WO2009145578A2 - Optical hydrogen sensor - Google Patents

Optical hydrogen sensor Download PDF

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Publication number
WO2009145578A2
WO2009145578A2 PCT/KR2009/002849 KR2009002849W WO2009145578A2 WO 2009145578 A2 WO2009145578 A2 WO 2009145578A2 KR 2009002849 W KR2009002849 W KR 2009002849W WO 2009145578 A2 WO2009145578 A2 WO 2009145578A2
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WO
WIPO (PCT)
Prior art keywords
optical
hydrogen
light
optical sensor
oxide
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PCT/KR2009/002849
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French (fr)
Korean (ko)
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WO2009145578A3 (en
Inventor
정현식
이세희
심재영
이재동
진정모
Original Assignee
서강대학교 산학협력단
동아공업 주식회사
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Publication of WO2009145578A2 publication Critical patent/WO2009145578A2/en
Publication of WO2009145578A3 publication Critical patent/WO2009145578A3/en

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
    • G01N21/783—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour for analysing gases
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01B—MEASURING LENGTH, THICKNESS OR SIMILAR LINEAR DIMENSIONS; MEASURING ANGLES; MEASURING AREAS; MEASURING IRREGULARITIES OF SURFACES OR CONTOURS
    • G01B11/00—Measuring arrangements characterised by the use of optical techniques
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/01—Arrangements or apparatus for facilitating the optical investigation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J3/00—Details of electron-optical or ion-optical arrangements or of ion traps common to two or more basic types of discharge tubes or lamps
    • H01J3/14—Arrangements for focusing or reflecting ray or beam

