WO2009133997A1 - Gasochromic thin film for hydrogen sensor with improved durability and hydrogen sensor containing the same - Google Patents

Gasochromic thin film for hydrogen sensor with improved durability and hydrogen sensor containing the same Download PDF

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Publication number
WO2009133997A1
WO2009133997A1 PCT/KR2008/006324 KR2008006324W WO2009133997A1 WO 2009133997 A1 WO2009133997 A1 WO 2009133997A1 KR 2008006324 W KR2008006324 W KR 2008006324W WO 2009133997 A1 WO2009133997 A1 WO 2009133997A1
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Prior art keywords
oxide
hydrogen
thin film
hydrogen sensor
layer
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PCT/KR2008/006324
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French (fr)
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Hyeonsik Cheong
Se Hee Lee
Jae Young Shim
Jae Dong Lee
Jung Mo Jin
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Industry-University Cooperation Foundation Sogang University
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Publication of WO2009133997A1 publication Critical patent/WO2009133997A1/en

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
    • 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

Definitions

  • the present invention relates to a gasochromic thin film for a hydrogen sensor, a hydrogen sensor having the same and a method for improving a durability of a thin film for hydrogen sensor.
  • a hydrogen sensor for detecting hydrogen leakage is indispensable in an era emerging hydrogen energy. Because hydrogen has a danger of ignition at concentrations of above 4% in atmosphere, the hydrogen sensor for sensing hydrogen leakage has to be developed as a key technique in all areas controlling hydrogen energy such as hydrogen storage or hydrogen delivery for common supply of hydrogen energy.
  • the hydrogen sensor according to its use is classified into two types: one used in production process of hydrogen and the other used in detection of hydrogen leakage.
  • the sensor for detecting hydrogen leakage is divided into a leakage sensor to detect a micro-leakage of hydrogen and a safety sensor to be operated where hydrogen concentration reaches at a particular level in a certain place. Particularly, stability and high confidence are required in the safety sensor because it should be operated for hydrogen where hydrogen leakage is potentially generated although long period is passed.
  • the safety sensor's structure is convenient and its fabrication cost is low due to various and universal utilization of user classes.
  • the hydrogen sensor is classified into two types according to its operation principle: electrical sensor and photographical sensor.
  • Photographical sensor is considerable as an ideal sensor in that it enables to detect hydrogen in a long distance and has no uneasiness to the safety because electrical circuit is not involved in sensor part. It will be very helpful in the expansion of hydrogen energy to prepare a hydrogen photosensor with briefer and higher credibility and safety. Therefore, the researches to improve the durability and reactivity of sensor thin film allow a sensor to possess high credibility and safety and permit to save its production cost where optical system is easily prepared using optical pick-up set in public CD or DVD with a cost of not more than 1,000 won per a unit.
  • the sensor to use a micro-involved energy source as power source could be not needed to replace the battery in a plurality of sensors for detecting hydrogen leakage, and be independently operated (5).
  • the hydrogen sensor based on Pt-gate AIGaN/GaN heterostructure diode hydrogen sensor is operated according to the method which the electric resistance is altered whereby it is contacted with hydrogen and is not necessary to supply an additional electric power due to energy supplement using microvibration.
  • gas selectivity and a circuit necessary to wireless communication placed at the same space with sensor.
  • the conventional hydrogen sensor used an inflexible Pd with high-purity of which cost is expensive, while a novel sensor was able to be flexible and was improved its fabrication cost and function using single-walled carbon nanotubes.
  • the development of this sensor will be helpful in environmental and ecological manner and be expected to enhance much more safety and potential probability in hydrogen-based ecological system.
  • the hydrogen sensor was fabricated according to two-step processes performed in high- and low-temperature.
  • the carbon nanotube was deposited on the silicon substrate at 900 0 C using a chemical vapor deposition (CVD), and was then decorated on the plastic substrate at 150 0 C using a dry transfer printing.
  • the delicate processes allowed carbon nanotube thin film to be formed on the plastic substrate and Pd nanoparticles to be deposited on the carbon nanotube, generating the sensor.
  • Pd nanoparticle enhances interactions between hydrogen and carbon nanotube such that resistance of device may be changed according to exposure of hydrogen molecule on device.
  • the sensors with excellent mechanical flexibility exhibited sensitivity ⁇ i.e., the change of resistance) of ⁇ 75% for 0.05% hydrogen in air and response time of ⁇ 3 sec for 1% hydrogen at room temperature.
  • the flexible sensor is also operated in the same manner.
  • the plastic substrate reduces the sensor weight and prevents disruptions caused from impacts or mechanical alterations.
  • the sensors can enclose the flexible surface and apply to a variety of portable electric devices, automobiles or airplanes.
  • the sensor permits to prevent a major disaster by sensing very small amount of hydrogen leakage in a place such as spaceship.
  • it is a problem to immediately sense hydrogen because the time to sense hydrogen is so long and is also problematic that the fabrication cost of the sensor is expensive, resulting in limitation in view of commercialization. Therefore, further studies have been urgently demanded.
  • the present inventors have made intensive studies to develop a hydrogen sensor thin film and a hydrogen sensor having an improved durability. As results, we have discovered that the sensor with a catalytic layer comprising palladium (Pb) and platinum (Pt) has not only excellent durability but also remarkable sensitivity.
  • a thin film for a hydrogen sensor comprising (a) a gasochromic layer; and (b) a catalytic layer comprising palladium (Pb) and platinum (Pt) deposited on the gasochromic layer.
  • a hydrogen sensor comprising the thin film for the hydrogen sensor deposited on a substrate.
