JP4899230B2 - Gas sensor material, manufacturing method thereof, and gas sensor - Google Patents

Description

  The present invention relates to an organic-inorganic hybrid material, a gas sensor material, a method for producing the same, and a gas sensor. More specifically, the present invention relates to a gas sensor using a specific organic-inorganic hybrid material as a chemical sensor element. It relates to a novel gas sensor material that has an effect of detecting gas by a change in value, has excellent long-term stability, and has a characteristic of responding more strongly to acetaldehyde than formaldehyde at a temperature of 100 ° C. or less, its manufacturing method, and gas sensor is there.

  In the technical field of a gas sensor using a highly functional organic / inorganic hybrid material in which an organic compound and an inorganic compound are combined at a nano level, the present invention is a kind of volatile organic compound (VOC). Although it responds selectively to a certain aldehyde-based gas, both of them respond more strongly to formaldehyde than acetaldehyde, so it was developed based on the problem that it is difficult to distinguish formaldehyde from acetaldehyde with this gas sensor alone. Is.

  In the highly functional organic / inorganic hybrid material in which an organic compound and an inorganic compound are combined, the present invention uses polynaphthylamine or a derivative thereof, or polyaminoanthracene or a derivative thereof as an organic compound to form acetaldehyde from formaldehyde. It is possible to produce and provide a chemical sensor element made of an organic-inorganic hybrid material that responds strongly.

  That is, the present invention, for example, combines a compound mainly composed of polynaphthylamine or a derivative thereof or polyaminoanthracene or a derivative thereof as an organic compound and a compound composed mainly of molybdenum oxide as an inorganic compound at a nano level. The present invention provides new technologies and new products related to a conductive organic-inorganic hybrid material and a chemical sensor element made of the material. Furthermore, the present invention provides a technique that enables determination of the concentrations of formaldehyde gas and acetaldehyde gas by simultaneously using the gas sensor using the organic-inorganic hybrid material of the present invention and the conventional organic-inorganic hybrid material. .

  In recent years, the health hazard called sick house syndrome caused by VOC pollution caused by high airtightness of houses and the use of building materials and interiors that dissipate chemical substances has been regarded as a problem. To monitor indoor VOC concentration Development of chemical sensors is expected. VOC components vary widely, and the toxicity and permissible concentration differ depending on each component. Therefore, chemical sensors for constantly monitoring VOCs require gas selectivity that identifies and detects each component. It has been.

  Conventionally used methods for measuring the VOC gas concentration include analysis by a detector tube method and analysis by gas chromatography. However, analysis by the detector tube method allows instantaneous measurement, but due to the nature of the measurement method that visually determines color changes, it is not only difficult to determine the exact concentration, but it is also consumed by a single use. Therefore, it is economically inefficient. In addition, the analysis by gas chromatography can measure a precise concentration, but due to the nature of the analytical instrument, instantaneous measurement is impossible and the analytical instrument itself is expensive.

  For these reasons, none of the methods is suitable for spreading as a device capable of constantly monitoring the VOC concentration. In addition, a chemical sensor using an n-type semiconductor made of a metal oxide has been used in the past. This is a technique for detecting a gas by changing a resistance value suitable for constant monitoring of the VOC concentration. It is difficult to contribute selectivity. From the above viewpoint, development of chemical sensors using new materials has been studied.

  Chemical sensors based on organic / inorganic hybrid materials combine layered organic and inorganic compounds at the nano level to provide signal conversion functions required for application to electrodevice materials and molecular recognition functions required for gas selectivity. It has been reported that it is effective for application to a new chemical sensor material having high gas selectivity by sharing an inorganic compound and an organic compound between the inorganic compound and the organic compound.

As a specific example, in an intercalation type organic-inorganic hybrid material in which molybdenum oxide (MoO ₃ ) having a layered structure is a main component and an organic compound is inserted between molybdenum oxide layers, the material is less than benzene and toluene. A chemical sensor element having excellent gas selectivity that selectively responds to aldehyde, alcohol, and chlorine-based gases while hardly responding has been proposed (Patent Document 1, Patent Document 2, Non-Patent Document). Reference 1).

