Method and apparatus for depositing thin films and thin films

Abstract

The present disclosure relates to a method and apparatus for depositing a thin film, and the thin film. According to one embodiment of the present disclosure, a method for depositing a thin film includes providing a substrate in a reaction chamber having one or more first chemical reactant outlets and one or more second chemical reactant outlets that are spatially independent from the one or more first chemical reactant outlets, and moving the substrate relative to the one or more first chemical reactant outlets and the one or more second chemical reactant outlets, and at least one of the first chemical reactant passing through the first chemical reactant outlet and the second chemical reactant passing through the second chemical reactant outlet is applied to the substrate in a pulsed manner.

Description

[Technical field]

[0001] FIELD OF THE DISCLOSURE The present disclosure relates generally to the field of semiconductor manufacturing, and more particularly to methods and apparatus for depositing thin films, and thin films. [Background technology]

[0002] Atomic layer deposition (ALD) technology has been widely used in the fields of semiconductors, new energy, etc., due to its advantages of dense films, high uniformity, and good step coverage. Based on this, a new technology called spatial atomic layer deposition (SALD) has also been developed. In an ideal spatial atomic layer deposition approach, the reaction cycle is performed in a spatial position sequence, and the substrate or base is exposed to a first chemical reactant and a second chemical reactant in the transfer process, so that the different chemical reactants or chemical raw materials are spatially separated, thereby realizing thin film deposition by layer-by-layer stacking. Since the separation is based on space rather than time, the deposition rate is increased, and as a result, the deposition time of spatial atomic layer deposition can be significantly shortened compared to the time required for the reaction cycle of traditional ALD.

[0003] However, in order to improve the performance of mass production in the actual mass production process, it is difficult to completely separate different chemical reactants, and undesirable chemical vapor deposition (CVD) may occur near the spray hole, in the exhaust tank, or in the area where the chemical raw materials are diffused. When the machine is operated for a long time, powder will accumulate in the CVD area and cause a certain degree of peeling. As a result, the accumulated powder will fall onto the surface of the product, thereby affecting the appearance, performance, and other various aspects of the product. At present, such problems can only be solved by expanding the machine body or shortening the maintenance interval of the machine and performing frequent maintenance, which increases the cost of the machine.

[0004] In view of this, there is an urgent need in the art to provide improved solutions to solve the above problems. Summary of the Invention [Problem to be solved by the invention]

[0005] In view of this, the present disclosure provides a method and apparatus for depositing a thin film, and a thin film, to at least address the above technical problems. [Means for solving the problem]

[0006] According to one embodiment of the present disclosure, the present disclosure provides a method of depositing a thin film, comprising the steps of: providing a substrate into a reaction chamber having one or more first chemical reactant outlets and one or more second chemical reactant outlets spatially independent from the one or more first chemical reactant outlets; and moving the substrate relative to the one or more first chemical reactant outlets and the one or more second chemical reactant outlets, wherein at least one of the first chemical reactants passing through the first chemical reactant outlets and the second chemical reactants passing through the second chemical reactant outlets are applied to the substrate in a pulsed manner.

[0007] According to another embodiment of the present disclosure, the substrate has an upper surface and a lower surface, and the one or more first chemical reactant outlets and the one or more second chemical reactant outlets are on opposite sides of at least one of the upper and lower surfaces of the substrate.

[0008] According to another embodiment of the present disclosure, the method of depositing a thin film further includes one or more purge outlets located between the one or more first chemical reactant outlets and the one or more second chemical reactant outlets.

[0009] According to another embodiment of the present disclosure, the method of depositing a thin film further includes constantly directing a first inert gas to the substrate through one or more purge outlets.

[0010] According to another embodiment of the present disclosure, in a method of depositing a thin film, the first inert gas comprises argon or nitrogen.

[0011] According to another embodiment of the present disclosure, the method of depositing a thin film further includes a first exhaust outlet located between the one or more first chemical reactant outlets and the one or more purge outlets, and a second exhaust outlet located between the one or more second chemical reactant outlets and the one or more purge outlets, the first exhaust outlet exhausting the first chemical reactant from the reaction chamber, and the second exhaust outlet exhausting the second chemical reactant from the reaction chamber.

[0012] According to another embodiment of the present disclosure, the first exhaust outlet and / or the second exhaust outlet include a throttling device.

[0013] According to another embodiment of the present disclosure, in the method of depositing a thin film, the relative movement includes rotating, advancing, or rocking.

[0014] According to another embodiment of the present disclosure, in a method of depositing a thin film, a first chemical reactant and / or a second chemical reactant are introduced into a reaction chamber by using a second inert gas as a carrier gas.

[0015] According to another embodiment of the present disclosure, in the method of depositing a thin film, the second inert gas comprises argon or nitrogen.

[0016] According to another embodiment of the present disclosure, in the method for depositing a thin film, the reaction temperature of the reaction chamber is 25°C to 400°C.

[0017] According to another embodiment of the present disclosure, in a method of depositing a thin film, the substrate comprises a flexible thin film, glass, or a silicon wafer, and the flexible thin film comprises polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polyimide (PI).

[0018] According to another embodiment of the present disclosure, in a method of depositing a thin film, a first chemical reactant is applied to a substrate in a pulsed manner and a second chemical reactant is applied to the substrate constantly.

[0019] According to another embodiment of the present disclosure, in a method of depositing a thin film, a first chemical reactant and a second chemical reactant are applied to a substrate in a gapless, alternating pulse configuration.

