Atomic layer deposition equipment and method for manufacturing two-dimensional heterogeneous film

Abstract

The invention discloses atomic layer deposition equipment and method for manufacturing a two-dimensional heterogeneous film. The apparatus comprises: a multi-source supply system for providing two or more precursor sources for atomic layer deposition; the multi-source same-cavity deposition cavity is matched with a heater to heat the multi-source same-cavity deposition cavity and provide a deposition reaction chamber for manufacturing a two-dimensional heterogeneous film, and a magnetic operation manipulator can perform multi-angle rotation, inclination or rapid switching on a deposition substrate in a sample deposition chamber of the multi-source same-cavity deposition cavity; and the bypass gas path system is matched with inert gas with the initial air pressure larger than the atmospheric pressure, conveys the various precursor source pulses of the multi-source supply system into the multi-source same-cavity deposition cavity and discharges the precursor source pulses after deposition. Through alternate or mixed supply of multiple precursor sources, controllable deposition of the two-dimensional heterogeneous film in a multi-source same-cavity deposition cavity is achieved, and the quality of the atomic layer deposition two-dimensional heterogeneous film is effectively improved through the in-situ annealing process.

Description

Technical Field

[0001] This invention relates to the field of semiconductor manufacturing technology, and in particular to an atomic layer deposition apparatus and method. Background Technology

[0002] Two-dimensional heterostructures, through the synergistic effect of multiple materials, offer a new paradigm for semiconductor technology, from device physics to system integration. They hold breakthrough potential in high-performance electronics, optoelectronics, energy, and biomedicine, and are expected to drive the semiconductor industry towards atomically precise control and multifunctional integration, becoming one of the core technologies in the post-Moore's Law era. However, atomically precise stacking of two-dimensional heterostructures still relies on manual transfer, making large-scale production difficult.

[0003] Atomic layer deposition (ALD) is a self-limiting reactive deposition technology. With its advantages of high conformality, high uniformity and low temperature compatibility, it can deposit a variety of two-dimensional thin films or two-dimensional heterogeneous thin films and precisely control the film thickness and composition. It has become the most promising solution for the fabrication of two-dimensional heterogeneous thin films, especially showing prospects for large-scale application in the fields of semiconductor devices and energy.

[0004] Chinese invention patent application number 114920239 A discloses a method for transferring or stacking two-dimensional materials based on water vapor. This method achieves two-dimensional material transfer and stacking in a water vapor environment by treating the target substrate with oxygen plasma and spin-coating the transfer medium. Chinese invention patent application number 116926472 A discloses a method for growing multilayer two-dimensional van der Waals heterostructures using physical vapor deposition (PVD) on a flat substrate through multiple depositions. Summary of the Invention

[0005] Technical issues:

[0006] This invention provides an atomic layer deposition apparatus and method for manufacturing two-dimensional heterogeneous thin films. The apparatus provides two or more precursor sources for atomic layer deposition through a multi-source supply system and performs two-dimensional heterogeneous thin film deposition and in-situ annealing processes within the multi-source co-cavity deposition chamber, achieving high-quality and controllable growth of the two-dimensional heterogeneous thin film. The apparatus utilizes a magnetically operated manipulator to rotate, tilt, or rapidly switch the deposition substrate at multiple angles, enabling continuous and uniform deposition of the two-dimensional heterogeneous thin film on the substrate surface. The in-situ annealing process within the multi-source co-cavity deposition chamber reduces "vacancy" defects within the two-dimensional heterogeneous thin film, achieving high-quality manufacturing of the two-dimensional heterogeneous thin film.

[0007] Technical solution:

[0008] In a first aspect, the present invention provides an atomic layer deposition apparatus for fabricating two-dimensional heterogeneous thin films, comprising:

[0009] A multi-source supply system, wherein the multi-source supply system provides two or more precursor sources for atomic layer deposition;

[0010] A multi-source co-cavity deposition chamber, wherein the multi-source co-cavity deposition chamber is equipped with a heater to heat the multi-source co-cavity deposition chamber and to provide a deposition reaction chamber for the fabrication of two-dimensional heterogeneous thin films;

[0011] A bypass gas path system, which is equipped with an inert gas at an initial pressure greater than one atmosphere, and is equipped with valves and flow meters, is used to deliver multiple precursor source pulses from the multi-source supply system into the multi-source co-cavity deposition chamber and discharge the reaction tail gas after deposition.

