ALD method and ALD device

Abstract

In this ALD method, a first precursor and a second precursor for performing an ALD cycle are alternately introduced into a reaction chamber (10, 10A, 10B) in an atmospheric-pressure atmosphere, and in the reaction chamber, laminar flow (LP) of the first precursor and laminar flow (LP) of the second precursor are alternately brought into contact with a film-formation target object (P, S1, S2) to form a film on the film-formation target object. Either the laminar flow of the first precursor or the laminar flow of the second precursor is laminar flow of an atmospheric-pressure plasma flow.

Description

ALD method and ALD apparatus

[0001] The present invention relates to an ALD (Atomic Layer Deposition) method and an ALD apparatus.

[0002] The present inventors have proposed a method for forming a film on powder using a swirling atmospheric pressure plasma flow (Patent Document 1).

[0003] Patent No. 7013062

[0004] If a film can be formed on a substrate other than powder in an atmospheric pressure environment, vacuum equipment is not required, which reduces equipment costs and running costs.

[0005] An object of the present invention is to provide an ALD method and apparatus for depositing films on various deposition materials, including powder, in an atmospheric pressure environment without using a swirling flow.

[0006] (1) One aspect of the present invention relates to an ALD method, which includes alternately introducing a first precursor and a second precursor for performing an ALD cycle into a reaction chamber under atmospheric pressure, alternately bringing a laminar flow of the first precursor and a laminar flow of the second precursor into contact with a film-forming object in the reaction chamber to form a film on the film-forming object, and one of the laminar flow of the first precursor and the laminar flow of the second precursor being a laminar flow of atmospheric pressure plasma.

[0007] According to one aspect (1) of the present invention, an ALD cycle is performed in a reaction chamber under atmospheric pressure by alternately contacting a laminar flow of a first precursor and a laminar flow of the second precursor with a substrate. This allows a film to be formed on the substrate without using a swirling flow. One of the laminar flows of the first precursor and the second precursor can be a laminar flow of atmospheric pressure plasma. For example, when OH radicals are used as precursors for forming an oxide film, the laminar flow can be a laminar flow of atmospheric pressure plasma formed by plasmatizing oxygen and hydrogen, or water vapor, etc., under atmospheric pressure.

[0008] (2) In the aspect (1) of the present invention, the first precursor and the second precursor may be introduced into the reaction chamber in opposite directions, which eliminates position dependency of the film formation quality on the film formation target and improves in-plane uniformity compared to when the first precursor and the second precursor are supplied from the same direction.

[0009] (3) In the aspect (1) of the present invention, the direction in which at least one of the first precursor and the second precursor is introduced into the reaction chamber may be changed at a predetermined timing. This eliminates position dependency of the film formation quality on the film formation target and improves in-plane uniformity compared to when the first precursor and / or the second precursor is always supplied from the same direction.

[0010] (4) In the aspect (1) of the present invention, the first precursor and the second precursor may be introduced into the reaction chamber in opposite directions, and the directions of introduction into the reaction chamber may be changed at predetermined times. In this way, position dependency of the film formation quality on the film formation target body is eliminated and in-plane uniformity is further improved compared to when the first precursor and the second precursor are always supplied from the same direction.

[0011] (5) In the aspects (1) to (4) of the present invention, the object to be coated can be a plurality of powder particles. In this case, the plurality of powder particles are mounted on a stage that vibrates and / or oscillates below the reaction chamber, and a coating is formed on the powder particles. In this way, the vibration and / or oscillation of the stage disperses any agglomerated powder particles, allowing a coating to be formed on all of the powder particles.

[0012] (6) In one aspect (5) of the present invention, the plurality of powders may be supplied to the reaction chamber from above the reaction chamber through one or more meshes. In this way, aggregated cluster-like powders can be broken down by the one or more meshes and supplied onto the stage. The one or more meshes may be vibrated, for example, laterally vibrated.

[0013] (7) In the aspects (1) to (4) of the present invention, the object to be coated may be, for example, a plate-like sheet other than a powder.