  In addition, a thinning technique for applying the hybrid material to an element (Patent Document 3, Non-Patent Document 2), a technique for producing a thin film made of an organic-inorganic hybrid material on an inexpensive silicon substrate (Patent Document 4), Has been reported. Furthermore, by realizing the nano-size of the thin film using the organic / inorganic hybrid material and improving the sensor sensitivity by using the porous technology (Patent Document 5), it is selected for aldehyde gas in the concentration range of 50 ppm or less. To respond responsively.

  Organic-inorganic hybrid materials using molybdenum oxide and organic compounds are expected to be used as new chemical sensor materials for aldehyde-based gases. However, each of the above organic-inorganic hybrid materials detects both formaldehyde and acetaldehyde and responds more strongly to formaldehyde than acetaldehyde. In this technical field, formaldehyde and acetaldehyde are determined in order to determine the respective concentrations of formaldehyde and acetaldehyde. The development of organic-inorganic hybrid materials that respond more strongly to acetaldehyde has become an urgent issue.

JP 2004-271482 A JP-A-2005-321326 JP-A-2005-179115 JP 2006-315933 A JP 2005-321327 A Bull. Chem. Soc. Jpn. , Vol. 77, 1231 (2004) Chem. Mater. , Vol. 17, 349 (2005)

  Under such circumstances, the present inventors have developed a chemical sensor that detects a gas by a change in resistance value using an organic-inorganic hybrid material that responds more strongly to acetaldehyde than formaldehyde, in view of the above-described conventional technology. As a result of earnest research as a target, organic-inorganic hybrid materials in which polynaphthylamine or a derivative thereof, or a compound mainly composed of polyaminoanthracene or a derivative thereof is inserted between molybdenum oxide layers respond more strongly to acetaldehyde than formaldehyde. As a result, the present invention was completed through further research.

  The present invention relates to a conductive organic-inorganic hybrid material, a chemical sensor element, a conductive material, a manufacturing method thereof, and a method for manufacturing a chemical sensor using a conductive organic-inorganic hybrid material that responds more strongly to acetaldehyde than formaldehyde, and An object of the present invention is to provide a product, particularly a conductive member and a highly sensitive chemical sensor member.

The present invention for solving the above-described problems comprises the following technical means.
(1) An organic-inorganic hybrid material in which an organic polymer is inserted between layers of an inorganic compound having a layered structure, wherein the inorganic compound having the layered structure is mainly composed of molybdenum oxide, and the organic polymer is polynaphthylamine or its An organic-inorganic hybrid material comprising a derivative, or polyaminoanthracene or a derivative thereof as a main component.
(2) The material according to (1), wherein the polynaphthylamine derivative is poly (5,6,7,8-tetrahydro-1-naphthylamine).
(3) The material according to (1), comprising a molded body of an organic-inorganic hybrid material in which an organic polymer is inserted between layers of an inorganic compound having a layered structure.
(4) The material according to (3), comprising a thin film, an alignment film, a thick film, or a pellet molded body.
(5) A gas sensor material comprising the organic-inorganic hybrid material according to any one of (1) to (4), wherein the gas sensor material has a characteristic of preferentially detecting acetaldehyde gas over formaldehyde gas due to a change in resistance value. Gas sensor material characterized by
(6) A conductive material comprising the organic-inorganic hybrid material according to any one of (1) to (4).
(7) An organic polymer is inserted between layers of an inorganic compound having a layered structure, and a gas sensor material made of an organic-inorganic hybrid material having the property of preferentially detecting acetaldehyde gas over formaldehyde gas by changing the resistance value. A compound comprising molybdenum oxide as a main component as the inorganic compound having the layered structure, and polynaphthylamine or a derivative thereof, or polyaminoanthracene or a derivative thereof as the organic polymer. Manufacturing method of gas sensor material.
(8) A method for producing a conductive material made of an organic-inorganic hybrid material by inserting an organic polymer between layers of an inorganic compound having a layered structure, wherein molybdenum oxide is the main component as the inorganic compound having the layered structure. And polynaphthylamine or a derivative thereof, or polyaminoanthracene or a derivative thereof as an organic polymer, and a method for producing a conductive material.
(9) The method for producing a gas sensor material or a conductive material according to (7) or (8) above, wherein an organic-inorganic hybrid material is molded into a molded body.
(10) The method for producing a gas sensor material or a conductive material according to (9), wherein the organic-inorganic hybrid material is molded into a thin film, an alignment film, a thick film, or a pellet.
(11) A conductive member comprising the conductive material according to (6) as a constituent element.
(12) A chemical sensor member comprising a sensor element made of the gas sensor material according to (5).