[0020] According to another embodiment of the present disclosure, in a method of depositing a thin film, a first chemical reactant and a second chemical reactant are applied to a substrate in an alternating pulse shape at a source intersection.

[0021] According to another embodiment of the present disclosure, in a method of depositing a thin film, a first chemical reactant and a second chemical reactant are applied to a substrate in a source gap alternating pulse configuration.

[0022] According to one embodiment of the present disclosure, the present disclosure provides an apparatus for depositing a thin film, the apparatus comprising: one or more first chemical reactant outlets for supplying a first chemical reactant into a reaction chamber; one or more second chemical reactant outlets spatially independent from the one or more first chemical reactant outlets for supplying a second chemical reactant into the reaction chamber; a transfer assembly for moving a substrate relative to the one or more first chemical reactant outlets and the one or more second chemical reactant outlets; an intake control assembly for pulsing at least one of the first chemical reactant and the second chemical reactant to the substrate; and an exhaust assembly for exhausting the first chemical reactant and the second chemical reactant from the reaction chamber.

[0023] According to another embodiment of the present disclosure, an intake control assembly includes a first intake control valve for controlling a first chemical reactant to be applied to a substrate in a pulsed manner and a second intake control valve for controlling a second chemical reactant to be applied to the substrate in a pulsed manner.

[0024] According to another embodiment of the present disclosure, the apparatus for depositing thin films further comprises one or more purge outlets located between the one or more first chemical reactant outlets and the one or more second chemical reactant outlets.

[0025] According to another embodiment of the present disclosure, the exhaust assembly further includes a first exhaust outlet located between the one or more first chemical reactant outlets and the one or more purge outlets for exhausting a first chemical reactant from the reaction chamber, and a second exhaust outlet located between the one or more second chemical reactant outlets and the one or more purge outlets for exhausting a second chemical reactant from the reaction chamber.

[0026] According to other embodiments of the present disclosure, the present disclosure further provides a thin film formed by any one of the above apparatuses or formed on a substrate by any one of the above methods. It is to be understood that the broad aspects of the present disclosure and their respective features may be used in combination, interchangeably, and / or independently and are not to be used as limiting references to the individual broad aspects.

[0027] Various aspects of the present disclosure can be readily understood by reading the following detailed description in conjunction with the accompanying drawings, in which: It is noted that the various features may not be drawn to scale, and in fact the dimensions of the various features may be arbitrarily increased or decreased for clarity. [Brief description of the drawings]

[0028] [Figure 1] FIG. 1 illustrates a prior art method for depositing thin films. [Diagram 2] 1 illustrates a method of depositing a thin film according to one embodiment of the present disclosure. [Figure 3A] FIG. 1 illustrates a chemical reactant single pulse application geometry according to one embodiment of the present disclosure. [Figure 3B] FIG. 1 illustrates a chemical reactant gapless alternating pulse application configuration according to one embodiment of the present disclosure. [Figure 3C] FIG. 13 illustrates an application shape of chemical reactant source intersection alternating pulses according to one embodiment of the present disclosure. [Figure 3D] FIG. 1 illustrates a chemical reactant source gap alternating pulse application profile according to one embodiment of the present disclosure. [Figure 4A] 1 is a schematic cross-sectional view illustrating an apparatus for depositing a thin film at a first time according to one embodiment of the present disclosure. [Figure 4B] 4 is a schematic cross-sectional view of an apparatus for depositing a thin film at a second time according to one embodiment of the present disclosure. [Diagram 5] 1 is a schematic cross-sectional view illustrating an apparatus for depositing thin films according to another embodiment of the present disclosure.

[0029] According to common practice, the various features illustrated in the drawings may not be drawn to actual scale. Thus, for clarity, the dimensions of the various features may be arbitrarily increased or decreased. The shapes of the components illustrated in the drawings are merely exemplary shapes and are not intended to limit the actual shapes of the components. Moreover, for clarity, the embodiments illustrated in the drawings may be simplified. Thus, the drawings may not depict all of the components of a given apparatus or device or all of the steps of a method. Finally, like reference numerals may be used throughout the specification and drawings to denote like features. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0030] In order to better understand the gist of the present disclosure, the present disclosure will be further described below along with some preferred embodiments thereof.

[0031] The following disclosure provides various embodiments or examples that can be used to realize different features of the present disclosure. The specific examples of assemblies and configurations described below are intended to simplify the present disclosure. It should be understood that the descriptions are merely examples and are not intended to limit the present disclosure. For example, in the following description, forming a first feature on a second feature may include, in some embodiments, the first feature and the second feature being in direct contact with each other, and may also include, in some embodiments, forming an additional assembly between the first feature and the second feature such that the first feature and the second feature are not in direct contact with each other. Also, the present disclosure may reuse symbols and / or numbers of assemblies in multiple embodiments. This reuse is for the purpose of brevity and clarity, and does not in itself represent a relationship between the various embodiments or configurations described.

[0032] In this specification, unless specified or limited, relative terms such as "center," "vertical," "lateral," "front," "rear," "right," "left," "inner," "outer," "low," "high," "horizontal," "vertical," "higher," "lower," "upper," "lower," "top," and "bottom," and their derivatives (e.g., "horizontally," "below," and "upper") should be construed as referring to directions in the description or drawings. These relative terms are used for convenience of description only and do not require that the present disclosure be constructed or operated in a particular orientation.

