Examined Patent Publication(B1)

Bibliographic Data

G01N 31/00 | B82Y 35/00 | G01N 33/00 | G01N 37/00

20070802

1007450250000

20070726

1020060037268

20060425

20060425

Yang, Young Pil

NA, Dae Seok | LEE, Min-Ho

Int.Cl.

Published Date

Registration No.

Registration Date

Application No.

Application Date

Requested Date of Examination

Agent.

Inventor

Title of Invention

The methanol concentration apparatus for detecting the state of the direct methanol fuel cell using the same and concentration detecting sensor using carbon nanotube.

Abstract

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The invention relates to the methanol concentration detecting apparatus. And it determines that the replacement time comes with the concentration reduction of the methanol if the reference value is exceeded and when the methanol concentration it is installed within the direct methanol fuel cell is compared with the fixed the reference value the small-signal amplifier amplifying the micro signal outputted from the methanol concentration sensor, the methanol concentration state judgment part determining the supplement time of the methanol and fixed the reference value the methanol concentration by the detection signal delivered to the small-signal amplifier, and the display unit are included the dielectric constant of the methanol concentration is detected, it indicates. As to the small-signal amplifier, the carbon nanotube is used as the sensor for sensing the driver which drives a car along the operation of the methanol concentration sensor if the power source is supplied in the power supply unit and the driver are enabled, and the methanol concentration sensor. As to the display unit, the chest indicates the signal outputted from the amplifier and the methanol concentration state judgment part amplified the signal detected from the state judgment part by the fixed the predetermined level as the methanol supplement time information by the character or the predetermining method. The methanol, the concentration, the carbon nanotube, the dielectric constant, the sensitivity .

Page 1 of 19

(Representative drawing)

Scope of Claims

1: Claim 1:

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The concentration detecting sensor comprising the electrode in which the power source is applied; the substrate in which the electrode pattern is molded; and the sensing film which covers the electrode pattern ; and comprises the deposited carbon nanotube among the total area of the substrate in the prescribed part.

2: Claim 2:

1 , 1, 2 .

As for claim 1, the concentration detecting sensor in which the second insulation layer is inserted between the first insulation layer, and the electrode pattern and sensing film and comprising between the electrode pattern and substrate.

3: Claim 3:

2 , .

As for claim 2, the concentration detecting sensor, wherein the insulating layer comprises the silicon oxide film or the nitride film.

4: Claim 4:

1 3 ,

Any one claim among claim 1 to claim 3, wherein the concentration detecting sensor in which it varies the deposition or the printed area on the substrate the sensi

Page 2 of 19

. ng film part can control drawing comprises the carbon nanotube.

5: Claim 5:

1 ;

; 2 ;

2 - ; -

.

The manufacturing method of concentration gradient detector and sensor comprising the step of forming the first insulation layer in the substrate surface, step of forming electrode by etching the metal after the metal material comprising the electrode being deposited and coating the upper part with the photosensitive material it patterns using the lithographic technique, the step of forming the second insulation layer covering the electrode on the substrate, the step it mixes the binder and alpha - taffy Knoll after the again patterns the photoresist in order to form the electrode pad for connecting the lead line and it removes the second insulation layer using dry or the wet etching and heating and melted, and the step that firstly performs the step mixed the material, and the step that firstly performs the step mixed the material mixes the glass frit and alpha - taffy Knoll and which heats up the carbon nanotube and melted and that the carbon nanotube is screen printed on the electrode and sintered.

6: Claim 6:

5 , 1 , 2

.

As for claim 5, the manufacturing method of concentration gradient detector and sensor which oxidize the silicon substrate and the first insulation layer forms or it deposits the nitride film on the substrate ; and the second insulation layer deposits and comprise the oxide film or the nitride film.

7: Claim 7:

:

;

; ;

; ;

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The power supply unit which converts the power supplied to the direct methanol fuel cell on operation reaction catalyst part into the necessity power and supplied: the methanol concentration detecting apparatus of the direct methanol fuel cell including the chest in which the carbon nanotube is used as the sensor for being installed at the methanol transportation pipeline or the repository and sensing the methanol concentration is the sensor; the driver in which the chest drives a car along the operation of the sensor if the power source is supplied in the power supply unit and it is enabled; the small-signal amplifier amplifying the micro signal outputted from the density sensation branch; the fixed the reference value the methanol concentration state within the direct methanol fuel cell by the detection signal delivered to the small-signal amplifier; and the display unit in which or the chest of the methanol indicates the signal outputted from the amplifier amplified and methanol concentration state judgment part the methanol concentration state judgment part: signal detected from the methanol concentration state judgment part by the fixed the predetermined level as the supplement time information by the character or the predetermining method determines state or the supplement time comparatively.

8: Claim 8:

7 , , As for claim 7, the methanol concentration detecting

Page 3 of 19

; ; ,

.

apparatus of the direct methanol fuel cell, wherein: the chest is the sensor of the sensor comprises the sensing film consisting of the electrode, the substrate, and the deposited carbon nanotube in the prescribed part among the total area of the substrate the electrode pattern is covered; as to the electrode, the power source is applied; and as to the substrate, the electrode pattern is molded.