Next, the present invention will be described in more detail.
The present invention uses an organic-inorganic hybrid material in which an organic polymer is inserted between layers of an inorganic compound having a layered structure as a gas sensor material, so that acetaldehyde gas is preferentially detected over formaldehyde gas due to changes in its resistance value. The gas sensor material has the characteristics of: In the present invention, it is possible to obtain a gas sensor material that preferentially detects acetaldehyde gas over formaldehyde gas by appropriately combining an inorganic compound having a layered structure and an organic polymer.

  In the present invention, a compound containing molybdenum oxide as a main component is used as the inorganic compound having the above layered structure. This makes it possible to impart a signal conversion function to the organic-inorganic hybrid material. In the present invention, as the organic polymer, polynaphthylamine or a derivative thereof, or a molecule mainly composed of polyaminoanthracene or a derivative thereof is used. By this, the organic-inorganic hybrid material has a molecular recognition function. In addition, a function of preferentially detecting acetaldehyde gas over formaldehyde gas can be provided.

  In the present invention, for example, poly (5,6,7,8-tetrahydro-1-naphthylamine) (hereinafter referred to as polynaphthylamine derivative) (hereinafter referred to as polynaphthylamine derivative) or polyaminoanthracene or derivative thereof. This substance may be referred to as PTHNA.), But is not limited to these, and may be polynaphthylamine or a derivative thereof, or polyaminoanthracene or a derivative thereof. Can be used similarly.

  In the present invention, for example, an organic-inorganic hybrid material in which an organic polymer is inserted between layers of an inorganic compound having a layered structure is used as a molded body such as a thin film, an alignment film, a thick film, and a pellet. In the present invention, by combining the inorganic compound and the organic polymer, it becomes possible to provide a gas sensor material that preferentially detects acetaldehyde gas over formaldehyde gas. Application to electro device materials and high sensitivity as gas sensor materials are realized. In the present invention, the shape and structure of the molded body can be arbitrarily designed.

  Also, in the present invention, a highly sensitive signal conversion function is provided by a thin film made of a highly oriented organic-inorganic hybrid material by using molybdenum oxide as the inorganic compound having a layered structure for the thin film made of a highly oriented organic-inorganic hybrid material. It becomes possible. In the present invention, the thin film made of the highly oriented organic-inorganic hybrid material is changed to a thin film made of the highly oriented organic-inorganic hybrid material by using polynaphthylamine or a derivative thereof, or polyaminoanthracene or a derivative thereof as the organic polymer. It is possible to provide a molecular recognition function and a function of preferentially detecting acetaldehyde gas over formaldehyde gas.

  In addition, in the present invention, an organic polymer is inserted between layers of an inorganic compound having a layered structure to form an organic-inorganic hybrid material, so that the property of detecting acetaldehyde gas preferentially over formaldehyde gas due to a change in resistance value. The manufacturing method of the gas sensor material which has can be constructed | assembled. This makes it possible to produce a gas sensor material that preferentially detects acetaldehyde gas over formaldehyde gas from an organic-inorganic hybrid material.

  In the present invention, an organic polymer is inserted between layers of an inorganic compound having a layered structure to form a highly oriented organic-inorganic hybrid material, so that acetaldehyde gas is preferentially detected over formaldehyde gas due to a change in resistance value. Thus, it is possible to construct a method for producing a gas sensor material having the following characteristics. This makes it possible to produce a gas sensor material that preferentially detects acetaldehyde gas over a formaldehyde gas made of an organic-inorganic hybrid material made into a highly oriented thin film on the substrate and to have a higher function.