[0014] (8) In aspects (1) to (4) of the present invention, the object to be coated can be a strip-shaped sheet fed from a first roll and collected by a second roll. In this case, the strip-shaped sheet may be moved forward or back and forth so that the area facing the reaction chamber disposed between the first roll and the second roll shifts. By moving the strip-shaped sheet forward in one direction, a film can be formed on the entire strip-shaped sheet. By moving the strip-shaped sheet back and forth, a film thickness can be ensured, similar to so-called overcoating.

[0015] (9) In one aspect (8) of the present invention, the first precursor and the second precursor may be introduced into the reaction chamber in a direction that intersects with the forward or backward movement of the strip sheet. In other words, while the strip sheet is moved in its longitudinal direction, the precursors may be introduced into the reaction chamber in a direction that is parallel to, for example, the width direction of the strip sheet. This allows a laminar flow to be formed across the width of the strip sheet, and the volume of the reaction chamber in which a film can be formed on the entire strip sheet by the feed movement can also be reduced.

[0016] (10) Another aspect of the present invention is a deposition apparatus comprising: a reaction chamber open to the atmosphere; a pair of laminar flow forming tubes connected to opposing wall portions of the reaction chamber; a first precursor source; a second precursor source; and a holding mechanism for holding a film-forming object, wherein a first precursor is introduced from the first precursor source through one of the pair of laminar flow forming tubes and the reaction chamber is evacuated through the other of the pair of laminar flow forming tubes to form a laminar flow of the first precursor in the reaction chamber; a second precursor is introduced from the second precursor source through one of the pair of laminar flow forming tubes and the reaction chamber is evacuated through the other of the pair of laminar flow forming tubes to form a laminar flow of the second precursor in the reaction chamber; and the laminar flow of the first precursor and the laminar flow of the second precursor are alternately brought into contact with the film-forming object held by the holding mechanism to perform an ALD cycle to form a film on the film-forming object, According to another aspect of the present invention, the method of the first aspect of the present invention can be suitably carried out in the ALD apparatus, wherein one of the laminar flow of the first precursor and the laminar flow of the second precursor is a laminar flow of atmospheric pressure plasma.

[0017] 1 is a schematic diagram of an ALD apparatus according to one embodiment of the present invention; FIG. 2 is a schematic cross-sectional view of the atmospheric pressure plasma source in FIG. 1; FIG. 3 is a diagram showing the main parts of an ALD apparatus for forming a film on powder; FIG. 4 is a plan view of the reaction chamber and stage shown in FIG. 3; FIG. 5 is a diagram for explaining the film forming operation on powder; FIG. 6 is a diagram showing the main parts of an ALD apparatus for forming a film on a belt-shaped sheet; FIG. 7 is a plan view of the ALD apparatus shown in FIG. 6; FIG. 8 is a diagram showing the main parts of an ALD apparatus for forming a film on a sheet; and FIG. 9 is a diagram showing an ALD cycle.

[0018] The following disclosure provides different embodiments and examples for implementing different features of the presented subject matter. Of course, these are merely examples and are not intended to be limiting. Furthermore, the present disclosure may repeat reference numerals and / or letters in various examples. Such repetition is for the sake of brevity and clarity and does not, in itself, require a relationship between the various embodiments and / or configurations described. Furthermore, when a first element is described as being "connected" or "coupled" to a second element, such a description includes embodiments in which the first and second elements are directly connected or coupled to each other, as well as embodiments in which the first and second elements are indirectly connected or coupled to each other with one or more other intervening elements therebetween. Furthermore, when a first element is described as "moving" relative to a second element, such a description includes embodiments in which at least one of the first and second elements moves relative to the other.

[0019] 1. ALD Apparatus Figure 1 shows an example of an ALD apparatus 1. The ALD apparatus 1 can include a reaction chamber 10, a first precursor source 2, a second precursor source 3, an exhaust pump 4, pipes 30 to 34, on-off valves V1 to V6, and switching valves SV1 and SV2. Note that a holding mechanism for holding a film-forming object is not shown in Figure 1.

[0020] The reaction chamber 10 is a container for forming a film on a substrate (powder P in FIG. 3 , strip-shaped sheet S1 in FIG. 6 , sheet S2 in FIG. 8 , etc.). The reaction chamber 10 does not need to be a vacuum container and is open to atmospheric pressure. For example, one end of laminar flow forming pipes 33, 34 is connected to two opposing walls of the reaction chamber 10, which is rectangular in plan view. For example, one of the plurality of laminar flow forming pipes 33 and a corresponding one of the plurality of laminar flow forming pipes 34 are arranged so that their openings face each other within the reaction chamber 10. A gas (precursor) supplied from one of the laminar flow forming pipes 33, 34 is exhausted from the other of the laminar flow forming pipes 33, 34. This forms a laminar flow of the gas (precursor) within the reaction chamber.