9: Claim 9:

7 8 , 1, 2 .

As for claim 7 or 8, the methanol concentration detecting apparatus of the direct methanol fuel cell in which the second insulation layer is inserted between the first insulation layer, and the electrode pattern and sensing film and the chest the sensor of the sensor is included between the electrode pattern and substrate.

10: Claim 10:

7 8 ,

.

As for claim 7 or 8, the methanol concentration detecting apparatus of the direct methanol fuel cell in which the carbon nanotube varies the deposited area and the chest the sensor of the sensor can control the sensitivity.

11: Claim 11:

;

;

;

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The methanol concentration detecting method of the direct methanol fuel cell comprising the step of disclosing the operation of all kinds of the load devices by the power source supplied from the reaction catalyst part the fuel cell driving starts after the chest contacts the sensor to the methanol transportation pipeline or the repository of the direct methanol fuel cell; the step of setting up the initially standard value it measures; and when the concentration of the methanol from the dielectric constant change of the methanol in which the chest the state judgment part is detected is compared with the fixed the reference value it determines, the fixed the reference value or greater the step of indicating through display means the information about that it exceeds the concentration gradient determines as the replacement time of the methanol.

Background Art

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The invention relates to the methanol concentration detecting apparatus checking the methanol concentration state used as the fuel in the direct methanol fuel cell the methanol concentration change is measured to be the change of the dielectric constant be throughed the sensor using the apparatus, for detecting the concentration of the used methanol more specifically, the carbon nanotube in the fuel cell, especially, the direct methanol fuel cell and instructs the supplement and replacement time on the detection.

.

While it worlds to the part of the effort that the fuel cell develops the energy source in which the energy efficiency is high and the environmental contamination is less while the concern about the environment increases being studied and developed to the actively the clean electricity which the energy conversion efficiency is hig

Page 4 of 19

h and does not generate the contaminant in the drive process because of the large advantage most directly oxidizing fuel and generating electricity can be produced.

(Direct Methanol Fuel Cell, DMFC) (PEMFC)

.

The direct methanol fuel cell (Direct Methanol Fuel Cell, DMFC) has polymer electrolyte fuel cell (PEMFC), the structure of being similar, and operation principle using hydrogen but the methanol is instead of supplied hydrogen to the direct anode as fuel and it uses.

. 1W 500W

.

Therefore, the fuel supply system is simple and the entire device is simple and the miniaturization is possible. Particularly, for several uses, if the use is possible and the suitable performance improvement in which about especially, the usability to the AC source for carrying by hand less than 1W microbattery for substitution power or 500W is very high and is accomplished as to the applicability the use seems to be possible with the engine for a vehicle.

. , 2 .

.

Presently, the lithium ion battery or the plastic lithium ion battery is used but the electric capacity these batteries is little and the life time is short and the miniature cellular phone battery recharges but it need the suitable time. Moreover, cost is very much required because the life span as to the battery, is 2 year or less. Particularly, there is a problem that the total volume has to be enlarged since the size of the battery is enlarged if the electric consumption is enlarged while the function of the cellular phone is increased.

. PDA, .

Alternatively while the direct methanol fuel cell rises to the sky as the plan solving this problem if the direct methanol fuel cell supplies the methanol it can be without limit increased the life time to reason for the and the inconvenience according to the limit of the capacity like the battery or the charging time can be solved. And the application is possible as the power supply source including PDA, the notebook etc.

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It is very important to measure the methanol concentration of the direct methanol fuel cell carrying the advantage as described above and various applicabilities. Ideally, the size of the energy generated with the direct methanol fuel cell mode is in proportion to the methanol solution concentration supplied to the battery. But the task in which the tendency which does not arouse reaction with the catalyst while the methanol passes through the polymer electrolyte membrane of the fuel cell if the concentration of the methanol is actually enhanced and is just passed is enlarged occurs. This phenomenon called as the methanol crossover drastically lowers the reaction efficiency of the fuel cell. It very much endeavors of measuring the concentration of the methanol which mounts the methanol concentration sensor within the methanol storage tank which mixes with the fuel cell inner portion or water in order to complement such disadvantage and is supplied on a real time basis and measuring the stability of the fuel cell system and exchange period of the methanol.

By having the method using thin film and this measuring the change of the flowing current to be the method used in below harm existing such measurement at the me

Page 5 of 19

.

.

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thod of measuring the concentration it uses in the thin film and measuring the conductivity of the thin film the concentration of the methanol is measured. In this method is the formation method of the thin film, the thin film is made using the polymer and this thin film is adhered to the catalyst of the direct methanol fuel cell and it measures. It has the disadvantage that the accuracy falls down with the current in which it drops down the efficiency of the fuel cell this method is generated in the thin film to the methanol concentration measurement.

(probe)

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The problem of lowering the sensitivity of the sensor can be generated in the process where the micro bubble is generated in the state the which has mode using the mode and the resonator signal which has the form forming the electrode of the probe form as the sensor and inserts this into the part in which has the methanol but in which the measuring method measures conductivity according to the property of the sensor depending on on the end of the probe of the form different from this but in which this inserts in the outside and measuring mode has the disadvantage of being difficult to be mounted to the mode inside the direct methanol fuel cell and measure and where the methanol and water mix.

