A method for detecting hydrogen diffusion inhibition performance of titanium nitride film

Abstract

The present invention provides a method for detecting the hydrogen diffusion inhibition performance of a titanium nitride film, relating to the technical field of titanium nitride materials. The present invention prepares a titanium nitride film into a sandwich composite structure; the sandwich composite structure includes a silicon substrate and a metal titanium film and a titanium nitride film sequentially stacked on the silicon substrate; the sandwich composite structure is first heated in a deuterium atmosphere, and the deuterium penetrates the titanium nitride film of the sandwich composite structure and diffuses into the metal titanium film, thereby obtaining a composite structure that adsorbs deuterium; the deuterium adsorbed composite structure is secondly heated under vacuum conditions to completely desorb the deuterium; and the hydrogen diffusion inhibition performance of the titanium nitride film is obtained by detecting the amount of deuterium desorbed. The present invention provides a method for detecting the hydrogen diffusion inhibition of a titanium nitride film based on temperature-driven deuterium particle transport, which does not damage the titanium nitride film and can accurately and highly sensitively reflect the hydrogen diffusion inhibition performance of the titanium nitride film.

Description

Technical Field

[0001] The present invention relates to the technical field of titanium nitride materials, and in particular to a method for detecting the hydrogen diffusion inhibition performance of a titanium nitride film. Background Art

[0002] Titanium nitride (TiN) is often chosen as a coating material for protection against corrosive media such as water, oxygen, and hydrogen due to its high hardness, excellent wear resistance, and low chemical reactivity. Currently prepared TiN thin film coatings offer good protection against larger oxygen particles, but their protection against smaller hydrogen particles is less than ideal. This is because tiny pores are easily generated during the preparation of TiN films, causing hydrogen particles to diffuse through the pores into the metal substrate, leading to severe hydrogen corrosion and ultimately failure of the coating. To improve the corrosion protection performance of TiN films, extensive research efforts have focused on upgrading preparation methods and optimizing process parameters, aiming to achieve dense TiN films. Detecting and evaluating the corrosion protection performance of TiN films against hydrogen particles is crucial for guiding the optimization of TiN film preparation.

[0003] Currently, the most common methods for evaluating titanium nitride's corrosion protection against water, oxygen, and hydrogen include electrochemical methods, hydrothermal corrosion methods, wet-heat oxidation corrosion methods, and gas-driven hydrogen isotope permeation methods. The electrochemical method evaluates the corrosion protection of titanium nitride films by measuring the corrosion potential and corrosion current using an electrochemical workstation. The hydrothermal corrosion method evaluates the corrosion protection based on the extent of the reaction between water and the film under high-temperature and high-pressure conditions. The wet-heat oxidation corrosion method evaluates the corrosion protection based on the oxidation reaction rate under wet-heat conditions. These three methods focus on the ease and rate of the film's own corrosion reaction and have nothing to do with its ability to inhibit hydrogen particle diffusion. Furthermore, the electrochemical and hydrothermal corrosion methods involve liquid-phase corrosion, which is inconsistent with the gaseous environment in which titanium nitride films operate. Gas-driven hydrogen isotope permeation methods apply high-pressure hydrogen gas to one side of the film and measure the permeating gas flow rate on the other side. While this method involves a gaseous corrosive environment and is associated with hydrogen diffusion inhibition, it suffers from two drawbacks. First, the sample needs to be squeezed and sealed before testing, which causes hard and brittle films such as titanium nitride to rupture, making the test results unable to truly reflect the hydrogen diffusion inhibition performance of the unbroken film; second, the diffusion and desorption of deuterium particles occur simultaneously during the experiment. The entire penetration process involves diffusion energy and desorption energy. When the desorption energy is greater than the diffusion energy, the experimental results cannot truly reflect the hydrogen diffusion inhibition performance of the film. Summary of the Invention

[0004] In light of this, the present invention aims to provide a method for detecting the hydrogen diffusion inhibition performance of titanium nitride films. This method, based on temperature-driven deuterium particle transport, does not damage the titanium nitride film and can accurately and sensitively reflect the hydrogen diffusion inhibition performance of the titanium nitride film.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0006] The present invention provides a method for detecting the hydrogen diffusion inhibition performance of a titanium nitride film, comprising the following steps:

[0007] (1) preparing a titanium nitride film into a sandwich composite structure; the sandwich composite structure includes a silicon substrate and a metal titanium film and a titanium nitride film sequentially stacked on the silicon substrate;

[0008] (2) heating the sandwich composite structure in a deuterium atmosphere for the first time, so that the deuterium penetrates the titanium nitride film of the sandwich composite structure and diffuses into the metal titanium film, thereby obtaining a composite structure that adsorbs deuterium;

[0009] (3) The composite structure adsorbing deuterium gas is subjected to a second heating under vacuum conditions to completely desorb the deuterium gas in the composite structure adsorbing deuterium gas; and the hydrogen diffusion inhibition performance of the titanium nitride film is obtained by detecting the desorption amount of the deuterium gas.

[0010] Preferably, the thickness of the metal titanium film in step (1) is 50 to 500 nm.

[0011] Preferably, the pressure of the deuterium gas in step (2) is 10 to 500 kPa.

[0012] Preferably, the first heating temperature in step (2) is 50-400° C., and the holding time is 1-96 hours.

[0013] Preferably, the pressure of the vacuum condition in step (3) is less than 5×10 -5 Pa.

[0014] Preferably, the heating rate of the second heating in step (3) is 5 to 30° C. / min.

[0015] Preferably, the method for detecting the desorption amount of deuterium gas in step (3) is mass spectrometry detection.

[0016] Preferably, the titanium nitride film in step (1) is also doped with oxygen.

[0017] Preferably, the method for preparing the sandwich composite structure in step (1) comprises the following steps:

[0018] (a) Using titanium metal as a target and argon as a working gas, ion plating or magnetron sputtering is performed on a silicon substrate to form a silicon substrate-titanium metal composite structure;

[0019] (b) Using titanium as a target and argon and nitrogen as working gases, ion plating or magnetron sputtering is performed on the surface of the titanium film of the silicon substrate-titanium composite structure to form the sandwich composite structure.

[0020] Preferably, the ion plating or magnetron sputtering process in step (b) further comprises introducing oxygen to perform oxygen doping.

[0021] The present invention provides a method for detecting the hydrogen diffusion inhibition performance of a titanium nitride film, comprising the following steps: preparing the titanium nitride film into a sandwich composite structure; the sandwich composite structure comprising a silicon substrate and a metal titanium film and a titanium nitride film sequentially stacked on the silicon substrate; performing a first heating on the sandwich composite structure in a deuterium atmosphere, so that the deuterium penetrates the titanium nitride film of the sandwich composite structure and diffuses into the metal titanium film, thereby obtaining a composite structure that adsorbs deuterium; performing a second heating on the composite structure that adsorbs deuterium under vacuum conditions, so that the deuterium in the composite structure that adsorbs deuterium is completely desorbed; and obtaining the hydrogen diffusion inhibition performance of the titanium nitride film by detecting the desorbed amount of deuterium. The present invention provides a method for detecting hydrogen diffusion inhibition in titanium nitride films based on temperature-driven deuterium particle transport. First, under deuterium gas working conditions, temperature drives deuterium particles to diffuse into the inner layer of the titanium nitride. Then, all the deuterium particles that have diffused into the titanium nitride are desorbed and the amount desorbed is detected. Based on the amount of desorbed deuterium particles, the amount of deuterium particles that have diffused into the titanium nitride film is determined, and the hydrogen diffusion resistance of the titanium nitride film is evaluated, thereby revealing the hydrogen corrosion resistance of the titanium nitride film. The present invention has the following beneficial effects:

[0022] The detection method of the present invention involves the gas-solid interaction between hydrogen and titanium nitride film, which is consistent with the working environment (gas working conditions) of titanium nitride film;

[0023] The present invention uses temperature-driven diffusion of deuterium particles into the titanium nitride film in a high-purity deuterium gas environment. The film is not oxidized to cause changes in chemical composition, and the titanium nitride film does not need to be sealed or squeezed to be damaged during the detection process. The test results can truly reflect the hydrogen diffusion inhibition performance of the film.

