KR20120129699A - Membrane for sensing hydrogen ion concentration and method for manufacturing the same - Google Patents

Abstract

PURPOSE: A hydrogen ion concentration sensing film and a manufacturing method thereof are provided to include an aluminum oxide layer in a hydrogen ion concentration sensing film, thereby obtaining high sensitivity and excellent reliability. CONSTITUTION: A hydrogen ion concentration sensing film comprises a substrate(10), an oxide silicon layer(12), a hafnium oxide layer(14), and an aluminum oxide layer(16). The oxide silicon layer is formed on the substrate. The hafnium oxide layer is arranged on the oxide silicon layer. The aluminum oxide layer is arranged on the hafnium oxide layer.

Description

Hydrogen ion concentration sensing membrane and its manufacturing method {MEMBRANE FOR SENSING HYDROGEN ION CONCENTRATION AND METHOD FOR MANUFACTURING THE SAME}

The present invention relates to a hydrogen ion concentration sensing film and a method of manufacturing the same. More specifically, the present invention relates to a hydrogen ion concentration sensing film having a high sensitivity and excellent reliability and a method of manufacturing the same.

The state of various solutions can be measured by detecting the pH (pH) contained in the solution. That is, whether the solution is acidic or basic is evaluated by measuring the concentration of hydrogen ions in the solution. Generally, hydrogen ion concentration is detected using the potential difference obtained by immersing a hydrogen ion concentration sensor in a solution.

The hydrogen ion concentration sensor is divided in various ways according to its structure and measuring method, but all hydrogen ion concentration sensors have a common point in that they include a hydrogen ion concentration sensing film. The hydrogen ion concentration sensing membrane is provided in the measurement unit of the hydrogen ion concentration sensor, and site-bound with ions to change the potential in the aqueous solution.

To provide a hydrogen ion concentration sensing membrane having high sensitivity and excellent reliability. In addition, an object of the present invention is to provide a method for producing a hydrogen ion concentration sensing film.

The hydrogen ion concentration sensing film according to an embodiment of the present invention comprises: i) a substrate, ii) a silicon oxide layer on the substrate, iii) a hafnium oxide layer on the silicon oxide layer, and iv) an aluminum oxide layer on the hafnium oxide layer. Include.

The thickness of the silicon oxide layer (SiO ₂ ) may be 10 nm to 1000 nm. The thickness of the hafnium oxide layer HfO ₂ may be 10 nm to 1000 nm. The thickness of the aluminum oxide layer (Al ₂ O ₃ ) may be 10nm to 1000nm. The substrate may be made of one or more materials selected from the group consisting of silicon (Si), germanium (Ge), gallium (Ga), arsenic (As), aluminum oxide (Al ₂ O ₃ ), and silicon carbide (SiC).

According to another aspect of the present invention, there is provided a method of manufacturing a hydrogen ion concentration sensing film, i) providing a substrate, ii) providing a silicon oxide layer (SiO ₂ ) on a substrate, iii) a silicon oxide layer (SiO ₂ ) It includes the step of providing a hafnium layer (HfO ₂₎ oxidation over, and v) screen providing a hafnium layer (HfO ₂₎ layer of aluminum (Al ₂ O ₃₎ on the oxide.

According to another exemplary embodiment of the present invention, a method for manufacturing a hydrogen ion concentration sensing film includes a substrate, a silicon oxide layer (SiO ₂ ), a hafnium oxide layer (HfO ₂ ), and an aluminum oxide layer (Al ₂ O ₃ ). It may further comprise the step of heat treatment in. In addition, according to another embodiment of the present invention, a method for manufacturing a hydrogen ion concentration sensing film may include providing a silicon oxide layer (SiO ₂ ), and then heat treating the substrate and the silicon oxide layer (SiO ₂ ) at 300 ° C. to 1050 ° C. It may further include. According to another embodiment of the present invention, a method of manufacturing a hydrogen ion concentration sensing film is provided with a hafnium oxide layer (HfO ₂ ), and then a substrate, a silicon oxide layer (SiO ₂ ), and a hafnium oxide layer (HfO ₂ ) are 300 ° C. to 1050. It may further comprise the step of heat treatment at ℃. According to another embodiment of the present invention, a method of manufacturing a hydrogen ion concentration sensing film is provided with aluminum oxide (Al ₂ O ₃ ), followed by a substrate, a silicon oxide layer (SiO ₂ ), a hafnium oxide layer (HfO ₂ ), and an aluminum oxide ( It may further comprise the step of heat-treating Al ₂ O ₃ ) at 300 ℃ to 1050 ℃.

