Plasma-assisted atomic layer deposition system and process
By using a double-necked and single-necked bottle design in a plasma-assisted atomic layer deposition system, combined with carrier gas-assisted delivery and an inductively coupled plasma generator, the problems of precursor degradation and difficulty in ensuring vacuum were solved, achieving high-quality nitride thin film deposition and improving electrical performance.
Patent Information
- Application Number
- CN202511522588.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-10-23
- Publication Date
- 2026-01-16
AI Technical Summary
In existing plasma atomic layer deposition processes, the use of alkyl or amino precursors requires long-term high-temperature heating, which makes the precursors prone to deterioration. Furthermore, it is difficult to guarantee the vacuum level of the reaction chamber, which makes the nitride film easily oxidized and affects its electrical properties.
Two-necked and one-necked bottles are used to contain precursor sources with higher and lower vapor pressures, respectively. The precursors are transported with the assistance of a carrier gas, and combined with an inductively coupled plasma generator and a vacuum pump to ensure vacuum and avoid high-temperature heating. Argon is used as the carrier gas and ammonia is used as the co-reactant to avoid oxidation.
It effectively prevents nitride films from being oxidized, ensures electrical performance, reduces the risk of precursor source degradation, improves deposition temperature control and vacuum level, and ensures film quality.
Smart Images
Figure CN121344564A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to a kind of plasma assisted atomic layer deposition system and process, belong to thin film deposition technical field. BACKGROUND
[0002] Ultra-thin niobium nitride film has wide application in many fields.For example, in the field of superconducting materials, ultra-thin niobium nitride film is widely concerned because it can maintain good superconducting performance at an ultra-thin thickness of 5 nanometers or less;For example, in the field of lithium batteries, ultra-thin niobium nitride film can enhance the cycle stability of lithium batteries at high current density through catalytic absorption.
[0003] Atomic layer deposition technology has incomparable advantages in ultra-thin film thickness control, because it is through self-limiting surface saturation reaction to deposit thin film, so it is more suitable for depositing ultra-thin niobium nitride film.In addition, atomic layer deposition has incomparable advantages in large-area uniformity and high-aspect-ratio structure conformality, so it is more suitable for depositing thin film on the surface of three-dimensional devices.
[0004] However, in the existing disclosed process, alkyl or amino-based precursors are used to deposit nitride thin film by plasma atomic layer deposition process.Because the saturated vapor pressure of some precursors is low, single precursor source bottle is used in conventional way, which requires high heating temperature.Long-term high-temperature heating of precursor source bottle not only easily leads to deterioration of the precursor, but also poses a great challenge to the heat resistance of the source bottle.At the same time, during the preparation of nitride thin film, the substrate is transported to the reaction chamber through the conveying channel.Because the sealing between the conveying channel and the reaction chamber cannot be guaranteed, impurity air in the conveying channel is easily brought into the reaction chamber, which makes it difficult to guarantee the vacuum degree of the reaction chamber.If the inert gas atmosphere in the reaction chamber is not pure, it is easy to be oxidized after contacting air or oxygen at high temperature, so the nitride thin film sample is easy to be oxidized, which leads to high oxygen impurity content on the surface of the thin film, and further affects the electrical properties. SUMMARY
[0005] In order to solve the problem that alkyl or amino-based precursors are used to deposit nitride thin film by plasma atomic layer deposition process, single precursor source bottle is used in conventional way, which requires long-term high-temperature heating of precursor source bottle because the saturated vapor pressure of some precursors is low, and the vacuum degree in the reaction chamber cannot be guaranteed during the preparation of nitride thin film, which leads to easy oxidation of nitride thin film and further affects the electrical properties, the present application provides a kind of plasma assisted atomic layer deposition system and process, the technical solution is as follows: A kind of plasma assisted atomic layer deposition system, the system includes: A process cavity is provided with a diffusion port at the top, a sample stage connected to the bottom through a lifting mechanism, and a vacuum pump connected to the bottom through an exhaust pipeline. An inductively coupled plasma generator is connected to the upper end of the process cavity. A first gas pipeline structure is connected to the upper end of the plasma generator. The first gas pipeline structure includes two gas pipelines connected to auxiliary carrier gas and ammonia gas sources. A second gas pipeline structure is connected to the side of the process cavity. A transfer cavity is provided with a pneumatic valve between the process cavity and the transfer cavity. A sample transfer rod is slidably connected inside the transfer cavity. The end of the sample transfer rod is connected to a sample fork. The bottom of the transfer cavity is connected to the vacuum pump through another exhaust pipeline.
