GAS SENSOR AND METHOD OF FABRICATING THE SAME
20170082574 ยท 2017-03-23
Assignee
Inventors
- Young Tae BYUN (Seoul, KR)
- Jae Seong KIM (Seoul, KR)
- Je Haeng LEE (Seoul, KR)
- Sun Ho KIM (Seoul, KR)
- Young Min JHON (Seoul, KR)
- Sun Woo Choi (Seoul, KR)
Cpc classification
B22F7/04
PERFORMING OPERATIONS; TRANSPORTING
B22F1/18
PERFORMING OPERATIONS; TRANSPORTING
H10K71/40
ELECTRICITY
Y02P70/50
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
B82Y40/00
PERFORMING OPERATIONS; TRANSPORTING
B22F9/026
PERFORMING OPERATIONS; TRANSPORTING
B22F2999/00
PERFORMING OPERATIONS; TRANSPORTING
B22F2301/25
PERFORMING OPERATIONS; TRANSPORTING
B22F2998/10
PERFORMING OPERATIONS; TRANSPORTING
Y02E10/549
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
B22F2007/042
PERFORMING OPERATIONS; TRANSPORTING
B22F9/026
PERFORMING OPERATIONS; TRANSPORTING
B22F1/18
PERFORMING OPERATIONS; TRANSPORTING
G01N27/12
PHYSICS
B22F2998/10
PERFORMING OPERATIONS; TRANSPORTING
B22F2304/054
PERFORMING OPERATIONS; TRANSPORTING
B82Y30/00
PERFORMING OPERATIONS; TRANSPORTING
B22F2999/00
PERFORMING OPERATIONS; TRANSPORTING
B22F2007/042
PERFORMING OPERATIONS; TRANSPORTING
International classification
G01N27/414
PHYSICS
B82Y40/00
PERFORMING OPERATIONS; TRANSPORTING
B82Y15/00
PERFORMING OPERATIONS; TRANSPORTING
Abstract
A gas sensor and a method of fabricating the same are provided. The gas sensor includes a substrate, carbon nanotubes (CNTs) adsorbed onto the substrate, platinum nanoparticles (NPs) decorated to surfaces of the CNTs, and an electrode formed on the substrate onto which the CNTs with the platinum NPs decorated thereto are adsorbed. When the platinum NPs and CNTs are used as a sensing material, the gas sensor can be useful in sensing gases with high sensitivity even when present at a low concentration of at least 2 ppm and stably sensing noxious gases such as C.sub.6H.sub.6, C.sub.7H.sub.8, C.sub.3H.sub.6O, CO, NO, and NH.sub.3 as well as NO.sub.2, and can have particularly excellent selectivity and response characteristics with respect to NO.sub.2 gas.
Claims
1. A gas sensor comprising: a substrate; carbon nanotubes (CNTs) adsorbed onto the substrate; platinum nanoparticles (NPs) decorated to surfaces of the CNTs; and an electrode formed on the substrate onto which the CNTs with the platinum NPs decorated thereto are adsorbed.
2. The gas sensor of claim 1, wherein the substrate comprises a silicon substrate.
3. The gas sensor of claim 1, wherein the substrate comprises a silicon substrate having a silicon dioxide film formed on a surface thereof.
4. The gas sensor of claim 1, wherein the CNTs comprise single-walled CNTs (SWCNTs).
5. The gas sensor of claim 1, wherein the platinum NPs have an average diameter of 2 nm to 10 nm.
6. A method of fabricating a gas sensor, comprising: (a) adsorbing carbon nanotubes (CNTs) onto a substrate; (b) depositing platinum (Pt) onto the substrate onto which the CNTs are adsorbed; and (c) heat-treating the substrate onto which the platinum (Pt) is deposited to form platinum (Pt) nanoparticles (NPs) on surfaces of the CNTs.
7. The method of claim 6, wherein the substrate comprises a silicon substrate.
8. The method of claim 6, wherein the substrate comprises a silicon substrate having a silicon dioxide film formed on a surface thereof.
9. The method of claim 6, wherein the CNTs comprises single-walled CNTs (SWCNTs).
10. The method of claim 6, wherein, in the absorbing of the CNTs onto the substrate, the absorption is performed in an argon atmosphere using a spraying method.
11. The method of claim 6, wherein, in the depositing of the platinum (Pt) on the substrate onto which the CNTs are adsorbed, the platinum (Pt) is coated onto the surfaces of the CNTs to form a core-shell structure.