  Moreover, in this invention, the chemical sensor element which can construct | assemble the electroconductive member which uses said organic-inorganic hybrid material as a component, and detects a gas component by monitoring the change of the resistance value of an organic-inorganic hybrid material. It becomes possible. Furthermore, in the present invention, a chemical sensor member (gas sensor) using the above organic-inorganic hybrid material as a sensor element can be constructed. By connecting the sensor material to an electrode, it is possible to monitor a change in resistance value. It can function as a sensor element.

  As described above, the present invention preferably employs formaldehyde gas as a chemical sensor for detecting gas based on a change in resistance value, for example, by inserting PTHNA between layers of molybdenum oxide having a nano-sized layered structure. It is possible to manufacture and provide a conductive organic-inorganic hybrid material having characteristics and functions that are preferentially detected with respect to acetaldehyde gas.

  The mechanism of a chemical sensor for measuring VOC concentration using a conductive organic-inorganic hybrid material is as follows. The conductivity of the organic-inorganic hybrid material is caused by charge transfer between the organic compound and the inorganic compound. In this organic-inorganic hybrid material, the resistance value of the organic-inorganic hybrid material fluctuates because the VOC gas penetrates between layers of the organic-inorganic hybrid material and interacts with the organic compound to change the balance of charge transfer. That is, the organic compound between the layers contributes to the gas selectivity of the chemical sensor using the conductive organic-inorganic hybrid material.

  As a chemical sensor using a conductive organic-inorganic hybrid material, the shape can be preferably used by molding it into a thin film, an alignment film, a thick film, a pellet, etc., but is not limited thereto. However, if they have the same or similar effects, they can be used in the same way. From the viewpoint of application to an electro device material and high sensitivity as a gas sensor material, it is desirable to produce a highly oriented thin film on a substrate having electrodes.

In the present invention, the chemical sensor material that preferentially detects acetaldehyde gas over formaldehyde gas as the chemical sensor is preferably, for example, a conductive organic-inorganic hybrid material (hereinafter, referred to as PTHNA) that is molybdenum oxide and a polynaphthylamine derivative. This material is referred to as (PTHNA) _x MoO ₃ ).

In FIG. 1, the schematic diagram of the crystal structure of the layered organic inorganic hybrid material by (PTHNA) _x MoO ₃ is shown. The conventional organic-inorganic hybrid material based on molybdenum oxide preferentially detects formaldehyde over acetaldehyde, whereas (PTHNA) _x MoO ₃ preferentially detects acetaldehyde gas over formaldehyde gas. The sensor material is realized by using polynaphthylamine or a derivative thereof, or polyaminoanthracene or a derivative thereof as an organic compound.

  PTHNA is a polymer of 5,6,7,8-tetrahydro-1-naphthylamine, which is a naphthylamine derivative having another hydrogen at positions 5,6,7,8 of 1-naphthylamine. Since PTHNA has a structure having two rings, a monomer having one ring is sterically bulky compared to an organic polymer obtained by polymerization, and therefore, a hybrid body inserted between layered inorganic compound layers is used. The interlayer distance is increased as compared with a hybrid of an organic polymer obtained by polymerizing a monomer having one ring and a layered inorganic compound.

  As a result, the hybrid of the polynaphthylamine derivative and the layered inorganic compound only changes the balance of charge transfer compared to the hybrid of the organic polymer polymerized with a monomer having one ring and the layered inorganic compound. Since the affinity for various VOC gas components also changes, the response as a chemical sensor is different.

The synthesis of a hybrid of PTHNA and molybdenum oxide is performed by a two-step reaction. In the first stage, [Na (H ₂ O) ₂ ] _x MoO _{3 in} which hydrated sodium ions are inserted between molybdenum oxide layers is synthesized. Dissolved molybdenum oxide (VI) disodium dihydrate and sodium hyposulfite in distilled water bubbled with argon gas, dissolved, and then immersed in a thin film of molybdenum oxide on a substrate having a comb-shaped electrode made of gold. Let The immersion time is preferably about 20 to 30 seconds. [Na (H ₂ O) ₂ ] _x MoO ₃ is obtained by washing and drying.