[0024] During the detection process, the present invention separates the diffusion and desorption of deuterium particles into two steps, thereby avoiding the influence and interference of desorption energy on diffusion energy when processing experimental results; based on the relationship that the "desorption amount" of deuterium particles is equal to the "diffusion amount", the present invention directly relates the deuterium particle desorption amount to the hydrogen diffusion inhibition performance of the titanium nitride film. By accurately detecting the deuterium particle desorption amount, the hydrogen inhibition performance of the film can be obtained. This method has a high sensitivity for detecting hydrogen diffusion inhibition performance, and the detection limit of deuterium retention is as high as 1ppm.

[0025] Therefore, the titanium nitride film hydrogen diffusion inhibition detection method based on temperature-driven deuterium particle transport provided by the present invention can truly and highly sensitively reflect the hydrogen diffusion inhibition performance of the titanium nitride film, breaking through the shortcomings of existing detection technologies, and has innovative principles and functional accuracy; in addition, the method is simple to operate, the equipment is domestically produced, and the cost is low. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 is the thermal desorption spectrum of deuterium particles in the MAIP# and MS# samples in Example 1;

[0027] Figure 2 is a scanning electron microscope image of the MAIP# and MS# samples in Example 1, Figure 2 (a) is a scanning electron micrograph of the surface of the MAIP# sample, (b) is a scanning electron micrograph of the cross section of the MAIP# sample, (c) is a scanning electron micrograph of the surface of the MS# sample, and (d) is a scanning electron micrograph of the cross section of the MS# sample;

[0028] Figure 3 is the deuterium particle thermal desorption spectrum of the LO# sample and the HO# sample in Example 2;

[0029] Figure 4 is the X-ray photoelectron spectrum of oxygen element of LO# and HO# samples in Example 2;

[0030] Figure 5 2 is the relationship between corrosion current and potential of Zr-MAIP# and Zr-MS# samples in Comparative Example 1;

[0031] Figure 6 This is an optical microscope photo of the surface of the sealed sample in Comparative Example 2;

[0032] Figure 7 Thermal desorption spectrum and permeation signal spectrum of zirconium-based alloy in Comparative Example 2; Figure 7 The middle left picture is the thermal desorption spectrum of zirconium-based alloy, and the right picture is the penetration signal spectrum of zirconium-based alloy. DETAILED DESCRIPTION

[0033] The present invention provides a method for detecting the hydrogen diffusion inhibition performance of a titanium nitride film, comprising the following steps:

[0034] (1) preparing a titanium nitride film into a sandwich composite structure; the sandwich composite structure includes a silicon substrate and a metal titanium film and a titanium nitride film sequentially stacked on the silicon substrate;

[0035] (2) heating the sandwich composite structure in a deuterium atmosphere for the first time, so that the deuterium penetrates the titanium nitride film of the sandwich composite structure and diffuses into the metal titanium film, thereby obtaining a composite structure that adsorbs deuterium;

[0036] (3) The composite structure adsorbing deuterium gas is subjected to a second heating under vacuum conditions to completely desorb the deuterium gas in the composite structure adsorbing deuterium gas; and the hydrogen diffusion inhibition performance of the titanium nitride film is obtained by detecting the desorption amount of the deuterium gas.

[0037] The present invention prepares the titanium nitride film into a sandwich composite structure; the sandwich composite structure includes a silicon substrate and a metal titanium film and a titanium nitride film sequentially stacked on the silicon substrate. In the present invention, the silicon substrate is preferably a single crystal silicon substrate, and the present invention has no special requirements for the thickness of the silicon substrate; on the one hand, the silicon substrate plays a supporting role, and on the other hand, the solubility of hydrogen in the silicon substrate is much smaller than that of titanium nitride and titanium film, so it does not interfere with the desorption signal, and the silicon substrate has a very strong ability to block the diffusion of hydrogen, so it is believed that all hydrogen diffused into the titanium layer diffuses into the titanium layer from the titanium nitride layer. In the present invention, the thickness of the metal titanium film is preferably 50 to 500 nm, more preferably 100 to 500 nm; the titanium nitride film is also preferably doped with oxygen, and the amount of oxygen doping is determined according to actual needs.

