WO2022064849A1 - Dispositif de dépôt de couche atomique - Google Patents

Dispositif de dépôt de couche atomique Download PDF

Info

Publication number
WO2022064849A1
WO2022064849A1 PCT/JP2021/028526 JP2021028526W WO2022064849A1 WO 2022064849 A1 WO2022064849 A1 WO 2022064849A1 JP 2021028526 W JP2021028526 W JP 2021028526W WO 2022064849 A1 WO2022064849 A1 WO 2022064849A1
Authority
WO
WIPO (PCT)
Prior art keywords
gas
raw material
film
chamber
material gas
Prior art date
Application number
PCT/JP2021/028526
Other languages
English (en)
Japanese (ja)
Inventor
直人 亀田
崇之 萩原
綾香 阿部
Original Assignee
株式会社明電舎
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社明電舎 filed Critical 株式会社明電舎
Priority to CN202180065452.6A priority Critical patent/CN116209786B/zh
Publication of WO2022064849A1 publication Critical patent/WO2022064849A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/54—Apparatus specially adapted for continuous coating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers

Definitions

  • the present invention relates to an atomic layer deposition method, and relates to a technique for forming a thin film applicable to, for example, a semiconductor device.
  • a layer deposition method As a method for forming a thin film of an advanced device such as a semiconductor device (for example, a CPU circuit) (hereinafter, simply referred to as a film formation), thin film deposition, sputtering, chemical vapor deposition (CVD), and atomic layer deposition are used.
  • a layer deposition method (ALD: Atomic Layer Deposition) is typical. Among them, ALD has the best step covering property and denseness, and is indispensable as a thin film forming means for cutting-edge devices (for example, Patent Document 1).
  • ALD mainly the process of evacuating the entire chamber (vacuum container, etc.) provided with the object to be deposited (for example, silicon wafer), the raw material gas of ALD (for example, TMA (trimethylaluminum)) in the chamber.
  • a step of introducing the raw material gas, a step of removing the raw material gas from the chamber, and a step of supplying an oxidizing agent (for example, steam) of the raw material gas to the chamber are repeatedly performed.
  • the raw material gas for one molecular layer is adsorbed on the surface of the object to be filmed, and the surface to be filmed of the object to be filmed is adsorbed.
  • a molecular layer of the raw material gas is formed in.
  • the molecular layer of the raw material gas formed on the surface to be formed is oxidized, and the oxide film of the raw material gas (for example, aluminum oxide) is formed on the surface to be formed.
  • the oxide film of the raw material gas for example, aluminum oxide
  • the film formation temperature tends to be high.
  • TMA time to heat
  • a relatively high temperature for example, 300 ° C. to 500 ° C.
  • MBE Molecular Beam Epitaxy
  • the film formation temperature by ALD is preferably room temperature to 100 ° C. Therefore, ALD in which the oxidizing agent is replaced with ozone (O 3 ) or plasma oxygen and the radicals generated by the oxidizing agent are used is being studied. Ozone was able to generate O radicals, which are powerful oxidizing agents, by thermal decomposition, and it was possible to lower the temperature, but it was still necessary to heat the object to be filmed to several hundred degrees Celsius. Further, even when plasma oxygen, which can supply O radicals from the beginning and is capable of the lowest temperature, is used, the temperature is lowered to about 100 ° C to 150 ° C, and further lowering is required.
  • O 3 ozone
  • plasma oxygen which can supply O radicals from the beginning and is capable of the lowest temperature
  • the film forming efficiency tends to be low due to a long film forming time or the like.
  • the raw material gas is first adsorbed on the film-deposited surface, the raw material gas is removed, and the film-formed surface is formed. It is necessary to carry out a step of oxidizing the raw material gas layer (adsorption layer). This process usually takes several minutes.
  • the thickness of one molecular layer is about 0.1 nm, so about 100 molecular layers are required for a practical film formation of about 10 nm, and it takes about 50 minutes even if 30 seconds per molecular layer. It will take.
  • the film forming time of ALD is longer than that of other film forming methods because the film forming of about 10 nm can be formed within 1 minute. This is a major demerit, and improvement in film formation efficiency (shortening of film formation time, etc.) is required.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a technique that contributes to a reduction in the film formation temperature and an improvement in the film formation efficiency in the film formation process by ALD.
  • the atomic layer deposition method according to the present invention can contribute to solving the above-mentioned problems, and as an embodiment thereof, an oxide film is formed on the surface to be deposited on the object to be deposited in the chamber of the atomic layer deposition apparatus.