[0012] A power supply structure is provided to supply power to the multi-source supply system and the multi-source co-cavity deposition cavity to enable their heating functions.

[0013] A controller for controlling the switching of valves and flow meters in the bypass gas system.

[0014] Furthermore, the multi-source supply system includes two, three, or four precursor source bottles and their heating tanks.

[0015] Furthermore, the precursor source bottle is made of 316L stainless steel or 316 stainless steel.

[0016] Furthermore, the multi-source co-cavity deposition chamber includes a sample deposition chamber and a transition chamber.

[0017] Furthermore, the sample deposition chamber of the multi-source co-cavity deposition chamber is made of 316L stainless steel.

[0018] Furthermore, the heating temperature of the multi-source co-cavity deposition chamber can be set to 50-1000 ℃.

[0019] Furthermore, the transition chamber of the multi-source co-cavity deposition chamber is made of 316L stainless steel, and is connected to the transition chamber via the 316L stainless steel transition chamber. A magnetic manipulator is installed in the transition chamber of the multi-source co-cavity deposition chamber.

[0020] Furthermore, the magnetically operated manipulator transmits power through non-contact magnetic coupling, eliminating the need for a mechanical shaft to penetrate the vacuum chamber.

[0021] Furthermore, the magnetic manipulator can rotate, tilt, or quickly switch the substrate within the sample deposition chamber of the multi-source co-cavity deposition chamber at multiple angles.

[0022] Furthermore, the bypass gas path system can use a vacuum pump to evacuate the multi-source co-cavity deposition chamber and discharge the reaction tail gas.

[0023] Secondly, the present invention also provides an atomic layer deposition method for fabricating two-dimensional heterogeneous thin films, comprising the following steps:

[0024] Place the deposition substrate into the sample deposition chamber of the multi-source co-cavity deposition cavity;

[0025] A low vacuum level is generated between the multi-source co-cavity deposition chamber and the bypass gas path system by a vacuum pump.

[0026] The bypass gas path system introduces inert gas with an initial pressure greater than one atmosphere into the multi-source co-cavity deposition cavity for inert gas atmosphere cleaning and then discharges it.

[0027] The power supply structure supplies power to the multi-source supply system and the multi-source co-cavity deposition cavity to activate their heating function, thereby heating and maintaining their temperature.

[0028] The power supply structure supplies power to the controller to control the valves and flow meter switches of the bypass gas path system, and to transmit the various precursor source pulses and inert gas to the multi-source co-cavity deposition chamber.

[0029] The magnetic manipulator can rotate, tilt, or quickly switch the substrate in the sample deposition chamber of the multi-source co-cavity deposition chamber at multiple angles.

[0030] The bypass gas path system purifies and treats the reaction exhaust gas from the multi-source co-cavity deposition chamber before releasing it.

[0031] After the atomic layer deposition method for manufacturing the two-dimensional heterogeneous thin film is completed, the multi-source co-cavity deposition cavity is heated a second time to perform an in-situ annealing process on the deposited two-dimensional heterogeneous thin film.

[0032] After the in-situ annealing process is completed, the multi-source co-cavity deposition chamber is cooled while maintaining an inert gas atmosphere.

[0033] Furthermore, the deposition substrate includes silicon oxide wafers, silicon wafers, aluminum oxide, copper sheets, etc.

[0034] Furthermore, the vacuum pump generates a low vacuum of 0-200 Pa between the multi-source co-cavity deposition chamber and the bypass gas path system.

[0035] Furthermore, the heating temperature of the multi-source supply system is 25-150 ℃, and the heating temperature of the multi-source co-cavity deposition cavity is 50-500 ℃.

[0036] Furthermore, the magnetic manipulator can rotate the deposition substrate from 0 to 180°, tilt it from 0 to 90°, or quickly change samples.

[0037] Furthermore, the original annealing process temperature of the multi-source co-cavity deposition cavity is 700-900 ℃.

