CN1871509A - Proton acceptance type sensor, hydrogen gas sensor and acid sensor - Google Patents
Proton acceptance type sensor, hydrogen gas sensor and acid sensor Download PDFInfo
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Abstract
An acid or hydrogen gas sensor, wherein an organic compound having a pyridine ring introduced therein (for example, pyridine DPP) is contacted with proton, and the change associated with the addition of proton in the electric resistance, optical conductivity or an optical absorption band is detected. The above sensor exhibits high sensory selectivity for proton and thus can provide a hydrogen gas sensor capable of operating at room temperature at a low cost and also a sensor having high sensitivity which is of great utility for the detection of a hydrogen gas and the prevention of troubles by the leakage of the gas, in a production factory using a hydrogen gas as a carrier, hydrogen gas storage facilities, and the so-called fuel battery using a hydrogen gas as the energy source thereof. The sensor is also effective as an acid sensor for hydrofluoric acid and the like.
Description
Technical Field
The invention relates to proton (H)+) The sensor of (2) has good sensing selectivity, and particularly relates to a hydrogen sensor and an acid sensor.
Background
In recent years, various gases are often used in the production process of products, and in particular, volatile or toxic gases are often used in semiconductor manufacturing plants because a gas chemical reaction process is employed on a single crystal silicon substrate. Here, hydrogen is used in large quantities as a carrier gas for this gas. However, hydrogen itself is a highly explosive gas, and leakage of hydrogen needs to be detected as early as possible.
Further, fossil fuels such as petroleum are at risk of depletion, and various alternative energy sources have been studied. Hydrogen can be easily obtained not only by electrolyzing water but also by using water as a combustion product with no CO emission2Or NOx、SOxAnd the like, and is said to be a very excellent next-generation energy source.
As a method of converting hydrogen energy into electric power, a fuel cell using a chemical reaction of hydrogen and oxygen is attracting attention. In particular, a fuel cell vehicle equipped with a fuel cell is considered as an "optimum environment-friendly vehicle". However, hydrogen is the lightest and small molecule, has a characteristic of being easily leaked, easily catches fire, and has a high combustion speed, and therefore, is considered to be an extremely dangerous gas. Therefore, it is conceivable that the position of the hydrogen sensor will become more and more important if the hydrogen energy system is popularized in the future.
At present, a semiconductor type product using a metal oxide is representative of a hydrogen sensor. Although such a product has high sensitivity and reliability, the sensor element itself needs to be heated at a high temperature. Therefore, there is a limit to downsizing, weight reduction, power consumption reduction, or cost reduction of the sensor, and it is not possible to cope with various applications.
Specific examples of the hydrogen gas sensor include Japanese patent application laid-open No. 59-120945. The hydrogen sensor mentioned therein has: a pair of opposed electrodes formed on one surface of the insulating substrate, and a gas-sensitive film (SnO) covering the electrodes2) The gas sensor includes a substrate, a heater provided on a surface opposite to the substrate, a lead connected to the heater, and a catalyst layer (Pt or the like) formed on the gas sensing film. However, in this hydrogen sensor, since the catalyst layer is formed by screen printing, it is difficult to control the film thickness, the unevenness is large, and it is difficult to control the film thicknessThe characteristics as sensors are managed. Furthermore, the hydrogen sensor has a difficulty that the operating temperature is as high as about 400 ℃.
In addition, isopropyl alcohol is used as a cleaning agent in, for example, a semiconductor manufacturing plant, and therefore is often volatilized into the air. Under such conditions, it is difficult to accurately detect the leakage of hydrogen gas, and therefore, as proposed in Japanese patent laid-open No. Hei 01-250851, a gas non-sensitive thin film layer (SiO) is provided on a gas sensitive film2And oxides such as alumina), however, the manufacturing method of the gas non-inductive thin film layer is difficult, and it is difficult to avoid an increase in cost, and the management cost for managing the sensor characteristics also increases.
Further, although there are reports of a gas detection element using a phthalocyanine deposited film, it monitors the conductivity accompanying gas adsorption/desorption, has no gas selectivity for electron-donating or electron-withdrawing gases, and is extremely unstable in operation.
Disclosure of Invention
The present invention has been made in view of the above-described conventional techniques, and an object of the present invention is to provide a proton-accepting gas sensor such as a hydrogen sensor or an acid sensor, which has excellent selectivity of sensing protons and operates at room temperature at low cost.