Definitions

  • the present invention relates to a hydrogen optical sensor.
  • Hydrogen energy a potent alternative energy, is at risk of explosion at concentrations of more than 4% in the air, so a hydrogen sensor that detects a leak of hydrogen is essential for the safe use of hydrogen energy.
  • Hydrogen sensors can be classified into process sensors and leak detection sensors according to their use.
  • the leak detection sensors can be classified into a leak detection sensor that detects a small amount of hydrogen leakage and a safety sensor that detects a leak of hydrogen in a space where hydrogen leakage is expected.
  • the safety sensor maintains a stable state without reacting with gases other than hydrogen in the air, and can immediately detect hydrogen leakage.
  • Conventional hydrogen sensor is similar to an electrical sensor manufactured by using a property of changing the resistance of hydrogen when it comes into contact with the hydrogen sensor material. It can be classified into an optical sensor that detects hydrogen by the difference in intensity of reflected light.
  • the optical sensor divides the semiconductor laser light having a wavelength of 632 nm into an optical splitter and connects the optical signal to the sensor signal and the other to the sensor signal.
  • the color of the sensor thin film is changed, and the degree of reflection of the laser light is changed.
  • the intensity of the light reflected by the photodiode is measured, and the signal is compared with a reference signal to detect hydrogen.
  • the equalization principle of a conventional hydrogen photoelectric sensor is as follows: Light generated from the light source 133 is incident to the light splitter 132 that passes through half of the incident light and reflects half of the incident light. One of the beams separated and separated by a beam splitter is used as a reference signal (reference signal), and the other is a hydrogen sensor thin film of the sensing modules 120 through the optical fiber 150. It moves to the gas-colored thin film 111. When the gas-colored thin film is exposed to hydrogen, the color of the thin film becomes dark due to the influence of tungsten oxide, a cathode coloring material.
  • the darkened thin film has a low reflectivity of light, and thus the intensity of reflected light decreases, the reflected light passes through the optical separator 132 along the optical fiber 150 again, and then the detector 131 measures the intensity of the reflected light.
  • the hydrogen is then detected by a circuit designed to compare with the reference signal in the control caps 140.
  • the present inventors made diligent research efforts to develop a hydrogen optical sensor that can be miniaturized and manufactured at a lower cost. As a result, the above-described object can be obtained by applying an optical pickup device of a conventional C ROM or DVD-ROM to a hydrogen optical sensor. By confirming that it is possible to provide a hydrogen optical sensor that can achieve the present invention was completed.
  • an object of the present invention is to provide a hydrogen optical sensor.
  • Other objects and advantages of the present invention will become apparent from the following detailed description, claims and drawings. According to an aspect of the present invention, the present invention
  • a light source for generating a wide range of light
  • a light separator for separating light beams from the light source
  • a collimating lens for converting a wide range separated by the light separator into parallel light, a collimating lens
  • a quarter wave plate for varying the polarization direction of the parallel light beam passing through the collimating lens by 90 o , an objective lens for converging a wide range passing through the quarter wave plate, and (vi) detecting light reflected from the sensational modules
  • Optical modules including a detector
  • (C) provides a hydrogen optical sensor comprising an optical fiber for optically connecting the sensing modules and optical fibers.
  • the present inventors earnestly researched to develop a hydrogen optical sensor that can be miniaturized and manufactured at a lower cost.
  • the optical pickup device of CE ) -R0M or DVD-ROM is applied to the optical part of the existing hydrogen optical sensor, It was confirmed that the present invention can provide a hydrogen optical sensor that can achieve the above object.
  • the hydrogen optical sensor of the present invention consists of three parts: (a) sensing modules 220; (b) optical fibers 230; And (c) optical fiber 250.
  • the sensing modules detect a hydrogen, and the gas-colored thin film 211 is located.
  • Gas-coloured thin films used in the present invention include any conventional gas-coloured thin film.
  • the gas-colored thin film is (i) tungsten oxide, tungstate, nioboxide, molybdenum oxide, molybdate, nickel oxide, titanium oxide, vanadium oxide, iridium oxide, manganese oxide, cobalt oxide and traces thereof Transition metal oxides selected from the group consisting of compounds; (ii) L ai - z Mg z H x , Yi- z Mg z H x , Gdi- z Mg z H x , Yh b , LaH b ) SmH b , NiMg 2 H x , CoMg 2 H x or a combination thereof a metal hydride selected from the group consisting of [z is 0-1, x is 0-5, and b is 0-3]; Or (iii
  • the gas-colored thin film is a group consisting of tungsten oxide, tungstate, nioboxide, molybdenum oxide, molybdate, nickel oxide, titanium oxide, vanadium oxide, iridium oxide, manganese oxide, cobalt oxide, and mixtures thereof. Transition metal oxides selected from. Even more preferably the gas-coloured thin film is tungsten oxide, most preferably W0 3 .
  • a catalyst layer is deposited on the gas-colored thin film.
  • the catalyst layer comprises palladium (Pd) and platinum (Pt).
  • Palladium and platinum contained in the catalyst layer constitute two layers, a layer made of palladium and a layer made of platinum, or constitute an alloy layer of palladium and platinum.
  • Catalyst layer Deposition is by a sputtering scheme (preferably radio frequency (RF) sputtering or DC sputtering).
  • the gas-coloured thin film is located on a solid substrate 212.
  • the materials available for the substrate are not particularly limited, and for example, silicon, glass, quartz, fused silica, stainless steel, mica, carbon, carbon nanotubes, polymers, ceramics and porcelain enamels can be used. .
