CoCr.SUB.2.O.SUB.4.-based gas sensor and method for manufacturing the same

Abstract

A method of manufacturing a gas sensor for detecting xylene is provided. A method of manufacturing a gas sensor includes reacting a mixed material including a first material containing a cobalt (Co) element and a second material containing a chromium (Cr) element to form a CoCr.sub.2O.sub.4 hollow structure having a hollow shape.

Claims

1. A gas sensor comprising: a gas sensing layer capable of reacting with xylene, wherein the gas sensing layer consisting of a CoCr.sub.2O.sub.4 hollow structure and a noble metal catalyst selected from the group consisting of Pt, Au, and Rh.

2. The gas sensor of claim 1, further comprising: an insulator substrate formed of an insulator material; and an electrode connected to the insulator substrate, wherein the gas sensing layer is coated on the insulator substrate, and wherein the electrode is connected between the insulator substrate and the gas sensing layer.

3. The gas sensor of claim 1, further comprising: a heater heating the gas sensing layer.

Description

BRIEF DESCRIPTION OF THE FIGURES

(1) The above and other objects and features will become apparent from the following description with reference to the following figures, wherein like reference numerals refer to like parts throughout the various figures unless otherwise specified, and wherein:

(2) FIG. 1 is a cross-sectional view illustrating a gas sensor according to an embodiment of the inventive concept;

(3) FIG. 2 is a flow chart illustrating a method of manufacturing a gas sensor according to an embodiment of the inventive concept;

(4) FIG. 3 is a graph illustrating results of X-ray diffraction analysis of Examples 1-1, 1-2, 2-1, 2-2, 2-3, and 2-4 and Comparative Examples 1-1 and 1-2;

(5) FIG. 4 is SEM and TEM pictures taken secondary particle structures of fine powders prepared in each Example and each Comparative Example;

(6) FIG. 5 is a graph illustrating gas sensitivity to ethanol, xylene, toluene, benzene, formaldehyde, trimethylamine, ammonia and carbon monoxide, each which had 5 ppm concentration at an operating temperature of 275° C. in Example 1-1 and Example 2-1, Comparative Example 1-1, and Comparative Example 1-2;

(7) FIG. 6 is a graph illustrating gas sensitivity for ethanol, xylene, toluene, benzene, formaldehyde, trimethylamine, ammonia and carbon monoxide, each which had 5 ppm concentration at an operating temperature of 275° C. in gas sensors manufactured by Examples 1-2, 1-3, 2-2, 2-3, 2-4;

(8) FIG. 7 is a graph illustrating changes of sensitivity ratios of xylene sensitivity to ethanol sensitivity of gas sensors manufactured in Examples 1-1, 1-2, 1-3, and 2-1 and Comparative Examples 1-1 and 1-2 with temperature;

(9) FIG. 8 is a graph illustrating selectivity (S.sub.X/S.sub.E) of xylene in Example 2-2, Example 2-3, and Example 2-4 at an operating temperature 275° C.;

(10) FIG. 9 is a graph illustrating sensitivity characteristics of xylene gas in Example 1-2 (300° C.) and Example 2-2 (275° C.) at sensor operating temperatures showing the highest selectivity with respect to changes of gas concentration;

(11) FIG. 10 is a graph illustrating results of comparing xylene sensitivity for each concentration with the existing studies; and

(12) FIG. 11 is a graph showing results of measuring gas sensitivity (R.sub.g R.sub.a.sup.−1) of Example 1-2 of the inventive concept for 30 days.

DETAILED DESCRIPTION

(13) Hereinafter, an embodiment of the inventive concept will be described in more detail with reference to the accompanying drawings. The embodiments of the inventive concept may be modified in various forms, and the scope of the inventive concept should not be construed as being limited to the following embodiments. This embodiment is provided to more completely explain the inventive concept to those skilled in the art. Therefore, the shape of the elements in the drawings is exaggerated to emphasize a more clear description.