Next, in the second stage, PTHNA is exchanged between the layers by ion exchange with hydrated sodium ions (Na (H ₂ O) ₂ ⁺ ) existing between the layers of [Na (H ₂ O) ₂ ] _x MoO _3. insert. A monomer of polynaphthylamine or a derivative thereof and concentrated hydrochloric acid are added to distilled water bubbled with argon gas or nitrogen gas, and ammonium persulfate is added as a polymerization initiator for polymerization to obtain PTHNA. The polymerization time is about 10 minutes to 5 hours, preferably about 2 to 3 hours. Thereafter, [Na (H ₂ O) ₂ ] _x MoO ₃ is immersed, and an ion exchange reaction between hydrated sodium ions and PTHNA is performed. The immersion time is preferably about 20 to 30 seconds. (PTHNA) _x MoO ₃ is obtained by washing and drying.

Next, the chemical sensor characteristics of the obtained (PTHNA) _x MoO ₃ were evaluated. The resistance value was monitored using a comb-shaped electrode, and a change in the resistance value caused by the balance of charge transfer that was changed when the atmosphere was in a VOC gas atmosphere having a specified concentration was used as a sensor response. All of the conventional organic-inorganic hybrid materials responded more strongly to formaldehyde than acetaldehyde. However, the chemical sensor of the present invention was found to respond more strongly to acetaldehyde than formaldehyde and to have a high selectivity that the response to acetaldehyde was about 5.8 times the response to formaldehyde.

  In the present invention, the gas sensor material that responds more strongly to acetaldehyde than formaldehyde by the organic-inorganic hybrid material is preferably used as a chemical sensor element for detecting a gas component by monitoring the change in resistance value. By connecting this gas sensor material to an appropriate electrode, it is possible to monitor a change in resistance value and to function as a chemical sensor element.

The present invention has the following effects.
(1) It is possible to obtain a novel gas sensor material which is a gas sensor material made of an organic-inorganic hybrid material and which responds more strongly to acetaldehyde than formaldehyde.
(2) By simultaneously using the organic-inorganic hybrid material and an organic-inorganic hybrid material that responds more strongly to formaldehyde than conventional acetaldehyde, the concentration of formaldehyde and acetaldehyde can be determined by monitoring changes in both resistance values. It is possible to provide a new chemical sensor device that can be used.
(3) Thereby, an inexpensive chemical sensor device for determining the concentrations of formaldehyde and acetaldehyde can be provided.
(4) By using the chemical sensor device of the present invention, it is possible to constantly monitor the concentrations of formaldehyde and acetaldehyde.

  Next, the present invention will be specifically described based on examples, but the present invention is not limited to the following examples.

(1) Application of a lanthanum aluminate (LaAlO ₃ ) buffer layer to a silicon (Si) substrate A 85 mmol / L LaAlO ₃ precursor xylene solution was dropped onto a 20 mm square Si oxide-coated Si substrate, and 500 seconds at 500 rpm. Then, spin coating was performed at 3000 rpm for 30 seconds. Then, it was dried at 90 ° C. for about 30 minutes, and then baked at 1000 ° C. for 30 minutes. Through the above steps, a LaAlO ₃ buffer layer having a crystal lattice constant close to that of molybdenum oxide was applied to a Si substrate with a thermal oxide film.

(2) Production of Molybdenum Oxide (MoO ₃ ) Thin Film A MoO ₃ thin film was produced by a CVD method. The substrate used was a gold substrate in which a 10 mm square gold electrode having an electrode width of 20 μm and a distance between electrodes of 20 μm was vapor-deposited on a Si substrate coated with a LaAlO ₃ buffer layer. The substrate was placed in a sample holder with a heater for heating. The system was replaced by flowing 50 mL / min of oxygen gas from the source chamber to the sample chamber, and the sample holder was heated to 500 ° C., the sample chamber to 455 ° C., and the source chamber to 40 ° C.

After the temperature was stabilized, a quartz glass boat containing 0.35 g of molybdenum hexacarbonyl (Mo (CO) ₆ ) was placed in the source chamber, and the system was depressurized to 110 Pa by a vacuum pump. Under reduced pressure, Mo (CO) ₆ volatilized and MoO ₃ grew. After film formation for 15 minutes, the vacuum pump was stopped, the entire system was returned to atmospheric pressure, and film formation was completed. FIG. 2 shows an X-ray diffraction pattern measured with CuKα rays of the obtained MoO ₃ thin film. The observed diffraction peak is attributed to (0k0) of the layered MoO ₃ except for the peak from the substrate and the peak of the gold comb electrode, and the MoO ₃ thin film is b-axis oriented with respect to the substrate. It was confirmed.