12. The method of claim 11, wherein a platinum (Pt) layer formed as a shell layer in the core-shell structure has a thickness of 5 nm to 10 nm.
13. The method of claim 6, wherein the heat treatment is performed at 500 to 600 C.
14. The method of claim 6, wherein the platinum NPs have an average diameter of 2 nm to 10 nm.
15. The method of claim 6, wherein the heat treatment is performed in argon atmosphere.
16. The method of claim 6, wherein the heat treatment is performed using a rapid thermal annealing furnace.
17. The method of claim 6, further comprising: forming an electrode on the substrate that underwent heat treatment operation.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0025] The above and other objects, features and advantages of the present invention will become more apparent to those of ordinary skill in the art by describing exemplary embodiments thereof in detail with reference to the accompanying drawings, in which:
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DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS
[0042] Exemplary embodiments of the present invention will be described in detail below with reference to the accompanying drawings. While the present invention is shown and described in connection with exemplary embodiments thereof, it should be apparent to those skilled in the art that various modifications can be made without departing from the scope of the invention.
[0043] Unless specifically stated otherwise, all of the technical and scientific terms used in this specification have the same meanings as that which are generally understood by a person skilled in the related art to which the present invention belongs. In general, the nomenclature used in this specification and the experimental methods described below are widely known and generally used in the related art.
[0044] The present invention is directed to a gas sensor which includes a substrate, carbon nanotubes (CNTs) adsorbed onto the substrate, platinum nanoparticles (NPs) decorated to surfaces of the CNTs, and an electrode formed on the substrate onto which the CNTs with the platinum NPs decorated thereto are adsorbed.
[0045] Hereinafter, a gas sensor according to one exemplary embodiment of the present invention will be described in further detail.
[0046] A Group III-V compound semiconductor material such as Si, GaAs, InP, InGaAs, etc., a glass, an oxide thin film, a dielectric thin film, and a metal thin film may be used as a material used for the substrate, but the present invention is not limited thereto. Preferably, the substrate may include a silicon substrate, more preferably a silicon substrate having an insulator film formed on a surface thereof. For example, the substrate may be a silicon substrate having a silicon oxide (SiO.sub.2) film formed on a surface thereof, as shown in
[0047] In the present invention, CNTs and platinum (Pt) NPs are used as a sensing material. As described above, when CNTs are used as the sensing material rather than an oxide, a gas sensor capable of being operable at room temperature (RT) may be provided. CNTs are formed by rolling a graphite sheet of a hexagonal honeycomb structure in a straw shape, and thus have a single-walled (SW), double-walled (DW) or multi-walled (MW) structure. CNTs may have electrical conductive or semiconductive characteristics in a rolling direction. CNTs include single-walled CNTs (SWCNTs) because SWCNTs exhibit superior performance to multi-walled CNTs (MWCNTs) in terms of sensitivity and response time.
[0048] Also, in the present invention, since platinum NPs are used as the sensing material together with CNTs, a gas sensor exhibiting very good sensitivity to react with a trace of noxious gases may be provided. The platinum NPs play a role as a catalyst in forcing the CNTs to sense NO.sub.2 gas. In this case, a catalytic reaction may be activated as the platinum NPs may have a smaller average diameter and may be present in an uncoupled state. Specifically,
[0049] The platinum NPs may have an average diameter ranging from several to several tens of nanometers (nm), preferably from 2 to 10 nm When the average diameter of the platinum NPs falls within this range, it is preferable because a change in electric resistance due to gases in contact with the CNTs may be more sensitively measured.
[0050] Referring to
[0051] An electrode is formed on the substrate on which the CNTs and the platinum NPs are formed as shown in
[0052] A method of fabricating such a gas sensor includes (a) adsorbing CNTs onto a substrate, (b) depositing platinum (Pt) on the substrate onto which the CNTs are adsorbed, and (c) heat-treating the substrate onto which the platinum (Pt) is deposited to form platinum (Pt) NPs on surfaces of the CNTs.
