Semiconductor-grade red phosphorus crystal vapor deposition intelligent regulation system and method

Abstract

The application relates to a semiconductor-grade red phosphorus crystal vapor deposition intelligent regulation and control system and method, which comprises a crystal type directional deposition module, a field application unit and a monitoring intelligent control module. The crystal type directional deposition module comprises a deposition substrate and a microporous partition plate assembly for partitioning an inner part of a deposition cavity into a first deposition area and a second deposition area. The field application unit comprises a laser induction unit, an electric field application unit and a magnetic field application unit arranged outside the second deposition area. The monitoring intelligent control module comprises a control system, a Raman spectrum probe inserted into the second deposition area, a spectrum analyzer arranged outside the second deposition area and a pressure sensor arranged in the first deposition area and the second deposition area. The application has the following advantages: through partition pressure temperature control, multi-field cooperation and dynamic micropore modulation, crystal type epitaxial directional growth and high-purity regulation and control of red phosphorus crystals are realized.

Description

Technical Field

[0001] This invention belongs to the interdisciplinary field of advanced functional materials and intelligent equipment, specifically relating to an intelligent control system and method for semiconductor-grade red phosphorus crystal vapor deposition. Background Technology

[0002] Red phosphorus, as an important elemental semiconductor material, exhibits significantly different physicochemical properties in its crystalline forms (Form II, Form IV, Form V, etc.), showing broad application prospects in photocatalysis, energy storage, and photoelectric detection. In particular, crystalline red phosphorus with a purple metallic luster has become a research hotspot in third-generation semiconductor materials and advanced optoelectronic functional materials due to its excellent structural order and environmental stability. Studies have shown that the crystal phase structure and growth orientation of red phosphorus play a decisive role in its photoelectric performance; regulating the growth of red phosphorus along specific crystal orientations can significantly enhance the separation efficiency of photogenerated carriers, thereby improving its performance in applications such as photocatalytic water splitting.

[0003] Currently, the vapor-phase growth of red phosphorus crystals mainly employs the chemical vapor transport method. A typical step of this method includes: using commercially available amorphous red phosphorus as a raw material, combined with mineralizers such as iodine (I₂), tin (Sn), and tellurium (Te), and sealing it in a quartz ampoule; sublimating the raw material through a high-temperature zone (typically >550°C), with phosphorus vapor transported to a low-temperature zone for deposition with the assistance of the mineralizer; and obtaining crystalline red phosphorus products after a reaction time of several hours to tens of hours. Existing research has enabled the selective preparation of red phosphorus with different crystal phases, such as Form II, Form IV, and Form V, by controlling the precursor ratio and temperature parameters, and can obtain single crystals with millimeter-sized crystals or crystalline materials with specific morphologies.

[0004] However, existing red phosphorus vapor deposition methods have the following technical drawbacks in practical applications:

[0005] 1. In existing deposition apparatus and methods, the transport and deposition of phosphorus vapor rely entirely on natural convection and static temperature gradients within the ampoule. The vapor concentration field distribution is in a free-diffusion state, making any active intervention impossible. Stagnant concentration boundary layers easily form in the deposition area, leading to uneven vapor distribution, restricted lateral grain growth, and the induction of impurity phases. This naturally diffused flow field makes it difficult to achieve uniform deposition over large areas. Furthermore, the unidirectional and fixed airflow direction creates deposition blind zones. This unidirectional flow field configuration easily leads to differences in deposition rates in different regions of the deposition substrate, resulting in uneven concentration distribution during deposition. Consequently, it is difficult to obtain crystal products with consistent crystalline phases and sizes on large-area deposition substrates.

[0006] 2. Nucleation induction and crystal growth have drastically different requirements for supersaturation—the former requires lower pressure to promote directional nucleation, while the latter requires higher pressure to support lateral grain growth. However, the pressure inside a traditional sealed ampoule is determined by temperature equilibrium, resulting in the entire reaction chamber operating at the same pressure level, making it impossible to achieve a "lower at the front, higher at the back" zoned pressure configuration. More seriously, pressure drift caused by raw material consumption or byproduct generation during deposition cannot be corrected online, making process repeatability difficult to guarantee. Summary of the Invention

[0007] The purpose of this invention is to overcome the above-mentioned shortcomings and provide a smart control system and method for vapor deposition of semiconductor-grade red phosphorus crystals. Through zoned pressure and temperature control, multi-field synergy and dynamic micropore modulation, the crystal form orientation growth and high purity control of red phosphorus crystals can be achieved.

[0008] The objective of this invention is achieved through the following technical solution: a smart control system for semiconductor-grade red phosphorus crystal vapor deposition, comprising...

[0009] A crystal-oriented deposition module includes a deposition chamber, a deposition substrate disposed within the deposition chamber, and a microporous partition assembly that divides the interior of the deposition chamber into a first deposition region and a second deposition region.

[0010] The external field application unit includes a laser induction unit placed in the first deposition zone, an electric field application unit placed in the second deposition zone, and a magnetic field application unit placed outside the second deposition zone. The external field application unit induces red phosphorus crystal nuclei in the first deposition zone and synergistically promotes the lateral growth of grains in the second deposition zone.

[0011] The monitoring and intelligent control module includes a control system, a Raman spectroscopy probe extending into the second deposition zone, a spectrometer placed outside the second deposition zone, and pressure sensors located inside the first and second deposition zones.

[0012] The microporous partition assembly includes a fixed microporous plate and a movable microporous plate, which are concentrically arranged and each has a correspondingly distributed microporous array. It also includes a rotation drive assembly and an oscillation drive assembly. The rotation drive assembly is connected to the movable microporous plate and drives it to rotate around its central axis to maintain the set pressure of the second deposition zone and realize online adjustment of the pressure of the second deposition zone. The oscillation drive assembly drives the fixed microporous plate and the movable microporous plate to oscillate synchronously and periodically, so that the direction of the phosphorus vapor jet through the microporous array is scanned at high frequency, forming a dynamically distributed concentration boundary layer on the surface of the deposition substrate.

[0013] The control system coordinates the rotation angle of the rotary drive component, the oscillation frequency and amplitude of the oscillation drive component, and the electric field strength, magnetic field strength and laser power density of the external field application unit based on the received Raman spectrum characteristic peak signal and the measured value of the pressure sensor, so as to achieve dynamic matching between the flow field parameters and the external field parameters.

[0014] A further improvement of the present invention is that: the deposition substrate extends continuously in the horizontal direction, with its first section located in the first deposition area and its tail section located in the second deposition area, and the microporous partition assembly is placed at the junction of the first deposition area and the second deposition area, and is suspended above the deposition substrate with gaps.