  • the light source 231 in the optical beams 230 is a means for generating a light beam.
  • the light source is preferably a laser light source, more preferably a laser diode, and most preferably a linear flat laser light source.
  • the wide range from the light source is separated by a beam splitter (232).
  • the separated light beams are converted into parallel light by a collimator lens (233, colliraating lens), and parallel to a wide range which has passed through the collimator lens is passed through the polarization direction 90 ⁇ change four branching pad (234, quarter wave plate) come to Isa.
  • the light beam having passed through the wavelength plate is condensed by the objective lens 235.
  • the light reflected by the sensory module is measured by the detector 236 and converted into an electrical signal.
  • the detector is a photodiode.
  • the hydrogen optical sensor of the present invention further comprises a collimator (237, collimator) between the objective lens and the optical fiber.
  • the hydrogen optical sensor of the present invention is A cylindrical lens 238 is further included between the optical separator and the detector to convert the light reflected by the sensing modules into the sectional light.
  • the hydrogen optical sensor of the present invention processes a signal of light reflected from the sensational modulus in comparison with a reference signal generated from a light beam separated by an optical splitter and is connected to the detector.
  • Module 240 additionally. More preferably, the control caps include alarm generating means for generating a warning sound or a warning indication when there is a hydrogen signal of a predetermined concentration or more.
  • the hydrogen optical sensor of the present invention further includes a diffraction grating 239 between the light source and the optical separator.
  • the diffraction grating 239 receives the light incident from the light source, for example, the laser light and the main light. Make it a sub light.
  • the optical fibers in the hydrogen optical sensor of the present invention have almost the same configuration as the conventional optical pickup apparatus. Therefore, the existing optical pickup apparatus can be modified slightly to be used for optical hairs. This replacement possibility makes the hydrogen optical sensor of the present invention more compact and easy to manufacture at low cost.
  • FIG. 1 is a schematic diagram of a conventional hydrogen optical sensor.
  • 111 gas-colored thin film
  • 112 substrate
  • 120 sensuous modules
  • 130 optical hairs
  • 132 optical splitter
  • 133 light source
  • 140 control hairs
  • 150 optical fiber
  • FIG. 2 is a view showing a specific embodiment of the hydrogen optical sensor of the present invention.
  • the separated laser light passes sequentially through the collimating lens 233, the quarter wave plate 234, the objective lens 235, and the collimator 237, followed by gas coloring deposited on the substrate 212 along the optical fiber 250.
  • the gas-coloured thin film 211 made of tungsten oxide is a cathode-colored material, which is a gas-colored material in which the color of the material changes dark when hydrogen is contacted.
  • the reflectivity of is decreased so that the reflected light is weaker than the initial light intensity.
  • the reflected light travels back along the optical fiber 250 and sequentially passes through the collimator 237, the objective lens 235, the quarter wave tube 234, the collimating lens 233 and the optical separator 232, followed by the cylindrical lens 238. Pass).
  • Light passing through the cylindrical lens is converted and measured by an electrical signal at photodiode 236.
  • the electrical signal generated at the photodiode 236 is transmitted to the adjusting heads 240.
  • the adjustment caps 240 include a circuit for processing a signal of light reflected by the sensing modules 220 in comparison with a reference signal. That is, the control hat 240 includes an alarm generating means for generating a warning sound or a warning display when there is a hydrogen signal of a predetermined concentration or more.
  • the present invention which uses an optical pickup such as an existing CD-ROM or DVD-ROM, can greatly contribute to miniaturizing the size of the hydrogen optical sensor.
  • the present invention can greatly contribute to spreading a small hydrogen safety sensor that is simple in construction, easy to assemble and small. Having described the specific part of the present invention in detail, for those skilled in the art these specific techniques are only desirable It is only an example implementation, it is obvious that the scope of the present invention is not limited. Thus, the substantial scope of the present invention will be defined by the appended claims and equivalents thereof.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Health & Medical Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Plasma & Fusion (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)
  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)

Abstract

The present invention relates to an optical hydrogen sensor which comprises: (a) a sensing module including gasochromic thin film; (b) an optical module; and (c) an optical fiber which optically connects the sensing module and optical module. The optical module comprises (i) a light source which generates a light beam, (ⅱ) a light splitter which splits the light beam from the light source, (ⅲ) a collimating lens which converts the light beam split by the light splitter into parallel lights, (ⅳ) a quarter-wave plate which changes the polarizing direction of the parallel light beams having passed through the collimating lens by 90 °, (v) an object lens which collects the light beams that have passed through the quarter-wave plate, and (vi) a detector which detects the light reflected from the sensing module. The present invention applies an optical pickup such as a conventional CD-ROM or DVD-ROM, and consequently the optical hydrogen sensor can be smaller. Furthermore, time and costs needed for manufacture can be greatly cut down if a cheap optical pick-up device is simply changed and applied to the optical hydrogen sensor.

