Preparation method for obtaining bulk material in-situ transmission atmosphere chip sample by using FIB

Abstract

The invention discloses a preparation method for obtaining a block material in-situ transmission atmosphere chip sample through FIB, and relates to the field of chip preparation methods. Comprising the following steps: collecting EBSD data of a target area of a sample, generating a pole figure of a crystal plane family of target orientation according to the EBSD data, and obtaining a crystal plane position of the target orientation according to the pole figure; depositing a protective material at the crystal face position to obtain a protective layer; removing the material of the sample on the periphery of the protective layer to obtain a first sample; reducing the target area of the first sample to obtain an intermediate sample with the thickness of the target area being a first preset thickness, and performing amorphous removal on the intermediate sample to obtain a second sample; and fixing the second sample on an observation window of the chip to obtain a chip sample. EBSD and FIB technologies are combined, and on the premise that the accuracy of the crystal face position is guaranteed, the sample suitable for the in-situ atmosphere experiment of the Protochips atmosphere chip is prepared.

Description

Technical Field

[0001] The present application relates to the field of chip preparation methods, and in particular to a preparation method for obtaining an in-situ atmosphere transmission chip sample of a bulk material by using FIB. Background Art

[0002] In-depth study of the solid-gas reaction mechanism under in-situ microscopic conditions is of great significance for the development of materials in the fields of catalysis and energy. The sample holder of the "closed" in-situ atmosphere system is a "single-tilt" sample holder, which makes it difficult to achieve the "rotation axis" operation that is crucial for TEM high-resolution imaging, and it is difficult to prepare bulk samples. Therefore, the existing "closed" in-situ atmosphere system is mostly used for nanomaterials, that is, the nanomaterials are dispersed droplets are dropped on the atmosphere chip, and suitable nanocrystals with low-index crystal plane orientation are found in the observation window, and then the corresponding in-situ atmosphere experiments are carried out. For bulk materials, the traditional transmission sample preparation methods, such as electrolytic double spraying, etc., the transmission samples obtained are limited by their large size and are difficult to be applied to the "closed" in-situ atmosphere system. It is difficult to obtain TEM samples with specific low-index crystal plane orientation by simply pre-processing the samples and then preparing them using FIB technology: for example, the specific orientation of single crystal samples cut by mechanical cutting is limited by the generally small size of single crystal samples, and it is difficult to ensure the accuracy of mechanical cutting; or simply positioning polycrystalline samples according to the grain morphology characteristics, and positioning only with the correspondence between EDS or EBSD and SEM morphology, the error is large. Summary of the invention

[0003] The main purpose of the present application is to provide a method for preparing an in-situ transmission atmosphere chip sample of a bulk material using FIB, aiming to solve the problem of large crystal plane position positioning error existing in the prior art.

[0004] To achieve the above-mentioned purpose, the present application provides a method for preparing an in-situ transmission atmosphere chip sample of a bulk material using FIB, comprising: collecting EBSD data of a target area of ​​the sample; generating a pole figure of a crystal plane family of a target orientation according to the EBSD data; obtaining a crystal plane position of the target orientation according to the pole figure; depositing a protective material at the crystal plane position to obtain a protective layer; removing the material of the sample outside the protective layer to obtain a first sample; reducing the target area of ​​the first sample to obtain an intermediate sample whose thickness of the target area is a first preset thickness, performing amorphous removal on the intermediate sample to obtain a second sample; fixing the second sample on the observation window of the chip to obtain a chip sample.

[0005] Optionally, the sample is a single crystal or a metal bulk material with a grain size of 20 to 200 μm; wherein, if the metal bulk material is a large-size polycrystalline material, the target area of ​​the sample belongs to the same grain.

[0006] Optionally, the crystal plane position of the target orientation is obtained according to the following steps: determine the direction perpendicular to the straight line connecting the center point on the pole figure and the highest intensity point as the distribution direction of the crystal plane family, and select the crystal plane position of the target orientation of a preset size in the highest intensity area on the pole figure corresponding to the distribution direction of the crystal plane family.