  • a method for improving a durability of a thin film for a hydrogen sensor comprising the steps of:
  • the present inventors have made intensive studies to develop a hydrogen sensor thin film and a hydrogen sensor having an improved durability. As results, we have discovered that the sensor with a catalytic layer comprising palladium (Pb) and platinum (Pt) has not only excellent durability but also remarkable sensitivity.
  • the present invention fundamentally senses hydrogen gas according to gasochromism. Any one of materials representing gasochromism may be used in the gasochromic layer in the thin film of the present invention.
  • the gasochromic layer includes (i) a transition metal oxide selected from the group consisting of tungsten oxide, tungstate, nioboxide, molybden oxide, molybdate, nickel oxide, titanium oxide, banadium oxide, iridium oxide, manganese oxide, cobalt oxide and a mixture thereof; (ii) a metal hydride selected from the group consisting of Lai- z Mg z H x , Y x- z Mg z H x , Gd 1-z Mg z H x , Yh b , LaH b , SmH b , NiMg 2 H x , CoMg 2 H x and the mixture thereof [z represents 0-1; x represents 0-5; and b represents 0-3]; or (iii) a switching polymer selected from the group consisting of polyviologen, polythiophene, polyanilin and Prussian blue.
  • a transition metal oxide selected from the group consist
  • the gasochromic layer includes the transition metal oxide selected from the group consisting of tungsten oxide, tungstate, nioboxide, molybden oxide, molybtate, nickel oxide, titanium oxide, banadium oxide, iridium oxide, manganese oxide, cobalt oxide and the mixture thereof.
  • the gasochromic layer is tungsten oxide, and most preferably WO 3 . It is one of most features of this invention that the catalytic layer consists of
  • Pb and Pt may be involved in the catalytic layer using two methods:
  • the catalytic layer includes a Pb layer and a Pt layer.
  • the catalytic layer includes a Pb-Pt alloy layer.
  • the second method is preferable in view of durability and sensitivity.
  • Pb and Pt in the thin film for the hydrogen sensor of this invention may be deposited on the gasochromic layer according to various methods, preferably a reactive sputtering method and more preferably a RF (radio frequency) or a DC sputtering method.
  • the content of Pb and Pt involved in the catalytic layer preferably is 20-50 wt% and 50-80 wt%, and more preferably 30-40 wt% and 60-70 wt%, respectively.
  • the substrate on which the thin film of this invention is coated includes any one of substrates used in the sensors known to those skilled in the art.
  • the substrate is selected from the group consisting of silicone, glass, quartz, fused silica, stainless steel, mica, carbon, carbon nanotube, polymer, ceramic and porcelain enamel.
  • the hydrogen sensor of this invention is based on the gasochromism and includes Pb and Pt in the gasochromic layer.
  • the hydrogen sensor of this invention represents much more improved durability having its reactivity in above 1000 cycles.
  • the hydrogen sensor of this invention represents much more enhanced sensitivity.
  • the hydrogen sensor of this invention for safe utilization of hydrogen energy may be used in a photosensor for sensing a hydrogen leakage, and be also promising in its marketability in the senses that the hydrogen energy as an alternative powerful energy source is widely used.
  • Fig. 1 schematically represents an embodiment of the present thin film for a hydrogen sensor.
  • the thin film for the hydrogen sensor represents a gasochromic material which is divided into a catalytic layer and a gasochromic layer.
  • Tungsten oxide layer in the thin film for sensor is deposited on the substrate according to a sputtering method and then the catalytic layer is fabricated by an alloy sputtering Pb and Pt simultaneously.
  • the catalytic layer is a part contacting with hydrogen in atmosphere and hydrogen gas on the thin film is disassociated into hydrogen cation and electron by catalyzer after contacting with the catalytic layer. Dissociated ions are diffused by Pb involved in the catalytic layer and are transferred to the chromic layer.
  • the light is absorbed into the gasochromic layer through small polaron transition whereby ionic bond of tungsten is partially reduced by the transferred ions.
  • the thin film absorbing the light is darkly changed due to properties of tungsten oxide, a cathodic gasochromic material and hydrogen photosensor is fabricated by measuring its optical transmittance and reflection.
  • Fig. 2 is a graph representing changes of Raman Spectra before and after hydrogen injection, (a) Pd/ ⁇ -W0 3 , (b) Pd-Pt/ ⁇ -WO 3 .
  • Fig. 3 is a graph representing changes of optical transmittance at an early cycling of heat-deposited Pd/ ⁇ -WO 3 and after 300 cycles of thermal-deposited Pd/ ⁇ - WO 3 .
  • Fig. 4 is a graph representing changes of optical transmittance at an early cycling of sputtered Pd/ ⁇ -W0 3 and after 300 cycles of sputtered Pd/ ⁇ -W0 3 .
  • Fig. 5 is a graph representing changes of optical transmittance at an early cycling of the present Pd/ ⁇ -WO 3 and after 300 cycles of the present Pd/ ⁇ -WO 3 .
  • Fig. 6 is a graph representing changes of optical transmittance by the repetitive cycles of heat-deposited Pd/ ⁇ -WO 3 .
  • Fig. 7 is a graph representing changes of optical transmittance by the repetitive cycles of sputtered Pd/ ⁇ -WO 3 .
  • Fig. 8 is a graph representing changes of optical transmittance by the repetitive cycles of the present Pd/ ⁇ -WO 3 .