Description

[명세서】  [Specification】
【발명의 명칭】  [Name of invention]
수소 광센서 【기술 분야】  Hydrogen Optical Sensor [Technical Field]
본 발명은수소 광센서에 관한 것이다.  The present invention relates to a hydrogen optical sensor.
【배경 기술】 [Background technology]
유력 대체 에너지인 수소 에너지는 공기 중에서 4% 이상의 농도에서 폭발의 위험성이 있기 때문에 수소 에너지를 안전하게 사용하기 위해서는 수소의 누출을 검지하는 수소센서가 필수적이다. 수소 센서는 용도에 따라 공정용 센서와 누출검지 센서로 구분할 수 있으며 누출검지 센서는 미량의 수소 누출을 검지하는 누출 검지센서와 수소 누출이 예상되는 공간에서 수소의 누출올 검지하는 안전센서로 분류할 수 있다. 안전센서는 공기 중에서 수소 이외의 기체와 반웅하지 않고 안정적인 상태를 유지하다가수소 누출시 즉각적으로 검지할 수 있다.  Hydrogen energy, a potent alternative energy, is at risk of explosion at concentrations of more than 4% in the air, so a hydrogen sensor that detects a leak of hydrogen is essential for the safe use of hydrogen energy. Hydrogen sensors can be classified into process sensors and leak detection sensors according to their use.The leak detection sensors can be classified into a leak detection sensor that detects a small amount of hydrogen leakage and a safety sensor that detects a leak of hydrogen in a space where hydrogen leakage is expected. Can be. The safety sensor maintains a stable state without reacting with gases other than hydrogen in the air, and can immediately detect hydrogen leakage.
종래의 수소 센서는 수소가 수소센서 물질에 접촉되었을 때 물질의 저항이 변하는 성질을 이용하여 제작하는 전기적 센서와 마찬가지로 수소가 센서물질에 접촉되었을 때 물질의 색이 변하는 성질을 이용하여 물질을 투과하거나 반사하는 빛의 세기 차이로 수소를 검지하는 광학적 센서로 구분할 수 있다. 광학적 센서는 632 nm 파장의 반도체 레이저광을 광분리기로 나누어 하나는 레퍼런스 신호로 다른 하나는 센서부로 광케이블을 이용하여 연결한다. 센서부에 수소가 접촉되면 센서박막의 색이 변하게 되어 레이저 빛이 반사되는 정도가 달라지게 되며 포토다이오드로 반사된 빛의 세기를 측정하여 그 신호를 레퍼런스 신호와 비교하여 수소를 검지한다.  Conventional hydrogen sensor is similar to an electrical sensor manufactured by using a property of changing the resistance of hydrogen when it comes into contact with the hydrogen sensor material. It can be classified into an optical sensor that detects hydrogen by the difference in intensity of reflected light. The optical sensor divides the semiconductor laser light having a wavelength of 632 nm into an optical splitter and connects the optical signal to the sensor signal and the other to the sensor signal. When hydrogen is in contact with the sensor, the color of the sensor thin film is changed, and the degree of reflection of the laser light is changed. The intensity of the light reflected by the photodiode is measured, and the signal is compared with a reference signal to detect hydrogen.
도 1을 참조하여， 종래의 일반적인 수소 광센서의 등작원리를 설명하면 다음과 같다: 광원 (133)으로부터 발생되어 입사된 광은 입사한 빛의 반은 통과하고 반은 반사하는 광분리기 (132, beam splitter)로 분리되어 분리된 광 중 하나는 기준신호 (레퍼런스 신호)로 사용되고, 다른 하나는 광섬유 (150)를 통하여 센싱 모들 (120)의 수소 센서 박막인 가스채색박막 (111)으로 이동한다. 가스채색박막은 수소에 노출되었을 때， 음극채색물질인 텅스텐 산화물의 영향으로 박막의 색이 어둡게 변하게 된다. 어둡게 된 박막은 빛의 반사도가 떨어져 반사되는 광의 세기가 작게 되며， 반사된 광이 다시 광섬유 (150)를 따라 광분리기 (132)를 통과하고, 이어 검출기 (131)가 반사광의 세기를 측정하며， 그런 다음조절모들 (140)에 있는 기준신호와 비교하도록 설계된 회로에 의해 수소를 검지하게 된다. 본 명세서 전체에 걸쳐 다수의 논문 및 특허문헌이 참조되고 그 인용이 표시되어 있다. 인용된 논문 및 특허문헌의 개시 내용은 그 전체로서 본 명세서에 참조로 삽입되어 본 발명이 속하는 기술 분야의 수준 및 본 발명의 내용이 보다 명확하게 설명된다. Referring to FIG. 1, the equalization principle of a conventional hydrogen photoelectric sensor is as follows: Light generated from the light source 133 is incident to the light splitter 132 that passes through half of the incident light and reflects half of the incident light. One of the beams separated and separated by a beam splitter is used as a reference signal (reference signal), and the other is a hydrogen sensor thin film of the sensing modules 120 through the optical fiber 150. It moves to the gas-colored thin film 111. When the gas-colored thin film is exposed to hydrogen, the color of the thin film becomes dark due to the influence of tungsten oxide, a cathode coloring material. The darkened thin film has a low reflectivity of light, and thus the intensity of reflected light decreases, the reflected light passes through the optical separator 132 along the optical fiber 150 again, and then the detector 131 measures the intensity of the reflected light. The hydrogen is then detected by a circuit designed to compare with the reference signal in the control caps 140. Throughout this specification, many papers and patent documents are referenced and their citations are indicated. The disclosures of cited papers and patent documents are incorporated herein by reference in their entirety, and the level of the technical field to which the present invention belongs and the contents of the present invention are more clearly explained.
【발명의 상세한설명】 Detailed Description of the Invention
본 발명자들은 소형화가 가능하고 보다 낮은 비용으로 제작할 수 있는 수소 광센서를 개발하고자 예의 연구 노력하였고， 그 결과 기존의 C으 ROM 또는 DVD-ROM의 광픽업 장치를 수소 광센서에 응용하면 상술한 목적을 달성할 수 있는 수소 광센서를 제공할 수 있음을 확인함으로써 , 본 발명을 완성하게 되었다.  The present inventors made diligent research efforts to develop a hydrogen optical sensor that can be miniaturized and manufactured at a lower cost. As a result, the above-described object can be obtained by applying an optical pickup device of a conventional C ROM or DVD-ROM to a hydrogen optical sensor. By confirming that it is possible to provide a hydrogen optical sensor that can achieve the present invention was completed.
