Semiconductor sensor and its manufacturing method

Abstract

The semiconductor sensor (100) comprises a semiconductor detection element (3), a detection chamber (7) to the inside of which the semiconductor detection element (3) is fixed, a signal terminal (11) having one end exposed inside the detection chamber (7) and the other end exposed to the outside from the detection chamber (7) for outputting an electrical signal output from the semiconductor detection element (3) to the outside, a wire (10) connecting the semiconductor detection element (3) and a signal terminal exposed portion (11a) which is a portion of one end of the signal terminal (11) exposed inside the detection chamber (7), and a protective film which continuously covers the semiconductor detection element (3), the wire (10), and the signal terminal exposed portion (11a), and the protective film is an inorganic barrier film (19).

Description

[Technical field]

[0001] The present disclosure relates to a semiconductor sensor and a method for manufacturing the same. [Background technology]

[0002] Semiconductor sensors have been used for controlling the power source systems of various types of mobility, including automobiles. In a semiconductor sensor, a semiconductor detection element is provided in a detection chamber, and the semiconductor detection element is exposed to a medium to be measured that is introduced into the detection chamber. The physical quantity detected by the semiconductor detection element is converted into an electrical signal, which is then transmitted via a wire to a signal terminal that is partially exposed in the detection chamber, and output to the outside via the signal terminal. By appropriately using the semiconductor detection element according to the physical quantity to be measured, various physical quantities such as temperature and pressure can be measured.

[0003] Conventionally, the driving source for such mobility has basically been an internal combustion engine. In an internal combustion engine, for example, semiconductor pressure sensors are attached to the intake system and exhaust system. Semiconductor pressure sensors are used at about 10 to 300 kPa in the intake system, whereas they are used at about 300 to 600 kPa in the exhaust system. In particular, the exhaust system has a higher pressure range than the intake system, and the measurement medium contains corrosive substances such as water, nitrogen oxides, and sulfur oxides. Therefore, these corrosive substances are easily penetrating the semiconductor pressure sensor, and therefore the semiconductor pressure sensor is required to have even higher chemical resistance and corrosion resistance.

[0004] Therefore, a semiconductor pressure sensor configuration with improved chemical resistance and corrosion resistance has been disclosed so that it can be used in such severe applications (for example, see Patent Document 1). In the configuration disclosed in Patent Document 1, the semiconductor detection element, the exposed portion of the signal terminal, and conductive members such as wires are covered with a polymer protective film made of a fluorine-containing polyparaxylylene-based polymer that has high chemical resistance and corrosion resistance. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent No. 5884921 Summary of the Invention [Problem to be solved by the invention]

[0006] By covering the semiconductor detection element, the exposed portion of the signal terminal, the conductive members such as the wires, etc. with a polyparaxylylene-based polymer, the semiconductor detection element, the exposed portion of the signal terminal, the conductive members such as the wires, etc. can be protected from corrosive substances, and corrosion of these members can be prevented. However, through various durability tests and subsequent disassembly investigations, the author found that the semiconductor pressure sensor disclosed in Patent Document 1 has a weak part in the protective film, the covering property of the protective film is insufficient, and there is a serious problem in the reliability of the semiconductor pressure sensor. The two problems are explained below.

[0007] First, the first problem will be described. In the semiconductor pressure sensor disclosed in Patent Document 1, which uses a semiconductor pressure detection element as the detection element, there are weak parts where a high-quality protective film is not formed with sufficient thickness in structural parts with a high aspect ratio such as narrow and deep grooves, and in the overhanging part of the ball at the base of the wire. The existence of the weak parts is basically caused by the protective film being formed by CVD (Chemical Vapor Deposition). In CVD, a relatively more conformal film is formed compared to PVD (Physical Vapor Deposition) represented by vacuum deposition or sputtering. Nevertheless, in principle, even CVD cannot form a sufficient film on the above-mentioned parts.

[0008] In fact, when the semiconductor pressure sensor was disassembled and cross-sectional observation was performed immediately after the formation of the protective film and after all the manufacturing processes were completed, the presence of various types of fragile parts was confirmed. The most typical example is a fragile part in which the protective films grown from both sides do not fully fuse with each other even when they meet at the center of the two during the film formation process of the protective film, resulting in a porous structure with so-called voids remaining. In addition, there are many cases in which this porous structure is completely broken and cracked due to external stress such as heat, stress, vibration, and impact during the manufacturing process or during use. Therefore, when such a semiconductor pressure sensor is installed in the exhaust system of an internal combustion engine, there is a problem that corrosive substances penetrate from the fragile parts and corrode the wires, electrode pads, etc., causing a fatal failure of the semiconductor pressure sensor.

[0009] Next, the second issue will be explained. In recent years, climate change countermeasures have become an urgent issue worldwide, so much so that it is said that we have entered the age of the boiling earth. As part of the countermeasures, there is a strong social demand for decarbonization and carbon neutrality in order to reduce greenhouse gases in all fields. Mobility is one of the fields that urgently needs to be addressed, and fuel cell systems have begun to spread as an effective means of response. The use of many semiconductor sensors is also required in fuel cell systems. However, unlike the exhaust system of an internal combustion engine that contains corrosive substances, it has been found that there is a serious problem with the reliability of the semiconductor pressure sensor disclosed in Patent Document 1 even in fuel cell systems that contain almost no corrosive substances. That is, the problem is that the semiconductor pressure sensor is very vulnerable to the water vapor contained in the hydrogen gas used as fuel for the fuel cell system and the condensation water brought about by the water vapor.

[0010] The vulnerability of semiconductor pressure sensors to water vapor and condensed water is mainly due to the fact that the polymer protective film made of polyparaxylylene polymer used as a protective film has almost no water vapor barrier properties. Specifically, the water vapor transmission rate was measured using the differential pressure gas transmission rate measurement method specified in ISO1105-1. For the measurement, a test piece was used in which a 125 μm thick PEN film (TEONEX manufactured by Toyobo) was used as the base material, and a 10 μm thick layer of dix-C (manufactured by Daisan Kasei), a representative example of a polyparaxylylene polymer film, was formed on top of it. Water vapor at 40°C and 90% RH was applied to the test piece. Water vapor permeates by diffusing inside the dix-C film, so the water vapor transmission rate is a time-dependent result. In the plot of water vapor transmission rate, the steady state portion represents the transmission rate of the material. The steady state portion is approximately 1.5 g / m 2 / day. This value is almost the same as the water vapor transmission rate of the PEN film, which is the base material. In other words, it suggests that dix-C does not have significant water vapor barrier properties. As described above, since the protective film used in the semiconductor sensor disclosed in Patent Document 1 does not have water vapor barrier properties, when the semiconductor pressure sensor disclosed in Patent Document 1 is installed in the fuel supply system of a fuel cell system, the water vapor contained in the fuel gas will easily permeate the protective film even if the measurement medium does not contain a corrosive substance. Therefore, there was a problem that each electronic component such as a semiconductor detection element would experience fluctuations, malfunctions, and failures due to water vapor.

[0011] Furthermore, it was also found that condensation water brought about by water vapor may cause even more fatal defects according to the following mechanism. When the semiconductor pressure sensor disclosed in Patent Document 1 is used in a fuel cell system and exposed to high-temperature and high-humidity hydrogen gas, which is the measurement target medium, first, hydrogen and water vapor are absorbed inside the gel that seals the semiconductor detection element, etc. Thereafter, the longer the operation time of the fuel cell system, the more water vapor accumulates inside the gel. When the fuel cell system is stopped after reaching this state, the hydrogen absorbed in the gel is released from the gel to the outside in a relatively short time of about several minutes. On the other hand, water vapor is difficult to release from the gel to the outside, and most of it continues to remain inside the gel. Then, as the temperature of the environment in which the fuel cell system is placed drops, the absorbed water vapor condenses inside the gel. In particular, in applications such as automobiles, condensation occurs significantly in winter, at night in cold areas, and in situations where the vehicle is used outdoors. In this way, once the water vapor condenses and undergoes a phase change to condensed water, its release to the outside is significantly reduced, so the condensed water generated by the condensation remains inside the gel and on the surface of each electronic component.

[0012] The condensed water generated by this condensation spreads in layers. The semiconductor pressure sensor disclosed in Patent Document 1 has the above-mentioned fragile part. Therefore, even if the measurement medium does not contain a corrosive substance, the condensed water that permeates from the fragile part forms an electric circuit that electrically connects conductive parts with different potentials on the semiconductor detection element, wires, signal terminals, etc. Since the potentials are different, the condensed water causes electrolysis, which causes a serious problem of corroding these conductive members.

[0013] A specific example of an application of the semiconductor sensor is the above-mentioned fuel cell system, such as for measuring the pressure of hydrogen containing high-temperature, high-humidity water vapor in the anode subsystem of the fuel cell system, and for measuring the pressure of high-temperature, high-humidity water vapor, which is generated water, in the cathode subsystem. Alternatively, an example of an application of the semiconductor sensor to other systems is for measuring the EGR gas pressure in an EGR system containing corrosive gas. In order to use the semiconductor sensor in these applications, the semiconductor sensor needs to be resistant to high-temperature, high-humidity water vapor and corrosive substances.

[0014] Therefore, an object of the present disclosure is to obtain a semiconductor sensor that has high durability and reliability even when the medium to be measured contains high-temperature and high-humidity water vapor and corrosive substances.

[0015] Another object of the present invention is to provide a method for manufacturing a semiconductor sensor that can stably manufacture a semiconductor sensor having high durability and reliability with high quality. [Means for solving the problem]

[0016] The semiconductor sensor of the present disclosure comprises a semiconductor detection element, a detection chamber to which the semiconductor detection element is fixed inside, a signal terminal having one end exposed inside the detection chamber and the other end exposed to the outside from the detection chamber for outputting an electrical signal output from the semiconductor detection element to the outside, a wire connecting the semiconductor detection element and a signal terminal exposed portion which is a portion of one end side of the signal terminal exposed inside the detection chamber, and a protective film continuously covering the semiconductor detection element, the wire, and the signal terminal exposed portion, wherein the protective film is self-stopping type It is an inorganic barrier film.

