JP6439577B2 - Gas sensor device, gas sensor device and manufacturing method thereof, information processing system - Google Patents

Description

  The present invention relates to a gas sensor device, a gas sensor device, a manufacturing method thereof, and an information processing system.

In recent years, medical expenses have increased with the aging of society, and it is necessary to reduce the number of serious patients and reduce medical expenses by early detection of serious diseases such as cancer by screening and early treatment. There is.
As a technique for detecting cancer at an early stage using this screening, for example, there is a method of detecting a marker gas peculiar to cancer contained in exhaled breath. For example, ammonia is known as a marker gas for infection with H. pylori, which is a risk factor for gastric cancer, and acetaldehyde and nonanal are known as marker gases for lung cancer.

JP 2003-232785 A Special table 2012-522991 gazette

By the way, for example, CuBr may be used for a sensitive film of a gas sensor device provided in a gas sensor that detects ammonia or the like.
However, the CuBr film deteriorates if it is exposed to the atmosphere for a long time before using the gas sensor or exposed to a solution or the like during the manufacturing process. As a result, the sensitivity of the gas sensor is lowered. It may become undetectable.

  Therefore, when CuBr is used for the sensitive film of the gas sensor device provided in the gas sensor, it is desired that the CuBr film does not deteriorate.

The device for a gas sensor includes a laminated film including a first CuBr film, a Cu film covering the first CuBr film, and two electrodes electrically connected through the laminated film.
When detecting the gas, the present gas sensor device is used as a sensitive film including the first CuBr film and the second CuBr film, and the Cu film of the gas sensor device described above is brominated to form a second CuBr film.

The information processing system includes a gas sensor including the gas sensor device described above, and a computer connected to the gas sensor via a network and processing data obtained by the gas sensor.
The manufacturing method of this gas sensor device is a process for producing a gas sensor device including a laminated film including a first CuBr film and a Cu film covering the first CuBr film, and two electrodes electrically connected via the laminated film. When the gas is detected, the Cu film of the gas sensor device is brominated to form a second CuBr film, the laminated film is a sensitive film including the first CuBr film and the second CuBr film, and the gas sensor device is formed. A gas sensor device.

  Therefore, according to the gas sensor device, the gas sensor device and the manufacturing method thereof, and the information processing system, when CuBr is used for the sensitive film of the gas sensor device included in the gas sensor, the advantage that the CuBr film can be prevented from deteriorating. There is.

It is typical sectional drawing for demonstrating the structure of the device for gas sensors concerning this embodiment, and its manufacturing method. It is typical sectional drawing for demonstrating the structure of the gas sensor device concerning this embodiment, and its manufacturing method. (A), (B) is typical sectional drawing for demonstrating the subject of this invention. It is a mimetic diagram showing composition of an information processing system concerning this embodiment.

Hereinafter, a gas sensor device, a gas sensor device, a manufacturing method thereof, and an information processing system according to an embodiment of the present invention will be described with reference to FIGS.
The gas sensor device according to the present embodiment is a gas sensor device that senses gas contained in exhaled breath and body odor, particularly marker gas peculiar to various diseases.

The gas sensor device of this embodiment is a gas sensor device provided in a gas sensor that detects, for example, a trace amount of ammonia contained in exhaled air with a high sensitivity of several ppm or less, and uses CuBr for the sensitive film.
In this gas sensor using CuBr, when ammonia molecules are adsorbed on the CuBr film, the concentration of Cu ⁺ ions in the adsorbed CuBr changes, and the resistance value (or potential) of CuBr as a semiconductor changes. A trace amount of ammonia can be detected by a change in resistance value (or potential).

As shown in FIGS. 1 and 2, the method for manufacturing a gas sensor device of the present embodiment includes a step of manufacturing a gas sensor device 1 and a step of using the gas sensor device 1 as a gas sensor device 10.
Here, the step of manufacturing the gas sensor device 1 includes the laminated film 4 including the first CuBr film 2 and the Cu film 3 covering the first CuBr film 2, and two electrodes electrically connected via the laminated film 4. 5 and 6 are steps for producing the gas sensor device 1. The laminated film 4 is also referred to as a sensor film.

