ALD Method and ALD Apparatus

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

Technical Field

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

Background Art

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

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] If a film can be formed on a film-forming object other than powder in an atmospheric pressure atmosphere, no vacuum equipment is required, and thus equipment costs and running costs can be reduced.

[0005] An object of the present invention is to provide an ALD method and apparatus for forming a film on various film-forming objects including powder in an atmospheric pressure atmosphere without using a swirling flow.

Means for Solving the Problems

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

[0007] According to one aspect (1) of the present invention, an ALD cycle is performed by alternately bringing a laminar flow of a first precursor and a laminar flow of the first precursor into contact with a film-forming object in a reaction chamber under an atmospheric pressure atmosphere. Thereby, a film can be formed on the film-forming object without using a swirling flow. One of the laminar flow of the first precursor and the laminar flow of the second precursor can be a laminar flow of an atmospheric pressure plasma flow. For example, when OH radicals are used as a precursor for forming an oxide film, it can be a laminar flow of an atmospheric pressure plasma flow obtained by plasmaizing oxygen and hydrogen, or water vapor, etc. under atmospheric pressure.

[0008] (2) In one aspect (1) of the present invention, the directions in which the first precursor and the second precursor are introduced into the reaction chamber may be opposite to each other. By doing so, compared with the case where the first precursor and the second precursor are supplied from the same direction, the position dependence of the film-forming quality of the film-forming object is eliminated and the in-plane uniformity is improved.

[0009] (3) In one 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. By doing so, compared with the case where the first precursor and / or the second precursor are always supplied from the same direction, the position dependence of the film-forming quality of the film-forming object is eliminated and the in-plane uniformity is improved.

[0010] (4) In one aspect (1) of the present invention, the directions in which the first precursor and the second precursor are introduced into the reaction chamber may be opposite to each other, and the direction in which they are introduced into the reaction chamber may be changed at a predetermined timing. By doing so, compared with the case where the first precursor and the second precursor are always supplied from the same direction, the position dependence of the film-forming quality of the film-forming object is eliminated and the in-plane uniformity is further improved.

[0011] (5) In one aspect (1) to (4) of the present invention, the film-forming object can be a plurality of powders. In this case, the plurality of powders are mounted on a stage that vibrates and / or swings below the reaction chamber and are film-formed. By doing so, the powders that were aggregated due to the vibration and / or swinging of the stage are dispersed, so that film formation can be performed on all the powder particles.

[0012] (6) In one aspect (5) of the present invention, the plurality of powders may be supplied to the reaction chamber through one or more meshes from above the reaction chamber. By doing so, the aggregated cluster-like powders can be crushed by one or more meshes and supplied onto the stage. One or more meshes may be vibrated, for example, horizontally vibrated.

[0013] (7) In one aspect (1) to (4) of the present invention, the film-forming object can be, for example, a plate-like sheet other than powders.

[0014] (8) In one aspect (1) to (4) of the present invention, the film-forming object can be a belt-like sheet that is fed out from a first roll and collected by a second roll. In this case, the belt-like sheet may be reciprocated or reciprocated so that the region facing the reaction chamber disposed between the first roll and the second roll shifts. By the forward movement of the belt-like sheet in one direction, film formation can be performed on the entire belt-like sheet. When the belt-like sheet is reciprocated, the film thickness can be ensured in the same manner as so-called overcoating.

[0015] (9) In one aspect (8) of the present invention, the directions in which the first precursor and the second precursor are introduced into the reaction chamber may intersect with the direction in which the belt-like sheet is reciprocated or reciprocated. That is, while the belt-like sheet is moved in its longitudinal direction, the precursor can be introduced into the reaction chamber in a direction parallel to, for example, the width direction of the belt-like sheet. By doing so, a laminar flow can be formed across the width of the belt-like sheet, and the volume of the reaction chamber that enables film formation on the entire belt-like sheet by feeding movement can also be reduced.

[0016] (10) Another aspect of the present invention is a reaction chamber open to the atmosphere, a pair of laminar flow forming tubes communicated with opposite wall portions of the reaction chamber, a first precursor source, a second precursor source, a holding mechanism for holding a film-forming object, and has introducing a first precursor from the first precursor source through one of the pair of laminar flow forming tubes, and evacuating the reaction chamber through the other of the pair of 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 pair of laminar flow forming tubes, and evacuating the reaction chamber through the other of the pair of laminar flow forming tubes to form a laminar flow of the second precursor in the reaction chamber, alternately bringing the laminar flow of the first precursor and the laminar flow of the second precursor 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, 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. According to another aspect of the present invention, the method of one aspect (1) of the present invention can be preferably implemented.