[0015] A further improvement of the present invention is that the pressure in the first deposition zone is 100-200 Pa, and the pressure in the second deposition zone is 800-1200 Pa.

[0016] A further improvement of the present invention is that: the laser induction unit is located at the top of the first deposition area and emits a scanning laser with a wavelength of 520-550 nm onto the surface of the deposition substrate. The laser energy forms a local high temperature area on the substrate surface to induce and regulate the initial orientation of red phosphorus crystal nuclei on the deposition substrate.

[0017] An electric field application unit is located in the second deposition area and includes a lower electrode placed on the lower end face of the deposition substrate and an upper electrode placed above the deposition substrate. The upper electrode and the lower electrode are distributed parallel to each other vertically. The lower electrode is a metal support plate with an internally integrated heating element. The electric field application unit generates an electrostatic field perpendicular to the deposition substrate in the second deposition area, with an electric field strength of 100-200V / cm.

[0018] The magnetic field application unit includes a Helmholtz coil located outside the second deposition zone, which generates a steady-state magnetic field parallel to the surface of the deposition substrate within the second deposition zone, with a magnetic field strength of 0.2-0.5T.

[0019] The directions of the electrostatic field, the steady-state magnetic field, and the normal direction of the deposited substrate are all perpendicular to each other, forming a spatially orthogonal external field control system.

[0020] A further improvement of the present invention is that: the swing drive assembly includes a connecting frame disposed at the side end of the connection between the fixed microporous plate and the movable microporous plate, a rotating shaft passing through the connecting frame and the fixed microporous plate along the axial direction of the fixed microporous plate, the end of the rotating shaft being located outside the deposition chamber, and a swing plate being connected to the end of the rotating shaft, a cylinder for driving the swing plate to reciprocate swinging is provided outside the deposition chamber, and a sealed bearing is provided through the outer circumference of the rotating shaft.

[0021] The rotary drive assembly includes a drive box mounted on a connecting frame. Rotary shafts are fixedly connected to the center of the movable microporous plate on both sides along its axis. One of the drive boxes contains a rotary motor that drives the rotary shafts and the movable microporous plate to rotate synchronously. The rotary shafts pass through the outer circumference of the drive box and have a sealed bearing.

[0022] A further improvement of the present invention is that the swing amplitude of the swing drive component is ±5° to ±15°, and the swing frequency is 2-8 Hz.

[0023] A further improvement of the present invention is that: the first deposition zone and the second deposition zone of the deposition chamber are respectively connected to vacuum pumps electrically connected to pressure sensors in the corresponding deposition zones. The vacuum pumps are electrically connected to a rotary drive assembly and a control system. The control system adjusts the pumping rate of the vacuum pump in the first deposition zone according to the measured value of the pressure sensor in the first deposition zone. The control system adjusts the pumping rate of the vacuum pump in the second deposition zone according to the measured value of the pressure sensor in the second deposition zone. On the other hand, it drives the movable microporous plate to rotate by controlling the rotary drive assembly to change the micropore overlap rate between the movable microporous plate and the fixed microporous plate, thereby synergistically regulating the pressure stability in the second deposition zone.

[0024] A further improvement of the present invention is that the deposition substrate is a metal substrate, which integrates at least one temperature sensor. The temperature sensor is located in or near the substrate area corresponding to the second deposition area and is electrically connected to the control system. The control system adjusts the power of the heating element integrated in the lower electrode in real time according to the temperature of the deposition substrate to ensure that the temperature of the deposition substrate is stable within the optimal temperature range for red phosphorus crystal growth.

[0025] A further improvement of the present invention is that both the fixed microporous plate and the movable microporous plate are alumina ceramic plates or silicon nitride ceramic plates, on which multiple through holes are uniformly distributed to form a microporous array, the diameter of the through holes is 0.2-0.5 mm, and the opening rate is 8-15%.

[0026] A control method for a semiconductor-grade red phosphorus crystal vapor deposition intelligent control system includes the following steps:

[0027] S1. Raw material sublimation and purification: The red phosphorus raw material is heated to 420-480℃ under an inert atmosphere to sublimate it and form phosphorus vapor; the phosphorus vapor is then passed through a transport pipe with a variable diameter spiral structure, and metal particles larger than 1μm and arsenic and antimony compound impurities are removed through inertial separation and adsorption collection.

[0028] S2, Zoned Deposition and Crystal Nucleus Induction: Purified phosphorus vapor is introduced into the deposition chamber. The deposition chamber is formed by pressure control, with a first deposition zone and a second deposition zone arranged sequentially along the airflow direction. The pressure of the first deposition zone is maintained at 100-200 Pa, and the pressure of the second deposition zone is maintained at 800-1200 Pa.

[0029] In the first deposition zone, phosphorus vapor is initially deposited on the surface of the deposition substrate at a temperature maintained at 220-280°C. At the same time, a laser beam with a wavelength of 520-550 nm is used to scan the deposition surface with a spot diameter of 0.5-2 mm to induce the formation of red phosphorus crystal nuclei with a specific orientation.

[0030] S3. External Field Synergistic Grain Growth: In the second deposition zone, an electrostatic field perpendicular to the deposition substrate direction is applied to the surface of the deposition substrate through electrodes located above and below the deposition substrate. The electric field strength is 100-200 V / cm. At the same time, a steady-state magnetic field parallel to the deposition substrate surface direction is applied. The magnetic field strength is 0.2-0.5 T. Under the synergistic effect of the electrostatic field and the magnetic field, the phosphorus vapor is oriented and attached along the crystal nucleus, realizing the lateral preferential growth of the grains.

[0031] S4. In-situ monitoring and dynamic feedback: During the deposition process, Raman spectral signals of the deposited film are acquired in real time, with a focus on monitoring the intensity and full width at half maximum (FWHM) of the characteristic peaks near 365 cm⁻¹. The control system executes the following dynamic adjustment logic based on the Raman spectral characteristic peak signals and the measured values ​​of pressure sensors in the first and second deposition zones:

[0032] When the measured pressure in the second deposition zone deviates from the set value by more than ±50 Pa, the control system first corrects the pressure by adjusting the pumping speed of the vacuum pump connected to the second deposition zone. If the pumping speed has been adjusted to the upper limit and the set pressure still cannot be restored, the control system drives the rotating drive component to rotate the movable microporous plate, changing the micropore overlap rate between it and the fixed microporous plate, thereby increasing the airflow resistance and bringing the pressure in the second deposition zone back to the set range.