[0038] Beneficial effects:

[0039] 1. The present invention provides an atomic layer deposition apparatus and method for manufacturing two-dimensional heterogeneous thin films, which provides two or more precursor sources for atomic layer deposition through the multi-source supply system and performs in-situ annealing within the multi-source co-cavity deposition chamber, thereby achieving high-quality and controllable growth of two-dimensional heterogeneous thin films.

[0040] 2. The present invention improves the continuous and uniform deposition of two-dimensional heterogeneous films on the surface of the substrate by using the magnetically operated manipulator to rotate, tilt, or quickly switch the substrate at multiple angles.

[0041] 3. The present invention reduces the "vacancy" defects inside the two-dimensional heterogeneous film by using the original annealing process of the multi-source co-cavity deposition cavity, thereby realizing high-quality manufacturing of two-dimensional heterogeneous films. Attached Figure Description

[0042] Figure 1 This is a schematic diagram of the device of the present invention.

[0043] List of reference numerals in the attached diagram:

[0044] 1-Multi-source supply system, 2-Multi-source co-cavity deposition chamber, 3-Magnetic manipulator, 4-Bypass gas path system, 5-Controller, 6-Deposition substrate. Detailed Implementation

[0045] The present invention will be further illustrated below with reference to the accompanying drawings and specific embodiments. It should be understood that the following specific embodiments are for illustrative purposes only and are not intended to limit the scope of the invention.

[0046] Example 1:

[0047] like Figure 1 As shown, this specific embodiment 1 provides an atomic layer deposition apparatus for fabricating two-dimensional heterogeneous thin films, including:

[0048] A multi-source supply system 1, comprising multiple precursor source bottles and their heating tanks, for providing two or more precursor sources for atomic layer deposition;

[0049] The multi-source co-cavity deposition chamber 2 includes a sample deposition chamber and a transition chamber, both made of 316L stainless steel. The sample deposition chamber has a heatable sample stage for placing the deposition substrate 6. The transition chamber is connected to the sample deposition chamber. The multi-source co-cavity deposition chamber is equipped with a heater to heat the chamber and provide a deposition reaction chamber for the fabrication of two-dimensional heterogeneous thin films.

[0050] A magnetic manipulator 3 is installed in the transition chamber of the multi-source co-cavity deposition chamber and is used to rotate, tilt, or quickly switch the deposition substrate in the sample deposition chamber of the multi-source co-cavity deposition chamber at multiple angles.

[0051] A bypass gas path system 4, equipped with an inert gas at an initial pressure greater than one atmosphere, and fitted with valves and a flow meter, is used to pulsely deliver various precursor sources from the multi-source supply system 1 into the multi-source co-cavity deposition chamber 2 and discharge the reaction tail gas after deposition.

[0052] Controller 5, the controller 5 is used to control the switching of valves and flow meters in the bypass gas system;

[0053] Deposition substrate 6, wherein the deposition substrate is a silicon oxide wafer.

[0054] In a specific embodiment 1 of the present invention, the multi-source supply system 1 consists of four precursor source bottles and their heating tanks. The multi-source co-cavity deposition chamber 2 is made of 316L stainless steel and can rapidly heat the sample deposition chamber to a temperature of 400 ℃. The magnetic manipulator 3 transmits power through non-contact magnetic coupling to rotate the deposition substrate from 0 to 180°. The bypass gas path system 4 is made of 316L stainless steel, uses nitrogen as the inert gas at a flow rate of 100 ppm, and is controlled by the controller 5 to control the opening and closing of valves and flow meters to generate alternating precursor source pulses that enter the sample deposition chamber of the multi-source co-cavity deposition chamber 2 to deposit a two-dimensional heterogeneous thin film on the surface of the silicon oxide wafer deposition substrate 6. The gas path system 4 uses nitrogen as the inert gas at a flow rate of 100 ppm. The controller 5 controls the valves and flow meters of the bypass gas path system 4 to control the entry of precursor source pulses and inert gas into the multi-source co-cavity deposition chamber 2. The pulse duration is 1 s, and the inert gas purging time is 60 s.