[0006] Further, the diffusion port is in the shape of a horn for uniform flow diffusion.
[0007] Further, the double-port bottle contains tert-butylimino tris(diethylamino) niobium, and the single-port bottle contains ultrapure water.
[0008] Further, the vacuum pump can be a molecular pump.
[0009] Further, the inductively coupled plasma generator includes a quartz tube, a spiral copper coil is wrapped around the outside of the quartz tube, the copper coil is connected to a radio frequency power source, and the radio frequency power source is connected to a matching device.
[0010] A plasma-assisted atomic layer deposition process based on the above plasma-assisted atomic layer deposition system, the process includes: Step 1: After the process cavity is filled with samples, it is evacuated. Step 2: Heat the process cavity and the first pipeline structure and the second pipeline structure connected thereto. Step 3: The auxiliary carrier gas enters the double-port bottle, transporting the precursor source in the bottle to the process cavity, and reacting with the substrate on the sample stage. When the reaction reaches saturation, the purge gas blows away the excess precursor source and byproducts. Step 4: Then, ammonia gas enters the plasma generator to be ionized into plasma ammonia gas. The carrier gas transports the plasma ammonia gas to the process cavity, where it reacts with the substrate. When the reaction reaches saturation, the purge gas blows away the excess precursor source and byproducts. One cycle is complete, forming a layer of niobium nitride film. Step 5: Repeat steps 3 and 4 above. The number of cycles is calculated based on the desired thickness of the film.
[0011] Further, in step 3, the double-port bottle is heated to 65-80℃ before being opened, and the heating time is greater than 1h; when the double-port bottle is working, the flow rate of the auxiliary carrier gas communicated with the double-port bottle is set to 5-10sccm, the opening time is set to 0.01-0.02s, and the valve opening time of the double-port bottle communicated with the process cavity is 1-5s.
[0012] Further, in step 4, the flow rate of the ammonia gas is set to 50-200sccm, and the opening time is set to 1-3s.
[0013] Further, or in step 4, the ultrapure water filled in the single-port bottle is transported to the process cavity to react with the substrate; when the reaction reaches saturation, the excess precursor source and by-product are cleaned by the purge gas, one cycle is completed, and a layer of niobium oxide film is formed.
[0014] Further, after step 5 is completed, annealing is performed in the ammonia gas to convert the niobium oxide film into a niobium nitride film.
[0015] The present application has the following beneficial effects: By respectively configuring the single-port bottle and the double-port bottle in the system of the present application, the precursor sources with high and low vapor pressures are respectively filled; in the double-port bottle, the carrier gas assisted precursor source delivery mode is adopted, the carrier gas is introduced into one port in the process, and the precursor source is diffused out of the other port by relying on the pressure difference, so that the heating temperature of the source bottle is reduced, and the deterioration of the precursor source and the damage of the bottle caused by high temperature heating are avoided; at the same time, the ammonia gas source and the gas sources of the single-port bottle and the double-port bottle are communicated with the auxiliary carrier gas, so as to ensure the vacuum degree in the gas transmission process; the pneumatic valve is arranged between the process cavity and the transmission cavity, and the bottoms of the two cavities are respectively communicated with the vacuum pump, so as to ensure the vacuum degrees of the two cavities and further ensure the vacuum degree in the process cavity, thereby effectively preventing the nitride film from being oxidized and further ensuring the electrical performance. BRIEF DESCRIPTION OF DRAWINGS
[0016] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed in the embodiment description will be briefly introduced as follows. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor.
