Coupled x-ray gas phase deposition in-situ characterization system

Abstract

The application provides a kind of coupling X-ray gas deposition in-situ characterization system, it is related to coating deposition technical field, including vacuum chamber, protective cover, target crucible, transmission mechanism, electron beam emission module and detection module, transmission mechanism includes first transmission part, and one end of first transmission part is equipped with holding device, and holding device is used to carry sample test piece;Electron beam emission module can generate electron beam to evaporate target material;Detection module is used to capture Debye ring or scattering pattern.The application realizes the real in-situ, real-time and dynamic coupling of electron beam physical vapor deposition (EB-PVD) process and synchrotron X-ray characterization technology, and effectively guarantees the stability of characterization process and the flexibility of process operation under extreme process conditions such as high temperature, high vacuum and strong electron beam irradiation, so as to realize real-time monitoring and quantitative analysis of thermal barrier coating growth process to reveal the microstructure dynamic evolution mechanism of thermal barrier coating in the deposition process.

Description

Technical Field

[0001] This invention relates to the field of coating deposition technology, and in particular to an in-situ characterization system for vapor phase deposition coupled with X-rays. Background Technology

[0002] Thermal barrier coatings (TBCs) are critical protective materials for hot-end components of aero-engines and gas turbines, and their performance directly determines the engine's thrust-to-weight ratio, turbine inlet temperature, and overall service life. Under extreme service environments such as high temperature, high pressure, and high thermal shock, TBCs must simultaneously possess low thermal conductivity, good high-temperature phase stability, resistance to sintering, resistance to high-temperature oxidation and corrosion, and excellent mechanical properties. Among these, low thermal conductivity is one of the most crucial functional characteristics of TBCs, playing a significant role in improving the thermal insulation effect of the substrate components and reducing cooling requirements. In non-magnetic insulating ceramic materials, heat conduction is mainly achieved through lattice vibrations. Phonons, as the energy quantum carriers of lattice vibrations, can have their transport behavior described by phonon theory. According to Debye phonon theory, the phonon heat transfer process in solids can be analogous to collisional heat transfer between gas molecules, and therefore can be analyzed using a model similar to gas heat conduction. The thermal conductivity of a material mainly depends on the mean free path of phonons, that is, the average propagation distance of phonons between two consecutive scatterings. In ideal crystals, intrinsic phonon-phonon scattering dominates the mean free path; however, in real materials, lattice defects such as vacancies, substituted atoms, and grain boundaries become important phonon scattering centers. These defects not only directly scatter phonons but also enhance the anharmonicity of lattice vibrations, intensifying phonon interactions and significantly shortening the phonon mean free path, effectively reducing the material's thermal conductivity. Therefore, introducing controllable lattice defects has become an important strategy for optimizing the thermophysical properties of thermal barrier coatings. However, existing research methods have significant limitations in resolving key parameters, such as the evolution of nanopores, the distribution of doped elements, phase transitions, and crystal orientation formation—dynamic processes that are difficult to observe and analyze in real-time, in-situ, and with high resolution. Therefore, how to monitor and quantitatively analyze the growth process of thermal barrier coatings in real time to deeply reveal the dynamic evolution mechanism of the microstructure during deposition has become an urgent technical problem to be solved. Summary of the Invention

[0003] In order to overcome the above-mentioned defects of the prior art, the technical problem to be solved by the embodiments of the present invention is to provide an in-situ characterization system for vapor deposition coupled with X-rays, which is used to monitor and quantitatively analyze the growth process of thermal barrier coatings in real time, so as to reveal in depth the dynamic evolution mechanism of the microstructure of thermal barrier coatings during the deposition process.

[0004] The above-mentioned objective of this invention can be achieved by the following technical solution: This invention provides an in-situ characterization system for vapor deposition coupled with X-rays, comprising: A vacuum chamber, comprising an X-ray inlet, an X-ray outlet, an electron beam interface, a vacuum pumping interface, and at least one observation window, wherein the X-ray inlet and the X-ray outlet are provided with window assemblies; A protective cover is disposed in the vacuum chamber, and the protective cover includes a light source inlet, a light source outlet, an electron beam inlet, and a track groove; A target material crucible, which is adjustablely disposed within the protective cover, is used to hold at least one target material; The transmission mechanism includes a first transmission component, which is adjustablely inserted into the track groove. One end of the first transmission component is disposed inside the protective cover and is provided with a holding device, which is used to support the sample piece. An electron beam emitting module, which is capable of generating an electron beam and irradiating the target crucible through the electron beam interface to evaporate the target material; A detection module, which is positioned facing the ray outlet, is used to capture Debye rings or scattering patterns.

[0005] In a preferred embodiment of the present invention, the vacuum chamber includes a vacuum furnace shell and a top cover that can be opened on the vacuum furnace shell, and the X-ray inlet, the X-ray outlet, the electron beam interface, the vacuum interface and at least one of the observation windows are disposed on the vacuum furnace shell.

[0006] In a preferred embodiment of the present invention, the X-ray coupled vapor deposition in-situ characterization system further includes a rotating rod rotatably connected to the vacuum chamber. The upper end of the rotating rod is connected to the target crucible, and the lower end of the rotating rod passes through the vacuum chamber for connecting to a motor. The target crucible includes a plurality of spaced-apart target loading slots.

[0007] In a preferred embodiment of the present invention, the bottom of the vacuum chamber is provided with an installation port, the installation port is detachably covered with a vacuum chamber flange, and the rotating rod is rotatably inserted through the vacuum chamber flange.

[0008] In a preferred embodiment of the present invention, the target crucible is provided with a water cooling channel.

[0009] In a preferred embodiment of the present invention, the protective cover includes a housing and a dome disposed on the housing, the electron beam inlet is disposed on the housing, the light source inlet, the light source outlet and the track groove are disposed on the dome, and the track groove is configured to be perpendicular to the light source direction.

[0010] In a preferred embodiment of the present invention, the protective cover further includes a first conical shell extending from the light source inlet to the ray inlet, and a second conical shell extending from the light source outlet to the ray outlet.

