WO2017110500A1 - Verre transmettant les infra-rouges - Google Patents

Verre transmettant les infra-rouges Download PDF

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Publication number
WO2017110500A1
WO2017110500A1 PCT/JP2016/086560 JP2016086560W WO2017110500A1 WO 2017110500 A1 WO2017110500 A1 WO 2017110500A1 JP 2016086560 W JP2016086560 W JP 2016086560W WO 2017110500 A1 WO2017110500 A1 WO 2017110500A1
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WO
WIPO (PCT)
Prior art keywords
infrared
glass
present
content
infrared transmitting
Prior art date
Application number
PCT/JP2016/086560
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English (en)
Japanese (ja)
Inventor
佳雅 松下
佐藤　史雄
Original Assignee
日本電気硝子株式会社
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 日本電気硝子株式会社 filed Critical 日本電気硝子株式会社
Publication of WO2017110500A1 publication Critical patent/WO2017110500A1/fr

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Classifications

    • 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
    • C03C3/00—Glass compositions
    • C03C3/32—Non-oxide glass compositions, e.g. binary or ternary halides, sulfides or nitrides of germanium, selenium or tellurium
    • 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
    • C03C4/00—Compositions for glass with special properties
    • C03C4/10—Compositions for glass with special properties for infrared transmitting glass
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements

Definitions

  • the present invention relates to an infrared transmitting glass used for an infrared sensor or the like.
  • In-vehicle night vision and security systems are equipped with infrared sensors that are used to detect living bodies at night. Since the infrared sensor senses infrared rays having a wavelength of about 8 to 14 ⁇ m emitted from a living body, an optical element such as a filter or a lens that transmits infrared rays in the wavelength range is provided in front of the sensor unit.
  • Examples of the material for the optical element as described above include Ge and ZnSe. Since these are crystal bodies, they are inferior in workability and difficult to process into a complicated shape such as an aspherical lens. Therefore, there are problems that it is difficult to mass-produce and it is difficult to reduce the size of the infrared sensor.
  • chalcogenide glass has been proposed as a vitreous material that transmits infrared rays having a wavelength of about 8 to 14 ⁇ m and is relatively easy to process (see, for example, Patent Document 1).
  • Patent Document 1 Since the glass described in Patent Document 1 has a significantly reduced infrared transmittance at a wavelength of 10 ⁇ m or more, the sensitivity to infrared rays emitted from a living body is particularly inferior, and the infrared sensor may not function sufficiently.
  • an object of the present invention is to provide a glass excellent in infrared transmittance and suitable for infrared sensor applications.
  • the infrared transmitting glass of the present invention has a mol% of Ge 0-33% (excluding 0%), Te 11-80%, S 0-80% (excluding 0%), Ga + It is characterized by containing Sn + Ag + Cu + Bi + Sb 0 to 50% and F + Cl + Br + I 0 to 50%.
  • ⁇ + ⁇ + Means the total content of the corresponding components.
  • the infrared transmitting glass of the present invention does not substantially contain Cd, Tl and Pb.
  • the infrared transmission glass of the present invention preferably has an infrared absorption edge wavelength of 20 ⁇ m or more at a thickness of 2 mm.
  • the “infrared absorption edge wavelength” refers to a wavelength at which the light transmittance is 0.5% in an infrared region having a wavelength of 8 ⁇ m or more.
  • the optical element of the present invention is characterized by using the above infrared transmitting glass.
  • the infrared sensor of the present invention is characterized by using the above optical element.
  • the infrared transmitting glass of the present invention is mol%, Ge 0 to 33% (excluding 0%), Te 11 to 80%, S 0 to 80% (excluding 0%), Ga + Sn + Ag + Cu + Bi + Sb 0 to 50 %, And F + Cl + Br + I 0 to 50%.
  • % means “mol%” unless otherwise specified.
  • Ge is an essential component for forming a glass skeleton.
  • the Ge content is 0 to 33% (however, not including 0%), preferably 1 to 32%, more preferably 5 to 31%, and further preferably 10 to 30%. preferable.
  • When there is too little content of Ge it will become difficult to vitrify.
  • the content of Ge is too large, Ge-based crystals are precipitated and it is difficult to transmit infrared rays, and the raw material cost tends to increase.
  • Te which is a chalcogen element, is an essential component that forms a glass skeleton.
  • the Te content is 11 to 80%, preferably 20 to 79%, and more preferably 30 to 78%. If the Te content is too small, it will be difficult to vitrify, while if it is too much, Te-based crystals will precipitate and will not be vitrified, and as a result it will be difficult to transmit infrared rays.
  • S which is a chalcogenide element
  • S is an essential component that enhances thermal stability (stability of vitrification).
  • the S content is 0 to 80% (excluding 0%), preferably 1 to 60%, more preferably 2 to 50%, and further preferably 3 to 40%. preferable.
  • the content of S is too large, the infrared absorption edge wavelength is shifted to the short wavelength side, and the infrared transmission characteristics are likely to deteriorate.
  • Ga, Sn, Ag, Cu, Bi, and Sb are components that increase the thermal stability of the glass without deteriorating the infrared transmission characteristics.
  • the content of Ga + Sn + Ag + Cu + Bi + Sb is 0 to 50% (excluding 0%), preferably 1 to 40%, more preferably 2 to 30%, and further preferably 3 to 25%. It is preferably 5 to 20%, particularly preferably.
  • the content of each component of Ga, Sn, Ag, Cu, Bi, and Sb is 0 to 50%, preferably 0 to 50% (however, not including 0%), preferably 1 to 40%. More preferably, it is 2 to 30%, more preferably 3 to 25%, and most preferably 5 to 20%.
  • Ag, Sn, or Cu is preferably used in that the effect of increasing the thermal stability of the glass is particularly great.
  • F, Cl, Br, and I are also components that increase the thermal stability of the glass.
  • the content of F, Cl, Br, I is 0 to 50%, preferably 1 to 40%, more preferably 1 to 30%, still more preferably 1 to 25%, 1 to 20% is particularly preferable. When there is too much content of F + Cl + Br + I, it will become difficult to vitrify and a weather resistance will fall easily.
  • the content of each component of F, Cl, Br, and I is 0 to 50%, preferably 1 to 40%, more preferably 1 to 30%, and more preferably 1 to 25%. More preferably, it is more preferably 1 to 20%. Among them, it is preferable to use I because elemental raw materials can be used and the effect of enhancing the thermal stability of the glass is particularly great.
  • the infrared transmitting glass of the present invention may contain the following components.
  • Zn, In, and P are components that widen the vitrification range and increase the thermal stability of the glass. Their contents are each preferably 0 to 20%, more preferably 0.5 to 10%. When there is too much content of these components, it will become difficult to vitrify.
  • Se and As are components that widen the vitrification range and increase the thermal stability of the glass. Their contents are each preferably 0 to 10%, more preferably 0.5 to 5%. However, since these substances are toxic, it is preferable not to contain them from the viewpoint of reducing the influence on the environment and the human body.
  • the infrared transmitting glass of the present invention does not substantially contain Cd, Tl and Pb which are toxic substances. In this way, the environmental impact can be minimized.
  • substantially does not contain means that the material is not intentionally contained in the raw material, and does not exclude mixing of impurity levels. Objectively, the content of each component indicates less than 0.1%.
  • the infrared transmitting glass of the present invention is excellent in infrared transmittance at a wavelength of about 8 to 18 ⁇ m.
  • an infrared absorption edge wavelength can be mentioned. It can be judged that the greater the infrared absorption edge wavelength, the better the infrared transparency.
  • the infrared absorption edge wavelength at a thickness of 2 mm of the infrared transmitting glass of the present invention is preferably 20 ⁇ m or more, and more preferably 21 ⁇ m or more.
  • the infrared transmitting glass of the present invention can be produced, for example, as follows. First, raw materials are prepared so as to have a desired composition. The raw material is put into a quartz glass ampule that has been evacuated while being heated, and sealed with an oxygen burner while being evacuated. The sealed quartz glass ampoule is held at about 650 to 800 ° C. for 6 to 12 hours, and then rapidly cooled to room temperature to obtain the infrared transmitting glass of the present invention.
  • raw materials elemental raw materials (Ge, Te, S, Ag, I, etc.) may be used, and compound raw materials (GeTe 4 , GeS 2 , AgI, etc.) may be used. These can also be used in combination.
  • Tables 1 and 2 show examples of the present invention and comparative examples, respectively.
  • Each sample was prepared as follows. The raw materials were mixed so that the glass composition described in Tables 1 and 2 was obtained, to obtain a raw material batch. The quartz glass ampule washed with pure water was evacuated while being heated, and then a raw material batch was placed, and the quartz glass ampule was sealed with an oxygen burner while evacuating.
  • the sealed quartz glass ampule was heated to 650-800 ° C. at a rate of 10-20 ° C./hour in a melting furnace and then held for 6-12 hours. During the holding time, the quartz glass ampoule was turned upside down every 2 hours to stir the melt. Thereafter, the quartz glass ampule was taken out of the melting furnace and rapidly cooled to room temperature to obtain a sample.
  • the obtained sample was subjected to X-ray diffraction, and it was confirmed from the diffraction spectrum whether it was vitrified.
  • those that are vitrified are indicated as “ ⁇ ”, and those that are not vitrified are indicated as “x”.
  • the light transmittance in thickness 2mm was measured about each sample, and the infrared absorption edge wavelength was measured.
  • the infrared transmitting glass of the present invention is suitable as an optical element such as a cover member for protecting the sensor portion of the infrared sensor and a lens for condensing infrared light on the sensor portion.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Glass Compositions (AREA)