  • Electrochromic material refers to substances that their colors are changed by injection or extraction of electric charge (cation ions or electrons) (1). Based on the fact that electrochromism is generated where ions and electrons is injected and extracted to the thin film such as WO 3 , gasochromism by hydrogen gas has been studied (2) and the possibility to apply optical sensor for detecting hydrogen has been intensively researched (3).
  • a representative gasochromic material is Pd/ ⁇ -W0 3 double layer thin film. Pd deposited on the WO 3 functions a catalyst material decomposing hydrogen molecule into proton and electron. Because the color of the gasochromic material is changed by contacting with hydrogen gas, hydrogen leakage could be detected by measuring the changes of its optical transmittance.
  • the optical sensor for detecting hydrogen gas measures the optical transmittance of the material in an optical manner, there are diverse advantages such as (i) exclusion of electrical spark by no use of the electric current at the position of sensor material and (ii) remote detection to hydrogen by separation of sensor part and control part using optical fibers.
  • an optical fiber sensor for detecting hydrogen its operation is much more stable than that of electrical sensor in that the loss in optical fiber is rare and the interference by external electromagnetic wave is not occurred (4).
  • high durability in addition to hydrogen reactivity is demanded.
  • Pd/ ⁇ -W0 3 sensor Pd/ ⁇ -W0 3 thin film is deteriorated where it is repeatedly exposed to hydrogen and the sensitivity of sensor thin film is rapidly decreased where the surface of Pd thin film is exposed in air for a long period. Therefore, the studies to improve the durability of thin film material of sensor are compelled.
  • Pd-Pt/ ⁇ -WO 3 was prepared using a sputtering method to fabricate hydrogen photosensor with improved durability, and its reactivity and durability depending on exposure to hydrogen were examined using Raman spectroscopy and optical transmittance. Based on the experimental results, application possibility was tested by preparing a prototype of photosensor for detecting hydrogen.
  • the present inventors have intensively studied to optimerize the combination of sensor thin film and catalytic thin film using a reactive sputtering method for preparing the sensor thin film with more excellent durability and with more improved cycling compared with the conventional thin films.
  • ⁇ -W0 3 electrochromic thin film was fabricated using RF (radio frequency) and DC sputtering method, and Pd as the catalytic, thin film was deposited on its surface.
  • Pd/ ⁇ -WO 3 thin film optimerized to hydrogen response was prepared by various combinations of the thickness ratio of sensor thin film to catalytic thin film.
  • Pt/Pd/ ⁇ -WO 3 double layer thin film and Pd-Pt/ ⁇ -WO 3 were prepared to enhance the durability of thin film.
  • RF sputtering method was carried out by regulating O 2 flux in Ar gas substrate using tungsten target.
  • Pd layer was prepared according to DC sputtering method using Pd target.
  • Pt/Pd/ ⁇ -WO 3 double layer catalytic thin film was fabricated according to the RF sputtering method utilizing Pt layer on the above-described Pd/ ⁇ -WO 3 as Pt target.
  • Pd-Pt alloy thin film was prepared according to a co-sputtering method which two materials are simultaneously deposited using a multi-target sputtering system.
  • the physical property of the thin films was investigated by measurement of their Raman spectra depending on exposure to hydrogen and air. To test improved durability, the change of optical transmittance was measured by repeatedly exposing the sensor thin films to 1% hydrogen and air.
  • Pd-Pt/ ⁇ -WO 3 was prepared using DC & RF sputtering chamber (Korea Vacuum Tech., Ltd.) with multi-target system.
  • Ci-WO 3 was deposited on the substrate via RF sputtering with 80 of RF POWER for 120 min after 2 x 10 "6 torr of Working pressure was given to tungsten target in the flux of 8 seem of Ar gas and 0.4 seem of O 2 gas according to the reactive sputtering method.
  • Each slide glass and stainless steel was used as the substrate for testing optical transmittance and measuring in-situ Raman spectroscopy.
  • the target used in the present invention was tungsten target with 99.9% purity (Asem Tech., Co.). Since the multi-target system could utilize Pd and Pt target simultaneous, Pd-Pt alloy thin film was deposited on the above-prepared ⁇ -W0 3 using co-sputtering method after each Pd and Pt target was equipped in DC sputter gun and RF sputter gun.
  • the co-sputtering method is a method which simultaneously deposits two materials on single substrate by concurrently sputtering two or more targets. In the present invention, it was carried out on the substrate in the flux of 5 seem of Ar gas, in which Pd and Pt targets (Asem Tech., Co.) with 99.9% purity were used.
  • Pd target was deposited for 3 min in a range of from 0.05 A to 0.1 A of DC POWER and Pt target was deposited for 3 min at 40 V of RF POWER.
  • the composition of alloy measured using EPMA Electro Probe Micro Analyzer, Japan JEOL Co., JXA- 8900R was 32% of Pd and 68% of Pt.
  • Optical transmittance was measured in the condition of hydrogen injection for practical application of Pd-Pt/ ⁇ -WO 3 as a sensor material. Artificial air containing 1% of hydrogen, 80% of nitrogen and 20% oxygen was repetitively injected for predetermined period at a rate of 2,000 seem and then the optical transmittance of Pd-Pt/ ⁇ -WO 3 was measured. In comparison with heat-deposited Pd-Pt/ ⁇ -WO 3 , sputtered Pd-Pt/ ⁇ -WO 3 and Pd-Pt/ ⁇ -WO 3 , the present inventors demonstrated that in others except heat deposition, each response time was within 1 sec and optical transmittance lowed by hydrogen injection was more rapidly restored where hydrogen injection was finished and then oxygen was injected.
  • the present inventors investigated changes of optical transmittance according to repetitive cycling.