[0011] In a preferred embodiment of the present invention, the cover is cylindrical and the dome is hemispherical.

[0012] In a preferred embodiment of the present invention, the transmission mechanism includes a first driving device coaxially connected to the first transmission member, a guide rail pair parallel to the track groove and located outside the protective cover, a connector slidably disposed on the guide rail pair, a second transmission member, a rotating joint disposed between the first transmission member and the second transmission member, and a second driving device for driving the second transmission member. The rotating joint includes a first rotating part and a second rotating part rotatably connected. The first rotating part has a first mounting hole for the first transmission member to pass through, the second rotating part has a second mounting hole for the second transmission member to pass through, and the connector has a third mounting hole for the first transmission member to pass through. The first driving device is used to drive the first transmission member to rotate and / or extend and retract along the axial direction. The second driving device is used to drive the second transmission member to extend and retract along the axial direction to drive the first transmission member to adjust in the track groove.

[0013] In a preferred embodiment of the present invention, the guide rail pair includes an arc-shaped guide rail parallel to the track groove, and the connector includes a slider slidably disposed on the guide rail, the slider having the third mounting hole.

[0014] In a preferred embodiment of the present invention, the window assembly includes a first flange disposed on the vacuum chamber, a second flange detachably connected to the first flange, a quartz glass disposed between the first flange and the second flange, and a sealing ring for sealing the quartz glass.

[0015] In a preferred embodiment of the present invention, the X-ray coupled vapor deposition in-situ characterization system further includes a positioning platform, and the vacuum chamber is disposed on the positioning platform.

[0016] In a preferred embodiment of the present invention, the positioning platform is a six-degree-of-freedom tilting table, which includes a base, a support platform, and a motion mechanism disposed between the base and the support platform.

[0017] In a preferred embodiment of the present invention, the electron beam emitting module includes an electron gun and a driving power supply adapted to the electron gun, wherein the electron gun is connected to the electron beam interface.

[0018] In a preferred embodiment of the present invention, the X-ray coupled vapor deposition in-situ characterization system further includes a camera device, which is used in conjunction with an observation window to achieve remote monitoring.

[0019] In a preferred embodiment of the present invention, the in-situ characterization system for coupled X-ray vapor deposition further includes an X-ray source, wherein the X-rays emitted by the X-ray source can enter the vacuum chamber through the X-ray inlet.

[0020] In a preferred embodiment of the present invention, the X-ray coupled vapor deposition in-situ characterization system further includes a control module, which is electrically connected to the transmission mechanism and the electron beam emission module for controlling the deposition process parameters and the movement of the sample specimen.

[0021] In a preferred embodiment of the present invention, the holding device is provided with a heating electrode, which is used to heat the sample piece.

[0022] In a preferred embodiment of the present invention, the X-ray coupled vapor deposition in-situ characterization system further includes a vacuum module, which is connected to the vacuum chamber through the vacuum port, and the vacuum module includes a composite molecular pump and a forepump.

[0023] The technical solution of the present invention has the following significant beneficial effects: The X-ray coupled vapor deposition in-situ characterization system described in this invention achieves true in-situ, real-time, and dynamic coupling between electron beam physical vapor deposition (EB-PVD) and synchrotron radiation X-ray characterization technology. It effectively ensures the stability of the characterization process and the flexibility of the process operation under extreme process conditions such as high temperature, high vacuum, and strong electron beam irradiation. This enables real-time monitoring and quantitative analysis of the thermal barrier coating growth process to deeply reveal the dynamic evolution mechanism of the microstructure of the thermal barrier coating during the deposition process.

[0024] This invention, by setting up X-ray inlet and outlet ports on a vacuum chamber, allows X-rays to penetrate the inlet ports and directly act on the growing coating surface. This overcomes the limitations of existing offline characterization methods, enabling continuous capture of key microstructural information during coating growth, such as phase evolution, crystal orientation evolution, nanopore formation, and dynamic changes in residual stress, on a millisecond to second timescale. This provides a foundation for revealing the growth kinetics of thermal barrier coatings and other functional thin films. The light source inlet and outlet ports on the protective cover provide an optical path for the X-rays, and the track grooves on the protective cover provide precise guidance for the movement of the sample. Furthermore, the protective cover significantly isolates the transmission mechanism from high-temperature metal vapor contamination, ensuring the reliability of the transmission mechanism. The transmission mechanism has multi-degree-of-freedom adjustment capabilities, ensuring that the test area on the sample is always precisely aligned with the fixed X-ray beam. In addition, the target crucible can hold one or more targets, enabling in-situ preparation and simultaneous characterization of multi-doped, compositionally gradient, or multi-layered structure coatings in a vacuum environment, providing greater experimental flexibility. The detection module can convert invisible X-ray signals emitted from the growing coating sample into digital images or data that can be analyzed and interpreted by computers in real time and with high precision.

[0025] This invention enables real-time monitoring of the correlation between process parameters and microstructure evolution during deposition, allowing for the rapid establishment of process-structure mapping relationships. This facilitates dynamic optimization and control of deposition parameters, driving a shift in materials research and development from traditional trial-and-error models to mechanism-driven and data-driven approaches. This invention is not only applicable to the development of novel high-performance thermal barrier coatings but can also be broadly extended to wear-resistant coatings, functional oxide thin films, semiconductor heterojunctions, and biomedical coatings, possessing significant scientific value and broad application prospects in aerospace, energy conversion, and electronic information engineering. Attached Figure Description

[0026] To more clearly illustrate the technical solutions in the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0027] The accompanying drawings described herein are for illustrative purposes only and are not intended to limit the scope of the invention in any way. Furthermore, the shapes and proportions of the components in the drawings are merely illustrative to aid in understanding the invention and do not specifically limit the shapes and proportions of the components. Those skilled in the art, guided by the teachings of this invention, can select various possible shapes and proportions to implement the invention according to specific circumstances.