[0017] The method for manufacturing a semiconductor sensor according to the present disclosure includes a member preparing step of preparing a semiconductor detection element, a detection chamber for fixing the semiconductor detection element inside, a signal terminal for outputting an electrical signal output from the semiconductor detection element to the outside, and a wire; a member fixing step of fixing the semiconductor detection element inside the detection chamber, exposing one end side of the signal terminal inside the detection chamber, and fixing the signal terminal to the detection chamber such that the other end side of the signal terminal is exposed from the detection chamber to the outside; a connecting step of connecting one end of the wire to the semiconductor detection element, and connecting the other end of the wire to a signal terminal exposed portion which is a portion of the one end side of the signal terminal exposed inside the detection chamber; and a film forming step of continuously covering the semiconductor detection element, the wire, and the signal terminal exposed portion with a protective film, the protective film being self-stopping type The film forming step is an inorganic barrier film. self-stopping type The inorganic barrier film is coated by atomic layer deposition. Effect of the Invention

[0018] The semiconductor sensor of the present disclosure comprises a semiconductor detection element, a detection chamber inside which the semiconductor detection element is fixed, a signal terminal having one end exposed inside the detection chamber and the other end exposed from the detection chamber to the outside for outputting an electrical signal output from the semiconductor detection element to the outside, a wire connecting the semiconductor detection element and the signal terminal exposed portion which is the portion of one end of the signal terminal exposed inside the detection chamber, and a protective film continuously covering the semiconductor detection element, the wire, and the signal terminal exposed portion, and since the protective film is an inorganic barrier film, the inorganic barrier film exhibits high gas barrier properties even with a very thin film thickness. Therefore, a semiconductor sensor 100 having high durability and reliability can be obtained while maintaining high measurement accuracy without impairing the characteristics of the semiconductor sensor, even when the medium to be measured contains high-temperature and high-humidity water vapor and corrosive substances.

[0019] According to the manufacturing method of the semiconductor sensor disclosed herein, the method includes a member preparing step of preparing a semiconductor detection element, a detection chamber for fixing the semiconductor detection element inside, a signal terminal for outputting an electrical signal output from the semiconductor detection element to the outside, and a wire; a member fixing step of fixing the signal terminal to the detection chamber so that the semiconductor detection element is fixed inside the detection chamber, one end side of the signal terminal is exposed inside the detection chamber, and the other end side of the signal terminal is exposed from the detection chamber to the outside; a connection step of connecting one end of the wire to the semiconductor detection element and connecting the other end of the wire to a signal terminal exposed portion that is a portion of one end side of the signal terminal exposed inside the detection chamber; and a film forming step of continuously covering the semiconductor detection element, the wire, and the signal terminal exposed portion with a protective film, wherein the protective film is an inorganic barrier film, and since the inorganic barrier film is covered by an atomic layer deposition method in the film forming step, it is possible to form an inorganic barrier film with a highly uniform film thickness even for a structure with a high aspect ratio, such as the back of a very narrow and deep groove, and therefore it is possible to stably manufacture a semiconductor sensor with high durability and reliability with high quality. [Brief description of the drawings]

[0020] [Figure 1] 1 is a cross-sectional view showing an outline of a semiconductor sensor according to a first embodiment. [Diagram 2] 2 is a cross-sectional view showing an outline of a detection chamber of the semiconductor sensor according to the first embodiment. [Diagram 3] 1 is a cross-sectional view showing an outline of a main part of a semiconductor sensor according to a first embodiment. [Figure 4] 1 is a cross-sectional view showing an outline of a main part of a semiconductor sensor according to a first embodiment. [Diagram 5] 11 is a cross-sectional view showing an outline of a main part of a semiconductor sensor according to a second embodiment. FIG. [Figure 6] 11 is a cross-sectional view showing an outline of a main part of a semiconductor sensor according to a second embodiment. FIG. [Figure 7] 11 is a cross-sectional view showing an outline of a main part of a semiconductor sensor according to a second embodiment. FIG. [Figure 8] 11 is a cross-sectional view showing an outline of a main part of a semiconductor sensor according to a third embodiment. FIG. [Figure 9]11 is a cross-sectional view showing an outline of a main part of a semiconductor sensor according to a fourth embodiment. FIG. [Figure 10] 13 is a cross-sectional view showing an outline of a main part of a semiconductor sensor according to an embodiment 5. FIG. [Figure 11] 13 is a cross-sectional view showing an outline of a detection chamber of a semiconductor sensor according to a sixth embodiment. FIG. [Figure 12] 3A to 3C are diagrams illustrating a manufacturing process of the semiconductor sensor according to the first embodiment. [Figure 13] 5A to 5C are schematic cross-sectional views showing differences in the structure of a protective film depending on a film formation method. [Figure 14] FIG. 4 is a cross-sectional view showing an outline of a detection chamber of a semiconductor sensor of a comparative example. [Figure 15] 1 is a cross-sectional view showing an outline of a main part of a semiconductor sensor of a comparative example. [Figure 16] 1 is a cross-sectional view showing an outline of a main part of a semiconductor sensor of a comparative example. [Figure 17] 1 is a cross-sectional view showing an outline of a main part of a semiconductor sensor of a comparative example. [Figure 18] 13 is a cross-sectional view showing an outline of a main part of a semiconductor sensor according to an eighth embodiment. FIG. [Figure 19] 13 is a cross-sectional view showing an outline of a main part of a semiconductor sensor according to an eighth embodiment. FIG. [Figure 20] FIG. 13 is a graph showing the water vapor permeability of a hybrid laminate film and a polyparaxylylene-based polymer film. [Figure 21] 13 is a cross-sectional view showing an outline of a main part of a semiconductor sensor according to an embodiment 9. FIG. [Figure 22] 13 is a cross-sectional view showing an outline of a main part of a semiconductor sensor according to an eleventh embodiment. FIG. [Figure 23] 12 is a cross-sectional view showing an outline of a main part of a semiconductor sensor according to a twelfth embodiment. FIG. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] Hereinafter, a semiconductor sensor and a manufacturing method thereof according to an embodiment of the present disclosure will be described with reference to the drawings. Note that the same or corresponding members and parts in each drawing will be denoted by the same reference numerals.

[0022] Embodiment 1 FIG. 1 is a cross-sectional view showing an outline of a semiconductor sensor 100 according to a first embodiment. FIG. 2 is a cross-sectional view showing an outline of a detection chamber 7 of the semiconductor sensor 100, and is an enlarged view of a portion A surrounded by a dashed line in FIG. 1. FIGS. 3 and 4 are cross-sectional views showing an outline of a main portion of the semiconductor sensor 100, and are enlarged views of a portion B surrounded by a dashed line in FIG. 2. It is. The semiconductor sensor 100 in this embodiment is a semiconductor pressure sensor that uses a semiconductor detection element 3 that detects pressure. The semiconductor detection element 3 of the semiconductor sensor 100 is not limited to an element that detects pressure. By appropriately selecting the semiconductor detection element 3, it is possible to configure the semiconductor sensor 100 that measures various physical quantities in addition to pressure.

[0023] <Semiconductor sensor 100> The semiconductor sensor 100 is a sensor that receives pressure of a medium to be measured with the semiconductor detection element 3, measures the absolute pressure of the medium to be measured, and outputs the measurement result. When the semiconductor sensor 100 is applied to the anode subsystem of a fuel cell system, the medium to be measured is hydrogen containing high-temperature and high-humidity water vapor. The medium to be measured is not limited to hydrogen containing high-temperature and high-humidity water vapor, and may be, for example, high-temperature and high-humidity water vapor.

[0024] The configuration of the semiconductor sensor 100 will be described. As shown in FIG. 2, the semiconductor sensor 100 includes a semiconductor detection element 3, a detection chamber 7 in which the semiconductor detection element 3 is fixed, a signal terminal 11 having one end exposed inside the detection chamber 7 and the other end exposed from the detection chamber 7 to the outside and outputting an electric signal output from the semiconductor detection element 3 to the outside, a wire 10 connecting the semiconductor detection element 3 and a signal terminal exposed part 11a which is a part of one end side of the signal terminal 11 exposed inside the detection chamber 7, and a protective film continuously covering the semiconductor detection element 3, the wire 10, and the signal terminal exposed part 11a. In this embodiment, the semiconductor sensor 100 includes a signal processing IC 9 which is fixed inside the detection chamber 7 and has a signal processing circuit. Therefore, wires 10a and 10b are provided as the wire 10, and the semiconductor detection element 3 and the signal terminal exposed part 11a are connected via the signal processing IC 9 by the wires 10a and 10b. The signal processing IC 9 appropriately amplifies the output of the semiconductor detection element 3 and performs signal processing such as temperature compensation. The signal processing IC 9 is also covered with a protective film. The protective film in this embodiment is an inorganic barrier film 19. The inorganic barrier film 19 will be described in detail later.