[0038] In the present invention, the method for preparing the sandwich composite structure preferably comprises the following steps:

[0039] (a) Using titanium metal as a target and argon as a working gas, ion plating or magnetron sputtering is performed on a silicon substrate to form a silicon substrate-titanium metal composite structure;

[0040] (b) Using titanium as a target and argon and nitrogen as working gases, ion plating or magnetron sputtering is performed on the surface of the titanium film of the silicon substrate-titanium composite structure to form the sandwich composite structure.

[0041] In the present invention, before ion plating or magnetron sputtering in step (a), the silicon substrate and target are preferably subjected to plasma cleaning. The plasma cleaning method is preferably as follows: placing the silicon substrate and target in a thin film preparation chamber, evacuating the chamber and heating the chamber; then introducing argon gas into the chamber to generate plasma to clean the surfaces of the silicon substrate and target. In the present invention, the pressure after evacuation is preferably less than 1×10 -3Pa, the heating temperature is preferably 200-250°C; the argon gas is preferably high-purity argon gas, and the pressure of the argon gas is preferably 0.1 Pa. In the present invention, during the ion plating or magnetron sputtering process, the pressure of the working gas (i.e., argon gas, preferably high-purity argon gas) is preferably 1-10 Pa, more preferably 2-5 Pa; through the ion plating or magnetron sputtering, the metal titanium target undergoes thermal evaporation (ion plating) or physical sputtering (magnetron sputtering) and is deposited on the surface of the silicon substrate to form a metal titanium film, and the time of the ion plating or magnetron sputtering is based on the thickness of the metal titanium film.

[0042] In the present invention, the argon and nitrogen in the working gas of step (b) are preferably high-purity argon and high-purity nitrogen, respectively, and the volume flow ratio of the nitrogen and argon is preferably 1:3; the pressure of the working gas is preferably 1 to 10 Pa, more preferably 3 to 6 Pa. During the ion plating or magnetron sputtering process, the metal titanium target undergoes thermal evaporation (ion plating) or physical sputtering (magnetron sputtering) and chemical reaction, and a titanium nitride film is deposited on the metal titanium surface of the silicon substrate-metal titanium composite structure, and the titanium nitride film completely wraps and covers the metal titanium; by controlling the time of ion plating or magnetron sputtering, the thickness of the titanium nitride film is regulated, specifically according to the thickness requirements of the titanium nitride film. In the present invention, during the ion plating or magnetron sputtering process, oxygen is preferably introduced for oxygen doping, and the amount of oxygen doping is set according to actual needs, thereby forming an oxygen-doped titanium nitride film. After the ion plating or magnetron sputtering coating is completed, the chamber temperature is preferably lowered to 50°C under vacuum conditions, and the formed sandwich composite structure is taken out; the pressure of the vacuum conditions is preferably less than 1×10 -3 Pa. In the present invention, the magnetron sputtering in step (a) and step (b) can be conventional magnetron sputtering or high-power pulse magnetron sputtering, and the present invention does not make any special requirements for this.

[0043] After the titanium nitride film is prepared into a sandwich composite structure, the present invention first heats the sandwich composite structure in a deuterium atmosphere, and the deuterium penetrates the titanium nitride film of the sandwich composite structure and diffuses into the metal titanium film, thereby obtaining a composite structure that adsorbs deuterium. The present invention preferably places the sandwich composite structure in a cavity and evacuates the cavity to a pressure of less than 1×10 -3Pa, then deuterium gas is introduced into the cavity, and the sandwich composite structure is first heated in a deuterium atmosphere. In the present invention, the pressure of the deuterium gas is preferably 10 to 500 kPa, more preferably 100 to 400 kPa, and the pressure of the deuterium gas is specifically set according to factors such as the thickness of the metal titanium film and the microstructure of the titanium nitride. In the present invention, the temperature of the first heating is preferably 50 to 400 ° C, more preferably 100 to 300 ° C, and the holding time is preferably 1 to 96 hours, more preferably 4 to 50 hours. The present invention has no special requirements for the heating rate to the temperature of the first heating; when the temperature of the first heating is lower than 50 ° C, it is difficult for deuterium gas to pass through the titanium nitride film to reach the metal titanium layer, and when the temperature of the first heating is higher than 400 ° C, it is easy to cause the titanium nitride film to undergo oxidation and decomposition; the present invention controls the temperature of the first heating to 50 to 400 ° C, while satisfying the diffusion of deuterium gas, ensuring that the titanium nitride film is not oxidized and causes changes in chemical composition. During the first heating process, deuterium, driven by temperature, penetrates the titanium nitride film, diffuses into the titanium metal layer, and remains there. The higher the heating temperature, the faster the deuterium diffusion rate, and thus the shorter the time to saturation. When evaluating titanium nitride films with excellent hydrogen suppression, the heating temperature should be increased; when evaluating titanium nitride films with poor hydrogen suppression, the heating temperature should be lowered. After deuterium diffusion is complete, heating is stopped and the chamber is allowed to cool naturally.