[0055] However, it should be understood that the specific embodiments of the present invention are not limited thereto. In some other specific embodiments, the precursor source bottle and its heating tank of the multi-source supply system 1 are 2-6. The deposition substrate 6 of the reaction chamber 2 includes silicon oxide wafers, silicon wafers, aluminum oxide, copper sheets, etc. The magnetic manipulator 3 can realize operations such as 0-180° rotation, 0-90° tilting, or rapid sample change of the deposition substrate. The bypass gas path system 4 uses nitrogen or argon as the inert gas, with a flow rate of 0-500 ppm. The controller 5 controls the opening and closing of the valves and flow meters of the bypass gas path system, and the pulse time can be adjusted from 0.5 to 5 s, and the inert gas purging time can be adjusted from 30 to 180 s.

[0056] Example 2:

[0057] Specific embodiment 2 of the present invention provides an atomic layer deposition method for fabricating two-dimensional heterogeneous thin films, comprising the following steps:

[0058] Place the deposition substrate into the sample deposition chamber of the multi-source co-cavity deposition cavity;

[0059] A low vacuum level is generated between the multi-source co-cavity deposition chamber and the bypass gas path system by a vacuum pump.

[0060] The bypass gas path system introduces inert gas with an initial pressure greater than one atmosphere into the multi-source co-cavity deposition cavity for inert gas atmosphere cleaning and then discharges it.

[0061] The power supply structure supplies power to the multi-source supply system and the multi-source co-cavity deposition cavity to activate their heating function, thereby heating and maintaining their temperature.

[0062] The power supply structure supplies power to the controller to control the valves and flow meter switches of the bypass gas path system, and to transmit the various precursor source pulses and inert gas to the multi-source co-cavity deposition chamber.

[0063] The magnetic manipulator can rotate, tilt, or quickly switch the substrate in the sample deposition chamber of the multi-source co-cavity deposition chamber at multiple angles.

[0064] The bypass gas path system purifies and treats the reaction exhaust gas from the multi-source co-cavity deposition chamber before releasing it.

[0065] After the atomic layer deposition method for manufacturing the two-dimensional heterogeneous thin film is completed, the multi-source co-cavity deposition cavity is heated a second time to perform an in-situ annealing process on the deposited two-dimensional heterogeneous thin film.

[0066] After the in-situ annealing process is completed, the multi-source co-cavity deposition chamber is cooled while maintaining an inert gas atmosphere.

[0067] Specifically, the atomic layer deposition process for manufacturing two-dimensional heterogeneous thin films is carried out in the multi-source co-cavity deposition chamber 2 of the atomic layer deposition equipment for manufacturing two-dimensional heterogeneous thin films. After the multi-source supply system 1 and the multi-source co-cavity deposition chamber 2 reach 150 ℃ and 400 ℃ respectively, they are kept at these temperatures for 60 min. The multi-source supply system 1 alternately or mixedly transmits a first type of precursor source pulse into the multi-source co-cavity deposition chamber 2. After the first type of precursor source pulse molecules react with the deposition substrate 6 of the multi-source co-cavity deposition chamber 2 through self-limiting adsorption, the bypass gas path system 4 discharges the reaction tail gas from the multi-source co-cavity deposition chamber 2 and performs inert gas cleaning treatment. The second type of precursor source pulse molecules enter the multi-source co-cavity deposition chamber 2 to react and clean the tail gas. The magnetically operated manipulator 3 rotates, tilts or quickly switches the deposition substrate 6 in the sample deposition chamber of the multi-source co-cavity deposition chamber 2 at multiple angles, and then performs alternating self-limiting adsorption reactions in sequence to achieve continuous deposition of two-dimensional heterogeneous thin films on the surface of the deposition substrate 6. After completing the atomic layer deposition process of a two-dimensional heterogeneous thin film of a certain thickness, the multi-source co-cavity deposition chamber 2 undergoes a secondary heating process to perform an in-situ annealing process on the deposited two-dimensional heterogeneous thin film, thereby improving the quality of the two-dimensional heterogeneous thin film. This atomic layer deposition method for manufacturing two-dimensional heterogeneous thin films provides two or more precursor sources for atomic layer deposition, and the deposition is carried out in the multi-source co-cavity deposition chamber. The magnetic manipulator 3 rotates, tilts, or rapidly switches the deposition substrate 6 at multiple angles, improving the continuous, uniform, and controllable growth of the two-dimensional heterogeneous thin film on the surface of the deposition substrate 6. In addition, the in-situ annealing process in the multi-source co-cavity deposition chamber 2 reduces the "vacancy" defects inside the two-dimensional heterogeneous thin film, realizing high-quality manufacturing of two-dimensional heterogeneous thin films.