[0025] The detection chamber 7 is made of, for example, resin. When the detection chamber 7 is made of resin, the signal terminal 11 is insert-molded into the detection chamber 7 and fixed to the detection chamber 7. The detection chamber 7 is a portion surrounding the semiconductor detection element 3 and the signal processing IC 9, and has an opening 7a for taking in the measurement target medium. The wire 10 is, for example, a wire made of gold. The signal terminal 11 is made of a metal such as copper. In this embodiment, the semiconductor detection element 3 and the signal processing IC 9 are separate bodies, but this is not limited thereto, and the semiconductor detection element 3 and the signal processing IC 9 may be integrated. Even when the semiconductor detection element 3 and the signal processing IC 9 are integrated, the semiconductor detection element 3 and the signal terminal exposed portion 11a are connected by a wire. Whether the semiconductor detection element 3 and the signal processing IC 9 are integrated or separate bodies, the wire 10 is used to transmit the electric signal output from the semiconductor detection element 3 to the signal terminal 11. The inside of the detection chamber 7 is covered with a gel 4. The present invention is not limited to a configuration in which the inside of the detection chamber 7 is covered with the gel 4 , and the inside of the detection chamber 7 may not be covered with the gel 4 .

[0026] 1, the semiconductor sensor 100 further includes an introduction tube 2 that communicates with the detection chamber 7 via an opening 7a and takes in the medium to be measured from the outside into the detection chamber 7, a housing 1 that holds the detection chamber 7, and a connector unit 5 that holds an input / output terminal 6 that is connected to a signal terminal 11 and handles input and output of electrical signals with the outside. The housing 1 is made of resin. The introduction tube 2 is also made of the same material as the housing 1. The input / output terminal 6 is made of a metal such as copper. The input / output terminal 6 is electrically connected to the signal terminal 11 by, for example, soldering.

[0027] The medium to be measured is taken into the detection chamber 7 from the outside in the direction of the arrow shown in the figure through the introduction pipe 2. The part of the housing 1 surrounding the detection chamber 7, the detection chamber 7, and the introduction pipe 2 are connected via an O-ring 8a. The introduction pipe 2 and an external flow path (not shown) of the medium to be measured are connected via an O-ring 8b. In this way, the part that serves as the flow path of the medium to be measured is sealed.

[0028] The semiconductor detection element 3 receives a physical quantity (pressure in this embodiment) of the measurement target medium introduced from the outside through the introduction tube 2, and converts the physical quantity into an electric signal. As shown in FIG. 2, the converted electric signal is transmitted to the signal processing IC 9 through the wire 10a. The processed electric signal is transmitted to the signal terminal 11 through the wire 10b, and then output to the outside from the input / output terminal 6. The semiconductor detection element 3 is, for example, an element that directly receives pressure with a single crystal silicon diaphragm and converts the distortion of the diaphragm into an electric signal by a piezoresistor provided on the outer edge or the like. The semiconductor detection element 3 has an electrode pad 17 on its surface that is connected to the wire 10a, as shown in FIG. 3. Although only one wire 10a is shown in FIG. 2, the number of wires 10a and the number of electrode pads 17 may be multiple.

[0029] <Comparative Example> Prior to the description of the protective film, which is the main part of the present disclosure, a comparative example will be described. FIG. 14 is a cross-sectional view showing an outline of the detection chamber 7 of a semiconductor sensor 101 of a comparative example, showing a part equivalent to FIG. 2, and FIG. 15 to FIG. 17 are cross-sectional views showing an outline of the main part of the semiconductor sensor 101 of the comparative example, showing an enlarged view of part C surrounded by a dashed line in FIG. 14. The semiconductor sensor 101 is a sensor that detects pressure. The semiconductor sensor 101 has a protective film 12, and the semiconductor detection element 3, the signal processing IC 9, and the wire 10 provided in the detection chamber 7 are covered with the protective film 12. In FIG. 14, the protective film 12 that covers the wire 10 is omitted. The semiconductor detection element 3, the signal processing IC 9, and the wire 10 provided in the detection chamber 7 are further covered with a gel 4. The semiconductor sensor 101 is different from the semiconductor sensor 100 in that the protective film 12 is a polymer protective film made of a polyparaxylylene-based polymer containing fluorine.

[0030] It seems that coating the semiconductor detection element 3, the exposed signal terminal portion 11a, and the wires 10a and 10b with a polyparaxylylene-based polymer can protect these portions from water vapor and corrosive substances. However, the polyparaxylylene-based polymer coating by CVD has a weak portion 18 where a high-quality protective film 12 is not formed with sufficient thickness in the overhanging portion of the ball at the base of the wire 10b, as shown in FIG. 15. The weak portion 18 is a gap where the protective film 12 is not formed. If a corrosive substance penetrates through the weak portion 18, it will corrode the wire 10b, the electrode pad 17 of the semiconductor detection element 3, etc., causing a fatal failure of the semiconductor sensor 101.

[0031] The polyparaxylylene-based polymer and the fragile portion 18 cause fatal failure of the semiconductor sensor 101 even against water vapor and condensation water brought about by water vapor. The polymer protective film made of the polyparaxylylene-based polymer has almost no water vapor barrier property. Therefore, when the semiconductor sensor 101 is used in an environment containing high-temperature and high-pressure water vapor, the water vapor easily passes through the protective film 12 because the protective film 12 has no water vapor barrier property. High-temperature and high-pressure water vapor is taken into the gel 4 from the direction of the arrow shown in FIG. 15. The white circles shown in the gel 4 are particles of water vapor 13a taken into the gel 4. Therefore, fluctuations, malfunctions, and failures caused by water vapor occur in each electronic component such as the semiconductor detection element 3.

[0032] Condensed water also causes fatal defects in the semiconductor sensor 101 according to the following mechanism. When the semiconductor sensor 101 is used in a fuel cell system and exposed to high-temperature and high-humidity hydrogen gas, which is the measurement target, first, hydrogen, water vapor, and the like are absorbed inside the gel 4 that seals the semiconductor detection element 3, etc. Thereafter, the longer the operation time of the fuel cell system, the more water vapor accumulates inside the gel 4. When the fuel cell system is stopped after this state is reached, the hydrogen absorbed inside the gel 4 is released to the outside from the gel 4 in a relatively short time of about several minutes. On the other hand, water vapor is difficult to release to the outside from the gel 4, and most of it continues to remain inside the gel 4.

[0033] Thereafter, as the temperature of the environment in which the fuel cell system is placed drops, the absorbed water vapor condenses inside the gel 4, producing condensed water 13, as shown in Fig. 16. In particular, in applications such as automobiles, condensation occurs significantly in winter, at night in cold regions, and when the vehicle is used outdoors. Once the water vapor condenses and undergoes a phase change to condensed water 13, its release to the outside is significantly reduced, so that the condensed water 13 continues to remain inside the gel 4 and on the surfaces of each electronic component.

[0034] The condensed water 13 spreads in layers. The semiconductor sensor 101 has the above-mentioned fragile portion 18. Therefore, even if the medium to be measured does not contain a corrosive substance, the condensed water 13 that permeates from the fragile portion 18 forms an electric circuit that electrically connects the conductive parts with different potentials on the semiconductor detection element 3, the wire 10b, the signal terminal 11, etc. Because the potentials are different, electrolysis begins in the condensed water 13. The electrolysis corrodes these conductive members. In FIG. 17, the corroded part caused by electrolysis is the part D surrounded by a curved line. The condensed water 13 spreads in the direction of the arrow and communicates with other conductive parts to form an electric circuit. The corrosion of the conductive members causes the conductive members to peel off and break, so the condensed water 13 causes a fatal malfunction of the semiconductor sensor 101.

[0035] <Protective film> The protective film, which is a main part of the present disclosure, will be described. In the present disclosure, as shown in FIG. 2, the protective film is an inorganic barrier film 19. The inorganic barrier film 19 continuously covers the semiconductor detection element 3, the wire 10, the signal processing IC 9, and the exposed signal terminal portion 11a. As shown in FIG. 3, the inorganic barrier film 19 does not have a fragile portion 18 where the inorganic barrier film 19 is not formed. The inorganic barrier film 19 is, for example, alumina, but is not limited thereto. The inorganic barrier film 19 has a thickness of, for example, about 10 to 100 nm. Even with such a very thin film thickness, the inorganic barrier film 19 exhibits very high barrier properties. This characteristic is the greatest feature of the inorganic barrier film 19. The inorganic barrier film 19 prevents the permeation of the water vapor 13a contained in the measurement target medium introduced from the outside into the detection chamber 7, and therefore can prevent problems such as characteristic fluctuations, malfunctions, and failures caused by the water vapor 13a of each electronic component such as the semiconductor detection element 3.

[0036] 4, there are cases where the external environmental temperature of a system provided with semiconductor sensor 100 drops, causing the water vapor absorbed by gel 4 to condense, spreading out in layers of condensed water 13. Even in such a case, inorganic barrier film 19 does not have fragile parts 18, preventing conduction between conductive members due to condensed water 13, and therefore does not cause corrosion in semiconductor sensor 100 due to electrolysis caused by the formation of an electrically closed circuit, as seen in semiconductor sensor 101 of the comparative example.

[0037] Since the protective film is the inorganic barrier film 19, the inorganic barrier film 19 exhibits high gas barrier properties even with a very thin film thickness. Therefore, it is possible to obtain a semiconductor sensor 100 that has high durability and reliability while maintaining high measurement accuracy without compromising the characteristics of the semiconductor sensor 100, even when the medium to be measured contains high-temperature and high-humidity water vapor and corrosive substances.

[0038] In this embodiment, as shown in FIG. 2, the inorganic barrier film 19, which is a protective film, further covers the inner part of the detection chamber 7 continuously. The reason for this configuration will be described. In principle, to improve durability against the measurement target medium containing corrosive substances and water vapor, it is sufficient to cover only the protection target members (in this embodiment, the semiconductor detection element 3, the signal processing IC 9, the wire 10, and the signal terminal exposed portion 11a) that may be defective when exposed to the measurement target medium with the inorganic barrier film 19. However, depending on the adhesion of the inorganic barrier film 19, the measurement target medium may penetrate from the interface between the inorganic barrier film 19 and its base at the boundary between the covered area and the uncovered area, and the predetermined reliability may not be obtained in the semiconductor sensor 100. In addition, in order to selectively cover only these protection target members with the inorganic barrier film 19, complex masking is required. Complicated masking procedures are not effective in terms of both throughput and cost.

