Thin film deposition method

Abstract

The invention discloses a thin film deposition method which is used for improving the overall crystallization performance, uniformity and conformality of a thin film. The method comprises the following steps: placing a substrate in a reaction chamber; heating the substrate, and heating the substrate to a first preset temperature; a first precursor is introduced, the first precursor is introduced into the reaction chamber, and after introduction of the first precursor is stopped, inert gas is introduced into the reaction chamber for a second preset time period; a second precursor is introduced, the second precursor is introduced into the reaction chamber, after introduction of the second precursor is stopped, inert gas is introduced into the reaction chamber for a fourth preset time period, and a layer of film grows on the surface of the substrate; repeating the steps to heat the substrate until the second precursor is introduced for n times, n being greater than or equal to 1, so that multiple layers of films grow on the surface of the substrate, and annealing once every m layers of films grow on the surface of the substrate, m being greater than or equal to 1; and when the temperature in the reaction chamber is reduced to room temperature, inflating the reaction chamber to a normal pressure state, and taking out the substrate.

Description

Technical Field

[0001] The present application relates to the field of semiconductor preparation technology, and in particular to a thin film deposition method. Background Art

[0002] Nanofilms are indispensable in various fields. For example, they can be used as reflective and refractive films in optical devices, functional films in semiconductor devices and sensors, such as ultra-thin continuous conductive films, or as adhesion layers on oxide surfaces for other metal ALD systems.

[0003] With the continuous development of integrated circuits, the requirements for thin films in integrated circuits are gradually increasing. Among them, the preparation technologies of single-element thin film materials mainly include physical vapor deposition (PVD), chemical vapor deposition (CVD), molecular beam epitaxy (MBE), metal-organic chemical vapor deposition (MOCVD) and atomic layer deposition (ALD). The PVD method for preparing single-element thin films is easy to damage the substrate and the prepared films are relatively thick and have poor conformality. CVD cannot accurately control the thickness of the film, and the grown films often coexist with single layers and multilayers, and the growth uniformity over large areas is poor. MOCVD equipment is expensive and complicated to operate, and it does not have obvious advantages for preparing uniform thin film materials with controllable number of layers. ALD can effectively control the number of layers by introducing reaction precursors to cause self-limiting chemical reactions on the substrate surface. However, during the ALD method of thin film deposition, multiple layers of thin films are generally grown and then annealed, which can easily lead to interlayer diffusion, and the overall crystallization performance of the thin film is low, and the uniformity and conformality are low. Summary of the Invention

[0004] The purpose of this application is to provide a thin film deposition method to improve the overall crystallization performance, uniformity and conformality of the thin film.

[0005] In order to achieve the above objectives, this application provides the following technical solutions:

[0006] A thin film deposition method, comprising:

[0007] Providing at least one substrate, and placing the substrate in a reaction chamber;

[0008] heating the substrate to a first preset temperature;

[0009] introducing a first precursor into the reaction chamber, wherein the temperature of the first precursor is a second preset temperature, the introduction time of the first precursor is a first preset time period or the introduction amount of the first precursor is a first preset amount, and after stopping the introduction of the first precursor, introducing an inert gas into the reaction chamber for a second preset time period;

[0010] introducing a second precursor into the reaction chamber, wherein the temperature of the second precursor is at a third preset temperature, the introduction time of the second precursor is a third preset time period or the introduction amount of the second precursor is a second preset amount, and after stopping the introduction of the second precursor, introducing an inert gas into the reaction chamber for a fourth preset time period, and growing a thin film on the surface of the substrate;

[0011] Repeat the steps of heating the substrate until the second precursor is introduced n times, n≥1, so that a multilayer thin film grows on the surface of the substrate, and annealing is performed once every m layers of thin film grown on the surface of the substrate, m≥1;

[0012] After the temperature in the reaction chamber drops to room temperature, the reaction chamber is inflated to normal pressure, and the substrate is taken out.

[0013] In one implementation, the step of introducing the first precursor into the reaction chamber and simultaneously introducing an inert gas into the reaction chamber; and / or,

[0014] In the step of introducing the second precursor, an inert gas is introduced into the reaction chamber while the second precursor is introduced into the reaction chamber.