[0028] Figure 1 This is a schematic diagram of an embodiment of the X-ray coupled vapor deposition in-situ characterization system described in this invention; Figure 2 This is a schematic cross-sectional view of an embodiment of the X-ray coupled vapor deposition in-situ characterization system described in this invention. Figure 3 This is a three-dimensional structural schematic diagram of an embodiment of the X-ray coupled vapor deposition in-situ characterization system described in this invention. Figure 4 This is a three-dimensional structural diagram of one embodiment of the protective cover described in this invention; Figure 5 This is a three-dimensional structural schematic diagram of one embodiment of the transmission mechanism described in this invention; Figure 6 This is a cross-sectional view of one embodiment of the window component described in this invention; Figure 7 This is a top view schematic diagram of one embodiment of the vacuum chamber and X-rays described in this invention.

[0029] The reference numerals in the above figures are as follows: 10. Sample; 20. X-rays; 100. Vacuum chamber; 101. Vacuum furnace shell; 102. Top cover; 110. X-ray entrance port; 120. X-ray exit port; 130. Electron beam interface; 140. Vacuum extraction interface; 150. Observation window; 160. Rotating rod; 170. Vacuum chamber flange; 180. Window assembly; 181. First flange; 182. Second flange; 183. Quartz glass; 184. Sealing ring; 200. Protective cover; 201. Housing; 202. Dome; 203. First conical shell; 204. Second conical shell; 210. Light source entrance; 220. Light source exit; 230. Electron beam entrance; 240. Track groove; 300. Target crucible; 310. Target loading tank; 320. Water cooling channel; 400. Transmission mechanism; 410. First transmission component; 420. First drive device; 430. Second transmission component; 440. Guide rail pair; 450. Second drive device; 460. Connecting component; 470. Rotating joint; 500. Electron beam emission module; 600. Detection module; 700. Positioning platform; 710. Base; 720. Supporting platform; 730. Motion mechanism; 800. Camera device; 900, Vacuum Module; 910, Composite Molecular Pump; 920, Backing Pump. Detailed Implementation

[0030] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0031] Please refer to the following: Figures 1 to 7 As shown, an embodiment of the present invention provides an X-ray coupled vapor deposition in-situ characterization system. This X-ray coupled vapor deposition in-situ characterization system includes a vacuum chamber 100, a protective shield 200, a target crucible 300, a transmission mechanism 400, an electron beam emission module 500, and a detection module 600. The vacuum chamber 100 includes a radiation inlet 110, a radiation outlet 120, an electron beam interface 130, a vacuum pumping interface 140, and at least one observation window 150. The protective shield 200 is disposed within the vacuum chamber 100 and includes a light source inlet 210, a light source outlet 220, and an electron beam inlet 230. 0, and track groove 240; target crucible 300 is adjustablely disposed inside protective cover 200, target crucible 300 is used to place at least one target; transmission mechanism 400 includes first transmission member 410, first transmission member 410 is adjustablely inserted into track groove 240, one end of first transmission member 410 is disposed inside protective cover 200 and is provided with holding device, holding device is used to carry sample 10; electron beam emission module 500 is capable of generating electron beam and irradiating target crucible 300 through electron beam interface 130 to evaporate target; detection module 600 is disposed facing X-ray exit port 120, used to capture Debye ring or scattering pattern.

[0032] Overall, this X-ray coupled in-situ vapor deposition characterization system achieves true in-situ, real-time, and dynamic coupling between electron beam physical vapor deposition (EB-PVD) and synchrotron X-ray characterization technology. It effectively ensures the stability of the characterization process and the flexibility of the process operation under extreme process conditions such as high temperature, high vacuum, and strong electron beam irradiation. This enables real-time monitoring and quantitative analysis of the thermal barrier coating growth process to deeply reveal the dynamic evolution mechanism of the microstructure of the thermal barrier coating during the deposition process.

[0033] This invention enables real-time monitoring of the correlation between process parameters and microstructure evolution during deposition, and can quickly establish a process-structure mapping relationship, thereby achieving dynamic optimization and control of deposition parameters, and promoting the transformation of materials research and development from the traditional experience-based trial-and-error mode to a mechanism-driven and data-driven mode.

[0034] This invention is not only applicable to the development of novel high-performance thermal barrier coatings, but can also be widely extended to wear-resistant coatings, functional oxide thin films, semiconductor heterojunctions and biomedical coatings. It has important scientific value and broad application prospects in engineering fields such as aerospace, energy conversion and electronic information.

[0035] Specifically, such as Figure 7 In the illustrated embodiment, the present invention, by setting an X-ray inlet 110 and an X-ray outlet 120 on the vacuum chamber 100, allows X-rays 20 to penetrate the X-ray inlet 110 and directly act on the surface of the growing coating. This overcomes the limitations of existing offline characterization methods and can continuously capture key microstructural information such as phase evolution, crystal orientation evolution, nanopore formation, and dynamic changes in residual stress during coating growth on a timescale of milliseconds to seconds. This provides an equipment basis for revealing the growth kinetics mechanism of thermal barrier coatings and other functional thin films.

[0036] like Figure 4 In the illustrated embodiment, the light source entrance 210 and light source exit 220 on the protective cover 200 provide an optical path for the X-ray 20. The track groove 240 on the protective cover 200 provides precise guidance for the movement of the sample 10. Furthermore, the protective cover 200 isolates the transmission mechanism 400 from contamination by high-temperature metal vapor, ensuring the long-term operational reliability of the transmission mechanism 400. The transmission mechanism 400 has multi-degree-of-freedom adjustment capabilities, ensuring that the area to be tested on the sample 10 is always precisely aligned with the fixed X-ray 20.

[0037] Furthermore, the target crucible 300 can hold one or more targets, enabling in-situ preparation and simultaneous characterization of multi-component doped, compositional gradient, or multi-layered structure coatings in a vacuum environment, thus providing greater experimental flexibility.

[0038] The detection module 600 can convert invisible X-ray signals emitted from the growing coating sample into digital images or data that can be analyzed and interpreted by computers in real time and with high precision. This enables in-situ, real-time, and non-destructive monitoring of various X-ray characterization techniques, and significantly improves the dynamic analysis capability of coating growth mechanism and microstructure evolution.