[0053] Hereinafter, one exemplary embodiment of the method of fabricating a gas sensor will be described in detail with reference to
[0054] (a) Adsorption of CNTs on Substrate
[0055] First of all, a substrate is prepared. As described above, the substrate may include a silicon substrate or may include a silicon substrate having an insulator film formed on a surface thereof, for example, a silicon substrate (SiO.sub.2/Si substrate) having a silicon oxide (SiO.sub.2) film formed on a surface thereof. The insulator film may be formed on the substrate using a method such as a thermal oxidation method, a deposition method, a spin coating method, etc., but the present invention is not limited thereto. In the case of the thermal oxidation method, a thermal insulator film may be formed by heating the silicon substrate at temperature of 1,000 C. or more using a thermal diffusion furnace. In the case of the deposition method, a SiO.sub.2 thin film may be formed on the silicon substrate using plasma-enhanced chemical vapor deposition (PECVD) or low-pressure CVD (LPCVD). In the case of the spin coating method, a SiO.sub.2 thin film may be formed on the silicon substrate using spin-on-glass (SOG). A thickness of the insulator film may be in a range of 120 to 300 nm.
[0056] Next, CNTs are adsorbed onto the substrate. As described above, the CNTs preferably include SWCNTs. In the adsorption of the CNTs, the adsorption may be performed using a dipping method of dipping a substrate in a solution in which CNTs are dispersed and removing the substrate from the solution or a spraying method of spraying a solution in which CNTs are dispersed. To uniformly disperse the CNTs, the spraying method may be preferred. Such a spraying method may be carried out using an argon (Ar) gas in order to prevent an oxidation reaction of CNTs with oxygen. The use of the spraying method is shown in
[0057] The solution may include at least one solvent selected from the group consisting of dichlorobenzene (DCB), ortho-dichlorobenzene (o-DCB), N-methyl-2-pyrrolidinone (NMP), hexamethylphosphoramide (HMPA), monochlorobenzene (MCB), N,N-dimethylformamide (DMF), dichloroethane (DCE), isopropyl alcohol (IPA), ethanol, chloroform, and toluene. Also, CNTs may be uniformly dispersed in the solution by applying ultrasonic waves to the solution.
[0058] In the solution in which the CNTs are dispersed, a concentration of the CNTs may be in a range of 0.01 to 0.50 mg/ml. When the concentration is less than 0.01 mg/ml, a function as a sensor may not be normally exerted due to a very small amount of adsorbed CNTs. On the other hand, when the concentration is greater than 0.50 mg/ml, a large amount of time is required to disperse the CNTs, sensitivity of the sensor may be degraded, and an excessive amount of the CNTs is consumed, resulting in increased manufacturing costs.
[0059] (b) Deposition of Platinum (Pt)
[0060] This operation includes depositing platinum (Pt) on the substrate onto which the CNTs are adsorbed. As a method of depositing the platinum (Pt), a conventional vacuum deposition may be used without limitation. For example, a method such as thermal evaporation, electron beam evaporation, sputtering, etc. may be used. Preferably, a sputtering method may be used.
[0061] For example, when the sputtering method is used, sputtering may be performed in an argon atmosphere in order to prevent an oxidation reaction of the CNTs with oxygen. Specifically, one exemplary embodiment of sputtering process conditions according to the present invention is described as follows:
[0062] Distance from target: 2 to 10 cm
[0063] Vacuum level of vacuum chamber: 5 to 20 mTorr
[0064] Vacuum level during vacuum deposition: 30 to 100 mTorr
[0065] (Provided that plasma is generated after the target is maintained in an argon atmosphere for at least 30 minutes)
[0066] Deposition time: 1 to 5 seconds
[0067] In the deposition of the platinum (Pt) on the substrate onto which the CNTs are adsorbed, surfaces of the CNTs may be coated with platinum to form a core-shell structure. Referring to
[0068] In the core-shell structure, a platinum (Pt) layer formed as the shell layer preferably has a thickness of 10 nm or less. More preferably, the thickness of the shell layer may be in a range of 5 nm to 10 nm When the thickness of the shell layer falls within this range, the shell layer of platinum (Pt) deposited on the substrate is preferably converted into NPs by a subsequent heat treatment.
[0069] (c) Heat Treatment Operation
[0070] This operation includes heat-treating the substrate on which the platinum (Pt) is deposited to form platinum (Pt) NPs on the surfaces of the CNTs.
[0071] The heat treatment is performed to convert the shell layer of platinum (Pt) deposited on the substrate into NPs. In this case, energy used to cause the platinum (Pt) particles to self-agglomerate is provided. The heat treatment is preferably performed at a temperature of 500 to 600 C. When a heat treatment temperature is less than 500 C., it is difficult to form platinum (Pt) NPs that play a role as a catalyst. On the other hand, when the heat treatment temperature is greater than 600 C., Pt may be oxidized into PtO. Since PtO is a p-type semiconductor material, it is impossible to expect a Pt catalytic effect.