  • the durability of heat-deposited Pd-Pt/ ⁇ -WO 3 is lower than that of sputtered Pd-Pt/ ⁇ -WO 3 .
  • Continuous changes of optical transmittance were observed in sputtered Pd-Pt/ ⁇ -WO 3 even and in Pd-Pt/ ⁇ -WO 3 even after 500 cycling and above 1,200 cycling, respectively (Figs. 6-8), suggesting that the durability of sensor thin film comprising the alloy is improved as compared with that of a conventional Pd/ ⁇ -WO 3 .
  • the catalytic activity of alloy layer permits the present thin film to enhance the resistance potential to contaminant materials.

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Abstract

The present invention provides a thin film for a hydrogen sensor comprising a catalytic layer which comprises (a) a gasochromic layer; and (b) palladium (Pb) and platinum (Pt) deposited on the gasochromic layer and a hydrogen sensor having the same. The hydrogen sensor of the present invention represents not only much more improved durability having its reactivity in above 1000 cycles but also much more enhanced sensitivity. The hydrogen sensor of this invention for safe utilization of hydrogen energy may be used in a photosensor for sensing a hydrogen leakage, and be also promising in its marketability in the senses that the hydrogen energy as an alternative powerful energy source is widely used.

Description

GASOCHROMIC THIN FILM FOR HYDROGEN SENSOR WITH IMPROVED DURABILITY AND HYDROGEN SENSOR CONTAINING THE SAME
BACKGROUND OF THE INVENTION
FIELD OF THE INVENTION
The present invention relates to a gasochromic thin film for a hydrogen sensor, a hydrogen sensor having the same and a method for improving a durability of a thin film for hydrogen sensor.
BACKGROUND OF TECHNIQUE
The oil prices have recently up-risen over 100 dollars per barrel. In addition to environment problem, high-cost oil was one of most problems of fossil energy, generating increase in global demands for alternative energy. Studies and commercial services for utilization technologies of hydrogen as a prominent alternative energy source have been gradually expanded in advanced countries. The techniques to utilize hydrogen have been developed in a main axis of Department of Energy in USA, and Japan and Germany have also invested numerous manpower and capital for exploiting the techniques for utilization of hydrogen energy to substitute for fossil energy. In addition, Iceland put spurs to development and commercial service of hydrogen energy with a goal of achieving a hydrogen society in 2040. To overcome an import-dependent energy problem, Korea has also researched the storage and utilization techniques of hydrogen energy. Since a hydrogen station has been initially built in Daedeok, it was established in the heart of Seoul in 2007. It is planning to build 1700 of hydrogen stations in the whole nation until 2020.
A hydrogen sensor for detecting hydrogen leakage is indispensable in an era emerging hydrogen energy. Because hydrogen has a danger of ignition at concentrations of above 4% in atmosphere, the hydrogen sensor for sensing hydrogen leakage has to be developed as a key technique in all areas controlling hydrogen energy such as hydrogen storage or hydrogen delivery for common supply of hydrogen energy. The hydrogen sensor according to its use is classified into two types: one used in production process of hydrogen and the other used in detection of hydrogen leakage. The sensor for detecting hydrogen leakage is divided into a leakage sensor to detect a micro-leakage of hydrogen and a safety sensor to be operated where hydrogen concentration reaches at a particular level in a certain place. Particularly, stability and high confidence are required in the safety sensor because it should be operated for hydrogen where hydrogen leakage is potentially generated although long period is passed. The safety sensor's structure is convenient and its fabrication cost is low due to various and universal utilization of user classes.
On the other hand, the hydrogen sensor is classified into two types according to its operation principle: electrical sensor and photographical sensor. Photographical sensor is considerable as an ideal sensor in that it enables to detect hydrogen in a long distance and has no uneasiness to the safety because electrical circuit is not involved in sensor part. It will be very helpful in the expansion of hydrogen energy to prepare a hydrogen photosensor with briefer and higher credibility and safety. Therefore, the researches to improve the durability and reactivity of sensor thin film allow a sensor to possess high credibility and safety and permit to save its production cost where optical system is easily prepared using optical pick-up set in public CD or DVD with a cost of not more than 1,000 won per a unit.
The most active field in utilization of hydrogen energy is a motorcycle technology. In particular, the study to develop hydrogen fuel cell automobile is more actively processed. The development of hydrogen sensor technique for commercial service to hydrogen fuel cell automobile also has been extensively studied.