[0033] When a non-target crystalline phase characteristic peak is detected in the Raman spectrum, such as near 410 cm⁻¹ or 320 cm⁻¹, or when the full width at half maximum (FWHM) of the target characteristic peak increases by more than 10%, it indicates a decrease in crystalline phase purity or crystal quality. The control system determines this to be due to uneven distribution of phosphorus vapor concentration or mismatch of external field coupling during grain growth. At this time, the oscillation drive component is activated to make the fixed microporous plate and the moving microporous plate oscillate synchronously and periodically. The oscillation amplitude is ±5° to ±15°, the oscillation frequency is 2-8 Hz, and the duration is 3-10 minutes. This dynamically disturbs the direction of the phosphorus vapor jet through the microporous array, forming a dynamic concentration boundary layer on the surface of the deposition substrate, improving the uniformity of vapor distribution, and suppressing the formation of impurity phases.

[0034] If the Raman spectral signal remains abnormal or the pressure fluctuations cannot be eliminated by the above adjustments, the control system will further coordinate the adjustment of the laser scanning power, electrostatic field strength, or deposition substrate temperature until the spectral characteristics return to normal.

[0035] S5. Annealing and Collection: After deposition, the deposited product is cooled to room temperature at a rate of 10-30℃ / min under an inert atmosphere to obtain flaky red phosphorus crystals with a purple metallic luster attached to the deposition substrate; these crystals are then peeled off from the substrate to obtain the high-purity, large-grained purple red phosphorus crystals.

[0036] Compared with the prior art, the present invention has the following advantages:

[0037] 1. This invention uses a microporous partition assembly to divide the deposition chamber into a first deposition zone (100-200 Pa) and a second deposition zone (800-1200 Pa), forming a pressure gradient that is lower in the first zone and higher in the second. The low-pressure zone is conducive to the directional induction of crystal nuclei, while the high-pressure zone promotes the lateral preferential growth of grains, thus decoupling the process conditions for crystal nuclei formation and crystal growth. More importantly, this invention uses a rotary drive assembly to drive the movable microporous plate to rotate independently, changing the micropore overlap rate between it and the fixed microporous plate, thereby adjusting the resistance of airflow through the micropore array online and achieving dynamic correction of the pressure in the second deposition zone. When the measured value of the pressure sensor deviates from the set value and the vacuum pump's pumping speed has reached its upper limit, the control system can automatically adjust the rotation angle of the movable microporous plate 52, increasing the airflow resistance and accurately correcting the pressure in the second deposition zone 4 back to the set range, significantly improving the repeatability and stability of the process.

[0038] 2. This invention divides the deposition chamber into a first deposition zone and a second deposition zone, necessitating the placement of a porous baffle between them. However, static porous baffles cannot achieve online adjustment of airflow resistance, nor do they possess the ability to change the jet direction. When uneven concentration distribution occurs during deposition, the operator cannot intervene through other means, ultimately affecting crystal quality. This invention designs a combined structure of a fixed microporous plate and a movable microporous plate that synchronously and periodically oscillates. An oscillation drive component drives the dual microporous plates to oscillate at a high frequency of ±5° to ±15° and 2-8 Hz, causing the phosphorus vapor jet direction through the microporous array to periodically scan, forming a dynamically changing concentration boundary layer on the deposition substrate surface. This jet scanning method breaks the spatial distribution lock-in state of the traditional static flow field, effectively eliminating the stagnation region of the concentration boundary layer, and enabling phosphorus vapor to achieve uniform coverage on the substrate surface. When the Raman spectrum detects the appearance of non-target crystalline phase characteristic peaks or the full width at half maximum (FWHM) of the target characteristic peaks increases beyond the predetermined value, the control system can automatically start the swing drive component to improve the uniformity of vapor distribution, suppress the generation of impurity phases, and ensure the purity and consistency of crystal growth by dynamically disturbing the flow field.

[0039] Secondly, the microporous partition assembly has two independent dynamic adjustment functions: the rotation drive component controls the movable microporous plate to rotate around the central axis, changing the micropore overlap rate with the fixed microporous plate, thereby realizing online adjustment of airflow resistance; the oscillation drive component drives the movable microporous plate and the fixed microporous plate to oscillate synchronously, thereby realizing high-frequency scanning of the jet direction. This dynamic jet scanning method allows different areas of the deposition substrate to alternately be in the incident area and the flow measurement area, averaging the local supersaturation differences, providing unprecedented flow field control freedom for the vapor phase growth of red phosphorus crystals, eliminating deposition blind zones, and achieving large-area uniform deposition. Attached Figure Description

[0040] Figure 1 This is a schematic diagram of the structure of a semiconductor-grade red phosphorus crystal vapor deposition intelligent control system according to the present invention.

[0041] Figure 2 for Figure 1 A schematic diagram of the microporous partition assembly 5.

[0042] Figure 3 for Figure 2 A schematic diagram showing the positions of the rotation drive component and the swing drive component.

[0043] Figure 4 This is a SEM comparison diagram of the deposition effect of the dynamic microporous partition assembly and the static microporous plate in this invention.

[0044] Numbering on the map:

[0045] 1-Deposition chamber, 2-Deposition substrate, 3-First deposition region, 4-Second deposition region, 5-Microporous partition assembly, 6-Laser induction unit, 7-Electric field application unit, 8-Magnetic field application unit, 9-Raman spectroscopy probe, 10-Pressure sensor, 11-Spectrometer, 12-Temperature sensor, 13-Vacuum pump;

[0046] 51-Fixed microporous plate, 52-Modible microporous plate, 53-Microporous array, 54-Rotation drive assembly, 55-Oscillating drive assembly; 541-Drive box, 542-Rotation shaft two, 543-Rotation motor; 551-Connecting frame, 552-Rotation shaft one, 553-Oscillating plate, 554-Cylinder;

[0047] 71-Lower electrode, 72-Upper electrode, 73-Heating element. Detailed Implementation

[0048] To enhance understanding of the present invention, the present invention will be further described in detail below with reference to embodiments and accompanying drawings. These embodiments are only used to explain the present invention and do not constitute a limitation on the scope of protection of the present invention.

[0049] In the description of this invention, it should be understood that the terms indicating orientation or positional relationship, such as those based on the orientation or positional relationship shown in the accompanying drawings, are only for the convenience of describing this invention and simplifying the description, and do not indicate or imply that the structure or unit referred to must have a specific orientation, and therefore should not be construed as a limitation of this invention.

[0050] In this invention, unless otherwise explicitly specified and limited, terms such as “connection,” “provided with,” and “have” should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection. They can be described as a mechanical connection, a direct connection, or a connection through an intermediate medium. Those skilled in the art can understand the basic meaning of the above terms in this invention according to the specific circumstances.