[0044] After obtaining the composite structure adsorbing deuterium, the present invention performs a second heating on the composite structure adsorbing deuterium under vacuum conditions to completely desorb the deuterium in the composite structure adsorbing deuterium; and the hydrogen diffusion inhibition performance of the titanium nitride film is obtained by detecting the desorbed amount of deuterium. In the present invention, the pressure of the vacuum condition is preferably less than 5×10 -5Pa is an ultra-high vacuum condition. In the present invention, the heating rate of the second heating is preferably 5 to 30°C / min, more preferably 10°C / min, and the temperature is raised to the point where the deuterium gas is completely desorbed. In the present invention, the heating rate and temperature of the second heating are preferably monitored by a temperature controller with an accuracy of ±0.1°C. In the present invention, the method for detecting the desorption amount of the deuterium gas is preferably mass spectrometry detection, and the detection limit of the mass spectrometry detection is 1ppm; the detection process is specifically as follows: during the second heating process, the deuterium gas is desorbed and detected by the mass spectrometer, and the desorption spectrum data is collected. According to the desorption signal intensity of different samples, the hydrogen diffusion inhibition performance of different samples is evaluated or compared. The present invention utilizes a high-precision programmed temperature rise thermal desorption method so that the deuterium gas retained in the metal titanium layer is driven by temperature to desorb into the vacuum cavity environment and is detected by a high-sensitivity mass spectrometer. During the detection process, the present invention separates the diffusion and desorption of deuterium particles into two steps to avoid the influence and interference of desorption energy on diffusion energy. Based on the relationship that the "desorption amount" of deuterium particles is equal to the "diffusion amount", the desorption amount of deuterium particles is directly related to the hydrogen diffusion inhibition performance of the titanium nitride film. By accurately detecting the desorption amount of deuterium particles, the hydrogen inhibition performance of the film can be obtained. This method has a high sensitivity for detecting hydrogen diffusion inhibition performance, and the detection limit of deuterium retention is as high as 1ppm.

[0045] The following describes in detail the method for detecting the hydrogen diffusion inhibition performance of the titanium nitride film provided by the present invention in conjunction with the examples, but they should not be understood as limiting the scope of protection of the present invention.

[0046] Example 1

[0047] (1) Si-Ti-TiN sandwich composite structures (referred to as Si-Ti-TiN film samples) were prepared by ion plating (MAIP) and magnetron sputtering (MS) methods, respectively. The corresponding samples are marked as MAIP# and MS#. The preparation methods are as follows:

[0048] Preparation of MS# samples (magnetron sputtering):

[0049] The cleaned single crystal silicon wafer and the titanium target were placed in the thin film preparation chamber, and the chamber was evacuated and heated. The temperature was controlled at 200 ° C and the pressure was less than 1×10 -3 Pa; high-purity argon gas is introduced at a pressure of 0.1 Pa, and the magnetron plasma power supply is turned on to generate plasma and clean the surfaces of the single crystal silicon and metal titanium targets;

[0050] By increasing the flow rate of high-purity argon gas and raising the pressure to 2 Pa, the titanium target undergoes physical sputtering and deposits a titanium film on the surface of the single crystal silicon. The film thickness is about 500 nm.

[0051] High-purity argon and high-purity nitrogen were introduced simultaneously, with a nitrogen to argon volume flow ratio of 1:3 and a chamber pressure of 3 Pa. The titanium target underwent physical sputtering and chemical reaction, and a titanium nitride film with a thickness of 300 nm was deposited on the titanium surface.

[0052] The sputtering reaction was stopped, the gas flow into the chamber was stopped, the chamber temperature was lowered to 50° C. under vacuum conditions, and the prepared Si—Ti—TiN thin film sample, ie, the MS# sample, was taken out.