[0033] Various embodiments of the present disclosure are described in detail below. Although specific embodiments are described, it should be understood that these embodiments are used for illustrative purposes only. Those skilled in the art will understand that other components and configurations can be used without departing from the spirit and scope of the present disclosure. The implementation of the present disclosure does not necessarily include all the components or steps of the embodiments described in the specification, and the execution order of the steps may be adjusted according to the actual application.

[0034] As described above, the present application provides a method and apparatus for depositing thin films to solve the problems of powder build-up and delamination in existing spatial atomic layer deposition apparatus and to prepare higher quality thin films.

[0035] FIG. 1 shows a method for depositing a thin film in the prior art. As shown in FIG. 1, the method for depositing a thin film includes the steps of: providing a substrate having a first surface in a reaction chamber, and moving the substrate relative to one or more first chemical reactant outlets, one or more second chemical reactant outlets, and an exhaust port in the reaction chamber (S11); moving the substrate to a first region corresponding to the first chemical reactant outlet, and applying a first chemical reactant through the first chemical reactant outlet in a constantly open manner to the first surface of the substrate (S12); and further moving the substrate to a second region corresponding to the second chemical reactant outlet, and applying a second chemical reactant through the second chemical reactant outlet in a constantly open manner to the first surface of the substrate (S13). After step (S13) is performed, if the deposition of the thin film is completed, the operation can be terminated. If the deposition of the thin film is not completed, step (S12) and step (S13) can be repeated until the deposition of the thin film is completed and the operation is terminated.

[0036] In the operation steps shown in FIG. 1, both the first and second different chemical reactants are applied to the first surface of the substrate in a constantly open state. Constantly open state not only increases the consumption of chemical reactants, but also causes chemical vapor deposition of the two different chemical reactants near the spray hole, in the exhaust tank and in the chemical source diffusion area, which causes powder accumulation. If the accumulated powder breaks off and falls onto the first surface of the substrate, it will adversely affect the appearance, performance and various aspects of the product. Such problems can be solved by shortening the maintenance interval of the machine and performing maintenance more frequently, or by expanding the machine body for better compartmentalization, etc., but this will inevitably increase the cost of the machine and will not help reduce the consumption of chemical reactants.

[0037] FIG. 2 illustrates a method of depositing a thin film according to one embodiment of the present disclosure. As shown in FIG. 2, the method of depositing a thin film includes the steps of: providing a substrate having a first surface into a reaction chamber; moving the substrate in the reaction chamber relative to one or more first chemical reactant outlets, one or more second chemical reactant outlets, and an exhaust port (S21); if the substrate is moved to one or more first regions corresponding to the one or more first chemical reactant outlets, applying a first chemical reactant to the first surface through the one or more first chemical reactant outlets (S22); purging the first surface of the substrate by constantly introducing an inert gas from an inert gas outlet in the reaction chamber (S23); and if the substrate is moved to one or more second regions corresponding to the one or more second chemical reactant outlets, depositing a thin film on the first surface by applying a second chemical reactant to the first surface through the one or more second chemical reactant outlets (S24), where at least one of the first chemical reactant and the second chemical reactant is applied to the first surface in a pulsed manner. In some embodiments, after step (S24) is performed, if the deposition of the thin film is complete, the operation may be terminated. If the deposition of the thin film is not complete, steps (S22)-(S24) may be repeated one or more times until the deposition of the thin film is complete and the operation is terminated.

[0038] In some embodiments, a total of 63 pairs of first and second chemical reactant outlets may be arranged in a period of a first set of first and second chemical reactant outlets, a second set of first and second chemical reactant outlets, ...63 pairs of first and second chemical reactant outlets. It should be understood that the number of pairs of first and second chemical reactant outlets is not limited to 63 and may be any number. It should also be understood that one or more first regions correspond to one or more first chemical reactant outlets, one or more second regions correspond to one or more second chemical reactant outlets, and one or more first chemical reactant outlets are spatially separated from one or more second chemical reactant outlets, such that one or more first regions are also spatially separated from one or more second regions.

[0039] In some embodiments, the relative movement of the substrate with respect to the one or more first chemical reactant outlets, the one or more second chemical reactant outlets, and the exhaust port can include, but is not limited to, rotating, advancing, or rocking. In one embodiment, the substrate can be any suitable silicon-containing substrate or base for manufacturing semiconductor devices (e.g., photovoltaic panels) and can have any suitable shape and size. For example, the substrate can include, but is not limited to, a flexible thin film, glass, or silicon wafer, and the flexible thin film can include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide (PI), and other materials.

[0040] In some embodiments, the first and second chemical reactants may be any suitable chemicals for depositing a thin film and may be selected according to the type and deposition method of the thin film. In one embodiment, the first chemical reactant may include at least one of trimethylaluminum (Al(CH3)3), dimethylisopropoxyaluminum ((CH3)2AlOCH(CH3)2), aluminum trichloride (AlCl3), or dimethylaluminum chloride (AlCl(CH3)2). The second chemical reactant may include at least one of oxygen (O2), water (H2O), ozone (O3), hydrogen peroxide (H2O2), or plasma excited oxygen. In another embodiment, the first and / or second chemical reactants may be introduced into the reaction chamber by using an inert gas as a carrier gas. For example, trimethylaluminum vapor may be introduced into the reaction chamber and directed toward the first surface using nitrogen as a carrier gas, and / or water vapor may be introduced into the reaction chamber and directed toward the first surface using nitrogen as a carrier gas.