(14) The inventive concept provides a highly sensitive and selective oxide semiconductor gas sensor having a high selectivity to xylene using pure CoCr.sub.2O.sub.4 while having a very low gas sensitivity to a hindered gas such as benzene, formaldehyde, alcohol, and the like. In addition, the inventive concept may provide a gas sensor where various catalysts (Pt, Au, or the like) are added to increase the sensitivity and selectivity to xylene through a synergistic effect of the catalysts and CoCr.sub.2O.sub.4.

(15) FIG. 1 is a cross-sectional view illustrating a gas sensor 10 according to an embodiment of the inventive concept. Referring to FIG. 1, the gas sensor 10 includes a sensitive layer 100, an insulator substrate 200, electrodes 301 and 302, and a heater 400. The gas sensor 10 detects xylene.

(16) The sensitive layer 100 is sensitive to xylene. For example, when the sensitive layer 100 is in contact with xylene, an electrical resistance changes. The sensitive layer 100 includes a CoCr.sub.2O.sub.4 hollow structure. According to an embodiment, the sensitive layer 100 may further include Cr.sub.2O.sub.3. Alternatively, the sensitive layer 100 may further include a noble metal catalyst. For example, Pt, Pd, Au, or Rh may be provided as the noble metal catalyst.

(17) The insulator substrate 200 is provided to electrically connect the electrodes 301 and 302 to the sensitive layer 100. The insulator substrate 200 is provided as an insulator. For example, alumina (Al2O3) may be provided as the insulator substrate 200.

(18) The electrodes 301 and 302 are connected to a top surface of the insulator substrate 200. The sensitive layer 100 is coated on the insulator substrate 200 whose the top surface is connected to the electrodes 301 and 302. Accordingly, the electrodes 301 and 302 are connected between the insulator substrate 200 and the sensitive layer 100. A resistance measuring device for measuring an electrical resistance is connected to the electrodes 301 and 302 which are connected to the insulator substrate 200 and the sensitive layer 100. When the sensitive layer 100 is in contact with xylene, the electrical resistance of the sensitive layer 100 may be changed and the changed electrical resistance of the sensitive layer 100 may be measured by the resistance measuring device to detect xylene.

(19) The heater 400 heats the sensitive layer 100 to a temperature at which the sensitive layer 100 is activated for detection of xylene. According to an embodiment, the heater 400 may be provided on a bottom surface of the insulator substrate 200. The heater 400 may include a heating wire which generates heat by the electrical resistance. According to an embodiment, the heater 400 may heat the sensitive layer 100 to 250 to 350° C.

(20) Hereinafter, a method of manufacturing a gas sensor according to an embodiment of the inventive concept will be described. The gas sensor 10 of FIG. 1 is an example of a gas sensor manufactured by the method of manufacturing the gas sensor according to an embodiment of the inventive concept.

(21) Pure Co.sub.3O.sub.4 (Comparative Example 1-1) and pure Cr.sub.2O.sub.3 (Comparative Example 1-2) were synthesized using a spray pyrolysis method as Comparative Examples for Examples of the inventive concept. Pure CoCr.sub.2O.sub.4 sensitive materials (Example 1-1, Example 2-1) were synthesized through adjusting addition of precursors of Co and Cr using the same method. It was confirmed that pure CoCr.sub.2O.sub.4 had a composition advantages for xylene gas sensitization through experimental data presented below, unlike pure Co.sub.3O.sub.4 and pure Cr.sub.2O.sub.3.