Professor Jenshan Lin and graduate students of Department of Electrical and Computer engineering in University of Florida developed a hydrogen microsensor to express an alarm using wireless communications after detecting hydrogen leakage. The sensor to use a micro-involved energy source as power source could be not needed to replace the battery in a plurality of sensors for detecting hydrogen leakage, and be independently operated (5). The hydrogen sensor based on Pt-gate AIGaN/GaN heterostructure diode hydrogen sensor is operated according to the method which the electric resistance is altered whereby it is contacted with hydrogen and is not necessary to supply an additional electric power due to energy supplement using microvibration. However, as shown in most sensors using a FEET method, there are several problems such as gas selectivity and a circuit necessary to wireless communication placed at the same space with sensor. In addition, the scientists of Argonne National Laboratory in USA have developed a flexible hydrogen sensor using a nanoparticle as a core part of hydrogen fuel-cell used in hydrogen automobile (6). The conventional hydrogen sensor used an inflexible Pd with high-purity of which cost is expensive, while a novel sensor was able to be flexible and was improved its fabrication cost and function using single-walled carbon nanotubes. The development of this sensor will be helpful in environmental and ecological manner and be expected to enhance much more safety and potential probability in hydrogen-based ecological system. The hydrogen sensor was fabricated according to two-step processes performed in high- and low-temperature. The carbon nanotube was deposited on the silicon substrate at 9000C using a chemical vapor deposition (CVD), and was then decorated on the plastic substrate at 1500C using a dry transfer printing. The delicate processes allowed carbon nanotube thin film to be formed on the plastic substrate and Pd nanoparticles to be deposited on the carbon nanotube, generating the sensor. Pd nanoparticle enhances interactions between hydrogen and carbon nanotube such that resistance of device may be changed according to exposure of hydrogen molecule on device. The sensors with excellent mechanical flexibility exhibited sensitivity {i.e., the change of resistance) of ~75% for 0.05% hydrogen in air and response time of ~3 sec for 1% hydrogen at room temperature. The flexible sensor is also operated in the same manner. In addition, it is advantageous in the senses that the plastic substrate reduces the sensor weight and prevents disruptions caused from impacts or mechanical alterations. Moreover, the sensors can enclose the flexible surface and apply to a variety of portable electric devices, automobiles or airplanes. In particular, the sensor permits to prevent a major disaster by sensing very small amount of hydrogen leakage in a place such as spaceship. However, it is a problem to immediately sense hydrogen because the time to sense hydrogen is so long and is also problematic that the fabrication cost of the sensor is expensive, resulting in limitation in view of commercialization. Therefore, further studies have been urgently demanded.
Throughout this application, various publications and patents are referred and citations are provided in parentheses. The disclosures of these publications and patents in their entities are hereby incorporated by references into this application in order to fully describe this invention and the state of the art to which this invention pertains.
DETAILED DESCRIPTION OF THE INVENTION
The present inventors have made intensive studies to develop a hydrogen sensor thin film and a hydrogen sensor having an improved durability. As results, we have discovered that the sensor with a catalytic layer comprising palladium (Pb) and platinum (Pt) has not only excellent durability but also remarkable sensitivity.
Accordingly, it is an object of this invention to provide a thin film for a hydrogen sensor. It is another object of this invention to provide a hydrogen sensor.
It is still another object of this invention to provide a method for improving a durability of a thin film for a hydrogen sensor. Other objects and advantages of the present invention will become apparent from the following detailed description together with the appended claims and drawings.
In one aspect of this invention, there is provided a thin film for a hydrogen sensor comprising (a) a gasochromic layer; and (b) a catalytic layer comprising palladium (Pb) and platinum (Pt) deposited on the gasochromic layer.
In another aspect of this invention, there is provided a hydrogen sensor comprising the thin film for the hydrogen sensor deposited on a substrate. In still another aspect of this invention, there is provided a method for improving a durability of a thin film for a hydrogen sensor comprising the steps of:
(a) fabricating a gasochromic layer; and
(b) preparing the thin film for the hydrogen sensor by depositing a catalytic layer comprising a Pb and a Pt on the gasochromic layer.
The present inventors have made intensive studies to develop a hydrogen sensor thin film and a hydrogen sensor having an improved durability. As results, we have discovered that the sensor with a catalytic layer comprising palladium (Pb) and platinum (Pt) has not only excellent durability but also remarkable sensitivity. The present invention fundamentally senses hydrogen gas according to gasochromism. Any one of materials representing gasochromism may be used in the gasochromic layer in the thin film of the present invention.
According to a preferable embodiment, the gasochromic layer includes (i) a transition metal oxide selected from the group consisting of tungsten oxide, tungstate, nioboxide, molybden oxide, molybdate, nickel oxide, titanium oxide, banadium oxide, iridium oxide, manganese oxide, cobalt oxide and a mixture thereof; (ii) a metal hydride selected from the group consisting of Lai-zMgzHx, Yx- zMgzHx, Gd1-zMgzHx, Yhb, LaHb, SmHb, NiMg2Hx, CoMg2Hx and the mixture thereof [z represents 0-1; x represents 0-5; and b represents 0-3]; or (iii) a switching polymer selected from the group consisting of polyviologen, polythiophene, polyanilin and Prussian blue.
More preferably, the gasochromic layer includes the transition metal oxide selected from the group consisting of tungsten oxide, tungstate, nioboxide, molybden oxide, molybtate, nickel oxide, titanium oxide, banadium oxide, iridium oxide, manganese oxide, cobalt oxide and the mixture thereof.
Much more preferably, the gasochromic layer is tungsten oxide, and most preferably WO3. It is one of most features of this invention that the catalytic layer consists of
Pb and Pt. Generally, Pb and Pt may be involved in the catalytic layer using two methods:
According to the first method, the catalytic layer includes a Pb layer and a Pt layer. According to the second method, the catalytic layer includes a Pb-Pt alloy layer.
Of them, the second method is preferable in view of durability and sensitivity.
Pb and Pt in the thin film for the hydrogen sensor of this invention may be deposited on the gasochromic layer according to various methods, preferably a reactive sputtering method and more preferably a RF (radio frequency) or a DC sputtering method.
The content of Pb and Pt involved in the catalytic layer preferably is 20-50 wt% and 50-80 wt%, and more preferably 30-40 wt% and 60-70 wt%, respectively.
The substrate on which the thin film of this invention is coated includes any one of substrates used in the sensors known to those skilled in the art. For example, the substrate is selected from the group consisting of silicone, glass, quartz, fused silica, stainless steel, mica, carbon, carbon nanotube, polymer, ceramic and porcelain enamel. The features and advantages of the present invention will be summarized as follows:
(i) The hydrogen sensor of this invention is based on the gasochromism and includes Pb and Pt in the gasochromic layer.
