FeCrNiWB / D thin film, and preparation method and application thereof

Abstract

The application belongs to the technical field of hydrogen isotope-containing materials and preparation, and particularly relates to a FeCrNiWB / D film, a preparation method and application thereof. The FeCrNiWB / D film provided by the application contains iron, chromium, nickel, tungsten, boron and deuterium elements, and covers most fusion reactor material elements, and can be used for quantitative calibration of deuterium content in fusion reactor materials by glow discharge optical emission spectrometry. The high-throughput preparation method of the deuterium-containing film based on the magnetron sputtering technology can obtain deuterium-containing films with different deuterium concentrations and different structures, and can be used to optimize the depth resolution and concentration resolution of the glow discharge optical emission spectrometry for detecting deuterium concentration. Meanwhile, the high-throughput preparation method of the deuterium-containing film material can obtain deuterium-containing films with various element compositions, contents and structures in the same batch, so that the composition difference of the films caused by the difference in equipment state in the preparation process of different batches of deuterium-containing film materials is avoided.

Description

Technical Field

[0001] This invention belongs to the field of hydrogen isotope materials and their preparation technology, specifically relating to a FeCrNiWB / D thin film, its preparation method, and its application. Background Technology

[0002] Hydrogen isotope-containing materials have wide applications and promising prospects, playing a crucial role in national energy strategies. For advanced fusion reactors, deuterium and tritium are the most promising fuels, and their diffusion, infiltration, and retention in the first wall and structural materials are unavoidable. However, tritium is radioactive and expensive, posing challenges to material replacement, decommissioning, and economic cost control in fusion reactors. It is necessary to control the tritium retention in fusion reactor materials to a low level. Therefore, developing quantitative measurement techniques for hydrogen isotopes in materials is essential to meet the scientific research needs of hydrogen isotope retention behavior in fusion reactor materials and the engineering control needs of the total amount of hydrogen isotopes retained.

[0003] Glow discharge spectroscopy is a spectroscopic analysis method that utilizes the discharge of gas under low pressure to sputter atoms from a target material. The elemental content can be determined by analyzing the characteristic spectra of the sputtered atoms. Glow discharge spectroscopy features high sensitivity and a low detection limit, enabling the detection of low concentrations of elements. For the detection of hydrogen isotope content in fusion reactor materials, glow discharge spectroscopy offers high accuracy, deep measurement, a simple testing process, low cost, and a short detection cycle, making it a promising method for application.

[0004] However, the quantitative detection of hydrogen isotopes in hydrogen-containing isotope materials by glow discharge spectroscopy relies on calibration techniques, requiring the preparation of a large number of hydrogen-containing isotope materials with complex compositions to establish a functional relationship between the hydrogen isotope concentration and the detection signal in different materials. Furthermore, the preparation process of hydrogen-containing isotope materials is relatively complex, costly, and lacks compositional diversity.

[0005] Therefore, providing a hydrogen isotope material with high safety, simple preparation process, and good composition and structural diversity is a technical problem that urgently needs to be solved by those skilled in the art. Summary of the Invention

[0006] The purpose of this invention is to provide a FeCrNiWB / D thin film, its preparation method, and its application. The FeCrNiWB / D thin film material provided by this invention has high safety, simple preparation process, and good compositional diversity.

[0007] To achieve the above objectives, the present invention provides the following technical solution:

[0008] This invention provides a FeCrNiWB / D thin film, wherein the D content is 0 to 1 × 10⁻⁶. 21 D / m 2And it is not 0.

[0009] Preferably, the thickness of the FeCrNiWB / D thin film is 10–5000 nm.

[0010] This invention also provides a method for preparing the FeCrNiWB / D thin film described in the above technical solution, comprising the following steps:

[0011] Using tungsten, iron, chromium-nickel, and boron targets as targets, thin films were deposited on the substrate surface by magnetron sputtering under argon and deuterium atmospheres to obtain the FeCrNiWB / D thin film.

[0012] Preferably, the substrate is converted using a photomask, which is located between the substrate and the target. The distance between the photomask and the substrate is 0-2 mm and not 0 mm; the distance between the photomask and the target is 75-150 mm.