[0041] In some embodiments, one or more first chemical reactant outlets and one or more second chemical reactant outlets may be separated by an inert gas outlet, i.e., the substrate may be moved sequentially from a first region corresponding to the first chemical reactant outlet, to a purge region corresponding to the inert gas outlet, to a second region corresponding to the second chemical reactant outlet to complete one full deposition cycle.

[0042] In some embodiments, the exhaust port may be located at any suitable location within the reaction chamber that can reliably exhaust the reactants. The number of exhaust ports may not be limited to one. In one embodiment, the exhaust port may have a throttling device to better control the flow rate, flow velocity, and other parameters associated with the exhaust of the chemical reactants.

[0043] In some embodiments, the reaction temperature of the reaction chamber may be set at 25° C. to 400° C., or any reaction temperature range suitable for the coating operation.

[0044] In the steps of the method for depositing a thin film shown in FIG. 2, it is to be understood that the purge step (S23) is a non-reaction step, and generally, the purge step can be performed with a gas that does not participate in the deposition reaction to remove excess reaction products and chemical reactants that have not reacted in time. For example, the purge can be performed with nitrogen or other inert gas (e.g., argon). However, the purge step (S23) is not a required step. The reason is that the first and second chemical reactants are applied through the spatially separated first and second chemical reactant outlets, so there is no need to perform an inert gas purge between the first and second chemical reactants. Therefore, there is no need to arrange an inert gas outlet between the first and second chemical reactant outlets in the reaction chamber.

[0045] It should also be appreciated that the first chemical reactant and the second chemical reactant may be applied to the first surface of the substrate with various pulse shapes, and the method of depositing a thin film in the present disclosure can reduce powder buildup and flaking, and extend machine maintenance intervals by designing the pulse shapes in step (S23) and / or step (S24), thus reducing machine costs, reducing chemical reactant consumption, and improving the quality of the formed film. Various pulse shapes in the present disclosure are described in detail below with reference to Figures 3A-3D.

[0046] 3A shows a chemical reactant single pulse application configuration according to one embodiment of the present disclosure. As shown in FIG. 3A, the first chemical reactant outlet is switched between an "open" state and a "closed" state, and the second chemical reactant outlet is always in the "open" state, so that the first chemical reactant is applied to the first surface of the substrate in a pulsed manner, and the second chemical reactant is always open and applied to the first surface of the substrate. In FIG. 3A, it should be understood that the pulse period T1 and the pause period T2 of the first chemical reactant may have a certain proportional relationship according to specific requirements.

[0047] In one embodiment, the temperature of the reaction chamber may be set to 120° C., the reaction chamber may be configured to include 63 pairs of first and second chemical reactant outlets, the first chemical reactant may be set to trimethylaluminum vapor (as described above, nitrogen may be used as a carrier gas to carry the first chemical reactant, trimethylaluminum vapor), and the second chemical reactant may be set to water vapor (as described above, nitrogen may be used as a carrier gas to carry the second chemical reactant, water vapor).

[0048] In this state, a substrate (e.g., a flexible PET substrate) can be advanced in the reaction chamber to move relative to the first chemical reactant outlet and the second chemical reactant, and the first chemical reactant can be introduced with a pulse period T1 of 0.5 seconds and a pause period T2 of 0.5 seconds to form an aluminum oxide (Al2O3) coating on a first surface of the substrate. Specifically, in one embodiment, during the T1+T2 period, the first deposition target area of ​​the substrate is in a first area corresponding to the first chemical reactant outlet. Then, during the T2+T1 period, the first deposition target area moves from the first area to a second area corresponding to the second chemical reactant outlet. Compared with the prior art where the first and second chemical reactants are both always on, the above embodiment can at least partially shorten the time for the first and second chemical reactants to contact and chemical vapor deposit near the spray holes, in the exhaust pipe, and / or in the chemical feedstock diffusion area, reduce the consumption of the first chemical reactant by half, and reduce the accumulation of powder near the spray holes, in the exhaust pipe, and / or in the chemical feedstock diffusion area.

[0049] After coating is completed, the thickness of the aluminum oxide coating may be further measured at multiple locations. For example, on the one hand, a coating may be formed in a two-source always-on mode (i.e., both the first and second chemical reactants are always on) as is common in the prior art, and the coating thickness and average thickness may be obtained at 10 locations after coating is completed. On the other hand, a coating may be formed in a single-pulse mode (i.e., only the first chemical reactant is pulsed) as shown in FIG. 3A of the present disclosure, and the coating thickness and average thickness may be obtained at substantially the same 10 locations after coating is completed.

[0050] Table 1 below shows data comparing the coating thickness obtained with the conventional two-ingredient continuous open coating method and the single pulse coating method. [Table 1]

[0051] When a 0.5 second-0.5 second single pulse method is used to form the coating, the consumption of the first chemical reactant and the accumulation of powder can be reduced by half, provided that the thickness (e.g., average thickness) of the coating remains essentially unchanged.

[0052] 3B illustrates a chemical reactant gapless alternating pulse application configuration according to one embodiment of the present disclosure. Unlike the chemical reactant single pulse application configuration illustrated in FIG. 3A, in FIG. 3B, the first chemical reactant and the second chemical reactant are both applied to the first surface of the substrate in pulses. Thus, both the first chemical reactant outlet and the second chemical reactant outlet can be switched between an "open" state and a "closed" state.

[0053] 3B, the pulse period T1 of the first chemical reactant corresponds to the pause period T2' of the second chemical reactant, and the pause period T2 of the first chemical reactant corresponds to the pulse period T1' of the second chemical reactant. In this manner, the first chemical reactant and the second chemical reactant can be applied to the first surface of the substrate in a gapless alternating pulse shape, since the pulse edges of the first chemical reactant and the pulse edges of the second chemical reactant are all aligned.