[0017] Figure 1 is a system internal schematic diagram of embodiment one of the present application; Figure 2 is a process cavity and transmission cavity partial structure schematic diagram (sample inlet at lower limit position) of embodiment one of the present application; Figure 3 This is a partial structural diagram of the process cavity and transfer cavity of Embodiment 1 of the present invention (sample injection is in the middle limit position). Figure 4 This is a partial structural diagram of the process cavity and transfer cavity of Embodiment 1 of the present invention (sample injection is at the upper limit). Figure 5 This is a flow chart of the plasma-assisted atomic layer deposition process according to Embodiment 2 of the present invention; Figure 6 These are scanning electron microscope images of the cross-section of the niobium nitride thin film prepared using the process described in Example 2 of this invention; Figure 7 This is the niobium X-ray photoelectron spectrum of the niobium nitride thin film prepared by the process of Example 2 of this invention; Figure 8 This is the nitrogen X-ray photoelectron spectrum of the niobium nitride thin film prepared by the process of Example 2 of this invention; Explanation of reference numerals in the attached figures: 1. Cabinet; 2. Process chamber; 3. Plasma generator; 4. Transfer chamber; 5 and 6 are vacuum pumps; 7. First gas path structure; 8. Second gas path structure; 9, 10, 11, and 12 are all mass flow controllers; 13. Single-necked bottle; 14. Double-necked bottle; 15, 16, 17, and 18 are all pneumatic valves; 19. Auxiliary carrier gas pipeline; 20. Auxiliary carrier gas; 21. Ammonia gas source; 22. Quartz tube; 23. Copper coil; 24. Copper bar; 25. Plasma matcher; 26. Coaxial cable; 27. Plasma RF power supply; 28. Diffuser port; 29. Sample stage; 30. Lifting mechanism; 31 and 32 are evacuation pipelines; 33. Pneumatic slide valve; 34. Chamber cover; 35. Sample fork; 36. Sample tray; 37. Sample transfer rod; 38. Slide rail; 39. Vent valve. Detailed Implementation
[0018] To make the objectives, technical solutions, and advantages of the present invention clearer, the embodiments of the present invention will be described in further detail below with reference to the accompanying drawings.
[0019] Example 1 This embodiment provides a plasma-assisted atomic layer deposition system; see [link to documentation]. Figure 1 As shown, the system includes: a cabinet 1, a process chamber 2, a plasma generator 3, and a transmission chamber 4. Specifically, the top of the process chamber 2 is provided with a diffusion port 28, which is funnel-shaped and used for uniform diffusion. The bottom of the process chamber 2 is connected to a sample stage 29 via a lifting mechanism 30. A sample tray 36 can be placed on the sample stage 29, and the substrate is placed on the sample tray 36 for coating process preparation. The height of the sample stage 29 can be adjusted by the lifting mechanism 30. The bottom of the process chamber 2 is also connected to a vacuum pump 5 via a vacuum pipe 31. The vacuum pump 5 can be a molecular pump.
[0020] An inductively coupled plasma generator 3 is connected to the upper end of the process chamber 2. The inductively coupled plasma generator 3 includes a quartz tube 22, and a spiral copper coil 23 is sleeved on the outside of the quartz tube 22. The copper coil 23 is electrically connected to the plasma matching device 25 and grounded to the cabinet 1 through two copper strips 24, respectively. The plasma matching device 25 is electrically connected to the plasma radio frequency power supply 27 through a coaxial cable 26. This invention application prefers an inductively coupled plasma generator to avoid the use of the capacitively coupled plasma generator in the prior art, which leads to unstable experimental results and poor repeatability of electrode coating after multiple experiments.