.

In the above case, it is difficult to be inserted inside disadvantage and the difficult fuel cell that the original sensor for measuring the concentration of the methanol uses as the sensor of the high-sensitivity and measure.

Summary of Invention

Effects of the Invention

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As illustrated in the above, the invention has the advantage that the concentration and replacement time of the methanol can be without any difficulties determined by the direct methanol fuel cell methanol concentration detecting apparatus which provides the sensor controlling the detection sensitivity and detects the dielectric constant change according to the methanol concentration of the desired kind utilizes this controls the sensitivity according to the various methanol concentrations and the concentration state of the methanol is measured at the same time alarming.

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Moreover, the durability according to the direct methanol fuel cell protection is increased since the methanol exchange attains in the correct replacement time. And the generation of the unnecessary repairing fees is excluded.

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In the above, it is natural that it has to the person skilled in the art and it is clear that it was particularly explained about the detailed embodiment in which the invention was reported but the various deformations and correction are possible in the scope of the spirit of the technique of the present invention. And it belongs to the patent claim in which this deformation and correction are attached.

Technical Task Page 6 of 19

,

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The present invention is to provide the sensor used and manufacturing method thereof the carbon nanotube having the sensitivity sensing the dielectric constant change according to the methanol concentration of the direct methanol fuel cell to solve problems described in the above, it suggests.

,

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Moreover, the methanol concentration detecting apparatus of the direct methanol fuel cell it raises the efficiency of the fuel cell by employing the carbon nanotube sensor and measuring the methanol concentration of the direct methanol fuel cell and alarming and which can fill up the methanol in the proper time and which the methanol concentration can exchange is to be provided.

Structure & Operation of the Invention

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The concentration detecting sensor using the carbon nanotube according to the present invention for realizing the purpose as described above comprises the power source which is the sensing film comprising the deposited carbon nanotube among the total area in the prescribed part of the substrate the applied electrode, the substrate in which the electrode pattern is molded, and the electrode pattern are covered.

, , 1, 2 .

Moreover, as to the concentration detecting sensor according to the present invention, the second insulation layer is inserted between the first insulation layer, and the electrode pattern and sensing film and it comprises between the electrode pattern and substrate.

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Moreover, the concentration detecting sensor according to the present invention comprises the insulating layer is the silicon oxide film or the nitride film.

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.

Moreover, as to the concentration detecting sensor according to the present invention, the deposition or the printed area is varied on the substrate the sensing film part including the carbon nanotube can control drawing.

, , 1 ,

, 2 ,

2 - , -

.

In the meantime, the manufacturing method of the concentration detecting sensor according to the present invention comprises the binder in order to form the electrode pad for connecting the step of forming the first insulation layer in the substrate surface, step of forming the electrode by etching the metal after the metal material comprising the electrode being deposited and coating the upper part with the photosensitive material it patterns using the lithographic technique, the step of forming the second insulation layer covering the electrode on the substrate, the lead line the photoresist the again is patterned and the second insulation layer is removed using dry or the wet etching and the step melted, and the step that firstly performs the step mixed the material the alpha - taffy Knoll is mixed and it heats. The step that firstly performs the step mixed the material mixes the glass frit and alpha - taffy Knoll and which heats up the carbon nanotube and melted and that the carbon nanotube is screen printed on the electrode and sintered.

Page 7 of 19

, , 1 , 2 .

Moreover, as to the manufacturing method of the concentration detecting sensor according to the present invention, the silicon substrate is oxidized and the first insulation layer forms or the nitride film is deposited on the substrate. The second insulation layer deposits and comprises the oxide film or the nitride film.

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In the meantime, the methanol concentration detecting apparatus of the direct methanol fuel cell according to the present invention comprises the small-signal amplifier amplifying the micro signal outputted from the power supply unit, which it supplies it converts the supplied power into the necessity power the driver in which the chest drives a car along the operation of the sensor if the power source is supplied in the sensor, and the power supply unit and the chest in which the carbon nanotube is used as the sensor for being installed at the methanol transportation pipeline or the repository and sensing the methanol concentration is enabled, and the density sensation branch in the direct methanol fuel cell on operation reaction catalyst part, and the fixed the reference value the methanol concentration state within the direct methanol fuel cell by the detection signal delivered to the small-signal amplifier and the display unit in which or the chest of the methanol indicates the signal outputted from the amplifier and the methanol concentration state judgment part amplified the methanol concentration state judgment part which determines state or the supplement time comparatively, and the signal detected from the methanol concentration state judgment part by the fixed the predetermined level as the supplement time information by the character or the predetermining method.

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Moreover, the methanol concentration detecting apparatus of the direct methanol fuel cell according to the invention comprises the sensing film consisting of the electrode, the substrate, and the deposited carbon nanotube in the prescribed part among the total area of the substrate the electrode pattern is covered. As to the electrode, the power source the chest the sensor of the sensor is applied. As to the substrate, the electrode pattern is molded.

, , 1, 2 .

Moreover, as to the methanol concentration detecting apparatus of the direct methanol fuel cell according to the invention, the second insulation layer is inserted between the first insulation layer, and the electrode pattern and sensing film and the chest the sensor of the sensor is included between the electrode pattern and substrate.