(3) Preparation of [Na (H ₂ O) ₂ ] _x MoO ₃ thin film After stirring 15 mL of distilled water in a flask and bubbling with argon gas for 25 minutes, molybdate (VI) disodium dihydrate (Na ₂ MoO ₄ .2H ₂ O: 6 g) was added and dissolved, and then sodium hyposulfite (Na ₂ S ₂ O ₄ : 0.4 g) was added. After dissolving this, stirring and bubbling of argon gas were stopped, and the MoO ₃ thin film was immersed for 20 seconds. The thin film changed from light blue to blue by reducing some of the molybdenum.

Thereafter, the thin film was washed with distilled water and dried in air at 90 ° C. for 30 minutes. FIG. 3 shows an X-ray diffraction pattern measured with CuKα rays of the obtained thin film. The observed diffraction peak is attributed to (0k0) of the layered structure [Na (H ₂ O) ₂ ] _x MoO ₃ except for the peak from the substrate and the peak of the gold comb electrode. The interlayer distance is 9.4 mm, which is 2.5 mm larger than the interlayer distance 6.9 mm of MoO ₃ . This increase in interlayer distance corresponds to an increase when hydrated sodium ions (Na (H ₂ O) ₂ ) are intercalated between the layers, so that the [Na (H ₂ O) ₂ ] _x MoO ₃ thin film It was confirmed that it was generated.

(4) Preparation of (PTHNA) _x MoO ₃ thin film 5,6,7,8-tetrahydro-1-naphthylamine (0.254 mL, 1.82 mmol) was added to an aqueous solution obtained by adding 0.5 mL of concentrated hydrochloric acid to 5 mL of distilled water. In addition, stirring was performed while bubbling with nitrogen gas. Further, 0.5 mL of an aqueous solution containing ammonium persulfate ((NH ₄ ) ₂ S ₂ O ₈ : 17 mg) was added as a polymerization initiator, and the mixture was stirred for 160 minutes while bubbling with nitrogen gas. Thereafter, bubbling and stirring were stopped, and suction filtration was performed using a hydrophilic PTFE membrane filter having a pore diameter of 0.5 μm and a diameter of 25 mm. The obtained PTHNA aqueous solution was subjected to the above [Na (H ₂ O) ₂ ] _x MoO _3. After immersing the thin film for 30 seconds, it was washed with distilled water and dried in air for 30 minutes at 90 ° C. to obtain a (PTHNA) _x MoO ₃ thin film.

FIG. 4 shows an X-ray diffraction pattern measured with CuKα rays of (PTHNA) _x MoO ₃ . The observed diffraction peak is attributed to (0k0) of (PTHNA) _x MoO ₃ having a layered structure except for the peak from the substrate and the peak of the gold comb electrode. The interlayer distance is 14.3 mm, which is increased by 4.9 mm from the interlayer distance of [Na (H ₂ O) ₂ ] _x MoO ₃ 9.4 mm. This increase in interlayer distance corresponds to an increase when PTHNA intercalates between the layers, so that it was confirmed that a (PTHNA) _x MoO ₃ thin film was formed.

(5) Evaluation of electrical characteristics and sensor characteristics (PTHNA) _x MoO _{3 The} chemical characteristics of a chemical sensor with respect to formaldehyde and acetaldehyde gas were evaluated by changes in electrical resistance values. The measurement is performed by connecting the gold comb electrode to the electrical resistance measuring instrument in the sample chamber, heating to 100 ° C. while flowing clean nitrogen in the sample chamber at 200 mL / min, and stabilizing the temperature. Nitrogen gas containing 4 ppm was flowed for 20 minutes, and then clean nitrogen was flowed again.