[0007] Optionally, before obtaining the protective layer, the preparation method further comprises: obtaining a positioning layer by depositing a positioning material at a crystal plane position using an electron beam, wherein the positioning material is Pt.

[0008] Optionally, the protective layer is obtained by the following steps: using ion beam to deposit a protective material on the surface of the positioning layer to obtain the protective layer, wherein the protective material is Pt.

[0009] Optionally, the first sample is obtained by the following steps: removing material of the sample on the side of the protective layer to connect one side of the protective layer to the sample; removing material of the sample of a second preset thickness at the bottom of the protective layer, and removing material of the sample of a preset width on one side of the protective layer to obtain a cut sample; bringing the robotic arm into contact with the cut sample and bonding the two by deposition; cutting off the connection between one side of the protective layer and the sample to obtain a first sample connected to the robotic arm.

[0010] Optionally, the second sample is obtained by the following steps: bringing the first sample into contact with the copper column of the carrier grid, bonding the two by deposition, and disconnecting the robot arm from the first sample; making the first sample parallel to the horizontal plane, using an ion beam to cut the target area of ​​the first sample, and forming grooves on the upper and lower surfaces of the first sample respectively; wherein the thickness of the target area is a first preset thickness; performing amorphous removal on the upper and lower surfaces of the intermediate sample to obtain the second sample.

[0011] Optionally, the second sample is fixed to the observation window of the chip through the following steps: the second sample is transferred to the robot arm through the carrier grid; the robot arm is brought into contact with the second sample, the two are bonded by deposition, and the connection between the copper column of the carrier grid and the second sample is cut off; the second sample is brought into contact with the observation window of the chip, and deposition is performed between the four corners of the second sample and the chip to obtain a chip sample.

[0012] The present application also provides a bulk material in-situ atmosphere transmission chip sample, which is obtained by the above-mentioned preparation method.

[0013] The present application also provides an application of a bulk material in-situ transmission atmosphere chip sample in analyzing the interaction between the material surface and gas.

[0014] Compared with the prior art, the present invention has the following beneficial effects: The invention discloses a method for preparing an in-situ transmission atmosphere chip sample of a bulk material by using FIB. The bulk sample of a metal single crystal or a large-size grain is used as the sample preparation object. The in-situ atmosphere experiment sample suitable for Protochips atmosphere chip is prepared by combining EBSD and FIB technology. The pole figures of the crystal plane family are generated according to EBSD data, and the crystal plane position of the target orientation is obtained in combination with the pole figures, so that the accuracy of the crystal plane position positioning can be ensured. The chip sample obtained has a specific crystal plane orientation, and the thickness is less than 90nm, the outer crystal plane is straight and has no defects, no Pt exists, and the surface amorphous is excluded. The sample is used to carry out an in-situ atmosphere experiment, and the TEM diffraction mode can be used to verify that a specific low-index crystal plane transmission sample is obtained, and the reaction process of the sample in a specific atmosphere and at different temperatures can be better observed, and the sample can obtain the imaging effect of a high-resolution lattice image. The application of the "closed" in-situ atmosphere system is expanded, so that researchers can obtain specific low-index crystal plane TEM in-situ samples, and conduct in-depth research on the solid-gas reaction mechanism under microscopic conditions, so as to provide guidance for the development of materials in the fields of catalysis and energy. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 A schematic diagram of a process for preparing a bulk material in-situ atmosphere transmission chip sample using FIB in this application; Figure 2 A state change diagram of the crystal plane position of the target orientation obtained in a method for preparing a bulk material in-situ transmission atmosphere chip sample using FIB in this application; Figure 3 This is a state change diagram of preparing a first sample in a method for preparing a bulk material in-situ transmission atmosphere chip sample using FIB in this application; Figure 4 This is a state change diagram of preparing a second sample in a method for preparing a bulk material in-situ transmission atmosphere chip sample using FIB in this application; Figure 5 This is a state change diagram of a chip sample prepared in a method for preparing a chip sample of a bulk material in-situ through-atmosphere using FIB; Figure 6 This is a chip sample obtained by a method for preparing a bulk material in-situ transmission atmosphere chip sample using FIB, and the effect diagram under a transmission electron microscope; Figure 7 This is a diffraction pattern of a TEM sample with (110) crystal plane orientation prepared in Example 1 of a method for preparing a bulk material in-situ transmission atmosphere chip sample using FIB in this application; Figure 8This is a high-resolution rendering obtained during an in-situ experiment of a TEM sample with a (110) crystal plane orientation prepared in Example 1 of a method for preparing an in-situ transmission atmosphere chip sample of a bulk material using FIB in this application; Fig. 9 This is a diagram showing the oxygen atmosphere experimental results of a chip sample prepared in Example 1 of a method for preparing a chip sample of a bulk material by using FIB to obtain an in-situ transmission atmosphere; The realization of the purpose, functional features and advantages of this application will be further explained in conjunction with embodiments and with reference to the accompanying drawings. DETAILED DESCRIPTION