, ,

.

Moreover, as to the methanol concentration detecting apparatus of the direct methanol fuel cell according to the invention, the carbon nanotube the chest the sensor of the sensor varies the deposited area and the sensitivity can be controlled.

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In the meantime, the methanol concentration detecting method of the direct methanol fuel cell according to the present invention comprises the fixed the reference value the step of disclosing the operation of all kinds of the load devices, the step of setting up the initially standard value it measures , and the chest determine the

Page 8 of 19

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concentration of the methanol with the power source supplied from the reaction catalyst part the fuel cell driving starts after the chest contacts the sensor to the methanol transportation pipeline or the repository of the direct methanol fuel cell from the dielectric constant change of the methanol in which the state judgment part is detected and the fixed the reference value or greater the step of indicating through display means the information about that it exceeds it determines as the replacement time of the methanol it compares.

, .

The attached preferred embodiment of the present invention is made to be equal to specifically, next.

1a

1b 1a - .

Figure 1a is a drawing 1b is the cross-sectional view of the level of the I-I of the drawing 1a it is the summary perspective drawing for illustrating the drive mechanism as the embodiment of dielectric constant change detector and sensor using the dielectric constant.

1a, 1b (21) (Al) (23) (23)

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The electrode (23) pattern composed of drawing 1a, and the sensor illustrated in Figure 1b is the semiconductor process, normal, the aluminum (Al) on the glass substrate (21) is deposited and when the material to detect the change of the dielectric constant is dipped between the electrode (23) the electric capacity is measured in the between electrode and the dielectric constant of the measurement substance is measured and accordingly the reduction of the deterioration of the measurement substance or the concentration is detected.

, 1a, 1b

.

But the sensors using the drawing 1a, as described in figure 1b, the dielectric constant is to the cylinder type or the parallel plate structure of bulkying and it can be influenced.

2 , 3 2 II-II .

Figure 2 is a perspective view which is summary to the embodiment of dielectric constant change detector and sensor using the carbon nanotube. Figure 3 is a cross-sectional view of the II-II line of fig. 2.

2, 3, (23), (23)

(22), (22) (23) (21) .

Dielectric constant change detector and sensor using fig. 2, and the carbon nanotube in fig. 3 are connected to the electrode (23) in which the power source is applied, and the electrode (23). And the substrate (21) incorporating the sensing film (22) formed with the carbon nanotube sensing the dielectric constant change according to the concentration state of the dipped material, and the sensing film (22) and electrode (23) are included.

, (21) .

Here, the substrate (21) of the sensor the glass or the silicone etc. are used.

(23) ITO(Indium Tin Oxide) , (22) .

The electrode (23) can be formed with the ITO (Indium Tin Oxide) or the metal. And it is possible to form the electrode into the carbon nanotube identically with the sensing film (22).

(22)

.

The carbon nanotube connected as the sensing film (22) can evaporate using the semiconductor process and screen printing technology or the direct growth process.

Page 9 of 19

(graphite) sp2 .

The tubular of the sp 2 bond in which the carbon nanotube roundly rolls the graphite is done and the surface area per the unit area is very broad and the adsorption capacity is excellent about the gas molecule or ion.

, , , .

The carbon nanotube includes electrically, the property of the metal or the semiconductor, and the property that the electrical attribute value, for example, the electric capacity, conductivity etc. change according to the adsorption of the gas molecule or ion.

, ITO (23) , (23) .

The carbon nanotube prints screen on the electrode (23) consisting of the metal in dielectric constant change detector and sensor or ITO with the deposition. But it is possible to form the electrode (23) into the carbon nanotube.

, 2 , (23) (22) , (22) (23)

.

Moreover, referring to Figure 2, in dielectric constant change detector and sensor, the electrode (23) and sensing film (22) do to the teeth of a comb shape with desirable that the kinds is branched. Since the surface area of the measure electrode of the electric capacity is broadened since the carbon nanotube which in this case, functions to the sensing film (22) is evaporated on the electrode (23) the measurement sensitivity be improved.

2, 3 ,

.

The carbon nanotube is screen printed on the basic electrode of comb electrode form using fig. 2, and the lithographically processing in the case of fig. 3 or the sensing film can be formed using the direct growth process.

, 100 , 100 , , 50 .

In the sensor, in case the screen printing method is used in order to measure the dielectric constant change the width of the comb electrode the gap of the electrode is 100 or less less than 100. And it is suitable in case of the direct growth process that the gap between the electrode does with 50 this harrow.

, (22) ,

.

And the carbon nanotube used in the sensing film (22) of the sensor has the advantage that size have the ionosorption and archiving facility even when size are small. And it physical chemicals even when sensitivity is high since the surface area per the unit area is broad and the response speed is fast the durability is excellent.

4 , 5 4 III-III .

Figure 4 is concentration state change detector and sensor perspective view according to the invention, the carbon nanotube is used. Figure 5 is a cross-sectional view of the III-III line of fig. 4.

6 7 6 - .

Figure 6 is fig. 7 is the cross-sectional view of the level of the IV-IV of fig. 6 it is the perspective view of concentration state change detector and sensor using the carbon nanotube according to the invention.

