WO2024009891A1 - 水素検知装置及びその製造方法 - Google Patents

水素検知装置及びその製造方法 Download PDF

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Publication number
WO2024009891A1
WO2024009891A1 PCT/JP2023/024224 JP2023024224W WO2024009891A1 WO 2024009891 A1 WO2024009891 A1 WO 2024009891A1 JP 2023024224 W JP2023024224 W JP 2023024224W WO 2024009891 A1 WO2024009891 A1 WO 2024009891A1
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Prior art keywords
electrode
resistance element
hydrogen
detection device
insulating film
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PCT/JP2023/024224
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English (en)
French (fr)
Japanese (ja)
Inventor
運也 本間
理 伊藤
賢 河合
幸治 片山
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Nuvoton Technology Corp Japan
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Nuvoton Technology Corp Japan
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Priority to JP2024532086A priority Critical patent/JPWO2024009891A1/ja
Priority to CN202380050081.3A priority patent/CN119452250A/zh
Publication of WO2024009891A1 publication Critical patent/WO2024009891A1/ja
Priority to US18/990,893 priority patent/US20250116623A1/en
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004—Gaseous mixtures, e.g. polluted air
    • G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
    • G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
    • G01N33/005—H2
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/045—Circuits
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid

Definitions

  • the present disclosure relates to a hydrogen detection device and a method of manufacturing the same, and particularly relates to a hydrogen detection device configured with a bridge circuit and a method of manufacturing the same.
  • Patent Document 1 requires a heater and a temperature control section, and further performance improvement is required.
  • the present disclosure aims to provide a hydrogen detection device that is configured with a bridge circuit, does not necessarily require a heater, and can operate stably, and a method for manufacturing the hydrogen detection device. purpose.
  • a hydrogen detection device includes a first resistance element, a second resistance element, a third resistance element, and a fourth resistance element that constitute a bridge circuit, and includes the first resistance element, a second resistance element, a third resistance element, and a fourth resistance element.
  • One end of the resistive element and one end of the second resistive element are connected, one end of the third resistive element and one end of the fourth resistive element are connected, and the other end of the first resistive element and the fourth resistive element are connected.
  • the other ends of the three resistance elements are connected, the other ends of the second resistance element and the other ends of the fourth resistance element are connected, and the first resistance element, the second resistance element, and the third resistance element are connected.
  • the first resistance element and the fourth resistance element are formed on one semiconductor chip, the first resistance element is a hydrogen sensor, and the main surfaces thereof are a first electrode and a second electrode arranged to face each other; a first metal oxide layer arranged in contact with the main surface of the first electrode and the main surface of the second electrode; an electrode, a first insulating film covering the second electrode and the first metal oxide layer;
  • the third resistance element has a first opening that is exposed without being covered with an insulating film, and the third resistance element is a reference element, and includes a third electrode and a fourth electrode whose main surfaces are arranged to face each other, and the third resistance element.
  • a second metal oxide layer disposed in contact with the main surface of the electrode and the main surface of the fourth electrode; and a second metal oxide layer covering the third electrode, the fourth electrode, and the second metal oxide layer. and an insulating film, and the second insulating film does not have an opening that exposes the other surface of the fourth electrode opposite to the main surface without being covered by the second insulating film.
  • a method for manufacturing a hydrogen detection device includes a first resistance element that is a hydrogen sensor, a second resistance element, and a third resistance element that is a reference element that constitute a bridge circuit. and a method for manufacturing a hydrogen detection device including a fourth resistance element, the step of forming a laminate for the first resistance element and the third resistance element, and forming an opening in the formed laminate.
  • the laminate for the first resistive element and the third resistive element includes a first electrode and a first electrode disposed with their main surfaces facing each other.
  • a metal oxide layer disposed in contact with the main surface of the first electrode and the main surface of the second electrode, and the first electrode, the second electrode, and the metal oxide layer.
  • the present disclosure provides a hydrogen detection device configured with a bridge circuit that does not necessarily require a heater and can operate stably, and a method for manufacturing the hydrogen detection device.
  • FIG. 1 is an equivalent circuit diagram of a hydrogen detection device according to an embodiment.
  • FIG. 2A is a cross-sectional view showing a configuration example of the hydrogen sensor shown in FIG. 1.
  • FIG. 2B is a top view showing a configuration example of the hydrogen sensor shown in FIG. 2A.
  • FIG. 3 is a cross-sectional view showing an example of the configuration of the reference element shown in FIG.
  • FIG. 4A is a schematic diagram showing an example of the overall configuration of the hydrogen detection device according to the embodiment.