Further, in the process of using the gas sensor device 1 as the gas sensor device 10, when detecting gas, the Cu film 3 of the gas sensor device 1 is brominated to form the second CuBr film 3X, and the laminated film 4 is changed to the first CuBr. In this process, the gas sensor device 1 is changed to the gas sensor device 10 by using the sensitive film 4X including the film 2 and the second CuBr film 3X.
Here, as a process for bromating the Cu film 3 to form the second CuBr film 3X, that is, a process for converting the Cu film 3 into CuBr, for example, it is immersed in a CuBr solution (CuBr ₂ solution; for example, CuBr ₂ 0.01M aqueous solution). What is necessary is just to perform the process (solution process) to perform.

For this reason, as shown in FIG. 1, the gas sensor device 1 of the present embodiment includes a laminated film 4 including a first CuBr film 2 and a Cu film 3 covering the first CuBr film 2, that is, the first CuBr film 2 and the Cu film. Two electrodes 5 and 6 are provided which are electrically connected via a laminated film 4 having a two-layer structure in which the film 3 is laminated.
In the present embodiment, an insulating film (insulating protective film) 7 partially covering the surface of the Cu film 3 is also provided. Here, the insulating film 7 may be an insulating film made of, for example, a photosensitive organic resist.

In this embodiment, the two electrodes 5 and 6 are provided on the opposite side of the first CuBr film 2 to the side covered with the Cu film 3. However, the present invention is not limited to this, and the two electrodes 5 and 6 may be provided one on each of the upper and lower sides of the laminated film 4 in which the first CuBr film 2 and the Cu film 3 are laminated.
Here, the insulating film 7 is provided on the surface of the Cu film 3 above the one electrode 6 of the two electrodes 5, 6, and the insulating film 7 is provided on the surface of the Cu film 3 above the other electrode 5. The surface of the Cu film 3 is exposed. That is, the insulating film 7 covering the surface of the Cu film 3 is provided so that the surface of the Cu film 3 is partially exposed.

With such a configuration, when ammonia is adsorbed on the exposed portion of the surface when the gas is detected by bromating the Cu film 3 to form the CuBr film 3X as described later, 2 A potential difference can be generated between the two electrodes 5 and 6, and a small amount of ammonia can be detected by the change in the potential difference.
Here, a gap g is provided between the two electrodes 5 and 6, and the surface of the Cu film 3 above the gap g is exposed. For this reason, when ammonia molecules are adsorbed on the exposed portion of the surface when the Cu film 3 is brominated to form the CuBr film 3X and gas is detected as described later, the two electrodes 5, 6 The resistance values of the CuBr films 2 and 3X also change between the two. For this reason, it is possible to detect a small amount of ammonia even by a change in the resistance value of the CuBr films 2 and 3X. Therefore, ammonia can be detected without providing the insulating film 7. That is, the gas sensor device 1 may not include the insulating film 7.

  Moreover, it is good also as a thing provided with the detection part which is connected to the two electrodes 5 and 6 and detects the change of the electrical property of the laminated film 4. FIG. Here, as will be described later, when detecting gas, the Cu film 3 of the gas sensor device 1 is brominated to form the second CuBr film 3X, and the laminated film 4 includes the first CuBr film 2 and the second CuBr film 3X. Since it uses as film | membrane 4X, a detection part will detect the change of the electrical property of the sensitive film | membrane 4X.

In the present embodiment, an insulating film 9 (for example, a SiO ₂ film) is provided on a substrate 8 (for example, a silicon substrate), and the gas sensor device 1 configured as described above is provided on the insulating film 9. . In addition, wirings and pads are embedded in the insulating film 9, and the two electrodes 5 and 6 of the gas sensor device 1 configured as described above are electrically connected to the pads, respectively. Then, it is connected to a circuit (for example, a circuit including a transistor) as a detection unit via a wiring connected to these pads. In this circuit, a change in electrical characteristics (for example, resistance value, current) of the sensitive film 4X. Value or change in potential difference) can be detected.