따라서， 본 발명의 목적은수소 광센서를 제공하는 데 있다. 본 발명의 다른 목적 및 이점은 하기의 발명의 상세한 설명, 청구범위 및 도면에 의해 보다 명확하게 된다. 본발명의 양태에 따르면, 본 발명은  Accordingly, an object of the present invention is to provide a hydrogen optical sensor. Other objects and advantages of the present invention will become apparent from the following detailed description, claims and drawings. According to an aspect of the present invention, the present invention
(a) 가스채색 박막 (gasochromic thin film)을포함하는 센성 모들; (a) Sensitive modalities comprising a gasochromic thin film;
(b) (i) 광범올 발생시키는 광원 (light source), (ii) 상기 광원에서 나온 광빔을 분리시키는 광분리기， (iii) 상기 광분리기에 의해 분리된 광범을 평행광으로 전환시키는 시준렌즈 (collimating lens), (iv) 상기 시준렌즈를 통과한 평행 광빔의 편광방향을 90ο 변화시키는 사분파장판 (quarter wave plate), (v) 상기 사분파장판을 통과한 광범을 집광하는 대물렌즈， 및 (vi) 상기 센성 모들에서 반사된 광을 검출하는 검출기를포함하는 광학모들 ; 그리고 (b) a light source for generating a wide range of light, (ii) a light separator for separating light beams from the light source, and (iii) a collimating lens for converting a wide range separated by the light separator into parallel light, a collimating lens, (iv) a quarter wave plate for varying the polarization direction of the parallel light beam passing through the collimating lens by 90 o , an objective lens for converging a wide range passing through the quarter wave plate, and (vi) detecting light reflected from the sensational modules Optical modules including a detector; And
(C) 상기 센싱 모들과 광학모들을 광학적으로 연결하는 광섬유를 포함하는수소 광센서를 제공한다. 본 발명자들은 소형화가 가능하고 보다 낮은 비용으로 제작할 수 있는 수소 광센서를 개발하고자 예의 연구 노력하였고, 그 결과 CE)-R0M 또는 DVD-ROM의 광픽업 장치를 기존 수소 광센서의 광학부에 응용하면 상술한 목적올 달성할 수 있는 수소 광센서를 제공할 수 있음을 확인하였다. 본 발명의 수소 광센서는 크게 3개의 부분으로 이루어져 있다: (a) 센싱 모들 (220); (b) 광학모들 (230); 및 (c) 광섬유 (250). (C) provides a hydrogen optical sensor comprising an optical fiber for optically connecting the sensing modules and optical fibers. The present inventors earnestly researched to develop a hydrogen optical sensor that can be miniaturized and manufactured at a lower cost. As a result, when the optical pickup device of CE ) -R0M or DVD-ROM is applied to the optical part of the existing hydrogen optical sensor, It was confirmed that the present invention can provide a hydrogen optical sensor that can achieve the above object. The hydrogen optical sensor of the present invention consists of three parts: (a) sensing modules 220; (b) optical fibers 230; And (c) optical fiber 250.
센싱 모들은 수소를 감지하는 부분으로서, 가스채색 박막 (211)이 위치해 있다. 본 발명에서 이용되는 가스채색 박막은 종래의 어떠한 가스채색 박막도 포함한다. 바람직하게는， 상기 가스채색 박막은 ( i ) 텅스텐 산화물, 텅스테이트， 니오복사이드， 몰리브덴 산화물， 몰리브테이드， 니켈 산화물， 티타늄 산화물， 바나듐 산화물, 이리듐 산화물， 망간산화물， 코발트 산화물 및 이의 흔합물로 구성된 군으로부터 선택되는 전이금속 산화물; (ii) Lai-zMgzHx, Yi-zMgzHx, Gdi-zMgzHx, Yhb, LaHb) SmHb, NiMg2Hx, CoMg2Hx 또는 이의 흔합물 [z는 0-1, x는 0-5， 그리고 b는 0-3]로 구성된 군으로부터 선택되는 금속 수소화물; 또는 (iii) 폴리비올로겐, 폴리티오펜， 폴리아닐린 및 프루시안 블루로 구성된 군으로부터 선택되는 스위칭 중합체를 포함한다. 보다 바람직하게는 가스채색 박막은 텅스텐 산화물， 텅스테이트, 니오복사이드, 몰리브덴 산화물, 몰리브테이드， 니켈 산화물， 티타늄 산화물， 바나듐 산화물, 이리듐 산화물, 망간 산화물, 코발트 산화물 및 이의 흔합물로 구성된 군으로부터 선택되는 전이금속 산화물을 포함한다. 보다 더 바람직하게는 가스채색 박막은 텅스텐 산화물이며, 가장바람직하게는 W03이다. The sensing modules detect a hydrogen, and the gas-colored thin film 211 is located. Gas-coloured thin films used in the present invention include any conventional gas-coloured thin film. Preferably, the gas-colored thin film is (i) tungsten oxide, tungstate, nioboxide, molybdenum oxide, molybdate, nickel oxide, titanium oxide, vanadium oxide, iridium oxide, manganese oxide, cobalt oxide and traces thereof Transition metal oxides selected from the group consisting of compounds; (ii) L ai - z Mg z H x , Yi- z Mg z H x , Gdi- z Mg z H x , Yh b , LaH b ) SmH b , NiMg 2 H x , CoMg 2 H x or a combination thereof a metal hydride selected from the group consisting of [z is 0-1, x is 0-5, and b is 0-3]; Or (iii) a switching polymer selected from the group consisting of polyviologen, polythiophene, polyaniline and prussian blue. More preferably, the gas-colored thin film is a group consisting of tungsten oxide, tungstate, nioboxide, molybdenum oxide, molybdate, nickel oxide, titanium oxide, vanadium oxide, iridium oxide, manganese oxide, cobalt oxide, and mixtures thereof. Transition metal oxides selected from. Even more preferably the gas-coloured thin film is tungsten oxide, most preferably W0 3 .
본 발명의 바람직한 구현예에 따르면， 상기 가스채색 박막에는 촉매층이 증착되어 있다. 보다 더 바람직하게는, 상기 촉매층은 팔라듐 (Pd) 및 백금 (Pt) 포함한다. 촉매층에 포함되어 있는 팔라듐 및 백금은 팔라듐으로 이루어진 층 및 백금으로 이루어진 층 등 2개의 층을 구성하거나 또는 팔라듐과 백금의 합금층을 구성한다. 촉매층은 반웅성 스퍼터링 (reactive sputtering) 방식 (바람직하게는, RF(radio frequency) 스퍼터링 또는 DC스퍼터링)으로 증착된다. According to a preferred embodiment of the present invention, a catalyst layer is deposited on the gas-colored thin film. Even more preferably, the catalyst layer comprises palladium (Pd) and platinum (Pt). Palladium and platinum contained in the catalyst layer constitute two layers, a layer made of palladium and a layer made of platinum, or constitute an alloy layer of palladium and platinum. Catalyst layer Deposition is by a sputtering scheme (preferably radio frequency (RF) sputtering or DC sputtering).