[0039] Designers can adjust the specific structure of the detection module 600 according to usage requirements, without making specific limitations. Preferably, the detection module 600 employs a two-dimensional surface detector to capture the entire Debye ring or scattering pattern, thereby providing raw data. Furthermore, the detection module 600 is mounted on a movable guide rail, allowing for precise setting of its angle and position.

[0040] In embodiments of the present invention, such as Figure 3 and Figure 7The illustrated embodiment of the in-situ vapor deposition characterization system coupled with X-rays further includes an X-ray source, wherein X-rays 20 emitted by the X-ray source can enter the vacuum chamber 100 through the X-ray entrance 110. The core of this invention lies in the use of three X-ray characterization techniques: X-ray diffraction: Utilizing the high throughput and high collimation of synchrotron radiation, in-situ, high-speed XRD measurements are performed. Real-time tracking of coating phase formation and transformation kinetics, preferred orientation (texture) evolution, and dynamic development of lattice strain / stress is achieved.

[0041] X-ray scattering: Combining small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS) techniques, we can monitor the nanoscale structure inside or on the surface of the coating in situ during the initial stage of deposition and throughout the entire process, such as the formation, size distribution and evolution of pores, and the distribution of nanoparticles.

[0042] X-ray imaging: Utilizing the high coherence and high penetration of synchrotron radiation, in-situ X-ray imaging is performed to provide real-time morphological information of the coating growth front, visualize coating thickness uniformity, dynamic generation and expansion of large-scale defects, and substrate-coating interface reaction behavior, etc.

[0043] By synergistically applying multimodal X-ray characterization techniques, an in-situ observation model coupled with multiple scales and physical fields was constructed. This not only greatly enhances the scientific understanding of the entire vapor deposition process, but also provides strong technical support for the dynamic optimization of process parameters, accurate prediction of material properties, and quality control. It has significant scientific research value and promising industrial application prospects.

[0044] In embodiments of the present invention, such as Figure 1 , Figure 2 and Figure 3 In the embodiment shown, the vacuum chamber 100 includes a vacuum furnace shell 101 and a top cover 102 that is openably disposed on the vacuum furnace shell 101. An X-ray inlet 110, an X-ray outlet 120, an electron beam interface 130, a vacuum interface 140, and at least one observation window 150 are disposed on the vacuum furnace shell 101.

[0045] Specifically, the X-ray inlet 110 and X-ray outlet 120 are arranged opposite each other on the vacuum furnace shell 101. The electron beam interface 130 is arranged at approximately 90° to the X-ray inlet 110 and X-ray outlet 120. An observation window 150 can be provided on the opposite side of the electron beam interface 130, and the vacuum interface 140 can be located above the observation window 150. Furthermore, multiple observation windows can be provided on the top cover 102.

[0046] By integrating a radiation inlet 110, a radiation outlet 120, an electron beam interface 130, a vacuum interface 140, and an observation window 150 onto the vacuum furnace shell 101, and in conjunction with an openable top cover 102, the maintainability, ease of operation, and in-situ monitoring capabilities of the vacuum chamber 100 are significantly improved while ensuring high vacuum sealing and multi-physics field synergy.

[0047] The vacuum furnace shell 101 provides a sealed environment for the coating deposition process and can be made of 304 stainless steel. The vacuum furnace shell 101 is cylindrical and made of double-layered stainless steel, with the interlayer capable of water cooling.

[0048] Furthermore, the vacuum furnace shell 101 may also be equipped with necessary interfaces such as an inert gas filling port and a thermocouple connection port, without specific limitations. The vacuum furnace shell 101 can be refilled with gases such as argon or nitrogen, but the maximum filling pressure cannot exceed atmospheric pressure. The inert gas filling port is equipped with an electric valve to control the opening and closing of the filling channel.

[0049] A pressure sensor can be installed inside the vacuum furnace shell 101. When the inflation pressure exceeds the set value, the electric valve will automatically cut off the inflation channel. Simultaneously, a mechanical safety valve can be installed on the vacuum furnace shell 101 to automatically release air when the internal pressure exceeds atmospheric pressure. Furthermore, the vacuum furnace shell 101 has a high-temperature removable liner. After long-term use, the vacuum chamber 100 requires regular cleaning, facilitating the cleaning of the main vacuum chamber 100.

[0050] In embodiments of the present invention, such as Figure 2 The embodiment shown further includes a rotating rod 160 rotatably connected to the vacuum chamber 100. The upper end of the rotating rod 160 is connected to the target crucible 300, and the lower end of the rotating rod 160 passes through the vacuum chamber 100 to connect to the rotation drive mechanism. The target crucible 300 includes a plurality of spaced target loading grooves 310.

[0051] Specifically, the target crucible 300 is provided with multiple spaced-apart target loading slots 310, each of which can hold one type of target. Preferably, the target crucible is made of copper with good thermal conductivity. More preferably, the multiple target loading slots 310 are arranged in a circular array. This multi-target design provides a hardware basis for achieving the deposition of multi-component, multi-layer, or gradient composition functional thin films in a single vacuum cycle.

[0052] The target crucible 300 is connected to the rotary drive mechanism via a rotating rod 160, enabling automatic switching and precise alignment of multiple targets. This allows for sequential or co-deposition of multi-component thin films, significantly improving process flexibility and composition control. Designers can adjust the specific composition of each target according to their needs; no specific limitations are imposed here.

[0053] The rotary drive mechanism includes a stepper motor or a servo motor, which can drive the rotating rod 160 to rotate precisely. During operation, the stepper motor or servo motor drives the rotating rod 160 and the target crucible 300 fixed thereto to rotate and position via commands from an external control system.

[0054] Users can automatically rotate the desired target material to the working position directly below the electron beam focal spot according to the preset process formula. After the deposition of one material is completed, the target crucible 300 can be rotated again to accurately deliver the next target material to the evaporation position. The entire process does not require breaking the vacuum.