[0015] In one implementation, the carrier gas flow rate of the inert gas is 5 sccm-100 sccm.

[0016] In one implementation, the first preset temperature ranges from 80°C to 400°C; and / or the temperature in the reaction chamber ranges from 0°C to 200°C; and / or the second preset temperature ranges from 0°C to 200°C; and / or the third preset temperature ranges from 0°C to 200°C.

[0017] In one implementation, the first preset time period is 0.01s to 1s; and / or, the second preset time period is 5s to 180s; and / or, the third preset time period is 0.01s to 1s; and / or, the fourth preset time period is 5s to 180s.

[0018] In one implementation, after each annealing, an inert gas is introduced into the reaction chamber for a fifth preset time period;

[0019] The fifth preset time period is 5s to 180s.

[0020] In one implementation, the annealing temperature during the annealing process is 400° C. to 1200° C.; and / or,

[0021] In the annealing process, infrared rays or resistance wires are used for heating.

[0022] In one implementation, the material of the thin film grown on the substrate surface includes C, Al, Si, Ti, Fe, Co, Ni, Cu, Zn, Ga, Ge, Mo, Ru, Rh, Pd, Ag, Ta, W, Os, Ir and / or Pt; and / or,

[0023] The substrate is a SiO2 / Si substrate, a Si substrate, a sapphire substrate or a quartz substrate.

[0024] In one implementation, before placing the substrate in the reaction chamber, at least one functional layer is processed on the base surface of the substrate;

[0025] And / or, before placing the substrate in the reaction chamber, the surface of the substrate is cleaned.

[0026] In one implementation, the first precursor includes silicon tetrachloride, molybdenum hexafluoride, tungsten hexafluoride, TMA and / or molybdenum hexacarbonyl; and / or,

[0027] The second precursor includes disilane, hydrogen and / or hydrogen sulfide.

[0028] In the process of depositing a thin film on a substrate surface using the thin film deposition method of the present application, annealing is performed once after each m layers of thin film are grown on the substrate surface, and multiple periodic annealings are performed in this manner. Compared with the prior art method of performing annealing once after all thin film growth is completed, annealing once after each m layers of thin film are grown on the substrate surface can ensure the single crystal atomic arrangement of the thin film and prevent diffusion between the thin film and other material layers. If a metal interconnect layer is prepared, rapid annealing can be performed to form good contact between the surface metal and the bottom layer. In addition, the thin film deposition method grows thin films in multiple layers, which can more accurately control the thickness of the film and the number of growth layers. The growth and annealing are performed alternately, which can improve the crystallization performance of each layer of the film. Each layer is epitaxially extended according to the lattice of the previous layer, making the overall uniformity and conformality of the film better, thereby improving the film quality. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] The drawings described herein are used to provide a further understanding of the present application and constitute a part of the present application. The illustrative embodiments of the present application and their descriptions are used to explain the present application and do not constitute an improper limitation on the present application. In the drawings:

[0030] Figure 1 A schematic flow chart of a thin film deposition method according to an embodiment of the present application;

[0031] Figure 2 A schematic diagram of thin film deposition is provided for an embodiment of the present application. DETAILED DESCRIPTION

[0032] In order to make the technical problems, technical solutions and beneficial effects to be solved by this application more clearly understood, this application is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain this application and are not intended to limit this application.

[0033] It should be noted that when an element is referred to as being “fixed on” or “disposed on” another element, it may be directly on the other element or indirectly on the other element. When an element is referred to as being “connected to” another element, it may be directly connected to the other element or indirectly connected to the other element.

[0034] In addition, the terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of the technical features indicated. Therefore, a feature defined as "first" or "second" may explicitly or implicitly include one or more of the features. In the description of this application, "multiple" means two or more, unless otherwise clearly and specifically defined. "Several" means one or more, unless otherwise clearly and specifically defined.