[0072] Such a heat treatment operation may be performed in an argon atmosphere to prevent oxidation of the CNTs and is preferably performed using a rapid thermal annealing furnace. The heat treatment operation is specifically described as follows. For example, a specimen is first mounted in a chamber and then maintained in a low vacuum state for 30 minutes or more. Then, argon gas is added to the chamber to minimize contact with oxygen. Then, the specimen is heated to 500 to 600 C. at a high speed for 1 to 5 minutes, maintained at that temperature for 30 minutes to 2 hours, and then quenched to RT. Accordingly, the heat treatment operation may be completed.
[0073] The average diameter of the platinum (Pt) NPs formed on the substrate onto which the CNTs are adsorbed by the heat treatment may be in a range of several nanometers to several tens of nanometers, preferably in a range of 2 to 10 nm
[0074] As shown in
[0075] Hereinafter, the present invention will be described in further detail with reference to Examples thereof, but the present invention is not limited thereto.
EXAMPLE 1
[0076] A SiO.sub.2/Si substrate in which a silicon dioxide (SiO.sub.2) insulator film was formed on the silicon substrate was prepared. In this case, a thickness of the insulator film was 300 nm.
[0077] SWCNTs were added to dichlorobenzene, and ultrasonic waves were applied to prepare a solution in which the SWCNTs were uniformly dispersed (see
[0078] The concentration of the SWCNTs in the dispersion solution was 0.04 mg/ml.
[0079] The solution in which the SWCNTs were dispersed was sprayed onto the substrate using an air-brush spray gun (commercially available from Mr. Hobby; Model name: PS-770) so that the CNTs were adsorbed onto the substrate (see
[0080] Platinum (Pt) was vacuum-deposited onto the substrate onto which the CNTs were adsorbed using a sputtering system (commercially available from SANYU ELECTRON COATER, Model name: SC-701MKII ADVANCE) (see
[0081] The substrate on which a platinum (Pt) thin film was vacuum-deposited was heat-treated using a rapid thermal annealing furnace (commercially available from ULVAC; Model name: MILA-3000). Specifically, the substrate was mounted in a chamber in the rapid thermal annealing furnace, and maintained in a low vacuum state for 30 minutes, and argon (Ar) gas was added to the chamber. Thereafter, the substrate was heated to 500 C. at a high speed for 1 minute, maintained for an hour, and then quenched to RT. The transmission electron microscope images of the substrate on which the heat treatment was completed are shown in
[0082] Next, a source electrode and a drain electrode were formed on the substrate on which platinum NPs were decorated according to a conventional photolithography process, thereby fabricating a gas sensor. In this case, Ti (50 nm)/Pt (200 nm) electrodes were used as the source electrode and the drain electrode (see
COMPARATIVE EXAMPLE 1
[0083] A SiO.sub.2/Si substrate in which a silicon dioxide (SiO.sub.2) insulator film was formed on the silicon substrate was prepared, and electrodes (Ni (20 nm)/Au (60 nm)) were then formed on the SiO.sub.2/Si substrate according to a conventional photolithography process.
[0084] Next, SWCNTs were deposited on the substrate on which the electrodes were formed using CVD, thereby fabricating a gas sensor.
COMPARATIVE EXAMPLE 2
[0085] An alumina (Al.sub.2O.sub.3) substrate was prepared, and electrodes (Cr (20 nm)/Au (350 nm)) were then formed on the alumina (Al.sub.2O.sub.3) substrate according to a conventional photolithography process.
[0086] Next, a MWCNT film was deposited on the substrate on which the electrodes were formed using radio-frequency PECVD (rf-PECVD), thereby fabricating a gas sensor.
COMPARATIVE EXAMPLE 3
[0087] A Si.sub.3N.sub.4/Si substrate was prepared, and an electrode (Pt) was then formed on the Si.sub.3N.sub.4/Si substrate according to a conventional photolithography process.
[0088] Next, a CNT film was deposited on the substrate on which the electrode was formed using rf-PECVD, thereby fabricating a gas sensor.
COMPARATIVE EXAMPLE 4
[0089] A polyimide substrate was prepared, and an electrode (Au) was then formed on the polyimide substrate according to a conventional photolithography process.