[0053] Preparation of MAIP# samples (ion plating):

[0054] The cleaned single crystal silicon wafer and the titanium target were placed in the thin film preparation chamber, and the chamber was evacuated and heated. The temperature was controlled at 200 ° C and the pressure was less than 1×10 -3 Pa; high-purity argon gas is introduced at a pressure of 0.1 Pa, and the multi-arc ion plating power supply is turned on to generate plasma and clean the surface of the single crystal silicon and metal titanium targets;

[0055] By increasing the flow rate of high-purity argon gas and raising the pressure to 2 Pa, the titanium target undergoes thermal evaporation and deposits a titanium film on the surface of the single crystal silicon. The film thickness is about 500 nm.

[0056] High-purity argon and high-purity nitrogen were introduced simultaneously, with a nitrogen to argon volume flow ratio of 1:3 and a chamber pressure of 3 Pa. The titanium target underwent thermal evaporation and chemical reaction, and a titanium nitride film with a thickness of 300 nm was deposited on the titanium surface.

[0057] The sputtering reaction was stopped, the gas flow into the chamber was stopped, the chamber temperature was lowered to 50° C. under vacuum conditions, and the prepared Si—Ti—TiN thin film sample, ie, the MAIP# sample, was taken out.

[0058] (2) Driven by temperature, hydrogen isotope deuterium gas penetrates the titanium nitride film and diffuses into the metal titanium layer and is retained. The specific operation is as follows:

[0059] The Si-Ti-TiN thin film samples (MAIP# and MS#) prepared in (1) were placed in small chambers and evacuated to a pressure less than 1×10 -3 Pa; introduce a certain amount of deuterium gas into the small cavity at a pressure of 400 kPa; slowly heat the small cavity to 300 ° C and keep the temperature constant for 4 hours; stop heating and cool the small cavity naturally.

[0060] (3) Using a high-precision temperature-programmed thermal desorption method, the retention of deuterium particles in the MAIP# and MS# samples was measured. The specific operation is as follows:

[0061] The film sample with retained deuterium particles (denoted as Si-Ti-TiN:D) was placed on the chamber heating stage, and the chamber was evacuated to a pressure less than 5×10 -5 Pa; turn on a high-precision mass spectrometer (mass spectrometer detection limit is 1 ppm) and perform calibration for quantitative measurement; heat the sample (temperature is monitored by a temperature controller with an accuracy of ±0.1°C) at a heating rate of 10°C / min to 700°C. During the heating process, deuterium particles desorb from the sample and are detected by the mass spectrometer. Desorption spectrum data is collected to obtain the desorption signal intensities of different samples.

[0062] Figure 1 is the thermal desorption spectrum of deuterium particles in MAIP# and MS# samples. Figure 1 It can be seen that the deuterium particle desorption signal of MS# is lower than that of MAIP# sample, that is, the retention is less, which means that the amount of deuterium particles diffused into MS# sample is small, that is, the MS# sample has a strong ability to block hydrogen diffusion.

[0063] The MAIP# and MS# samples were characterized by scanning electron microscopy. Figure 2 As shown, Figure 2 (a) is a scanning electron microscope image of the surface of the MAIP# sample, (b) is a scanning electron microscope image of the cross section of the MAIP# sample, (c) is a scanning electron microscope image of the surface of the MS# sample, and (d) is a scanning electron microscope image of the cross section of the MS# sample. Figure 2 It can be seen that the MAIP# film contains more particles, resulting in poor film density, while the MS# sample is relatively dense; the film structure is not dense, which provides more diffusion channels for hydrogen particles to diffuse. Therefore, the film structure characterization results clearly explain why MS# has a stronger hydrogen diffusion resistance than MAIP#.

[0064] Example 2

[0065] (1) Si-Ti-TiN thin film samples were prepared using the magnetron sputtering (MS) method. The preparation process was the same as in Example 1, except that a small amount of oxygen was introduced into the cavity during the deposition of the titanium nitride film. When the volume percentage of oxygen (oxygen / argon) was 1.0% and 3.0%, titanium nitride films with different oxygen contents were formed, which were marked as low-oxygen (LO#) samples and high-oxygen (HO#) samples, respectively.