Abstract

La présente invention concerne un verre qui présente une excellente transmittance des infra-rouges et qui est approprié pour des applications de détecteur à infra-rouges. Ce verre transmettant les infra-rouges est caractérisé en ce qu'il comprend, en % en moles, 0 à 33 % (à l'exclusion de 0 %) de Ge, 11 à 80 % de Te, 0 à 80 % (à l'exclusion de 0 %) de S, 0 à 50 % de Ga + Sn + Ag + Cu + Bi + Sb, et 0 à 50 % de F + Cl + Br + I.
PCT/JP2016/086560 2015-12-25 2016-12-08 Verre transmettant les infra-rouges WO2017110500A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015-253111 2015-12-25
JP2015253111A JP6804030B2 (ja) 2015-12-25 2015-12-25 赤外線透過ガラス

Publications (1)

Publication Number Publication Date
WO2017110500A1 true WO2017110500A1 (fr) 2017-06-29

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WO (1) WO2017110500A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020066928A1 (fr) * 2018-09-27 2020-04-02 日本電気硝子株式会社 Verre à transmission dans l'infrarouge
WO2020105719A1 (fr) * 2018-11-21 2020-05-28 日本電気硝子株式会社 Lentille en verre de chalcogénure
CN111491903A (zh) * 2018-03-28 2020-08-04 日本电气硝子株式会社 硫属化合物玻璃材料
CN111491904A (zh) * 2018-02-28 2020-08-04 日本电气硝子株式会社 红外线透射玻璃
CN113735440A (zh) * 2021-08-16 2021-12-03 宁波阳光和谱光电科技有限公司 Ge基硫系玻璃及其制备方法
EP3932883A4 (fr) * 2019-02-28 2022-12-07 Nippon Electric Glass Co., Ltd. Verre transmettant les infrarouges
JP2022186810A (ja) * 2017-09-12 2022-12-15 日本電気硝子株式会社 カルコゲナイドガラス材
WO2023095900A1 (fr) * 2021-11-29 2023-06-01 日本電気硝子株式会社 Verre transmettant les infrarouges
WO2023243407A1 (fr) * 2022-06-17 2023-12-21 日本電気硝子株式会社 Verre de transmission de rayons infrarouges

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113302165B (zh) * 2019-02-28 2023-08-01 日本电气硝子株式会社 红外线透射玻璃