(ii) The hydrogen sensor of this invention represents much more improved durability having its reactivity in above 1000 cycles.
(iii) The hydrogen sensor of this invention represents much more enhanced sensitivity. (iv) The hydrogen sensor of this invention for safe utilization of hydrogen energy may be used in a photosensor for sensing a hydrogen leakage, and be also promising in its marketability in the senses that the hydrogen energy as an alternative powerful energy source is widely used.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 schematically represents an embodiment of the present thin film for a hydrogen sensor. The thin film for the hydrogen sensor represents a gasochromic material which is divided into a catalytic layer and a gasochromic layer. Tungsten oxide layer in the thin film for sensor is deposited on the substrate according to a sputtering method and then the catalytic layer is fabricated by an alloy sputtering Pb and Pt simultaneously. The catalytic layer is a part contacting with hydrogen in atmosphere and hydrogen gas on the thin film is disassociated into hydrogen cation and electron by catalyzer after contacting with the catalytic layer. Dissociated ions are diffused by Pb involved in the catalytic layer and are transferred to the chromic layer. The light is absorbed into the gasochromic layer through small polaron transition whereby ionic bond of tungsten is partially reduced by the transferred ions. The thin film absorbing the light is darkly changed due to properties of tungsten oxide, a cathodic gasochromic material and hydrogen photosensor is fabricated by measuring its optical transmittance and reflection.
Fig. 2 is a graph representing changes of Raman Spectra before and after hydrogen injection, (a) Pd/α-W03, (b) Pd-Pt/α-WO3. Fig. 3 is a graph representing changes of optical transmittance at an early cycling of heat-deposited Pd/α-WO3 and after 300 cycles of thermal-deposited Pd/α- WO3.
Fig. 4 is a graph representing changes of optical transmittance at an early cycling of sputtered Pd/α-W03 and after 300 cycles of sputtered Pd/α-W03. Fig. 5 is a graph representing changes of optical transmittance at an early cycling of the present Pd/α-WO3 and after 300 cycles of the present Pd/α-WO3.
Fig. 6 is a graph representing changes of optical transmittance by the repetitive cycles of heat-deposited Pd/α-WO3.
Fig. 7 is a graph representing changes of optical transmittance by the repetitive cycles of sputtered Pd/α-WO3.
Fig. 8 is a graph representing changes of optical transmittance by the repetitive cycles of the present Pd/α-WO3.
The present invention will now be described in further detail by examples. It would be obvious to those skilled in the art that these examples are intended to be more concretely illustrative and the scope of the present invention as set forth in the appended claims is not limited to or by the examples.
EXAMPLES Materials and Methods
Electrochromic material refers to substances that their colors are changed by injection or extraction of electric charge (cation ions or electrons) (1). Based on the fact that electrochromism is generated where ions and electrons is injected and extracted to the thin film such as WO3, gasochromism by hydrogen gas has been studied (2) and the possibility to apply optical sensor for detecting hydrogen has been intensively researched (3). A representative gasochromic material is Pd/α-W03 double layer thin film. Pd deposited on the WO3 functions a catalyst material decomposing hydrogen molecule into proton and electron. Because the color of the gasochromic material is changed by contacting with hydrogen gas, hydrogen leakage could be detected by measuring the changes of its optical transmittance. Because the optical sensor for detecting hydrogen gas measures the optical transmittance of the material in an optical manner, there are diverse advantages such as (i) exclusion of electrical spark by no use of the electric current at the position of sensor material and (ii) remote detection to hydrogen by separation of sensor part and control part using optical fibers. In an optical fiber sensor for detecting hydrogen, its operation is much more stable than that of electrical sensor in that the loss in optical fiber is rare and the interference by external electromagnetic wave is not occurred (4). To apply the sensor as safety sensor detecting hydrogen for a long period, high durability in addition to hydrogen reactivity is demanded. However, in Pd/α-W03 sensor, Pd/α- WO3 thin film is deteriorated where it is repeatedly exposed to hydrogen and the sensitivity of sensor thin film is rapidly decreased where the surface of Pd thin film is exposed in air for a long period. Therefore, the studies to improve the durability of thin film material of sensor are compelled. In this invention, Pd-Pt/α-WO3 was prepared using a sputtering method to fabricate hydrogen photosensor with improved durability, and its reactivity and durability depending on exposure to hydrogen were examined using Raman spectroscopy and optical transmittance. Based on the experimental results, application possibility was tested by preparing a prototype of photosensor for detecting hydrogen.
The present inventors have intensively studied to optimerize the combination of sensor thin film and catalytic thin film using a reactive sputtering method for preparing the sensor thin film with more excellent durability and with more improved cycling compared with the conventional thin films. α-W03 electrochromic thin film was fabricated using RF (radio frequency) and DC sputtering method, and Pd as the catalytic, thin film was deposited on its surface. As results, Pd/α-WO3 thin film optimerized to hydrogen response was prepared by various combinations of the thickness ratio of sensor thin film to catalytic thin film. In addition, Pt/Pd/α-WO3 double layer thin film and Pd-Pt/α-WO3 were prepared to enhance the durability of thin film. To prepare α-W03 layer, RF sputtering method was carried out by regulating O2 flux in Ar gas substrate using tungsten target. Pd layer was prepared according to DC sputtering method using Pd target. Pt/Pd/α-WO3 double layer catalytic thin film was fabricated according to the RF sputtering method utilizing Pt layer on the above-described Pd/α-WO3 as Pt target. Pd-Pt alloy thin film was prepared according to a co-sputtering method which two materials are simultaneously deposited using a multi-target sputtering system. The physical property of the thin films was investigated by measurement of their Raman spectra depending on exposure to hydrogen and air. To test improved durability, the change of optical transmittance was measured by repeatedly exposing the sensor thin films to 1% hydrogen and air.