(22) In addition, the CoCr.sub.2O.sub.4 sensitive materials (Example 1-2, Example 1-3) which were produced with Cr.sub.2O.sub.3 in the same manner and CoCr.sub.2O.sub.4 sensitive materials added with Pt, Pd, or Au (Examples 2-2, 2-3, 2-4) were synthesized and gas sensitive properties were checked. In particular, the addition of the Pt catalyst greatly improved sensitivity to xylene, while lowering sensitivity to indoor environmental gases such as benzene, ethanol, formaldehyde, carbon monoxide, and the like, thereby increasing the detection selectivity of xylene. Accordingly, the embodiment of the inventive concept for sensitively and selectively detecting the specific gas is not limited to a manufacturing method having only CoCr.sub.2O.sub.4 content, includes a nanocomposite and a solid mixture containing Cr and Co of various compositions, and includes the sensitive material in which a noble metal catalyst, such as Pd or Au, is added to CoCr.sub.2O.sub.4.

(23) In the inventive concept, pure Co.sub.3O.sub.4 (Comparative Example 1-1), pure Cr.sub.2O.sub.3 (Comparative Example 1-2), pure CoCr.sub.2O.sub.4 (Example 1-1, Example 2-1) and Cr.sub.2O.sub.3—CoCr.sub.2O.sub.4 (Example 1-2, Example 1-3), Pt—CoCr.sub.2O.sub.4 (Example 2-2), Pd—CoCr.sub.2O.sub.4 (Example 2-3), Au—CoCr.sub.2O.sub.4 (Example 2-4) were synthesized using the spray pyrolysis method to manufacture gas sensors, respectively. After manufacturing each gas sensor using each prepared sensitive material, the gas sensitivity of ethanol, xylene, toluene and the like were compared. In addition, the selectivity of xylene relative to ethanol was measured for all the Comparative Examples and Examples and the lowest limits of xylene detection of Examples 1-2 and Example 2-2 were measured.

(24) As described above, a catalytic reaction between CoCr.sub.2O.sub.4 and Cr.sub.2O.sub.3, which are effective for decomposition of xylene, and Pt reduces the gas sensitivity of the oxide semiconductor gas sensor to ethanol or formaldehyde, which is highly reactive while the gas sensitivity to xylene known for being weak reactivity is significantly increased to be capable of selectively sensitive to xylene, i.e., an indoor environmental gas.

(25) FIG. 2 is a flow chart illustrating a method of manufacturing a gas sensor according to an embodiment of the inventive concept. Referring to FIGS. 1 and 2, a method of manufacturing a gas sensor according to an embodiment of the inventive concept manufactures a gas sensor for detecting xylene. The method of manufacturing the gas sensor includes forming a hollow structure in S10 and performing coating in S14.

(26) In the forming of the hollow structure in S10, a mixed material including a first material containing a cobalt (Co) element, a second material containing a chromium (Cr) element, and citric acid is reacted to form the CoCr.sub.2O.sub.4 hollow structure to have a hollow shape.

(27) The first material and the second material are provided to the mixed material such that a molar ratio between the cobalt element and the chromium element is 1:2 to 1:4. According to an embodiment, cobalt (II) nitrate hexahydrate (Co(NO.sub.3).sub.2.6H.sub.2O) may be provided as the first material and chromium (III) nitrate nonahydrate (Cr(NO.sub.3).sub.3.9H.sub.2O) may be provided as the second material.

(28) The mixed material may further include a noble metal catalyst. For example, Pt, Pd, Au, or Rh may be provided as the noble metal catalyst.

(29) According to an embodiment, the forming of the hollow structure in S10 includes preparing a spray solution in S11, heating spray in S12, and performing heat treatment in S13.

(30) According to an embodiment, in the preparing of the spray solution in S11, the mixed material is dissolved in distilled water to prepare the spray solution.

(31) In the heating of spray in S12, the spray solution prepared in the forming of the spray solution in S11 is sprayed and the sprayed spray solution is heated to form a CoCr.sub.2O.sub.4 precursor.

(32) In the performing of the heat treatment in S13, the CoCr.sub.2O.sub.4 precursor prepared in the heating of spray in S12 is heat-treated.

(33) In the performing of the coating in S14, the CoCr.sub.2O.sub.4 hollow structure prepared in the forming of the hollow structure in S10 is coated on the insulator substrate 200 where the electrodes 301 and 302 are provided.