  • FIG. 4B is a plan view showing an example of the layout of wiring patterns of a hydrogen sensor and a reference element in the hydrogen detection device shown in FIG. 4A.
  • FIG. 5 is a flowchart showing a method for manufacturing a hydrogen detection device according to an embodiment.
  • FIG. 5 is a flowchart showing a method for manufacturing a hydrogen detection device according to an embodiment.
  • FIG. 6 is a diagram showing experimental results regarding the time dependence and distance dependence of the output voltage (differential voltage) of the hydrogen detection device according to the embodiment.
  • FIG. 7 is a diagram showing experimental results regarding the reaction of the hydrogen detection device according to the embodiment to hydrogen.
  • FIG. 8 is a schematic diagram showing an example of the overall configuration of a hydrogen detection device according to Modification 1 of the embodiment.
  • FIG. 9A is a schematic diagram showing an example of the overall configuration of a hydrogen detection device according to Modification 2 of the embodiment.
  • FIG. 9B is a plan view showing an example of the layout of wiring patterns of the hydrogen sensor and reference element in the hydrogen detection device shown in FIG. 9A.
  • FIG. 10 is a flowchart showing a method for manufacturing a hydrogen detection device according to modification 2 of the embodiment.
  • FIG. 11 is a schematic diagram showing an example of the overall configuration of a hydrogen detection device according to modification 3 of the embodiment.
  • FIG. 1 is an equivalent circuit diagram of a hydrogen detection device 10 according to an embodiment. This figure also shows a voltmeter 20 and a DC voltage source 21 as external devices.
  • the hydrogen detection device 10 includes a hydrogen sensor 100 that is a first resistance element that constitutes a bridge circuit, a resistor R1 that is a second resistance element, a reference element 100a that is a third resistance element, and a resistor R2 that is a fourth resistance element. Equipped with The hydrogen sensor 100 and the resistor R1 have their respective ends connected to the terminal B, and the reference element 100a and the resistor R2 have their respective ends connected to the terminal D. The other ends of the hydrogen sensor 100 and the reference element 100a are connected to the terminal A, and the other ends of the resistor R1 and the resistor R2 are connected to the terminal D. Hydrogen sensor 100, resistor R1, reference element 100a, and resistor R2 are formed on one semiconductor chip 12.
  • the hydrogen sensor 100 and the reference element 100a have the same resistance value. In an environment where hydrogen does not exist, only the hydrogen sensor 100 has a resistance value that decreases depending on the concentration of hydrogen.
  • the resistor R1 and the resistor R2 have the same resistance value, and are made of polysilicon or the like and have a fixed resistance value, for example, 20 ⁇ .
  • the voltage at the terminal B with respect to the terminal D is measured with the voltmeter 20. Since the resistance value of the hydrogen sensor 100 decreases in accordance with the hydrogen concentration, the resistance balance of the bridge circuit is disrupted, and a potential difference is generated between terminals B and D, and this potential difference is measured by the voltmeter 20.
  • FIG. 2A is a cross-sectional view showing a configuration example of the hydrogen sensor 100 shown in FIG. 1.
  • FIG. 2B is a top view showing a configuration example of the hydrogen sensor 100 shown in FIG. 2A. Note that FIG. 2A shows a schematic cross section taken along the IA-IA cutting line in FIG. 2B when viewed in the direction of the arrow.
  • the hydrogen sensor 100 includes, as main components, a first electrode 103 and a second electrode 106 whose main surfaces are arranged to face each other, and a structure between the main surface (that is, the upper surface) of the first electrode 103 and the second electrode 106.
  • a metal oxide layer 104 as a first metal oxide layer disposed in contact with the main surface (that is, the bottom surface), and a first insulating film covering the first electrode 103, the second electrode 106, and the metal oxide layer 104. (insulating films 107a to 107c, 109a and 109b).
  • the first insulating film has an opening 106a that exposes the other surface (that is, the upper surface) opposite to the main surface of the second electrode 106 without being covered by the first insulating film.
  • the metal layer 106s is also removed from the opening 106a to expose the second electrode 106.
  • This hydrogen sensor 100 has three terminals (first terminal TE1, second terminal TE2, and third terminal BE) for connection with the outside.
  • the first terminal TE1 and the second terminal TE2 are connected to the other surface of the second electrode 106 via a via 108.
  • the third terminal BE is connected to the other surface (that is, the lower surface) opposite to the main surface (that is, the upper surface) of the first electrode 103 via the wiring 114 and the via 108.
  • one of the first terminal TE1 and the second terminal TE2 and the third Terminal BE is connected to another resistance element as one end and the other end of hydrogen sensor 100.