[0021] The upper end of the plasma generator 3 is connected to the first gas path structure 7. The first gas path structure 7 includes two gas paths connecting the auxiliary carrier gas 20 and the ammonia gas source 21. Mass flow controllers (11, 12) are installed on each of the two gas paths to control the flow rate. The auxiliary carrier gas 20 uses argon as the gas source. Typically, high-purity nitrogen is used as the inert gas in atomic layer deposition processes. However, since nitrogen provides a nitrogen source to the process chamber during plasma-assisted processes, making it difficult to control the reaction variables, high-purity argon is used here. The side of the process chamber 2 is connected to the second gas path structure 8. The second gas path structure 8 includes one opening connecting the single-necked bottle 13 and the double-necked bottle 14, and one gas path connecting the auxiliary carrier gas 20. A mass flow controller 9 for controlling the flow rate of the precursor source purge gas is installed on this gas path. The other opening of the double-necked bottle 14 is connected to the auxiliary carrier gas 20 via an auxiliary carrier gas pipeline 19. A mass flow controller 10 for controlling the flow rate of the carrier gas entering the double-necked bottle is installed on this auxiliary carrier gas pipeline 19. Specifically, pneumatic valves (15, 16, 17) are respectively installed at the mouth of the single-necked bottle 13 and at the two mouths of the double-necked bottle 14. The single-necked bottle 13 is used to fill precursor sources with high saturated vapor pressure (i.e., the saturated vapor pressure can reach more than 1 Torr when the heating temperature is below 80°C). The single-necked bottle 13 is filled with ultrapure water. The double-necked bottle 14 is used to fill precursor sources with low saturated vapor pressure (i.e., the saturated vapor pressure is less than 1 Torr when the heating temperature is above 80°C). The double-necked bottle 14 contains tert-butyliminotris(diethylamino)niobium. The saturated vapor pressure of tert-butyliminotris(diethylamino)niobium is low, only 1 Torr at 91°C. Therefore, it is filled into the double-necked bottle and heated to 80°C.
[0022] A transfer chamber 4 is provided, with a pneumatic slide valve 33 between the transfer chamber 4 and the process chamber 2. Inside the transfer chamber 4, a sample transfer rod 37 is slidably connected to an internal fixed slide rail 38. The end of the sample transfer rod 37 is connected to a sample fork 35, and a sample tray 36 can be placed on the upper end of the sample fork 35. Due to the high deposition temperature, a titanium alloy sample tray is preferred to carry the sample. A substrate is placed on the upper end of the sample tray 36, preferably a silicon wafer or a silicon oxide wafer. A chamber cover 34 and a vent valve 39 are provided above the transfer chamber 4. The bottom of the transfer chamber 4 is connected to a vacuum pump 6 through another evacuation pipe 32. This vacuum pump 6 can also be a molecular pump.
[0023] See Figure 1 , Figure 2 , Figure 3 , Figure 4 As shown in the first embodiment, the plasma-assisted atomic layer deposition system has the following substrate sample transfer steps during operation: (1) Open the vent valve 39 to allow air to enter the transfer chamber to the atmosphere; (2) Open the chamber cover 34; (3) Place the substrate to be deposited on the sample tray 36; (4) Close the chamber cover 34; (5) Turn on the vacuum pump 6 to evacuate the transfer chamber 4 to the ultimate vacuum; (6) Check the vacuum level of the process chamber 2. If it is not a vacuum, turn on the vacuum pump 5 to evacuate the process chamber 2 to the ultimate vacuum; (7) Turn off the vacuum pumps 5 and 6 to ensure that both the process chamber 2 and the transfer chamber 4 are in a stable airflow state; (8) Control the sample stage 29 to descend to the lower limit position (e.g., using the lifting mechanism 30) through the lifting mechanism 30. Figure 2 (9) Open the pneumatic slide gate valve 33; (10) Slide the sample transfer rod 37 through the slide rail 38 so that the sample fork 35 holding the sample tray 36 extends into the process chamber 2 and is finally located directly above the sample stage 29; (11) Control the sample stage 29 to rise to the middle limit through the lifting mechanism 30 to lift the sample tray 36 (as shown); Figure 3 (12) Slide the sample transfer rod 37 through the slide rail 38 to make the sample fork 35 exit the process chamber 2 and return to the transfer chamber 4; (13) Close the pneumatic slide valve 33; (14) Control the sample stage 29 to rise to the upper limit position through the lifting mechanism 30 (as shown); Figure 4 (as shown) (15) Turn on the vacuum pump 6 to pump the transmission chamber 4 to the ultimate vacuum.