(34) Hereinafter, detailed Examples manufacturing gas sensors using the above-described method of manufacturing the gas sensor and effects of the gas sensors manufactured according to each embodiment will be described.

Example 1-1

(35) According to Example 1-1, in the preparing the spray solution in S11, a molar ratio of Cr/Co was calculated to be 2.0 in distilled water of 200 mL and cobalt (II) nitrate hexahydrate [Co(NO.sub.3).sub.2.6H.sub.2O, 99.999%, Sigma-Aldrich, US] of 1.5 g, chromium (III) nitrate nonahydrate [Cr(NO.sub.3).sub.3.9H.sub.2O, 99%, Sigma-Aldrich, US] of 4.1 g, and citric acid [C.sub.6H.sub.8O.sub.7, 99.5%, Sigma-Aldrich, USA] of 4.2 g were mixed and stirred until all the reagents are dissolved to prepare the spray solution.

(36) In the heating of the spray in S12, the spray solution prepared in the preparing the spray solution in S11 was ultrasonically sprayed in air at a flow rate of 10 L min.sup.−1 and simultaneously passed through an electric furnace (600° C.) connected to a spray outlet to form the pure CoCr.sub.2O.sub.4 hollow structure precursor.

(37) In the performing of the heat treatment in S13, the CoCr.sub.2O.sub.4 precursor formed in the heating of the spray in S12 was heat-treated for 2 hours at 700° C. to form the CoCr.sub.2O.sub.4 hollow structure having the hollow shape.

(38) In the performing of the coating step in S14, fine powders of the CoCr.sub.2O.sub.4 hollow structure in the performing of the heat treatment in S13 were mixed with distilled water, were dropped onto an alumina (Al.sub.2O.sub.3) substrate in which an Au electrode was formed to be coated, and performed the heat treatment at 450° C. for 2 hours to manufacture the gas sensor.

(39) A method of measuring gas sensitivity of the manufactured gas sensor is as follows.

(40) The manufactured gas sensor was placed inside a gas sensing chamber having a quartz tube, pure air or mixed gas was alternately injected, and the resistance change of the gas sensor was measured in real time. Gases were mixed at an appropriate concentration in advance through a mass flow controller (MFC), and then rapidly injected using a 4-way valve to change the gas concentration inside the gas sensing chamber. The total flow rate inside the gas sensing chamber was fixed at 200 SCCM to maintain a temperature of the gas sensor in spite of a sudden change in gas concentration.

Example 1-21

(41) According to Example 1-2, in the preparing of the spray solution in S11, a molar ratio of Cr/Co was calculated to be 3.0 in distilled water of 200 mL to synthesize the CoCr.sub.2O.sub.4 hollow structure with preparing Cr.sub.2O.sub.3 and cobalt (II) nitrate hexahydrate of 1.5 g, chromium (III) nitrate nonahydrate of 6.1 g, and citric acid of 4.2 g were mixed and stirred until all the reagents are dissolved to prepare the spray solution.

(42) Thereafter, the method of manufacturing the gas sensor and the method of measuring the gas sensitivity were the same as in Example 1-1.

Example 1-31

(43) According to Example 1-3, in the preparing of the spray solution in S11, a molar ratio of Cr/Co was calculated to be 4.0 higher than Example 1-2 in distilled water of 200 mL and cobalt (II) nitrate hexahydrate of 1.5 g, chromium (III) nitrate nonahydrate of 8.2 g, and citric acid of 4.2 g were mixed and stirred until all the reagents are dissolved to prepare the spray solution.

(44) Thereafter, the method of manufacturing the gas sensor and the method of measuring the gas sensitivity were the same as in Example 1-1.

Example 2-11

(45) According to Example 2-1, in the preparing of the spray solution in S11, a molar ratio of Cr/Co was calculated to be 2.0 in distilled water of 200 mL and cobalt (II) nitrate hexahydrate of 0.38 g, chromium (III) nitrate nonahydrate of 1.02 g, and citric acid of 1.0 g were mixed and stirred until all the reagents are dissolved to prepare the spray solution.