According to another aspect of the present invention, there is provided a method for producing a hydrogen ion concentration sensing film, in which a silicon oxide layer (SiO ₂ ) is provided, wherein the silicon oxide layer (SiO ₂ ) is thermally oxidized, sputtered, and atoms. It may be provided by atomic layer deposition (ALD) or chemical vapor deposition (CVD). According to another aspect of the present invention, there is provided a method of manufacturing a hydrogen ion concentration sensing film, in which a hafnium oxide layer (HfO ₂ ) is provided, and the hafnium oxide layer (HfO ₂ ) is provided by sputtering, atomic layer deposition, or chemical vapor deposition. Can be. The pH sensing membrane production process according to another embodiment of the present invention is an aluminum oxide layer (Al ₂ O ₃₎ in the step of providing an aluminum layer (Al ₂ O ₃₎ oxide sputtering, atomic layer deposition or chemical vapor deposition May be provided by

Since the hydrogen ion concentration detection film according to an embodiment of the present invention includes an aluminum oxide layer or the like, it has high sensitivity and excellent reliability in an aqueous solution. In addition, the hydrogen ion concentration sensing film according to an embodiment of the present invention not only has a simple manufacturing process but also consumes a lower manufacturing cost than the rare earth metal. And the characteristics such as sensitivity, drift and hysteresis are all uniform. In addition, in the hydrogen ion concentration sensing film according to an embodiment of the present invention, the interface bonding state between each layer and the substrate is good.

1 is a schematic partial stereoscopic cross-sectional view of a hydrogen ion concentration sensing film according to an embodiment of the present invention.
FIG. 2 is a schematic flowchart of a method of manufacturing the hydrogen ion concentration sensing film of FIG. 1.
FIG. 3 is a schematic diagram of a hydrogen ion concentration sensor having a hydrogen ion concentration sensing film of FIG. 1.
4A to 4C are transmission electron microscope (TEM) photographs of cross-sectional structures of hydrogen ion concentration sensing membranes prepared according to Experimental Examples, Comparative Examples 1 and 2, respectively.
5A to 5C are energy band diagrams of hydrogen ion concentration sensing membranes prepared according to Experimental Example, Comparative Example 1 and Comparative Example 2, respectively.
6 is a graph showing the sensitivity characteristics of the hydrogen ion concentration detection film prepared according to Experimental Example, Comparative Example 1 and Comparative Example 2.
7 is a graph showing drift characteristics of the hydrogen ion concentration sensing film prepared according to Experimental Example, Comparative Example 1 and Comparative Example 2.
8 is a graph showing the hysteresis of the hydrogen ion concentration sensing film prepared according to Experimental Example, Comparative Example 1 and Comparative Example 2.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the invention. As used herein, the singular forms “a,” “an,” and “the” include plural forms as well, unless the phrases clearly indicate the opposite. As used herein, the term "comprising" embodies a particular characteristic, region, integer, step, operation, element, and / or component, and other specific characteristics, region, integer, step, operation, element, component, and / or group. It does not exclude the presence or addition of.

Unless defined otherwise, all terms including technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. Commonly used predefined terms are further interpreted as having a meaning consistent with the relevant technical literature and the present disclosure, and are not to be construed as ideal or very formal meanings unless defined otherwise.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

1 is a three-dimensional cross-sectional view schematically showing a partial decomposition of the hydrogen ion concentration detection film 100 according to an embodiment of the present invention. The decomposition structure of the hydrogen ion concentration detecting film 100 of FIG. 1 is merely to illustrate the present invention, but the present invention is not limited thereto. Therefore, the structure of the hydrogen ion concentration sensing film 100 may be modified in other forms.

As shown in FIG. 1, the hydrogen ion concentration sensing film 100 includes a substrate 10, a silicon oxide layer (SiO ₂ ) 12, a hafnium oxide layer (HfO ₂ ) 14, and an aluminum oxide layer (Al _2). O ₃ ) (16). In addition, the hydrogen ion concentration sensing film 100 may further include other elements as necessary.