[0039] By continuously covering the inner part of the detection chamber 7 with the inorganic barrier film 19, the interface distance between the area covered with the protected member and the area not covered with the inorganic barrier film 19 can be significantly increased, thereby improving the reliability of the semiconductor sensor 100. In addition, since complicated masking is no longer necessary, it is effective in terms of both throughput and cost, thereby improving the productivity of the semiconductor sensor 100. In addition, all conductive parts in the detection chamber 7 can be reliably protected.

[0040] As described above, the semiconductor sensor 100 according to the first embodiment includes the semiconductor detection element 3, the detection chamber 7 to which the semiconductor detection element 3 is fixed inside, the signal terminal 11 having one end exposed inside the detection chamber 7 and the other end exposed outside from the detection chamber 7 for outputting an electrical signal output from the semiconductor detection element 3 to the outside, the wire 10 connecting the semiconductor detection element 3 and the signal terminal exposed portion 11a which is a portion of one end side of the signal terminal 11 exposed inside the detection chamber 7, and a protective film continuously covering the semiconductor detection element 3, the wire 10, and the signal terminal exposed portion 11a. Since the protective film is the inorganic barrier film 19, the inorganic barrier film 19 exhibits high gas barrier properties even with a very thin film thickness. Therefore, it is possible to obtain a semiconductor sensor 100 having high durability and reliability while maintaining high measurement accuracy without impairing the characteristics of the semiconductor sensor 100, even when the medium to be measured contains high-temperature and high-humidity water vapor and corrosive substances.

[0041] When the inorganic barrier film 19, which is a protective film, further continuously covers the inner portion of the detection chamber 7, the interface distance between the region covered with the member to be protected and the region not covered with the inorganic barrier film 19 can be significantly increased, thereby improving the reliability of the semiconductor sensor 100. In addition, since complicated masking is no longer necessary, it is effective in terms of both throughput and cost, and therefore the productivity of the semiconductor sensor 100 can be improved.

[0042] Embodiment 2 A semiconductor sensor 100 according to embodiment 2 will be described. Figures 5 and 6 are cross-sectional views showing an outline of the main part of semiconductor sensor 100 according to embodiment 2, showing the same position as in Figure 3, and Figure 7 is a cross-sectional view showing an outline of the main part of semiconductor sensor 100 according to embodiment 2, enlarging the portion of semiconductor detection element 3 on the side of the medium to be measured to diagrammatically show the principle of the detouring effect. The semiconductor sensor 100 according to embodiment 2 has a different configuration of the protective film from that of embodiment 1.

[0043] The protective film of the semiconductor sensor 100 shown in the second embodiment is a laminated inorganic barrier film 19. The laminated inorganic barrier film 19 shown in FIG. 5 is an inorganic barrier film 19a and an inorganic barrier film 19b. In FIG. 5, an example in which the inorganic barrier film 19 is two layers is shown from the viewpoint of simplifying the drawing, but the number of layers of the inorganic barrier film 19 is not limited to this. Of course, the inorganic barrier film 19 may be further laminated as necessary. In principle, the more layers of the inorganic barrier film 19 are laminated, the more the barrier properties of the inorganic barrier film 19 as a whole are improved. In FIG. 5, the particles of water vapor 13a taken into the gel 4 are indicated by white circles.

[0044] As described above, even if the inorganic barrier film 19 is a single-layer film, it exhibits a remarkable barrier property against gases such as water vapor. By stacking the inorganic barrier film 19, a robust structure can be formed against defects in the inorganic barrier film 19 caused by adhesion of foreign matter during the manufacturing process. This principle will be described with reference to FIG. 7. In FIG. 7, gas is applied in the direction of the large arrow. The inorganic barrier film 19 shown in FIG. 7 is made of four layers. The four-layer inorganic barrier film 19 covers the wiring 15 of the semiconductor base 16. The semiconductor sensor 100 is basically manufactured in a clean room that is managed to minimize the inclusion of foreign matter. However, even if manufactured in a clean room, it is theoretically impossible to reduce the amount of foreign matter to zero. Therefore, it is expected that the inorganic barrier film 19 will contain a certain amount of defects 14 caused by foreign matter in the clean room as well as in the film forming device. Since the inorganic barrier film 19 itself is very thin, about 10 to 100 nm, once a defect occurs, the defect often penetrates the inorganic barrier film 19. Such penetrating defects become paths for various gases to permeate, and therefore significantly reduce the gas barrier properties of the inorganic barrier film 19 .

[0045] However, by forming the inorganic barrier film 19 not as a single layer film but as a laminated structure in which each film formation process is separated and film formation is performed multiple times, the defects 14 in each layer of the inorganic barrier film 19 can be connected to each other and not penetrate the entire inorganic barrier film 19. With this configuration, even if the permeation speed of various gases is increased due to the defects 14 in each layer, the only way for the permeated gas to reach the defects in the next layer is to propagate between the inorganic barrier films 19 by diffusion, as shown by the arrows superimposed on the inorganic barrier film 19 in FIG. 7. Therefore, the effective length of the path through which the applied gas permeates is significantly extended, and the time for the gas to permeate to the semiconductor detection element 3 can be significantly extended. Since the time for the gas to permeate to the semiconductor detection element 3 is significantly extended, the time until various adverse effects caused by gas permeation, such as characteristic fluctuations and corrosion of the semiconductor detection element 3, begin to occur can be significantly delayed.

[0046] In this way, by forming the inorganic barrier film 19 as a laminated film, an effect of diverting the applied gas can be obtained, and therefore the gas barrier property of the semiconductor sensor 100 can be further improved, and the reliability of the semiconductor sensor 100 can be further improved. In addition, as shown in Fig. 6, even if the condensed water 13 spreads in layers, the laminated inorganic barrier film 19 does not have interconnected and penetrating defects 14, and therefore prevents the condensed water 13 from causing conduction between the conductive members, and therefore it is possible to suppress corrosion caused by electrolysis due to the formation of an electrically closed circuit as seen in the semiconductor sensor 101 of the comparative example.

[0047] As described above, the semiconductor sensor 100 according to the second embodiment has an effect of diverting the applied gas because the protective film of the semiconductor sensor 100 is the laminated inorganic barrier film 19. Since the applied gas is diverted, the gas barrier property of the semiconductor sensor 100 can be further improved, and the reliability of the semiconductor sensor 100 can be further improved. Even if the condensed water 13 spreads in layers, the laminated inorganic barrier film 19 does not have the interconnected and penetrating defects 14, so that the condensed water 13 is prevented from causing conduction between the conductive members. This makes it possible to suppress corrosion caused by electrolysis due to the formation of an electrically closed circuit as seen in the semiconductor sensor 101 of the comparative example.

[0048] Embodiment 3 A semiconductor sensor 100 according to embodiment 3 will be described. Fig. 8 is a cross-sectional view showing an outline of a main part of the semiconductor sensor 100 according to embodiment 3, and shows a position equivalent to that shown in Fig. 3. The semiconductor sensor 100 according to embodiment 3 uses a self-terminating inorganic barrier film 30 as a protective film.

[0049] The inorganic barrier film, which is the protective film of the semiconductor sensor 100 shown in the third embodiment, is a self-stopping inorganic barrier film 30. As described above, the inorganic barrier film 19 shown in FIG. 3 is very thin, so even a slight variation in film thickness is likely to lead to variation in the barrier effect. Therefore, it is very important to increase the uniformity of the film thickness. Therefore, in order to increase the uniformity of the film thickness, the third embodiment uses a self-stopping inorganic barrier film 30 as the inorganic barrier film.

[0050] Generally, no matter what kind of film, the film thickness varies depending on the supply amount of the material gas of the film. Therefore, in order to form a film with a uniform thickness, it is necessary to precisely control the supply amount of the material gas. However, by using the self-stopping inorganic barrier film 30, it is not necessary to precisely control the supply of the material gas, and it is possible to form an inorganic barrier film with a uniform thickness. The principle is explained below. Here, as an example, the self-stopping inorganic barrier film 30 is explained using alumina (Al2O3). The self-stopping inorganic barrier film 30 is not limited to alumina, and the principle is the same even if it is another barrier film.

[0051] First, the material gas TMA (trimethylaluminum), which is the main material of alumina and is called a precursor, is introduced onto the object to be coated. At this time, there is no need to precisely control the amount of TMA gas, and it is sufficient to supply an excess onto the object to be coated. When TMA gas molecules settle on the object to be coated, only the methyl groups of the gas molecules are released on the surface side, so no matter how much TMA gas molecules are supplied thereafter, they cannot bond with these methyl groups. As a result, the settlement of any more TMA gas molecules on the object to be coated is inhibited, and the deposition of the TMA gas molecules automatically stops.

[0052] In this state, the excess unreacted TMA gas remains on the coating target, so it is exhausted. Next, water vapor is introduced to oxidize the methyl groups and replace them with hydroxyl groups. To completely replace them, a sufficient amount of water vapor is supplied in anticipation of the excess, and then exhausted. After this state is achieved, TMA gas is supplied. The TMA gas bonds with the hydroxyl groups on the surface, and new film formation begins. The inorganic barrier film formed by repeating these cycles is the self-terminating inorganic barrier film 30. By making the inorganic barrier film into the self-terminating inorganic barrier film 30 in this way, the fixation of gas molecules on the coating target is inhibited after the initial fixation in each cycle of forming the self-terminating inorganic barrier film 30, so that an inorganic barrier film with a very uniform thickness can be formed on the coating target.

[0053] As described above, since the inorganic barrier film that is the protective film of the semiconductor sensor 100 according to embodiment 3 is the self-stopping inorganic barrier film 30, in each cycle of forming the self-stopping inorganic barrier film 30, the settlement of gas molecules on the target to be coated is inhibited after the initial settlement, so that an inorganic barrier film having a highly uniform thickness can be formed on the target to be coated.