(46) Thereafter, the method of manufacturing the gas sensor and the method of measuring the gas sensitivity were the same as in Example 1-1.

Example 2-2

(47) According to Example 2-2, in the preparing of the spray solution in S11, a molar ratio of Cr/Co was calculated to be 2.0 in distilled water of 200 mL to synthesize Pt-added CoCr.sub.2O.sub.4 hollow structure and cobalt (II) nitrate hexahydrate of 0.38 g, chromium (III) nitrate nonahydrate of 1.02 g, chloroplatinic acid solution (8 wt % in H.sub.2O, H.sub.2PtCl.sub.6, Sigma-Aldrich, USA) of 0.05 mL, and citric acid of 1.0 g were mixed and stirred until all the reagents are dissolved to prepare the spray solution.

(48) Thereafter, the method of manufacturing the gas sensor and the method of measuring the gas sensitivity were the same as in Example 1-1.

Example 2-3

(49) According to Example 2-3, in the preparing of the spray solution in S11, a molar ratio of Cr/Co was calculated to be 2.0 in distilled water of 200 mL to synthesize Pd-added CoCr.sub.2O.sub.4 hollow structure and cobalt (II) nitrate hexahydrate of 0.38 g, chromium (III) nitrate nonahydrate of 1.02 g, palladium nitrate hydrate (Pd(NO.sub.3).sub.2.xH.sub.2O, Sigma-Aldrich, USA) of 0.0014 g, and citric acid of 1.0 g were mixed and stirred until all the reagents are dissolved to prepare the spray solution.

(50) Thereafter, the method of manufacturing the gas sensor and the method of measuring the gas sensitivity were the same as in Example 1-1.

Example 2-4

(51) According to Example 2-4, in the preparing of the spray solution in S11, a molar ratio of Cr/Co was calculated to be 2.0 in distilled water of 200 mL to synthesize Au-added CoCr.sub.2O.sub.4 hollow structure and cobalt (II) nitrate hexahydrate of 0.38 g, chromium (III) nitrate nonahydrate of 1.02 g, gold chloride trihydrate (HAuCl.sub.4.3H.sub.2O, Sigma-Aldrich, USA) of 0.0012 g, and citric acid of 1.0 g were mixed and stirred until all the reagents are dissolved to prepare the spray solution.

(52) Thereafter, the method of manufacturing the gas sensor and the method of measuring the gas sensitivity were the same as in Example 1-1.

(53) The gas sensors were prepared using the fine powders synthesized in the above Examples and Comparative Examples and were measured at various temperatures, to exhibit p-type semiconductor type characteristics in which resistances were increased for all measured reducing gases. Therefore, gas sensitivity was defined as R.sub.gR.sub.a.sup.−1 (R.sub.g: device resistance in gas, R.sub.a: device resistance in air). The gas sensors were manufactured using the synthesized fine powders, and then the gas sensitivity was measured, and the selectivity was calculated based on the difference in sensitivity from other gases.

(54) When the resistance of each sensor stabilized in the air, the atmosphere was changed to test gas (ethanol, xylene, toluene, benzene, formaldehyde, trimethylamine, ammonia, carbon monoxide each of 5 ppm), and when the resistance in the test gas was constant, the atmosphere was changed back to the air to measure the resistance change. A final resistance reached when exposed to the test gas was defined as R.sub.g and a resistance in the air was defined as R.sub.a. The xylene selectivity measured by each gas sensor was calculated from a ratio (S.sub.X/S.sub.E) of xylene sensitivity “S.sub.X” to ethanol sensitivity S.sub.E”. Here, ethanol is the hindered gas.