[0024] Example 2 This embodiment provides a plasma-assisted atomic layer deposition process; see [link to documentation]. Figure 5 As shown, the process includes: Step 1: After the sample is injected into process chamber 2, turn on vacuum pump 5 to evacuate process chamber 2 to below 1 Pa; Step 2: Heat the process chamber 2 and the first pipeline structure 7 and the second pipeline structure 8 connected to it. Heat the process chamber 2 to 300~400℃, heat the pneumatic valves 15, 16 and 17 in the second pipeline structure 8 to 120~200℃, and heat the pipelines 7 and 8 of the two pipeline structures to 150~200℃ to ensure that the precursor source does not condense during the transportation process. Step 3: Heat the precursor source tert-butyliminotris(diethylamino)niobium in the double-necked flask 14 to 65~80℃. This ensures that the precursor source can be volatilized and avoids the precursor source from decomposing due to excessive heating temperature. Before starting the preparation, it is necessary to ensure that the heating time exceeds 1 hour to ensure temperature stability. Auxiliary carrier gas 20 enters the double-necked flask 14, carrying out tert-butyliminotris(diethylamino)niobium inside the flask. The flow rate of the auxiliary carrier gas 20 is set to 5-10 sccm, and the opening time of the pneumatic valve 16 at the inlet of the double-necked flask 14 controlling the auxiliary carrier gas input is set to 0.01-0.02 s. This ensures that sufficient carrier gas is introduced into the double-necked flask 14 while avoiding excessive flow rate that would lead to excessive precursor sources that are difficult to purge. The opening time of the pneumatic valve 17 at the outlet of the double-necked flask 14 is set to 1-5 s. This ensures that sufficient precursor sources are volatilized to saturate the reaction while avoiding excessive pulse time that would lead to excessive precursor sources that are difficult to purge. The flow rate of the purge gas (argon in this application) is set to 50-200 sccm, and the purge time is set to 20-30 seconds. This ensures purge quality while avoiding excessive flow rate that would lead to excessively high base pressure and affect precursor volatilization. The precursor source is transported to the process chamber 2 via auxiliary carrier gas 20 and reacts with the substrate on the sample disk 36. When the reaction reaches saturation, the purge gas removes the excess precursor source and by-reaction products.
[0025] Step 4: Subsequently, ammonia gas source 21 enters plasma generator 3 and is ionized to generate plasma ammonia gas. The ammonia gas flow rate is set to 50~200 sccm, and the valve opening time of pneumatic valve 18 is set to 1~3 s. This ensures that there is enough ammonia gas entering plasma generator 3 to generate plasma and carry out subsequent reactions, while avoiding excessive ammonia gas that is difficult to purge. Carrier gas 20 delivers plasma ammonia gas to process chamber 2 to react with the substrate. When the reaction reaches saturation, purge gas (argon gas in this application) purges away excess precursor sources and by-reaction products. The purge gas flow rate is set to 50~200 sccm, and the purge time is set to 20~30 s. This ensures sufficient purging while avoiding excessive purging time that could affect the uniformity of the film. One cycle ends, forming a niobium nitride film.
[0026] Step 5: Repeat steps 3 and 4 above for 300 cycles to deposit the required film thickness. The number of cycles is calculated using the formula "Number of cycles = Required thickness ÷ Deposition rate". Then, cool process chamber 2 to room temperature to prevent the niobium nitride film from contacting air at high temperatures and forming impurities; take a sample and anneal it in argon gas.
[0027] The prepared samples were then characterized. See [link / reference]. Figure 6 As shown in the scanning electron microscope image, a niobium nitride film with a thickness of approximately 21.77 nm was obtained after 300 cycles. See also... Figure 7 and Figure 8 As shown, the X-ray photoelectron spectra of niobium and nitrogen obtained from the test are compared with the test results of samples prepared using a mixture of hydrogen and nitrogen in the prior art. The peak positions are consistent, which once again confirms that the prepared film is indeed a niobium nitride film.