The sensor sensitivity with respect to the VOC gas was an electric resistance value normalized by an electric resistance value immediately before introducing nitrogen gas containing 0.4 ppm of the target VOC gas. FIG. 5 shows measurement results of sensor characteristics with respect to 0.4 ppm formaldehyde and 0.4 ppm acetaldehyde. FIG. 5 shows that the chemical sensor using the (PTHNA) _x MoO ₃ thin film has a sensitivity to acetaldehyde of about 5.8 times that of formaldehyde. A substantially similar result was obtained when polyaminoanthracene or a derivative thereof was the main component as the organic compound.

  As described above in detail, the present invention relates to a gas sensor material, a manufacturing method thereof, and a gas sensor. According to the present invention, a novel gas sensor that responds more strongly to acetaldehyde than formaldehyde in a gas sensor material made of an organic-inorganic hybrid material. The material can be obtained. Simultaneously use the organic-inorganic hybrid material and organic-inorganic hybrid material that responds more strongly to formaldehyde than conventional acetaldehyde, thereby monitoring the change in resistance value of both, thereby determining the concentration of formaldehyde and acetaldehyde It is possible to provide a new chemical sensor device that can be used.

It shows a schematic diagram of a crystal structure of _(PTHNA) x MoO _3. Is a diagram showing an X-ray diffraction pattern of the MoO ₃ film shown in Examples. Is a diagram showing a _{[Na (H 2 O) 2} ] x MoO 3 thin film X-ray diffraction pattern shown in the Examples. Is a diagram showing an X-ray diffraction pattern of _(PTHNA) x MoO ₃ film shown in Examples. It is a diagram showing the sensor characteristics with respect to formaldehyde and 0.4ppm acetaldehyde of 0.4ppm chemical sensor according to _(PTHNA) x MoO ₃ film shown in Examples.

Explanation of symbols

(Reference in FIG. 1)
1 Molybdenum oxide layer 2 Poly (5,6,7,8-tetrahydro-1-naphthylamine) (PTHNA) layer

Claims (12)

  An organic-inorganic hybrid material in which an organic polymer is inserted between layers of an inorganic compound having a layered structure, wherein the inorganic compound having the layered structure is mainly composed of molybdenum oxide, and the organic polymer is polynaphthylamine or a derivative thereof, or An organic-inorganic hybrid material comprising, as a main component, polyaminoanthracene or a derivative thereof.   The material according to claim 1, wherein the polynaphthylamine derivative is poly (5,6,7,8-tetrahydro-1-naphthylamine).   The material according to claim 1, comprising a molded body of an organic-inorganic hybrid material in which an organic polymer is inserted between layers of an inorganic compound having a layered structure.   The material according to claim 3, comprising a thin film, an alignment film, a thick film, or a pellet molded body.   A gas sensor material comprising the organic-inorganic hybrid material according to any one of claims 1 to 4, wherein the gas sensor material has a property of detecting acetaldehyde gas preferentially over formaldehyde gas by a change in resistance value. .   A conductive material comprising the organic-inorganic hybrid material according to claim 1.   In this method, an organic polymer is inserted between layers of an inorganic compound having a layered structure, and a gas sensor material made of an organic-inorganic hybrid material having a property of detecting acetaldehyde gas preferentially over formaldehyde gas by changing the resistance value. A gas sensor material comprising: a compound mainly composed of molybdenum oxide as the inorganic compound having a layered structure; and polynaphthylamine or a derivative thereof, or polyaminoanthracene or a derivative thereof as the organic polymer. Production method.   A method for producing a conductive material comprising an organic-inorganic hybrid material by inserting an organic polymer between layers of an inorganic compound having a layered structure, wherein the compound is composed mainly of molybdenum oxide as the inorganic compound having the layered structure And polynaphthylamine or a derivative thereof, or polyaminoanthracene or a derivative thereof as an organic polymer.   The method for producing a gas sensor material or a conductive material according to claim 7 or 8, wherein the organic-inorganic hybrid material is molded into a molded body.   The method for producing a gas sensor material or a conductive material according to claim 9, wherein the organic-inorganic hybrid material is molded into a thin film, an alignment film, a thick film, or a pellet.   A conductive member comprising the conductive material according to claim 6 as a constituent element.   A chemical sensor member comprising a sensor element made of the gas sensor material according to claim 5.