[0054] Embodiment 4 A semiconductor sensor 100 according to embodiment 4 will be described. Fig. 9 is a cross-sectional view showing an outline of a main part of the semiconductor sensor 100 according to embodiment 4, and shows a position equivalent to that shown in Fig. 3. The semiconductor sensor 100 according to embodiment 4 uses a silicon nitride film or the like as a protective film.

[0055] The inorganic barrier film, which is a protective film of the semiconductor sensor 100 shown in the fourth embodiment, is made of at least one of a silicon nitride film (SiN) and a metal oxide film such as alumina (Al2O3), titanium oxide (TiO2), and zinc oxide (ZnO). The inorganic barrier film shown in FIG. 9 is a silicon nitride film 31, but the inorganic barrier film is not limited to the silicon nitride film 31.

[0056] Various films are considered as the inorganic barrier film used in the semiconductor sensor 100. From the viewpoint of industrial use and inexpensive and stable procurement of materials, the inorganic barrier film is preferably made of at least one of a silicon nitride film and a metal oxide film of alumina, titanium oxide, and zinc oxide. The inorganic barrier film is not limited to a single layer, and may be a laminated film made of multiple layers selected from these materials. In addition, a configuration in which, for example, a polyparaxylylene-based polymer film is laminated on a film made of these materials may be used. Since various protective films can be formed by combining the film type and the laminated structure, the material of the film may be appropriately selected depending on the application, cost, manufacturing constraints, and the like.

[0057] As described above, the inorganic barrier film, which is the protective film of the semiconductor sensor 100 according to the fourth embodiment, is made of at least one of silicon nitride film (SiN) and metal oxide films of alumina (Al2O3), titanium oxide (TiO2), and zinc oxide (ZnO), so that a highly practical inorganic barrier film can be formed and the material for the inorganic barrier film can be procured inexpensively and stably. In addition, since the inorganic barrier film can be made of a plurality of different representative types of films, it is possible to realize the desired barrier properties according to the application by arbitrarily combining these.

[0058] Embodiment 5. A semiconductor sensor 100 according to embodiment 5 will be described. Fig. 10 is a cross-sectional view showing an outline of a main part of the semiconductor sensor 100 according to embodiment 5, and shows a position equivalent to that shown in Fig. 3. The semiconductor sensor 100 according to embodiment 5 uses silica for a protective film.

[0059] The inorganic barrier film, which is a protective film of the semiconductor sensor 100 shown in the fifth embodiment, is silica 32. It is also effective to use silica (SiO2) for the inorganic barrier film. By using silica 32 for the inorganic barrier film, not only can it provide a barrier property against various gases, but also an effect of trapping water vapor, since silica 32 has a very high absorbency for water vapor, etc.

[0060] For example, particularly when the measurement target medium contains a large amount of water vapor, the inorganic barrier film traps the water vapor, thereby delaying the permeation of the water vapor. In addition, the inorganic barrier film can be heated as necessary to release the trapped water vapor to the outside. By releasing the water vapor to the outside, the delay effect caused by the trapped water vapor is temporarily reset, and the permeation of the water vapor can be further delayed.

[0061] As described above, the inorganic barrier film that is the protective film of the semiconductor sensor 100 according to the fifth embodiment is made of silica 32, and since silica 32 has a very high absorbency for water vapor and the like, it is possible to obtain a water vapor trapping effect by silica 32. By having silica 32 trap water vapor, it is possible to further improve the water vapor barrier property of the protective film.

[0062] Embodiment 6 A semiconductor sensor 100 according to embodiment 6 will be described. Fig. 11 is a cross-sectional view showing an outline of the detection chamber 7 of the semiconductor sensor 100 according to embodiment 6, and shows a position equivalent to that of Fig. 2 with the inorganic barrier film 19 omitted. The semiconductor sensor 100 according to embodiment 6 differs from embodiment 1 in the location where the gel 4 is provided.

[0063] In the semiconductor sensor 100 shown in the sixth embodiment, at least the connection portion between the wire 10 and the semiconductor detection element 3 and the connection portion between the wire 10 and the signal terminal exposed portion 11a are covered with a protective member made of gel 4. In the configuration shown in Fig. 11, the connection portion between the wire 10a and the semiconductor detection element 3, the connection portion between the wire 10a and the signal processing IC 9, the connection portion between the wire 10b and the signal processing IC 9, and the connection portion between the wire 10b and the signal terminal exposed portion 11a are covered with a protective member made of gel 4.

[0064] The medium to be measured may contain solid matter, or the medium to be measured itself may be solidified. For example, in the intake system of an internal combustion engine, various types of dust may be mixed into the air drawn into the medium to be measured from the outside. Similarly, in the exhaust system of an internal combustion engine, soot generated by combustion may be included. In a fuel cell system, in a hydrogen circulation system, water vapor contained in the circulating hydrogen may condense in a sub-freezing environment, and the condensed water may freeze. In an air system, the generated water may freeze. In such a case, if a solid matter acts on the semiconductor detection element 3, the impact and stress of the solid matter may physically damage the semiconductor detection element 3.

[0065] 2 of the first embodiment, the inside of the detection chamber 7 is covered with gel 4. By covering the inside of the detection chamber 7 with gel 4, it is possible to protect members such as the semiconductor detection element 3 provided inside the detection chamber 7 from physical impacts and stresses due to, for example, the collision of foreign objects such as solid objects. Since the members such as the semiconductor detection element 3 are protected from solid objects, it is possible to improve the reliability of the semiconductor sensor 100.

[0066] The gel 4 has a function of protecting the inside of the detection chamber 7 from the physical impact of solid objects, and also a function of absorbing and releasing water vapor. The property of the gel 4 of absorbing water vapor is undesirable for the semiconductor sensor 100. Therefore, in the sixth embodiment, the locations where the gel 4 is provided are limited to at least the connection portion between the wire 10 and the semiconductor detection element 3, and the connection portion between the wire 10 and the exposed signal terminal portion 11a. These locations are fragile and are important connection portions mechanically and electrically.

[0067] As described above, in the semiconductor sensor 100 according to embodiment 6, at least the connection portion between the wire 10 and the semiconductor detection element 3, and the connection portion between the wire 10 and the exposed signal terminal portion 11a are covered with a protective member made of gel 4. Since these connection portions are fragile and are important connection portions mechanically and electrically, by covering at least these connection portions with gel 4, the absorption of water vapor by the gel 4 can be minimized, and a semiconductor sensor 100 can be obtained that has high durability and reliability while protecting these connection portions from solid objects.

[0068] Embodiment 7 In the seventh embodiment, a method for manufacturing the semiconductor sensor 100 will be described. Fig. 12 is a diagram showing the manufacturing process of the semiconductor sensor 100 shown in the first embodiment, and Fig. 13 is a schematic cross-sectional view showing the difference in the structure of the protective film depending on the film formation method. The manufacturing method for the semiconductor sensor 100 shown in the first embodiment includes a member preparation step (S11), a member fixing step (S12), a connection step (S13), and a film formation step (S14).

[0069] Each step will be described in detail. The member preparation step is a step of preparing the semiconductor detection element 3, the detection chamber 7 for fixing the semiconductor detection element 3 inside, the signal terminal 11 for outputting an electrical signal output from the semiconductor detection element 3 to the outside, and the wire 10. The semiconductor sensor 100 of the first embodiment shown in Fig. 1 further has a signal processing IC 9, an input / output terminal 6, O-rings 8a, 8b, and an introduction tube 2, and these are also prepared in this step.

[0070] The member fixing step is a step of fixing the semiconductor detection element 3 inside the detection chamber 7 and fixing the signal terminal 11 to the detection chamber 7 so that one end of the signal terminal 11 is exposed inside the detection chamber 7 and the other end of the signal terminal 11 is exposed to the outside from the detection chamber 7. Since the semiconductor sensor 100 of the first embodiment shown in Fig. 2 has a signal processing IC 9, the signal processing IC 9 is also fixed inside the detection chamber 7 in this step. The fixing method is, for example, adhesion.

[0071] The connecting step is a step of connecting one end of the wire 10 to the semiconductor detection element 3, and connecting the other end of the wire 10 to the signal terminal exposed portion 11a which is a portion on one end side of the signal terminal 11 exposed inside the detection chamber 7. Since the semiconductor sensor 100 of the first embodiment has a signal processing IC 9, wires 10a and 10b are provided as the wire 10, and the semiconductor detection element 3 and the signal terminal exposed portion 11a are connected by the wires 10a and 10b via the signal processing IC 9.

[0072] The film forming step is a step of continuously covering the semiconductor detection element 3, the wires 10, and the exposed signal terminal portions 11a with a protective film. In the first embodiment, the protective film continuously covers the semiconductor detection element 3, the wires 10, the signal processing IC 9, and the detection chamber 7 that are exposed to the medium to be measured. The protective film is an inorganic barrier film 19. In the film forming step, the inorganic barrier film 19 is formed by atomic layer deposition (hereinafter referred to as ALD).

[0073] After the film formation process, the input / output terminals 6 are electrically connected to the signal terminals 11 by, for example, soldering. Next, the housing 1 and the connector portion 5 are formed around the detection chamber 7 by insert molding. Next, the portion of the housing 1 around the detection chamber 7, the detection chamber 7, and the introduction tube 2 are connected via an O-ring 8a. A flow path (not shown) for the external medium to be measured is connected to the introduction tube 2 via an O-ring 8b. Through these processes, the semiconductor sensor 100 shown in FIG. 1 is manufactured.