[0055] In embodiments of the present invention, such as Figure 2 In the illustrated embodiment, the bottom of the vacuum chamber 100 is provided with an installation port, which is detachably covered by a vacuum chamber flange 170. A rotating rod 160 is rotatably mounted on the vacuum chamber flange 170. By providing a detachable vacuum chamber flange 170 at the bottom of the vacuum chamber 100, it is convenient to remove the target crucible 300 to replenish or replace the target, thus improving operational convenience.

[0056] Furthermore, such as Figure 2 In the illustrated embodiment, the target crucible 300 is provided with a water-cooling channel 320. By providing a water-cooling channel 320 inside the target crucible 300, the heat on the target crucible 300 can be effectively removed under high-energy electron beam bombardment, preventing the target crucible 300 from overheating and melting or deforming, ensuring the stability of the deposition process and the quality of the film, and extending the service life of the target crucible 300.

[0057] In embodiments of the present invention, such as Figure 4 In the embodiment shown, the protective cover 200 includes a housing 201 and a dome 202 disposed on the housing 201. An electron beam inlet 230 is disposed on the housing 201, and a light source inlet 210, a light source outlet 220, and a track groove 240 are disposed on the dome 202. The track groove 240 is configured to be perpendicular to the light source direction.

[0058] During coating deposition, the protective shield 200 can construct a physical barrier to effectively isolate highly active metal, oxide vapors and particle flows generated by high-temperature evaporation sources, typically molten target material in a crucible, preventing these atmospheric contaminants from depositing, adhering to or corroding the precision transmission mechanism 400.

[0059] Specifically, the light source inlet 210 and the light source outlet 220 are arranged opposite each other on the dome 202, and the track groove 240 extends on the dome 202 and connects the light source inlet 210 and the light source outlet 220. X-rays 20 can enter the protective cover 200 through the ray inlet 110 and the light source inlet 210, irradiate the sample 10, and then exit the vacuum chamber 100 through the light source outlet 220 and the ray outlet 120.

[0060] The electron beam inlet 230 is located on the side radially aligned with the electron gun to ensure that the high-energy electron beam bombards the target material inside the target crucible 300 without obstruction. The light source inlet 210 and the light source outlet 220 are circular with a large diameter to ensure that the diffraction / scattering signal is completely transmitted outside the vacuum chamber 100.

[0061] The track groove 240 provides ample, interference-free space for the lifting, rotating, and other motion trajectories required for the sample 10. The track groove 240 allows control of the sample 10's movement path, enabling it to be adjusted between the light source entrance 210 and the light source exit 220. This ensures that the area to be measured on the sample 10 is always precisely aligned with the fixed X-ray 20, reducing stray light interference and improving the signal-to-noise ratio and measurement accuracy of in-situ optical characterization.

[0062] In embodiments of the present invention, such as Figure 2 In the embodiment shown, the protective cover 200 also includes a first conical shell 203 extending from the light source inlet 210 to the ray inlet 110, and a second conical shell 204 extending from the light source outlet 220 to the ray outlet 120.

[0063] By setting the first conical shell 203 and the second conical shell 204, shielding and isolation of the area between the protective cover 200 and the vacuum chamber 100 are achieved, effectively reducing stray light interference and isolating high-temperature metal vapor, thereby improving the accuracy of optical signal acquisition and system stability.

[0064] Designers can adjust the specific shapes and structures of the housing 201 and the dome 202 according to usage requirements, without making specific limitations. Preferably, the housing 201 is cylindrical and the dome 202 is hemispherical. By setting the housing 201 as cylindrical and the dome 202 as hemispherical, the structural strength and resistance to deformation are improved.

[0065] In embodiments of the present invention, such as Figure 2 and Figure 5In the embodiment shown, the transmission mechanism 400 includes a first drive device 420 coaxially connected to the first transmission member 410, a guide rail pair 440 parallel to the track groove 240 and located outside the protective cover 200, a connector 460 slidably disposed on the guide rail pair 440, a second transmission member 430, a rotating joint 470 disposed between the first transmission member 410 and the second transmission member 430, and a second drive device 450 for driving the second transmission member 430. The rotating joint 470 includes a first rotating part and a second rotating part rotatably connected. The first rotating part has a first mounting hole for the first transmission member 410 to pass through, the second rotating part has a second mounting hole for the second transmission member 430 to pass through, and the connector 460 has a third mounting hole for the first transmission member to pass through. The first drive device 420 is used to drive the first transmission member 410 to rotate and / or to extend and retract along the axial direction. The second drive device 450 is used to drive the second transmission member 430 to extend and retract along the axial direction to drive the first transmission member 410 to adjust in the track groove 240.

[0066] Specifically, the first rotating part is provided with a first mounting hole, and the first transmission member 410 can be configured as a first transmission rod. The first transmission rod can slide through the first mounting hole. At this time, the first rotating part can be used to support the first driving device 420, and the first driving device 420 is used to drive the first transmission rod to perform rotation adjustment and / or extension adjustment.

[0067] Furthermore, the second transmission component 430 can be configured as a second transmission rod, with one end of the second transmission rod passing through the second mounting hole to connect to the second rotating part. The second transmission rod can extend and retract axially to drive the first transmission component 410 to adjust within the track groove 240. Designers can adjust the specific shape of the second transmission rod according to usage requirements, such as a straight rod or a curved rod; no specific limitations are imposed here.

[0068] In an embodiment of the present invention, the guide rail pair 440 includes an arc-shaped guide rail parallel to the track groove 240, and the connector 460 includes a slider slidably disposed on the guide rail, the slider having the third mounting hole. The first transmission rod slidably passes through the third mounting hole, and the guide rail pair 440 and the slider enable the first transmission rod to be adjusted along the track groove 240, thereby adjusting the position of the sample 10.

[0069] The first driving device 420 can drive the first transmission component 410 to rotate, thereby adjusting the angular position of the sample 10. Alternatively, the first driving device 420 can drive the first transmission component 410 to extend and retract axially, thereby adjusting the height position of the sample 10.