Brief Description of the Drawings

[0017]

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Embodiments for Carrying Out the Invention

[0018] In the following disclosure, different embodiments and examples for implementing different features of the presented subject matter are provided. Of course, these are merely examples and are not intended to be limiting. Further, in this disclosure, reference numerals and / or letters may be repeated in various examples. Such repetition is for the purpose of simplicity and clarity and does not necessarily require that there be a relationship between the various embodiments and / or the configurations being described. Further, when a first element is described as being “connected to” or “coupled to” a second element, such description includes embodiments where the first and second elements are directly connected or coupled to each other, as well as embodiments where the first and second elements are indirectly connected or coupled to each other with one or more other elements intervening therebetween. Also, when a first element is described as “moving” relative to a second element, such description includes embodiments of relative movement where at least one of the first and second elements moves relative to the other.

[0019] 1. ALD Apparatus In FIG. 1, an example of an ALD apparatus 1 is shown. 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, SV2. Note that in FIG. 1, a holding mechanism for holding the object to be film-formed is not shown.

[0020] The reaction chamber 10 is a container for forming a film on a film-forming object (powder P in FIG. 3, belt-like 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 each of the laminar flow forming pipes 33 and 34 is connected to two opposing wall portions of the rectangular reaction chamber 10 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 inside the reaction chamber 10. The gas (precursor) supplied from one of the laminar flow forming pipes 33 and 34 is exhausted from the other of the laminar flow forming pipes 33 and 34. Thereby, a laminar flow of gas (precursor) is formed in the reaction chamber.

[0021] The other ends of the plurality of laminar flow forming pipes 33 are joined and connected to the first switching valve SV1. Similarly, the other ends of the plurality of laminar flow forming pipes 34 are joined and connected to the second switching valve SV2. The first switching valve SV1 selectively communicates one of the first precursor pipe 30, the second precursor pipe 31, and the exhaust pipe 32 with the laminar flow forming pipe 33. Thus, the laminar flow forming pipe 33 is selectively used for the supply of the first precursor, the supply of the second precursor, or exhaust. Similarly, the second switching valve SV2 selectively communicates one of the first precursor pipe 30, the second precursor pipe 31, and the exhaust pipe 32 with the laminar flow forming pipe 34. Thus, the laminar flow forming pipe 34 is selectively used for the supply of the first precursor, the supply of the second precursor, or exhaust. However, when the first precursor or the second precursor is supplied from the laminar flow forming pipe 33, it 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, it 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 the 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 the 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 the 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 the on-off valve V4. The exhaust pipe 32 connected to the first switching valve SV1 is connected to the exhaust pump 4 via the on-off valve V5. The exhaust pipe 32 connected to the second switching valve SV2 is connected to the exhaust pump 4 via the on-off valve V6.

[0023] The first precursor source 2 can include a reaction 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. With reference to FIG. 2, the first precursor source 2 including the atmospheric pressure plasma source 20 will be described. The atmospheric pressure plasma source 20 includes, for example, a grounded outer tube 21 and a high-voltage electrode 22 disposed inside 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. Further, cooling water may be supplied to the water channel 21A provided in the outer tube 21 and the water channel 22A provided in the high-voltage electrode 22. The reaction gas source (first precursor source) 2A is connected to the reaction gas introduction port 20A of the outer tube 21 via the mass flow controller (MFC) 2B and the on-off valve 2C. The atmospheric pressure plasma flow outlet port 20B of the outer tube 21 is connected to the 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 the reaction gas is introduced from the reaction gas source 2, the reaction gas can be ionized to generate an atmospheric pressure plasma flow. Note that an on-off valve may also be provided on the outlet side of the mass flow controller (MFC) 3B for the second precursor source 3.

[0024] 2. Reaction Chamber, Holding Mechanism, and Mesh for Film Formation on Powder FIG. 3 shows a reaction chamber 10A, a holding mechanism 40, and a mesh F for forming a film on powder P, which is an example of a body to be film-formed. The reaction chamber 10A has the same function as the reaction chamber 10 in FIG. 1 and includes a frame body 11. The holding mechanism 40 for holding the powder P has a stage (bottom plate) 41 located on the lower surface of the frame body 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 body 11 and the stage 41. The internal space (reaction space) 11A of the frame body 11 is open to the atmosphere at the upper edge 11B of the frame body 11 as shown in FIG. 3.