(55) FIG. 3 is a graph illustrating results of X-ray diffraction analysis of Examples 1-1, 1-2, 2-1, 2-2, 2-3, and 2-4 and Comparative Examples 1-1 and 1-2. Referring to FIG. 3, it was confirmed that Example 1-1 and Example 2-1 included CoCr.sub.2O.sub.4 without Co.sub.3O.sub.4 or Cr.sub.2O.sub.3 diffraction patterns through the results of the X-ray diffraction analysis, same as Comparative Examples 1-1 and 1-2. It was confirmed that Example 1-2 had a pattern of a nanocomposite in which Cr.sub.2O.sub.3 and CoCr.sub.2O.sub.4 are mixed at a specific ratio and Examples 2-2, 2-3, and 2-4 showed CoCr.sub.2O.sub.4 diffraction patterns. The diffraction patterns of the noble metal catalysts (Pt, Pd, and Au) in Examples 2-2, 2-3 and 2-4 were not confirmed due to detection limit of the X-ray diffraction analysis.

(56) FIG. 4 is SEM and TEM pictures taken secondary particle structures of fine powders prepared in each Example and each Comparative Example. Referring to FIG. 4, it was confirmed that the particles prepared in all Examples and Comparative Examples had a spherical hollow structure.

(57) FIG. 5 is a graph illustrating gas sensitivity to ethanol, xylene, toluene, benzene, formaldehyde, trimethylamine, ammonia and carbon monoxide, each which had 5 ppm concentration at an operating temperature of 275° C. in Example 1-1, Example 2-1, Comparative Example 1-1, and Comparative Example 1-2. Referring to FIG. 5, Comparative Examples 1-1 and 1-2, which were hollow structures synthesized only with Co.sub.3O.sub.4 and Cr.sub.2O.sub.3 respectively, were confirmed to have little sensitivity to the above-described gases. It was confirmed that pure CoCr.sub.2O.sub.4 showed excellent sensitivity to xylene (S.sub.X=61.4) through evaluation of gas sensitivity characteristics of Example 1-1. In addition, it was confirmed that the gas sensitivity of Example 2-1, which was pure CoCr.sub.2O.sub.4 having a thin shell by reducing addition amounts of Co and Cr, was greatly increased (S.sub.X=319.5). This showed that CoCr.sub.2O.sub.4 exhibited high sensitivity and selectivity to xylene, regardless of its structure, and the sensitive material having the thin shell rapidly spreads the gas introduced into the gas sensitive material to the gas sensitive material inside, thereby increasing the gas sensitivity.

(58) FIG. 6 is a graph illustrating gas sensitivity for ethanol, xylene, toluene, benzene, formaldehyde, trimethylamine, ammonia and carbon monoxide, each which had 5 ppm concentration at an operating temperature of 275° C. in gas sensors manufactured by Examples 1-2, 1-3, 2-2, 2-3, and 2-4. Referring to FIG. 6, it was confirmed that the sensitivity to xylene increased when a specific amount of Cr.sub.2O.sub.3 secondary phase was generated through Examples 1-2 and 1-3 but when the Cr.sub.2O.sub.3 secondary phase was excessively generated, the gas sensitivity was low for all gases. Therefore, it could be predicted that the gas sensitivity was low for all gases when the molar ratio of Cr/Co was 4.0 or more. The xylene sensitivity of Example 1-2 was greater than the xylene sensitivity of Example 1-1. This was because transfer of charge between two p-type semiconductors having different work functions occurs to generate electrical sensitization of the CoCr.sub.2O.sub.4 sensitive material when the CrC2O4 phase was predominant and Cr.sub.2O.sub.3 was discontinuously added. Furthermore, the addition of the noble metal catalysts Pt and Au through Examples 2-2 and 2-4 greatly increased the xylene sensitivity. However, it was thought that the addition of Au also increased the sensitivity of ethanol, i.e., the hindered gas, by the electronic sensitization to have the xylene selectivity slightly lower than that of the addition of Pt. It was shown that Pd-added CoCr.sub.2O.sub.4 of Example 2-3 had the xylene sensitivity (S.sub.X=225.8) lower than that of pure CoCr.sub.2O.sub.4 (S.sub.X=319.5). It was thought to be due to oxidation of xylene at an upper end of a sensor sensitive layer by catalytic activity of Pd, which was known as an oxidation catalyst for methylbenzene, such as xylene and toluene, and CoCr.sub.2O.sub.4. Therefore, it could be confirmed that the Pt catalyst served as greatly improving the sensitivity and selectivity to xylene in the CoCr.sub.2O.sub.4 sensor.