[0068] Example 3:

[0069] Specific embodiment 3 of the present invention provides a method for fabricating two-dimensional heterostructure thin films by atomic layer deposition of vertically stacked molybdenum disulfide (MoS2) / rhenium disulfide (ReS2) van der Waals heterostructure thin films. The deposition substrate was a wafer-level silicon oxide wafer. The multi-source supply system used three precursor source bottles: precursor source 1 was MoCl5 at 150 ℃, precursor source 2 was ReCl5 at 110 ℃, and precursor source 3 was H2S at room temperature. The temperature of the multi-source co-cavity deposition chamber was 400 ℃. The precursor source pulse parameters for atomic layer deposition of the vertically stacked MoS2 / ReS2 van der Waals heterostructure films were: 1 s MoCl5 pulse – 60 s N2 cleaning – 1 s H2S pulse – 60 s N2 cleaning – 0.5 s ReCl5 pulse – 60 s N2 cleaning – 1 s H2S pulse – 60 s N2 cleaning. The in-situ annealing temperature was 750 ℃, and the time was 30 min.

[0070] Specifically, firstly, the vacuum level of the multi-source co-cavity deposition chamber 2 is reduced to below 50 Pa, and then the multi-source supply system 1 and the multi-source co-cavity deposition chamber 2 are heated. The temperature of the MoCl5 precursor source in the multi-source supply system 1 reaches 150 ℃, the temperature of the ReCl5 precursor source reaches 110 ℃, and the multi-source co-cavity deposition chamber 2 reaches a predetermined temperature of 400 ℃. After holding at this temperature for 60 min, the control valve and flow meter of the MoCl5 precursor source are activated via the controller to perform a 1 s MoCl5 pulse. The reaction chamber 2 is then thoroughly cleaned with inert gas N2 for 60 s, followed by a 1 s H2S pulse and another 60 s N2 pulse, completing the first atomic layer deposition cycle of the MoS2 thin film. Next, an atomic layer deposition cycle of the ReS2 thin film is performed using a 0.5 s ReCl5 pulse – 60 s N2 cleaning – 1 s H2S pulse – 60 s N2 cleaning cycle. By employing alternating atomic layer deposition cycles of MoS2 and ReS2 films, a van der Waals heterostructure of alternating vertically stacked MoS2 / ReS2 / MoS2 / ReS2 films is deposited on the surface of a wafer-level silicon oxide wafer. Finally, the multi-source co-cavity deposition chamber 2 is heated to 750 °C and held for 30 min in an H2S atmosphere to achieve in-situ annealing of the MoS2 / ReS2 / MoS2 / ReS2 van der Waals heterostructure. This reduces the "S-vacancy" defects within the MoS2 / ReS2 / MoS2 / ReS2 van der Waals heterostructure, achieving high-quality manufacturing of the MoS2 / ReS2 / MoS2 / ReS2 van der Waals heterostructure.

[0071] The technical means disclosed in this invention are not limited to those disclosed in the above embodiments, but also include technical solutions composed of any combination of the above technical features. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of this invention, and these improvements and modifications are also considered within the scope of protection of this invention.

Claims

1. An atomic layer deposition apparatus for fabricating two-dimensional heterogeneous thin films, characterized in that, include: A multi-source supply system, wherein the multi-source supply system provides two or more precursor sources for atomic layer deposition; A multi-source co-cavity deposition chamber, wherein the multi-source co-cavity deposition chamber is equipped with a heater for heating and provides a deposition reaction chamber for the fabrication of two-dimensional heterogeneous thin films; A bypass gas path system, equipped with an inert gas at an initial pressure greater than one atmosphere, and with valves and flow meters, is used to deliver multiple precursor source pulses from the multi-source supply system into the multi-source co-cavity deposition chamber and discharge the reaction tail gas after deposition.

2. The atomic layer deposition apparatus for manufacturing two-dimensional heterogeneous thin films according to claim 1, characterized in that, Also includes: A power supply structure is provided to supply power to the multi-source supply system and the multi-source co-cavity deposition cavity to enable their heating functions. A controller for controlling the switching of valves and flow meters in the bypass gas system.