[0013] Preferably, the substrate is further subjected to bias cleaning before magnetron sputtering, and the bias cleaning time is 5 to 30 minutes; the gas used for bias cleaning is argon, and the volumetric flow rate of argon is 30 to 50 sccm; the gas pressure in the magnetron sputtering chamber during bias cleaning is 2 to 5 Pa, and the substrate bias voltage is -200 to -600 V.

[0014] Preferably, the volumetric flow rate of argon gas during magnetron sputtering is 40 sccm, and the volumetric flow rate of deuterium gas is 2 to 200 sccm.

[0015] Preferably, the gas pressure in the magnetron sputtering chamber during magnetron sputtering is 0.5 to 1 Pa, and the substrate bias voltage is -20 to -200 V.

[0016] Preferably, the magnetron sputtering includes DC power supply sputtering and radio frequency power supply sputtering; the target material for DC power supply sputtering is a tungsten target, an iron target, and a chromium-nickel target; the target material for radio frequency power supply sputtering is a boron target; and the power density of the tungsten target, iron target, chromium-nickel target, and boron target is independently 0–20 W / cm². 2 And it is not 0.

[0017] The present invention also provides the application of the FeCrNiWB / D thin film described in the above technical solution or the FeCrNiWB / D thin film prepared by the preparation method described in the above technical solution in the detection of elemental content by glow discharge spectroscopy.

[0018] Preferably, the application includes quantitative calibration of the deuterium content in fusion reactor materials using glow discharge spectroscopy and optimization of the depth and concentration resolution of glow discharge spectroscopy equipment.

[0019] This invention provides a FeCrNiWB / D thin film, wherein the D content is 0 to 1 × 10⁻⁶. 21D / m 2 And not 0. The thin film material provided by this invention contains iron, chromium, nickel, tungsten, boron, and deuterium, encompassing most of the elements in fusion reactor materials. In this invention, for deuterium-containing materials, the power density of each target material can be controlled by magnetron sputtering technology, and ionized deuterium ions can be introduced into the plasma to obtain thin film materials with various elemental compositions, structures, and different deuterium contents.

[0020] This invention also provides a method for preparing the FeCrNiWB / D thin film described in the above technical solution, comprising the following steps: using tungsten, iron, chromium-nickel, and boron targets as target materials, and depositing the thin film on the substrate surface by magnetron sputtering under an argon and deuterium atmosphere to obtain the FeCrNiWB / D thin film. The high-throughput preparation method for deuterium-containing thin film materials provided by this invention can obtain deuterium-containing thin films with multiple elemental compositions, contents, and structures in the same batch, avoiding differences in film composition caused by differences in equipment conditions during the preparation of different batches of deuterium-containing film materials. The preparation method of FeCrNiWB / D thin films provided by this invention is simple, the film structure, thickness, and elemental content are precisely controllable, and the production cost is low. It can obtain batches of deuterium-containing thin film materials with different structures and compositions without removing samples. The FeCrNiWB / D thin film preparation method provided by this invention yields deuterium-containing thin films with different deuterium concentrations and structures. These films can be used for quantitative calibration of the deuterium content in fusion reactor materials detected by glow discharge spectroscopy, and can also be used to optimize the depth resolution and concentration resolution of deuterium concentration.

[0021] This invention also provides the application of the FeCrNiWB / D thin film described in the above-described technical solution or the FeCrNiWB / D thin film prepared by the preparation method described in the above-described technical solution in the detection of elemental content by glow discharge spectroscopy. The application of the deuterium thin film material provided by this invention can be extended to scientific research and engineering feasibility analysis in fields such as the study of hydrogen isotope-material interactions in nuclear fusion reactors, solid-state tritium storage materials, and tritium-based photovoltaic cells. Attached Figure Description

[0022] Figure 1 The images show cross-sectional SEM images of the FeCrNiWB / D thin film materials obtained in Examples 1-6.