8 .

Figure 8 is a Electron micrograph of the carbon nanotube applied to the sensing film of the invention.

, 02 mol ,

For example, the distribution of the concentration in which the methanol used in the direct methanol fuel cel

Page 10 of 19

80 2324 .

l dilutes with water and using but which is used is 0~2 mol. Whereas the relative dielectric constant of water is about 80 the whole amount of change of the relative dielectric constant changes among the methanol solution in which the dielectric constant of the methanol is about 23~24 and which is diluted according to the concentration of ethanol.

(22) (22) (23) ,

.

When the methanol solution is absorbed to the carbon nanotube the dielectric constant change is detected between the sensing film (22) comprising the carbon nanotube according to the concentration reduction of the methanol and the electrode (23) connected to the sensing film (22). Therefore it uses as the methanol concentration detecting sensor in which dielectric constant change detector and sensor can detect the change according to the concentration reduction of the methanol particle.

4 (23), (23) (21), (23) (21) (22) .

Detector and sensor illustrated in fig. 4 comprises the power source which is the sensing film (22) comprising the deposited carbon nanotube among the total area in the prescribed part of the substrate (21) the applied electrode pattern (23), the substrate (21) in which the electrode pattern (23) is formed, and the electrode pattern (23) are covered.

2, 3 (23) , 4, 5 (23) (21)

(21) .

Fig. 2, and the carbon nanotube called the sensing film in the embodiment illustrated in Figure 3 are fig. 4 it is evaporated in the electrode (23) part, and the sensing film illustrated in fig. 5 is the structure where as to the this, the substrate (21) is possible while the electrode pattern (23) altogether covers and it is coated the c with on the whole and it is formed as the carbon nanotube paste on the prescribed part of the substrate (21) when being the non-conductor like the glass.

6 7 (23) (21) .

The electrode pattern (23) altogether covers and it is coated the c with on the whole and the sensing film illustrated in the figures 6 and 7 is formed as the carbon nanotube paste on the prescribed part of the substrate (21).

, 7 , (21) (23) 1(25) (21) (23) , (23) (22) 2(26) .

Moreover, referring to Figure 7, the first insulation layer (25) of the oxide or the nitride series is evaporated between the substrate (21) and electrode pattern (23) and the substrate (21) and electrode pattern (23) are insulated. Manufacture is possible with the sensor forming the second insulation layer (26) of the oxide or the nitride series between the electrode pattern (23) and sensing film (22) and measures the electrostatic capacity.

(21) .

This may be the substrate (21) is the semiconductor like the silicone or the metallic foil or the structure of being possible when being the conductor.

(21) (21) (23) 1(25) (SiO2) , 1(25) .

The oxide which is first insulation layer (25) formed between the substrate (21) the substrate (21) is the silicone and electrode pattern (23) can form into the oxidation silicon (SiO(SB)2(/SB)). And the first insulation layer (25) can be formed into the nitride film.

6 7 (23) (22) 2(26)

In figures 6 and 7, while it does not make conducted and the electrostatic capacity is more easily measured

Page 11 of 19

(23) (22) .

the yield of the sensor is raised to form the second insulation layer (26) of the oxide or the nitride series between the electrode pattern (23) and sensing film (22).

5 , (22a, 22b) (22) (23) (23) .

Referring to Figure 5, while carbon nanotube particles (22a, 22b) are comprised the sensing film (22) it can know for not only the electrode (23) but also the electrode (23) on the substrate to be covered.

7 , (22a, 22b) (22) (23) (26) .

Referring to Figure 7, it can know to be covered in not only the electrode (23) but also the insulating layer (26) interval and upper part while carbon nanotube particles (22a, 22b) are comprised the sensing film (22).

5, 7, 8 , (22)

.

Since fig. 5 , fig. 7 , and the carbon nanotube which referring to Figure 8, functions to the sensing film (22) arouse the change of the electric capacity according to the amount of change of the ion absorbed in the carbon nanotube in which the voltage is applied the change of the dielectric constant is detected.

, (22) (22a, 22b) (d) , (22a) (22b) .

Here, when the various separation distances (d) is formed between carbon nanotube particles (22a, 22b) of the sensing film (22) carbon nanotube particles (22a, 22b) have the minute electric capacity between the carbon nanotube particle (22a) and the neighboring carbon nanotube particle (22b).

(22a) (22b) , (22a) (22a) (summation) .

It has the carbon nanotube particle in which the carbon nanotube particle which is adjacent to one carbon nanotube particle (22a) is excellently many besides the carbon nanotube particle (22b). It shows up as the total (summation) of the micro electrical capacitance value generated around one carbon nanotube particle (22a) with the other numerous particles in which one electric capacity is adjacent to the particle (22a).

, (22b) , (22a) (22b) (summation) .

In the meantime, and if it thinks around the other carbon nanotube particle (22b) with the above the carbon nanotube particle (22a) is included and since excellently many another particle is adjacent it shows up as the total (summation) of the micro electrical capacitance value generated between particles which are thus adjacent to the carbon nanotube particle (22b).

,

(summation of summation) .

Therefore, it shows up as the value (summation of summation) in which the micro electrical capacitance value by carbon nanotube particles in which the electrical capacitance value detected from the sensing film is whole again altogether adds up total.