However, the present invention is not limited to this. For example, a circuit (for example, a circuit including a transistor) as a detection unit is provided on the surface side of the substrate 8, and the electrical characteristics of the sensitive film 4 </ b> X change (for example, a potential difference). Or a change in resistance value) may be detected.
Further, when the gas sensor device 10 according to the present embodiment detects (measures) a gas, as shown in FIG. 2, the Cu film 3 of the gas sensor device 1 described above is brominated to form a second CuBr film 3X. The film 4 is used as a sensitive film 4X including the first CuBr film 2 and the second CuBr film 3X.

  That is, the gas sensor device 10 of the present embodiment includes a laminated film 4 including the first CuBr film 2 and a Cu film 3 covering the first CuBr film 2, and two electrodes 5 electrically connected via the laminated film 4. , 6, and when detecting gas, the Cu film 3 is brominated to form a second CuBr film 3X, and the laminated film 4 is used as a sensitive film 4X including the first CuBr film 2 and the second CuBr film 3X It is.

Here, when the gas is detected, the Cu film 3 whose surface is partially exposed is brominated from the surface in the thickness direction (CuBr conversion) to form a CuBr film 3X.
In this way, the gas sensor device 1 in which the surface of the CuBr film 2 is covered with the Cu film 3 is manufactured, and when the gas is detected, the Cu film 3 is subjected to a treatment for forming a CuBr, and the gas sensor device 1 is converted into the gas sensor device. 10 is assumed.

In this case, the subsequent manufacturing process is performed and distributed with the surface of the CuBr film 2 covered with the Cu film 3. That is, the state in which the surface of the CuBr film 2 is covered with the Cu film 3 is maintained after the formation of the CuBr film 2 until the gas sensor is used (when the gas is measured).
Thereby, it is possible to prevent the CuBr film 2 from being deteriorated by being exposed to the air for a long time before using the gas sensor or being exposed to a solution or the like during the manufacturing process. . For example, it is possible to prevent the surface from being deteriorated by being exposed to the atmosphere during the device manufacturing process after the formation of the CuBr film 2 and being oxidized or adsorbing gas in the atmosphere. . Further, for example, it is possible to prevent the CuBr film 2 from coming into contact with the solution and dissolving and deteriorating during the manufacturing process.

As a result, when detecting the gas, it is possible to prevent the sensitivity of the gas sensor from being lowered, and in some cases, from being undetectable (unmeasurable).
And when detecting gas (for example, just before a measurement), the process which converts the Cu film | membrane 3 on the CuBr film | membrane 2 into CuBr is performed. For example, a treatment of immersing in a CuBr solution (CuBr ₂ solution; for example, CuBr ₂ 0.01M aqueous solution) is performed. For example, the Cu film 3 of the gas sensor device 1 may be immersed in a CuBr solution, or the CuBr solution may be deposited on the Cu film 3 of the gas sensor device 1.

Thereby, it becomes the gas sensor device 10 which has the sensitive film | membrane 4X in which the clean CuBr film | membrane 3X is exposed on the surface, and a stable measurement with high sensitivity is attained.
That is, it is possible to stably detect the gas with high sensitivity in a clean state in which the detection target gas of the sensitive film 4X of the gas sensor device 10 contacts (adsorbs) the surface that is not deteriorated.

For example, it becomes possible to detect (sense) a gas such as a trace amount of ammonia of several ppm or less with high sensitivity and stability.
In addition, Cu is not greatly deteriorated in the atmosphere like CuBr, but also resists to an organic solvent used for removing a resist in a manufacturing process, for example, an alkali developer for producing a resist pattern, etc. There is also.