[0035] In the description of this application, it should be understood that the terms "up", "down", "front", "back", "left", "right", etc., indicating directions or positional relationships, are based on the directions or positional relationships shown in the accompanying drawings. They are only for the convenience of describing this application and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific direction, be constructed and operated in a specific direction. Therefore, they should not be understood as limitations on this application.

[0036] In the description of this application, it should be noted that, unless otherwise expressly specified or limited, the terms "installed," "connected," and "connected" should be understood in a broad sense. For example, they can refer to fixed connections, detachable connections, or integral connections; they can refer to mechanical connections or electrical connections; they can refer to direct connections or indirect connections through an intermediate medium; they can refer to internal communication between two components or the interaction between two components. Those skilled in the art will understand the specific meanings of the above terms in this application based on the specific circumstances.

[0037] See also Figure 1 The thin film deposition method provided in the embodiment of the present application includes the following steps:

[0038] S1: providing at least one substrate and placing the substrate in a reaction chamber;

[0039] That is, a substrate of any material can be provided according to actual manufacturing requirements, and one substrate or multiple substrates can be provided to simultaneously perform thin film deposition on the surfaces of multiple substrates. The substrate is placed in a reaction chamber for subsequent steps.

[0040] S2: heating the substrate to a first preset temperature;

[0041] Specifically, the substrate may be heated by electric heating or infrared heating to heat the substrate to a first preset temperature.

[0042] S3: introducing a first precursor into the reaction chamber, wherein the temperature of the first precursor is a second preset temperature, the introduction time of the first precursor is a first preset time period or the introduction amount of the first precursor is a first preset amount, and after stopping the introduction of the first precursor, an inert gas is introduced into the reaction chamber for a second preset time period;

[0043] Specifically, the reaction chamber is evacuated, the gas pipeline and the first precursor are heated, and when the temperature of the gas pipeline and the first precursor rises to a second preset temperature, the first precursor is introduced into the reaction chamber, and the temperature of the first precursor introduced into the reaction chamber is the second preset temperature. The introduction time of the first precursor is a first preset time period, so that the introduction amount of the first precursor is controlled by the introduction time of the first precursor; or, the introduction amount of the first precursor is a first preset amount. In this embodiment, the first preset amount can be a first preset volume or a first preset mole, etc. After stopping the introduction of the first precursor, an inert gas is introduced into the reaction chamber for a second preset time period, that is, the reaction chamber is purged with an inert gas to remove the first precursor remaining in the reaction chamber. In this application, the inert gas can be nitrogen, argon, helium, neon, krypton, xenon or radon.

[0044] S4: introducing a second precursor, introducing the second precursor into the reaction chamber, the temperature of the second precursor is at a third preset temperature, the introduction time of the second precursor is a third preset time period or the introduction amount of the second precursor is a second preset amount, after stopping the introduction of the second precursor, introducing an inert gas into the reaction chamber for a fourth preset time period, and growing a thin film on the surface of the substrate.

[0045] Specifically, a second precursor is introduced into the reaction chamber, and the temperature of the second precursor introduced into the reaction chamber is a third preset temperature. The introduction time of the second precursor is a third preset time period, so that the introduction amount of the second precursor is controlled by the introduction time of the second precursor; alternatively, the introduction amount of the second precursor is a second preset amount. In this embodiment, the second preset amount can be a second preset volume or a second preset mole, etc. After the introduction of the second precursor is stopped, an inert gas is introduced into the reaction chamber for a fourth preset time period, that is, the reaction chamber is purged with an inert gas to remove the second precursor remaining in the reaction chamber. A thin film grows on the surface of the substrate, that is, after steps S2-S4 are completed, a thin film grows on the surface of the substrate, and a thin film grows on the surface of the substrate each time steps S2-S4 are cycled.

[0046] S5: Repeat the steps of heating the substrate until the second precursor is introduced n times, n ≥ 1, so that a multilayer thin film grows on the surface of the substrate, and the surface of the substrate is annealed once every m layers of thin film grown, m ≥ 1;

[0047] That is, steps S2 to S4 are repeated n times in total, and n thin film layers are grown on the substrate surface, where n≥1. The materials of the n thin film layers can be the same or different, and the thicknesses of the n thin film layers can be the same or different.