[0028] Example 3 A plasma-assisted atomic layer deposition process, based on the above-mentioned plasma-assisted atomic layer deposition system, the process comprising: Step 1: After the sample is injected into process chamber 2, turn on vacuum pump 5 to evacuate process chamber 2 to below 1 Pa; Step 2: Heat the process chamber 2 and the first pipeline structure 7 and the second pipeline structure 8 connected to it. Heat the process chamber 2 to 200~300℃, heat the pneumatic valves 15, 16 and 17 in the second pipeline structure 8 to 120~200℃, and heat the pipelines 7 and 8 of the two pipeline structures to 150~200℃ to ensure that the precursor source does not condense during the transportation process. Step 3: Heat the precursor source tert-butyliminotris(diethylamino)niobium in the double-necked flask 14 to 65~80℃. This ensures that the precursor source can be volatilized and avoids the precursor source from decomposing due to excessive heating temperature. Before starting the preparation, it is necessary to ensure that the heating time exceeds 1 hour to ensure temperature stability. Auxiliary carrier gas 20 enters the two-necked bottle 14, carrying out tert-butyliminotris(diethylamino)niobium inside the bottle. The flow rate of the auxiliary carrier gas 20 is set to 5~10 sccm, and the opening time of the pneumatic valve 16 at the inlet of the two-necked bottle 14 controlling the auxiliary carrier gas input is set to 0.01~0.02 s. This ensures that sufficient carrier gas is introduced into the two-necked bottle 14 while avoiding excessive flow rate that would lead to excessive precursor sources that are difficult to purge. The opening time of the pneumatic valve 17 at the outlet of the two-necked bottle 14 is set to 1~5 s. This ensures that sufficient precursor sources can be volatilized while avoiding excessive pulse time that would lead to excessive precursor sources that are difficult to purge. The flow rate of the purging gas is set to 50~200 sccm. This ensures purging quality while avoiding excessive flow rate that would lead to excessively high base pressure and affect precursor source volatilization. The precursor source is transported to the process chamber 2 via auxiliary carrier gas 20 and reacts with the substrate on the sample disk 36. When the reaction reaches saturation, the purge gas removes the excess precursor source and by-reaction products.
[0029] In step 4, ultrapure water from the single-necked bottle 13 is transported to the process chamber 2 via auxiliary carrier gas 20 to react with the substrate. The opening time of the ultrapure water pneumatic valve 15 is set to 0.01~0.02 s to ensure sufficient precursor volatilization while avoiding excessive precursor source due to excessive pulse time, which would make purging difficult. When the reaction reaches saturation, the purging gas removes excess precursor source and by-reaction products, completing one cycle and forming a niobium oxide thin film.
[0030] Step 5: Repeat steps 3 and 4 above. The number of cycles can be calculated according to the required film thickness using the formula "number of cycles = required thickness ÷ deposition rate". After the coating is completed, cool the process chamber 2 to room temperature to prevent the niobium oxide film from coming into contact with air at high temperature and forming impurities. Take a sample and anneal it in ammonia to convert the niobium oxide film into a niobium nitride film.
[0031] Advantages and effects of the present invention: (1) The present invention preferably uses plasma-assisted atomic layer deposition technology to reduce the deposition temperature and avoid substrate damage caused by excessively high deposition temperature; (2) The present invention preferably uses an inductively coupled plasma generator to avoid the electrode coating caused by capacitively coupled plasma generators after multiple experiments, resulting in unstable experimental results and poor repeatability. (3) The present invention preferably uses remote plasma technology, which can adjust the distance between the plasma generator and the substrate to be longer through the lifting mechanism, so as to avoid the plasma from damaging the substrate or producing an etching effect; (4) The present invention preferably uses amino-based precursors to avoid dust and byproduct contamination of the substrate during the process of using chloride precursors in the prior art; (5) The present invention adopts a carrier gas-assisted precursor source delivery method. During the process, carrier gas is introduced into one of the ports, and the precursor source is driven to diffuse out from the other port by relying on the pressure difference, thereby reducing the heating temperature of the source bottle and avoiding the deterioration of the precursor source and damage to the manual valve caused by high temperature heating. (6) In this invention, ammonia is preferred as a co-reactant. Compared with the prior art, which uses plasma of nitrogen-hydrogen mixture as a co-reactant, this can effectively reduce the possibility of safety accidents. (7) The process chamber of the present invention is connected to a vacuum transmission chamber on the outside to avoid the film from directly contacting the atmosphere after preparation, which would cause surface oxidation. (8) The present invention can be equipped with a molecular pump according to process requirements. If equipped, it can further reduce the risk of impurity contamination and oxidation of the sample caused by residual gas in the cavity.