[0070] Through the cooperation of the first transmission component 410, the first driving device 420, the second transmission component 430, the second driving device 450, the guide rail pair 440, the connecting component 460, and the rotating joint 470, the second driving device 450 can drive the sample 10 to swing along the track groove 240, and the first driving device 420 can drive the sample 10 to rotate, or the first driving device 420 can axially adjust the height position of the sample 10. The transmission mechanism 400 can achieve multi-degree-of-freedom adjustment within the chamber, enabling repeated positioning of the sample 10 and ensuring that the X-ray 20 is always aligned with the target position of the sample 10. Furthermore, the target material can serve as a deposition source, thereby providing ceramic / metal evaporation gas.

[0071] In embodiments of the present invention, such as Figure 6 In the embodiment shown, the window assembly 180 includes a first flange 181 disposed on the vacuum chamber 100, a second flange 182 detachably connected to the first flange 181, a quartz glass 183 disposed between the first flange 181 and the second flange 182, and a sealing ring 184 for sealing the quartz glass 183.

[0072] By setting up detachable first flange 181 and second flange 182 to clamp quartz glass 183 and sealing ring 184, efficient sealing and stable transmission between vacuum chamber 100 and the outside world are achieved, ensuring the airtightness of the vacuum environment and facilitating the maintenance and replacement of quartz glass 183.

[0073] Furthermore, by utilizing the excellent light transmittance and radiation resistance of quartz glass 183, low-loss X-ray transmission is ensured, while preventing external contaminants from entering the vacuum chamber, thus improving the reliability and long-term stability of the system. The sealing ring 184 can be configured as a fluororubber O-ring.

[0074] In embodiments of the present invention, such as Figure 1 and Figure 2 The embodiment shown further includes a positioning platform 700, on which a vacuum chamber 100 is disposed.

[0075] Preferably, the positioning platform 700 is a six-degree-of-freedom tilting table, which includes a base 710, a support platform 720, and a motion mechanism 730 disposed between the base 710 and the support platform 720.

[0076] Through the coordinated adjustment of the base 710, the support platform 720, and the motion mechanism 730, high-precision multi-dimensional attitude adjustment of the vacuum chamber 100 and its internal sample 10 in space can be achieved, significantly improving alignment flexibility and positioning accuracy. Designers can adjust the specific structure of the motion mechanism 730 according to usage needs, without specific limitations. For example, the motion mechanism 730 includes multiple telescopic devices.

[0077] A six-DOF tilting stage is an actuator for achieving spatial alignment and complex attitude adjustment. Through a parallel or series-parallel hybrid kinematic structure, the six-DOF tilting stage integrates translational degrees of freedom along the X, Y, and Z axes of the Cartesian coordinate system, as well as rotational degrees of freedom around these three axes. This enables continuous and coordinated control of any position and any attitude in three-dimensional space, making it more suitable for dynamic light source alignment in in-situ characterization processes, such as complex optical path construction, dynamic tracking and compensation, and multimodal alignment.

[0078] Furthermore, the positioning platform 700 not only supports in-situ dynamic observation and multimodal characterization under complex angles, but also facilitates the coupling optimization of different deposition directions and detection perspectives, improving the comprehensiveness and reliability of experimental data. At the same time, the telescopic device, combined with precise control, can achieve micron-level displacement and second-level angle adjustment, meeting the stringent requirements of stability and repeatability for high-performance in-situ characterization.

[0079] In embodiments of the present invention, such as Figure 1 , Figure 2 and Figure 3 In the illustrated embodiment, the electron beam emission module 500 includes an electron gun and a driving power supply adapted to the electron gun. The electron gun is connected to the electron beam interface 130. Designers can adjust the specific model of the electron gun and its driving power supply according to usage requirements; no specific limitations are imposed here.

[0080] By using an electron gun in conjunction with a dedicated driving power supply, precise control over the electron beam intensity, energy, and emission stability is achieved. The electron gun is directly connected to the electron beam interface 130, ensuring efficient injection and low-loss transmission of the electron beam in a vacuum environment, thereby improving the efficiency and signal-to-noise ratio of exciting the sample 10 to generate characteristic signals.

[0081] In embodiments of the present invention, such as Figure 1 The embodiment shown further includes an X-ray coupled vapor deposition in-situ characterization system, which also includes a camera device 800 for use with an observation window 150 to enable remote monitoring.

[0082] The camera device 800, in conjunction with the observation window 150, enables remote real-time monitoring of the sample 10 and the deposition process within the vacuum chamber 100. This effectively avoids the safety risks and environmental interference associated with direct manual observation. Without disrupting the vacuum state, it continuously acquires visualized information on the surface morphology evolution of the sample 10, the dynamics of film growth, and the operational status of the equipment, improving the observability and controllability of the experimental process. Furthermore, the camera device 800 can also link the positioning platform 700 with the transmission mechanism 400, providing intuitive and accurate visual feedback support for in-situ experiments.

[0083] In an embodiment of the present invention, the in-situ characterization system for coupled X-ray vapor deposition further includes a control module, which is electrically connected to the transmission mechanism 400 and the electron beam emission module 500 for controlling the deposition process parameters and the movement of the sample 10.

[0084] By setting up a control module and electrically connecting the transmission mechanism 400 and the electron beam emission module 500, the system achieves coordinated and precise control of deposition process parameters and sample 10 movement, significantly improving the system's automation level.

[0085] Specifically, the control module can adjust the position and orientation (such as rotation, translation, and tilt) of the sample 10 in real time to match the requirements of different characterization areas and deposition angles, while simultaneously controlling the energy, flux, and scanning path of the electron beam to ensure the spatial selectivity and dosage accuracy of the deposition process.

[0086] Furthermore, the control module can be integrated and linked with the X-ray source, camera device 800, positioning platform 700 and other sensors, so that process parameters can be optimized in real time based on in-situ monitoring data during dynamic deposition, thereby achieving intelligent control and improving the material growth quality and structural controllability.

[0087] Designers can adjust the specific structure of the control module according to their needs, and no specific restrictions are imposed here. For example, the control module can be set as a computer and / or PLC controller, thereby enabling the execution of an industrial PC+PLC control mode with better control performance.