[0074] As described above, it is mainly the effect of the inorganic barrier film 19 that exhibits the barrier properties against various gases including water vapor. In order to ensure the effect of the inorganic barrier film 19, it is important that the fragile portion 18 that occurred in the semiconductor sensor 101 of the comparative example shown in FIG. 15 is not formed. In the schematic cross-sectional view of FIG. 13 showing the difference in the structure of the protective film depending on the film formation method, FIG. 13(a) shows the film formation result by ALD, FIG. 13(b) shows the film formation result by CVD, and FIG. 13(c) shows the film formation result by PVD. The film formation method by CVD or PVD used in the semiconductor sensor 101 of the comparative example shows insufficient coverage as shown in FIG. 13(b) or FIG. 13(c), and these are film formation methods that inevitably leave uncovered portions, especially in structures with high aspect ratios such as narrow and deep grooves.

[0075] 13(a), in order to coat a structure having a high aspect ratio such as a narrow and deep groove with a uniform film thickness, it is preferable to form the film by ALD, which has excellent penetration into gaps. ALD has excellent coating properties that allow a film of uniform thickness to be formed even on the bottom of a narrow groove and on an overhanging portion, so that a semiconductor sensor 100 with high barrier properties can be obtained.

[0076] By forming the inorganic barrier film 19 of the semiconductor sensor 100 by ALD, it is possible to form the inorganic barrier film 19 with a highly uniform thickness even for structures with high aspect ratios, such as the backs of very narrow and deep trenches, and therefore it is possible to manufacture semiconductor sensors 100 with high durability and reliability with stable, high quality.

[0077] As described above, the manufacturing method of the semiconductor sensor 100 according to the seventh embodiment includes a member preparing step of preparing the semiconductor detection element 3, the detection chamber 7 for fixing the semiconductor detection element 3 inside, the signal terminal 11 for outputting an electrical signal output from the semiconductor detection element 3 to the outside, and the wire 10; a member fixing step of fixing the semiconductor detection element 3 inside the detection chamber 7, exposing one end side of the signal terminal 11 inside the detection chamber 7, and fixing the signal terminal 11 to the detection chamber 7 so that the other end side of the signal terminal 11 is exposed from the detection chamber 7 to the outside; and a member fixing step of connecting one end of the wire 10 to the semiconductor detection element 3, and exposing the other end of the wire 10 inside the detection chamber 7. The method includes a connection step of connecting to the signal terminal exposed portion 11a, which is a portion on one end side of the signal terminal 11, and a film formation step of successively covering the semiconductor detection element 3, the wire 10, and the signal terminal exposed portion 11a with a protective film. The protective film is an inorganic barrier film 19. In the film formation step, the inorganic barrier film 19 is covered by atomic layer deposition (ALD). Therefore, the inorganic barrier film 19 can be formed with a highly uniform film thickness even for structures with a high aspect ratio, such as the back of a very narrow and deep trench. As a result, a semiconductor sensor 100 with high durability and reliability can be manufactured with stable high quality.

[0078] Embodiment 8 A semiconductor sensor 100 according to an eighth embodiment will be described. Fig. 18 and Fig. 19 are cross-sectional views showing an outline of a main part of the semiconductor sensor 100 according to the eighth embodiment, showing the same position as in Fig. 3, and Fig. 20 is a diagram showing the water vapor transmission rates of the hybrid laminated film 21 and the polyparaxylylene-based polymer film. In the semiconductor sensor 100 according to the eighth embodiment, the protective film is composed of the hybrid laminated film 21. The configuration other than the protective film is the same as that shown in the first embodiment.

[0079] In this embodiment, the protective film is a hybrid laminated film 21 in which an inorganic barrier film 19 and an organic barrier film 20 are alternately laminated. In the first embodiment, the protective film is only the inorganic barrier film 19, whereas in this embodiment, the protective film has a hybrid laminated structure in which the inorganic barrier film 19 and the organic barrier film 20 are alternately laminated. In FIG. 18, the inorganic barrier film 19a, the organic barrier film 20a, the inorganic barrier film 19b, and the organic barrier film 20b are laminated in this order, and two layers of each of the inorganic barrier film 19 and the organic barrier film 20 are laminated, but the number of layers of each film is not limited to this. The number of layers of each film may be further increased according to necessity. In principle, the barrier property of the protective film is improved as the number of layers of each film is increased. On the other hand, if the number of layers of each film is increased, the protective film is formed thicker on the semiconductor detection element 3, which increases undesirable effects such as a decrease in the detection sensitivity of the semiconductor detection element 3. Therefore, it is desirable to select an optimal number of layers in consideration of the desired barrier property, detection sensitivity, throughput of the manufacturing process, etc.

[0080] The inorganic barrier film 19 is made of at least one of a silicon nitride film (SiN) and a metal oxide film such as alumina (Al2O3), titanium oxide (TiO2), and zinc oxide (ZnO). The inorganic barrier film 19 has a thickness of, for example, about 10 to 100 nm. The organic barrier film 20 is a polymer film made of, for example, a polyparaxylylene-based polymer. The organic barrier film 20 has a thickness of, for example, about 1 to 5 μm.

[0081] The water vapor permeability of the hybrid laminated film 21 and the polyparaxylylene-based polymer film will be described with reference to FIG. 20. The water vapor permeability was measured using a differential pressure gas permeability measurement method specified in ISO1105-1. For the measurement of the polyparaxylylene-based polymer film, a test piece was used in which a 125 μm thick PEN film (TEONEX manufactured by Toyobo) was used as a substrate, and a 10 μm thick hybrid laminated film 21 consisting of a 30 nm thick alumina and a 3 μm thick dix-C was formed thereon. For the measurement of the hybrid laminated film 21, a test piece was used in which a 125 μm thick PEN film (TEONEX manufactured by Toyobo) was used as a substrate, and a 10 μm thick hybrid laminated film 21 consisting of a 30 nm thick alumina and a 3 μm thick dix-C was formed thereon.

[0082] Water vapor at 40°C and 90% RH was applied to the test piece. In the figure, the results for the hybrid laminated film 21 are shown by a solid line, and the results for the polyparaxylylene-based polymer film are shown by a dashed line. In the plot of water vapor transmission rate, the steady-state portion represents the transmission rate of the material. The water vapor transmission rate of the steady-state portion of the polyparaxylylene-based polymer film is approximately 1.5 g / m 2 / day. This value is almost the same as the water vapor transmission rate of the PEN film, which is the base material, and dix-C does not have significant water vapor barrier properties. The steady-state water vapor transmission rate of the hybrid laminate film 21 was 1.1×10 -5 g / m 2 / day. It was confirmed by this measurement that the hybrid laminated film 21 has a water vapor barrier property that is about 140,000 times that of the polyparaxylylene polymer film.

[0083] By forming the hybrid laminated film 21, the water vapor barrier property of the inorganic barrier film 19 can be further improved by the synergistic effect of the gas bypass effect brought about by the lamination. In addition, the high gas barrier property of the inorganic barrier film 19 and the high corrosive solution resistance of the organic barrier film 20 can be achieved at the same time. In addition, the inorganic barrier film 19 has a characteristic of being easily cracked due to its relatively high brittleness, but since the organic barrier film 20 has the effect of mitigating stress, the lamination can make the inorganic barrier film 19 less likely to crack. The flexibility of the organic barrier film 20 complements the brittleness of the inorganic barrier film 19, making the protective film less likely to crack even when deformed due to repeated application of stress, thereby significantly improving the mechanical reliability of the protective film. Since no gaps due to cracks or the like are generated in the protective film, even if water vapor condenses and spreads in layers as shown in FIG. 19, no electric closed circuit is formed with other conductive members having different potentials, so corrosion due to electrolysis can be suppressed.

[0084] In this embodiment, similarly to the configuration shown in FIG. 2 of the first embodiment, the hybrid laminated film 21, which is a protective film, further continuously covers the inner part of the detection chamber 7. By continuously covering the inner part of the detection chamber 7 with the hybrid laminated film 21, the interface distance between the area where the protected member is covered and the area where the hybrid laminated film 21 is not covered can be significantly increased, so that the reliability of the semiconductor sensor 100 can be improved. In addition, since complicated masking is not required, it is effective in terms of both throughput and cost, so that the productivity of the semiconductor sensor 100 can be improved. In addition, all conductive parts in the detection chamber 7 can be reliably protected.

[0085] As described above, the semiconductor sensor 100 according to the eighth embodiment includes the semiconductor detection element 3, the detection chamber 7 in which the semiconductor detection element 3 is fixed, the signal terminal 11 having one end exposed inside the detection chamber 7 and the other end exposed from the detection chamber 7 to the outside and outputting an electric signal output from the semiconductor detection element 3 to the outside, the wire 10 connecting the semiconductor detection element 3 and the signal terminal exposed portion 11a which is the part of the one end side of the signal terminal 11 exposed inside the detection chamber 7, and the protective film continuously covering the semiconductor detection element 3, the wire 10, and the signal terminal exposed portion 11a, and the protective film is a hybrid laminated film 21 in which the inorganic barrier film 19 and the organic barrier film 20 are alternately laminated, so that the water vapor barrier property of the inorganic barrier film 19 can be further improved by the synergistic effect with the effect of bypassing gas brought about by lamination. In addition, the high gas barrier property of the inorganic barrier film 19 and the high corrosive solution resistance of the organic barrier film 20 can be achieved at the same time. Furthermore, the inorganic barrier film 19 is relatively brittle and therefore prone to cracking, but the organic barrier film 20 has the effect of relieving stress, and therefore this lamination can make the inorganic barrier film 19 less likely to crack.

[0086] When the hybrid laminated film 21, which is a protective film, further continuously covers the inner part of the detection chamber 7, the interface distance between the area where the protected member is covered and the area where the hybrid laminated film 21 is not covered can be significantly increased, thereby improving the reliability of the semiconductor sensor 100. In addition, since complicated masking is no longer necessary, it is effective in terms of both throughput and cost, and therefore the productivity of the semiconductor sensor 100 can be improved.