[0021] The other ends of the plurality of laminar flow forming pipes 33 are joined together and connected to a first switching valve SV1. Similarly, the other ends of the plurality of laminar flow forming pipes 34 are joined together and connected to a second switching valve SV2. The first switching valve SV1 selectively connects one of the first precursor pipe 30, the second precursor pipe 31, and the exhaust pipe 32 to the laminar flow forming pipe 33. Thus, the laminar flow forming pipe 33 is selectively used for supplying the first precursor, supplying the second precursor, or exhausting. Similarly, the second switching valve SV2 selectively connects one of the first precursor pipe 30, the second precursor pipe 31, and the exhaust pipe 32 to the laminar flow forming pipe 34. Thus, the laminar flow forming pipe 34 is selectively used for supplying the first precursor, supplying the second precursor, or exhausting. However, when the first precursor or the second precursor is supplied from the laminar flow forming pipe 33, the gas is exhausted from the laminar flow forming pipe 34. Alternatively, when the first precursor or the second precursor is supplied from the laminar flow forming pipe 34, the gas is exhausted from the laminar flow forming pipe 33.

[0022] The first precursor pipe 30 connected to the first switching valve SV1 is connected to the first precursor source 2 via an on-off valve V1. The first precursor pipe 30 connected to the second switching valve SV2 is connected to the first precursor source 2 via an on-off valve V2. The second precursor pipe 31 connected to the first switching valve SV1 is connected to the second precursor source 3 via an on-off valve V3. The second precursor pipe 31 connected to the second switching valve SV2 is connected to the second precursor source 3 via an on-off valve V4. The exhaust pipe 32 connected to the first switching valve SV1 is connected to the exhaust pump 4 via an on-off valve V5. The exhaust pipe 32 connected to the second switching valve SV2 is connected to the exhaust pump 4 via an on-off valve V6.

[0023] The first precursor source 2 can include a reactant gas source 2A, a mass flow controller (MFC) 2B, and an atmospheric pressure plasma source 20. The second precursor source 3 can include a raw material gas source 3A and a mass flow controller (MFC) 3B. The first precursor source 2 including the atmospheric pressure plasma source 20 will be described with reference to FIG. 2 . The atmospheric pressure plasma source 20 includes, for example, a grounded outer tube 21 and a high-voltage electrode 22 disposed within the outer tube 21. A high-voltage AC power supply 23 is connected to the high-voltage electrode 22. The inner surface of the outer tube 21 and the outer surface of the high-voltage electrode 22 are coated with a dielectric. Cooling water may be supplied to a water channel 21A provided in the outer tube 21 and a water channel 22A provided in the high-voltage electrode 22. A reactive gas source (first precursor source) 2A is connected to a reactive gas inlet port 20A of the outer tube 21 via a flow rate controller (MFC) 2B and an on-off valve 2C. An atmospheric pressure plasma flow outlet port 20B of the outer tube 21 is connected to an atmospheric pressure plasma flow inlet port of the reaction chamber 10. A high-voltage electric field is formed between the outer tube 21 and the high-voltage electrode 22, and when a reactive gas is introduced from the reactive gas source 2, the reactive gas is ionized to generate an atmospheric pressure plasma flow. Note that the second precursor source 3 may also be provided with an on-off valve on the outlet side of the flow rate controller (MFC) 3B.

[0024] 2. Reaction chamber, holding mechanism, and mesh for forming a film on powder Fig. 3 shows a reaction chamber 10A, holding mechanism 40, and mesh F for forming a film on powder P, which is an example of a film-forming object. The reaction chamber 10A has the same function as the reaction chamber 10 in Fig. 1 and includes a frame 11. The holding mechanism 40 for holding the powder P has a stage (bottom plate) 41 located on the underside of the frame 11. The powder P is placed and held on the upper surface 41A of the stage 41. Fig. 4 is a plan view of the frame 11 and the stage 41. The internal space (reaction space) 11A of the frame 11 is open to the atmosphere at the upper edge 11B of the frame 11, as shown in Fig. 3.