(59) FIG. 7 is a graph illustrating changes of sensitivity ratios of xylene sensitivity to ethanol sensitivity of gas sensors manufactured in Examples 1-1, 1-2, 1-3, and 2-1 and Comparative Examples 1-1 and 1-2 with temperature. Referring to FIG. 7, Comparative Example 1-1 and Comparative Example 1-2 were shown that it was impossible to selectively detect xylene using Co.sub.3O.sub.4 and Cr.sub.2O.sub.3 because the selectivity (S.sub.X/S.sub.E) of the gas sensor with respect to xylene had a value within 1 at all temperatures. Example 1-1 and Example 2-1 showed values of S.sub.X/S.sub.E=12.3 and 30.7 at 275° C., respectively and the possibility of highly selective detection of xylene with CoCr.sub.2O.sub.4 alone. It was shown that the sensitivity to xylene gas increased to increase the selectivity of xylene when a certain amount of Cr.sub.2O.sub.3 secondary phase was generated through Example 1-2. Furthermore, it was confirmed that, when the amount of Cr.sub.2O.sub.3 secondary phase excessively increased (Examples 1-3, the molar ratio of Cr/Cr was 4.0), the low xylene selectivity similar to Comparative Example 1-2 i.e., pure Cr.sub.2O.sub.3, was exhibited because the gas sensitivity occurred mainly through Cr.sub.2O.sub.3 having a low sensitivity. The above results showed that in order to detect xylene gas with high sensitivity and high selectivity, it was preferable that CoCr.sub.204 phase was predominant and Cr.sub.2O.sub.3 was discontinuously added. In this embodiment, the results were shown that the most appropriate concentration ratio of Cr/Co was 3.0. This was thought to reduce the sensitivity to xylene and all hindered gases when Cr.sub.2O.sub.3 was added in excess. In addition, it could be confirmed that the selectivity to xylene was lowered at 350° C. or more. Furthermore, it was thought that the gas sensor according to an embodiment of the inventive concept was capable of having the selectivity to xylene in a temperature range of 250° C. to 350° C. considering that the oxide semiconductor gas sensor was capable of detecting the gas at a temperature higher than 250° C., normally.

(60) FIG. 8 is a graph illustrating selectivity (S.sub.X/S.sub.E) of xylene in Example 2-2, Example 2-3, and Example 2-4 at an operating temperature 275° C. Referring to FIG. 8, the xylene selectivity (S.sub.X/S.sub.E) of Examples 2-2, 2-3, and 2-4 was confirmed at the gas sensor operating temperature of 275° C. As a result of measurement, it was confirmed that Example 2-2 had a very good selectivity of xylene to ethanol (S.sub.X/S.sub.E=87.8). Due to the addition of Pt known as an ethanol oxidation catalyst, ethanol was all oxidized at the upper end of the sensor sensitive layer but all xylene was not decomposed at the upper end of the sensitive layer to diffuse to a lower end of the sensitive layer. It was thought that as xylene diffused into the sensitive material, was converted into a highly reactive gas by Pt and CoCr.sub.2O.sub.4, and promoted a gas sensitive reaction, the addition of Pt decreased the sensitivity of ethanol and greatly increased the sensitivity of xylene to have high sensitivity and selectivity to xylene. On the other hand, the xylene selectivity (S.sub.X/S.sub.E=31.0) of Example 2-3 having Pd-add CoCr.sub.2O.sub.4 and the xylene selectivity (S.sub.X/S.sub.E=25.4) of Example 2-4 having Au-add CoCr.sub.2O.sub.4 showed similar or lower values to the xylene selectivity of Example 2-1 having pure CoCr.sub.2O.sub.4. It was shown that in Pd-add CoCr.sub.2O.sub.4, ethanol and some xylene were oxidized and decomposed in the upper end of the sensor sensitive layer by excessively high catalytic activity of Pd, to decrease both sensitivity of xylene and ethanol similar to the xylene selectivity of pure CoCr.sub.2O.sub.4. It was shown that in Au-add CoCr.sub.2O.sub.4, the sensitivity of the gases was all increased by the electrical sensitization, but the sensitivity to ethanol was highly increased and the xylene selectivity was low compared to pure CoCr.sub.2O.sub.4.