3. The atomic layer deposition apparatus for fabricating two-dimensional heterogeneous thin films according to claim 1, characterized in that, The multi-source supply system includes two, three, or four precursor source bottles and their heating tanks; the precursor source bottles are made of 316L stainless steel or 316 stainless steel.

4. The atomic layer deposition apparatus for fabricating two-dimensional heterogeneous thin films according to claim 1, characterized in that, The multi-source co-cavity deposition chamber includes a sample deposition chamber and a transition chamber; the sample deposition chamber of the multi-source co-cavity deposition chamber is made of 316L stainless steel; the heating temperature of the multi-source co-cavity deposition chamber is set to 50-1000℃; the transition chamber of the multi-source co-cavity deposition chamber is made of 316L stainless steel, connected to the sample deposition chamber, and a magnetic manipulator is installed through the transition chamber.

5. The atomic layer deposition apparatus for fabricating two-dimensional heterogeneous thin films according to claim 4, characterized in that, The magnetic manipulator transmits power through non-contact magnetic coupling, eliminating the need for a mechanical shaft to penetrate the multi-source co-cavity deposition chamber; the magnetic manipulator can rotate, tilt, or rapidly switch the deposition substrate within the sample deposition chamber of the multi-source co-cavity deposition chamber at multiple angles.

6. The atomic layer deposition apparatus for fabricating two-dimensional heterogeneous thin films according to claim 1, characterized in that, The bypass gas path system uses a vacuum pump to evacuate the multi-source co-cavity deposition chamber and discharge the reaction tail gas.

7. An atomic layer deposition method for fabricating two-dimensional heterogeneous thin films, based on the atomic layer deposition apparatus as described in any one of claims 1-6, characterized in that, The atomic layer deposition equipment includes a multi-source supply system, a multi-source co-cavity deposition chamber, a bypass gas path system, a power supply structure, a controller, and a magnetically operated manipulator, and includes the following steps: Place the deposition substrate into the sample deposition chamber of the multi-source co-cavity deposition cavity; A low vacuum level is generated between the multi-source co-cavity deposition chamber and the bypass gas path system by a vacuum pump. The bypass gas path system introduces inert gas with an initial pressure greater than one atmosphere into the multi-source co-cavity deposition cavity for inert gas atmosphere cleaning and then discharges it. The power supply structure supplies power to the multi-source supply system and the multi-source co-cavity deposition cavity to activate their heating function, thereby heating and maintaining their temperature. The power supply structure supplies power to the controller to control the valves and flow meter switches of the bypass gas path system, and to transmit the various precursor source pulses and inert gas to the multi-source co-cavity deposition chamber. The magnetic manipulator can rotate, tilt, or quickly switch the substrate in the sample deposition chamber of the multi-source co-cavity deposition chamber at multiple angles. The bypass gas path system purifies and treats the reaction exhaust gas from the multi-source co-cavity deposition chamber before releasing it. After the atomic layer deposition method for manufacturing the two-dimensional heterogeneous thin film is completed, the multi-source co-cavity deposition cavity is heated a second time to perform an in-situ annealing process on the deposited two-dimensional heterogeneous thin film. After the in-situ annealing process is completed, the multi-source co-cavity deposition chamber is cooled while maintaining an inert gas atmosphere.

8. The atomic layer deposition method for fabricating two-dimensional heterogeneous thin films according to claim 7, characterized in that, The deposition substrate includes, but is not limited to, silicon oxide wafers, silicon wafers, aluminum oxide, and copper wafers.

9. The atomic layer deposition method for fabricating two-dimensional heterogeneous thin films according to claim 7, characterized in that, The vacuum pump generates a low vacuum of 0-200 Pa between the multi-source co-cavity deposition chamber and the bypass gas path system; the heating temperature of the multi-source supply system is 25-150 ℃; the heating temperature of the multi-source co-cavity deposition chamber is 50-500 ℃; and the original annealing process temperature of the multi-source co-cavity deposition chamber is 700-900 ℃.

10. The atomic layer deposition method for fabricating two-dimensional heterogeneous thin films according to claim 7, characterized in that, The magnetic manipulator can rotate the deposition substrate from 0 to 180°, tilt it from 0 to 90°, or quickly change samples.

Images