[0066] (2) Using the same operating method as step (2) in Example 1, deuterium gas (400 kPa) was driven to diffuse into the LO# sample and the HO# sample at a temperature of 300° C. for 4 hours.

[0067] (3) The retention of deuterium particles in the LO# sample and the HO# sample was measured using the same temperature-programmed desorption method and temperature-programmed desorption conditions as in Example 1. The results are as follows: Figure 3 As shown, Figure 3 is the deuterium particle thermal desorption spectrum of LO# sample and HO# sample. Figure 3 It can be seen that the deuterium particle desorption signal of the HO# sample is lower than that of the LO# sample, that is, the retention is less, which means that the amount of deuterium particles diffused into the HO# sample is small, that is, the HO# sample has a strong ability to block hydrogen diffusion.

[0068] The LO# and HO# samples were characterized by X-ray photoelectron spectroscopy. The results are as follows: Figure 4 As shown, Figure 4 The X-ray photoelectron spectra of oxygen element of LO# and HO# samples are shown in Figure 2. Figure 4 As can be seen, the HO# sample has a higher oxygen content, accounting for about 11%, while the LO# sample has a lower oxygen content, accounting for about 7%. The HO# sample has a strong resistance to hydrogen diffusion, indicating that oxygen atoms block the diffusion channels of hydrogen particles in the titanium nitride.

[0069] Comparative Example 1 Traditional electrochemical characterization method

[0070] Using a zirconium-based alloy as the substrate, Zr-Ti-TiN sandwich composite structures were prepared using magnetron sputtering (MS) and magnetron ion plating (MAIP), respectively. The corresponding samples are labeled Zr-MAIP# and Zr-MS#. The preparation process parameters for this sandwich structure were identical to those in Example 1, except that the single-crystal silicon substrate was replaced with a zirconium-based alloy. The zirconium-based alloy was replaced with the single-crystal silicon substrate because single-crystal silicon has poor electrical conductivity, which reduces the accuracy of electrochemical performance test results, while the zirconium-based alloy has good electrical conductivity and does not interfere with electrochemical performance testing.

[0071] The relationship between corrosion current and potential of Zr-MAIP# and Zr-MS# sample films was measured using traditional electrochemical methods. The measurement equipment used was a CS310 electrochemical workstation produced by Wuhan Cost Instrument Co., Ltd. Zr-MAIP# or Zr-MS# sample films were used as working electrodes, platinum electrodes were used as counter electrodes, Ag / AgCl was used as reference cells, the electrolyte was a 3.5wt% NaCl aqueous solution, and a dynamic potential scanning mode was adopted with a scanning potential range of -0.8 to -0.3V. The results are shown in Figure 2. Figure 5 As shown, Figure 5 Figure 2 is the relationship between corrosion current and potential of Zr-MAIP# and Zr-MS# samples.

[0072] Depend on Figure 5It can be seen that there is no significant difference in the self-corrosion potentials of the Zr-MAIP# and Zr-MS# samples prepared by ion plating and magnetron sputtering, and the self-corrosion current of the Zr-MS# sample is slightly smaller than that of the Zr-MAIP# sample. The self-corrosion potential reflects the corrosion resistance of the material, while the self-corrosion current reflects the rate of corrosion reaction under the applied corrosion potential. This is fundamentally different from the hydrogen diffusion inhibition behavior of the film. Therefore, traditional electrochemical methods cannot characterize the hydrogen diffusion inhibition properties of the material.

[0073] Comparative Example 2 Gas-driven hydrogen isotope permeation method

[0074] A Ti-TiN film (denoted as Zr-Ti-TiN film) with a zirconium-based alloy substrate was prepared using the same process parameters as the ion plating method in Example 1, except that the single-crystal silicon substrate was replaced with a zirconium-based alloy. The gas-driven hydrogen isotope infiltration method requires compression during sample sealing and mounting, and a silicon substrate would break. Therefore, a zirconium-based alloy metal substrate with greater elasticity was used instead.