[0048] Furthermore, the substrate surface is annealed once every m thin film layers grown, where m ≥ 1. That is, after every m cycles of steps S2-S4, annealing is performed once every m thin film layers grown on the substrate surface. In this embodiment, the thin film grown on the substrate surface is periodically annealed, with m cycles of steps S2-S4 followed by one annealing cycle, and m cycles of steps S2-S4 between each annealing cycle.

[0049] S6: After the temperature in the reaction chamber drops to room temperature, the reaction chamber is filled with inert gas to atmospheric pressure and the substrate is removed. In this step, after the last annealing is completed and the temperature in the reaction chamber drops to room temperature, the reaction chamber can be filled with inert gas to atmospheric pressure and the substrate can be removed.

[0050] In the process of depositing a thin film on the substrate surface using the thin film deposition method of the present application, annealing is performed once every m cycles of steps S2-S4, that is, annealing is performed once after each m layers of thin film are grown on the substrate surface. Multiple periodic annealing is performed in this way. Compared with the prior art in which annealing is performed once after all thin film growth is completed, annealing is performed once after each m layers of thin film are grown on the substrate surface. This can ensure the single crystal atomic arrangement of the thin film and prevent diffusion between the thin film and other material layers. If a metal interconnect layer is prepared, rapid annealing can be performed to form good contact between the surface metal and the bottom layer. In addition, the thin film deposition method grows thin films in multiple layers, which can more accurately control the thickness of the thin film and the number of growth layers. The growth and annealing are performed alternately, which can improve the crystallization performance of each layer of the thin film. Each layer is epitaxially grown according to the lattice of the previous layer, making the overall uniformity and conformality of the thin film better, thereby improving the quality of the film.

[0051] In a specific embodiment, step S3 is passed into the first precursor, and while the first precursor is passed into the reaction chamber, an inert gas is passed into the reaction chamber, that is, the inert gas and the first precursor enter the reaction chamber at the same time to prevent oxygen from entering the reaction chamber and generating impurities. The temperature of the inert gas passed into this step can be the same as the temperature of the first precursor to ensure the reaction temperature in the reaction chamber. The carrier gas flow rate of the first precursor is 5sccm-100sccm, that is, the flow rate of the inert gas is 5sccm-100sccm. Exemplary, the carrier gas flow rate of the first precursor is 5sccm, 10sccm, 15sccm, 20sccm, 25sccm, 30sccm, 35sccm, 40sccm, 45sccm, 50sccm, 55sccm, 60sccm, 65sccm, 70sccm, 75sccm, 80sccm, 85sccm, 90sccm, 95sccm or 100sccm. Preferably, it is 20sccm.

[0052] In addition, in step S4, when the second precursor is introduced into the reaction chamber, an inert gas is introduced into the reaction chamber. That is, the inert gas and the second precursor enter the reaction chamber at the same time to prevent oxygen from entering the reaction chamber and generating impurities. The temperature of the inert gas introduced in this step can be the same as the temperature of the second precursor to ensure the reaction temperature in the reaction chamber. The carrier gas flow rate of the second precursor is 5 sccm-100 sccm, that is, the flow rate of the inert gas is 5 sccm-100 sccm. Exemplary, the carrier gas flow rate of the second precursor is 5 sccm, 10 sccm, 15 sccm, 20 sccm, 25 sccm, 30 sccm, 35 sccm, 40 sccm, 45 sccm, 50 sccm, 55 sccm, 60 sccm, 65 sccm, 70 sccm, 75 sccm, 80 sccm, 85 sccm, 90 sccm, 95 sccm or 100 sccm. Preferably, it is 20 sccm.

[0053] In step S2, the first preset temperature ranges from 80°C to 400°C. Specifically, the substrate can be heated by infrared heating or resistance heating. The first preset temperature can be set according to actual conditions. For example, the first preset temperature is 80°C, 100°C, 150°C, 200°C, 250°C, 300°C, 350°C, or 400°C.