Results
Pd-Pt/a-W03 Preparation
Pd-Pt/α-WO3 was prepared using DC & RF sputtering chamber (Korea Vacuum Tech., Ltd.) with multi-target system. To prepare Pd-Pt/α-WO3 alloy catalytic thin film, Ci-WO3 was deposited on the substrate via RF sputtering with 80 of RF POWER for 120 min after 2 x 10"6 torr of Working pressure was given to tungsten target in the flux of 8 seem of Ar gas and 0.4 seem of O2 gas according to the reactive sputtering method. Each slide glass and stainless steel was used as the substrate for testing optical transmittance and measuring in-situ Raman spectroscopy. The target used in the present invention was tungsten target with 99.9% purity (Asem Tech., Co.). Since the multi-target system could utilize Pd and Pt target simultaneous, Pd-Pt alloy thin film was deposited on the above-prepared α-W03 using co-sputtering method after each Pd and Pt target was equipped in DC sputter gun and RF sputter gun. The co-sputtering method is a method which simultaneously deposits two materials on single substrate by concurrently sputtering two or more targets. In the present invention, it was carried out on the substrate in the flux of 5 seem of Ar gas, in which Pd and Pt targets (Asem Tech., Co.) with 99.9% purity were used. Pd target was deposited for 3 min in a range of from 0.05 A to 0.1 A of DC POWER and Pt target was deposited for 3 min at 40 V of RF POWER. In addition, the composition of alloy measured using EPMA (Electron Probe Micro Analyzer, Japan JEOL Co., JXA- 8900R) was 32% of Pd and 68% of Pt.
Based on the results to compare in-situ Raman spectrum of Pd-Pt/α-WO3 with that of Pd/α-WO3 for, W5+=O bond was shifted to W6+=O before and after hydrogen injection, demonstrating that gasochromic phenomenon of Pd-Pt/α-WO3 is similar to that of Pd/ Q-WO3 (Fig. 2).
Measurement of Optical Transmittance Change of Pd-Pt/α-WO3
Optical transmittance was measured in the condition of hydrogen injection for practical application of Pd-Pt/α-WO3 as a sensor material. Artificial air containing 1% of hydrogen, 80% of nitrogen and 20% oxygen was repetitively injected for predetermined period at a rate of 2,000 seem and then the optical transmittance of Pd-Pt/α-WO3 was measured. In comparison with heat-deposited Pd-Pt/α-WO3, sputtered Pd-Pt/α-WO3 and Pd-Pt/α-WO3, the present inventors demonstrated that in others except heat deposition, each response time was within 1 sec and optical transmittance lowed by hydrogen injection was more rapidly restored where hydrogen injection was finished and then oxygen was injected. In injection of each hydrogen and oxygen for 60 sec per a cycle, it could be appreciated that the decrease and restoration of optical transmittance was improved in alloy even after 500 cycles. These results demonstrated that irrespective of contacting with hydrogen for a long period, the operation of the decrease and restoration of optical transmittance to hydrogen response is more excellent in the present invention than in a conventional method (Figs. 3-5).
Durability Measurement of Pd-Pt/α-WO3
The present inventors investigated changes of optical transmittance according to repetitive cycling. The durability of heat-deposited Pd-Pt/α-WO3 is lower than that of sputtered Pd-Pt/α-WO3. Continuous changes of optical transmittance were observed in sputtered Pd-Pt/α-WO3 even and in Pd-Pt/α-WO3 even after 500 cycling and above 1,200 cycling, respectively (Figs. 6-8), suggesting that the durability of sensor thin film comprising the alloy is improved as compared with that of a conventional Pd/α-WO3. In addition, the catalytic activity of alloy layer permits the present thin film to enhance the resistance potential to contaminant materials. As shown in changes of optical transmittance, its change in Pd/α-WO3 was about 35% while that in Pd-Pt/α-WO3 was not less than about 80%, representing that the catalytic layer including Pd and Pt is more effective than that including only Pd. Accordingly, the durability and sensitivity of Pd-Pt/α-WO3 was improved much higher than that of Pd/α-WO3 prepared by the conventional sputtering method because the change of α-W03, the gasochromic layer, was remarkably facilitated via efficient decomposition of hydrogen by Pt.
Having described a preferred embodiment of the present invention, it is to be understood that variants and modifications thereof falling within the spirit of the invention may become apparent to those skilled in this art, and the scope of this invention is to be determined by appended claims and their equivalents. References
1. F. J. A. den Broeder, S. J. van der Molen, M. Kremers, J. N. Huiberts, D. G. Nagengast, A. T. M. van Gogh, W. H. Huisman, N. J. Koeman, B. Dam, J. H. Rector, S. Plota, M. Haaksma, R. M. N. Hanzen, R. M. Jungblut, P. A. Duine, and R. Griessen, "Visualization of hydrogen migration in solids using switchable mirrors," Nature 394, 656 (1998).
2. R. D. Smith, R. Pitts, S.-H. Lee, and E. Tracy, "Fiber Optic Hydrogen Sensors Based on Gasochromic Thin Films," International Meeting on Electrochromics, Brno, Czech Republic, August 29 - September 2, (2004). 3. H. Cheong, H. C. Jo, K. M. Kim, and S.-H. Lee, "Hydrogen Sensors Based on Gasochromic Oxide Thin Films," Journal of the Korean Physical Society 46, S121-124 (2005).