[0016] In order to make the purpose, technical solutions and advantages of this application clearer, the technical solutions in this application will be clearly and completely described below in conjunction with the drawings in this application. Obviously, the described embodiments are part of the embodiments of this application, not all of them. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of this application.

[0017] The present invention adopts FIB to prepare in-situ transmission atmosphere chip samples. FIB is a focused ion beam-scanning electron microscope (FIB-SEM) dual beam system. In the present invention, FIB-SEM is abbreviated as FIB, which specifically refers to a system with both focused ion beam (FIB) and scanning electron microscope (SEM) functions. FIB includes an electron beam window, an ion beam window, a sample stage, a mechanical arm, a grid, etc., wherein the mechanical arm is an Easylift needle.

[0018] The present invention provides a method for preparing a bulk material in-situ transmission atmosphere chip sample by using FIB, such as Figure 1 As shown, the following steps are included: Step S1, collecting EBSD data of a target area of ​​a sample, generating a pole figure of a crystal plane family of a target orientation according to the EBSD data, and obtaining a crystal plane position of the target orientation according to the pole figure; The sample may be a single crystal or a bulk metal material with a grain size of 20 to 200 μm. If the bulk metal material is a large-size polycrystalline material (i.e., a bulk metal material with a grain size of 20 to 200 μm), the target area of ​​the sample should belong to the same grain.

[0019] Specifically, step S1 includes the following steps: Step S11, selecting a reasonable grinding and polishing method to process the sample, so that the polished sample reaches a level that can be analyzed by EBSD; Step S12, placing the sample on the sample stage, obtaining EBSD data of the target area of ​​the sample (which may be a position with a smooth and flat surface), generating a pole figure of the crystal plane family of the target orientation based on the EBSD data, determining the direction perpendicular to the straight line connecting the center point on the pole figure and the highest intensity point as the distribution direction of the crystal plane family, and selecting the crystal plane position of the target orientation of a preset size in the highest intensity area on the pole figure corresponding to the distribution direction of the crystal plane family.

[0020] It can be understood that since the sample is a single crystal or a large grain, this set of mutually perpendicular straight line positions can directly correspond to the SEM image, and thus the crystal plane position of the target orientation can be determined in combination with the SEM image. The specific method of determining the crystal plane position in combination with the SEM image is an existing method and will not be repeated here.

[0021] Step S2, depositing a protective material on the crystal plane to obtain a protective layer; Step S21, depositing a positioning material at a crystal plane position along the electron beam window to facilitate positioning and obtain a positioning layer; wherein the positioning material is Pt.

[0022] Step S22, horizontally rotate the sample stage to flatten the crystal plane position of the positioning layer to facilitate subsequent processing; then tilt the sample stage to a predetermined angle so that the sample stage is perpendicular to the ion beam window, and use the GIS system to deposit protective material on the surface of the positioning layer along the ion beam window to obtain a protective layer of a preset size, wherein the protective material is Pt.