[0054] In each of the above steps, the temperature in the reaction chamber ranges from 0° C. to 200° C., specifically, from room temperature to 200° C. Illustratively, the temperature in the reaction chamber is 0° C., 20° C., 40° C., 50° C., 80° C., 100° C., 120° C., 140° C., 150° C., 180° C., or 200° C.

[0055] In step S3, the second preset temperature ranges from 0°C to 200°C. That is, the first precursor is heated to the second preset temperature before being introduced into the reaction chamber. Exemplarily, the second preset temperature is 0°C, 20°C, 40°C, 50°C, 80°C, 100°C, 120°C, 140°C, 150°C, 180°C, or 200°C.

[0056] In step S3, the first preset time period is 0.01s to 1s, that is, the time for the first precursor to be introduced is 0.01s to 1s, so as to control the amount of the first precursor introduced by the time of the first precursor introduced. It should be noted that the reaction chamber is always in a vacuum state, and the first precursor can be introduced into the reaction chamber by simply opening the vent valve of the first precursor. The first preset time period is the duration of opening the vent valve of the first precursor. Exemplarily, the first preset time period is 0.01s, 0.05s, 0.1s, 0.15s, 0.2s, 0.25s, 0.3s, 0.35s, 0.4s, 0.45s, 0.5s, 0.55s, 0.6s, 0.65s, 0.7s, 0.75s, 0.8s, 0.85s, 0.9s, 0.95s or 1s.

[0057] In step S3, the second preset time period is 5 seconds to 180 seconds. Specifically, after the introduction of the first precursor is stopped, an inert gas is introduced into the reaction chamber for 5 seconds to 180 seconds to purge the reaction chamber with the inert gas. Exemplarily, the inert gas is introduced into the reaction chamber for 5 seconds, 10 seconds, 20 seconds, 30 seconds, 40 seconds, 50 seconds, 60 seconds, 70 seconds, 80 seconds, 90 seconds, 100 seconds, 110 seconds, 120 seconds, 130 seconds, 140 seconds, 150 seconds, 160 seconds, 170 seconds, or 180 seconds.

[0058] In step S4, the third preset temperature ranges from 0°C to 200°C. That is, the second precursor is heated to the third preset temperature before being introduced into the reaction chamber. Exemplarily, the third preset temperature is 0°C, 20°C, 40°C, 50°C, 80°C, 100°C, 120°C, 140°C, 150°C, 180°C, or 200°C.

[0059] In step S4, the third preset time period is 0.01s to 1s, that is, the passage time of the second precursor is 0.01s to 1s, so as to control the amount of the second precursor by the passage time of the second precursor. It should be noted that the reaction chamber is always in a vacuum state, and the second precursor can be passed into the reaction chamber by simply opening the vent valve of the second precursor. The third preset time period is the duration of opening the vent valve of the second precursor. Exemplarily, the third preset time period is 0.01s, 0.05s, 0.1s, 0.15s, 0.2s, 0.25s, 0.3s, 0.35s, 0.4s, 0.45s, 0.5s, 0.55s, 0.6s, 0.65s, 0.7s, 0.75s, 0.8s, 0.85s, 0.9s, 0.95s or 1s.

[0060] In step S4, the fourth preset time period is 5 seconds to 180 seconds. Specifically, after the introduction of the second precursor is stopped, an inert gas is introduced into the reaction chamber for 5 seconds to 180 seconds to purge the reaction chamber with the inert gas. Exemplarily, the inert gas is introduced into the reaction chamber for 5 seconds, 10 seconds, 20 seconds, 30 seconds, 40 seconds, 50 seconds, 60 seconds, 70 seconds, 80 seconds, 90 seconds, 100 seconds, 110 seconds, 120 seconds, 130 seconds, 140 seconds, 150 seconds, 160 seconds, 170 seconds, or 180 seconds.