The present invention relates to a proton-accepting gas sensor, wherein protons are brought into contact with an organic compound into which a nitrogen-containing heterocycle is introduced, and changes in the resistivity, optical conductivity, or optical absorption band of the organic compound accompanying the addition of the protons are detected.
The present invention also relates to the proton-accepting gas sensor as described above, wherein the nitrogen-containing heterocycle is a pyridine-based heterocycle.
Further, the present invention relates to the proton-accepting gas sensor as described above, wherein the organic compound is an organic pigment into which a nitrogen-containing heterocycle is introduced.
Further, the present invention relates to a hydrogen sensor in which protons are brought into contact with an organic compound having a pyridine ring introduced therein, and changes in the resistivity, optical conductivity, or optical absorption band of the organic compound accompanying the addition of protons are detected.
The present invention also relates to the above-mentioned hydrogen sensor, wherein the organic compound is an organic pigment into which a nitrogen-containing heterocycle is introduced.
Further, the present invention relates to the hydrogen sensor as described above, wherein the organic pigment is pyrrolopyrroledione, quinacridone, indigo, phthalocyanine, anthraquinone, indigo anthraquinone, anthanthrone, perylene, pyrazolone, perylenequinone (ペリノン), isoindolinone, isoindoline, dioxazine or a derivative thereof.
Further, the present invention relates to the hydrogen sensor as described above, wherein the protonation catalyst is in contact with the organic compound and hydrogen.
Further, the present invention relates to the hydrogen sensor as described above, characterized in that the protonation catalyst is Pt, Pd, Ni or a two-component alloy thereof or a three-component alloy thereof.
The present invention also relates to the above-mentioned hydrogen gas sensor, wherein a film of an organic pigment as a sensor promoter is laminated on one or both surfaces of the film of the organic compound.
The present invention also relates to the above-mentioned hydrogen sensor, wherein at least one pair of electrodes is disposed in contact with the film of the organic compound to detect a change in resistivity or light transmittance.
Further, the present invention relates to the above hydrogen sensor, wherein the film of the organic compound is a vacuum deposited film or a sputtered film.
Further, the present invention relates to the hydrogen sensor as described above, characterized in that it is an element that: at least one pair of electrodes is arranged on the substrate so as to face each other, the organic compound film is provided on the electrodes, the protonation catalyst is in contact with one or both surfaces of the organic compound film, or the protonation catalyst is distributed in the organic compound film, and the resistance pattern is a pattern for detecting a change in resistivity between the electrodes.
The present invention also relates to the above-described hydrogen gas sensor, wherein the protonation catalyst is provided in an island form on the substrate and the electrode, on the organic compound film or in the organic compound film by a vacuum deposition method or a sputtering method.
The present invention also relates to the hydrogen sensor as described above, which has a field effect transistor structure (FET) of n+A Si substrate as a gate electrode, a source electrode and a drain electrode formed on the Si substrate with a silicon oxide insulating film interposed therebetween, and the organic compound film formed on the silicon oxide and the electrode.
The present invention also relates to the hydrogen sensor described above, wherein the light transmission mode is a light transmission mode in which the light transmission degree is detected by combining excitation light sources.
Further, the present invention relates to the hydrogen sensor as described above, characterized in that it is an optical absorption band mode in which a photodiode or an electron multiplier tube is incorporated to detect a change in an optical absorption band.
Further, the present invention relates to an acid sensor in which a proton is brought into contact with an organic compound having a pyridine ring introduced therein, and a change in resistivity, optical conductivity, or optical absorption band of the organic compound accompanying the addition of the proton is detected.
The present invention also relates to the acid sensor as described above, wherein the organic compound is an organic pigment having a pyridine ring introduced therein.
The present invention also relates to the above-mentioned acid sensor, wherein the organic pigment is pyrrolopyrroledione, quinacridone, indigo, phthalocyanine, anthraquinone, indigo anthraquinone, anthanthrone, perylene, pyrazolone, perylenequinone, isoindolinone, isoindoline, dioxazine, or a derivative thereof.
The content of the present application is related to the subject matters described in Japanese patent application No. 2003-362412 filed on Japanese 10/22 2003 and Japanese patent application No. 2004-144138 filed on Japanese 5/13 2004, the disclosures of which are incorporated herein by reference.
Drawings
FIG. 1 is a schematic diagram of the structure of a first element of the present invention.
FIG. 2 is a schematic diagram of the structure of a second element of the present invention.
Fig. 3 is a schematic diagram of the structure of a third element of the present invention.
Fig. 4 is a graph showing a change in resistivity of the pyridine DPP element (catalyst Pd) shown in fig. 1.