The substrate 10 may be made of a semiconductor or an insulator. More specifically, the material of the substrate 10 may be silicon (Si), germanium (Ge), gallium (Ga), arsenic (As), aluminum oxide (Al ₂ O ₃ ), silicon carbide (SiC) or a mixture thereof. Can be used. By doping these materials, the substrate 10 made of an n-type semiconductor or a p-type semiconductor can be manufactured.

Meanwhile, a silicon oxide layer (SiO ₂ ) 12 is provided on the substrate 10. By using the silicon oxide layer (SiO ₂ ) 12, the adhesion with the hafnium oxide layer (HfO ₂ ) 14 having poor adhesion with the substrate 10 can be greatly improved. Here, the thickness t12 of the silicon oxide layer (SiO ₂ ) 12 may be 10 nm to 1000 nm. When the thickness t12 of the silicon oxide layer (SiO ₂ ) 12 is too large, the manufacturing cost and manufacturing time of the silicon oxide layer (SiO ₂ ) 12 are greatly increased. In addition, when the thickness t12 of the silicon oxide layer (SiO ₂ ) 12 is too small, the substrate 10 and the hafnium oxide layer (HfO ₂ ) 14 may be substantially in contact with each other. It is not good and peeling phenomenon may occur. Therefore, the thickness t12 of the silicon oxide layer (SiO ₂ ) 12 is adjusted in the above-described range.

A hafnium oxide layer (HfO ₂ ) 14 is provided over the silicon oxide layer (SiO ₂ ) 12. The hafnium oxide layer (HfO ₂ ) 14 efficiently transfers the changing potential to the substrate 10 when the ion concentration of the aqueous solution changes. Here, the thickness t14 of the hafnium oxide layer (HfO ₂ ) 14 may be 10 nm to 1000 nm. When the thickness t14 of the hafnium oxide layer (HfO ₂ ) 14 is too large or too small, the potential that changes when the ion concentration of the aqueous solution changes may not be efficiently transferred to the substrate 10. Therefore, the thickness t14 of the hafnium oxide layer (HfO ₂ ) 14 is adjusted in the above-described range. The hafnium oxide layer (HfO ₂ ) 14 may be formed by depositing on the silicon oxide layer (SiO ₂ ) 12. Through deposition, the interfacial adhesion between the silicon oxide layer (SiO ₂ ) 12 and the hafnium oxide layer (HfO ₂ ) 14 may be improved.

As shown in FIG. 1, an aluminum oxide layer (Al ₂ O ₃ ) 16 is provided over the hafnium oxide layer (HfO ₂ ) 14. Since the aluminum oxide layer (Al ₂ O ₃ ) 16 is chemically stable, even when the hydrogen ion concentration sensing membrane 100 is immersed in an aqueous solution, the degradation or ion sensing performance of the hydrogen ion concentration sensing membrane 100 may be protected. Can be. To this end, the thickness t16 of the aluminum oxide layer (Al ₂ O ₃ ) 16 may be adjusted to 10 nm to 1000 nm. When the thickness t16 of the aluminum oxide layer (Al ₂ O ₃ ) 16 is too small, the chemical stability with respect to the aqueous solution is significantly lowered. In addition, when the thickness t16 of the aluminum oxide layer (Al ₂ O ₃ ) 16 is too large, the manufacturing cost of the aluminum oxide layer (Al ₂ O ₃ ) 16 increases. Therefore, it is preferable to adjust the thickness t16 of the aluminum oxide layer (Al ₂ O ₃ ) 16 to the above-mentioned range. Meanwhile, the aluminum oxide layer (Al ₂ O ₃ ) 16 may be deposited on the hafnium oxide layer (HfO ₂ ) 14. Through vapor deposition, the interfacial adhesion of the hafnium oxide layer (HfO ₂ ) 14 of the aluminum oxide layer (Al ₂ O ₃ ) 16 can be improved.

As described above, the hydrogen ion concentration sensing film 100 according to an embodiment of the present invention uses the aforementioned materials instead of using a material having a high dielectric constant (K) or a rare earth element. As a result, the manufacturing cost of the hydrogen ion concentration sensing film 100 can be reduced, and the adhesion between the substrate 10 and other layers can be improved. Hereinafter, a method of manufacturing the hydrogen ion concentration sensing film 100 of FIG. 1 will be described in more detail with reference to FIG. 2.