[0054] In FIG. 3B, it should be understood that as long as the pulse edges of the two chemical reactants are aligned, the pulse period T1 and the pause period T2 of the first chemical reactant may have a certain proportional relationship according to specific requirements, and similarly, the pulse period T1' and the pause period T2' of the second chemical reactant may have a certain proportional relationship according to specific requirements.

[0055] In one embodiment, the temperature of the reaction chamber may be set to 250° C., the reaction chamber may be set to include 21 pairs of first and second chemical reactant outlets, the first chemical reactant may be set to diethylzinc vapor, and the second chemical reactant may be set to water vapor. In this state, a substrate (e.g., a glass substrate) is advanced in the reaction chamber so as to move relative to the first and second chemical reactant outlets, the first chemical reactant is introduced with a pulse period T1 of 0.5 seconds and a pause period T2 of 0.5 seconds, and the second chemical reactant is introduced with a pause period T2′ of 0.5 seconds and a pulse period T1′ of 0.5 seconds, thereby forming a zinc oxide (ZnO) coating on a first surface of the substrate. Specifically, in one embodiment, in the T1+T2 period, the first deposition target area of ​​the substrate is present in a first area corresponding to the first chemical reactant outlet. Then, in the period T2'+T1', the first deposition target area moves from the first area to the second area corresponding to the second chemical reactant outlet. Compared with the prior art in which the first and second chemical reactants are both always open, the above embodiment can at least partially shorten the time that the first and second chemical reactants contact and chemical vapor deposit near the spray hole, in the exhaust pipe, and / or in the chemical raw material diffusion area, reduce the consumption of the first and second chemical reactants by half, and reduce the accumulation of powder near the spray hole, in the exhaust pipe, and / or in the chemical raw material diffusion area.

[0056] After coating is completed, the thickness of the ZnO coating may be further measured at multiple locations. For example, on the one hand, the coating may be formed in a two-source always-on mode (i.e., both the first and second chemical reactants are always on) as is common in the prior art, and the coating thickness and average thickness may be obtained at 10 locations after coating is completed. On the other hand, the coating may be formed by a gapless alternating pulse mode as shown in FIG. 3B of the present disclosure, and the coating thickness and average thickness may be obtained at substantially the same 10 locations after coating is completed.

[0057] Table 2 below shows data comparing the coating thickness obtained with a conventional two-source constantly open coating method and a gapless alternating pulse coating method. [Table 2]

[0058] When a 0.5 second-0.5 second gapless alternating pulse method is used to form the coating, the consumption of the first and second chemical reactants can be reduced by half and the powder accumulation can be reduced by three-quarters, under the condition that the thickness (e.g., average thickness) of the coating is essentially unchanged.

[0059] FIG. 3C illustrates a chemical reactant source intersection alternating pulse application shape according to one embodiment of the present disclosure. Unlike the chemical reactant gapless alternating pulse application shape illustrated in FIG. 3B, in FIG. 3C, the first chemical reactant and the second chemical reactant are both applied to the first surface of the substrate in a pulsed manner, but the pulse period T1 of the first chemical reactant and the pulse period T1' of the second chemical reactant have an intersection O, and thus is referred to as a reactant source intersection alternating pulse shape. In this manner, the first chemical reactant and the second chemical reactant can be applied to the first surface of the substrate with a chemical reactant source intersection alternating pulse shape.

[0060] In FIG. 3C, it should be understood that the pulse period T1 and the pause period T2 of the first chemical reactant may have a certain proportional relationship according to specific requirements, and similarly, the pulse period T1' and the pause period T2' of the second chemical reactant may have a certain proportional relationship according to specific requirements, as long as the pulse periods of the two chemical reactants have an intersection.

[0061] In this state, a substrate (e.g., a silicon wafer) can be advanced within the reaction chamber in relative movement with respect to the first chemical reactant outlet and the second chemical reactant, the first chemical reactant being introduced during a pulse period T1 and a pause period T2, and the second chemical reactant being introduced during a pause period T2' and a pulse period T1' to form a coating on a first surface of the substrate. Specifically, in one embodiment, during a period T1+T2, the first deposition target region of the substrate is in a first region corresponding to the first chemical reactant outlet. Then, during a period T2'+T1', the first deposition target region moves from the first region to a second region corresponding to the second chemical reactant outlet. Compared with the prior art in which the first and second chemical reactants are both always on, the above embodiment can at least partially shorten the time for the first and second chemical reactants to contact and chemical vapor deposit near the spray holes, in the exhaust pipe, and / or in the chemical feedstock diffusion area, reduce the consumption of the first and second chemical reactants by half, and reduce the accumulation of powder near the spray holes, in the exhaust pipe, and / or in the chemical feedstock diffusion area.

[0062] FIG. 3D illustrates a chemical reactant source gap alternating pulse application shape according to one embodiment of the present disclosure. Unlike the chemical reactant intersection alternating pulse application shape illustrated in FIG. 3C, in FIG. 3D, the first chemical reactant and the second chemical reactant are both applied to the first surface of the substrate in a pulsed manner, but there is no intersection between the pulse period T1 of the first chemical reactant and the pulse period T1' of the second chemical reactant, with a gap G. Thus, it is referred to as a reactant source gap alternating pulse shape. In this case, the first chemical reactant and the second chemical reactant can be applied to the first surface of the substrate with a chemical reactant source gap alternating pulse shape.