  • the hydrogen sensor 100 shown in this figure is a dual-use type that can be used in both horizontal mode and vertical mode, but the hydrogen sensor composing the hydrogen detection device 10 is not limited to such a dual-use type.
  • it may be a type dedicated to horizontal mode in which the third terminal BE is not formed.
  • the first electrode 103 is a planar electrode and has two surfaces. One of the two surfaces of the first electrode 103 (that is, the upper surface in FIG. 2A) is in contact with the metal oxide layer 104, and the other surface (that is, the lower surface in FIG. 2A) is in contact with the insulating film 107a and the via 108. come into contact with The first electrode 103 has a rectangular shape with the same size as the second electrode 106 in FIG. 2B.
  • the first electrode 103 may be made of a material such as tungsten, nickel, tantalum, titanium, aluminum, tantalum nitride, titanium nitride, or the like, which has a lower standard electrode potential than the metal constituting the metal oxide.
  • the first electrode 103 in FIG. 2A is formed of, for example, a transition metal nitride such as tantalum nitride (TaN) or titanium nitride (TiN), or a stack thereof.
  • a transition metal nitride such as tantalum nitride (TaN) or titanium nitride (TiN)
  • TiN titanium nitride
  • the metal oxide layer 104 is sandwiched between the two opposing main surfaces of the first electrode 103 and the second electrode 106, is composed of a metal oxide as a gas-sensitive resistive film, and is in contact with the second electrode 106. It has a resistance value that changes reversibly depending on the presence or absence of hydrogen-containing gas in the gas.
  • the metal oxide layer 104 only needs to have a property that its resistance changes with hydrogen.
  • the metal oxide layer 104 is made of an oxygen-deficient metal oxide.
  • the base metal of the metal oxide layer 104 is tantalum (Ta), hafnium (Hf), titanium (Ti), zirconium (Zr), niobium (Nb), tungsten (W), nickel (Ni), iron (Fe), etc. may be selected from at least one transition metal and aluminum (Al).
  • the "oxygen deficiency degree" of a metal oxide refers to the amount of oxygen deficiency in the metal oxide relative to the amount of oxygen in an oxide with a stoichiometric composition composed of the same elements as the metal oxide. Refers to the ratio.
  • the insufficient amount of oxygen is the value obtained by subtracting the amount of oxygen in the metal oxide from the amount of oxygen in the metal oxide having a stoichiometric composition. If there are multiple metal oxides with stoichiometric composition composed of the same element as the metal oxide, the degree of oxygen deficiency of the metal oxide is It is defined based on the one having the highest resistance value. Stoichiometric metal oxides are more stable and have higher resistance values than metal oxides of other compositions.
  • the oxide having the stoichiometric composition according to the above definition is Ta 2 O 5 , so it can be expressed as TaO 2.5 .
  • a metal oxide with excess oxygen has a negative oxygen deficiency degree.
  • the degree of oxygen deficiency may take a positive value, 0, or a negative value.
  • An oxide with a low degree of oxygen deficiency has a high resistance value because it is closer to an oxide with a stoichiometric composition, and an oxide with a higher degree of oxygen deficiency has a low resistance value because it is closer to the metal constituting the oxide.
  • the metal oxide layer 104 shown in FIG. 2A includes a first layer 104a in contact with the first electrode 103, a second layer 104b in contact with the first layer 104a and the second electrode 106, and an insulating separation layer 104i.
  • the degree of oxygen deficiency in the second layer 104b is smaller than that in the first layer 104a.
  • the first layer 104a is TaOx .
  • the second layer 104b is made of Ta 2 O 5 , which has a lower degree of oxygen deficiency than the first layer 104a.
  • the metal oxide layer 104 has an insulating separation layer 104i on the outer periphery of the first electrode 103 in a plan view.
  • Planar view here refers to viewing the hydrogen sensor 100 according to the present disclosure from a certain viewpoint in the stacking direction of FIG. It refers to viewing from a viewpoint in the normal direction of the surface, for example, when looking at the top surface of the hydrogen sensor 100 shown in FIG. 2B.
  • the resistance state of the metal oxide layer 104 becomes smaller depending on the amount of hydrogen-containing gas in contact with the second electrode 106 (as the amount increases). Specifically, when a hydrogen-containing gas is present in the gas to be detected, hydrogen atoms are dissociated from the hydrogen-containing gas at the second electrode 106. The dissociated hydrogen atoms penetrate into the metal oxide layer 104 and form an impurity level. In particular, it is concentrated near the interface with the second electrode 106, making the thickness of the second layer 104b apparently thin. As a result, the resistance value of metal oxide layer 104 decreases.