2 illustrates a schematic manufacturing method of the hydrogen ion concentration sensing film 100 of FIG. 1. The method for producing the hydrogen ion concentration detecting film of FIG. 2 is merely for illustrating the present invention, and the present invention is not limited thereto. Therefore, the method of manufacturing the hydrogen ion concentration sensing film of FIG. 2 may be modified in various forms.

As shown in FIG. 2, in step S10, a substrate is provided. The substrate may be provided in a thin sheet in the form of a wafer.

Next, in step S20, a silicon oxide layer is provided on the substrate. Here, the silicon oxide layer may be formed using a method such as thermal oxidation, sputtering, atomic layer deposition (ALD) or chemical vapor deposition (CVD).

In operation S30, a hafnium oxide layer is provided on the silicon oxide layer. Here, the hafnium oxide layer may be formed through sputtering, atomic layer deposition, or chemical vapor deposition.

In step S40, an aluminum oxide layer is provided on the hafnium oxide layer. Here, the aluminum oxide layer may be formed through sputtering, atomic layer deposition, or chemical vapor deposition.

Finally, in step S50, the substrate, the silicon oxide layer, the hafnium oxide layer, and the aluminum oxide layer are heat treated. That is, the substrate, the silicon oxide layer, the hafnium oxide layer, and the aluminum oxide layer which are sequentially stacked are all heat treated at 100 ° C to 500 ° C. If the aforementioned heat treatment temperature is too low or too high, the properties of the silicon oxide layer, hafnium oxide layer, and aluminum oxide layer cannot be exhibited efficiently.

Although not shown in FIG. 2, the silicon oxide layer, the hafnium oxide layer, and the aluminum oxide layer may be heat-treated after the steps S20, S30, and S40 of FIG. 2. In this case, the heat treatment temperatures of the steps S20, S30, and S40 may be 300 ° C. to 1050 ° C. If the heat treatment temperature is too low, the silicon oxide layer, the hafnium oxide layer and the aluminum oxide layer may not adhere well to each other. In addition, when the heat treatment temperature is too high, the silicon oxide layer, hafnium oxide layer, and aluminum oxide layer may deteriorate. Therefore, the heat treatment temperature is adjusted to the above range.

FIG. 3 schematically shows a hydrogen ion concentration sensor 1000 having the hydrogen ion concentration sensing film 100 of FIG. 1. The structure of the hydrogen ion concentration sensor 1000 of FIG. 3 is merely for illustrating the present invention, and the present invention is not limited thereto. Therefore, the structure of the hydrogen ion concentration sensor 1000 of FIG. 3 may be modified differently.

As shown in FIG. 3, the hydrogen ion concentration sensor 1000 includes a hydrogen ion concentration detecting film 100, a first electrode 20, a second electrode 30, a chamber 40, and a voltmeter 50. Include. In addition, the hydrogen ion concentration sensor 1000 may further include other components as necessary.

The first electrode 20 may be manufactured by applying Ag / AgCl with a paste to function as a reference electrode under the hydrogen ion concentration sensing film 100. Meanwhile, the second electrode 30 formed on the hydrogen ion concentration detecting film 100 may be formed by depositing aluminum (Al) with an electron beam for electrical connection. The second electrode 30 contacts the aqueous solution L to generate a potential difference with the first electrode 20, and the potential difference is a voltmeter 50 electrically connected to the first electrode 20 and the second electrode 30. Is measured. Meanwhile, the chamber 40 is formed on the first electrode 20 so that the aqueous solution L is stably maintained without leaking, and the gap between the chamber 40 and the first electrode 20 is sealed. As a result, there is no possibility that the aqueous solution L flows out. To this end, the chamber 40 may be made of a resin material such as polydimethylsiloxane (PDMS). Therefore, since the aqueous solution L contacts the first electrode 20 stably, it is possible to stably maintain the measurement environment of the hydrogen ion concentration.

Hereinafter, the present invention will be described in more detail with reference to experimental examples. These experimental examples are only for illustrating the present invention, and the present invention is not limited thereto.

