodulation, Optical Logic Elements (AREA)
  • Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)
  • Transforming Light Signals Into Electric Signals (AREA)

Abstract

L'invention concerne un élément de conversion visible par infrarouge disposé sur la surface réceptrice de lumière d'un photodétecteur possédant une sensibilité à une lumière visible, et comprenant un substrat disposé sur une surface recevant la lumière visible et étant transparent à cette lumière, ainsi qu'une couche phosphorescente disposée sur le substrat, contenant un phosphore de conversion-élévation destiné à convertir un rayon infrarouge en une lumière visible et possédant une épaisseur de film de 5-120 νm. Selon l'invention, un compromis de haut niveau peut être effectué entre l'intensité et la résolution d'émission de lumière visible, et un excellent élément de détection de rayonnement infrarouge peut être mis en oeuvre du fait qu'une image convertie par un rayon infrarouge par une lumière visible peut être détectée avec une sensibilité et une résolution élevées.
PCT/JP2002/009232 2001-09-10 2002-09-10 Element de conversion visible par infrarouge et detecteur de rayonnement infrarouge WO2003023338A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2001-274002 2001-09-10
JP2001274002A JP2003083809A (ja) 2001-09-10 2001-09-10 赤外可視変換部材及び赤外線検出装置。

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8018442B2 (en) 2008-09-22 2011-09-13 Microsoft Corporation Calibration of an optical touch-sensitive display device
JP2014522578A (ja) * 2011-06-06 2014-09-04 ユニバーシティー オブ フロリダ リサーチ ファウンデーション，インコーポレイテッド Ｃｍｏｓ画像センサー内蔵ｉｒアップコンバージョン装置を組み込んだ赤外線撮像装置

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SG175565A1 (en) 2006-09-29 2011-11-28 Univ Florida Method and apparatus for infrared detection and display
JP5778261B2 (ja) 2010-05-24 2015-09-16 ユニバーシティ オブ フロリダ リサーチ ファウンデーション，インク．Ｕｎｉｖｅｒｓｉｔｙ Ｏｆ Ｆｌｏｒｉｄａ Ｒｅｓｅａｔｃｈ Ｆｏｕｎｄａｔｉｏｎ，Ｉｎｃ． 赤外光アップコンバージョンデバイス上に電荷遮断層を設けるための方法および装置
RU2013158845A (ru) * 2011-06-06 2015-07-20 Юниверсити Оф Флорида Рисеч Фаундэйшн, Инк. Прозрачное устройство преобразования инфракрасного излучения в видимое излучение с повышением частоты
RU2014102650A (ru) 2011-06-30 2015-08-10 Юниверсити Оф Флорида Рисеч Фаундэйшн, Инк. Усиливающий инфракрасный фотодетектор и его применение для обнаружения ик-излучения
KR20180018660A (ko) 2015-06-11 2018-02-21 유니버시티 오브 플로리다 리서치 파운데이션, 인코포레이티드 단분산, ir-흡수 나노입자, 및 관련 방법 및 장치
WO2017154444A1 (fr) * 2016-03-09 2017-09-14 ソニー株式会社 Élément de conversion photoélectrique et dispositif de capture d'image

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57156528A (en) * 1981-03-22 1982-09-27 Nec Corp Image detector using infrared rays
JPH0280928A (ja) * 1988-09-16 1990-03-22 Seiko Instr Inc 赤外線イメージセンサ
JPH083550A (ja) * 1994-06-15 1996-01-09 Mitsubishi Materials Corp 強い発光輝度を示す赤外線感知透明膜形成用塗料

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57156528A (en) * 1981-03-22 1982-09-27 Nec Corp Image detector using infrared rays
JPH0280928A (ja) * 1988-09-16 1990-03-22 Seiko Instr Inc 赤外線イメージセンサ
JPH083550A (ja) * 1994-06-15 1996-01-09 Mitsubishi Materials Corp 強い発光輝度を示す赤外線感知透明膜形成用塗料

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8018442B2 (en) 2008-09-22 2011-09-13 Microsoft Corporation Calibration of an optical touch-sensitive display device
JP2014522578A (ja) * 2011-06-06 2014-09-04 ユニバーシティー オブ フロリダ リサーチ ファウンデーション，インコーポレイテッド Ｃｍｏｓ画像センサー内蔵ｉｒアップコンバージョン装置を組み込んだ赤外線撮像装置

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