[0051] A semiconductor-grade red phosphorus crystal vapor deposition intelligent control system, referring to Figure 1 ,include

[0052] A crystal-oriented deposition module includes a deposition chamber 1, a deposition substrate 2 disposed in the deposition chamber 1, and a microporous partition assembly 5 that divides the interior of the deposition chamber 1 into a first deposition region 3 and a second deposition region 4.

[0053] The external field application unit includes a laser induction unit 6 placed in the first deposition zone 3, an electric field application unit 7 placed in the second deposition zone 4, and a magnetic field application unit 8 placed outside the second deposition zone 4. The external field application unit induces red phosphorus crystal nuclei in the first deposition zone 3 and synergistically promotes the lateral growth of grains in the second deposition zone 4.

[0054] The monitoring and intelligent control module includes a control system, a Raman spectroscopy probe 9 extending into the second deposition zone 4, a spectrometer 11 placed outside the second deposition zone 4, and a pressure sensor 10 located inside the first deposition zone 3 and the second deposition zone 4.

[0055] The microporous partition assembly 5 includes a fixed microporous plate 51 and a movable microporous plate 52. The fixed microporous plate 51 and the movable microporous plate 52 are concentrically arranged and each has a correspondingly distributed microporous array 53. It also includes a rotation drive assembly 54 and an oscillation drive assembly 55. The rotation drive assembly 54 is connected to the movable microporous plate 52 and drives it to rotate around its central axis, thereby adjusting the airflow resistance of the airflow through the microporous array 53 to maintain the set pressure of the second deposition zone 4. The oscillation drive assembly 55 drives the fixed microporous plate 51 and the movable microporous plate 52 to oscillate synchronously and periodically, so that the direction of the phosphorus vapor jet through the microporous array 53 is scanned at high frequency, forming a dynamically distributed concentration boundary layer on the surface of the deposition substrate 2.

[0056] The control system coordinates the rotation angle of the rotary drive component 54, the oscillation frequency and amplitude of the oscillation drive component 55, and the electric field strength, magnetic field strength and laser power density of the external field application unit based on the received Raman spectrum characteristic peak signal and the measured value of the pressure sensor, so as to achieve dynamic matching between the flow field parameters and the external field parameters.

[0057] This application divides the deposition chamber 1 into a first deposition zone 3 and a second deposition zone 4. A porous baffle must be set between the first deposition zone 3 and the second deposition zone 4. However, a static porous baffle cannot achieve online adjustment of airflow resistance, nor does it have the ability to change the jet direction. When uneven concentration distribution occurs during the deposition process, the operator cannot intervene by other means, which ultimately affects the crystal quality.

[0058] This invention designs a combined structure of a fixed microporous plate 51 and a movable microporous plate 52 that oscillate synchronously and periodically. The oscillation drive component 55 drives the dual microporous plates to oscillate at a high frequency of 2-8 Hz at ±5° to ±15°, causing the direction of the phosphorus vapor jet passing through the microporous array 53 to periodically scan, forming a dynamically changing concentration boundary layer on the surface of the deposition substrate 2. This jet scanning method breaks the spatial distribution lock-in state of the traditional static flow field, effectively eliminating the stagnation region of the concentration boundary layer, and enabling uniform coverage of phosphorus vapor on the substrate surface. When Raman spectroscopy detects the appearance of non-target crystalline phase characteristic peaks or when the full width at half maximum (FWHM) of the target characteristic peak increases beyond a predetermined value, the control system automatically activates the oscillation drive component 55. By dynamically perturbing the flow field, it improves the uniformity of vapor distribution, suppresses impurity phase formation, and ensures the purity and consistency of crystal growth.

[0059] Secondly, the microporous partition assembly 5 has two independent dynamic adjustment functions: the rotation drive assembly 54 controls the movable microporous plate 52 to rotate around the central axis, changing the micropore overlap rate with the fixed microporous plate 51, thereby realizing online adjustment of airflow resistance; the swing drive assembly 55 drives the movable microporous plate 52 to swing back and forth synchronously with the fixed microporous plate 51, thereby realizing high-frequency scanning of the jet direction. This dynamic jet scanning method allows different regions of the deposition substrate 2 to alternately be in the incident area and the flow measurement area, averaging the local supersaturation differences, providing unprecedented flow field control freedom for the vapor phase growth of red phosphorus crystals, eliminating deposition blind zones, and achieving large-area uniform deposition.

[0060] Furthermore, the deposition substrate 2 extends continuously in the horizontal direction, with its first section located in the first deposition area 3 and its tail section located in the second deposition area 4. The microporous partition assembly 5 is placed at the junction of the first deposition area 3 and the second deposition area 4 and is suspended above the deposition substrate 2 with gaps.

[0061] It should be noted that the microporous baffle assembly 5 exerts a dual modulation on the deposition flow field through the synergistic effect of oscillation and gap variation. The specific principle is as follows:

[0062] First modulation: The microporous partition assembly 5 is suspended above the deposition substrate 2 and performs periodic oscillation. When the microporous partition assembly 5 is tilted, the relative angle of the microporous channels changes, causing the jet direction of the gas ejected from the microporous array 53 to deflect accordingly. This allows the deposited material to impact the surface of the deposition substrate 2 at different angles, directly changing the deposition angle and the distribution of the landing point, and achieving precise control of the jet direction.

[0063] Secondary modulation: As the microporous septum assembly 5 oscillates, the horizontal gap between its edge and the deposition substrate 2 also changes periodically. When the gap decreases, the lateral airflow under the deposition substrate 2 is obstructed, the flow velocity decreases, and a local high-pressure zone is formed; when the gap increases, the airflow becomes unobstructed, and the flow velocity increases. This periodic change in the gap has a dynamic throttling and unblocking effect on the lateral airflow above the deposition substrate 2, thereby disturbing and reshaping the flow field distribution on the surface of the deposition substrate 2.

[0064] Furthermore, the pressure in the first sedimentation zone 3 is 100-200 Pa, and the pressure in the second sedimentation zone 4 is 800-1200 Pa.

[0065] This invention uses a microporous partition assembly 5 to divide the deposition chamber 1 into a first deposition zone 3 (100-200 Pa) and a second deposition zone 4 (800-1200 Pa), forming a pressure gradient that is lower in the front and higher in the back. The low-pressure zone is conducive to the directional induction of crystal nuclei, while the high-pressure zone promotes the lateral preferential growth of grains, thus decoupling the process conditions for crystal nuclei formation and crystal growth. More importantly, this invention uses a rotary drive assembly 54 to drive the movable microporous plate 52 to rotate independently, changing the micropore overlap rate between it and the fixed microporous plate 51, thereby adjusting the resistance of airflow through the micropore array online and achieving dynamic correction of the pressure in the second deposition zone 4. When the measured value of the pressure sensor 10 deviates from the set value and the vacuum pump's pumping speed has reached its upper limit, the control system can automatically adjust the rotation angle of the movable microporous plate 52 to increase the airflow resistance, accurately returning the pressure in the second deposition zone 4 to the set range, significantly improving the repeatability and stability of the process.