4. R. D. Smith, R. Pitts, S.-H. Lee, and E. Tracy, "Fiber Optic Hydrogen Sensors Based on Gasochromic Thin Films," International Meeting on Electrochromics, Brno, Czech Republic, August 29 - September 2, (2004).
5. Hung-Ta Wang, T. J. Anderson, B. S. Kang, and F. Ren, Jenshan, "Lin Stable hydrogen sensors from AIGaN/GaN heterostructure diodes with TiB2-based Ohmic contacts," Applied Physics Letters 90, 252109 (2007).
6. Yugang Sun, H. Hau Wang, "Electrodeposition of Pd nanoparticles on single-walled carbon nanotubes for flexible hydrogen sensors," Applied Physics Letters 90, 213107
(2007)
7. J. N. Huiberts, R. Griessen, J. H. Rector, R. J. Wijngaarden, J. P. Dekker, D. G. de Groot, and N. J. Koeman, "Yttrium and lanthanum hydride films with switchable optical properties," Nature 380, 231 (1996). 8. S.-H. Lee, E. Tracy, R. Pitts, and P. Liu, "Pd/Ni-WO3 Anodic Double Layer Gasochromic Device," U.S. Patent No. 6,723,566 (2004).

Claims

What is claimed is:
1. A thin film for a hydrogen sensor comprising (a) a gasochromic layer; and (b) a catalytic layer comprising palladium (Pb) and platinum (Pt) deposited on the gasochromic layer.
2. The thin film for the hydrogen sensor according to claim 1, wherein the gasochromic layer comprises (i) a transition metal oxide selected from the group consisting of tungsten oxide, tungstate, nioboxide, molybden oxide, molybdate, nickel oxide, titanium oxide, banadium oxide, iridium oxide, manganese oxide, cobalt oxide and a mixture thereof; (ii) a metal hydride selected from the group consisting of Lai-zMgzHx, Yi-zMgzHx, Gd1-zMgzHx, Yhb, LaHb, SmHb, NiMg2Hx, CoMg2Hx and the .mixture thereof [z represents 0-1; x represents 0-5; and b represents 0-3]; or (iii) a switching polymer selected from the group consisting of polyviologen, polythiophene, polyanilin and prussian blue.
3. The thin film for the hydrogen sensor according to claim 2, wherein the gasochromic layer comprises the transition metal oxide selected from the group consisting of tungsten oxide, tungstate, nioboxide, molybden oxide, molybtate, nickel oxide, titanium oxide, banadium oxide, iridium oxide, manganese oxide, cobalt oxide and the mixture thereof.
4. The thin film for the hydrogen sensor according to claim 1, wherein the catalytic layer comprises a Pb layer and a Pt layer.
5. The thin film for the hydrogen sensor according to claim 1, wherein the catalytic layer comprises a Pb-Pt alloy layer.
6. The thin film for the hydrogen sensor according to claim 1, wherein the catalytic layer is deposited on the gasochromic layer using a reactive sputtering method. -
7. The thin film for the hydrogen sensor according to claim 6, wherein the reactive sputtering method is a RF (radio frequency) method or a DC sputtering method.
8. The thin film for the hydrogen sensor according to claim 1, wherein the catalytic layer comprises 20-50 wt% of Pb and 50-80 wt% of Pt.
9. A hydrogen sensor comprising the thin film for the hydrogen sensor according to any one of claims 1-8 deposited on a substrate.
10. The hydrogen sensor according to claim 9, wherein the substrate is selected from the group consisting of silicone, glass, quartz, fused silica, stainless steel, mica, carbon, carbon nanotube, polymer, ceramic and porcelain enamel.
11. A method for improving a durability of a thin film for a hydrogen sensor comprising the steps of: (a) fabricating a gasochromic layer; and
(b) preparing the thin film for the hydrogen sensor by depositing a catalytic layer comprising a Pb and a Pt on the gasochromic layer.
12. The method according to claim 11, wherein the gasochromic layer comprises (i) a transition metal oxide selected from the group consisting of tungsten oxide, tungstate, nioboxide, molybden oxide, molybdate, nickel oxide, titanium oxide, banadium oxide, iridium oxide, manganese oxide, cobalt oxide and the mixture thereof; (ii) a metal hydride selected from the group consisting of Lai-zMgzHx, Yi- zMgzHx, Gd1-zMgzHx, Yhb, LaHb, SmHb, NiMg2Hx, CoMg2Hx and the mixture thereof [z represents 0-1; x represents 0-5; and b represents 0-3]; or (Ni) a switching polymer selected from the group consisting of polyviologen, polythiophene, polyanilin and Prussian blue.
13. The method according to claim 12, wherein the gasochromic layer comprises the transition metal oxide selected from the group consisting of tungsten oxide, tungstate, nioboxide, molybden oxide, molybtate, nickel oxide, titanium oxide, banadium oxide, iridium oxide, manganese oxide, cobalt oxide and mixtures thereof.
14. The method according to claim 11, wherein the catalytic layer comprises the Pb layer and the Pt layer.
15. The method according to claim 11, wherein the catalytic layer comprises the Pb-Pt alloy layer.
16. The method according to claim 11, wherein the catalytic layer is deposited on the gasochromic layer using the reactive sputtering method.
17. The method according to claim 16, wherein the reactive sputtering method comprises the RF (radio frequency) or the DC sputtering method.
18. The method according to claim 11, wherein the catalytic layer comprises 20- 50 wt% of Pb and 50-80 wt% of Pt.
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