Experimental Example

In the experimental example of the present invention, an experiment was performed to prepare an electrolysinssemiconductor (EIS) sensor having a hydrogen ion concentration sensing film of SiO ₂ HfO ₂ Al ₂ O ₃ (OHA). Here, the structure of the EIS sensor was the same as that of the hydrogen ion concentration sensor shown in FIG. In order to manufacture a hydrogen ion concentration sensor, a substrate was first manufactured from a single crystal silicon wafer having a (100) plane having a thickness of 550 μm p-doped with boron at 1 × 10 ¹⁵ cm ³ . The substrate was thermally oxidized to form a silicon oxide layer (SiO ₂ ) having a thickness of 5 nm. Next, a hafnium oxide layer (HfO ₂ ) and an aluminum oxide layer (Al ₂ O ₃ ) were sequentially deposited by the ALD method so as to have a thickness of 7.8 nm and 13.6 nm, respectively, to prepare a hydrogen ion concentration sensing film. The prepared hydrogen ion concentration sensing film was rapidly heat-treated for 30 seconds in a mixed gas atmosphere of nitrogen and oxygen at 850 ° C., and then heat-treated in a mixed gas atmosphere of nitrogen and hydrogen at 450 ° C. for 30 minutes. Next, an aluminum (Al) electrode deposited to a thickness of 300 nm was manufactured through an electron beam evaporator to apply a voltage to the rear surface of the substrate. On the other hand, an Ag / AgCl electrode was paste printed onto the aluminum oxide layer (Al ₂ O ₃ ) as a reference electrode. A chamber was made of polydimethylsiloxane (PDMS) on the Ag / AgCl electrode, and an aqueous solution was injected into the chamber. The pH of the aqueous solution was changed little by little depending on the experimental conditions. After the Ag / AgCl electrode and the aluminum (Al) electrode were electrically connected to the voltmeter through a wire, the potential difference between the two electrodes was measured.

Comparative example  One

For comparison with the above experimental example, a hydrogen ion concentration sensing film different from the hydrogen ion concentration sensing film of the experimental example was prepared. SiO ₂ having a thickness of about 28.2 nm was deposited on the substrate of the experiment by sputtering. A layer was formed. The remaining experimental conditions were the same as the above-described experimental example. Through these experiments, an EIS sensor having a hydrogen ion concentration sensing film of SiO ₂ (O) was prepared.

Comparative example  2

For comparison with the above experimental example, a hydrogen ion concentration sensing film different from the hydrogen ion concentration sensing film of the experimental example was prepared. SiO _{2 with a} thickness of about 5 nm by sputtering on the substrate of the Experimental Example A layer was formed. Next, using a sputtered SiO ₂ 22.5 nm thick Si ₃ N ₄ on the layer A layer was formed. The remaining experimental conditions were the same as the above-described experimental example. Through these experiments, SiO ₂ Si ₃ N ₄ An EIS sensor having a hydrogen ion concentration sensing film of (ON) was prepared.

Experiment result

Transmission electron micrograph

4A to 4C show transmission electron micrographs of cross sections of the hydrogen ion concentration sensing membrane according to Experimental Example, Comparative Example 1 and Comparative Example 2, respectively. As shown in Figures 4a to 4c, it can be seen that the hydrogen ion concentration sensing films having a uniform thickness, respectively.

Energy band

5A to 5C show energy bands of the hydrogen ion concentration sensing film according to Experimental Example, Comparative Example 1 and Comparative Example 2, respectively. In the hydrogen ion concentration sensing membrane prepared according to the experimental example shown in FIG. 5a, the effective thickness of the band was thin, and Al ₂ O ₃ The layer was well tolerated with aqueous solution. As a result, it was judged that the sensitivity of the hydrogen ion concentration sensing film was high. Therefore, it was judged that a reliable hydrogen ion concentration sensor could be manufactured using the hydrogen ion concentration sensing film of the experimental example.

In contrast, in the hydrogen ion concentration sensing membrane of Comparative Example 1, it was determined that the effective thickness of the band was so large that it was difficult to transfer the potential changed by the ion concentration of the aqueous solution to the substrate. In addition, in the hydrogen ion concentration sensing film of Comparative Example 2, it was determined that the effective thickness of the band was thin so that the potential could be efficiently transferred to the substrate. However, there was a problem that the properties of the Si ₃ N ₄ layer is degraded by the aqueous solution.