  • the second electrode 106 is a planar electrode that has hydrogen dissociation properties and has two surfaces. One of the two surfaces of the second electrode 106 (i.e., the lower surface in FIG. 2A) is in contact with the metal oxide layer 104, and the other surface (i.e., the upper surface in FIG. 2A) is in contact with the metal layer 106s and the outside air. .
  • the second electrode 106 has an exposed portion 106e exposed to the outside air within the opening 106a.
  • the second electrode 106 is made of, for example, a noble metal such as platinum (Pt), iridium (Ir), or palladium (Pd), or nickel (Ni), or an alloy containing at least one of these.
  • the second electrode 106 in FIG. 2A is assumed to be platinum (Pt).
  • Two terminals, ie, a first terminal TE1 and a second terminal TE2, are connected to the second electrode 106.
  • the first terminal TE1 is connected to the second electrode 106 via the via 108.
  • the second terminal TE2 is connected to the second electrode 106 via the via 108.
  • the first terminal TE1 and the second terminal TE2 are connected to an external detection circuit (here, a resistor R1) that drives the hydrogen sensor 100 via the openings TE1a and TE2a. and the reference element 100a).
  • the first terminal TE1 and the second terminal TE2 are arranged at positions sandwiching the exposed portion 106e of the second electrode 106 in a plan view, as shown in FIG. 2B.
  • the exposed portion 106e of the second electrode 106 is energized, that is, a current is caused to flow through the exposed portion 106e. It is thought that this energization of the exposed portion 106e of the second electrode 106 activates the hydrogen dissociation effect of the exposed portion 106e.
  • the predetermined voltages may be voltages having opposite polarities.
  • the hydrogen sensor 100 changes the resistance value between the first terminal TE1 and the second terminal TE2 when gas molecules containing hydrogen atoms touch the exposed portion 106e while the exposed portion 106e is energized.
  • this detection is also referred to as "horizontal mode"
  • gas molecules containing a low concentration of hydrogen atoms are detected.
  • the third terminal BE is connected to the first electrode 103 via the opening BEa, the via 108, the wiring 114, and the via 108.
  • the third terminal BE is connected to an external detection circuit that drives the hydrogen sensor 100 via the opening BEa.
  • gas molecules containing hydrogen atoms touch the exposed portion 106e while the exposed portion 106e is energized, thereby changing the resistance between the first electrode 103 and the second electrode 106.
  • gas molecules containing hydrogen atoms come into contact with the exposed portion 106e while the exposed portion 106e is energized, thereby causing a gap between at least one of the first terminal TE1 and the second terminal TE2 and the third terminal BE.
  • change the resistance value of Gas molecules containing a high concentration of hydrogen atoms are also detected by the above-mentioned detection circuit detecting this change in resistance value (this detection is also referred to as "vertical mode").
  • the insulating film 102, the insulating films 107a to 107c, and the insulating films 109a and 109b, which cover the main parts of the hydrogen sensor 100 are formed of a silicon oxide film, a silicon nitride film, or the like.
  • a metal layer 106s is formed on the upper surface of the second electrode 106 other than the opening 106a.
  • the metal layer 106s is made of TiAlN, for example, and is formed as an etching stopper for via formation, but is not essential.
  • the stacked body of the first electrode 103, the metal oxide layer 104, and the second electrode 106 is an element that can be used as a storage element of a resistance change memory (ReRAM).
  • ReRAM resistance change memory
  • two states, a high resistance state and a low resistance state, among the states that the metal oxide layer 104 can take are used as a digital storage element.
  • the hydrogen sensor 100 of the present disclosure utilizes a high resistance state among the possible states of the metal oxide layer 104.
  • the hydrogen detection device 10 according to the present disclosure is not limited to the use of a high resistance state, and may be of a form that uses a resistance state.
  • the metal oxide layer 104 has a two-layer structure consisting of a first layer 104a made of TaO x and a second layer 104b made of Ta 2 O 5 with a small oxygen deficiency.
  • a single layer structure made of Ta 2 O 5 or TaO x which has a small degree of oxygen deficiency, may be used.
  • FIG. 3 is a cross-sectional view showing a configuration example of the reference element 100a shown in FIG. 1.
  • the reference element 100a corresponds to the hydrogen sensor 100 shown in FIG. 2A in which the opening 106a is not formed (that is, the opening 106a is closed).
  • the reference element 100a includes, as main components, a third electrode (first electrode 103 in FIG. 3) and a fourth electrode (second electrode 106 in FIG. 3) whose main surfaces are arranged to face each other.
  • a second metal oxide layer (metal oxide layer in FIG. 3) disposed in contact with the main surface of the third electrode (first electrode 103 in FIG. 3) and the main surface of the fourth electrode (second electrode 106 in FIG. 3) material layer 104), a third electrode (first electrode 103 in FIG.