[0025] The holding mechanism 40 may further include a swing shaft 42 that swings the frame 11 and the stage 41 together. In this case, the holding mechanism 40 is equipped with a swing mechanism that swings the frame 11 and the stage 41 around the swing shaft 42 in the direction A in the figure. The swing mechanism may be a known mechanism that converts reversible rotation or unidirectional rotation into swinging motion in the direction A in the figure. Instead of or in addition to the swing mechanism, the holding mechanism 40 may have a known vibration mechanism that vertically vibrates the stage 41, for example, in the direction B in the figure. When both the swing mechanism and the vibration mechanism are used, the vibration mechanism can vertically vibrate the stage 41 during swinging motion by the swing mechanism.

[0026] The laminar flow forming pipes 33, 34 are connected to two opposing sides of the rectangular frame 11. In the example shown in FIGS. 3 and 4 , the laminar flow forming pipes 33, 34 are connected in a direction perpendicular to the oscillation axis 42, but they may also be connected in a direction parallel to the oscillation axis 42. The stage 41 can be fixed to the underside of the frame 11. In this case, by tilting the frame 11 and the stage 41, the powder P after film formation can be moved from within the frame 11 toward the recovery section. The stage 41 may also be movable toward and away from the underside of the frame 11. In this case, for example, by tilting the frame 11 and the stage 41 and moving the stage 41 away from the underside of the frame 11, the powder P can be easily recovered from the gap between the frame 11 and the stage 41.

[0027] A powder supply port 43 for supplying powder P into the frame 11 can be provided in the upper part of the frame 11. In order to prevent aggregated cluster-like powder P from being supplied into the frame 11 from the powder supply port 43, a mesh F can be further provided between the powder supply port 43 and the reaction chamber 10A. In this case, the mesh F may be laterally vibrated by a horizontal vibration mechanism including, for example, a drive cylinder 44 and a spring 45. In addition, the powder supply port 43 may be moved in a scanning manner to supply powder P to almost the entire area of ​​the mesh F. The mesh F may have multiple types, for example, first to third meshes F1 to F3, with the mesh openings wider as they are positioned higher.

[0028] 5, powder P supplied from powder supply port 43 passes through first to third meshes F1 to F3 in order, whereby even if the powder P has aggregated, it is diffused or broken down and supplied onto stage 41. As will be described in detail later, a laminar flow LP of the first precursor and a laminar flow LP of the second precursor are alternately formed on stage 41, and an ALD cycle is performed to form a predetermined film on the surface of the powder P. During this process, stage 41 is swung and / or vertically vibrated, making it possible to form a film on the entire surface of the powder P that is being dispersed and moved.

[0029] 3. Reaction chamber and holding mechanism for forming a film on a strip-shaped sheet Figures 6 and 7 show a reaction chamber 10B and holding mechanism 50 for forming a film on a strip-shaped sheet S1, which is another example of a film-forming object. The reaction chamber 10B has the same functions as the reaction chamber 10 in Figure 1 and is similar to the reaction chamber 10A in that it includes a frame 11. However, as shown in Figure 6, the reaction chamber 10B may differ from the reaction chamber 10A in that it further includes a ceiling plate 12. The presence of the ceiling plate 12 makes it easier to form and maintain a laminar flow LP within the reaction chamber 10B. However, the ceiling plate 12 is not essential.

[0030] The holding mechanism 50 for the strip sheet S1 may be a roll-to-roll system. The roll-to-roll system 50 supplies the strip sheet S1 from a supply roller 51 and collects it on a collection roller 52. The roll-to-roll system 50 may further include a drive roller 53 and a driven roller 54 for moving the strip sheet S1 in a forward direction D1 and a backward direction D2 in FIG. 7 below the reaction chamber 10B. Note that the spatial space (reaction space) 11A of the frame 11 shown in FIG. 6 is surrounded by the frame 11, the ceiling panel 12, and the strip sheet S1, but does not need to be an airtight structure and may be open to the atmosphere.