[0063] In FIG. 3D, it should be understood that as long as the pulse periods of the two chemical reactants have a gap, the pulse period T1 and the pause period T2 of the first chemical reactant may have a certain proportional relationship according to specific requirements, and similarly, the pulse period T1' and the pause period T2' of the second chemical reactant may have a certain proportional relationship according to specific requirements.

[0064] In this state, a substrate (e.g., a semiconductor wafer) can be advanced within the reaction chamber to move relative to the first chemical reactant outlet and the second chemical reactant, where the first chemical reactant is introduced during pulse periods T1 and pause periods T2, and the second chemical reactant is introduced during pulse periods T1' and pause periods T2', to form a coating on a first surface of the substrate. Specifically, in one embodiment, during the period T1+T2, the first deposition target region of the substrate is in a first region corresponding to the first chemical reactant outlet. Then, during the period T1'+T2', the first deposition target region moves from the first region to a second region corresponding to the second chemical reactant outlet. Compared with the prior art where the first and second chemical reactants are both always on, the above embodiment can at least partially shorten the time for the first and second chemical reactants to contact and undergo chemical vapor deposition near the spray holes, in the exhaust pipe, and / or in the chemical feedstock diffusion area, reduce consumption of the first and second chemical reactants, and reduce powder accumulation near the spray holes, in the exhaust pipe, and / or in the chemical feedstock diffusion area.

[0065] In this way, the gases can be exhausted using one and the same exhaust system. Since the two chemical reactants are both introduced in a staggered manner in a pulsed manner, there is no need to place separate exhausts or add purge gas between the chemical reactant outlets. That is, no purge outlets are placed between the different reactant outlets, and one and the same exhaust is used. This ensures a reduction in powder buildup, while simplifying and miniaturizing the device, reducing costs and extending maintenance intervals.

[0066] FIG. 4A is a schematic cross-sectional view of an apparatus for depositing a thin film at a first time according to an embodiment of the present disclosure. As shown in FIG. 4A, the apparatus for depositing a thin film (400) has a plurality of gas ports (405) located on a cover plate (404). The plurality of gas ports (405) include a first chemical reactant outlet and a second chemical reactant outlet that are spatially independent from each other. The first chemical reactant outlet can be configured to supply a first chemical reactant (Gas A) into the reaction chamber (40) of the apparatus for depositing a thin film (400), and the second chemical reactant outlet can be configured to supply a second chemical reactant (Gas B) into the reaction chamber (40). On both sides of the first chemical reactant outlet, there are exhaust ports (A pumps) that can exhaust excess Gas A in the reaction chamber (40) by the action of a Gas A exhaust pump outside the reaction chamber (40). Similarly, on either side of the second chemical reactant outlet, there are exhaust ports (B pumps) that can exhaust excess Gas B within the reaction chamber (40) by the action of a Gas B exhaust pump outside the reaction chamber (40). It should be understood that the apparatus (400) for depositing a thin film can further include a pedestal (401).

[0067] In one embodiment, the first and second chemical reactant outlets may receive a first chemical reactant (Gas A) and a second chemical reactant (Gas B) from outside the reaction chamber (40) under the control of the intake control assemblies (406, 407). In this manner, the intake control assemblies (406, 407) may control at least one of the first and second chemical reactants to be applied to the substrate (403) in a pulsed manner as described above in FIGS. 2-3D. In one embodiment, the first intake control valve (406) may be used to control the first chemical reactant to be applied to the substrate in a pulsed manner, and the second intake control valve (407) may be used to control the second chemical reactant to be applied to the substrate in a pulsed manner. It should be understood that the intake control assembly is not limited to the first intake control valve (406) and the second intake control valve (407) and that any suitable assembly for controlling the delivery of chemical reactants may be used.

[0068] In other embodiments, a purge outlet may be further disposed between the first and second chemical reactant outlets. The purge outlet may receive a purge gas (e.g., an inert gas such as argon or nitrogen) from outside the reaction chamber (40) and direct the purge gas to the substrate (403) to purge the surface of the substrate (403). In this case, a first exhaust outlet is located between the first chemical reactant outlet and the purge outlet, and a second exhaust outlet is located between the second chemical reactant outlet and the purge outlet. However, it should be understood that the thin film deposition apparatus (400) does not necessarily have to have a purge outlet, and the first and second exhaust outlets may be combined into one exhaust outlet, and excess gas A and excess gas B in the reaction chamber (40) may be exhausted through the same exhaust outlet assembly.

[0069] The thin film deposition apparatus (400) further includes a transport assembly (402) that can move along a track or any suitable moving mechanism. The transport assembly (402) can, for example, but not limited to, move horizontally back and forth within the reaction chamber (40) along a linear path (as indicated by the double-headed arrow in FIG. 4A). In this manner, the transport assembly (402) can move horizontally back and forth within the reaction chamber (40) of the thin film deposition apparatus (400) carrying the substrate (403). As a result, the substrate (403) moves relative to the first and second chemical reactant outlets. It should be understood that the substrate (403) can be, for example, a processed element such as a chip or a wafer. The substrate (403) can also be a free-standing substrate or a continuous substrate (for example, but not limited to, a flexible substrate and a rolled substrate), allowing for flexibility in the thin film deposition apparatus (400). One skilled in the art will appreciate that the substrate (403) may be a bare substrate or a substrate having one or more films or features deposited thereon, and may be, for example, one or more of silicon, silicon germanium, gallium arsenide, gallium nitride, germanium, gallium phosphide, indium phosphide, sapphire, or silicon carbide.