Fig. 5 is a graph showing a change in resistivity of the pyridine DPP element (catalyst Pt) shown in fig. 1.
FIG. 6 shows absorption spectra before and after proton addition to pyridine DPP.
FIG. 7 shows the light transmission spectra before and after proton addition to pyridine DPP.
FIG. 8 is a schematic diagram of a circuit for detecting changes in resistivity.
Fig. 9 is a schematic diagram of a fourth element structure of the present invention.
Fig. 1O is a graph showing a change in resistivity of the pyridine DPP element (catalyst Pd) shown in fig. 1.
FIG. 11 shows the resistivities before and after proton addition to pyridine DPP.
Fig. 12 shows the correlation between the change in resistivity and the hydrogen concentration of the pyridine DPP element (catalyst Pd) shown in fig. 1.
Fig. 13 shows the time response characteristics of the resistivity of the pyridine DPP element (catalyst Pd) shown in fig. 1.
Fig. 14 is a graph showing a change in resistivity of the pyridine perylene element (catalyst Pd) of fig. 1.
Detailed Description
The proton-accepting gas sensor of the present invention is characterized in that a proton is brought into contact with an organic compound into which a nitrogen-containing heterocycle is introduced, and a change in the resistivity, the optical conductivity, or the optical absorption band of the organic compound accompanying the addition of the proton is detected.
The proton-accepting gas sensor of the present invention will be described below, focusing on a hydrogen gas sensor using a pyridopyrrolopyrroledione pigment subjected to a pyridine treatment.
The present inventors clarified the electronic structure (particularly, color tone in a solid state) of pyrrolopyrroledione (hereinafter, referred to as DPP) known as an organic pigment from the viewpoint of the molecular structure, crystal structure and intermolecular interaction, and proposed various proposals for the application thereof. However, among the DPPs, DPP with a pyridine ring (preferably, nitrogen atom is in para position) (hereinafter referred to as pyridine DPP or DPPP) has been found to react extremely sensitively to protons. That is, a pyridine DPP having a pyridine ring in the DPP skeleton has extremely high sensitivity to protons, and the resistivity, the light transmittance, the optical absorption band, and the like change greatly at room temperature with the addition of protons. The present invention has been completed based on these findings, and it has been confirmed that a highly reliable hydrogen sensor can be provided. Pyridine DPP has two Crystal phases, whereas hydrogen sensors are particularly preferred for the Crystal phase I (Crystal phase in which the nitrogen atom of the pyridine ring does not form a hydrogen bond in NH … N), as described in the literature (J.Mizuguchi, H.Takahashi and H.Yamakami: Crystal structure of 3, 6-bis (4' -pyridyl) -pyro [3, 4-c ] pyroole-1, 4-dione, Z.Krist.NCS 217, 519-520 (2002)).
Although pyridine DPP is extremely stable to light and heat, when contacted with protons (H +), it reacts immediately at room temperature, changing the optical absorption band region from 540nm (red) to 580nm (violet). Then, the resistivity is reduced by 3-5 orders of magnitude, and the light transmission is large. By utilizing any of these phenomena, a highly sensitive hydrogen sensor that operates at room temperature can be provided.
The organic compound used in the present invention is preferably an organic pigment into which a nitrogen-containing heterocycle is introduced, and examples thereof include the above-mentioned pyridine DPP and derivatives thereof (chemical formula 2), quinacridone and derivatives thereof which undergo pyridine cyclization (chemical formula 3), indigo and derivatives thereof (chemical formula 4), phthalocyanine and derivatives thereof (chemical formula 5), anthraquinone and derivatives thereof (chemical formula 6), indigo anthraquinone and derivatives thereof (chemical formula 7), anthanthrone and derivatives thereof (chemical formula 8), perylene and derivatives thereof (chemical formula 9-1), (chemical formula 9-2), pyrazolone and derivatives thereof (chemical formula 10), perylenequinone and derivatives thereof (chemical formula 11-1), (chemical formula 11-2) isoindolinone and derivatives thereof (chemical formula 12), isoindoline and derivatives thereof (chemical formula 13), Dioxazine (chemical formula 14) and its derivatives, and the like.