[0075] The gas-driven hydrogen isotope permeation method was used. First, the Zr-Ti-TiN film sample was sealed on both sides and installed in a gas pipeline. A certain pressure (100 kPa) of hydrogen isotope deuterium gas was introduced from one side of the sample through the pipeline, and the other side was connected to an ultra-high vacuum environment (pressure less than 1×10 -4 Pa). Such high vacuum conditions require the sample to be squeezed and sealed to obtain a small leakage rate, but squeezing and sealing will destroy the hard and brittle film. Figure 6 This is an optical microscope photo of the surface of the sealed sample. It can be seen that the titanium nitride film is damaged and its density has changed. Therefore, the hydrogen diffusion resistance obtained in the test is not the original property of the film.

[0076] The gas-driven hydrogen isotope penetration method involves two steps: "diffusion of hydrogen isotope deuterium particles from the film surface to the bulk phase" and "desorption on another surface". This method characterizes the film's resistance to hydrogen diffusion based on the penetration rate of deuterium particles. This method is effective and correct only when the first step, "diffusion to the bulk phase", is the rate-determining step; and when the second step, "desorption on another surface", is the rate-determining step, the method is invalid. For example, in the zirconium-based alloy matrix film Zr-Ti-TiN, a large number of deuterium particles have penetrated the titanium nitride film into the zirconium-based alloy matrix (such as Figure 7 As shown in the left figure, the deuterium particle desorption signal was not detected on the other surface (the surface of the zirconium-based alloy substrate without film coating). Figure 7 (As shown in the middle right figure). This experimental result indicates that the "desorption of Zr-Ti-TiN on another surface" is the rate-determining step, meaning that the gas-driven hydrogen isotope permeation method is not suitable for characterizing the ability of titanium nitride films with large desorption energy on the substrate surface to block the diffusion of deuterium particles.

[0077] It can be seen from the above embodiments that the method for detecting hydrogen diffusion inhibition of titanium nitride film based on temperature-driven deuterium particle transport provided by the present invention will not damage the titanium nitride film and can truly and highly sensitively reflect the hydrogen diffusion inhibition performance of the titanium nitride film.

[0078] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A method for detecting the hydrogen diffusion inhibition performance of titanium nitride thin films, characterized in that: The following steps are involved: (1) preparing a titanium nitride film into a sandwich composite structure; the sandwich composite structure includes a silicon substrate and a metal titanium film and a titanium nitride film sequentially stacked on the silicon substrate; (2) heating the sandwich composite structure in a deuterium atmosphere for the first time, so that the deuterium penetrates the titanium nitride film of the sandwich composite structure and diffuses into the metal titanium film, thereby obtaining a composite structure that adsorbs deuterium; (3) The composite structure adsorbing deuterium gas is subjected to a second heating under vacuum conditions to completely desorb the deuterium gas in the composite structure adsorbing deuterium gas; and the hydrogen diffusion inhibition performance of the titanium nitride film is obtained by detecting the desorption amount of the deuterium gas.

2. The detection method according to claim 1, wherein The thickness of the metal titanium film in step (1) is 50 to 500 nm.

3. The detection method according to claim 1, wherein The pressure of the deuterium gas in step (2) is 10 to 500 kPa.

4. The detection method according to claim 1 or 3, characterized in that The temperature of the first heating in step (2) is 50-400° C., and the insulation time is 1-96 hours.

5. The detection method according to claim 1, wherein The pressure of the vacuum condition in step (3) is less than 5×10 -5 Pa.

6. The detection method according to claim 1 or 5, characterized in that The heating rate of the second heating in step (3) is 5 to 30°C / min.

7. The detection method according to claim 1, characterized in that The method for detecting the desorption amount of deuterium gas in step (3) is mass spectrometry detection.

8. The detection method according to claim 1, wherein In the step (1), the titanium nitride film is also doped with oxygen.

9. The detection method according to claim 1, wherein The method for preparing the sandwich composite structure in step (1) comprises the following steps: (a) Using titanium metal as a target and argon as a working gas, ion plating or magnetron sputtering is performed on a silicon substrate to form a silicon substrate-titanium metal composite structure; (b) Using titanium as a target and argon and nitrogen as working gases, ion plating or magnetron sputtering is performed on the surface of the titanium film of the silicon substrate-titanium composite structure to form the sandwich composite structure.

10. The detection method according to claim 9, characterized in that: The ion plating or magnetron sputtering process in step (b) further includes introducing oxygen to perform oxygen doping.

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