본 발명의 바람직한 구현예에 따르면， 상기 가스채색 박막은 고상의 기질 (212) 상에 위치해 있다. 기질로 이용 가능한 물질은 특별하게 제한되지 않으며, 예를 들어 실리콘， 유리， 석영， 융합 실리카， 스테인레스강， 마이카, 카본， 탄소나노튜브， 폴리머, 세라믹 및 자기 (porcelain) 에나멜 등이 이용될 수 있다.  According to a preferred embodiment of the present invention, the gas-coloured thin film is located on a solid substrate 212. The materials available for the substrate are not particularly limited, and for example, silicon, glass, quartz, fused silica, stainless steel, mica, carbon, carbon nanotubes, polymers, ceramics and porcelain enamels can be used. .
광학모들 (230)에서 광원 (231)은 광빔을 발생시키는 수단이다. 상기 광원으로는 레이저광원이 바람직하며, 보다 바람직하게는 레이저 다이오드이며， 가장 바람직하게는， 선형 평광된 레이저광원이다.  The light source 231 in the optical beams 230 is a means for generating a light beam. The light source is preferably a laser light source, more preferably a laser diode, and most preferably a linear flat laser light source.
상기 광원에서 나온 광범은 광분리기 (232， beam splitter)에 의래 분리된다. 분리된 광빔은 시준렌즈 (233， colliraating lens)에 의해 평행광으로 전환되고， 시준렌즈를 통과한 평행 광범은 편광방향을 90ο 변화시키는 사분파장판 (234， quarter wave plate)올 통과하며, 사분파장판을 통과한 광빔은 대물렌즈 (235)에 의해 집광된다. 센성 모듈에서 반사된 광은 검출기 (236)에서 측정되며 전기적 신호로 전환된다. 바람직하게는 검출기는 포토다이오드이다. The wide range from the light source is separated by a beam splitter (232). The separated light beams are converted into parallel light by a collimator lens (233, colliraating lens), and parallel to a wide range which has passed through the collimator lens is passed through the polarization direction 90 ο change four branching pad (234, quarter wave plate) come to Isa. The light beam having passed through the wavelength plate is condensed by the objective lens 235. The light reflected by the sensory module is measured by the detector 236 and converted into an electrical signal. Preferably the detector is a photodiode.
본 발명의 바람직한 구현예에 따르면, 본 발명의 수소 광센서는 대물렌즈와 광섬유 사이에 시준기 (237， collimator)를 추가적으로 포함한다ᅳ 본 발명의 바람직한 구현예에 따르면， 본 발명의 수소 광센서는 상기 광분리기와 검출기 사이에 센싱 모들에서 반사된 광을 단면광으로 전환시키는 원통형 렌즈 (238， cylindrical lens)를 추가적으로 포함한다. 본 발명의 바람직한 구현예에 따르면, 본 발명의 수소 광센서는 광분리기에 의해 분리된 광빔으로부터 생성된 레퍼런스 신호와 비교하여 상기 센성 모들에서 반사된 광의 신호를 처리하고， 상기 검출기에 연결되어 있는 조절모듈 (240)을 추가적으로 포함한다. 보다 바람직하게는, 조절모들에는 일정 농도 이상의 수소 신호가 있는 경우에는 경고음 또는 경고표시가 발생하도록 하는 알람 (alarm) 발생수단을 포함한다.  According to a preferred embodiment of the present invention, the hydrogen optical sensor of the present invention further comprises a collimator (237, collimator) between the objective lens and the optical fiber. According to a preferred embodiment of the present invention, the hydrogen optical sensor of the present invention is A cylindrical lens 238 is further included between the optical separator and the detector to convert the light reflected by the sensing modules into the sectional light. According to a preferred embodiment of the present invention, the hydrogen optical sensor of the present invention processes a signal of light reflected from the sensational modulus in comparison with a reference signal generated from a light beam separated by an optical splitter and is connected to the detector. Module 240 additionally. More preferably, the control caps include alarm generating means for generating a warning sound or a warning indication when there is a hydrogen signal of a predetermined concentration or more.
본 발명의 바람직한 구현예에 따르면, 본 발명의 수소 광센서는 상기 광원과 광분리기 사이에 회절격자 (239)를 추가적으로 포함한다. 회절격자 (239)는 광원으로부터 입사된 광， 예컨대， 레이저광을 메인광 및 서브광으로 만든다. According to a preferred embodiment of the present invention, the hydrogen optical sensor of the present invention further includes a diffraction grating 239 between the light source and the optical separator. The diffraction grating 239 receives the light incident from the light source, for example, the laser light and the main light. Make it a sub light.
흥미롭게도, 본 발명의 수소 광센서에서 광학모들은 기존의 광픽업 장치과 거의 동일한 구성을 갖는다. 따라서, 기존의 광픽업 장치를 조금 변형하여 광학모들에 이용할 수 있다. 이러한 대체 가능성은， 본 발명의 수소 광센서를 보다 소형화 되고， 간편하면서도 저가의 비용으로 제작할 수 있도록 한다.  Interestingly, the optical fibers in the hydrogen optical sensor of the present invention have almost the same configuration as the conventional optical pickup apparatus. Therefore, the existing optical pickup apparatus can be modified slightly to be used for optical hairs. This replacement possibility makes the hydrogen optical sensor of the present invention more compact and easy to manufacture at low cost.
【도면의 간단한 설명】 [Brief Description of Drawings]
도 1은 종래의 수소 광센서의 모식도이다.  1 is a schematic diagram of a conventional hydrogen optical sensor.
<도면의 주요부호의 설명 >  <Description of Major Symbols in Drawing>
111: 가스채색박막， 112: 기질， 120: 센성 모들， 130: 광학모들， 131： 검출기， 132: 광분리기, 133: 광원， 140: 조절모들, 150: 광섬유  111: gas-colored thin film, 112: substrate, 120: sensuous modules, 130: optical hairs, 131: detector, 132: optical splitter, 133: light source, 140: control hairs, 150: optical fiber
도 2는 본 발명의 수소 광센서의 구체적인 일 실시예를 나타내는 도면이다.  2 is a view showing a specific embodiment of the hydrogen optical sensor of the present invention.
<도면의 주요부호의 설명〉  <Description of Major Symbols in Drawing>