[0087] Embodiment 9 A semiconductor sensor 100 according to a ninth embodiment will be described. Fig. 21 is a cross-sectional view showing an outline of a main part of the semiconductor sensor 100 according to the ninth embodiment, and shows a position equivalent to that shown in Fig. 3. In the semiconductor sensor 100 according to the ninth embodiment, the protective film is composed of a hybrid laminated film 21, and the organic barrier film is an organic polymer film 33.

[0088] The organic barrier film of the semiconductor sensor 100 shown in the ninth embodiment is an organic polymer film 33. The organic barrier film shown in FIG. 21 has two layers, an organic polymer film 33a and an organic polymer film 33b. As the organic barrier film 20 shown in FIG. 18, a polymer film made of a polyparaxylylene-based polymer is preferable, but it is more effective to select a suitable material according to the desired durability. Specifically, in the semiconductor sensor 100 that requires high electrical insulation, it is preferable to select Parylene N, which is the organic polymer film 33, as the organic barrier film. On the other hand, when the measurement target medium contains water vapor and corrosive gas, it is preferable to select Parylene C, which is the organic polymer film 33. When the semiconductor sensor 100 is used in a high-temperature environment, it is preferable to select Parylene D, which is the organic polymer film 33. In the application of the semiconductor sensor 100 in which the usage time at high temperatures is further extended, Parylene HT, which is the organic polymer film 33, is also an option.

[0089] As described above, since the organic barrier film of the semiconductor sensor 100 according to the ninth embodiment is the organic polymer film 33, the optimum organic polymer film 33 can be selected from a plurality of organic polymer films 33 having different properties, and therefore the semiconductor sensor 100 can be flexibly adapted to various media to be measured. In addition, since the organic polymer film 33 can be formed at room temperature, residual stress that causes output fluctuations in the semiconductor detection element 3 can be eliminated from the protective film, so that the semiconductor sensor 100 can be obtained that has high durability against corrosive substances while maintaining high measurement accuracy without impairing the properties of the semiconductor sensor 100.

[0090] Embodiment 10 A semiconductor sensor 100 according to a tenth embodiment will be described with reference to Fig. 18. As described above, Fig. 18 is a cross-sectional view showing an outline of a main part of the semiconductor sensor 100. In the semiconductor sensor 100 according to the tenth embodiment, the protective film is composed of a hybrid laminated film 21, and the thickness ratio of each film is specified.

[0091] In the tenth embodiment, the ratio of the thickness of the inorganic barrier film 19 to the thickness of the organic barrier film 20 is not less than 10 and not more than 500. In FIG.

[0092] From the viewpoint of barrier properties alone, the thicker the thickness of each film constituting the hybrid laminated film 21, the better. However, the thicker the protective film, the longer the deposition time, which reduces throughput and increases costs. In addition, there are also significant drawbacks, such as a decrease in the measurement accuracy and responsiveness of the semiconductor sensor 100. Therefore, in practice, it is necessary to optimize the thickness of each film in consideration of the required barrier properties. Through verification through prototype production and durability evaluation, it was found that the ratio of the thickness of the inorganic barrier film 19 to the thickness of the organic barrier film 20 is 10 or more and 500 or less, which is the appropriate thickness of each film in consideration of the required barrier properties.

[0093] As described above, since the ratio of the thickness of the inorganic barrier film 19 to the thickness of the organic barrier film 20 in the semiconductor sensor 100 according to embodiment 10 is greater than or equal to 10 and less than 500, it is possible to obtain a semiconductor sensor 100 that combines the gas barrier properties against water vapor and the like provided by the inorganic barrier film 19 and the durability against corrosive substances provided by the organic barrier film 20, while suppressing the total thickness of the protective film.

[0094] Embodiment 11 A semiconductor sensor 100 according to an eleventh embodiment will be described. Fig. 22 is a cross-sectional view showing an outline of a main part of the semiconductor sensor 100 according to the eleventh embodiment, and shows a position equivalent to that shown in Fig. 3. In the semiconductor sensor 100 according to the eleventh embodiment, the protective film is composed of a hybrid laminated film 21, and the film exposed to the outside is an inorganic barrier film 19.

[0095] The film exposed to the outside in the protective film of the semiconductor sensor 100 shown in the eleventh embodiment is the inorganic barrier film 19. The configuration shown in Fig. 22 includes an inorganic barrier film 19c exposed to the outside in addition to the configuration shown in Fig. 18.

[0096] Generally, there are few measurement target media with a single composition. Even in the same system, the composition of the measurement target medium generally varies greatly depending on the location where the semiconductor sensor 100 is attached. Therefore, if there is concern about the reliability of the semiconductor sensor 100 due to the composition of the measurement target medium, it is necessary to optimize the structure of the protective film taking into account the environment of the location where the semiconductor sensor 100 is attached.

[0097] For example, when the semiconductor sensor 100 is mounted in the hydrogen circulation system of a fuel cell system, the medium to be measured contains high-temperature and high-humidity hydrogen, but contains almost no corrosive substances. Therefore, it is necessary to take special precautions against water vapor and corrosion caused by electrolysis when the water vapor condenses. When the semiconductor sensor 100 is mounted in such an environment, it is preferable to use an inorganic barrier film 19 that has a high barrier property against water vapor. In order to improve the coverage and realize the gas bypass effect described above, the inorganic barrier film 19 is used as the outermost surface of the protective film that is directly exposed to the medium to be measured, as shown in FIG. 22, while based on a hybrid laminated structure of the inorganic barrier film 19 and the organic barrier film 20.

[0098] As described above, since the film exposed to the outside in the protective film of the semiconductor sensor 100 according to the eleventh embodiment is the inorganic barrier film 19, the durability of the protective film, particularly against water vapor, can be improved.

[0099] Embodiment 12 A semiconductor sensor 100 according to embodiment 12 will be described. Fig. 23 is a cross-sectional view showing an outline of a main part of the semiconductor sensor 100 according to embodiment 12, and shows a position equivalent to that shown in Fig. 3. In the semiconductor sensor 100 according to embodiment 12, the protective film is composed of a hybrid laminated film 21, and the film exposed to the outside is an organic barrier film 20.

[0100] The film exposed to the outside in the protective film of the semiconductor sensor 100 shown in the twelfth embodiment is the organic barrier film 20. The configuration shown in Fig. 23 is provided with an organic barrier film 20b exposed to the outside, similar to the configuration shown in Fig. 18.

[0101] When the semiconductor sensor 100 is mounted in the exhaust system of an EGR system of an internal combustion engine, the medium to be measured contains a large amount of corrosive substances. When the semiconductor sensor 100 is mounted in such an environment, it is preferable to use an organic barrier film 20 such as a polyparaxylylene-based polymer film. In order to improve the above-mentioned coverage and to realize the gas bypass effect, the hybrid laminated structure of the inorganic barrier film 19 and the organic barrier film 20 is used as the basis, and as shown in FIG. 23, the outermost surface of the protective film that is directly exposed to the medium to be measured is made of an organic barrier film 20 such as a polyparaxylylene-based polymer film.

[0102] As described above, since the film exposed to the outside in the protective film of the semiconductor sensor 100 according to embodiment 12 is the organic barrier film 20, the durability of the protective film, particularly against the corrosive gas 13b and the corrosive solution 13c, can be improved.

[0103] Embodiment 13 In the thirteenth embodiment, a method for manufacturing the semiconductor sensor 100 will be described. The method for manufacturing the semiconductor sensor 100 shown in the eighth embodiment includes a member preparation step (S11), a member fixing step (S12), a connection step (S13), and a film formation step (S14), similar to the method for manufacturing the semiconductor sensor 100 shown in the seventh embodiment shown in Fig. 12. Only the film formation step, which is different from the method for manufacturing the semiconductor sensor 100 shown in the seventh embodiment, will be described.

[0104] The protective film of the semiconductor sensor 100 is a hybrid laminated film in which inorganic barrier films 19 and organic barrier films 20 are alternately laminated. In order to stably realize the desired function of the protective film in industrial mass production, management of the manufacturing process is important. In other words, it is necessary to minimize defects in each barrier film in the manufacturing process. Possible causes of defects in the protective film include external substances or foreign matter in the manufacturing equipment. The former basically means that the manufacturing process should be performed in a clean room that is managed to suppress the generation of foreign matter, and the latter suggests that regular cleaning should be performed, including the inside of the manufacturing equipment such as the film formation chamber.

[0105] In the present embodiment, in the film forming process, the semiconductor detection element 3, the wire 10, and the signal terminal exposed portion 11a are successively covered with the inorganic barrier film 19 and the organic barrier film 20 without taking out the semiconductor detection element 3, the wire 10, and the signal terminal exposed portion 11a covered with the hybrid laminated film 21 from the film forming chamber to the outside. By performing the film forming process in this manner, the portion covered with the hybrid laminated film 21 is not taken out from the film forming chamber to the outside, so that defects that may occur in the protective film due to foreign matter can be suppressed. In addition, a high-quality protective film is formed with sufficient thickness even in structural portions with a high aspect ratio such as narrow and deep grooves, where the protective film was not formed or was weak as in the comparative example, and in the overhanging portion of the ball at the base of the wire, so that a highly reliable semiconductor sensor 100 can be obtained.

[0106] As described above, in the manufacturing method of the semiconductor sensor 100 according to the thirteenth embodiment, the protective film of the semiconductor sensor 100 is a hybrid laminated film in which the inorganic barrier films 19 and the organic barrier films 20 are alternately laminated, and in the film formation process, the semiconductor detection element 3, the wire 10, and the signal terminal exposed portion 11a, which are covered with the hybrid laminated film 21, are successively coated with the inorganic barrier film 19 and the organic barrier film 20 without removing them from the film formation chamber to the outside, thereby suppressing defects that may occur in the protective film due to foreign matter.