[0088] In embodiments of the present invention, designers may adjust the specific structure of the clamping device according to usage needs, and no specific limitations are imposed here. For example, the clamping device may be configured as a claw, a fixing frame, a base, or other structures.

[0089] Preferably, the holding device is equipped with a heating electrode for heating the sample 10. Furthermore, the holding device is also equipped with a temperature sensor for real-time monitoring of the temperature of the sample 10.

[0090] Specifically, the holding device is used to support the sample 10, the heating electrode is set on the sample 10, and the sample 10 acts as a resistor to achieve self-heating, with a maximum temperature of 1200℃.

[0091] By integrating heating electrodes into the bearing device, the sample 10 can be heated in situ under vacuum, effectively simulating the high-temperature deposition conditions in actual working conditions, promoting atomic diffusion and surface migration, and improving the density and crystal quality of the coating.

[0092] In embodiments of the present invention, such as Figure 1The embodiment shown further includes a vacuum module 900, which is connected to a vacuum chamber 100 via a vacuum port 140. The vacuum module 900 includes a composite molecular pump 910 and a forepump 920.

[0093] The backing pump 920, acting as the primary pumping unit, is responsible for reducing the pressure in vacuum chamber 100 from atmospheric pressure to a medium vacuum range (typically 1 Pa–10 Pa), providing suitable pre-vacuum conditions for the compound molecular pump 910. The compound molecular pump 910 further pumps gas based on the backing pump 920, utilizing the momentum transfer effect of high-speed rotating blades on gas molecules to achieve efficient removal of light gases (such as hydrogen and helium) and residual organic vapors, ultimately reducing the pressure in vacuum chamber 100 to 10 Pa. -3 Pa or even lower, meeting the stringent requirements for a clean vacuum environment in electron beam evaporation, molecular beam epitaxy, and other processes.

[0094] In the optical path design of the X-ray coupled-X-ray vapor deposition in-situ characterization system coupled with synchrotron X-rays 20, determining the diameters of the X-ray inlet 110 and the X-ray outlet 120 is crucial. Since the incident light is parallel to the high-energy X-rays 20, the size of the X-ray inlet 110 has little impact on the optical path. The radius of the X-ray outlet 120 is designed based on the Bragg diffraction equation, and the radii of the X-ray inlet 110 and the X-ray outlet 120 are determined by combining parameters such as the radius of the X-ray coupled-X-ray vapor deposition in-situ characterization system and the interplanar spacing of the coating. The Bragg diffraction equation is: nλ=2dsinθ; Where d is the specific interplanar spacing of the crystal material, in Å; λ is the incident X-ray wavelength of 20 nm, selected by the monochromator of the synchrotron radiation source according to experimental requirements, in Å; and θ is the diffraction angle (angle between the incident / reflected beam and the crystal plane) that satisfies the Bragg condition, in °. For a specific diffraction peak (specific d value, specific diffraction order n, usually n=1), once the source energy (determines λ) and the object of analysis (determines d) are determined, θ is uniquely determined.

[0095] In the design of the X-ray coupled vapor deposition in-situ characterization system of this invention, the interplanar spacing of the thermal barrier coating components must be fully considered, as well as the interplanar spacing of other coating components based on equipment scalability, to ultimately determine the maximum exit window size. When the d value is smaller, the θ value is larger; therefore, the minimum d value should be found within the coating system.

[0096] The target heating source of this system is an electron gun, which can be used to study coating systems such as thermal barrier coatings, tool coatings, hard coatings, and metal coatings. After researching various coating systems, the minimum interplanar spacing d is approximately 0.8 Å; in this system, a d value of 0.6 Å is used. The λ value corresponding to an 80 keV synchrotron X-ray source is 0.154980 Å; therefore, θ is approximately 7.42°. With the radius of the vacuum furnace shell 101 of the vacuum chamber 100 set to 300 mm, the radius of the X-ray exit port 120 is approximately 39.07 mm. Considering that this system can obtain diffraction information from as many coating systems as possible, the radius of the X-ray exit port 120 in this system is set to 50 mm.

[0097] In the in-situ characterization system of vapor deposition coupled with X-rays of the present invention, high-intensity, high-collimation, and wavelength-tunable (after monochromaticization) X-rays 20 are provided by an X-ray source.

[0098] The X-ray coupled vapor deposition in-situ characterization system may also include an entrance slit or collimation system, a monochromator, and focusing optics disposed on the incident light path. Specifically, the entrance slit or collimation system is used to adjust the size and divergence of the incident beam; the monochromator is used to select X-rays 20 of specific energy; focusing optics, such as a curved crystal monochromator, a multilayer mirror, or a KB mirror, focus the X-ray beam 20 onto the surface of the sample 10 to ensure flux and spatial resolution; the window assembly 180 on the X-ray entrance 110 is disposed on the vacuum chamber 100 and connected by a flange structure, and the window material is quartz glass 183 to ensure that there is still a high flux of X-rays 20 at the sample 10.

[0099] X-rays 20 interact with the coating on sample 10, resulting in physical phenomena such as Bragg diffraction, small-angle X-ray scattering, and diffuse scattering, forming diffraction, scattering, imaging, or exit light paths. The window assembly 180 on the X-ray exit port 120 is another high-transmittance X-ray window, made of the same material as the window assembly 180 on the X-ray entrance port 110, allowing diffraction, scattering, or imaging signals to pass through the deposition chamber in the vacuum chamber 100. The radius of the X-ray exit port 120 is approximately 50 mm.

[0100] All articles and references disclosed herein, including patent applications and publications, are incorporated herein by reference for various purposes. The term “substantially constitutes…” used to describe a combination should include the identified element, component, part, or step, as well as other elements, components, parts, or steps that do not substantially affect the essential novelty of the combination. The use of the terms “comprising” or “including” to describe combinations of elements, components, parts, or steps herein also contemplates embodiments substantially constituted by such elements, components, parts, or steps. The use of the term “may” herein is intended to indicate that any described attribute “may” include is optional. Multiple elements, components, parts, or steps can be provided by a single integrated element, component, part, or step. Alternatively, a single integrated element, component, part, or step can be divided into multiple separate elements, components, parts, or steps. The disclosure of “a” or “an” used to describe an element, component, part, or step does not imply exclusion of other elements, components, parts, or steps.