[0025] The holding mechanism 40 can further include a swing shaft 42 that swings the frame body 11 and the stage 41 integrally. In this case, the holding mechanism 40 is provided with a swing mechanism, and the frame body 11 and the stage 41 are swung in the direction A shown in the figure around the swing shaft 42 by the swing mechanism. The swing mechanism can use a known mechanism that converts reversible rotation or one-way rotation into a swing motion in the direction A shown in the figure. Instead of or in addition to the swing mechanism, the holding mechanism 40 can have a known vibration mechanism that vertically vibrates the stage 41, for example, in the direction B shown in the figure. When the swing mechanism and the vibration mechanism are provided together, the vibration mechanism can vertically vibrate the stage 41 during the swing motion by the swing mechanism.

[0026] The above-described laminar flow forming pipes 33 and 34 are connected to two opposite sides of the rectangular frame body 11. In the examples of FIGS. 3 and 4, the laminar flow forming pipes 33 and 34 are connected in a direction orthogonal to the swing shaft 42, but they may be connected in a direction parallel to the swing shaft 42. The stage 41 can be fixed to the lower surface of the frame body 11. In this case, by tilting the frame body 11 and the stage 41, the film-formed powder P can be moved from inside the frame body 11 toward the recovery part. The stage 41 may be moved so as to be able to approach and separate from the lower surface of the frame body 11. In this way, for example, by tilting the frame body 11 and the stage 41 and separating the stage 41 from the lower surface of the frame body 11, the powder P can be easily recovered from the gap between the frame body 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. Additionally, 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, and a predetermined film is formed on the surface of 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 powder P that is being dispersed and moved.

[0029] 3. Reaction chamber and holding mechanism for film formation on the belt-shaped sheet 6 and 7 show a reaction chamber 10B and a 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 FIG. 1 and is similar to the reaction chamber 10A in that it includes a frame 11. However, as shown in FIG. 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 of the belt-shaped sheet S1 can be a Roll to Roll system. The Roll to Roll system 50 supplies the belt-shaped sheet S1 from the supply roller 51 and collects it on the recovery roller 52. The Roll to Roll system 50 can further have drive rollers 53 and driven rollers 54 for moving the belt-shaped sheet S1 in the forward movement direction D1 and the reverse movement direction D2 shown in FIG. 7 below the reaction chamber 10B. Note that the space (reaction space) 11A of the frame 11 shown in FIG. 6 is surrounded by the frame 11, the ceiling plate 12, and the belt-shaped sheet S1, but it does not necessarily have to be an airtight structure and may be open to the atmosphere.

[0031] Also in the reaction chamber 10B, the laminar flow forming pipes 33 and 34 are connected to two opposite sides of the rectangular frame 11. In the examples of FIGS. 6 and 7, the laminar flow forming pipes 33 and 34 are connected in a direction orthogonal (broadly intersecting) to the forward movement direction D1 and the reverse movement direction D2 of the belt-shaped sheet S1, but they may be connected in a direction parallel to the directions D1 and D2. However, if it is as in the examples of FIGS. 6 and 7, for forming the laminar flow LP across the width direction of the belt-shaped sheet S1, at least one pipe 33 and 34 is sufficient, and it is not necessary 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, if the belt-shaped sheet S1 is scanned and moved, a film can be formed on the entire surface of the belt-shaped sheet S1. Also, if it is as in the examples of FIGS. 6 and 7, the laminar flow forming pipes 33 and 34 can be easily arranged without interfering with the drive rollers 5, etc.

[0032] Note that the belt-shaped sheet S1 and the frame 11 may be relatively moved so that the belt-shaped sheet S1 can be separated from and contacted with the lower surface of the frame 11. In this way, when the belt-shaped sheet S1 is scanned and moved, by separating the belt-shaped sheet S1 from the lower surface of the frame 11, it can be performed at high speed without considering friction. Similarly, when the belt-shaped sheet S1 is intermittently moved in the forward movement direction D1 and the reverse movement direction D2 shown in FIG. 7 during film formation, the belt-shaped sheet S1 can be separated from the lower surface of the frame 11. Note that the belt-shaped sheet S1 and the frame 11 do not necessarily have to be in contact, and if they are non-contact, the separating and contacting movement mechanism is unnecessary.