Chemical formula 2: pyrrolopyrrolediones
R1～R12＝H、CH3、CF3、Cl、Br、N(CH3)2、C2H5、NH2、COOH、SO3H. COOR '(R' ═ alkyl)
R1 to R12 are the same or different
X ═ Y or X ≠ Y
Chemical formula 3: quinacridones
R1～R12＝H、CH3、CF3、Cl、Br、N(CH3)2、C2H5、NH2、COOH、SO3H. COOR '(R' ═ alkyl)
R1 to R12 are the same or different
X ═ Y or X ≠ Y
Chemical formula 4: indigo blue
R1～R12＝H、CH3、CF3、Cl、Br、N(CH3)2、C2H5、NH2、COOH、SO3H. COOR '(R' ═ alkyl)
R1 to R12 are the same or different
X ═ Y or X ≠ Y
Chemical formula 5: phthalocyanine (I)
R1～R12＝H、CH3、CF3、Cl、Br、N(CH3)2、C2H5、NH2、COOH、SO3H. COOR '(R' ═ alkyl)
R1 to R12 are the same or different
X1 to X4 are the same or different
Chemical formula 6: anthraquinone
R1～R12＝H、CH3、CF3、Cl、Br、N(CH3)2、C2H5、NH2、COOH、SO3H. COOR '(R' ═ alkyl)
R1 to R12 are the same or different
X ═ Y or X ≠ Y
Chemical formula 7: indigo anthraquinone
R1～R12＝H、CH3、CF3、Cl、Br、N(CH3)2、C2H5、NH2、COOH、SO3H. COOR '(R' ═ alkyl)
R1 to R12 are the same or different
X ═ Y or X ≠ Y
Chemical formula 8: anthracene-ring anthraquinones
R1～R6＝H、CH3、CF3、Cl、Br、N(CH3)2、C2H5、NH2、COOH、SO3H. COOR '(R' ═ alkyl)
R1 to R6 are the same or different
X ═ Y or X ≠ Y
Chemical formula 9-1: perylene as well as perylene
R1～R12＝H、CH3、CF3、Cl、Br、N(CH3)2、C2H5、NH2、COOH、SO3H. COOR '(R' ═ alkyl)
R1 to R12 are the same or different
X ═ Y or X ≠ Y
Chemical formula 9-2: perylene as well as perylene
R1～R12＝H、CH3、CF3、Cl、Br、N(CH3)2、C2H5、NH2、COOH、SO3H. COOR '(R' ═ alkyl)
R1 to R12 are the same or different
X ═ Y or X ≠ Y
Chemical formula 10: pyrazolones
R1～R12＝H、CH3、CF3、Cl、Br、N(CH3)2、C2H5、NH2、COOH、SO3H. COOR '(R' ═ alkyl)
R1 to R12 are the same or different
Chemical formula 11-1: perylenequinones
R1～R12＝H、CH3、CF3、Cl、Br、N(CH3)2、C2H5、NH2、COOH、SO3H. COOR '(R' ═ alkyl)
R1 to R12 are the same or different
X ═ Y or X ≠ Y
Chemical formula 11-2: perylenequinones
R1～R12＝H、CH3、CF3、Cl、Br、N(CH3)2、C2H5、NH2、COOH、SO3H. COOR '(R' ═ alkyl)
R1 to R12 are the same or different
X ═ Y or X ≠ Y
Chemical formula 12: isoindolinone
R1～R12＝H、CH3、CF3、Cl、Br、N(CH3)2、C2H5、NH2、COOH、SO3H. COOR '(R' ═ alkyl)
R1 to R12 are the same or different
X ═ Y or X ≠ Y
Chemical formula 13: isoindoline
R1～R6＝H、CH3、CF3、Cl、Br、N(CH3)2、C2H5、NH2、COOH、SO3H. COOR '(R' ═ alkyl)
R1 to R6 are the same or different
Chemical formula 14: dioxazines
R1～R12＝H、CH3、CF3、Cl、Br、N(CH3)2、C2H5、NH2、COOH、SO3H. COOR '(R' ═ alkyl)
R1 to R12 are the same or different
X ═ Y or X ≠ Y
Further, the organic compound selected in the present invention is not limited to the above. The organic compound selected in the present invention is an organic compound into which a nitrogen-containing heterocycle, preferably a pyridine-based heterocycle, is introduced. For example, the organic compound may be an organic compound having a nitrogen-containing six-membered ring (also referred to as a pyridine-based heterocycle in the present invention) (chemical formula 15) or an organic compound having a nitrogen-containing condensed ring such as cinnoline (chemical formula 16), phthalazine (chemical formula 17), phenazine (chemical formula 18).
Specifically, as the compounds of the above chemical formulas 2 to 14, compounds in which the pyridine ring is substituted with chemical formulas 15 to 18 may be cited.