[0070] Figure 4A shows the transient positions of a substrate (403) moving horizontally from left to right relative to a first and second chemical reactant outlets until time T1, at which time a first chemical reactant (Gas A), a second chemical reactant (Gas B), and a second chemical reactant (Gas A) are simultaneously deposited on the top surface of the substrate (403) at three locations (as shown by the three dashed boxes in Figure 4A) from left to right (as shown by the three downward arrows in Figure 4A). The relative movement of the substrate (403) allows different reactants to be deposited on the substrate (403), as described below.

[0071] FIG. 4B is a schematic cross-sectional view of an apparatus for depositing a thin film at a second time according to an embodiment of the present disclosure. The apparatus for depositing a thin film in FIG. 4B has the same structure as the apparatus for depositing a thin film shown in FIG. 4A. The difference is that FIG. 4B shows the transient position of the substrate (403) moving further horizontally to the right relative to the first and second chemical reactant outlets until time T2. At time T2, the second chemical reactant (Gas B), the first chemical reactant (Gas A), and the second chemical reactant (Gas B) are simultaneously deposited on the top surface of the substrate (403) from left to right (as shown by the dashed boxes in FIG. 4B that correspond one-to-one to the three dashed boxes in FIG. 4A) at three locations. In this way, as the substrate (403) moves from time T1 to time T2, spatial atomic layer deposition of different chemical reactants (e.g., Gas A and Gas B) can be performed at three locations on the top surface of the substrate (403). The above three locations are merely examples, and in practice, the number of different locations or regions can be any number, and the number of first chemical reactant outlets and second chemical reactant outlets is not limited to the number shown in Figures 4A and 4B, but can be any required number.

[0072] FIG. 5 is a schematic cross-sectional view showing an apparatus for depositing a thin film according to another embodiment of the present disclosure. Unlike the apparatus for depositing a thin film shown in FIG. 4A and FIG. 4B, in the apparatus for depositing a thin film (500) shown in FIG. 5, the first and second chemical reactant outlets are arranged spatially independent from each other at the upper and lower parts of the reaction chamber (50), respectively, and the first and second chemical reactant outlets at the upper part and the first and second chemical reactant outlets at the lower part may preferably correspond to each other. The substrate (503) may move relative to the first and second chemical reactant outlets (e.g., horizontally reciprocating or moving in one direction) along a linear path in the reaction chamber (50). In this way, the apparatus for depositing a thin film (500) shown in FIG. 5 can perform spatial atomic layer deposition on both the upper and lower surfaces of the substrate (503), thereby further improving process efficiency.

[0073] In the apparatus for depositing a thin film, the first chemical reactant outlet, the second chemical reactant outlet, and the exhaust port can be movably arranged in the chamber, and the relative positions of the first chemical reactant outlet, the second chemical reactant outlet, and the exhaust port can be adjusted through a moving device. The first chemical reactant outlet, the second chemical reactant outlet, and the exhaust port can be arranged through independent mechanical structures, and multiple outlets and exhaust ports of different types can be arranged and adjusted separately. By adjusting the size of the first region and the second region, the duration of the substrate moving linearly through the first region and the second region can be adjusted, so that different process requirements for reaction under different reactant conditions and the duration of contact with gas can be met. The gas pressure in the first region and the second region can be adjusted simultaneously by a throttling device.

[0074] In the case of a linearly moving substrate, reactants are introduced in pulses as a location of the substrate passes through the first and second regions, so that the location of the substrate can be exposed to two or more pulses in the first and second regions to ensure completeness of the ALD half-reaction; introducing reactant gas in pulses can reduce contact between the two reactants, thereby reducing the probability and amount of dust generation, and shortening equipment maintenance time while ensuring quality.

[0075] Thus, the thin film deposition apparatus illustrated in Figures 4A-5 can deposit thin films on the top and / or bottom surfaces of a substrate by the method described in Figures 2-3D (i.e., by pulsing at least one of a first chemical reactant and a second chemical reactant to the substrate).

[0076] The method of depositing thin films provided in the present disclosure can reduce the probability of chemical vapor deposition of two different chemical reactants in a unit time, extend the time before powder buildup becomes significant, extend maintenance intervals (avoid frequent maintenance), and reduce equipment costs by increasing process efficiency.

[0077] In addition, the method of depositing a thin film provided in the present disclosure can significantly reduce the consumption of chemical reactants to form a coating, thereby increasing the utilization rate of chemical reactants and further reducing equipment costs. The present disclosure further provides an apparatus for depositing a thin film. The apparatus can deposit a thin film on a substrate by performing the method of depositing a thin film of the present disclosure. The apparatus for depositing a thin film of the present disclosure can effectively reduce powder accumulation and peeling, and extend the maintenance interval of the machine, thereby reducing the cost of the machine, reducing the consumption of chemical reactants, and forming a high-quality thin film.

[0078] It should be understood that the thin film depositing apparatus of the present disclosure is any suitable apparatus capable of carrying out the method of depositing a thin film of the present disclosure. In some embodiments, the thin film depositing apparatus of the present disclosure may be a chemical vapor deposition apparatus or an apparatus based on the working principle of chemical vapor deposition. In some embodiments, the thin film depositing apparatus of the present disclosure may be a plasma enhanced chemical vapor deposition apparatus, in which the plasma can reduce the surface binding energy of the chemical reactants, thereby facilitating the formation of the thin film. It should also be understood that the thin film depositing apparatus of the present disclosure can deposit thin films on silicon substrates in a batch manner to further increase production capacity.