[0033] 4. Reaction chamber and holding mechanism for film formation on a sheet FIG. 8 shows a reaction chamber 10B and a holding mechanism 60 for film formation on a sheet S2 as the object to be film-formed. The reaction chamber 10B is the same as that shown in FIGS. 6 and 7. However, the ceiling plate 12 is not essential. The holding mechanism 60 has a mounting table 61 for placing, for example, a plate-like sheet S2 which is another example of the object to be film-formed. The mounting table 61 is driven to move up and down relatively in the direction of E1 shown in FIG. 8, and may be moved horizontally relatively in the direction of E2 shown in the figure if necessary. After the sheet S2 is placed on the mounting table 61 and the sheet S2 is brought close to or into contact with the frame body 11, film formation is performed on the sheet S2. During this film formation operation, the sheet S2 may be moved horizontally relatively and intermittently. The contact between the sheet S2 and the frame body 11 may be released during the horizontal movement.

[0034] 5. ALD method The ALD method for film formation on the object to be film-formed (powder P, belt-like sheet S1 or sheet S2) is carried out by repeating the 1 cycle (ALD cycle) shown in FIG. 9 N (N is an integer of 2 or more) times. That is, in the reaction chamber 10, 10A or 10B, four steps of laminar flow, exhaust or purge of the second precursor, laminar flow, exhaust or purge of the first precursor are performed to complete 1 cycle (ALD cycle), and this is repeated N cycles to complete film formation. The thickness of the film formed on the object to be film-formed is proportional to the number N of ALD cycles.

[0035] 5.1. First step (Laminar flow of the second precursor) Time T in FIG. 9 A -T BIn the first step among them, the source gas from the source gas source (second precursor source) 3A is supplied to the reaction chambers 10, 10A or 10B. For this purpose, for example, the first switching valve SV1 is communicated with the second precursor pipe 31, and the second switching valve SV2 is connected to the exhaust pipe 32. Further, the on-off valves V3 and V6 are opened, and the other on-off valves V1, V2, V4 and V5 are closed. In this way, the source gas from the source gas source 3A is supplied to the reaction chambers 10, 10A or 10B through the flow 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 through the laminar flow forming pipes 34, the second switching valve SV2, the exhaust pipe 32 and the on-off valve V6. The source gas supplied and exhausted through the laminar flow forming pipes 33 and 34 forms a laminar flow parallel to the stage 41 in FIG. 3, the belt-like sheet S1 in FIG. 6 or the plate-like sheet S2 in FIG. 8 in the reaction chambers 10, 10A or 10B. In this way, the second precursor penetrates the surface of the film-forming object (powder P, belt-like 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 introducing the source gas into the reaction chambers 10, 10A or 10B may be switched. For example, after introducing the source gas from left to right in FIG. 1, it may be switched to be introduced from right to left in FIG. 1, and such 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. In this way, by switching the direction in which the laminar flow flows, the position dependence of the penetration of the second precursor on the surfaces of the plurality of powders P, belt-like sheets S1 or sheets S2 is reduced, and the uniformity of film formation is enhanced.

[0037] 5.2. Second step (exhaust or purge) Time T in FIG. 9 B -T CIn the second step between, the second precursor remaining in the reaction chambers 10, 10A or 10B is exhausted. In the first step, since the raw material gas is exhausted while being supplied, if the raw material gas does not remain to such an extent as to cause adverse effects after the completion of the first step, the second step may be omitted. Alternatively, the exhaust may be performed for a relatively short period of time. The exhaust operation is carried out by communicating at least one of the switching valves SV1 and SV2 with the reaction chambers 10, 10A or 10B via the laminar flow forming pipes 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 reaction chambers 10, 10A or 10B may be purged with an inert gas to discharge the remaining raw material gas.

[0038] 5.3. Third step (laminar flow of the first precursor) Time T in FIG. 9 C -T DIn the third step between them, the reaction gas from the reaction gas source 2 (the first precursor source) A is introduced into the atmospheric pressure plasma source 20 via the flow rate controller 2B, and the atmospheric pressure plasma flow is supplied to the reaction chambers 10, 10A or 10B. For this purpose, for example, the first switching valve SV1 is communicated with the first precursor pipe 30, and the second switching valve SV2 is connected to the exhaust pipe 32. Further, the on-off valves V1, V6 are opened, and the other on-off valves V2 to V5 are closed. In this way, the atmospheric pressure plasma flow is supplied to the reaction chambers 10, 10A or 10B through 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 through 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 through the laminar flow forming pipes 33, 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 chambers 10, 10A or 10B. Thus, on the surface of the film-forming object (powder P, strip-shaped sheet S1 or sheet S2) in 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, and a predetermined film is formed.