  • a fourth electrode (second electrode 106 in FIG. 3), and a second metal oxide layer (metal oxide layer 104 in FIG. 3). and a second insulating film (insulating films 107a to 107c, 109a and 109b in FIG. 3).
  • the second insulating film does not have an opening that exposes the other surface facing the main surface of the fourth electrode (second electrode 106 in FIG. 3) without being covered by the second insulating film.
  • FIG. 4A is a schematic diagram showing an example of the overall configuration of the hydrogen detection device 10 according to the embodiment.
  • the hydrogen sensor 100 and the reference element 100a are of a type exclusively for horizontal mode (that is, a type that does not have the third terminal BE), and their cross-sectional structures are shown, while the resistors R1 and R2 are , functionally illustrated.
  • the feature of the hydrogen detection device 10 is that four resistance elements (hydrogen sensor 100, reference element 100a, resistors R1 and R2) forming a bridge circuit are formed on one semiconductor chip 12. More specifically, the distance in plan view between the hydrogen sensor 100 and the reference element 100a, which have basically the same structure, is 2000 ⁇ m or less.
  • FIG. 4B is a plan view showing an example of the layout of the wiring patterns of the hydrogen sensor 100 and the reference element 100a in the hydrogen detection device 10 shown in FIG. 4A.
  • This plan view shows wiring that connects the second terminal TE2 of the hydrogen sensor 100 in which the opening 106a is formed and the second terminal TE2 of the reference element 100a in which no opening is formed, and also connects to the terminal A of the bridge circuit.
  • a pattern A1, a wiring pattern B1 connecting the first terminal TE1 of the hydrogen sensor 100 to the terminal B of the bridge circuit, and a wiring pattern D1 connecting the first terminal TE1 of the reference element 100a to the terminal D of the bridge circuit are illustrated.
  • FIG. 5 is a flowchart showing a method for manufacturing the hydrogen detection device 10 according to the embodiment. Here, a manufacturing method focusing on the hydrogen sensor 100 and the reference element 100a among the four resistance elements that constitute the hydrogen detection device 10 shown in FIG. 4A is shown.
  • HDP-FSG fluorine oxide film using high-density plasma
  • An insulating film 102 such as (added glass), an insulating film 107a as an interlayer insulating film such as P-TEOS (plasma-generated tetraethoxysilane), a first electrode 103 such as TaN or TiN, Ta 2 O 5 and TaO 1.5
  • Insulating film 109a as a protective film such as (oxynitride film), first terminal TE1 and second terminal TE2 as electrodes such as Au, insulation as an interlayer insulating film such as HDP-NSG (nitrogen added glass by high-density plasma), etc.
  • a laminate consisting of the film 107c and an insulating film 109b as a protective film such as P-SiON is formed (laminate formation step S10). Through this process, an intermediate product of the hydrogen sensor 100 before the opening 106a is formed and a completed product of the reference element 100a are produced.
  • the intermediate product of the hydrogen sensor 100 is subjected to photolithography (pattern transfer and etching) to expose the metal layer 106s, the insulating film 107b, the insulating film 109a, and the insulating film so that the upper surface of the second electrode 106 is exposed.
  • 107c and a part of the insulating film 109b are removed in a rectangular shape to form the opening 106a of the hydrogen sensor 100 (opening formation step S11).
  • the hydrogen sensor 100 is completed.
  • FIG. 6 is a diagram showing experimental results regarding the time dependence and distance dependence of the output voltage (differential voltage) of the hydrogen detection device 10 according to the embodiment.
  • FIG. 6 shows that the distance between the hydrogen sensor 100 of the hydrogen detection device 10 shown in FIG. 4A and the reference element 100a in plan view is changed as a parameter in an environment where no hydrogen exists, and the bridge circuit is It is a diagram recording the time (horizontal axis) dependence of the differential voltage (vertical axis) appearing between terminals BD. Regarding distances, samples of the hydrogen detection device 10 having distances of 27 ⁇ m, 1920 ⁇ m, 3300 ⁇ m, 5220 ⁇ m, and 6600 ⁇ m were manufactured, and the differential voltages were measured.
  • the differential voltage was almost 0 (V), indicating the ideal value, but at distances of 3300 ⁇ m, 5220 ⁇ m, and 6600 ⁇ m, the differential voltage deviated from the ideal value. showed a significant value (i.e. offset voltage). Note that, regardless of the distance, the differential voltage hardly changed over time.