[0031] In the reaction chamber 10B, laminar flow forming pipes 33, 34 are also connected to two opposing sides of the rectangular frame 11. In the examples of Figures 6 and 7, the laminar flow forming pipes 33, 34 are connected in a direction perpendicular (broadly intersecting) to the forward movement direction D1 and the backward movement direction D2 of the strip sheet S1, but they may also be connected in a direction parallel to the directions D1 and D2. However, if the examples of Figures 6 and 7 are used, at least one pipe 33, 34 is sufficient to form a laminar flow LP across the width of the strip sheet S1, and there is no need to increase the number of pipes to increase the volume of the reaction chamber 10B. This is because, even without increasing the volume of the reaction chamber 10B, a film can be formed on the entire surface of the strip sheet S1 by scanning the strip sheet S1. Furthermore, if the examples of Figures 6 and 7 are used, the laminar flow forming pipes 33, 34 can be easily arranged without interfering with the drive roller 53, driven roller 54, etc.

[0032] The strip sheet S1 and the frame 11 may be moved relative to each other so that the strip sheet S1 can be brought into contact with and separated from the lower surface of the frame 11. In this way, scanning movement of the strip sheet S1 can be performed at high speed without considering friction by separating the strip sheet S1 from the lower surface of the frame 11. Similarly, when the strip sheet S1 is intermittently moved in the forward direction D1 and the backward direction D2 in Figure 7 during film formation, the strip sheet S1 can be separated from the lower surface of the frame 11. It is not necessary for the strip sheet S1 and the frame 11 to be in contact with each other, and if they are not in contact, no contact / separation movement mechanism is required.

[0033] 4. Reaction Chamber and Holding Mechanism for Film Formation on Sheet FIG. 8 shows a reaction chamber 10B and holding mechanism 60 for forming a film on a sheet S2, which is a film-forming target. The reaction chamber 10B is the same as those shown in FIGS. 6 and 7. However, the ceiling panel 12 is not essential. The holding mechanism 60 has a mounting table 61 on which another example of a film-forming target, such as a plate-shaped sheet S2, is placed. The mounting table 61 is driven to move up and down relatively in the direction E1 shown in FIG. 8 and, if necessary, may be moved horizontally relatively in the direction E2 shown. After the sheet S2 is placed on the mounting table 61, the sheet S2 approaches or comes into contact with the frame 11, and then a film is formed on the sheet S2. During this film-forming operation, the sheet S2 may be moved horizontally relatively and intermittently. The sheet S2 may be released from contact with the frame 11 during horizontal movement.

[0034] 5. ALD Method The ALD method for forming a film on a substrate (powder P, strip-shaped sheet S1, or sheet S2) is carried out by repeating one cycle (ALD cycle) shown in Figure 9 N times (N is an integer of 2 or more). That is, one cycle (ALD cycle) is completed in reaction chamber 10, 10A, or 10B by performing four steps: laminar flow of second precursor, evacuation or purging, laminar flow of first precursor, evacuation or purging, and this cycle is repeated N times to complete film formation. The thickness of the film formed on the substrate is proportional to the number N of ALD cycles.

[0035] 5.1. First step (laminar flow of second precursor) Time T in FIG. Ａ -T ＢIn the first step, the source gas from the source gas source (second precursor source) 3A is supplied to the reaction chamber 10, 10A, or 10B. To this end, for example, the first switching valve SV1 is connected to the second precursor pipe 31, and the second switching valve SV2 is connected to the exhaust pipe 32. Furthermore, the on-off valves V3 and V6 are opened, and the other on-off valves V1, V2, V4, and V5 are closed. In this manner, the source gas from the source gas source 3A is supplied to the reaction chamber 10, 10A, or 10B via the flow rate controller 3B, the valve V3, the second precursor pipe 31, the first switching valve SV1, and the laminar flow forming pipe 33. The source gas in the reaction chamber is exhausted by the exhaust pump 4 via the laminar flow forming pipe 34, the second switching valve SV2, the exhaust pipe 32, and the on-off valve V6. The source gas supplied and exhausted via the laminar flow forming pipes 33 and 34 forms a laminar flow parallel to the stage 41 in Fig. 3, the strip-shaped sheet S1 in Fig. 6, or the plate-shaped sheet S2 in Fig. 8 in the reaction chamber 10, 10A, or 10B. In this way, the second precursor permeates the surface of the substrate (powder P, strip-shaped sheet S1, or sheet S2) that comes into contact with the laminar flow of the second precursor.