[0101] The various embodiments in this specification are described in a progressive manner, with each embodiment focusing on its differences from other embodiments. Similar or identical parts between embodiments can be referred to interchangeably. The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement it accordingly. They should not be construed as limiting the scope of protection of the present invention. All equivalent changes or modifications made according to the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A vapor deposition in-situ characterization system coupled with X-rays, characterized in that, include: A vacuum chamber, comprising an X-ray inlet, an X-ray outlet, an electron beam interface, a vacuum pumping interface, and at least one observation window, wherein the X-ray inlet and the X-ray outlet are provided with window assemblies; A protective cover is disposed in the vacuum chamber, and the protective cover includes a light source inlet, a light source outlet, an electron beam inlet, and a track groove; A target material crucible, which is adjustablely disposed within the protective cover, is used to hold at least one target material; The transmission mechanism includes a first transmission component, which is adjustablely inserted into the track groove. One end of the first transmission component is disposed inside the protective cover and is provided with a holding device, which is used to support the sample piece. An electron beam emitting module, which is capable of generating an electron beam and irradiating the target crucible through the electron beam interface to evaporate the target material; A detection module, which is positioned facing the ray outlet, is used to capture Debye rings or scattering patterns.

2. The in-situ characterization system for coupled X-ray vapor deposition as described in claim 1, characterized in that, The vacuum chamber includes a vacuum furnace shell and an openable top cover disposed on the vacuum furnace shell. The X-ray inlet, the X-ray outlet, the electron beam interface, the vacuum pumping interface, and at least one of the observation windows are disposed on the vacuum furnace shell.

3. The in-situ characterization system for coupled X-ray vapor deposition as described in claim 1, characterized in that, The X-ray coupled vapor deposition in-situ characterization system further includes a rotating rod rotatably connected to the vacuum chamber. The upper end of the rotating rod is connected to the target crucible, and the lower end of the rotating rod passes through the vacuum chamber to connect to a rotation drive mechanism. The target crucible includes multiple spaced, circumferentially arranged target loading slots. The bottom of the vacuum chamber is provided with an installation port, which is detachably covered with a vacuum chamber flange. The rotating rod is rotatably mounted on the vacuum chamber flange. A water-cooling channel is provided inside the target crucible.

4. The in-situ characterization system for coupled X-ray vapor deposition as described in claim 1, characterized in that, The protective shield includes a housing and a dome disposed on the housing. The electron beam inlet is disposed on the housing, and the light source inlet, the light source outlet, and the track groove are disposed on the dome. The track groove is configured to be perpendicular to the light source direction. The protective shield also includes a first conical shell extending from the light source inlet to the ray inlet, and a second conical shell extending from the light source outlet to the ray outlet. The housing is cylindrical, and the dome is hemispherical.

5. The in-situ characterization system for coupled X-ray vapor deposition as described in claim 1, characterized in that, The transmission mechanism includes a first driving device coaxially connected to the first transmission member, a guide rail pair parallel to the track groove and located outside the protective cover, a connector slidably disposed on the guide rail pair, a second transmission member, a rotating joint disposed between the first transmission member and the second transmission member, and a second driving device for driving the second transmission member. The rotating joint includes a first rotating part and a second rotating part rotatably connected. The first rotating part has a first mounting hole for the first transmission member to pass through, the second rotating part has a second mounting hole for the second transmission member to pass through, and the connector has a third mounting hole for the first transmission member to pass through. The first driving device is used to drive the first transmission member to rotate and / or extend and retract axially. The second driving device is used to drive the second transmission member to extend and retract axially to drive the first transmission member to adjust in the track groove. The guide rail pair includes an arc-shaped guide rail parallel to the track groove, and the connector includes a slider slidably disposed on the guide rail. The slider has the third mounting hole.

6. The in-situ characterization system for coupled X-ray vapor deposition as described in claim 1, characterized in that, The ray inlet and the ray outlet are provided with window assemblies, the window assembly including a first flange disposed on the vacuum chamber, a second flange detachably connected to the first flange, a quartz glass disposed between the first flange and the second flange, and a sealing ring for sealing the quartz glass.

7. The in-situ characterization system for coupled X-ray vapor deposition as described in claim 1, characterized in that, The X-ray coupled vapor deposition in-situ characterization system further includes a positioning platform, on which the vacuum chamber is disposed; the positioning platform is a six-degree-of-freedom tilting stage, which includes a base, a support platform, and a motion mechanism disposed between the base and the support platform.

8. The in-situ characterization system for coupled X-ray vapor deposition as described in claim 1, characterized in that, The electron beam emission module includes an electron gun and a driving power supply adapted to the electron gun, and the electron gun is connected to the electron beam interface.

9. The in-situ characterization system for coupled X-ray vapor deposition as described in claim 1, characterized in that, The X-ray coupled vapor deposition in-situ characterization system further includes an imaging device, which is used in conjunction with the observation window to achieve remote monitoring; and / or, the X-ray coupled vapor deposition in-situ characterization system further includes an X-ray source, the X-rays emitted by the X-ray source being able to enter the vacuum chamber through the X-ray entrance port; and / or, the X-ray coupled vapor deposition in-situ characterization system further includes a control module, the control module being electrically connected to the transmission mechanism and the electron beam emission module for controlling the deposition process parameters and the movement of the sample; and / or, the X-ray coupled vapor deposition in-situ characterization system further includes a vacuum module, the vacuum module being connected to the vacuum chamber through the vacuum interface, the vacuum module including a composite molecular pump and a backing pump.

10. The in-situ characterization system for coupled X-ray vapor deposition as described in claim 1, characterized in that, The holding device is equipped with a heating electrode, which is used to heat the sample piece.

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