[0039] Here, during the third step, the direction of introducing the atmospheric pressure plasma flow into the reaction chambers 10, 10A or 10B may be switched. For example, after introducing the atmospheric pressure plasma flow from left to right in FIG. 1, it may be switched to be introduced from right to left in FIG. 1, and this switching may be repeated. To introduce the raw material gas from right to left in FIG. 1, the on-off valves V1, V6 may be switched from open to closed, and the on-off valves V2, V5 may be switched from closed to open, respectively. In this way, by switching the direction in which the laminar flow of the atmospheric pressure plasma flow flows, the position dependence of the contact of the first precursor with the surfaces of the plurality of powders P, strip-shaped sheets S1 or sheets S2 is reduced, and the film formation uniformity is enhanced. 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 made opposite.

[0040] 5.4. Fourth Step (Exhaust or Purge) At time T in FIG. 9 D -T E During the fourth step between, the first precursor remaining in the reaction chambers 10, 10A or 10B is exhausted or replaced with an inert gas that has been purged. For the same reason as in the second step, the exhaust or purge may be omitted or may be carried out for a relatively short time only.

[0041] In the first and third steps, rocking in the direction of illustration A shown in FIG. 3 and / or vertical vibration in the direction of illustration B, reciprocating motion in the direction of illustration D1 shown in FIG. 7 and / or reciprocating motion in the direction of illustration D2, or horizontal movement in the direction of illustration E2 shown in FIG. 8 can be carried out. Thereby, the film formation uniformity is further enhanced.

[0042] 6. Types of Film Formation By selecting a reaction gas and a source gas, various films can be formed on the object to be film-formed. For example, an oxide film can be formed on the object to be film-formed. In this case, an oxidizing gas is used as the reaction gas. Examples of the oxidizing gas include a mixed gas of a carrier gas such as argon Ar and water vapor. When this mixed gas is supplied to the atmospheric pressure plasma source 20, Ar + H2O → Ar * + OH * + H * results, and OH radicals (OH * ) can be generated as the first precursor. Alternatively, examples of the oxidizing gas include a mixed gas of a carrier gas such as argon Ar, oxygen, and hydrogen. When this mixed gas is supplied to the atmospheric pressure plasma source 20, Ar + O2 + H2 → Ar * + 2OH * results, and OH radicals (OH * ) can be generated. On the other hand, for example, ТMA (Al(CH3)3) is supplied as the source gas (second precursor), for example, using Ar as the carrier gas. Then, ТMA (Al(CH3)3) reacts with OH radicals (OH * ) to generate aluminum oxide Al2O3. Thereby, the surface of the object to be film-formed is covered with an oxide film.

[0043] A nitride film can also be formed on the film-forming object. In this case, nitrogen gas NH3 can be used as the reaction gas. When nitrogen gas NH3 is supplied to the atmospheric pressure plasma source 20, NH radicals are generated. On the other hand, when, for example, TDMAS (SiH[N(CH3)2]3) is used as the source gas, SiN can be formed on the film-forming object by the reaction of NH radicals and TDMAS. Alternatively, when, for example, TDMAT (Ti[N(CH3)2]4) is used as the source gas, TiN can be formed on the film-forming object by the reaction of NH radicals and TDMAT.

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

[0045] Note that the present invention can be variously modified within the scope of the gist of the present invention. For example, in the above embodiment, the direction in which the laminar flow flows is switched at a predetermined timing, but it is not limited to this. That is, 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. Further, the laminar flow forming pipes 33 and 34 do not necessarily have to be a plurality of parallel pipes, and may have a single slit opening corresponding to the width of the laminar flow. Furthermore, as long as the gas is pumped from the first and second precursor sources at, for example, 0.1 MPa or more and the laminar flow is maintained in the reaction chambers 10, 10A, and 10B, it is not always necessary to perform forced exhaust, and natural exhaust may be used. The reaction chambers 10, 10A, and 10B are not limited to being rectangular in plan view, and it is sufficient that the laminar flow forming pipes 33 and 34 communicate with two opposing wall portions. Also, the atmospheric pressure plasma is not limited to that using a high voltage electric field, and for example, high frequency or microwave may be used.