[0032] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.
Claims
1. A plasma-assisted atomic layer deposition system, characterized in that, The system comprises: A process cavity, the top of which is provided with a diffusion port, the bottom of which is connected to a sample table through a lifting mechanism, and the bottom of which is further connected to a vacuum pump through a gas extraction pipeline, the upper end of the process cavity is connected to an inductively coupled plasma generator, the upper end of the plasma generator is connected to a first gas path structure, the first gas path structure comprises two gas paths connected to an auxiliary carrier gas and an ammonia gas source, and the side of the process cavity is connected to a second gas path structure; the second gas path structure comprises a single-port bottle, one port of a double-port bottle and one gas path of the auxiliary carrier gas, the other port of the double-port bottle is communicated with the auxiliary carrier gas through a pipeline, the single-port bottle is used to fill a precursor source with a high saturated vapor pressure, and the double-port bottle is used to fill a precursor source with a low saturated vapor pressure; A transmission cavity, which is provided with a pneumatic valve between the process cavity and the transmission cavity, the inside of the transmission cavity is provided with a slidingly connected sample transmission rod, the end of the sample transmission rod is connected to a sample fork, and the bottom of the transmission cavity is connected to a vacuum pump through another gas extraction pipeline.
2. A plasma assisted atomic layer deposition system according to claim 1, characterized in that The diffusion port is in a horn shape for uniform flow diffusion.
3. A plasma assisted atomic layer deposition system according to claim 1, characterized in that The double-port bottle is internally filled with tert-butylimino tris (diethylamino) niobium, and the single-port bottle is internally filled with ultrapure water.
4. The plasma-assisted atomic layer deposition system of claim 1, wherein, The vacuum pump can be a molecular pump.
5. The plasma-assisted atomic layer deposition system of claim 1, wherein, The inductively coupled plasma generator comprises a quartz tube, the outside of the quartz tube is sleeved with a spiral copper coil, the copper coil is connected to a radio frequency power supply, and the radio frequency power supply is connected to a matcher.
6. A plasma assisted atomic layer deposition process, a plasma assisted atomic layer deposition system according to any one of claims 1 to 5, characterized by, The process comprises: Step 1, after the process cavity is filled with a sample, vacuum extraction is performed; Step 2, the process cavity and the first pipeline structure and the second pipeline structure connected thereto are heated; Step 3, the auxiliary carrier gas enters the double-port bottle, the precursor source in the bottle is transported to the process cavity, and reacts with the substrate on the sample table, when the reaction reaches saturation, the excess precursor source and byproduct are cleaned by a purge gas; Step 4, then the ammonia gas enters the plasma generator to be ionized to generate plasma ammonia, the carrier gas transports the plasma ammonia to the process cavity to react with the substrate, when the reaction reaches saturation, the excess precursor source and byproduct are cleaned by a purge gas, one cycle is completed, and a layer of niobium nitride film is formed; Step 5, the above steps 3 and 4 are repeated, and the cycle number is calculated according to the thickness of the required film.
7. The plasma-assisted atomic layer deposition process of claim 6, wherein, In step 3, before the double-port bottle is opened, the double-port bottle is heated to 65-80 DEG C, and the heating time is greater than 1 h, when the double-port bottle is working, the flow rate of the double-port bottle communicated with the auxiliary carrier gas is set to 5-10 sccm, the opening time is set to 0.01-0.02 s, and the valve opening time of the double-port bottle communicated with the process cavity is 1-5 s.
8. The plasma-assisted atomic layer deposition process of claim 7, wherein, In step 4, the flow rate of the ammonia gas is set to 50-200 sccm, and the opening time is set to 1-3 s.
9. The plasma-assisted atomic layer deposition process of claim 7, wherein, Or step 4 is that the ultrapure water filled in the single-port bottle is transported to the process cavity to react with the substrate, when the reaction reaches saturation, the excess precursor source and byproduct are cleaned by a purge gas, one cycle is completed, and a layer of niobium oxide film is formed.
10. The plasma-assisted atomic layer deposition process of claim 9, wherein, After the step 5, the niobium oxide film is converted into a niobium nitride film by annealing in ammonia.