, 6 12, 13 .

In the meantime, the measurement result graph obtained in the sensor illustrated in Figure 6 is illustrated in fig. 12, and fig. 13.

12 , (21) (25) (SiO2) 3000 (22) (Al) 3000 , 15, 15 (22) (26) 68 25 0 mol 2 mol 116 pF .

Referring to Figure 12, the substrate (21) is 3000 angstrom which is done by the glass and deposits the insulating layer (25) on 3000 angstrom which enhances by the oxidation silicon (SiO(SB)2(/SB)) and enhances the electrode (22) to the aluminum (Al), and the amount of change of the electrical capacitance value of the sensor output value according to the concentration of the methanol which measures the electrode pattern called the electrode width 15, and the electrode spacin

Page 12 of 19

g 15 in the room temperature 25 in case of forming the sensing film using the carbon nanotube it forms and the insulating layer (26) is deposited on the electrode (22) into paste with 6~8 the methanol concentration 0 mol and 2 mol is 116 pF.

13, (21) (25) (SiO2) 3000 (22) (Al) 3000 , 15, 15 (22) (26) 68 70 0 mol 2 mol 619 pF .

In the meantime, the substrate (21) in fig. 13 is 3000 angstrom which is done by the glass and deposits the insulating layer (25) on 3000 angstrom which enhances by the oxidation silicon (SiO(SB)2(/SB)) and enhances the electrode (22) to the aluminum (Al), and the amount of change of the electrical capacitance value of the sensor output value according to the concentration of the methanol which measures the electrode pattern called the electrode width 15, and the electrode spacing 15 in 70 called the working temperature range of the direct methanol fuel cell in case of forming the sensing film using the carbon nanotube it forms and the insulating layer (26) is deposited on the electrode (22) into paste with 6~8 the methanol concentration 0 mol and 2 mol is 619 pF.

.

In the result, it can know that the electric capacity measuring sensor using the carbon nanotube very can show the output according to the concentration of the methanol.

02 mol 80 2324

.

The methanol used in the direct methanol fuel cell dilutes with water and it uses but the distribution of the mainly used concentration is 0~2 mol but whereas the relative dielectric constant of water is about 80 the dielectric constant of the methanol is about 23~24 and the amount of change of the relative dielectric constant changes according to the extent in which the methanol and water mix.

,

.

That is, in the direct methanol fuel cell, since it is influenced of the relative dielectric constant of water as the methanol is wasted while reaction is progressed the dielectric constant increases.

. The sensor which is the fact manufactured to the basis with the invention sensitively can know the measured value than the detectivity of the carbon nanotube.

, 9 .

In the meantime, figure 9 is a schematic diagram of the sensor area of the dielectric constant change sensor according to the invention.

9 ,

.

Referring to Figure 9, if the initial electrical capacitance value tries to be changed in order to control the detection sensitivity of the sensor the printing area of the carbon nanotube paste is varied.

, 9 , A, B (21) , A B .

That is, as shown in Figure 9, the area A, and B represent the area of the carbon nanotube printed on the substrate (21). And the area A more shows up with the area B.

A B

, A B

In the sensing film consisting of the area A, more carbon nanotube particle is included than the sensing film consisting of the area B. And it is greater that will show up and the deposited in that case the whole elect

Page 13 of 19

. rical capacitance value of the carbon nanotube of A area the initial electrical capacitance value is enlarged according to that than B area according to that.

,

.

Therefore, if the deposition area of the carbon nanotube is changed the initial electrical capacitance value can be controlled and the detection sensitivity of the dielectric constant change sensor can be controlled according to that.

,

.

In the meantime, dielectric constant change detector and sensor depositing the carbon nanotube and are manufactured are able to manufacture to the new order in comparison with the existing manufacturing method.

, , , , , , , ,

.

The semiconductor process technology as the first method may be referred to the be desirable it is the step of patterning thirdly, the electrode in the substrate firstly it performs the step of patterning the second, the cobalt in the substrate, iron, and the catalyst like nickel it performs the lithography step including the first as the fabrication sequence of the carbon nanotube sensor, used the photoresist coating in the substrate, and the exposure and the etching process made of the order of the step of growing the carbon nanotube on the substrate it passes.

, 1(25) , ,

, , (24)

2(26) - , -

.

The screen printing technology as the second method may be referred to the be desirable the step it mixes the binder and alpha - taffy Knoll after the again patterns the photoresist in order to form the electrode pad for forming the insulating layer using thirdly, again, the oxide and nitride it forms and connecting the lead line (24) and it removes the second insulation layer (26) using dry or the wet etching and heating up the first insulation layer (25) using the first as the fabrication sequence of the carbon nanotube sensor used, and the oxide in the substrate and nitride and melted is performed.

,

.

Now, it describes the direct methanol fuel cell methanol concentration apparatus for detecting the state and the detecting method using the carbon nanotube sensor according to the present invention.

10 , 11

.

Figure 10 is a summary configurated block diagram of the direct methanol fuel cell methanol concentration apparatus for detecting the state according to the invention. Figure 11 is a flowchart of the embodiment performing the direct methanol concentration state detection according to the invention.