[0036] Here, during the first step, the direction of introduction of the source gas into the reaction chamber 10, 10A, or 10B may be switched. For example, the source gas may be introduced from left to right in FIG. 1 , and then switched to be introduced from right to left in FIG. 1 , and this switching may be repeated. To introduce the source gas from right to left in FIG. 1 , the on-off valves V3 and V6 may be switched from open to closed, and the on-off valves V4 and V5 may be switched from closed to open, respectively. In this way, the direction of the laminar flow is switched, thereby reducing the position dependency of the penetration of the second precursor into the surfaces of the multiple powders P, the strip-shaped sheet S1, or the sheet S2, and improving the uniformity of the film formation.

[0037] 5.2. Second step (exhaust or purge) Time T in FIG. Ｂ -T ＣIn the second step between the first and second steps, the second precursor remaining in the reaction chamber 10, 10A, or 10B is evacuated. Since the source gas is evacuated while being supplied in the first step, the second step may be omitted if the source gas does not remain in a harmful amount after the first step is completed. Alternatively, the exhaust may be performed for a relatively short period of time. The exhaust operation is performed by connecting at least one of the switching valves SV1 and SV2 to the reaction chamber 10, 10A, or 10B via the laminar flow forming pipe 33 and / or 34, opening at least one of the on-off valves V5 and V6, closing the other valves V1 to V4, and driving the exhaust pump 4. Instead of exhausting, the remaining source gas may be purged from the reaction chamber 10, 10A, or 10B with an inert gas.

[0038] 5.3. Third step (laminar flow of first precursor) Time T in FIG. 9 Ｃ -T Ｄ In the third step, the reactive gas from the reactive gas source 2 (first precursor source) A is introduced into the atmospheric pressure plasma source 20 via the flow rate controller 2B, and an atmospheric pressure plasma flow is supplied to the reaction chamber 10, 10A, or 10B. To this end, for example, the first switching valve SV1 is connected to the first precursor pipe 30, and the second switching valve SV2 is connected to the exhaust pipe 32. Furthermore, the on-off valves V1 and V6 are opened, and the other on-off valves V2 to V5 are closed. In this manner, the atmospheric pressure plasma flow is supplied to the reaction chamber 10, 10A, or 10B via the valve V1, the first precursor pipe 30, the first switching valve SV1, and the laminar flow forming pipe 33. The atmospheric pressure plasma flow in the reaction chamber is exhausted by the exhaust pump 4 via the laminar flow forming pipe 34, the second switching valve SV2, the exhaust pipe 32, and the on-off valve V6. The atmospheric pressure plasma flow supplied and exhausted via the laminar flow forming pipes 33, 34 forms a laminar flow in the reaction chamber 10, 10A or 10B that is parallel to the stage 41 in Fig. 3, the strip-shaped sheet S1 in Fig. 6 or the plate-shaped sheet S2 in Fig. 8. In this way, on the surface of the substrate (powder P, strip-shaped sheet S1 or sheet S2) that comes into contact with the laminar flow of the atmospheric pressure plasma flow, the second precursor that has penetrated in the first step reacts with the first precursor in the atmospheric pressure plasma flow, thereby forming a predetermined film.

[0039] Here, during the third step, the direction of introduction of the atmospheric pressure plasma flow into the reaction chamber 10, 10A, or 10B may be switched. For example, the atmospheric pressure plasma flow may be introduced from left to right in FIG. 1 , and then switched to be introduced from right to left in FIG. 1 , and this switching may be repeated. To introduce the source gas from right to left in FIG. 1 , the on-off valves V1 and V6 may be switched from open to closed, and the on-off valves V2 and V5 may be switched from closed to open, respectively. In this way, the direction of the laminar flow of the atmospheric pressure plasma flow is switched, thereby reducing the positional dependency of the contact of the first precursor with the surfaces of the multiple powders P, the strip-shaped sheet S1, or the sheet S2, and improving the uniformity of the film formation. Alternatively, the direction of the laminar flow of the second precursor in the first step and the direction of the laminar flow of the first precursor in the third step may be reversed.