Further, for example, nitrogen (N ₂ ) gas is preferably sealed by sealing, for example, in a vacuum state so that the surface of the Cu film 3 is not oxidized after use, for example, before use. It should be noted that even if the surface of the Cu film 3 is oxidized after use until the time of use, there is no effect, and the Cu film 3 can be turned into the CuBr film 3X by the above-described treatment for converting the Cu film 3 to CuBr.
In addition, a protective film may be provided so as to cover the CuBr film 2, and when the gas is detected, this protective film may be removed by wet etching. However, the CuBr film is deteriorated by the solution used for wet etching. This is done as described above. In addition, a protective film may be provided so as to cover the CuBr film, and when the gas is detected, the protective film may be removed by dry etching. However, a large-scale apparatus is required to perform dry etching. Therefore, it is as described above.

Specifically, the gas sensor device 1 may be manufactured and the gas sensor device 10 may be manufactured as follows.
First, on a Si substrate 8 with a thermal oxide film (SiO ₂ film; insulating film) 9 having a thickness of about 300 nm, for example, a Ti film (adhesion layer) having a thickness of about 50 nm and an Au film having a thickness of about 100 nm, for example. For example, it forms into a film by RF sputtering method and forms the two electrodes 5 and 6 with which the device 1 for gas sensors is equipped (refer FIG. 1). Here, the size of these two electrodes 5 and 6 is about 10 nm × about 50 mm, and the distance between electrodes (gap g) is about 1 mm.

Next, a CuBr film 2 having a thickness of, for example, about 300 nm and a Cu film 3 having a thickness of, for example, about 300 nm are formed by, for example, RF sputtering so as to straddle these two electrodes 5, 6. 1 is formed (see FIG. 1).
Next, for example, a photosensitive organic resist is patterned as the insulating protective film 7 (see FIG. 1).

In this way, the gas sensor device 1 is manufactured (see FIG. 1).
And, until the time of use, nitrogen _{(N 2)} stored in the gas. For example, the exposed portion of the Cu film 3 constituting the laminated film 4 that is not covered with the insulating protective film 7 is sealed with nitrogen (N ₂ ) gas.
Thereafter, when detecting the gas, that is, before measuring the gas, the gas sensor device 1 is immersed in a CuBr ₂ 0.01M aqueous solution for about 30 seconds, washed with pure water, and dried. Thereby, the Cu film 3 on the CuBr film 2 is converted to CuBr, and the gas sensor device 10 in which the CuBr film 3X is exposed on the surface as the sensitive film 4X is manufactured (see FIG. 2).

Thus, first, the gas sensor device 1 in which the surface of the CuBr film 2 is covered with the Cu film 3 is manufactured, and when the gas is detected, the Cu film 3 is converted into CuBr, so that the gas sensor device 1 is formed. The gas sensor device 10 is assumed.
The gas sensor device 10 fabricated in this manner, N ₂ gas, ammonia gas (here 1ppm ammonia gas), exposed in the order of N ₂ gas, where the resistance value was measured three times in N ₂ at the ammonia gas About the resistance value increased.

That is, in the gas sensor device 10 manufactured as described above, the clean CuBr film 3X which is not deteriorated is exposed. As a result, when the gas sensor device 10 is exposed to ammonia gas, the resistance value changes about three times. It was.
For this reason, the resistance value of the gas sensor device 10 is measured, and whether or not ammonia is contained in the measurement target gas is determined (determined) by checking whether or not the resistance value changes before and after exposure to the measurement target gas. be able to.

  On the other hand, as shown in FIG. 3 (A), when the CuBr film 2 is not provided on the CuBr film and only the CuBr film 2 is provided as the sensitive film, the subsequent CuBr film 2 is exposed. Since the manufacturing process is performed, the CuBr film 2 deteriorates as shown in FIG. 3B due to elution in the solution used in the manufacturing process or exposure to the atmosphere for a long time before use. . As a result, since the change in resistance value as described above cannot be obtained, it is difficult to measure whether the measurement target gas contains ammonia.

Therefore, according to the gas sensor device, the gas sensor device, and the manufacturing method thereof according to the present embodiment, when CuBr is used for the sensitive film of the gas sensor device provided in the gas sensor, it is possible to prevent the CuBr film from deteriorating. There is.
By the way, data (information) measured using a gas sensor including the gas sensor device 10 of the above-described embodiment is collected and accumulated via a network, a database is constructed, and these data are analyzed. It is also possible to provide feedback.