[0023] Figure 2 The graph shows the test results of the total deuterium content in the deuterium-containing thin film materials obtained in Examples 1-6 of this invention;

[0024] Figure 3 This is a schematic diagram of the multilayer deuterium-containing thin film material obtained in Application Example 1 of the present invention;

[0025] Figure 4 This is a deuterium desorption signal diagram in the multilayer deuterium-containing thin film material obtained in Application Example 1 of the present invention. Detailed Implementation

[0026] This invention provides a FeCrNiWB / D thin film, wherein the D content is 0 to 1 × 10⁻⁶. 21 D / m 2 And it is not 0.

[0027] In this invention, the atomic percentage of each element other than D is preferably less than 100% and not 0%.

[0028] In this invention, the thickness of the FeCrNiWB / D thin film is preferably 10-5000 nm, more preferably 100-2000 nm, and even more preferably 1000 nm.

[0029] This invention also provides a method for preparing the FeCrNiWB / D thin film described in the above technical solution, comprising the following steps:

[0030] Using tungsten, iron, chromium-nickel, and boron targets as targets, thin films were deposited on the substrate surface by magnetron sputtering under argon and deuterium atmospheres to obtain the FeCrNiWB / D thin film.

[0031] In this invention, unless otherwise specified, all raw materials used in the preparation are commercially available products well known to those skilled in the art.

[0032] In this invention, the atomic ratio of chromium to nickel in the chromium-nickel target is preferably 1:1. In this invention, the purity of the tungsten target, iron target, chromium-nickel target, and boron target is preferably 99.99% independently. In this invention, the target material is preferably mounted on four independent magnetron sputtering device heads.

[0033] In this invention, the substrate is preferably a monocrystalline silicon substrate; the monocrystalline silicon substrate is preferably placed in a rotatable sample dish. Before placing the monocrystalline silicon substrate in the rotatable sample dish, this invention also preferably includes ultrasonic cleaning of the substrate using anhydrous ethanol; this invention does not have any particular limitations on the ultrasonic cleaning process, and any cleaning process well known to those skilled in the art can be used.

[0034] In this invention, the rotatable sample disk is preferably placed at the focal point of four independent magnetron sputtering targets. This invention does not impose any special limitations on the material and size of the rotatable sample disk; materials well-known to those skilled in the art can be used. In this invention, the rotation of the rotatable sample disk is preferably controlled by a rotary potentiometer in conjunction with a limit switch.

[0035] In this invention, the substrate is preferably converted using a photomask, which is preferably connected to and fixed to the magnetron sputtering chamber; the photomask is preferably located between the substrate and the target. In this invention, the distance between the photomask and the substrate is preferably 0–2 mm, more preferably 0–1 mm, and not 0; the distance between the photomask and the target is 75–150 mm, more preferably 90–135 mm, and more preferably 120 mm. In this invention, the photomask is fixed during magnetron sputtering, and by controlling the rotation angle of the sample disk, different substrates can be exposed to the plasma to obtain FeCrNiWB / D thin films with different compositions, structures, and microstructures.

[0036] Before magnetron sputtering of the substrate, the present invention preferably includes bias cleaning of the substrate. Before bias cleaning, the magnetron sputtering chamber is preferably evacuated, and the pressure of the magnetron sputtering chamber is preferably below 1.5 × 10⁻⁶. - 3 Pa, more preferably below 1.0 × 10 Pa -3 Pa, more preferably below 8.0 × 10 Pa -4 Pa.

[0037] In this invention, the gas used for bias cleaning is preferably argon, and the volumetric flow rate of the argon is preferably 30-50 sccm, more preferably 35-45 sccm, and even more preferably 40 sccm.

[0038] In this invention, the gas pressure in the magnetron sputtering chamber during bias cleaning is preferably 2–5 Pa, more preferably 3–4 Pa. In this invention, the gas pressure in the magnetron sputtering chamber is preferably adjusted via a molecular pump gate valve. In this invention, the substrate bias voltage during bias cleaning is preferably -200 to -600 V, more preferably -300 to -500 V, and even more preferably -400 V. In this invention, the substrate bias voltage can excite argon plasma to perform surface cleaning on the substrate surface, removing surface oxides and other impurities.

[0039] In this invention, the bias cleaning time is preferably 5 to 15 minutes, and more preferably 10 minutes.