211： 가스채색박막, 212: 기질， 220: 센성 모듈, 230: 광학모들, 231： 광원， 232： 광분리기, 233: 시준렌즈, 234: 사분파장판， 235: 대물렌즈， 236: 검출기， 237: 시준기， 238: 원통형 렌즈， 239: 회절격자， 240： 조절모들, 250: 광섬유. 이하, 실시예를 통하여 본 발명을 더욱 상세히 설명하고자 한다. 이들 실시예는 오로지 본 발명을 보다 구체적으로 설명하기 위한 것으로， 본 발명의 요지에 따라 본 발명의 범위가 이들 실시예에 의해 제한되지 않는다는 것은 당업계에서 통상의 지식을 가진 자에 있어서 자명할 것이다.  211: gas-coloured thin film, 212: substrate, 220: sensitive module, 230: optical modules, 231: light source, 232: optical separator, 233: collimating lens, 234: quarter-wave plate, 235: objective lens, 236: detector, 237: collimator, 238: cylindrical lens, 239: diffraction grating, 240: adjusting heads, 250: optical fiber. Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are only for illustrating the present invention more specifically, it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples in accordance with the gist of the present invention. .
【실시예】 EXAMPLE
본 발명의 구체적인 일 실시예를 도 2 를 참조하여 설명하면 다음과 같다. 광원 (231)， 바람직하게는 레이저 다이오드에서 발생된 630 nm 파장의 반도체 다이오드 레이저광은 회절격자 (239)를 통하여 광분리기 (232)로 입사되며 광분리기는 입사된 레이저광을 분리한다. 분리된 레이저광은 순차적으로 시준렌즈 (233) , 사분파장판 (234) , 대물렌즈 (235) 및 시준기 (237)를 통과하고 이어 광섬유 (250)를 따라 기질 (212) 상에 증착된 가스채색박막 (211)이 포함된 센성모들 (220)에 전달된다ᅳ 텅스텐 산화물로 이루어진 가스채색박막 (211)은 음극채색 물질로서 수소가 접촉되면 물질의 색이 어둡게 변하는 가스채색 물질이며 어둡게 변했을 시 박막의 반사도가 감소하여 반사된 광은 초기 광의 세기에 비해 약하게 된다. 반사광은 다시 광섬유 (250)를 따라 이동하고 순차적으로 시준기 (237) , 대물렌즈 (235)， 사분파장관 (234)， 시준렌즈 (233) 및 광분리기 (232)를 통과하고 이어 원통 렌즈 (238)를 통과한다. 원통형 렌즈를 통과한 광은 포토다이어드 (236)에서 전기적 신호로 전환되고 측정된다. 포토다이오드 (236)에서 발생된 전기 신호는 조절모들 (240)에 전달된다. 조절모들 (240)에는 레퍼런스 신호와 비교하여 상기 센싱 모들 (220)에서 반사된 광의 신호를 처리하는 회로가 있다. 즉 , 조절모들 (240)에는 일정 농도 이상의 수소 신호가 있는 경우에는 경고음 또는 경고표시가 발생하도록 하는 알람 (alarm) 발생수단이 포함되어 있다. 본 발명의 특징 및 이점을 요약하면 다음과 같다: A specific embodiment of the present invention will be described with reference to FIG. 2 as follows. The 630 nm wavelength semiconductor diode laser light generated by the light source 231, preferably the laser diode, is incident to the optical separator 232 through the diffraction grating 239, and the optical separator separates the incident laser light. The separated laser light passes sequentially through the collimating lens 233, the quarter wave plate 234, the objective lens 235, and the collimator 237, followed by gas coloring deposited on the substrate 212 along the optical fiber 250. The gas-coloured thin film 211 made of tungsten oxide is a cathode-colored material, which is a gas-colored material in which the color of the material changes dark when hydrogen is contacted. The reflectivity of is decreased so that the reflected light is weaker than the initial light intensity. The reflected light travels back along the optical fiber 250 and sequentially passes through the collimator 237, the objective lens 235, the quarter wave tube 234, the collimating lens 233 and the optical separator 232, followed by the cylindrical lens 238. Pass). Light passing through the cylindrical lens is converted and measured by an electrical signal at photodiode 236. The electrical signal generated at the photodiode 236 is transmitted to the adjusting heads 240. The adjustment caps 240 include a circuit for processing a signal of light reflected by the sensing modules 220 in comparison with a reference signal. That is, the control hat 240 includes an alarm generating means for generating a warning sound or a warning display when there is a hydrogen signal of a predetermined concentration or more. The features and advantages of the present invention are summarized as follows:
( i ) 기존 CD-ROM 또는 DVD-ROM 등의 광픽 업을 웅용한 본 발명은 수소 광센서의 크기를 소형화하는데 크게 기여할 수 있다.  (i) The present invention, which uses an optical pickup such as an existing CD-ROM or DVD-ROM, can greatly contribute to miniaturizing the size of the hydrogen optical sensor.
( ii ) 더욱이 , 단가가 매우 저렴한 광픽업 장치를 간단하게 변형하여 본 발명의 수소 광센서에 적용하면 제작하는 시간과 비용을 크게 절감할 수 있다.  (ii) Furthermore, by simply modifying the optical pickup device, which is very inexpensive, and applying it to the hydrogen optical sensor of the present invention, the manufacturing time and cost can be greatly reduced.
(iii) 기존 수소 광센서의 경우 광학 기성품을 구입하고 조립하여 제작했기 때문에 상당한 비용과 시간이 필요하고 그 크기도 컸으나 광학계가 정밀하게 제작된 기성 광픽 업 장치를 사용하면 비용과 시간올 크게 절감할 수 있다.  (iii) Existing hydrogen optical sensors require considerable cost and time because they are purchased and manufactured by making optical ready-made products. However, using the ready-made optical pick-up device with precisely manufactured optical system can greatly reduce cost and time. Can be.
( iv ) 따라서， 본 발명은 구성이 간단하고 조립이 용이하면서 소형인 수소 안전센서를 보급하는데 크게 기여할 수 있다. 이상으로 본 발명의 특정한 부분을 상세히 기술하였는 바, 당업계의 통상의 지식을 가진 자에게 있어서 이러한 구체적인 기술은 단지 바람직한 구현 예일 뿐이며， 이에 본 발명의 범위가 제한되는 것이 아닌 점은 명백하다. 따라서, 본 발명의 실질적인 범위는 첨부된 청구항과 그의 등가물에 의하여 정의된다고 할 것이다. (iv) Therefore, the present invention can greatly contribute to spreading a small hydrogen safety sensor that is simple in construction, easy to assemble and small. Having described the specific part of the present invention in detail, for those skilled in the art these specific techniques are only desirable It is only an example implementation, it is obvious that the scope of the present invention is not limited. Thus, the substantial scope of the present invention will be defined by the appended claims and equivalents thereof.