[0066] Furthermore, the laser induction unit 6 is located at the top of the first deposition area 3 and emits a scanning laser with a wavelength of 520-550 nm onto the surface of the deposition substrate 2. The laser energy forms a local high temperature area on the substrate surface to induce and regulate the initial orientation of red phosphorus crystal nuclei on the deposition substrate 2.

[0067] An electric field application unit 7 is disposed in the second deposition region 4, including a lower electrode 71 placed on the lower end face of the deposition substrate 2 and an upper electrode 72 placed above the deposition substrate 2. The upper electrode 72 and the lower electrode 71 are distributed vertically in parallel. The lower electrode 71 is a metal support plate with an internally integrated heating element 73. The electric field application unit 7 generates an electrostatic field perpendicular to the deposition substrate 2 in the second deposition region 4, with an electric field strength of 100-200V / cm.

[0068] The magnetic field application unit 8 includes a Helmholtz coil located outside the second deposition zone 4, which generates a steady magnetic field parallel to the surface of the deposition substrate 2 within the second deposition zone 4, with a magnetic field strength of 0.2-0.5T.

[0069] The directions of the electrostatic field, the steady-state magnetic field, and the normal direction of the deposition substrate 2 are all perpendicular to each other, forming a spatially orthogonal external field control system.

[0070] The laser induction unit is a conventional structural combination that can be implemented by those skilled in the art based on the disclosure in the specification. It includes a light source capable of emitting 520-550nm scanning laser and a corresponding optical path adjustment device. Its specific implementation method (such as using a semiconductor laser in conjunction with a scanning galvanometer) is a well-known technology in the art, and its specific structure is not limited.

[0071] Furthermore, refer to Figure 2 , Figure 3 The swing drive assembly 55 includes a connecting frame 551 disposed on the side of the fixed microporous plate 51 and the movable microporous plate 52. A rotating shaft 552 is provided through the connecting frame 551 and the fixed microporous plate 51 along the axial direction of the fixed microporous plate 51. The end of the rotating shaft 552 is located outside the deposition chamber 1, and a swing plate 553 is connected to the end of the rotating shaft 552. A cylinder 554 is provided on the outside of the deposition chamber 1 to drive the swing plate 553 to swing back and forth. A sealed bearing is provided through the outer circumference of the rotating shaft 552.

[0072] The rotary drive assembly 54 includes a drive box 541 mounted on a connecting frame 551. Rotary shafts 542 are fixedly connected to the center of the movable microporous plate 52 along its axis on both sides. One of the drive boxes 541 contains a rotary motor 543 that drives the rotary shafts 542 and the movable microporous plate 52 to rotate synchronously. The rotary shafts 542 pass through the outer circumference of the drive box 541 and have a sealed bearing.

[0073] The swing amplitude of the swing drive component 55 is ±5° to ±15°, and the swing frequency is 2-8 Hz.

[0074] The first deposition zone 3 and the second deposition zone 4 of the deposition chamber 1 are respectively connected to vacuum pumps 13 electrically connected to pressure sensors 10 in the corresponding deposition zones. Vacuum pumps 13 are electrically connected to rotary drive assembly 54 and control system. The control system adjusts the pumping speed of vacuum pump 13 in the first deposition zone 3 according to the measured value of pressure sensor in the first deposition zone 3. The control system adjusts the pumping speed of vacuum pump 13 in the second deposition zone 4 according to the measured value of pressure sensor in the second deposition zone 4. On the other hand, it drives the movable microporous plate 52 to rotate by controlling rotary drive assembly 54 to change the micropore overlap rate between movable microporous plate 52 and fixed microporous plate 51, thereby synergistically regulating the pressure stability in the second deposition zone 4.

[0075] The deposition substrate 2 is a metal substrate, which integrates at least one temperature sensor 12. The temperature sensor 12 is located in or near the substrate area corresponding to the second deposition area 4 and is electrically connected to the control system. The control system adjusts the power of the heating element 73 integrated in the lower electrode 71 in real time according to the temperature of the deposition substrate 2 to ensure that the temperature of the deposition substrate 2 is stable within the optimal temperature range for red phosphorus crystal growth.

[0076] Metals possess excellent thermal conductivity, enabling them to rapidly respond to changes in heating power and quickly and evenly conduct heat, eliminating localized hot spots and ensuring a consistent temperature distribution in the second deposition zone 4. Simultaneously, the metal substrate exhibits structural stability and resistance to deformation at high temperatures, guaranteeing precise control of the minute gap between it and the microporous separator assembly 5, providing a stable physical basis for the uniform nucleation of red phosphorus crystals. A temperature sensor monitors the substrate temperature in the second deposition zone 4 in real time, feeding the actual signal back to the control system. The heating element, acting as an actuator, dynamically adjusts its output power according to the control system's instructions. Together, they form a closed-loop temperature control system. The sensor detects temperature deviations, and the heating element adjusts its power to ensure the substrate temperature remains stable within the optimal range for red phosphorus crystal growth, providing constant thermodynamic conditions for directional crystal growth.

[0077] It is important to note that the first deposition region 3 and the second deposition region 4 are spatially connected, and the deposition substrate 2 is a continuously extending metal plate. The heat from the second deposition region 4 can be conducted to the first deposition region through the metal substrate, allowing the first deposition region 3 to reach a relatively low temperature. When the laser induction unit 6 located at the top of the first deposition region 3 scans and induces crystal nuclei, the laser itself will generate a local heating effect on the deposition surface, helping to maintain the temperature of this area. Therefore, the first deposition region 3 does not require an independent heating element. Its temperature is maintained by the heat conduction from the second deposition region 4 and the thermal effect of laser scanning, forming a natural temperature gradient from the first deposition region (220-280℃) to the second deposition region (380-420℃), which meets the process requirements of low-temperature nucleation and high-temperature growth of red phosphorus crystals.

[0078] The fixed microporous plate 51 and the movable microporous plate 52 are both alumina ceramic plates or silicon nitride ceramic plates, with multiple through holes evenly distributed on them to form a microporous array 53. The diameter of the through holes is 0.2-0.5 mm and the opening rate is 8-15%.