Chemical formula 15
Chemical formula 16
Chemical formula 17
Chemical formula 18
DPP having a pyridine ring can be synthesized from cyanopyridine and succinic acid according to the method described in Japanese patent publication (B2) No. 4-25273, for example. Further, other Organic compounds having a nitrogen atom can be synthesized, for example, by the method described in W.Herbst and K.Hunger, Industrial Organic Pigments-Production, Properties, Applications-VCH Weinheim, New York, Basel, Cambridge (1993).
The following description will be made mainly of examples of pyridine DPP, but the basic process of the present inventionThe process consists of two processes, the first being the dissociation and protonation of hydrogen (hydrogen molecules) (ii) a ) The second process is a process of detecting a change in physical properties due to addition of protons to pyridine DPP.
In the first process, protonation of hydrogen becomes a problem, but can be solved by preferably using catalysts such as Pt, Pd, Ni, or a two-component alloy or a three-component alloy thereof. That is, when hydrogen molecules come into contact with these metals, the hydrogen molecules become unstable and become protons via atomic hydrogen (H). Specifically, the protonation of hydrogen gas is promoted by sputtering Pd and Pt.
In the second process, the device structure basically includes at least one pair of electrodes, and the catalyst for protonating hydrogen gas is arranged in an island form because pyridine DPP is arranged between the electrodes. The island-like shape here means a state in which metal particles are dispersed in island-like shapes on a film formed by a sputtering method to such an extent that the film does not exhibit electrical conductivity.
Thus, for the hydrogen sensor of the present invention, it is preferable that the organic compound and the hydrogen protonation catalyst are contacted.
In the hydrogen sensor of the present invention, it is preferable that at least one pair of electrodes is disposed in contact with the film of the organic compound to detect a change in resistivity or light transmittance. In the hydrogen sensor of the present invention, it is particularly preferable that the hydrogen sensor is a resistance mode hydrogen sensor in which at least one pair of electrodes are arranged on a substrate so as to face each other, the organic compound film is provided thereon, and the protonation catalyst is in contact with one surface or both surfaces of the organic compound film, or the protonation catalyst is distributed in the organic compound layer, and the change in resistivity between the electrodes is detected. The film of the organic compound can be formed by a vacuum deposition method or a sputtering method, and is preferably formed by a vacuum deposition method. Further, according to the vacuum deposition method or the sputtering method, it is preferable that the protonation catalyst is provided in an island shape on the substrate and the electrode, on the organic compound film, or in the organic compound film according to the sputtering method.
One specific example shown in FIG. 1 is an element structure (A) in which comb-shaped electrodes (2, 2) are alternately arranged on a substrate (1) such as glass1、22) A catalyst such as Pd (3) (about Å) (E-1030 ion sputtering device, manufactured by Hitachi Kagaku K.K.) is sputter-deposited in an island form, and then vacuum-deposited in a film form (about Å) (EG240, manufactured by Tokyo vacuum Co., Ltd.) on the catalyst (DPP 4) pyridine, wherein X is Y and X is a pyridine ring having a nitrogen atom in the para-position in Compound 21＝R2＝R3＝R4H. In this example, sufficient sensitivity was obtained under a 1% hydrogen atmosphere at room temperature.
Here, the area of the element (electrode portion) shown in FIG. 1 was 5 mm. times.10 mm, and the width of the electrode and the interval between the electrodes were 100. mu.m.
In addition, the second example is an element structure (B) as shown in FIG. 2, that is, in the electrodes (2, 2)1、22) Then, pyridine DPP (4) is deposited in a film form, and Pd (3) is sputtered in an island form on the surface thereof.
Further, the third example is the element structure (C) shown in fig. 3, that is, the protonation catalyst is distributed in the film of the organic compound. The electrode is not particularly limited, and for example, Al, ITO (Indium-Tin-Oxide: transparent electrode), Au, Ag, Pd, Pt, Pd-Pt alloy, or the like can be used. The hydrogen sensor in the resistance mode is realized by detecting the resistivity change between the relevant electrodes. The hydrogen gas sensor having this structure can naturally detect a vaporous proton gas present in an acid, and can function as an acid sensor with the same element structure.
Of course, it is also possible to provide a hydrogen sensor combining a light conduction mode of an excitation light source or combining an optical absorption band change mode of a photodiode, a photomultiplier tube, or the like. These elements can of course also have the function of an acid sensor as described above.