[0023] Step S3, removing the material of the sample outside the protective layer to obtain a first sample; the specific method is: Further, step S3 includes: Step S31, removing the material of the sample on the side of the protective layer along the ion beam window, so that one side of the protective layer is connected to the sample; Furthermore, the outer side of the protective layer is respectively recorded as the first area, the second area, the third area, and the fourth area, and the materials of the samples in the first area, the second area, and the third area are removed along the ion beam window. At this time, the fourth area of ​​the protective layer is still connected to the sample; wherein the x and y of the removed area are set according to the actual exposed side size, and z can be set to 3 μm; After the sample materials of the first, second and third regions are removed, the remaining sample thickness should be close to 1 μm, and the side of the sample is basically perpendicular to the ion beam observation window. If it is too thin, it will be difficult to extract the sample later, and if it is too thick, it will easily damage the chip film. Therefore, it is necessary to perform fine trimming through step S32; Step S32, using a relatively large current ion beam, sequentially fine-tune the side surfaces of the sample in the first, second, and third regions to ensure that each side surface is disconnected from the bottom material at a depth of 15 μm. If the sample thickness or side surface condition in the previous step does not meet the requirements, fine-tune two to three more times; Step S33, making the sample stage form a preset angle with the horizontal plane, using the Rectangle mode, removing the material of the sample with a second preset thickness (the second preset thickness can be set to 3 μm) at the bottom of the protective layer along the ion beam window, and removing the material of the sample with a preset width on one side of the protective layer (removing the sample material with the preset width is to ensure that the sample outside the protective layer is not completely separated from the sample at the bottom of the protective layer to prevent the sample from falling), and obtaining the excised sample; Step S34, make the sample stage parallel to the horizontal plane, adjust the robotic arm through the ion beam window and the electron beam window, make the robotic arm contact with the cut sample, and start the GIS system, deposit Pt between the two to make them adhere to each other, and the x, y dimensions of the deposition area are set according to the actual size, and z can be set to 1μm; then use the Rectangle mode to cut off the remaining sample material on one side of the protective layer to obtain the first sample connected to the robotic arm.

[0024] It is worth noting that in the process of achieving adhesion by deposition in the embodiments of the present application, if it is obviously observed that the connection is not firm after one deposition, deposition should be performed again to ensure that the sample will not fall off after it is finally cut.

[0025] Step S4, cutting the target area of ​​the first sample to obtain an intermediate sample whose target area thickness is a first preset thickness, and performing amorphous removal on the intermediate sample to obtain a second sample; Specifically, step S41, the sample stage is made perpendicular to the ion beam window, the mechanical arm is adjusted through the ion beam window and the electron beam window, the first sample is brought into contact with any copper column of the carrier grid, the GIS system is started to deposit Pt between the side of the copper column and the first sample, so that the two are adhered, and the connection between the mechanical arm and the first sample is disconnected using the Rectangle mode, wherein the x and y dimensions of the deposition area are set according to the actual size, and z is set to 1 μm; Step S42, making the sample stage parallel to the horizontal plane, using the ion beam to cut the target area of ​​the first sample, forming grooves on the upper and lower surfaces of the first sample, respectively, to obtain an intermediate sample; Specifically, in step S421, the sample stage is made parallel to the horizontal plane, the side of the first sample is made to face the ion beam, and the sample stage is rotated so that T (the angle between the sample stage and the horizontal plane) is within the range of (-4°~4°) so that the thickness of the protective layer and the sample layer in the first sample exposed to the ion beam window is substantially equal, so as to ensure that the crystal plane orientation will not be changed during the thinning process; Step S422, in CCS mode, set the size of the thinning area and T, and thin the upper and lower surfaces of the first sample at ±2° with T as the center. For example, if T=1° is selected, the upper surface of the first sample is thinned at T=-1°, and the lower surface of the first sample is thinned at T=3°. Each angle is thinned multiple times, and the thinning is cyclical. Further, according to the thickness of each thinning area, the thinning thickness and ion beam intensity are adjusted until the thickness of the thin area drops below 100nm. During the entire thinning process, it is necessary to ensure that sufficient thickness of material is left behind the thin area to prevent the sample from bending.

[0026] Step S43, performing amorphous removal on the upper and lower surfaces of the intermediate sample to obtain a second sample.