[0040] After the substrate is cleaned by bias, the present invention preferably introduces deuterium gas, and thin film deposition is performed on the substrate surface by magnetron sputtering under an atmosphere of argon and deuterium.

[0041] In this invention, the purity of the argon gas is preferably greater than 99.99%; during magnetron sputtering, the volumetric flow rate of the argon gas is preferably 40 sccm. In this invention, the purity of the deuterium gas is preferably greater than 99.99%; the flow rate of the deuterium gas is preferably 2–200 sccm. In this invention, the volumetric flow rate of the deuterium gas is preferably controlled automatically by a programmable method. In this invention, FeCrNiWB / D thin films with different deuterium contents can be obtained by controlling the flow rate of the deuterium gas.

[0042] In this invention, the gas pressure in the magnetron sputtering chamber during magnetron sputtering is preferably 0.5–1 Pa, more preferably 0.6–0.8 Pa, and even more preferably 0.75 Pa; the gas pressure in the magnetron sputtering chamber during magnetron sputtering is preferably adjusted by the opening of the molecular pump gate valve. In this invention, the substrate bias voltage during magnetron sputtering is preferably -20–-200 V, more preferably -50–-180 V, and even more preferably -150 V.

[0043] In this invention, the film deposition time is preferably 5 to 360 min.

[0044] In this invention, the magnetron sputtering preferably includes DC power supply sputtering and radio frequency power supply sputtering; the target material for the DC power supply sputtering is preferably a tungsten target, an iron target, or a chromium-nickel target; the target material for the radio frequency power supply sputtering is preferably a boron target; and the power density of the tungsten target, iron target, chromium-nickel target, and boron target is preferably 0–20 W / cm². 2 More preferably 0–10 W / cm 2 And it is not 0. In this invention, the power density of the target material is preferably controlled by programmable automation. This invention obtains thin film materials with different elemental compositions, gradients / multilayers, and other structures by controlling the power density of the target material.

[0045] The present invention also provides the application of the FeCrNiWB / D thin film described in the above technical solution or the FeCrNiWB / D thin film prepared by the preparation method described in the above technical solution in the detection of elemental content by glow discharge spectroscopy.

[0046] In this invention, the preferred application includes quantitative calibration of the deuterium content in fusion reactor materials using glow discharge spectroscopy and optimization of the depth and concentration resolution of the glow discharge spectroscopy equipment.

[0047] To further illustrate the present invention, the FeCrNiWB / D thin film, its preparation method, and its application provided by the present invention will be described in detail below with reference to the accompanying drawings and embodiments, but these should not be construed as limiting the scope of protection of the present invention.

[0048] Example 1

[0049] Tungsten, iron, chromium-nickel (Cr:Ni = 1:1) and boron targets are respectively mounted on four independent magnetron sputtering heads. The tungsten, iron and chromium-nickel targets are equipped with independent DC power supplies, while the boron target is equipped with an RF power supply.

[0050] After ultrasonically cleaning the single-crystal silicon substrate with anhydrous ethanol, it was placed in the sample tray of the magnetron sputtering equipment chamber. A mask was placed and fixed in the equipment chamber. The distance between the mask and the substrate was adjusted to 1 mm, and the distance between the mask and the target was adjusted to 90 mm.

[0051] Evacuate the magnetron sputtering equipment until the cavity pressure is below 1.5 × 10⁻⁶. -3 After Pa, high-purity argon gas with a flow rate of 40 sccm is introduced. The pressure in the chamber is adjusted to 3 Pa by adjusting the molecular pump gate valve. A bias voltage of -500V is applied to the substrate, and the surface of the substrate is cleaned by the ionized high-energy argon ions. This process lasts for 5 minutes.

[0052] A deuterium-containing thin film was deposited by introducing 40 sccm of argon and 2 sccm of deuterium gas, adjusting the chamber pressure to 0.75 Pa, and sputtering tungsten, iron, and chromium-nickel targets using a DC power supply, and sputtering a boron target using an RF power supply. The power densities of the tungsten, iron, chromium-nickel, and boron targets were 3.2 W / cm². 2 3.2W / cm 2 3.2W / cm 2 6.4W / cm 2 This process involves applying a -150V bias voltage to the sample pan and depositing for 60 minutes to obtain sample number 1.