[0079] The present disclosure further provides a thin film that can be formed by the disclosed thin film depositing apparatus. The present disclosure further provides a thin film that can be formed on a substrate by the disclosed thin film depositing method. The disclosed thin film has the advantages of being defect-free, highly uniform, high quality, etc.

[0080] The specification is written to enable any person skilled in the art to make or use the disclosure. Various modifications of the disclosure will be apparent to those skilled in the art, and the general principles defined herein can be applied to other modifications without departing from the spirit and scope of the disclosure. Thus, the disclosure is not limited to the examples and designs described herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

[0081] Up to now, the technical contents and features of the present disclosure have been described through the above-mentioned related embodiments, but the above-mentioned embodiments are merely examples for implementing the present disclosure. Those skilled in the art can make various substitutions and modifications based on the teachings of the present disclosure without departing from the spirit of the present disclosure. Therefore, the scope of the present disclosure is not limited by the embodiments of the present disclosure. On the contrary, all modifications and equivalent configurations falling within the spirit and scope of the claims are included in the scope of the present disclosure.

Claims

1. 1. A method for depositing a thin film comprising the steps of: providing a substrate into a reaction chamber having one or more first chemical reactant outlets and one or more second chemical reactant outlets spatially independent from the one or more first chemical reactant outlets; moving the substrate relative to the one or more first chemical reactant outlets and the one or more second chemical reactant outlets; At least one of a first chemical reactant passing through the first chemical reactant outlet and a second chemical reactant passing through the second chemical reactant outlet is applied to the substrate in a pulsed manner.

2. 10. The method of claim 1 , wherein the substrate has a top surface and a bottom surface, and the one or more first chemical reactant outlets and the one or more second chemical reactant outlets are on opposite sides of at least one of the top surface and the bottom surface of the substrate.

3. 10. The method of claim 1, further comprising one or more purge outlets located between the one or more first chemical reactant outlets and the one or more second chemical reactant outlets.

4. The method of claim 3 , further comprising the step of constantly applying a first inert gas to the substrate through the one or more purge outlets.

5. The method of claim 4 , wherein the first inert gas comprises argon or nitrogen.

6. a first exhaust outlet located between the one or more first chemical reactant outlets and the one or more purge outlets, and a second exhaust outlet located between the one or more second chemical reactant outlets and the one or more purge outlets; 4. The method of claim 3, wherein the first exhaust outlet exhausts the first chemical reactant from the reaction chamber and the second exhaust outlet exhausts the second chemical reactant from the reaction chamber.

7. The method of claim 6 , wherein the first exhaust outlet and / or the second exhaust outlet comprises a throttling device.

8. The method of claim 1 , wherein the relative movement includes a rotation, a advance, or a rocking motion.

9. 10. The method of claim 1, wherein the first chemical reactant and / or the second chemical reactant are introduced into the reaction chamber by using a second inert gas as a carrier gas.

10. The method of claim 9 , wherein the second inert gas comprises argon or nitrogen.

11. The method of claim 1, wherein the reaction temperature of the reaction chamber is between 25°C and 400°C.

12. 10. The method of claim 1, wherein the substrate comprises a flexible thin film, glass, or a silicon wafer, the flexible thin film comprising polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polyimide (PI).

13. The method of any one of claims 1 to 12, wherein the first chemical reactant is applied to the substrate in a pulsed manner and the second chemical reactant is applied to the substrate in a constantly on manner.

14. The method of any one of claims 1 to 12, wherein the first chemical reactant and the second chemical reactant are applied to the substrate in a gapless alternating pulse shape.

15. The method of any one of claims 1 to 12, wherein the first chemical reactant and the second chemical reactant are applied to the substrate in a source intersection alternating pulse shape.

16. The method of any one of claims 1 to 12, wherein the first chemical reactant and the second chemical reactant are applied to the substrate in a source gap alternating pulse shape.

17. one or more first chemical reactant outlets for delivering a first chemical reactant into the reaction chamber; one or more second chemical reactant outlets, spatially independent from the one or more first chemical reactant outlets, for delivering a second chemical reactant into the reaction chamber; a transfer assembly for moving a substrate relative to the one or more first chemical reactant outlets and the one or more second chemical reactant outlets; an intake control assembly for pulsing at least one of the first chemical reactant and the second chemical reactant onto the substrate; and an exhaust assembly for exhausting the first chemical reactant and the second chemical reactant from the reaction chamber.

18. the intake control assembly includes a first intake control valve and a second intake control valve; 20. The apparatus of claim 17, wherein the first intake control valve controls the first chemical reactant to be applied to the substrate in pulses, and the second intake control valve controls the second chemical reactant to be applied to the substrate in pulses.

19. 20. The thin film deposition apparatus of claim 17, further comprising one or more purge outlets located between the one or more first chemical reactant outlets and the one or more second chemical reactant outlets.

20. The exhaust assembly includes: a first exhaust outlet located between the one or more first chemical reactant outlets and the one or more purge outlets for exhausting the first chemical reactant from the reaction chamber; 20. The apparatus of claim 19, further comprising: a second exhaust outlet located between the one or more second chemical reactant outlets and the one or more purge outlets for exhausting the second chemical reactant from the reaction chamber.

21. A thin film formed by the thin film depositing apparatus according to any one of claims 17 to 20, or formed on a substrate by the method according to any one of claims 1 to 16.

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