10 , , (80) (30),

(10), (30)

Referring to Figure 10, the methanol concentration apparatus for detecting the state of the direct methanol fuel cell according to the present invention comprises the small-signal amplifier (40) amplifying the micro signal outputted from the power supply unit (30), which it supplies it converts the supplied power into the necessi

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(10) (20), (10) (40), (40)

(50), (50) (60) (50)

(70) .

ty power the driver (20) in which the chest drives a car along the operation of the sensor (10) if the power source is supplied in the sensor (10), and the power supply unit (30) and the chest in which the carbon nanotube is used as the sensor for being installed at the methanol transportation pipeline or the repository and sensing the methanol concentration is enabled, and the density sensation branch (10) in the direct methanol fuel cell on operation reaction catalyst part (80), and the fixed the reference value the direct methanol fuel cell methanol concentration state by the detection signal delivered to the small-signal amplifier (40) and the display unit (70) indicating the signal outputted from the amplifier (60) and the methanol concentration state judgment part (50) amplified the methanol concentration state judgment part (50) which determines state and replacement time comparatively, and the signal detected from the methanol concentration state judgment part (50) by the fixed the predetermined level as the concentration and replacement time information of the methanol by the character or the predetermining method.

(30) (80) .

The power in which the power supply unit (30) is supplied in the direct methanol fuel cell driving to the reaction catalyst part (80) is converted into the necessity power demanded in each load and it supplies.

(30) (80) (40), (50) (60) (70) 1V , (20) (10) 1V DC/AC (31), DC/AC (31) (32) .

It is comprised of the small-signal amplifier (40) the power source supplied from the power supply unit (30) is the reaction catalyst part (80), the power source of 1V, and the regulator (32) stabilizing the power source transformed in the DC / AC converter (31). The power source of 1V the methanol concentration state judgment part (50), the amplifier (60) and display unit (70) request or 1V which converts into the power source of less and demanded in the driver (20) and methanol concentration sensor (10). Or less the respective DC / AC converter (31) converted.

, (20) (30) (32) AC 1V (10) .

Moreover, if the power source of the AC 1V or less the driver (20) is supplied from the regulator (32) within the power supply unit (30) and the power source is enabled the chest drive-controls the operation of the sensor (10).

(10) ,

.

It is installed at the methanol transportation pipeline or the repository and the sensor (10) measures the dielectric constant change of the methanol varied according to the methanol concentration to be the microsensor in the methanol transportation pipeline or the repository and the chest outputs the micro signal about that.

, (10) (22), (21), (22) (21)

.

Here, while covering the electrode pattern (22), in which the power source the sensor of the density sensation branch (10) is applied the substrate (21) in which the electrode pattern is molded, and the electrode pattern (22) it is evaporated in the prescribed part among the total area of the substrate (21) and the dielectric constant change of the engine oil absorbed into the carbon nanotube is sensed.

, , (23) .

Moreover, as to the direct methanol concentration apparatus for detecting the state according to the invention, it is possible that the electrode (23) is formed with the carbon nanotube.

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, AC

.

Moreover, the AC voltage is authorized and dielectric constant change detector and sensor using the carbon nanotube as the density sensation paper sensor compare the dielectric constant change according to the methanol concentration with the initially standard value of the electrical capacitance value and the concentration state of the methanol is determined and the methanol concentration of the direct methanol fuel cell is detected.

, , (40) (10) (50) .

And as to the methanol concentration detecting apparatus of the direct methanol fuel cell according to the invention, the chest the carbon nanotube to the sensing film amplifies the minute output of the sensor (10) to the fixed predetermined level and the small-signal amplifier (40) delivers to the methanol concentration state judgment part (50).

(50) ,

,

.

The chest is the state judgment part (50) the concentration state of the methanol is determined. And about concentration reduction of being compared determines the fixed the reference value as the replacement time of the methanol in case the exceeds and the information about that is outputted compared to the fixed the reference value the dielectric constant of the methanol detected to the microprocessor.

, (60) (50)

.

Moreover, the chest amplifies the applied signal in the state judgment part (50) to the fixed predetermined level and the amplifier (60) outputs to the display unit.

(40) (60) OP-AMP .

By the small-signal amplifier (40) and amplifier (60) using as the OP-AMP and designing it can implement.

, (30) (20), (10), (40), (50), (60) (100, PCB) .

Here, it is possible that the sensor (10), the small-signal amplifier (40) , and the chest mount the state judgment part (50), and the amplifier (60) to one printed circuit board (100, PCB) and the methanol concentration state machine detecting apparatus of the direct methanol fuel cell according to the invention the power supply unit (30) and driver (20) , and the chest organize on one unit.

, (70) LED, LCD , (60)

.

Moreover, the display unit (70) is comprised of LED, and the lamp or the LCD display means. And or the information about the methanol replacement time applied from the amplifier (60) is indicated by the predetermined method as the character and it notifies user.

, , (20) () 10 Hz1 .

In the meantime, the dielectric constant change may be referred to the be desirable the range of the mains frequency applied with the oscillator (not illustrated) having in the driver (20) consists of 10 Hz~1 as to the operation of the sensor measuring.

,

11 .