[0061] In one embodiment, after each annealing step, an inert gas is introduced into the reaction chamber for a fifth preset time period. Specifically, after the annealing step, an inert gas is introduced into the reaction chamber for purging to prevent oxygen and other gases from entering the reaction chamber and contaminating the growing thin film. Specifically, the fifth preset time period is 5 seconds to 180 seconds, for example, 5 seconds, 10 seconds, 20 seconds, 30 seconds, 40 seconds, 50 seconds, 60 seconds, 70 seconds, 80 seconds, 90 seconds, 100 seconds, 110 seconds, 120 seconds, 130 seconds, 140 seconds, 150 seconds, 160 seconds, 170 seconds, or 180 seconds.

[0062] In addition, the annealing temperature during the annealing process is 400° C. to 1200° C., and of course, the annealing temperature can be adjusted according to actual needs. For example, the annealing temperature is 400° C., 500° C., 600° C., 700° C., 800° C., 900° C., 1000° C., 1100° C., or 1200° C.

[0063] During the annealing process, infrared rays or resistance wires can be used for heating, which is easy to operate and has low cost. Of course, other heating methods can also be used, which are not limited here.

[0064] Depending on actual needs, the material of the thin film grown on the substrate surface includes C, Al, Si, Ti, Fe, Co, Ni, Cu, Zn, Ga, Ge, Mo, Ru, Rh, Pd, Ag, Ta, W, Os, Ir, and / or Pt. Of course, the material of the thin film grown on the substrate surface may also include other materials, which are not limited here. Suitable first precursors and second precursors can be selected according to needs.

[0065] The first precursor includes silicon tetrachloride, molybdenum hexafluoride, tungsten hexafluoride, TMA (trimethylamine), and / or molybdenum hexacarbonyl. The second precursor includes disilane, hydrogen, and / or hydrogen sulfide. Of course, the first and second precursors may also be any other type of substances, which are not limited here.

[0066] The substrate may be a SiO2 / Si substrate, a Si substrate, a sapphire substrate or a quartz substrate. Of course, the substrate may also be made of other materials.

[0067] Before placing the substrate in the reaction chamber, at least one functional layer may be processed on the substrate surface. After the substrate is placed in the reaction chamber, a thin film is deposited on the functional layer on the substrate surface, thereby facilitating the processing and manufacturing of various types of semiconductor thin films.

[0068] Before placing the substrate in the reaction chamber, the surface of the substrate is cleaned to prevent impurities remaining on the substrate surface from affecting the quality of the growing film.

[0069] Example 1:

[0070] A silicon substrate, silicon / silicon oxide substrate, or sapphire substrate is placed in a reaction chamber, which is evacuated. The pipeline, first precursor, and second precursor are heated. The heating temperature of the first and second precursors can be determined based on the saturated vapor pressure of the substances and the peak pressure on the device. In this example, a single-element silicon thin film is grown using silicon tetrachloride as the first precursor and disilane as the second precursor. The heating temperature of silicon tetrachloride is 0-100°C, with an optimal temperature of 40°C. The heating temperature of disilane is 0-120°C, with an optimal temperature of 26°C.

[0071] When the pipeline, the first precursor, and the second precursor are heated to the desired temperature and the vacuum degree in the reaction chamber meets the requirement, silicon tetrachloride is introduced into the reaction chamber for a time of 0.01-1s, preferably 0.1s. Then, argon is purged for 5-180s, preferably 60s. Thereafter, disilane is introduced into the reaction chamber for a time of 0.01-1s, preferably 0.05s. Argon is purged again for 5-180s, preferably 60s. The carrier gas flow rate of silicon tetrachloride and disilane can be 10-150sccm, preferably 20sccm.

[0072] The substrate surface is heated to the reaction temperature, and the process steps of introducing silicon tetrachloride and then purging with argon, and introducing disilane and then purging with argon are repeated. This cycle is repeated 10 times to grow 10 layers of thin film.

[0073] The elemental silicon film is annealed at a temperature of 400-1000°C, preferably 650°C. After the above steps are completed, argon is purged for 50s-800s to return to the reaction temperature. The process steps of introducing silicon tetrachloride, then purging with argon, and then introducing disilane, then purging with argon are repeated 10 times, and annealing is performed again. In this embodiment, the process steps of introducing silicon tetrachloride, then purging with argon, and then introducing disilane, then purging with argon are repeated 10 times between two adjacent annealing steps, for a total of 15 annealing steps.