[0040] 5.4. Fourth step (exhaust or purge) Time T in FIG. Ｄ -T Ｅ In the fourth step between the first and second steps, the first precursor remaining in the reaction chamber 10, 10A, or 10B is evacuated or replaced with a purged inert gas. For the same reasons as in the second step, evacuation or purging may be omitted or may be performed for a relatively short period of time.

[0041] In the first and third steps, it is possible to perform oscillation in the direction A and / or vertical vibration in the direction B shown in Fig. 3, forward movement in the direction D1 and / or backward movement in the direction D2 shown in Fig. 7, or horizontal movement in the direction E2 shown in Fig. 8. This further improves the uniformity of the film formation.

[0042] 6. Types of Film Formation By selecting the reaction gas and source gas, various films can be formed on the substrate. For example, an oxide film can be formed on the substrate. In this case, an oxidizing gas is used as the reaction gas. The oxidizing gas can be a mixture of a carrier gas, such as argon (Ar), and water vapor. When this mixture gas is supplied to the atmospheric pressure plasma source 20, Ar+H ２ O → Ar ＊ +OH ＊ +H ＊and the first precursor is the OH radical (OH ＊ Alternatively, the oxidizing gas may be a mixture of a carrier gas, such as argon (Ar), oxygen, and hydrogen. When this mixture is supplied to the atmospheric pressure plasma source 20, Ar+O ２ +H ２ →Ar ＊ +2OH ＊ and the OH radical (OH ＊ On the other hand, as a raw material gas (second precursor), for example, TMA(Al(CH ３ ) ３ ) is supplied using, for example, Ar as a carrier gas. ３ ) ３ ) is an OH radical (OH ＊ ) to form aluminum oxide, Al ２ O ３ As a result, the surface of the object to be coated is covered with an oxide film.

[0043] A nitride film can also be formed on the substrate. In this case, nitriding gas NH ３ Nitriding gas NH ３ is supplied to the atmospheric pressure plasma source 20, NH radicals are generated. On the other hand, when the source gas is, for example, TDMAS(SiH[N(CH ３ ) ２ ] ３ When TDMAT (Ti[N(CH ３ ) ２ ] ４ ) is used, a TiN film can be formed on a substrate by a reaction between NH radicals and TDMAT.

[0044] A metal film can also be formed on the substrate. In this case, for example, a halogen gas can be used as the reactive gas. When halogen is supplied to the atmospheric pressure plasma source 20, for example, Cl radicals are generated. On the other hand, when sublimated CuCl is used as the source gas, for example, CuCl + Cl ＊ →Cu+Cl２ By the reaction above, a copper (Cu) film can be formed on the substrate.

[0045] The present invention can be modified in various ways within the scope of the present invention. For example, in the above embodiment, the laminar flow direction is switched at a predetermined timing, but this is not limiting. For example, the laminar flow forming pipe 33 may be used exclusively for gas introduction, and the laminar flow forming pipe 34 may be used exclusively for exhaust. Furthermore, the laminar flow forming pipes 33 and 34 do not necessarily have to be multiple parallel pipes, but may have a single slit opening corresponding to the width of the laminar flow. Furthermore, as long as laminar flow is maintained within the reaction chambers 10, 10A, and 10B by pumping gas from the first and second precursor sources at, for example, 0.1 MPa or more, natural exhaust is also acceptable. The reaction chambers 10, 10A, and 10B are not necessarily rectangular in plan view, but may be formed by connecting the laminar flow forming pipes 33 and 34 to two opposing walls. Furthermore, atmospheric pressure plasma is not limited to that using a high-voltage electric field; for example, high frequency or microwaves may be used.