[0107] Embodiment 14 In the fourteenth embodiment, a method for manufacturing the semiconductor sensor 100 will be described. The method for manufacturing the semiconductor sensor 100 shown in the eighth embodiment includes a member preparation step (S11), a member fixing step (S12), a connection step (S13), and a film formation step (S14), similar to Fig. 12 shown in the seventh embodiment. Only the film formation step, which is different from the method for manufacturing the semiconductor sensor 100 shown in the seventh embodiment, will be described.

[0108] In improving the quality of the hybrid laminated structure in which the inorganic barrier film 19 and the organic barrier film 20 are alternately laminated, it is important to ensure the adhesion between the films. For example, if the films are formed and then removed from the deposition chamber and left outside for a long time, the surface state of each film may change due to moisture absorption or the like. In such a case, it becomes difficult to form the next film by a stable chemical reaction on the film whose surface state has changed, and the adhesion of each film decreases. As a result, if the interface between each film peels off, the peeled part becomes a permeation path for water vapor and corrosive substances, and the penetration of these substances may cause corrosion in the semiconductor sensor 100. In the worst case, the barrier film peels off, significantly shortening the life of the semiconductor sensor 100.

[0109] In order to prevent such a decrease in adhesion between the films, it is desirable to perform the coating of the inorganic barrier film 19 and the coating of the organic barrier film 20 successively without taking the film out of the film-forming chamber, as described above. However, there may be cases in which such processing cannot be performed in the manufacturing process due to various circumstances. In the manufacturing method of the semiconductor sensor 100 of this embodiment, a plasma activation process is performed between the coating of the inorganic barrier film 19 and the coating of the organic barrier film 20 in the film-forming process. By adding a plasma activation process before the deposition of each barrier film in this way, the surface state of the film can be normalized and activated, so that the adhesion between the barrier films can be ensured. Since the adhesion between the films is improved, each film does not peel off, so that the protective film becomes resistant to external stress such as heat and vibration, and a more reliable semiconductor sensor 100 can be obtained. Note that even when the coating of the inorganic barrier film 19 and the coating of the organic barrier film 20 are performed successively, a plasma activation process may be added before the deposition of each barrier film.

[0110] As described above, in the manufacturing method of the semiconductor sensor 100 according to the fourteenth embodiment, the protective film of the semiconductor sensor 100 is a hybrid laminated film in which the inorganic barrier film 19 and the organic barrier film 20 are alternately laminated, and in the film forming process, a plasma activation treatment is performed between the coating of the inorganic barrier film 19 and the coating of the organic barrier film 20, so that the surface state of the film can be normalized and activated, and therefore the adhesion between the barrier films can be ensured. Since the adhesion between the films is improved and the films do not peel off, the protective film becomes resistant to external stresses such as heat and vibration, and a more reliable semiconductor sensor 100 can be obtained.

[0111] Although the present disclosure describes various exemplary embodiments and examples, the various features, aspects, and functions described in one or more embodiments are not limited to application to a particular embodiment, but may be applied to the embodiments alone or in various combinations. Therefore, countless modifications not exemplified are assumed within the scope of the technology disclosed in this specification, including, for example, modifying, adding, or omitting at least one component, and further, extracting at least one component and combining it with a component of another embodiment. [Explanation of symbols]

[0112] 1 housing, 2 introduction tube, 3 semiconductor detection element, 4 gel, 5 connector portion, 6 input / output terminal, 7 detection chamber, 7a opening, 8a, 8b O-ring, 9 signal processing IC, 10, 10a, 10b wire, 11 signal terminal, 11a exposed signal terminal portion, 12 protective film, 13 condensed water, 13a water vapor, 13b corrosive gas, 13c corrosive solution, 14 defect, 15 wiring, 16 semiconductor base, 17 electrode pad, 18 fragile portion, 19, 19a, 19b, 19c inorganic barrier film, 20, 20a, 20b organic barrier film, 21 hybrid laminated film, 30 self-terminating inorganic barrier film, 31 silicon nitride film, 32 silica, 33, 33a, 33b organic polymer film, 100, 101 semiconductor sensor

Claims

1. a semiconductor detection element; a detection chamber in which the semiconductor detection element is fixed; a signal terminal having one end exposed inside the detection chamber and the other end exposed to the outside from the detection chamber for outputting an electrical signal output from the semiconductor detection element to the outside; a wire connecting the semiconductor detection element and an exposed signal terminal portion, which is a portion of one end of the signal terminal exposed inside the detection chamber; a protective film continuously covering the semiconductor detection element, the wire, and the exposed signal terminal portion; The semiconductor sensor, wherein the protective film is a self-stopping inorganic barrier film.

2. 2. The semiconductor sensor according to claim 1, wherein the protective film further covers an inner portion of the detection chamber continuously.

3. 2. The semiconductor sensor according to claim 1, wherein the protective film is a laminated self-stopping inorganic barrier film.

4. 4. The semiconductor sensor according to claim 1, wherein the self-stopping inorganic barrier film is made of at least one of a silicon nitride film and a metal oxide film of alumina, titanium oxide, and zinc oxide.

5. 4. The semiconductor sensor according to claim 1, wherein the self-terminating inorganic barrier film is silica.

6. a semiconductor detection element; a detection chamber in which the semiconductor detection element is fixed; a signal terminal having one end exposed inside the detection chamber and the other end exposed to the outside from the detection chamber for outputting an electrical signal output from the semiconductor detection element to the outside; a wire connecting the semiconductor detection element and an exposed signal terminal portion, which is a portion of one end of the signal terminal exposed inside the detection chamber; a protective film continuously covering the semiconductor detection element, the wire, and the exposed signal terminal portion; The protective film is a hybrid laminated film in which a self-terminating inorganic barrier film and an organic barrier film are alternately stacked.

7. 7. The semiconductor sensor according to claim 6, wherein the protective film further covers an inner portion of the detection chamber continuously.

8. 7. The semiconductor sensor according to claim 6, wherein the organic barrier film is an organic polymer film.

9. 7. The semiconductor sensor according to claim 6, wherein the ratio of the thickness of the self-terminating inorganic barrier film to the thickness of the organic barrier film is 10 or more and 500 or less.

10. 10. The semiconductor sensor according to claim 6, wherein the film exposed to the outside of the protective film is the self-terminating inorganic barrier film.

11. 10. The semiconductor sensor according to claim 6, wherein the film exposed to the outside in the protective film is the organic barrier film.

12. 7. The semiconductor sensor according to claim 1, wherein at least the connection portion between the wire and the semiconductor detection element and the connection portion between the wire and the exposed signal terminal portion are covered with a protective member made of gel.

13. a member preparation step of preparing a semiconductor detection element, a detection chamber for fixing the semiconductor detection element therein, a signal terminal for outputting an electrical signal output from the semiconductor detection element to the outside, and a wire; a member fixing step of fixing the semiconductor detection element inside the detection chamber, and fixing the signal terminal to the detection chamber so that one end side of the signal terminal is exposed inside the detection chamber and the other end side of the signal terminal is exposed to the outside from the detection chamber; a connecting step of connecting one end of the wire to the semiconductor detection element and the other end of the wire to a signal terminal exposed portion that is a portion on the side of one end of the signal terminal exposed inside the detection chamber; a film-forming step of successively covering the semiconductor detection element, the wire, and the exposed signal terminal portion with a protective film; the protective film is a self-terminating inorganic barrier film; In the film-forming step, the self-terminating inorganic barrier film is coated by atomic layer deposition.

14. a member preparation step of preparing a semiconductor detection element, a detection chamber for fixing the semiconductor detection element therein, a signal terminal for outputting an electrical signal output from the semiconductor detection element to the outside, and a wire; a member fixing step of fixing the semiconductor detection element inside the detection chamber, and fixing the signal terminal to the detection chamber so that one end side of the signal terminal is exposed inside the detection chamber and the other end side of the signal terminal is exposed to the outside from the detection chamber; a connecting step of connecting one end of the wire to the semiconductor detection element and the other end of the wire to a signal terminal exposed portion that is a portion on the side of one end of the signal terminal exposed inside the detection chamber; a film-forming step of successively covering the semiconductor detection element, the wire, and the exposed signal terminal portion with a protective film; the protective film is a hybrid laminated film in which a self-terminating inorganic barrier film and an organic barrier film are alternately laminated, In the film-forming process, the semiconductor detection element, the wire, and the exposed signal terminal portion to be coated with the hybrid laminated film are not removed from the film-forming chamber, and the self-terminating inorganic barrier film and the organic barrier film are successively coated on the semiconductor detection element, the wire, and the exposed signal terminal portion.

15. a member preparation step of preparing a semiconductor detection element, a detection chamber for fixing the semiconductor detection element therein, a signal terminal for outputting an electrical signal output from the semiconductor detection element to the outside, and a wire; a member fixing step of fixing the semiconductor detection element inside the detection chamber, and fixing the signal terminal to the detection chamber so that one end side of the signal terminal is exposed inside the detection chamber and the other end side of the signal terminal is exposed to the outside from the detection chamber; a connecting step of connecting one end of the wire to the semiconductor detection element and the other end of the wire to a signal terminal exposed portion that is a portion on the side of one end of the signal terminal exposed inside the detection chamber; a film-forming step of successively covering the semiconductor detection element, the wire, and the exposed signal terminal portion with a protective film; the protective film is a hybrid laminated film in which a self-terminating inorganic barrier film and an organic barrier film are alternately laminated, A method for manufacturing a semiconductor sensor, wherein a plasma activation process is performed between the coating of the self-terminating inorganic barrier film and the coating of the organic barrier film in the film-forming step.

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