[0090] Next, the substrate on which the electrode was formed was spin-coated with an aqueous suspension of graphene oxide to form a graphene oxide film, and a CNT film was deposited on the graphene oxide film using PECVD, thereby fabricating a gas sensor. In this case, a thickness of the graphene oxide film was 7 nm, and a thickness of the CNT film was 20 m. Here, the graphene oxide film was a reduced graphene oxide (RGO) film which was heat-treated at 600 C. in a mixture of hydrogen and ammonia gas.
[0091] Characterization of Gas Sensors
[0092] The gas sensor fabricated in Example 1 was connected to a direct current (DC) power supply (KEITHLEY 2400), and nitrogen dioxide (NO.sub.2), benzene (C.sub.6H.sub.6), toluene (C.sub.7H.sub.8), acetone (C.sub.3H.sub.6O), carbon monoxide (CO), ammonia (NH.sub.3) and nitrogen monoxide (NO) gases were allowed to flow thereto using a mass flow controller, and changes in resistance due to the adsorption of target gases-flowing around a sensing material were measured while applying a constant DC power source. The measurement results are shown in
[0093] Sensitivities of the gas sensor to the test gases were calculated using the following Equation 1. A comparison of the sensitivities to the test gases calculated by the following equation is shown in
Sensitivity=(R/R.sub.0) Equation 1
[0094] In Equation 1, R.sub.0 represents an initial resistance value when there is no reactive gas, and AR represents a value obtained by subtracting the R.sub.0 value from a resistance value when there is a reactive gas.
[0095] In the case of the gas sensors fabricated in Comparative Examples 1 to 4, NO.sub.2 gas was allowed to flow thereto in the same manner as described above, and changes in resistance due to the adsorption of the NO.sub.2 gas flowing around a sensing material were measured while applying a constant DC power source. As can be seen from the measurement results, response characteristics of the gas sensors with respect to the NO.sub.2 gas are compared to those of the gas sensor of Example 1 and listed in the following Table 1. Here, the sensitivity (%) in the following Table 1 represents a value (%) obtained by multiplying the value calculated by Equation 1 by 100.
TABLE-US-00001 TABLE 1 Sensing Detection Sensitivity Response Operating material limit (%) time temperature Reversibility Example 1 Pt- 2 ppm 37.5% <180 sec RT Reversible SWCNTs Comparative SWCNTs 2 ppm 6.5% <600 sec RT Irreversible Example 1 Comparative MWCNTs 1 ppm <3% <90 sec 200 C. Reversible Example 2 (at 200 C.) Comparative CNT film 10 ppb <2% 120 min 165 C. Reversible Example 3 (at 165 C.) Comparative CNT/RGO 2 ppm <8% <60 min RT Irreversible Example 4 fiml
[0096] Referring to Table 1, it was confirmed that the gas sensor of Example 1 in which the platinum NPs and CNTs were used as the sensing material according to the present invention had a somewhat low or similar detection limit as compared to those of the gas sensors of Comparative Examples 1 to 4, but that the gas sensor of Example 1 was able to detect a gas present at a low concentration of 2 ppm and exhibited high sensitivity. Also, it could be seen that the gas sensors of Comparative Examples 1 and 4 were operable at RT like the gas sensor of Example 1, but had a slow response time and non-reversible characteristics. Further, it could be seen that the gas sensors of Comparative Examples 2 and 3 were not operable at RT.
[0097] Also, referring to
[0098] According to the present invention, a gas sensor and a method of fabricating the same can be provided. Here, when the platinum NPs and CNTs are used as the sensing material, the gas sensor can be useful in sensing gases with high sensitivity even when the gases are present at a low concentration of at least 2 ppm, stably sensing noxious gases such as C.sub.6H.sub.6, C.sub.7H.sub.8, C.sub.3H.sub.6O, CO, NO, and NH.sub.3 as well as NO.sub.2, and can have particularly excellent selectivity and response characteristics with respect to NO.sub.2 gas.
[0099] Further, the gas sensor according to one exemplary embodiment of the present invention can have an effect of minimizing power consumption since the gas sensor is operable at RT without using a heater.
[0100] It should be apparent to those skilled in the art that various modifications can be made to the above-described exemplary embodiments of the present invention without departing from the scope of the invention. Thus, it is intended that the present invention covers all such modifications provided they come within the scope of the appended claims and their equivalents.