Explanation of reference numerals

[0046] 1…ALD apparatus, 2…First precursor source, 2A…Reaction gas, 2B…Flow controller (MFC), 3…Second precursor source, 3A…Raw material gas, 3B…Flow controller (MFC), 4 pump, 10, 10A, 10B…Reaction chamber, 11…Frame body, 11A…Internal space, 11B…Upper edge, 12 ceiling plate, 20…Atmospheric pressure plasma source, 20A…Reaction gas introduction port, 20B…Atmospheric 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 axis, 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…Driven roller, 60…Holding mechanism, 61…Mounting table, A…Swing direction, B…Vertical vibration direction, C…Horizontal vibration direction, D1…Forward movement direction, D2…Return movement direction, F, F1~F3…Mesh, LF…Laminar flow, P…Powder (film formation target), S1…Strip-shaped sheet (film formation target), S2…Plate-shaped sheet (film formation target), V1~V6…On-off valve, SV1, SV2…Switching valve

Claims

1. In a reaction chamber in an atmospheric pressure atmosphere, a first precursor for performing an ALD cycle is introduced through either one of a first and a second laminar flow forming tubes communicated with opposing wall portions of the reaction chamber, and the reaction chamber is exhausted through the other one of the first and second laminar flow forming tubes to form a laminar flow of the first precursor in the reaction chamber. A second precursor for performing the ALD cycle is introduced through either one of the first and second laminar flow forming tubes, and the reaction chamber is exhausted through the other one of the first and second laminar flow forming tubes to form a laminar flow of the second precursor in the reaction chamber. 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 to form 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 from an atmospheric pressure plasma source provided outside the reaction chamber. The first precursor and the second precursor supplied and exhausted through the first and second laminar flow forming tubes are oriented in opposite directions when introduced into the reaction chamber, or an ALD method in which the orientation when introduced into the reaction chamber is changed at a predetermined timing.

2. In Claim 1, The first precursor and the second precursor are oriented in opposite directions when introduced into the reaction chamber, and an ALD method in which the orientation when introduced into the reaction chamber is changed at a predetermined timing.

3. In Claim 1 or 2, The film-forming object is a plurality of powders, An ALD method in which the plurality of powders are mounted on a stage that vibrates and / or swings below the reaction chamber to form a film.

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

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

6. In Claim 1 or 2, The film-forming object is a belt-like sheet fed from a first roll and collected by a second roll, An ALD method in which the belt-like sheet is reciprocated or reciprocated so that a region facing the reaction chamber disposed between the first roll and the second roll shifts.

7. In claim 6, a method of ALD in which the directions in which the first precursor and the second precursor are introduced into the reaction chamber intersect the direction in which the belt-like sheet is reciprocated or reciprocated.

8. a reaction chamber open to the atmosphere, first and second laminar flow forming pipes communicated with opposite wall portions of the reaction chamber, a first precursor source, a second precursor source, 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 on-off valve provided in the pipe between the first precursor source and the first switching valve, a second on-off valve provided in the pipe between the first precursor source and the second switching valve, a third on-off valve provided in the pipe between the second precursor source and the first switching valve, a fourth on-off valve provided in the pipe between the second precursor source and the second switching valve, a fifth on-off valve provided in the pipe between the exhaust pump and the first switching valve, a sixth on-off valve provided in the pipe between the exhaust pump and the second switching valve, a holding mechanism for holding the film-forming object, having introducing a first precursor from the first precursor source through either one of the first and second laminar flow forming pipes, and exhausting the reaction chamber through the other one of the first and second laminar flow forming pipes to form a laminar flow of the first precursor in the reaction chamber, introducing a second precursor from the second precursor source through either one of the first and second laminar flow forming pipes, and exhausting the reaction chamber through the other one of the first and second laminar flow forming pipes to form a laminar flow of the second precursor in the reaction chamber, alternately bringing the laminar flow of the first precursor and the laminar flow of the second precursor into contact with the film-forming object held by the holding mechanism to perform an ALD cycle and form a film on the film-forming object, one of the first precursor source and the second precursor source includes an atmospheric pressure plasma source, and 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 from the atmospheric pressure plasma source, An ALD apparatus in which the first precursor and the second precursor supplied and exhausted through the first and second laminar flow forming tubes are introduced into the reaction chamber in opposite directions to each other, or the directions of introduction into the reaction chamber are changed at a predetermined timing.

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