Claims

【청구의 범위】 [Range of request]
【청구항 1】  [Claim 1]
(a) 가스채색 박막 (gasochromic thin film)을포함하는 센싱 모들; (a) sensing modules comprising a gasochromic thin film;
(b) (i) 광범을 발생시키는 광원 (light source) , (ii) 상기 광원에서 나온 광빔을 분리시키는 광분리기， (iii) 상기 광분리기에 의해 분리된 광범을 평행광으로 전환시키는 시준렌즈 (collimating lens), (iv) 상기 시준렌즈를 통과한 평행 광빔의 편광방향을 90ο 변화시키는 사분파장관 (quarter wave plate), (v) 상기 사분파장판을 통과한 광범을 집광하는 대물렌즈, 및 (vi) 상기 센싱 모들에서 반사된 광을 검출하는 검출기를포함하는 광학모들; 그리고 (b) (i) a light source for generating a wide range, (ii) an optical separator for separating light beams from the light source, and (iii) a collimating lens for converting a wide range separated by the optical separator into parallel light, a collimating lens, (iv) a quarter wave plate for varying the polarization direction of the parallel light beam passing through the collimating lens by 90 o , an objective lens for converging a wide range passing through the quarter wave plate, and (vi) optical fibers including a detector for detecting light reflected from the sensing modules; And
(c) 상기 센성 모들과 광학모들을 광학적으로 연결하는 광섬유를 포함하는수소광센서ᅳ  (c) a hydrogen optical sensor 를 comprising an optical fiber for optically connecting the sensuous modules and the optical fibers
【청구항 2】 [Claim 2]
제 1 항에 있어서, 상기 가스채색 박막은 ( i ) 텅스텐 산화물， 텅스테이트， 니오복사이드， 몰리브덴 산화물, 몰리브테이드， 니켈 산화물, 티타늄 산화물, 바나듐 산화물， 이리듐 산화물, 망간 산화물, 코발트 산화물 및 이의 흔합물로 구성된 군으로부터 선택되는 전이금속 산화물; (ii) Lai-zMgzHX) Yi-zMgzHXl Gdi-zMgzHx, Yhb, LaHbj SraHb) NiMg2Hx, CoMg2¾또는 이의 혼합물 [z는 0-1, x는 0-5, 그리고 b는 0-3]로 구성된 군으로부터 선택되는 금속 수소화물; 또는 (iii) 폴리비올로겐, 폴리티오펜， 폴리아닐린 및 프루시안 블루로 구성된 군으로부터 선택되는 스위칭 중합체를 포함하는 것을특징으로하는수소광센서 . The method of claim 1, wherein the gas-coloured thin film is (i) tungsten oxide, tungstate, nioboxide, molybdenum oxide, molybdate, nickel oxide, titanium oxide, vanadium oxide, iridium oxide, manganese oxide, cobalt oxide and Transition metal oxides selected from the group consisting of combinations thereof; (ii) Lai- z Mg z H X) Yi- z Mg z H Xl Gdi- z Mg z H x , Yh b , LaH bj SraH b) NiM g2 H x , CoM g2 ¾ or mixtures thereof [z is 0- 1, x is 0-5, and b is 0-3]; Or (iii) a switching polymer selected from the group consisting of polyviologen, polythiophene, polyaniline and prussian blue.
【청구항 3】 [Claim 3]
제 1 항에 있어서, 상기 가스채색 박막은 고상의 기질 상에 위치해 있는 것을특징으로하는수소 광센서 .  2. The hydrogen optical sensor of claim 1, wherein the gas-coloured thin film is located on a solid substrate.
【청구항 4】 [Claim 4]
제 1 항에 있어서, 상기 광원은 레이저 다이오드인 것을 특징으로 하는수소 광센서 . 2. The hydrogen optical sensor of claim 1, wherein the light source is a laser diode.
【청구항 5] [Claim 5]
제 1 항에 있어서， 상기 수소 광센서는 대물렌즈와 광섬유 사이에 시준기 (collimator)를 추가적으로 포함하는 것을 특징으로 하는 수소 광센서 .  The hydrogen optical sensor of claim 1, wherein the hydrogen optical sensor further comprises a collimator between the objective lens and the optical fiber.
【청구항 6】 [Claim 6]
제 1 항에 있어서 상기 수소 광센서는 상기 광분리기와 검출기 사이에 센성 모들에서 반사된 광을 단면광으로 전환시키는 원통형 렌즈 (cyl indrical lens)-! 추가적으로 포함하는 것을 특징으로 하는 수소 광센서 .  The cylindrical lens of claim 1, wherein the hydrogen optical sensor converts the light reflected by the sensitive modules between the optical separator and the detector into cross section light. Hydrogen optical sensor further comprises.
【청구항 7】 [Claim 7]
제 1 항에 있어서， 상기 검출기는 포토다이오드인 것을 특징으로 하는수소 광센서 .  2. The hydrogen optical sensor of claim 1, wherein the detector is a photodiode.
【청구항 8】 [Claim 8]
제 1 항에 있어서, 상기 수소 광센서는 광분리기에 의해 분리된 광범으로부터 생성된 레퍼런스 신호와 비교하여 상기 센싱 모들에서 반사된 광의 신호를 처리하고， 상기 검출기에 연결되어 있는 조절모들올 추가적으로 포함하는 것을 특징으로 하는 광센서 .  The optical sensor of claim 1, wherein the hydrogen photo sensor processes a signal of light reflected from the sensing modules in comparison with a reference signal generated from a wide range separated by an optical splitter, and further includes a control module connected to the detector. Optical sensor, characterized in that.
【청구항 9] [Claim 9]
제 1 항에 있어서, 상기 수소 광센서는 상기 광원과 광분리기 사이에 희절격자를 추가적으로 포함하는 것을 특징으로 하는 광센서 .  The optical sensor of claim 1, wherein the hydrogen optical sensor further comprises a rare lattice between the light source and the optical separator.
PCT/KR2009/002849 2008-05-28 2009-05-28 Optical hydrogen sensor WO2009145578A2 (en)

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KR101282768B1 (en) * 2010-12-21 2013-07-05 서강대학교산학협력단 Hydrogen sensing apparatus and method for producing sensor thereof

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KR0127519B1 (en) * 1994-06-29 1998-04-04 배순훈 Light pick-up apparatus
JP2005265590A (en) * 2004-03-18 2005-09-29 Fujikura Ltd Hydrogen sensor and its use

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KR0127519B1 (en) * 1994-06-29 1998-04-04 배순훈 Light pick-up apparatus
JP2005265590A (en) * 2004-03-18 2005-09-29 Fujikura Ltd Hydrogen sensor and its use

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