Sensitivity characteristics

6 shows the sensitivity characteristics of the hydrogen ion concentration sensing film prepared according to Experimental Example, Comparative Example 1 and Comparative Example 2. The sensitivity characteristics of the hydrogen ion concentration sensing film may be evaluated by observing a change in capacitance according to the voltage shown in FIG. 6. Here, the change in capacitance according to the voltage was measured using an HP 4284B precision LCR meter.

As shown in FIG. 6, when the hydrogen ion concentration of the aqueous solution changed from pH 3 to pH 12, it was confirmed that the capacitance was changed while moving. Here, the hydrogen ion concentration detection film according to the experimental example showed a voltage of 54.4mV according to the pH. On the other hand, the hydrogen ion concentration sensing membrane according to Comparative Example 1 exhibited a voltage of 37.3 mV according to pH, and the hydrogen ion concentration sensing membrane according to Comparative Example 2 showed a voltage of 49.7 mV according to pH. That is, the voltage of the hydrogen ion concentration sensing film according to the experimental example showed more change than the voltage of the hydrogen ion concentration sensing film according to Comparative Example 1 and Comparative Example 2. Therefore, it was confirmed that the hydrogen ion concentration sensing membrane according to the experimental example had the highest sensitivity to the hydrogen ion concentration.

Drift  characteristic

Figure 7 shows the drift characteristics of the hydrogen ion concentration detection film prepared according to Experimental Example, Comparative Example 1 and Comparative Example 2. The drift characteristics of the hydrogen ion concentration sensing membrane of FIG. 7 were measured in an aqueous solution of pH 7. In this case, as shown in FIG. 7, the drift of the hydrogen ion concentration sensing membrane according to the experimental example was 2.1 mV / h, while the drift of the hydrogen ion concentration sensing membranes according to Comparative Example 1 and Comparative Example 2 was 45.2 mV / h, respectively. h and 3.8 mV / h. Therefore, it was found that the drift of the hydrogen ion concentration sensing membranes according to Comparative Examples 1 and 2 was larger than the drift of the hydrogen ion concentration sensing membranes according to the Experimental Examples. Was found to be smaller than Comparative Example 1 and Comparative Example 2.

Hysteresis

Figure 8 shows the hysteresis of the hydrogen ion concentration detection film prepared according to Experimental Example, Comparative Example 1 and Comparative Example 2. As shown in FIG. 8, the hysteresis of the hydrogen ion concentration sensing membrane was determined while changing the hydrogen ion concentration of the aqueous solution to pH 7, pH 10, pH 7, pH 4, and pH 7. As a result, 14.2 mV was measured in the hydrogen ion concentration sensing membrane according to the experimental example, while 45.2 mV and 20.9 mV were measured in the hydrogen ion concentration sensing membranes according to Comparative Example 1 and Comparative Example 2, respectively. Therefore, the hydrogen ion concentration sensing membranes according to the experimental example were found to exhibit high reliability because the hysteresis was lower than the hydrogen ion concentration sensing membranes according to Comparative Example 1 and Comparative Example 2, respectively.

As described above, SiO ₂ used in the hydrogen ion concentration sensing film of Comparative Example 1 has low sensitivity, and drift and hysterisis in which the measured value changes with time become severe. On the other hand, Si ₃ N ₄ used in the hydrogen ion concentration sensing film of Comparative Example 2 is a chemically stable insulator and is generally used because it has a higher lamination than SiO ₂ and operates stably when used in a hydrogen ion concentration sensor. However, as the Si ₃ N ₄ is repeated in the aqueous solution, hydration occurs due to oxidation of the surface. As a result, the sensitivity of the hydrogen ion concentration sensing film is lowered, and drift and hysteresis become more severe. Therefore, in order to solve this problem, a hydrogen ion concentration sensing film using a high dielectric constant insulator or a rare earth element has been studied, but there is a problem that cannot improve all of sensitivity, drift, and hysteresis. In addition, in the case of forming the hydrogen ion concentration sensing film, there is a disadvantage in that the uniformity of characteristics is lowered and the manufacturing cost is high due to the scarcity of the material.