[0027] Step S5, fixing the second sample on the observation window of the chip to obtain a chip sample.

[0028] Specifically, in step S51, the pre-tilt table of the grid is updated to make the grid parallel to the horizontal plane, and the second sample is vertically extracted through the grid and transferred to the robot arm. The vertical extraction can ensure that the crystal plane orientation is parallel to the observation window during the transfer process; Step S52, adjusting the mechanical arm through the ion beam window and the electron beam window so that the mechanical arm contacts the second sample, and the contact point is located outside the groove as much as possible, so that the ion beam window avoids the thin area to prevent the irradiation from affecting the thin area; depositing Pt on the mechanical arm and the second sample to adhere the two, and cutting off the connection between the copper column of the carrier grid and the second sample; Step S53, make the sample stage parallel to the horizontal plane, find the circular observation window on the chip under the electron beam window, and adjust the common height; adjust the mechanical arm through the ion beam window and the electron beam window to make the second sample contact with the observation window of the chip, fix the second sample on the observation window of the chip by deposition, and cut off the connection between the mechanical arm and the second sample to obtain a chip sample.

[0029] Furthermore, after the second sample is brought into contact with the observation window of the chip, the specific deposition method is as follows: The second sample is fixed on the observation window of the chip by deposition, the second sample is brought into contact with the observation window of the chip by adjusting the mechanical arm through the ion beam window and the electron beam window, a bonding layer is deposited between one corner of the second sample and the observation window of the chip, and the connection between the mechanical arm and the second sample is cut off; The direction of the robot arm is adjusted through the ion beam window and the electron beam window, and the field of view of the FIB is adjusted to deposit bonding layers between the remaining three corners of the second sample and the chip to obtain a chip sample, so as to ensure that the sample remains level with the chip surface.

[0030] Through the above methods, the method for preparing an in-situ transmission atmosphere chip sample of a bulk material using FIB of the present invention takes a bulk sample of a metal single crystal or a large-size grain as the sample preparation object, and combines EBSD and FIB technology to prepare an in-situ atmosphere experiment sample suitable for Protochips atmosphere chip; generates a polar figure of a crystal plane family according to EBSD data, and obtains the crystal plane position of a target orientation in combination with the polar figure, which can ensure the accuracy of crystal plane position positioning; obtains a chip sample with a specific crystal plane orientation, and a thickness of less than 90nm, a straight outer crystal plane without defects, no Pt, and excludes surface amorphous; uses the sample to carry out an in-situ atmosphere experiment, and through the TEM diffraction pattern, it can be verified that a specific low-index crystal plane transmission sample is obtained, and the reaction process of the sample in a specific atmosphere and at different temperatures can be better observed, and the sample can obtain an imaging effect of a high-resolution lattice image; expands the application of the "closed" in-situ atmosphere system, so that researchers can obtain specific low-index crystal plane TEM in-situ samples, and conduct in-depth research on the solid-gas reaction mechanism under microscopic conditions, providing guidance for the development of materials in the fields of catalysis and energy.