[0074] Example 2:

[0075] A silicon substrate, silicon / silicon oxide substrate, or sapphire substrate is placed in a reaction chamber, which is evacuated. The pipeline, first precursor, and second precursor are heated. The heating temperature of the first and second precursors can be determined based on the saturated vapor pressure of the substances combined with the peak pressure on the device. In this embodiment, a single-element tungsten thin film is grown using tungsten hexafluoride as the first precursor and disilane as the second precursor. The heating temperature for tungsten hexafluoride is 0-120°C, with an optimal temperature of 26°C. The heating temperature for disilane is 0-120°C, with an optimal temperature of 26°C.

[0076] After the pipeline, the first precursor, and the second precursor are heated to the desired temperature and the vacuum level in the reaction chamber reaches the required level, tungsten hexafluoride is introduced into the reaction chamber for 0.01-1 second, preferably 0.05 second, followed by an argon purge for 5-180 seconds, preferably 60 seconds. Disilane is then introduced into the reaction chamber for 0.01-1 second, preferably 0.05 second, followed by an argon purge for 5-180 seconds, preferably 60 seconds. The carrier gas flow rate for tungsten hexafluoride and disilane can be 10-150 sccm, preferably 20 sccm.

[0077] The substrate surface is heated to the reaction temperature, and the process steps of introducing tungsten hexafluoride and then purging with argon, and introducing disilane and then purging with argon are repeated. This cycle is repeated 150 times to grow 150 layers of thin film.

[0078] The elemental tungsten film is annealed at a temperature of 400-1000°C. After the above steps are completed, argon is purged for 50s-800s to return to the reaction temperature. The process steps of introducing tungsten hexafluoride, then purging with argon, and then introducing disilane, then purging with argon are repeated 150 times, and annealing is performed again. In this embodiment, the process steps of introducing tungsten hexafluoride, then purging with argon, and then introducing disilane, then purging with argon are repeated 150 times between two adjacent annealing steps, for a total of 100 annealing steps.

[0079] Example 3:

[0080] A silicon substrate, a silicon / silicon oxide substrate, or a sapphire substrate is placed in a reaction chamber, which is evacuated. The pipeline, the first precursor, and the second precursor are heated. The heating temperature of the first precursor and the second precursor can be determined based on the saturated vapor pressure of the substance and the peak pressure on the device. In this embodiment, a single molybdenum thin film is grown, with molybdenum hexafluoride as the first precursor and disilane as the second precursor. The heating temperature of molybdenum hexafluoride is 0-100°C, with an optimal temperature of 40°C. The heating temperature of disilane is 0-120°C, with an optimal temperature of 26°C.

[0081] When the pipeline, the first precursor, and the second precursor are heated to the required temperature and the vacuum degree in the reaction chamber meets the requirement, molybdenum hexafluoride is introduced into the reaction chamber for a time of 0.01-1s, preferably 0.05s. Then argon is purged for 5-180s, preferably 60s. Thereafter, disilane is introduced into the reaction chamber for a time of 0.01-1s, preferably 0.05s. Argon is purged again for 5-180s, preferably 60s. The carrier gas flow rate of tungsten hexafluoride and disilane can be 5-100sccm, preferably 25sccm.

[0082] The substrate surface is heated to the reaction temperature, and the process steps of introducing molybdenum hexafluoride and then purging with argon, and introducing disilane and then purging with argon are repeated. This cycle is repeated 30 times to grow 30 layers of thin film.

[0083] The molybdenum thin film is annealed at a temperature of 50°C to 1000°C. After the above steps are completed, argon is purged for 200s to 800s to return to the reaction temperature. The process steps of introducing molybdenum hexafluoride, then purging with argon, and introducing disilane, then purging with argon are repeated 30 times, and annealing is performed again. In this embodiment, the process steps of introducing molybdenum hexafluoride, then purging with argon, and introducing disilane, then purging with argon are repeated 30 times between two adjacent annealing steps, for a total of five annealing steps.