[0053] Example 2

[0054] Based on Example 1, keeping other parameters such as target material, argon atmosphere and magnetron sputtering parameters unchanged, the sample disk was rotated to expose substrate No. 2 to plasma, and the deuterium flow rate was adjusted to 10 sccm to perform the deposition of deuterium-containing thin film No. 2.

[0055] Example 3

[0056] Based on Example 1, keeping other parameters such as target material, argon atmosphere and magnetron sputtering parameters unchanged, the sample disk was rotated to expose substrate No. 3 to plasma, and the deuterium flow rate was adjusted to 20 sccm to perform the deposition of deuterium-containing thin film No. 3.

[0057] Example 4

[0058] Based on Example 1, keeping other parameters such as target material, argon atmosphere and magnetron sputtering parameters unchanged, the sample disk was rotated to expose substrate No. 4 to plasma, and the deuterium flow rate was adjusted to 30 sccm to perform the deposition of deuterium-containing thin film No. 4.

[0059] Example 5

[0060] Based on Example 1, keeping other parameters such as target material, argon atmosphere and magnetron sputtering parameters unchanged, the sample disk was rotated to expose substrate No. 5 to plasma, and the deuterium flow rate was adjusted to 40 sccm to perform deuterium-containing thin film deposition on substrate No. 5.

[0061] Example 6

[0062] Based on Example 1, keeping other parameters such as target material, argon atmosphere and magnetron sputtering parameters unchanged, the sample disk was rotated to expose substrate No. 6 to plasma, and the deuterium flow rate was adjusted to 50 sccm to perform deuterium-containing thin film deposition on substrate No. 6.

[0063] Performance testing

[0064] Figure 1 These are cross-sectional SEM images of the deuterium-containing thin films prepared in Examples 1-6. Figures 1-4 It can be seen that the film thickness in Examples 1 to 6 is approximately 1000 nm.

[0065] The deuterium content in the deuterium-containing thin films obtained in Examples 1-6 was tested. The deuterium content was analyzed using a thermal desorption method. In this method, the deuterium-containing thin film was placed in a quartz tube and evacuated. The material was heated using a tube muffle furnace from room temperature to 900°C at a heating rate of 10°C / min. The deuterium desorption signal was detected using a quadrupole mass spectrometer calibrated with a standard leak bottle to obtain the total deuterium content in the thin film. The test results are as follows: Figure 2 As shown;

[0066] Test results show that the total deuterium content of the FeCrNiWB / D thin film materials prepared in Examples 1-6 is 5.0 × 10⁻⁶, respectively. 18 D / m 2 2.4×10 19 D / m 2 1.1×10 20 D / m 2 1.8×10 20 D / m 2 2.5×10 20 D / m 2 2.8×10 20 D / m 2 .

[0067] The contents of all elements except deuterium in the FeCrNiWB / D thin film materials prepared in Examples 1-6 were tested. The test results showed that:

[0068] In Example 1, the atomic percentages of each element were: 13% W, 28% Fe, 18% Cr, 35% Ni, and 6% B.

[0069] In Example 2, the atomic percentages of each element were: 12% W, 28% Fe, 18% Cr, 36% Ni, and 6% B.

[0070] In Example 3, the atomic percentages of each element were: 13% W, 29% Fe, 19% Cr, 34% Ni, and 5% B.

[0071] In Example 4, the atomic percentages of each element were: 12% W, 29% Fe, 18% Cr, 36% Ni, and 5% B.

[0072] In Example 5, the atomic percentages of each element were: 11% W, 27% Fe, 19% Cr, 37% Ni, and 6% B.

[0073] In Example 6, the atomic percentages of each element were: 11% W, 28% Fe, 19% Cr, 37% Ni, and 5% B.