Further, a fourth example is shown in fig. 9. The hydrogen sensor shown in FIG. 9 is so-called organicA sensor of FET (field effect transistor) structure. It was confirmed that the sensitivity of the hydrogen sensor having the electrode configuration of the FET structure was further improved by sputtering the protonation catalyst on the element and forming the organic compound layer thereon. The hydrogen sensor shown in FIG. 9 has n+The Si substrate (14) is used as a gate electrode, a source electrode and a drain electrode (12) are formed on the gate electrode with a silicon oxide insulating film (13) therebetween, and the above-mentioned two layers (a protonation catalyst layer and an organic compound layer formed in an island shape) (11) are formed between the source electrode and the drain electrode. Vg, Id, and Vs-d are gate voltage, drain current, and source/drain voltage, respectively. The sensor having such an FET structure can further improve the sensitivity by several times by controlling the gate voltage as compared with the sensor having only the comb-shaped electrode.
To further illustrate the principles of the present invention, hydrogen gas is initially adsorbed onto the surface of the pyridine DPP (4) and then diffused into the pyridine DPP (4) by way of example in FIG. 1. Then, the hydrogen gas is contacted with Pd (3) and dissociated into protons: ( ). This proton is added to the nitrogen atom on the pyridine ring of the pyridine DPP (4). The resistivity of the pyridine DPP (4) is reduced by 2 to 4 orders of magnitude at room temperature according to the electrons released at this time. When this decrease in resistivity is electrically detected, the hydrogen sensor is obtained.
FIG. 4 shows an example of the element shown in FIG. 1 at 100% H2Graph of change in resistivity under atmosphere, electrode was ITO, thickness of pyridine DPP was 500 Å, catalyst was Pd., and graph of change in resistivity under atmosphere was 5Is the result of using Pt as a catalyst in the same experiment. In the figure, a (black circle) indicates the result before proton addition, and b (white mark) indicates the result after proton addition.
When a proton is added to the nitrogen atom in the pyridine ring of pyridine DPP, the electrical resistance value is reduced as described above, and the optical conductivity is also exhibited. Further, the optical absorption band of pyridine DPP at about 540nm in the visible light region shifts to 580nm, and the color tone changes from red to purple. Therefore, as a detection method of the hydrogen sensor, any one of a change in resistivity (resistance mode), a change in display light conductivity (light conduction mode), or a change in long wavelength of an optical absorption band (540nm → 580nm) (color change mode) is used as a detection function.
FIG. 6 shows a pyridine DPP deposited film (thickness 1200 Å) according to HNO3Absorption spectra before and after the addition of protons to the vapor, and fig. 7 is a light transmission spectrum.
FIG. 10 shows another example of the element of FIG. 1 at 100% H2Graph of change in resistivity under atmosphere, electrode being ITO, thickness of pyridine DPP being 500 Å, catalyst Pd. pyridine DPP being X ═ Y in the compound 2, X being pyridine ring with nitrogen atom in para position1＝R2＝R3＝R4H. In this example, a sublimation purified pyridine DPP was used.
FIG. 11 shows a pyridine DPP deposited film (thickness 1200 Å) according to HNO3The change in resistivity due to proton attachment of the vapor.
FIG. 12 is a graph showing the dependence of the change in resistivity on the hydrogen concentration of the element of FIG. 1 in other examples, in which the electrode was ITO, the thickness of pyridine DPP was 500 Å, and Pd was used as the catalyst.
FIG. 13 is a graph showing time response characteristics of the element of FIG. 1 in another example, in which the electrode was ITO, the thickness of pyridine DPP was 500 Å, and Pd was used as the catalyst.
Fig. 14 is a graph showing another example of the element structure of fig. 1, in which a pyridine perylene element is used instead of pyridine DPP as a change in resistivity of the element of the organic compound. Pyridine perylene in the compound 9-1 is X ═ Y, and X is a pyridine ring with a nitrogen atom at the para-position. Only, R1＝R2＝R3＝R4The electrode was ITO, the thickness of pyridine perylene was 500 Å, and Pd. was used as the catalyst, wherein a (black circle) indicates the result before proton addition and b (white mark) indicates the result after proton addition, the resistivity of pyridine perylene was changed by about 20000 times or more depending on the presence or absence of hydrogen.
In addition, in the case of using the above-mentioned various organic compounds, as in the case of pyridine DPP and pyridine perylene, a large change in resistivity can be confirmed depending on the presence or absence of hydrogen gas.