[0031] Example 1 Step S10, grinding and polishing the W single crystal to make its surface smooth enough to collect EBSD data; placing the W single crystal on the sample stage, obtaining EBSD data of the position where the W single crystal surface is smooth and flat, generating the pole figure of the crystal plane family of the target orientation according to the EBSD data, and constructing a rectangular coordinate system on the pole figure, such as Figure 2 As shown in a, the direction perpendicular to the straight line connecting the center point (the origin of the rectangular coordinate system) on the pole figure and the highest intensity point is determined as the distribution direction of the crystal plane family, that is, Figure 2 In the dotted line direction shown in b, the highest intensity area on the pole figure corresponding to the distribution direction of the crystal plane family is selected, and the crystal plane position of the target orientation of the preset size is selected; Step S20, using the GIS system to deposit Pt on the crystal plane along the electron beam window to facilitate positioning and obtain a positioning layer; rotating the sample stage horizontally, then tilting the sample stage to T = 52°, depositing on the surface of the positioning layer along the ion beam window to obtain a protective layer with a size of 25×1×1μm, such as Figure 2 As shown in c; Step S30, using a large current ion beam (30 kV, 9.3 nA) to remove surrounding materials from the protective layer, that is, to remove materials from the first, second, and third regions of the sample outside the protective layer, the first and second regions are sized to "x×y×z=30×15×15 μm", and the third region is sized to "x×y×z=15×12×15 μm"; Figure 2 c. Figure 2 d. Figure 2 e are the effect diagrams of removing the first area, the second area, and the third area respectively. Figure 2e is rotated to obtain Figure 2 f; Using a larger beam current ion beam (30 kV, 2.5 nA), the side surfaces of the samples in the first, second and third regions were refined at T = 50°, T = 54° and T = 52°, respectively. Figure 3 a; Cut bottom, see Figure 3 b. Specifically, T=7°, and in the Rectangle mode, a small beam current ion beam (30 kV, 0.79 nA) is used to remove the material of the sample of 3 μm at the bottom of the protective layer along the ion beam window, and the material of the sample of a preset width on one side of the protective layer is removed (ensuring that the connection length between the sample outside the protective layer and the sample at the bottom of the protective layer is 1 / 2 of the sample width), to obtain a cut sample; Set T=0° and insert the Easylift needle. When inserting the Easylift needle, set the beam current in the ion beam window preview mode to "30kV, 40pA". The speed should be fast at first and then slow. The step length of inserting the Easylift needle is gradually reduced from 10μm / s to 200nm / s. In this process, adjust the Easylift needle through the ion beam window and the electron beam window to make the Easylift needle contact with the cut sample, and start the GIS system to deposit Pt between the two to make them adhere to each other, so as to realize the transfer of the sample to the Easylift needle. The x and y dimensions of the deposition area are set according to the actual size, z can be set to 1μm, and the ion beam intensity is "30kV, 80pA". Then use the Rectangle mode to cut off the remaining sample material on one side of the protective layer, and the cut-off area z is still set to 3μm, and the ion beam intensity is "30kV, 0.79nA" to obtain the first sample connected to the robotic arm.

[0032] Step S40, rotate the sample stage to T = 52° so that the sample stage is perpendicular to the ion beam window, adjust the Easylift needle through the ion beam window and the electron beam window, make the first sample contact with any copper column of the carrier grid, start the GIS system to deposit Pt between the side of the copper column and the first sample, so that the two are adhered, and realize the transfer of the sample to the same side of the carrier grid, see Figure 3 c, and use the Rectangle mode to disconnect the needle and the sample (first sample), where the x and y dimensions of the deposition area are set according to the actual size, z is set to 1 μm, and the ion beam intensity is "30 kV, 0.23 nA"; Make the sample stage parallel to the horizontal plane, make the side of the first sample face the ion beam, and rotate the sample stage within the range of (-4°~4°) so that the thickness of the protective layer and the sample layer in the first sample exposed at the ion beam window are basically equal; set the size and T of the thinning area in the CCS mode, and thin the upper and lower surfaces of the first sample with T as the center and ±2°. Figure 4a, thinning area x=4μm, z is set to 2μm at the beginning of thinning, and the ion beam intensity is set to "30kV, 0.23nA" at this time. When the thickness of the thin area drops to 400nm, z is set to less than 1.5μm, and the ion beam intensity is set to "16kV, 0.15nA" at this time; when the thickness of the thin area drops to 200nm, z is set to 1μm, and the ion beam intensity is set to "8kV, 66pA" at this time. Each angle is thinned twice, and the thinning is cyclic. The crystal plane orientation of the first sample after thinning is a low-index crystal plane of {100}, and the thickness is thinned to less than 80nm. The protective layer is completely removed by the ion beam, and there is no obvious ion beam irradiation damage in the first sample after thinning, see Figure 4 b, its top view is shown in Figure 4 c; The ion beam current intensity was set to "5 kV, 43 pA", and the upper and lower surfaces of the thinning position were de-amorphized at a deviation angle of ±4° from the reference angle. The processing time was about 20 s, and the second sample was obtained.