In contrast, in the case of using the hydrogen ion concentration sensing film according to the experimental example of the present invention, it is superior to the hydrogen ion concentration sensing film according to Comparative Examples 1 and 2 in energy band, sensitivity characteristic, drift characteristic and hysteresis. Judging. Therefore, when the hydrogen ion concentration sensor is manufactured using the hydrogen ion concentration sensing film according to an embodiment of the present invention, high reliability in hydrogen ion concentration measurement can be ensured.

It will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the following claims.

10. Substrate
12. Silicon Oxide Layer
14. Hafnium oxide layer
16. Aluminum oxide layer
20, 30. Electrode
40. Chamber
50. Voltmeter
100. Hydrogen ion concentration sensor
1000. Hydrogen ion concentration sensor
L. Solution

Claims (13)

Board,
A silicon oxide layer (SiO ₂ ) positioned on the substrate,
The silicon oxide layer (SiO ₂₎ oxidation, located on the hafnium layer (HfO _2), and
Aluminum oxide layer (Al ₂ O ₃ ) located on the hafnium oxide layer (HfO ₂ )
Hydrogen ion concentration detection film comprising a. The method of claim 1,
The silicon oxide layer (SiO ₂ ) has a thickness of 10nm to 1000nm hydrogen ion concentration sensing film. The method of claim 1,
The hafnium oxide layer (HfO ₂ ) has a thickness of 10nm to 1000nm hydrogen ion concentration sensing film. The method of claim 1,
The thickness of the aluminum oxide layer (Al ₂ O ₃ ) is a hydrogen ion concentration sensing film of 10nm to 1000nm. The method of claim 1,
The substrate is hydrogen ion made of at least one material selected from the group consisting of silicon (Si), germanium (Ge), gallium (Ga), arsenic (As), aluminum oxide (Al ₂ O ₃ ), and silicon carbide (SiC). Concentration sensor Providing a substrate,
Providing a silicon oxide layer (SiO ₂ ) on the substrate,
Providing a hafnium oxide layer (HfO ₂ ) on the silicon oxide layer (SiO ₂ ), and
Providing an aluminum oxide layer (Al ₂ O ₃ ) on the hafnium oxide layer (HfO ₂ )
Method for producing a hydrogen ion concentration detection film comprising a. The method according to claim 6,
The substrate of the hydrogen ion concentration sensing film further comprises the step of heat-treating the silicon oxide layer (SiO ₂ ), the hafnium oxide layer (HfO ₂ ) and the aluminum oxide layer (Al ₂ O ₃ ) at 100 ℃ to 500 ℃ Manufacturing method. The method according to claim 6,
After providing the silicon oxide layer (SiO _2), the substrate and the pH sensing membrane production method further comprising a step of heat treatment at the silicon oxide layer (SiO ₂₎ 300 ℃ to 1050 ℃. The method according to claim 6,
After providing the hafnium oxide layer (HfO _2), the substrate, the silicon oxide layer (SiO _2), and the pH value further comprises the step of annealing the hafnium oxide layer (HfO ₂₎ at 300 ℃ to 1050 ℃ Method of manufacturing the sensing film. The method according to claim 6,
After providing the aluminum oxide (Al ₂ O ₃ ), the substrate, the silicon oxide layer (SiO ₂ ), the hafnium oxide layer (HfO ₂ ) and the aluminum oxide (Al ₂ O ₃ ) 300 ℃ to 1050 ℃ Method for producing a hydrogen ion concentration sensing film further comprising the step of heat treatment in. The method according to claim 6,
In the providing of the silicon oxide layer (SiO ₂ ), the silicon oxide layer (SiO ₂ ) may be thermally oxidized, sputtered, atomic layer deposition (ALD) or chemical vapor deposition (ALD). A method for producing a hydrogen ion concentration sensing film provided by chemical vapor deposition (CVD). The method according to claim 6,
In the step of providing the hafnium oxide layer (HfO ₂ ), the hafnium oxide layer (HfO ₂ ) is a method of manufacturing a hydrogen ion concentration sensing film provided by sputtering, atomic layer deposition or chemical vapor deposition. The method according to claim 6,
In the providing of the aluminum oxide layer (Al ₂ O ₃ ), the aluminum oxide layer (Al ₂ O ₃ ) is a method of manufacturing a hydrogen ion concentration sensing film provided by sputtering, atomic layer deposition or chemical vapor deposition.

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