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51136288A (en) * 1975-05-21 1976-11-25 Nippon Telegr & Teleph Corp <Ntt> Photo etching using non-crystalline carchogenide glass thin film
JPS51135913A (en) * 1975-05-21 1976-11-25 Nippon Telegraph & Telephone Membrane for photoetching
JPH04342438A (ja) * 1991-05-21 1992-11-27 Matsushita Electric Ind Co Ltd 赤外線透過性レンズおよびそれを用いた赤外線検出センサ
JPH0524879A (ja) * 1991-07-24 1993-02-02 Matsushita Electric Ind Co Ltd 赤外線透過性ガラスの製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51136288A (en) * 1975-05-21 1976-11-25 Nippon Telegr & Teleph Corp <Ntt> Photo etching using non-crystalline carchogenide glass thin film
JPS51135913A (en) * 1975-05-21 1976-11-25 Nippon Telegraph & Telephone Membrane for photoetching
JPH04342438A (ja) * 1991-05-21 1992-11-27 Matsushita Electric Ind Co Ltd 赤外線透過性レンズおよびそれを用いた赤外線検出センサ
JPH0524879A (ja) * 1991-07-24 1993-02-02 Matsushita Electric Ind Co Ltd 赤外線透過性ガラスの製造方法

Non-Patent Citations (3)

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Title
FAGEN E.A.: "OPTICAL PROPERTIES OF AMORPHOUS CHALCOGENIDE ALLOY FILMS", JOURNAL OF NON- CRYSTALLINE SOLIDS, vol. 2, 1970, pages 18 0 - 191, XP024063352 *
JOHANSON ROBERT E.: "UNIVERSAL BEHAVIOR OF THE NORMALIZED PHOTOCONDUCTIVITY AT LOW TEMPERATURES IN AMORPHOUS SEMICONDUCTORS", JOURNAL OF NON-CRYSTALLINE SOLIDS, vol. 114, 1989, pages 274 - 276, XP024066083 *
PAMUKCHIEVA.V: "Evaluation of basic physical parameters of quaternary Ge-Sb-(S,Te) chalcogenide glasses", JOURNAL OF NON- CRVSTALLINE SOLIDS., vol. 355, 24 September 2009 (2009-09-24), pages 2485 - 2490, XP026722334 *

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022186810A (ja) * 2017-09-12 2022-12-15 日本電気硝子株式会社 カルコゲナイドガラス材
JP7519019B2 (ja) 2017-09-12 2024-07-19 日本電気硝子株式会社 カルコゲナイドガラス材
CN111491904A (zh) * 2018-02-28 2020-08-04 日本电气硝子株式会社 红外线透射玻璃
US11919806B2 (en) 2018-02-28 2024-03-05 Nippon Electric Glass Co., Ltd. Infrared transmitting glass
CN111491903A (zh) * 2018-03-28 2020-08-04 日本电气硝子株式会社 硫属化合物玻璃材料
JP7472793B2 (ja) 2018-09-27 2024-04-23 日本電気硝子株式会社 赤外線透過ガラス
JPWO2020066928A1 (ja) * 2018-09-27 2021-09-02 日本電気硝子株式会社 赤外線透過ガラス
WO2020066928A1 (fr) * 2018-09-27 2020-04-02 日本電気硝子株式会社 Verre à transmission dans l'infrarouge
WO2020105719A1 (fr) * 2018-11-21 2020-05-28 日本電気硝子株式会社 Lentille en verre de chalcogénure
JPWO2020105719A1 (ja) * 2018-11-21 2021-10-14 日本電気硝子株式会社 カルコゲナイドガラスレンズ
JP7495667B2 (ja) 2018-11-21 2024-06-05 日本電気硝子株式会社 カルコゲナイドガラスレンズ
EP3932883A4 (fr) * 2019-02-28 2022-12-07 Nippon Electric Glass Co., Ltd. Verre transmettant les infrarouges
CN113735440A (zh) * 2021-08-16 2021-12-03 宁波阳光和谱光电科技有限公司 Ge基硫系玻璃及其制备方法
WO2023095900A1 (fr) * 2021-11-29 2023-06-01 日本電気硝子株式会社 Verre transmettant les infrarouges
WO2023243407A1 (fr) * 2022-06-17 2023-12-21 日本電気硝子株式会社 Verre de transmission de rayons infrarouges

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JP6804030B2 (ja) 2020-12-23
JP2017114733A (ja) 2017-06-29

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