  • FIG. 6(b) is a diagram in which the results obtained in FIG. 6(a) are rewritten into the dependence of the differential voltage (vertical axis) on the distance (horizontal axis).
  • the bridge circuit can be bridged without generating an offset voltage due to the distance between them. It can be seen that the circuit enables highly sensitive and stable hydrogen detection.
  • FIG. 7 is a diagram showing experimental results regarding the reaction of the hydrogen detection device 10 according to the embodiment to hydrogen.
  • the hydrogen detection device 10 in which the distance between the hydrogen sensor 100 and the reference element 100a is 27 ⁇ m, it is confirmed that the differential voltage is 0 mV in an environment where hydrogen does not exist, and then the hydrogen detection device 10 is The environment was changed to a hydrogen concentration of 0.01% for a period of 300 msec, then replaced with 100% air (that is, a hydrogen concentration of 0%) for a period of 600 msec, and then a hydrogen concentration of 0.1% for a period of 300 msec.
  • the air was replaced with 100% (i.e., hydrogen concentration 0%), and then the hydrogen concentration was changed to 1.0% during the 300 msec period, and after that, the air was replaced with 100% (i.e., hydrogen concentration 0%).
  • the difference voltage (vertical axis) output by the hydrogen detection device 10 when the hydrogen detection device 10 is replaced with a hydrogen concentration of 0% is shown. Note that the concentration value is a percentage (%) of the volume ratio of the gas.
  • the hydrogen detection device 10 which includes the hydrogen sensor 100 and the reference element 100a that are arranged at a distance of 27 ⁇ m, outputs a differential voltage in accordance with changes in the hydrogen concentration of the environment.
  • the differential voltage output from the hydrogen detection device 10 returns to the base voltage of 0 mV and does not generate an offset voltage when the environment is free of hydrogen.
  • the distance between the hydrogen sensor 100 and the reference element 100a was 27 ⁇ m, but it is presumed that similar results would be obtained if the distance was 2000 ⁇ m or less.
  • FIG. 8 is a schematic diagram showing an example of the overall configuration of a hydrogen detection device 10a according to Modification 1 of the embodiment.
  • the difference from the hydrogen detection device 10 according to the embodiment shown in FIG. 4A is that in the hydrogen detection device 10a according to the first modification, the hydrogen sensor 100 and the reference element are Only the resistor 100a is formed on one semiconductor chip 12, and the other two resistors R1 and R2 are mounted outside the semiconductor chip 12 (on a printed circuit board, etc., not shown).
  • the hydrogen sensor 100 and the reference element 100a are formed on one semiconductor chip 12 and have basically the same structure, and Since it is similar to the hydrogen detection device 10 according to the embodiment in that the distance between them in plan view is 2000 ⁇ m or less, it has the same characteristics as the hydrogen detection device 10 according to the embodiment (see FIGS. 6 and 7). It is considered to have the indicated properties).
  • FIG. 9A is a schematic diagram showing an example of the overall configuration of a hydrogen detection device 10b according to Modification 2 of the embodiment. The difference from the hydrogen detection device 10 according to the embodiment shown in FIG. The opening 110a is once formed, and then the inner surface and bottom surface of the opening 110a are covered with the hydrogen-impermeable film 110.
  • FIG. 9B is a plan view showing an example of the layout of the wiring patterns of the hydrogen sensor 100 and the reference element 100b in the hydrogen detection device 10b shown in FIG. 9A.
  • This plan view shows wiring that connects the second terminal TE2 of the hydrogen sensor 100 in which the opening 106a is formed and the second terminal TE2 of the reference element 100b in which the opening 110a is formed, and also connects to the terminal A of the bridge circuit.
  • a pattern A1, a wiring pattern B1 connecting the first terminal TE1 of the hydrogen sensor 100 to the terminal B of the bridge circuit, and a wiring pattern D1 connecting the first terminal TE1 of the reference element 100b to the terminal D of the bridge circuit are illustrated.
  • the hydrogen sensor 100 and the reference element 100b are formed on one semiconductor chip 12 and have basically the same structure, and Since it is similar to the hydrogen detection device 10 according to the embodiment in that the distance between them in plan view is 2000 ⁇ m or less, it has the same characteristics as the hydrogen detection device 10 according to the embodiment (see FIGS. 6 and 7). It is considered to have the indicated properties).
  • FIG. 10 is a flowchart showing a method for manufacturing a hydrogen detection device 10b according to modification 2 of the embodiment. Here, a manufacturing method focusing on the hydrogen sensor 100 and the reference element 100b among the four resistance elements that constitute the hydrogen detection device 10b shown in FIG. 9A is shown.