For the purpose of improving the sensitivity of the sensor, an organic pigment film such as phthalocyanine may be provided as a sensitivity promoter on the upper or lower surface of the pyridine/DPP or on the upper or lower surface of the pyridine/DPP. Further, pyridine DPP and phthalocyanine may be deposited together by vapor deposition. The ratio of pyridine DPP to phthalocyanine is about 10: 1 in terms of film thickness ratio, and the weight ratio in co-deposition is about 10: 1.
The above description has been mainly made of a sensor for detecting hydrogen gas using pyridine DPP as an organic compound containing a nitrogen-containing heterocycle, but as described above, the nitrogen-containing heterocycle is not limited to pyridine, and triazine, pyrazine, pyrimidine, pyridazine, and the like described above can be used. The detection gas is not limited to hydrogen gas, and any gas that can be dissociated to generate protons, such as nitric acid gas, hydrogen chloride gas, and hydrogen fluoride gas, may be used for the detection by the sensor of the present invention.
The present invention can provide a hydrogen sensor having excellent selectivity of sensing protons at low cost, and the provided sensor can detect hydrogen and prevent a leak accident in a manufacturing plant, a hydrogen storage facility, or a so-called fuel cell using hydrogen as an energy source, in which hydrogen is used as a carrier gas in recent years. The present invention is not limited to a hydrogen gas sensor, and can provide a wide range of high-sensitivity proton-accepting gas sensors such as an acid sensor at low cost, and the provided sensors can also serve to detect various proton-donating gases and prevent leakage accidents in manufacturing plants and the like in which toxic gases such as nitric acid gas, hydrogen fluoride gas, hydrogen chloride gas, and the like are likely to be generated.
Examples
Example 1
1. Resistance mode
When the element having the structure shown in fig. 1 is placed in an atmosphere of hydrogen gas, nitric acid gas, hydrogen chloride gas, hydrogen fluoride gas, ammonia gas, or the like, the resistance drops sharply. Generally, since the resistivity of pyridine DPP is very high and close to that of an insulator, a voltage is applied between electrodes to detect a minute current flowing therethrough. That is, by detecting and amplifying the change in the minute current, it is used as a sensor. The element of the invention is very easy to detect because the resistivity change is more than 1-4 orders of magnitude. However, since the detection system, i.e., the input system, has a high resistance, it is preferable to take countermeasures in designing the circuit. For example, it is effective to perform a process such as impedance conversion by placing a buffer using a high input impedance OP amplifier in a stage preceding the detection signal amplifying circuit.
As a specific example, a circuit shown in FIG. 8 can be manufactured using the elements shown in FIG. 1, andcounter electrode (2)1、22) Alternately connected, one of the electrodes is connected to a cathode of a power source (5), and the other is connected to an anode. A circuit (6) for detecting current is provided in a closed circuit between the electrode and a power supply, and a current change due to a change in resistivity of pyridine DPP/Pd is detected.
Example 2
2. Light transmission mode
The same as the resistance mode element structure, except that a glass plate was used as the substrate, and ITO was used as the electrode. When the element is irradiated with visible light, the resistance is greatly reduced (light transmission phenomenon), and hydrogen gas can be detected.
Example 3
3. Absorption band mode
No electrodes are required in this optical absorption band mode, and the other structures are the same as the resistive mode and the light-conducting mode. This is a mode in which, if proton addition occurs on the pyridine DPP film, the 540nm absorption band shifts to 580nm, and thus the change in the optical absorption band is detected by a semiconductor detector or a photomultiplier tube and applied to a hydrogen sensor.
The resistive and light conductive modes are in any case basically capable of applying a change in resistance to the sensor. In the operation mode, a detection method using either dc or ac may be used.
Industrial applicability
The present invention provides a proton-accepting gas sensor, particularly a hydrogen gas sensor, having excellent selectivity of proton-sensing at low cost, and various detection means, which can detect changes in a resistance mode, a light transmission mode, and an optical absorption band mode, and which is important for detecting hydrogen gas and preventing leakage accidents, and has a wide range of applications. Furthermore, the sensor can be effectively used as an acid sensor for hydrogen fluoride gas or the like.
Claims (19)
1. A proton-accepting gas sensor is characterized in that a proton is brought into contact with an organic compound into which a nitrogen-containing heterocycle is introduced, and a change in the resistivity, the optical conductivity, or the optical absorption band of the organic compound accompanying the addition of the proton is detected.
2. The proton-accepting gas sensor according to claim 1, wherein the nitrogen-containing heterocycle is a pyridine-based heterocycle.