[0074] Application Example 1

[0075] Keeping the target material, magnetron sputtering parameters, and other parameters unchanged from Example 1, 40 sccm of argon and 20 sccm of deuterium were introduced, and the chamber pressure was adjusted to 0.75 Pa. Tungsten, iron, and nickel-chromium targets were sputtered using a DC power supply, and a boron target was sputtered using an RF power supply to deposit a deuterium-containing layer. The power densities of the tungsten, iron, nickel-chromium, and boron targets were 3.2 W / cm². 2 3.2W / cm 2 3.2W / cm 2 6.4W / cm 2 This process involves applying a -150V bias voltage to the sample disk and a deposition time of 5 minutes.

[0076] The power densities of the tungsten target, iron target, chromium-nickel target, and boron target were maintained at 3.2 W / cm². 2 3.2W / cm 2 3.2W / cm 2 6.4W / cm 2 Keep argon gas flowing in and turn off deuterium gas flow to perform a deuterium-free layer deposition process, which takes 5 minutes.

[0077] Repeat the above steps to obtain a multilayered thin film with / without deuterium. In this application example, the total coating time was 60 minutes, resulting in 12 layers of deuterium-containing / deuterium-free thin films.

[0078] The deuterium-containing multilayer thin film prepared in this application example has a total thickness of 1.1 μm, with each layer having a similar thickness of approximately 90 nm. The film structure is as follows: Figure 3 As shown.

[0079] The total deuterium content in the thin film was tested using thermal desorption technology, following the same testing method as in Example 1. The measured deuterium desorption signal is shown below. Figure 4 As shown. The total deuterium content in the multilayer deuterium-containing thin film material prepared in this application example is 9.2 × 10⁻⁶. 19 D / m 2 .

[0080] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, and not all embodiments. Other embodiments can be obtained based on these embodiments without creative effort, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A FeCrNiWB / D thin film, characterized in that, The content of D is 0 to 1 × 10⁻⁶. 21 D / m 2 And it is not 0.

2. The FeCrNiWB / D thin film according to claim 1, characterized in that, The thickness of the FeCrNiWB / D thin film is 10–5000 nm.

3. The method for preparing the FeCrNiWB / D thin film according to claim 1 or 2, characterized in that, Includes the following steps: Using tungsten, iron, chromium-nickel, and boron targets as targets, thin films were deposited on the substrate surface by magnetron sputtering under argon and deuterium atmospheres to obtain the FeCrNiWB / D thin film.

4. The preparation method according to claim 3, characterized in that, The substrate is transformed using a photomask located between the substrate and the target. The distance between the photomask and the substrate is 0–2 mm and is not zero; the distance between the photomask and the target is 75–150 mm.

5. The preparation method according to claim 3, characterized in that, The process before magnetron sputtering also includes bias cleaning of the substrate, the bias cleaning time being 5 to 30 minutes; the gas used for bias cleaning is argon, the volumetric flow rate of the argon is 30 to 50 sccm; the gas pressure in the magnetron sputtering chamber during bias cleaning is 2 to 5 Pa, and the substrate bias voltage is -200 to -600 V.

6. The preparation method according to claim 3, characterized in that, The volumetric flow rate of argon gas during magnetron sputtering is 40 sccm, and the volumetric flow rate of deuterium gas is 2–200 sccm.

7. The preparation method according to claim 6, characterized in that, During magnetron sputtering, the gas pressure in the magnetron sputtering chamber is 0.5 to 1 Pa, and the substrate bias voltage is -20 to -200 V.

8. The preparation method according to claim 3, characterized in that, The magnetron sputtering includes DC power supply sputtering and radio frequency power supply sputtering; the target material for DC power supply sputtering is a tungsten target, an iron target, and a chromium-nickel target; the target material for radio frequency power supply sputtering is a boron target; the power density of the tungsten target, iron target, chromium-nickel target, and boron target is independently 0–20 W / cm². 2 And it is not 0.

9. The application of the FeCrNiWB / D thin film according to any one of claims 1 to 2 or the FeCrNiWB / D thin film prepared by the preparation method according to any one of claims 3 to 8 in the determination of elemental content by glow discharge spectroscopy.

10. The application according to claim 9, characterized in that, The applications include quantitative calibration of deuterium content in fusion reactor materials using glow discharge spectroscopy and optimization of the depth and concentration resolution of glow discharge spectroscopy equipment.

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