(61) FIG. 9 is a graph illustrating sensitivity characteristics of xylene gas in Example 1-2 (300° C.) and Example 2-2 (275° C.) at sensor operating temperatures showing the highest selectivity with respect to changes of gas concentration. Referring to FIG. 9, it was confirmed that Example 1-2 showed xylene sensitivity values of 2.19, 3.28, 6.70, 34.65 and 109.5 to xylene concentrations of 0.25, 0.5, 1, 2.5 and 5 ppm, respectively, at the operating temperature of 300° C. This was a result showing that Example 1-2 was an excellent gas sensor which was capable of being measured with high sensitivity of xylene at a concentration level of 250 ppb. In addition, it was confirmed that Example 2-2 showed xylene sensitivity values of 1.33, 1.58, 1.97, 2.08, and 2.22 to xylene concentrations of 25, 50, 75, 100, and 125 ppb, respectively, at the operating temperature of 275° C. It was shown that the sensor of Example 2-2 was capable of measuring trace amounts of xylene at the level of 10 ppb. Therefore, the gas sensor according to an embodiment of the inventive concept is capable of measuring the concentration of the trace amount of xylene and a change amount of xylene in real time.

(62) FIG. 10 is a graph illustrating results of comparing xylene sensitivity for each concentration with the existing studies. Referring to FIG. 10, it was confirmed that each xylene sensitivity of Examples 1-2 and 2-1 of the inventive concept was much higher than that of studies (6, 7, 8, 9, 10, 11, 12, 13) previously conducted. In particular, it was shown that the sensitivity and selectivity to xylene in Example 2-2 were significantly superior to the existing results (10, 11, 12, 13). In addition, it was confirmed that low concentration of xylene was capable of being effectively detected compared with NiO, Co.sub.3O.sub.4 and the like, which were generally known to have high methylbenzene sensitivity. A conventional oxide semiconductor-based xylene sensor had very poor sensitivity and selectivity and was difficult to measure only xylene, while the sensor of the inventive concept may measure extremely small amounts of xylene with high sensitivity and high selectivity.

(63) FIG. 11 is a graph showing results of measuring gas sensitivity (R.sub.g R.sub.a.sup.−1) of Example 1-2 of the inventive concept for 30 days. Referring to FIG. 11, it was confirmed that the gas sensor according to an embodiment of the inventive concept was capable of maintaining stable gas sensitivity for at least 30 days.

(64) The gas sensor according to an embodiment of the inventive concept may have a high selectivity and high sensitivity to xylene.

(65) The above detailed description illustrates the inventive concept. In addition, the above-mentioned contents show and explain preferred embodiments of the inventive concept and the inventive concept may be used in various other combinations, modifications, and environments. That is, changes or modifications may be made within the scope of the concept of the inventive concept disclosed in the present specification, the scope equivalent to the disclosures described above, and/or the skill or knowledge in the art. The described embodiments illustrate the best state for implementing the technical idea of the inventive concept and various modifications required in the specific application field and use of the inventive concept are possible. Thus, the detailed description of the inventive concept is not intended to limit the inventive concept to the disclosed embodiments. Also, the appended claims should be construed to include other embodiments.