  • HDP-FSG fluorine oxide film using high-density plasma
  • An insulating film 102 such as (added glass), an insulating film 107a as an interlayer insulating film such as P-TEOS (plasma-generated tetraethoxysilane), a first electrode 103 such as TaN or TiN, Ta 2 O 5 and TaO 1.5
  • a laminate consisting of the film 107c and an insulating film 109b as a protective film such as P-SiON is formed (laminate formation step S20). Through this step, an intermediate product of the hydrogen sensor 100 before the opening 106a is formed and an intermediate product of the reference element 100b before the opening 110a is formed are produced.
  • the metal layer 106s, The insulating film 107b, the insulating film 109a, the insulating film 107c, and a part of the insulating film 109b are removed in a rectangular shape to form the opening 106a of the hydrogen sensor 100 and the opening 110a of the reference element 100b (opening formation step S21 ). Through this process, the hydrogen sensor 100 is completed.
  • the inner surface and bottom surface of the opening 110a formed in the reference element 100b are covered with a hydrogen-impermeable film 110 such as P-SiON (hydrogen-impermeable film forming step S22).
  • a reference element 100b is completed in which an opening 110a whose inner side and bottom are covered with a hydrogen-impermeable film 110 is formed.
  • the formation of the hydrogen-impermeable film 110 may be performed in the same process as the formation of the insulating film 109b (that is, film formation using the same material).
  • FIG. 11 is a schematic diagram showing an example of the overall configuration of a hydrogen detection device 10c according to Modification 3 of the embodiment.
  • the difference from the hydrogen detection device 10b according to the second modification of the embodiment shown in FIG. 9A is that in the hydrogen detection device 10c according to the third modification, the hydrogen sensor Only the resistor 100 and the reference element 100b are formed on one semiconductor chip 12, and the other two resistors R1 and R2 are mounted outside the semiconductor chip 12 (on a printed circuit board, etc., not shown).
  • the hydrogen sensor 100 and the reference element 100b are formed on one semiconductor chip 12 and have basically the same structure, and Since it is similar to the hydrogen detection device 10 according to the embodiment in that the distance between them in plan view is 2000 ⁇ m or less, it has the same characteristics as the hydrogen detection device 10 according to the embodiment (see FIGS. 6 and 7). It is considered to have the indicated properties).
  • the hydrogen detection device 10 and the like includes the hydrogen sensor 100 which is the first resistance element that constitutes the bridge circuit, the resistor R1 which is the second resistance element, and the reference element which is the third resistance element. 100a and a resistor R2 which is a fourth resistance element, one end of the hydrogen sensor 100 and one end of the resistor R1 are connected, one end of the reference element 100a and one end of the resistor R2 are connected, and the hydrogen sensor 100 is The other end and the other end of the reference element 100a are connected, the other end of the resistor R1 and the other end of the resistor R2 are connected, and among the hydrogen sensor 100, the resistor R1, the reference element 100a, and the resistor R2, At least the hydrogen sensor 100 and the reference element 100a are formed on one semiconductor chip 12.
  • the hydrogen sensor 100 includes a first electrode 103 and a second electrode 106 whose main surfaces face each other, and a first electrode 103 and a second electrode 106 which are arranged in contact with the main surfaces of the first electrode 103 and the second electrode 106.
  • the first insulating film has an opening 106a that exposes the other surface facing the main surface of the second electrode 106 without being covered by the first insulating film.
  • the reference element 100a includes a third electrode (the first electrode 103 in FIG.
  • a fourth electrode (the second electrode 106 in FIG. 3), which are arranged so that their main surfaces face each other, and a third electrode (the second electrode in FIG. 3).
  • a second metal oxide layer (metal oxide layer 104 in FIG. 3) disposed in contact with the main surface of the first electrode 103) and the main surface of the fourth electrode (second electrode 106 in FIG. 3);
  • a second insulating film (see FIG. 3) that covers the electrode (first electrode 103 in FIG. 3), fourth electrode (second electrode 106 in FIG. 3), and second metal oxide layer (metal oxide layer 104 in FIG. 3).
  • the second insulating film has the other surface facing the main surface of the fourth electrode (second electrode 106 in FIG. 3) covered with the second insulating film. It does not have an opening that exposes the device without removing it.
  • the hydrogen sensor 100 and the reference element 100a that constitute a highly sensitive bridge circuit are resistance change elements that basically have the same structure and are formed on one semiconductor chip 12, hydrogen is present.
  • the resistance values are very close to each other, but in an environment where hydrogen is present, the resistance balance of the bridge circuit made up of them is disrupted, and a potential difference occurs between the two connection points. Therefore, a hydrogen detection device that does not necessarily require a heater and can operate stably is realized.