[0079] The fixed microporous plate 51 and the movable microporous plate 52 are made of alumina and silicon nitride ceramics, which have excellent high-temperature stability, corrosion resistance and low coefficient of thermal expansion. They do not deform or react in the red phosphorus vapor environment, ensuring the long-term accuracy and structural reliability of the microporous array. The uniformly distributed microporous array forms a precise airflow channel. By rotating the microporous plates to change the overlap ratio of the two layers of micropores, the airflow resistance and the pressure in the second deposition zone can be adjusted online. By oscillating the microporous plates synchronously, the jet direction is changed, forming a dynamic concentration boundary layer on the substrate surface, improving the uniformity of vapor distribution, suppressing the formation of impurity phases and achieving crystal form orientation control.

[0080] A control method for a semiconductor-grade red phosphorus crystal vapor deposition intelligent control system includes the following steps:

[0081] S1. Raw material sublimation and purification: The red phosphorus raw material is heated to 420-480℃ under an inert atmosphere to sublimate it and form phosphorus vapor; the phosphorus vapor is then passed through a transport pipe with a variable diameter spiral structure, and metal particles larger than 1μm and arsenic and antimony compound impurities are removed through inertial separation and adsorption collection.

[0082] S2, Zoned Deposition and Crystal Nucleus Induction: Purified phosphorus vapor is introduced into the deposition chamber 1. The first deposition zone 3 and the second deposition zone 4 are formed sequentially along the airflow direction in the deposition chamber 1 by pressure control. The pressure of the first deposition zone 3 is maintained at 100-200 Pa, and the pressure of the second deposition zone 4 is maintained at 800-1200 Pa.

[0083] In the first deposition zone 3, phosphorus vapor is initially deposited on the surface of the deposition substrate 2 at a temperature maintained at 220-280℃. At the same time, a laser beam with a wavelength of 520-550 nm is used to scan the deposition surface with a spot diameter of 0.5-2 mm to induce the formation of red phosphorus crystal nuclei with a specific orientation.

[0084] S3. External Field Synergistic Grain Growth: In the second deposition zone 4, an electrostatic field perpendicular to the direction of the deposition substrate 2 is applied to the surface of the deposition substrate 2 through electrodes located above and below the deposition substrate 2. The electric field strength is 100-200 V / cm. At the same time, a steady-state magnetic field parallel to the direction of the deposition substrate surface is applied. The magnetic field strength is 0.2-0.5 T. Under the synergistic effect of the electrostatic field and the magnetic field, phosphorus vapor is oriented and attached along the crystal nucleus, realizing the lateral preferential growth of grains.

[0085] S4. In-situ monitoring and dynamic feedback: During the deposition process, Raman spectral signals of the deposited film are acquired in real time, with a focus on monitoring the intensity and full width at half maximum (FWHM) of the characteristic peaks near 365 cm⁻¹. The control system executes the following dynamic adjustment logic based on the Raman spectral characteristic peak signals and the measured values ​​from pressure sensors in the first deposition zone 3 and the second deposition zone 4:

[0086] When the measured pressure in the second deposition zone 4 deviates from the set value by more than ±50 Pa, the control system first corrects the pressure by adjusting the pumping speed of the vacuum pump 13 connected to the second deposition zone 4. If the pumping speed has been adjusted to the upper limit and the set pressure still cannot be restored, the control system drives the rotary drive assembly 54 to drive the movable microporous plate 52 to rotate, changing the micropore overlap rate between it and the fixed microporous plate 51, thereby increasing the airflow resistance and restoring the pressure in the second deposition zone 4 back to the set range.

[0087] When a non-target crystalline phase characteristic peak is detected in the Raman spectrum, such as near 410 cm⁻¹ or 320 cm⁻¹, or when the full width at half maximum (FWHM) of the target characteristic peak increases by more than 10%, it indicates a decrease in crystalline phase purity or crystal quality. The control system judges this as uneven distribution of phosphorus vapor concentration or mismatch of external field coupling during grain growth. At this time, the oscillation drive component 55 is activated to make the fixed microporous plate 51 and the movable microporous plate 52 oscillate synchronously and periodically. The oscillation amplitude is ±5° to ±15°, the oscillation frequency is 2-8 Hz, and the duration is 3-10 minutes. This dynamically disturbs the direction of the phosphorus vapor jet through the microporous array, forming a dynamic concentration boundary layer on the surface of the deposition substrate 2, improving the uniformity of vapor distribution, and suppressing the generation of impurity phases.

[0088] If the Raman spectral signal remains abnormal or the pressure fluctuations cannot be eliminated by the above adjustments, the control system will further coordinate the adjustment of the laser scanning power, electrostatic field strength, or deposition substrate temperature until the spectral characteristics return to normal.

[0089] S5. Annealing and Collection: After deposition, the deposited product is cooled to room temperature at a rate of 10-30℃ / min under an inert atmosphere to obtain flaky red phosphorus crystals with a purple metallic luster attached to the deposition substrate 2; these crystals are then peeled off from the substrate to obtain the high-purity, large-grained purple red phosphorus crystals.

[0090] In this invention, by precisely designing the dimensions of the micropore array 53 (through-hole diameter 0.2-0.5 mm) and matching them with the pressure range of the first deposition zone 3 (100-200 Pa) and the second deposition zone (4) (800-1200 Pa), the gas flow through the micropores is made to be in a transitional flow region dominated by molecular flow. Under this condition, the mean free path of gas molecules (approximately 0.5-1 mm at 100 Pa) is greater than or equal to the micropore diameter, and the collisions between molecules and the pore walls are far more frequent than the collisions between molecules. Therefore, the behavior of phosphorus vapor through the micropores is dominated by the interaction between molecules and the wall surface, rather than a macroscopic collective flow driven by pressure difference. Even if the movable micropore plate 52 and the fixed micropore plate 51 are instantly fully or partially aligned during the swinging process, the high-pressure gas molecules in the second deposition zone 4 and the low-pressure gas molecules in the first deposition zone 3 pass through the micropores independently and randomly, without generating a destructive large-scale reverse macroscopic airflow. This allows for the net transport of phosphorus vapor molecules between the first deposition zone 3 and the second deposition zone 4 while maintaining a significant pressure gradient. The system maintains the base pressure of each zone through pressure sensor 10 and vacuum pump 13. The rotation of movable microporous plate 52 is used to finely adjust the overall airflow resistance, while the dynamic scanning of oscillating drive component 55 is used independently to optimize the concentration distribution. Together, they ensure that directional deposition under zone pressure control is achieved.