[0084] In the description of the above embodiments, specific features, structures, materials or characteristics may be combined in an appropriate manner in any one or more embodiments or examples.

[0085] The above description is merely a specific embodiment of the present application, but the scope of protection of the present application is not limited thereto. Any changes or substitutions that can be easily conceived by a person skilled in the art within the technical scope disclosed in this application should be included in the scope of protection of this application. Therefore, the scope of protection of this application should be based on the scope of protection of the claims.

Claims

1. A thin film deposition method, characterized in that: include: Providing at least one substrate, and placing the substrate in a reaction chamber; heating the substrate to a first preset temperature; introducing a first precursor into the reaction chamber, wherein the temperature of the first precursor is a second preset temperature, the introduction time of the first precursor is a first preset time period or the introduction amount of the first precursor is a first preset amount, and after stopping the introduction of the first precursor, introducing an inert gas into the reaction chamber for a second preset time period; introducing a second precursor into the reaction chamber, wherein the temperature of the second precursor is at a third preset temperature, the introduction time of the second precursor is a third preset time period or the introduction amount of the second precursor is a second preset amount, and after stopping the introduction of the second precursor, introducing an inert gas into the reaction chamber for a fourth preset time period, and growing a thin film on the surface of the substrate; Repeat the steps of heating the substrate until the second precursor is introduced n times, n≥1, so that a multilayer thin film grows on the surface of the substrate, and annealing is performed once every m layers of thin film grown on the surface of the substrate, m≥1; After the temperature in the reaction chamber drops to room temperature, the reaction chamber is inflated to normal pressure, and the substrate is taken out.

2. The thin film deposition method according to claim 1, wherein: In the step of introducing the first precursor into the reaction chamber, an inert gas is introduced into the reaction chamber at the same time as the first precursor is introduced into the reaction chamber; and / or, In the step of introducing the second precursor, an inert gas is introduced into the reaction chamber while the second precursor is introduced into the reaction chamber.

3. The thin film deposition method according to claim 2, wherein: The carrier gas flow rate of the inert gas is 5 sccm-100 sccm.

4. The thin film deposition method according to claim 1, wherein: The first preset temperature range is 80°C to 400°C; and / or, the temperature in the reaction chamber ranges from 0°C to 200°C; and / or, the second preset temperature range is 0°C to 200°C; and / or, the third preset temperature range is 0°C to 200°C.

5. The thin film deposition method according to claim 1, wherein: The first preset time period is 0.01s to 1s; and / or, the second preset time period is 5s to 180s; and / or, the third preset time period is 0.01s to 1s; and / or, the fourth preset time period is 5s to 180s.

6. The thin film deposition method according to claim 1, wherein: After each annealing, introducing an inert gas into the reaction chamber for a fifth preset time period; The fifth preset time period is 5s to 180s.

7. The thin film deposition method according to claim 1, wherein: During the annealing process, the annealing temperature is 400° C. to 1200° C.; and / or, In the annealing process, infrared rays or resistance wires are used for heating.

8. The thin film deposition method according to claim 1, wherein: The material of the thin film grown on the substrate surface includes C, Al, Si, Ti, Fe, Co, Ni, Cu, Zn, Ga, Ge, Mo, Ru, Rh, Pd, Ag, Ta, W, Os, Ir and / or Pt; and / or, The substrate is a SiO2 / Si substrate, a Si substrate, a sapphire substrate or a quartz substrate.

9. The thin film deposition method according to claim 1, wherein: Before placing the substrate in a reaction chamber, processing at least one functional layer on the base surface of the substrate; And / or, before placing the substrate in the reaction chamber, the surface of the substrate is cleaned.

10. The thin film deposition method according to claim 1, wherein: The first precursor includes silicon tetrachloride, molybdenum hexafluoride, tungsten hexafluoride, TMA and / or molybdenum hexacarbonyl; and / or, The second precursor includes disilane, hydrogen and / or hydrogen sulfide.

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