  • the distance between the hydrogen sensor 100 and the reference element 100a is 2000 ⁇ m or less.
  • the hydrogen sensor 100 has a first terminal TE1 and a second terminal TE2, which are connected to the other surface of the second electrode 106 via a via 108, as one end and the other end of the hydrogen sensor 100.
  • the hydrogen sensor 100 can be used in a highly sensitive horizontal mode, thereby realizing a hydrogen detection device suitable for detecting low concentration hydrogen.
  • the opening 106a is formed between the first terminal TE1 and the second terminal TE2 in a plan view of the second electrode 106. Thereby, the aperture 106a is located on the current path, and a change in resistance in the aperture 106a can be reliably detected.
  • the hydrogen sensor 100 has a terminal (first terminal TE1 or second terminal TE2) connected to the other surface of the second electrode 106 via a via 108 and a first terminal as one end and the other end of the hydrogen sensor 100.
  • the electrode 103 may have a third terminal BE connected to the other surface opposite to the main surface via a via 108.
  • the hydrogen sensor 100 has lower sensitivity than when used in the horizontal mode, so a hydrogen detection device suitable for detecting high concentration hydrogen is realized.
  • the second insulating film in the reference element 100b has an inner surface and a bottom surface formed by the hydrogen-impermeable film 110 at a position corresponding to the opening 106a in the first insulating film of the hydrogen sensor 100. 9A (opening 110a in FIG. 9A).
  • the hydrogen sensor 100, the resistor R1, the reference element 100a, and the resistor R2 are formed on one semiconductor chip 12. This realizes a small-sized hydrogen detection device.
  • the hydrogen detection device 10 and the like includes a hydrogen sensor 100 that is a first resistance element that constitutes a bridge circuit, a resistor R1 that is a second resistance element, a reference element 100a that is a third resistance element, and a hydrogen sensor 100 that is a first resistance element that constitutes a bridge circuit.
  • a method for manufacturing a hydrogen detection device 10 including a resistor R2, which is a four-resistance element, includes a laminate forming step S20 for forming a laminate for the hydrogen sensor 100 and a reference element 100a, and an opening in the formed laminate.
  • a first electrode 103 and a second electrode whose principal surfaces are arranged facing each other are formed as a laminate for the hydrogen sensor 100 and the reference element 100a.
  • the opening forming step S21 at least the other surface of the insulating film 107b and the like opposite to the main surface of the second electrode 106 is formed.
  • a first opening (opening 106a) is formed to expose the substrate without being covered with the insulating film 107b or the like.
  • the hydrogen sensor 100 and the reference element 100a which constitute a highly sensitive bridge circuit, are resistance change elements having basically the same structure and are formed on one semiconductor chip 12, so a heater is not necessarily required.
  • a hydrogen detection device is manufactured that can operate stably without the need for hydrogen detection.
  • the second electrode 106 is attached to the insulating film 107b etc. with respect to the stacked body of the reference element 100b.
  • the method for manufacturing a hydrogen detection device further includes forming a second opening (110a) that exposes the other surface opposite to the main surface of the insulating film 107b without being covered with the insulating film 107b or the like.
  • the hydrogen impermeable film forming step S22 includes a hydrogen impermeable film forming step S22 of covering the inner side surface and bottom surface of the hydrogen impermeable film 110.
  • the distance between the hydrogen sensor 100 and the reference element 100a was 2000 ⁇ m or less, but it does not necessarily have to be this distance or less. If the hydrogen sensor 100 and the reference element 100a, which have basically the same structure, are formed on the same semiconductor chip 12, they will have extremely similar characteristics, so even if the distance between the hydrogen sensor 100 and the reference element 100a exceeds 2000 ⁇ m, This is because, depending on the concentration of hydrogen to be detected, the minute offset voltage output from the bridge circuit may not be a hindrance.
  • any distance can be set as long as the distance between the other hydrogen sensor 100 and the reference element 100a is 2000 ⁇ m or less.
  • the distance may be 1500 ⁇ m or less, 1000 ⁇ m or less, 500 ⁇ m or less, 100 ⁇ m or less, 50 ⁇ m or less, 30 ⁇ m or less, the minimum distance in the manufacturing process, etc.
  • a circuit other than the hydrogen detection device such as a buffer that amplifies the differential voltage output by the bridge circuit.
  • a constant voltage power supply circuit or the like that generates a voltage to be applied to the amplifier and bridge circuit may also be formed.
  • the hydrogen detection device according to the present disclosure can be used as a hydrogen detection device that uses a bridge circuit and operates stably with high sensitivity, for example, as a hydrogen detection device installed in a fuel cell vehicle.

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