[0091] Table 1 shows the pressure data of the first and second sedimentation zones, recorded every hour during the 6-hour continuous deposition process:

[0092] Time (hours) Pressure in the first sedimentary zone (Pa) Pressure in the second sedimentary zone (Pa) 0 150.2 1001.5 1 150.5 1000.8 2 149.8 999.2 3 150.1 1000.5 4 150.3 1001.5 5 149.3 998.9 6 150.4 1000.3

[0093] As can be seen from the data in Table 1, even under continuous high-frequency oscillation of the microplate, the pressures in the first deposition zone 3 and the second deposition zone 4 can still be stably maintained near the set values ​​of 150 Pa and 1000 Pa, respectively, with fluctuation ranges far smaller than the system's set threshold of ±50 Pa. This indicates that, under the molecular flow mechanism, the periodic interconnection of the microplate does not cause macroscopic pressure disturbances, and the pressure gradient between the two zones is effectively maintained.

[0094] After deposition, the obtained red phosphorus crystals were characterized. For comparison, under the same process parameters, a static microporous plate was used instead of the microporous separator assembly in this invention for a comparative experiment. The results were observed using a scanning electron microscope, referring to... Figure 4 Static microporous plates remain fixed during deposition, resulting in obvious deposition blind spots and localized over-thickness in the deposition area, leading to poor uniformity. In contrast, this solution introduces relative motion through a dynamic swinging partition microporous assembly, achieving full coverage of the deposition area, effectively eliminating blind spots and localized accumulation, resulting in uniform grain size and higher quality deposition layer.

[0095] The control system in this invention, based on the crystal growth state signals (characteristic peak intensity and full width at half maximum) acquired in real time by the Raman spectroscopy probe and the measured values ​​of the pressure sensors in each deposition zone, coordinates the rotation angle of the rotation drive component, the oscillation frequency and amplitude of the oscillation drive component, the power density of the laser induction unit, the electric field strength of the electric field application unit, the magnetic field strength of the magnetic field application unit, and the heating temperature of the deposition substrate. This achieves dynamic matching and intelligent optimization of flow field parameters, external field parameters, and crystal growth state. When the Raman spectrum remains abnormal or pressure fluctuations cannot be eliminated through conventional adjustments, the system can further coordinately adjust multiple field parameters until the spectral characteristics return to normal, forming a complete technical closed loop from state perception and real-time decision-making to precise execution.

[0096] This invention, through its innovative microporous partition component 5 and its deep synergy with multiple external fields and intelligent control, fundamentally breaks through the limitations of existing red phosphorus vapor deposition technology in terms of flow field regulation, pressure control, and dynamic response. It achieves a technological leap from static passive deposition to dynamic active regulation, providing a brand-new solution for the controllable preparation of high-purity, large-grained, and crystal-type controllable red phosphorus crystals.

[0097] Those skilled in the art should understand that this invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to this invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the invention as claimed. The scope of protection of this invention is defined by the appended claims and their equivalents.

Claims

1. A smart control system for semiconductor-grade red phosphorus crystal vapor deposition, characterized in that: include A crystal-oriented deposition module includes a deposition chamber, a deposition substrate disposed within the deposition chamber, and a microporous partition assembly that divides the interior of the deposition chamber into a first deposition region and a second deposition region. An external field application unit includes a laser induction unit placed in a first deposition zone, an electric field application unit placed in a second deposition zone, and a magnetic field application unit placed outside the second deposition zone. The external field application unit induces red phosphorus nuclei in the first deposition zone and synergistically promotes lateral grain growth in the second deposition zone. The monitoring and intelligent control module includes a control system, a Raman spectroscopy probe extending into the second deposition zone, a spectrometer placed outside the second deposition zone, and pressure sensors located inside the first and second deposition zones. The microporous partition assembly includes a fixed microporous plate and a movable microporous plate, which are concentrically arranged and each has a correspondingly distributed microporous array. It also includes a rotation drive assembly and an oscillation drive assembly. The rotation drive assembly is connected to the movable microporous plate and drives it to rotate around its central axis, thereby adjusting the airflow resistance of the airflow through the microporous array to maintain the set pressure of the second deposition zone. The oscillation drive assembly drives the fixed microporous plate and the movable microporous plate to oscillate synchronously and periodically, so that the direction of the phosphorus vapor jet through the microporous array is scanned at high frequency, forming a dynamically distributed concentration boundary layer on the surface of the deposition substrate. The control system coordinates the rotation angle of the rotary drive component, the oscillation frequency and amplitude of the oscillation drive component, and the electric field strength, magnetic field strength and laser power density of the external field application unit based on the received Raman spectral characteristic peak signal and the measured value of the pressure sensor, so as to achieve dynamic matching between the flow field parameters and the external field parameters.

2. The intelligent control system for semiconductor-grade red phosphorus crystal vapor deposition according to claim 1, characterized in that: The deposition substrate extends continuously in the horizontal direction, with its first section located in the first deposition area and its tail section located in the second deposition area. The microporous partition assembly is placed at the junction of the first and second deposition areas and is suspended above the deposition substrate with gaps.

3. The intelligent control system for semiconductor-grade red phosphorus crystal vapor deposition according to claim 2, characterized in that: The pressure in the first sedimentation zone is 100-200 Pa, and the pressure in the second sedimentation zone is 800-1200 Pa.

4. The intelligent control system for semiconductor-grade red phosphorus crystal vapor deposition according to claim 3, characterized in that: The laser induction unit is located at the top of the first deposition area and emits a scanning laser with a wavelength of 520-550 nm onto the surface of the deposition substrate. The laser energy forms a local high-temperature area on the substrate surface to induce and regulate the initial orientation of red phosphorus crystal nuclei on the deposition substrate. The electric field application unit is located in the second deposition area and includes a lower electrode placed on the lower end face of the deposition substrate and an upper electrode placed above the deposition substrate. The upper electrode and the lower electrode are distributed parallel to each other vertically. The lower electrode is a metal support plate with an internally integrated heating element. The electric field application unit generates an electrostatic field perpendicular to the deposition substrate in the second deposition area, with an electric field strength of 100-200V / cm. The magnetic field application unit includes a Helmholtz coil located outside the second deposition zone, which generates a steady-state magnetic field parallel to the surface of the deposition substrate within the second deposition zone, with a magnetic field strength of 0.2-0.5T. The directions of the electrostatic field, the steady-state magnetic field, and the normal direction of the deposition substrate are all perpendicular to each other, forming a spatially orthogonal external field control system.