3. The proton-accepting gas sensor according to claim 1 or 2, wherein the organic compound is an organic pigment into which a nitrogen-containing heterocycle is introduced.
4. A hydrogen sensor is characterized in that protons are brought into contact with an organic compound having a pyridine ring introduced therein, and changes in the resistivity, optical conductivity, or optical absorption band of the organic compound accompanying the addition of the protons are detected.
5. The hydrogen sensor according to claim 4, wherein the organic compound is an organic pigment into which a nitrogen-containing heterocycle is introduced.
6. The hydrogen sensor according to claim 5, wherein the organic pigment is a pyrrolopyrroledione, quinacridone, indigo, phthalocyanine, anthraquinone, indigo anthraquinone, anthanthrone, perylene, pyrazolone, perylenequinone, isoindolinone, isoindoline, dioxazine, or a derivative thereof.
7. A hydrogen gas sensor according to any one of claims 4 to 6, characterized in that it contacts the protonation catalyst of the organic compound and hydrogen gas.
8. The hydrogen sensor according to claim 7, wherein the protonation catalyst is Pt, Pd, Ni or a two-component alloy thereof or a three-component alloy thereof.
9. A hydrogen sensor according to any one of claims 4 to 8, wherein a film of an organic pigment as a sensor promoter is laminated on one or both surfaces of the film of the organic compound.
10. A hydrogen sensor according to any one of claims 4 to 9, wherein at least one pair of electrodes is provided in contact with the film of the organic compound to detect a change in resistivity or light transmittance.
11. A hydrogen gas sensor according to any one of claims 4 to 10, wherein the film of the organic compound is a vacuum deposited film or a sputtered film.
12. A hydrogen gas sensor according to any one of claims 4 to 11, characterized by being an element that: at least one pair of electrodes are arranged to face each other on the substrate, the electrodes have the organic compound film on the upper surface thereof, and the protonation catalyst is in contact with one surface or both surfaces of the organic compound film, or the protonation catalyst is distributed in the organic compound film, and the mode is a resistance mode for detecting a change in resistivity between the electrodes.
13. A hydrogen sensor according to any one of claims 10 to 12, wherein the protonation catalyst is provided in an island form on the substrate and the electrode, on the organic compound film or in the organic compound film by a vacuum evaporation method or a sputtering method.
14. A hydrogen sensor according to any one of claims 4 to 13, characterised by a field effect transistor structure of n+A Si substrate as a gate electrode, a source electrode and a drain electrode formed on the Si substrate with a silicon oxide insulating film interposed therebetween, and the organic compound film formed on the silicon oxide and the electrode.
15. A hydrogen sensor according to any one of claims 4 to 14, wherein the light transmission mode is a mode in which the excitation light source is combined to detect the degree of light transmission.
16. A hydrogen sensor according to any one of claims 4 to 15, characterized by being combined with a photodiode or an electron multiplier to detect the optical absorption band pattern of the optical absorption band change.
17. An acid sensor comprising an organic compound having a pyridine ring introduced therein and a proton in contact therewith, wherein a change in resistivity, optical conductivity or optical absorption band of the organic compound accompanying proton addition is detected.
18. The acid sensor according to claim 17, wherein the organic compound is an organic pigment having a pyridine ring introduced therein.
19. An acid sensor according to claim 17 or 18, wherein the organic pigment is a pyrrolopyrroledione, quinacridone, indigo, phthalocyanine, anthraquinone, indigo anthraquinone, anthanthrone, perylene, pyrazolone, perylenequinone, isoindolinone, isoindoline, dioxazine or a derivative thereof.
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| JP2003362412 | 2003-10-22 | ||
| JP362412/2003 | 2003-10-22 | ||
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2004
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1908641B (en) * | 2005-08-01 | 2011-07-06 | 本田技研工业株式会社 | Gas sensor and gas sensor system |
| CN103755153A (en) * | 2014-01-22 | 2014-04-30 | 南通天盛新能源科技有限公司 | Method for preparing substrate for high formyl group functional group density biological chip |
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| CN104020201A (en) * | 2014-06-19 | 2014-09-03 | 电子科技大学 | Low-temperature palladium-based hydrogen sensor and manufacturing method thereof |
| CN107238646A (en) * | 2016-03-28 | 2017-10-10 | Tdk株式会社 | Detector and the electrochemical element for possessing detector |
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| CN106198635A (en) * | 2016-07-13 | 2016-12-07 | 电子科技大学 | A kind of humidity sensor based on organic field effect tube and preparation method thereof |
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