Now, the function as described above is made to be equal to next, referring to Figure 11, the detection procedure by the methanol concentration apparatus for detecting the state of the direct methanol fuel cell according to the invention implied is explained.

, Firstly, disclosed is the operation of all kinds of the

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(10) (80) (S101).

load devices by the power source supplied from the reaction catalyst part (80) the fuel cell driving starts after contacting the carbon nanotube called the chest in the methanol transportation pipeline or the repository is the sensing film of the sensor (10) of the direct methanol fuel cell (S101).

, (30) DC/AC(31) (80) (40), (50) (60) (70) , (20) (10) AC 1V (32) (S102).

At this time, the small-signal amplifier (40) , and the chest convert the power source supplied from the DC / AC converter (31) within the power supply unit (30) is the reaction catalyst part (80) into the power source demanded in the state judgment part (50), the amplifier (60) and display unit (70). After the driver (20) and chest convert into the power source of the AC 1V which the sensor (10) requests or less the power source is stabilized through the regulator (32) and it supplies to each load described in the above (S102).

, (20) (30) (32) AC 1V (10) ,

(10)

(S103)

Therefore, the density sensation branch (10) which if the driver (20) is enabled with the power source of the AC 1V supplied from the regulator (32) within the power supply unit (30) or less and it drives a car along the operation of the density sensation branch (10) it comprises the microsensor including the carbon nanotube and is installed within the methanol transportation pipeline or the repository are for the establishment of the initially standard value the dielectric constant of the methanol which firstly is afresh injected is measured (S103)

, (10)

(40) (50) (50) (S104), (S105).

Thereafter, if it authorizes in the methanol concentration state judgment part (50) called the microprocessor after doing the amplification the information about that in the small-signal amplifier (40) the dielectric constant change according to the concentration of the methanol in which the density sensation branch (10) is varied according to the fuel cell reaction is detected so that the chest determine the concentration of the methanol from the dielectric constant change of the methanol in which the state judgment part (50) is detected it compares with the fixed reference value (S104). And as a result of being compared the concentration determines whether it is the fixed reference value or greater (S105).

S105

S104 , ,

(60) .

It determines that the concentration state of the methanol is normal if the dielectric constant according to the methanol concentration which as a result of the above judgement, is detected of the S105 does not exceed the fixed reference value and it returns to the process of the S104. If exceeding the fixed reference value it is determined it determines as the replacement time in which the concentration gradient of the methanol goes on over the standard and the concentration of the methanol is unable to progress the normal reaction of the fuel cell and the information about that is outputted to the amplifier (60).

, (60) (50)

LCD (70)

(S106).

Therefore, or the information is indicated by the fixed predetermined level through display unit (70) consisting of the lamp it amplifies or the LCD display means as the character by the predetermined method and state or the replacement time of the methanol came the methanol replacement time indication in which the amplifier (60) is applied from the methanol state judgment part (50) is notified user of (S106).

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Disclaimer

. , . , . DB , , . (The document produced by using the high-tech machine translation system for the patent and science & technology literature. Therefore, the document can include the mistranslation, and it should not be used as a translation by a professional translator. We hold no legal liability for inconsistency of mistranslation, partial omission, and data generated by feature of system and network. We would like to inform you that the document cannot be regenerated, copied, and distributed by being stored in DB and system for unauthorized general public without our consent.)

Brief explanation of the drawing 1a, 1b .

Drawing 1a. And figure 1b is a schematic diagram and cross-sectional view of the measuring sensor using the electric capacity change.

2 .

Figure 2 is a summary perspective view of dielectric constant change detector and sensor using the carbon nanotube.

3 2 II-II . Figure 3 is a cross-sectional view of the II-II line of fig. 2.

4 .

Figure 4 is a perspective view of concentration state change detector and sensor using the carbon nanotube according to the invention.

5 4 III-III . Figure 5 is a cross-sectional view of the III-III line of fig. 4.

6 .

Figure 6 is a perspective view of concentration state change detector and sensor using the carbon nanotube according to the invention.

7 6 - . Figure 7 is a cross-sectional view of the level of the IV-IV of fig. 6.

8 .

Figure 8 is a Electron micrograph of the carbon nanotube applied to the sensing film of the invention.

9 .

Figure 9 is a schematic diagram of the sensor area of the dielectric constant change sensor according to the invention.

10 .

Figure 10 is a summary configurated block diagram of the direct methanol fuel cell methanol concentration apparatus for detecting the state according to the invention.

11 .

Figure 11 is a flowchart of the embodiment performing the direct methanol concentration state detection according to the invention.

12, 13 6 .

Fig. 12. And figure 13 is a measurement result graph obtained in the sensor being illustrated in fig. 6.

#60# > 10 : 20 : 10: density sensation branch 20: driver. 21 : 22 : 21: substrate 22: sensing film. 23 : 24 : 23: electrode 24: lead line. 25 : 1 26 : 2 25: first insulation layer 26: second insulation layer. 30 : 31 : 30: power supply unit 31: converter. 32 : 40 : 32: regulator 40: small-signal amplifier. 50 : 60 : 50: concentration state determining unit 60: amplifier. 70 : 80 : 70: display unit 80: reaction catalyst part.

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