5. The intelligent control system for semiconductor-grade red phosphorus crystal vapor deposition according to claim 4, characterized in that: The swing drive assembly includes a connecting frame disposed at the side end of the connection between the fixed microporous plate and the movable microporous plate. A rotating shaft is provided through the connecting frame and the fixed microporous plate along the axial direction of the fixed microporous plate. The end of the rotating shaft is located outside the deposition chamber and is connected to a swing plate. A cylinder is provided outside the deposition chamber to drive the swing plate to swing back and forth. A sealed bearing is provided through the outer circumference of the rotating shaft. The rotary drive assembly includes a drive box mounted on a connecting frame. Rotary shafts are fixedly connected to the center of the movable microporous plate along its axis on both sides. One of the drive boxes contains a rotary motor that drives the rotary shafts and the movable microporous plate to rotate synchronously. The rotary shafts pass through the outer circumference of the drive box and have a sealed bearing.

6. The intelligent control system for semiconductor-grade red phosphorus crystal vapor deposition according to claim 5, characterized in that: The swing amplitude of the swing drive component is ±5° to ±15°, and the swing frequency is 2-8 Hz.

7. The intelligent control system for semiconductor-grade red phosphorus crystal vapor deposition according to claim 6, characterized in that: The first and second deposition zones of the deposition chamber are respectively connected to vacuum pumps electrically connected to pressure sensors in the corresponding deposition zones. The vacuum pumps are electrically connected to a rotary drive assembly and a control system. The control system adjusts the pumping rate of the vacuum pump in the first deposition zone based on the measured value of the pressure sensor in the first deposition zone. Based on the measured value of the pressure sensor in the second deposition zone, the control system adjusts the pumping rate of the vacuum pump in the second deposition zone on the one hand, and drives the movable microporous plate to rotate by controlling the rotary drive assembly on the other hand, so as to change the micropore overlap rate between the movable microporous plate and the fixed microporous plate, thereby synergistically regulating the pressure stability in the second deposition zone.

8. The intelligent control system for semiconductor-grade red phosphorus crystal vapor deposition according to claim 7, characterized in that: The deposition substrate is a metal substrate, which integrates at least one temperature sensor. The temperature sensor is located in or near the substrate area corresponding to the second deposition area and is electrically connected to the control system. The control system adjusts the power of the heating element integrated in the lower electrode in real time according to the temperature of the deposition substrate to ensure that the temperature of the deposition substrate is stable within the optimal temperature range for red phosphorus crystal growth.

9. The intelligent control system for semiconductor-grade red phosphorus crystal vapor deposition according to claim 8, characterized in that: Both the fixed microporous plate and the movable microporous plate are alumina ceramic plates or silicon nitride ceramic plates, with multiple through holes evenly distributed on them to form a microporous array. The diameter of the through holes is 0.2-0.5 mm, and the porosity is 8-15%.

10. A control method using the intelligent control system for semiconductor-grade red phosphorus crystal vapor deposition as described in claim 9, characterized in that: Includes the following steps: S1. Raw material sublimation and purification: The red phosphorus raw material is heated to 420-480℃ under an inert atmosphere to sublimate it and form phosphorus vapor; the phosphorus vapor is then passed through a transport pipe with a variable diameter spiral structure, and metal particles larger than 1μm and arsenic and antimony compound impurities are removed through inertial separation and adsorption collection. S2, Zoned Deposition and Crystal Nucleus Induction: Purified phosphorus vapor is introduced into the deposition chamber. The deposition chamber is formed by pressure control, with a first deposition zone and a second deposition zone arranged sequentially along the airflow direction. The pressure of the first deposition zone is maintained at 100-200 Pa, and the pressure of the second deposition zone is maintained at 800-1200 Pa. In the first deposition zone, phosphorus vapor is initially deposited on the surface of the deposition substrate at a temperature maintained at 220-280°C. At the same time, a laser beam with a wavelength of 520-550 nm is used to scan the deposition surface with a spot diameter of 0.5-2 mm to induce the formation of red phosphorus crystal nuclei with a specific orientation. S3. External Field Synergistic Grain Growth: In the second deposition zone, an electrostatic field perpendicular to the deposition substrate direction is applied to the surface of the deposition substrate through electrodes located above and below the deposition substrate. The electric field strength is 100-200 V / cm. At the same time, a steady-state magnetic field parallel to the deposition substrate surface direction is applied. The magnetic field strength is 0.2-0.5 T. Under the synergistic effect of the electrostatic field and the magnetic field, the phosphorus vapor is oriented and attached along the crystal nucleus, realizing the lateral preferential growth of the grains. S4. In-situ monitoring and dynamic feedback: During the deposition process, the Raman spectral signal of the red phosphorus crystal layer on the deposition substrate is acquired in real time, with a focus on monitoring the intensity and full width at half maximum (FWHM) of the characteristic peak located near 365 cm⁻¹; the control system executes the following dynamic adjustment logic based on the Raman spectral characteristic peak signal and the measured values ​​of the pressure sensors in the first and second deposition zones: When the measured pressure in the second deposition zone deviates from the set value by more than ±50 Pa, the control system first corrects the pressure by adjusting the pumping speed of the vacuum pump connected to the second deposition zone. If the pumping speed has been adjusted to the upper limit and the set pressure still cannot be restored, the control system drives the rotating drive component to rotate the movable microporous plate, changing the micropore overlap rate between it and the fixed microporous plate, thereby increasing the airflow resistance and bringing the pressure in the second deposition zone back to the set range. When a non-target crystalline phase characteristic peak is detected in the Raman spectrum, such as near 410 cm⁻¹ or 320 cm⁻¹, or when the full width at half maximum (FWHM) of the target characteristic peak increases by more than 10%, it indicates a decrease in crystalline phase purity or crystal quality. The control system determines this to be due to uneven distribution of phosphorus vapor concentration or mismatch of external field coupling during grain growth. At this time, the oscillation drive component is activated to make the fixed microporous plate and the moving microporous plate oscillate synchronously and periodically. The oscillation amplitude is ±5° to ±15°, the oscillation frequency is 2-8 Hz, and the duration is 3-10 minutes. This dynamically disturbs the direction of the phosphorus vapor jet through the microporous array, forming a dynamic concentration boundary layer on the surface of the deposition substrate, improving the uniformity of vapor distribution, and suppressing the formation of impurity phases. If the Raman spectral signal remains abnormal or the pressure fluctuations cannot be eliminated by the above adjustments, the control system will further coordinate the adjustment of the laser scanning power, electrostatic field strength, or deposition substrate temperature until the spectral characteristics return to normal. S5. Annealing and Collection: After deposition, the deposited product is cooled to room temperature at a rate of 10-30℃ / min under an inert atmosphere to obtain flaky red phosphorus crystals with a purple metallic luster attached to the deposition substrate; these crystals are then peeled off from the substrate to obtain the high-purity, large-grained purple red phosphorus crystals.

Images