As a result, it can be used effectively for improving screening accuracy of diseases, investigating the presence or absence of correlation with other diseases, etc., and it is possible to feed back measurement results without much effort. It becomes.
For example, by analyzing the presence or absence of cancer or the correlation with other illnesses in exhaled breath subjects, it is possible to improve screening accuracy and develop other illness screening, and the aging society will increase medical costs. The contribution to is great.

In this case, as shown in FIG. 4, the information processing system 11 that performs such data processing (information processing) is connected to the gas sensor 12 including the gas sensor device 10 of the above-described embodiment and the gas sensor 12 via the network 13. And a server (computer) 14 for processing data obtained by the gas sensor 12.
In addition to the gas sensor device 10 of the above-described embodiment, the gas sensor 12 may include, for example, a circuit as a detection unit, a controller, a communication circuit, and the like. The information processing system 11 is also referred to as a sensor network system.

Note that the present invention is not limited to the configurations described in the above-described embodiments and modifications, and various modifications can be made without departing from the spirit of the present invention.
Hereinafter, additional notes will be disclosed regarding the above-described embodiment and modifications.
(Appendix 1)
A laminated film comprising a first CuBr film and a Cu film covering the first CuBr film;
A gas sensor device comprising: two electrodes electrically connected via the laminated film.

(Appendix 2)
The device for a gas sensor according to appendix 1, further comprising an insulating film partially covering a surface of the Cu film.
(Appendix 3)
3. The gas sensor device according to appendix 1 or 2, wherein the two electrodes are provided on the opposite side of the first CuBr film to the side covered with the Cu film.

(Appendix 4)
The gas sensor device according to any one of appendices 1 to 3, further comprising a detection unit that is connected to the two electrodes and detects a change in electrical characteristics of the laminated film.
(Appendix 5)
When detecting gas, the Cu film of the gas sensor device according to any one of appendices 1 to 4 is brominated to form a second CuBr film, and the stacked film is formed from the first CuBr film and the second CuBr film. A gas sensor device that is used as a sensitive film.

(Appendix 6)
A gas sensor comprising the gas sensor device according to appendix 5,
An information processing system comprising: a computer connected to the gas sensor via a network and processing data obtained by the gas sensor.
(Appendix 7)
Producing a gas sensor device comprising: a laminated film comprising a first CuBr film and a Cu film covering the first CuBr film; and two electrodes electrically connected through the laminated film;
When detecting gas, the Cu film of the gas sensor device is brominated to form a second CuBr film, and the laminated film is a sensitive film including the first CuBr film and the second CuBr film, And a step of using the gas sensor device as a gas sensor device.

DESCRIPTION OF SYMBOLS 1 Gas sensor device 2 1st CuBr film 3 Cu film 3X 2nd CuBr film 4 Laminated film 4X Sensitive film 5, 6 Electrode 7 Insulating film (insulating protective film)
8 Substrate (silicon substrate)
9 Insulating film (SiO ₂ film)
DESCRIPTION OF SYMBOLS 10 Gas sensor device 11 Information processing system 12 Gas sensor 13 Network 14 Server (computer)

Claims (4)

A laminated film comprising a first CuBr film and a Cu film covering the first CuBr film;
A gas sensor device comprising: two electrodes electrically connected via the laminated film.   When detecting gas, the Cu film of the gas sensor device according to claim 1 is brominated to form a second CuBr film, and the laminated film is used as a sensitive film including the first CuBr film and the second CuBr film. A gas sensor device. A gas sensor comprising the gas sensor device according to claim 2;
An information processing system comprising: a computer connected to the gas sensor via a network and processing data obtained by the gas sensor. Producing a gas sensor device comprising: a laminated film comprising a first CuBr film and a Cu film covering the first CuBr film; and two electrodes electrically connected through the laminated film;
When detecting gas, the Cu film of the gas sensor device is brominated to form a second CuBr film, and the laminated film is a sensitive film including the first CuBr film and the second CuBr film, And a step of using the gas sensor device as a gas sensor device.

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