[0046] 1...ALD device, 2...first precursor source, 2A...reactant gas, 2B...flow rate controller (MFC), 3...second precursor source, 3A...source gas, 3B...flow rate controller (MFC), 4 pump, 10, 10A, 10B...reaction chamber, 11...frame, 11A...internal space, 11B...upper edge, 12 ceiling plate, 20...atmospheric pressure plasma source, 20A...reactant gas introduction port, 20B...atmosphere Pressure plasma flow outlet port, 21... outer tube, 21A... water channel, 22... high voltage electrode, 22A... water channel, 23... AC power supply, 30... first precursor pipe, 31... second precursor pipe, 32... exhaust pipe, 33, 32... laminar flow forming pipe, 40... holding mechanism, 41... stage, 42... swing shaft, 43... powder supply port, 44... reciprocating cylinder, 45... spring, 50... holding mechanism (Roll to Roll system), 51...supply roller, 52...recovery roller, 53...drive roller, 54...follower roller, 60...holding mechanism, 61...mounting table, A...oscillation direction, B...vertical vibration direction, C...horizontal vibration direction, D1...forward movement direction, D2...return movement direction, F, F1 to F3...mesh, LF...laminar flow, P...powder (subject to be coated), S1...strip-shaped sheet (subject to be coated), S2...plate-shaped sheet (subject to be coated), V1 to V6...opening and closing valves, SV1, SV2...switching valves

Claims

1. Alternately introducing a first precursor and a second precursor for performing an ALD cycle into a reaction chamber under atmospheric pressure; In the reaction chamber, the laminar flow of the first precursor and the laminar flow of the second precursor are alternately brought into contact with a film-forming object, thereby forming a film on the film-forming object; one of the laminar flow of the first precursor and the laminar flow of the second precursor is a laminar flow of an atmospheric pressure plasma flow; An ALD method in which the first precursor and the second precursor are introduced into the reaction chamber in opposite directions to each other, or the directions in which the first precursor and the second precursor are introduced into the reaction chamber are changed at a predetermined timing.

2. In claim 1, The ALD method, in which the first precursor and the second precursor are introduced into the reaction chamber in mutually opposite directions, and the directions in which the precursors are introduced into the reaction chamber are changed at a predetermined timing.

3. In claim 1 or 2, The film-forming object is a plurality of powders, The ALD method in which the powders are mounted on a vibrating and / or oscillating stage below the reaction chamber and a film is formed.

4. In claim 3, An ALD method in which the plurality of powders are supplied to the reaction chamber from above the reaction chamber through one or more meshes.

5. In claim 1 or 2, The ALD method in which the film-forming object is a plate-like sheet.

6. In claim 1 or 2, the substrate is a strip-shaped sheet that is fed from a first roll and collected by a second roll, The ALD method, in which the belt-like sheet is moved forward or backward so that the area facing the reaction chamber arranged between the first roll and the second roll is shifted.

7. In claim 6, An ALD method, wherein the direction in which the first precursor and the second precursor are introduced into the reaction chamber intersects with the direction in which the belt-shaped sheet is moved forward or backward.

8. a reaction chamber open to the atmosphere; First and second laminar flow forming pipes communicating with opposing walls of the reaction chamber; a first precursor source; and a second precursor source; and An exhaust pump; a first switching valve connected to the first laminar flow forming pipe; a second switching valve connected to the second laminar flow forming pipe; a first opening / closing valve provided in a pipe between the first precursor source and the first switching valve; a second opening / closing valve provided in a pipe between the first precursor source and the second switching valve; a third opening / closing valve provided in a pipe between the second precursor source and the first switching valve; a fourth opening / closing valve provided in a pipe between the second precursor source and the second switching valve; a fifth opening / closing valve provided in a pipe between the exhaust pump and the first switching valve; a sixth opening / closing valve provided in a pipe between the exhaust pump and the second switching valve; a holding mechanism for holding the object to be coated; having introducing a first precursor from the first precursor source through one of the first and second laminar flow forming tubes and evacuating the reaction chamber through the other of the first and second laminar flow forming tubes to form a laminar flow of the first precursor in the reaction chamber; introducing a second precursor from the second precursor source through one of the first and second laminar flow forming tubes and evacuating the reaction chamber through the other of the first and second laminar flow forming tubes to form a laminar flow of the second precursor in the reaction chamber; a laminar flow of the first precursor and a laminar flow of the second precursor are alternately brought into contact with the substrate held by the holding mechanism, and an ALD cycle is performed to form a film on the substrate; one of the laminar flow of the first precursor and the laminar flow of the second precursor is a laminar flow of an atmospheric pressure plasma flow; The ALD apparatus wherein the first precursor and the second precursor are introduced into the reaction chamber in mutually opposite directions, or the directions in which the first precursor and the second precursor are introduced into the reaction chamber are changed at a predetermined timing.