[0033] Step S50, transfer the grid from the 38° pre-tilt stage to the 0° pre-tilt stage, insert the needle for extraction at T=0°, set the ion beam intensity to "30 kV, 7.7 pA", extract vertically through the grid and transfer the second sample to the robot arm; The robot arm is adjusted through the ion beam window and the electron beam window to make the robot arm contact with the second sample, and the ion beam intensity is adjusted to "30kV, 40pA". Pt is deposited on the robot arm and the second sample to adhere the two. The ion beam intensity is adjusted back to "30kV, 7.7pA", and the magnification and the position of the robot arm are continuously adjusted so that only the image of the connection between the second sample and the grid exists in the ion beam field of view. Then, the ion beam intensity is adjusted to "30kV, 0.23nA", and the connection between the copper column of the grid and the second sample is cut off. Make the sample stage parallel to the horizontal plane and find the circular observation window on the chip under the electron beam window. Figure 5 a, and adjust the common height; set the ion beam intensity to "30kV, 7.7pA", adjust the robotic arm through the ion beam window and the electron beam window, make the second sample contact with the observation window of the chip, make the ion beam window field of view avoid the thin area, adjust the ion beam intensity to "30kV, 40pA", and connect the upper left corner and the upper right corner of the second sample to the chip surface in turn by depositing Pt; adjust the ion beam intensity back to "30kV, 7.7pA", readjust the magnification and the position of the robotic arm, make the ion beam window field of view come to the connection position between the robotic arm and the second sample, increase the ion beam current to 40pA, set z to 1μm in the Rectangle mode, and cut the connection; finally, rotate the sample stage 180° as a whole, position it to the second sample, insert the needle to press the chip sample to prevent the sample from warping, and deposit Pt at the upper left and upper right corners of the chip sample, see Figure 5b, chip samples after transfer Figure 5 c.

[0034] The chip samples obtained in this embodiment are specifically analyzed below in conjunction with the accompanying drawings.

[0035] Figure 6 a is the bright field image (BF) of the sample in the transmission electron microscope after preparation. It can be seen that there are no obvious defects or stress streaks on the surface, and the thin area can meet the requirements of high-resolution analysis. Figure 6 b is the high-angle annular dark field (HAADF) image in the transmission electron microscope after the sample preparation is completed. Through the energy spectrum analysis in this mode, it can be found that there is no Pt protective layer on the surface, and the in-situ atmosphere reaction experiment on the surface can be carried out. Figure 7 for Figure 6 The electron diffraction pattern of the prepared in-situ transmission sample shown in the figure can determine that the crystal plane orientation of the prepared sample is the orientation required by the design by calibrating the diffraction pattern, which proves that this technical solution can regulate the crystal plane orientation of sample preparation. Figure 8 for Figure 6 The high-resolution image of the in-situ transmission sample prepared during the experiment shows a clear high-resolution lattice image, which proves that the high-resolution characterization of the samples prepared by this technical solution is excellent.

[0036] On the basis of the above-mentioned embodiments, the present application also provides a bulk material in-situ transmission atmosphere chip sample, which is obtained by the above-mentioned preparation method.

[0037] On the basis of the above-mentioned embodiments, the present application also provides an application of a bulk material in-situ transmission atmosphere chip sample in analyzing the interaction between the material surface and gas.

[0038] The chip sample obtained in Example 1 was used to conduct an oxygen atmosphere experiment. The experimental results are as follows: Fig. 9 a-9b. Specifically, from Fig. 9 It can be seen from a that as the temperature increases, the surface of the chip sample reacts with oxygen, and oxide particles are first formed on the surface at 270°C. Fig. 9 b It can be seen that when the temperature continues to rise to 410°C, destructive oxidation occurs, causing surface cracking. Combining the high-resolution image and element distribution spectrum of the oxidation process, the process of metal oxidation can be well observed at a microscopic scale, including the transformation of phases and structures. It can be seen that the chip sample obtained by the preparation method of the present invention can be used to analyze the interaction between the material surface and gas.

[0039] The above are only preferred embodiments of the present application, and are not intended to limit the patent scope of the present application. Any equivalent structure or equivalent process transformation made using the contents of the present application specification and drawings, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present application.

Claims

1. A method for preparing an in-situ atmosphere transmission chip sample of a bulk material using FIB, characterized in that: include: Collect EBSD data of the target area of ​​the sample; generating a pole figure of a family of crystal planes of a target orientation based on the EBSD data; Obtain the crystal plane position of the target orientation according to the pole figure; Depositing a protective material at the crystal plane position to obtain a protective layer; Removing material from the sample outside the protective layer to obtain a first sample; The target area of ​​the first sample is cut to obtain an intermediate sample whose target area thickness is a first preset thickness, and amorphous removal is performed on the intermediate sample to obtain a second sample; The second sample is fixed on the observation window of the chip to obtain a chip sample.

2. The method for preparing a bulk material in-situ atmosphere transmission chip sample using FIB according to claim 1, characterized in that: The sample is a single crystal or a metal bulk material with a grain size of 20 to 200 μm; wherein, if the metal bulk material is a metal bulk material with a grain size of 20 to 200 μm, the target area of ​​the sample belongs to the same grain.

3. The method for preparing a bulk material in-situ atmosphere transmission chip sample using FIB according to claim 1, characterized in that: The crystal plane position of the target orientation is obtained according to the following steps: The direction perpendicular to the straight line connecting the center point on the pole figure and the highest intensity point is determined as the distribution direction of the crystal plane family, and the crystal plane position of the target orientation with a preset size is selected in the highest intensity area on the pole figure corresponding to the distribution direction of the crystal plane family.

4. The method for preparing a bulk material in-situ atmosphere transmission chip sample using FIB according to claim 1, characterized in that: Before obtaining the protective layer, the preparation method further comprises: The positioning material is deposited at the crystal plane position by electron beam to obtain a positioning layer, wherein the positioning material is Pt.

5. The method for preparing a bulk material in-situ atmosphere transmission chip sample using FIB according to claim 4, characterized in that: The protective layer is obtained by the following steps: A protective material is deposited on the surface of the positioning layer by ion beam deposition to obtain a protective layer, wherein the protective material is Pt.

6. The method for preparing a bulk material in-situ atmosphere transmission chip sample using FIB according to claim 5, characterized in that: The first sample is obtained by the following steps: Removing the material of the sample on the side of the protective layer so that one side of the protective layer is connected to the sample; Removing a sample material of a second preset thickness at the bottom of the protective layer, and removing a sample material of a preset width at one side of the protective layer to obtain a cut sample; The robot arm is brought into contact with the excised sample, and the two are bonded together by deposition; The connection between one side of the protective layer and the sample is cut off to obtain a first sample connected to the robot arm.

7. The method for preparing a bulk material in-situ atmosphere transmission chip sample using FIB according to claim 6, characterized in that: The second sample is obtained by the following steps: The first sample connected to the robot arm is brought into contact with the copper column of the grid, the two are bonded by deposition, and the connection between the robot arm and the first sample is disconnected; adjusting the copper column so that the first sample is parallel to the horizontal plane, using an ion beam to cut the target area of ​​the first sample, forming grooves on the upper and lower surfaces of the first sample, respectively, to obtain an intermediate sample; Amorphous removal is performed on the upper and lower surfaces of the intermediate sample to obtain a second sample.

8. The method for preparing a bulk material in-situ atmosphere transmission chip sample using FIB according to claim 1, characterized in that: The second sample is fixed on the observation window of the chip by the following steps: Transferring the second sample to the robotic arm via a carrier grid; The mechanical arm is brought into contact with the second sample, the two are bonded together by deposition, and the connection between the copper column of the grid and the second sample is cut off; The second sample is brought into contact with the observation window of the chip, and deposition is performed between the four corners of the second sample and the chip to obtain a chip sample.

9. A bulk material in-situ atmosphere transmission chip sample, characterized in that: The method is obtained by the preparation method according to any one of claims 1 to 8.

10. Application of a bulk material in-situ transmission atmosphere chip sample in analyzing the interaction between material surface and gas.

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