  • the raw material gas supply step of supplying the raw material gas containing the elements constituting the oxide film into the chamber to form an adsorption layer of the raw material gas on the surface to be formed
  • the raw material gas supply step A raw material gas purging step of removing the surplus gas of the raw material gas and the gas generated by adsorbing the raw material gas on the surface to be formed, and ozone gas of 80% by volume or more in the chamber.
  • Oxidizing agent supply step that oxidizes the adsorption layer formed on the surface to be deposited, and the excess ozone gas supplied in the oxidant supply step, and the gas generated by oxidizing the adsorption layer of the raw material gas.
  • the oxidant purging step for removing and removing from the surface to be deposited is provided, and the oxidant supply step has an exposure amount of ozone gas to the surface to be deposited of 1 ⁇ 10 5 Langmuir or more and a pressure of 1000 Pa in the chamber. It is as follows.
  • the first aspect of the atomic layer depositing device is a chamber in which an object to be deposited can be freely taken in and out, a support portion for supporting the object to be deposited, a gas supply unit for supplying gas into the chamber, and a gas supply unit.
  • a gas discharge unit that takes in gas in the chamber and discharges it to the outside of the chamber to maintain a depressurized state in the chamber is provided. It may have an ozone gas outlet for ejecting ozone gas into the chamber and an inert gas outlet for ejecting an inert gas into the chamber.
  • the gas flow in the chamber may be adjusted by supplying the inert gas into the chamber.
  • the supply amount of the inert gas may be adjusted based on the volume or shape in the chamber.
  • the support portion has a housing-shaped accommodating wall capable of accommodating a plurality of objects to be filmed in and out freely and arranging them in the chamber, and at least a part of the accommodating wall is in the chamber. It is also possible that a ventilation portion that allows the passage of gas and blocks the passage of the object to be filmed is provided.
  • the support unit movably supports the object to be filmed in two of the four directions along the surface to be filmed
  • the gas supply unit is a chamber.
  • the shower head is arranged so as to face the surface of the object to be filmed, and the shower head has a raw material gas outlet and an ozone gas outlet, and the surface of the object to be filmed is formed.
  • Inactive gas outlets are provided between the raw material gas outlet and the ozone gas outlet so as to face each other in the two directions at intervals of predetermined intervals.
  • At least one of the outlets of the shower head is provided with an exhaust port between the outlets.
  • the support portion has one end side roll that winds and supports one end side of the object to be filmed, and the other end side roll that winds and supports the other end side of the object to be filmed.
  • the object to be film-formed may be movably supported by a roll-to-roll method.
  • the support portion may have a support base for supporting the object to be filmed, and the support base may be movable along the surface of the object to be filmed to be filmed.
  • the shower head may have a plurality of pairs of raw material gas outlets and ozone gas outlets adjacent to each other arranged at predetermined intervals in the two directions.
  • a plurality of raw material gas outlets are arranged in the intersecting direction intersecting the two directions out of the four directions along the film formation surface to form a raw material gas outlet group, and the intersection is formed.
  • a plurality of ozone gas outlets may be arranged in the direction to form a group of ozone gas outlets.
  • each outlet of the shower head has dimensions in the two directions in the range of 1 mm to 50 mm, and the distance between the object to be filmed and the surface to be filmed is in the range of 1 mm to 20 mm. It is also good.
  • At least one of the outlets of the shower head may have a slit shape that is long in the intersecting direction intersecting the two directions among the four directions along the film-deposited surface.
  • the gas supply amount of the raw material gas is 0.0001 to 1 sccm per unit length in the direction perpendicular to the two directions at the raw material gas outlet, and the supply amount of ozone gas is in the direction perpendicular to the two directions at the ozone gas outlet. It may be 0.1 sccm to 10 sccm per unit length.
  • the chamber is a raw material gas processing furnace provided with a raw material gas ejection port, an ozone gas processing furnace provided with an ozone gas ejection port, a raw material gas processing furnace and an ozone gas processing furnace. It has an inert gas treatment furnace, which is interposed between the two and is provided with an inert gas outlet, and the support portion is one end that winds and supports one end side of the object to be deposited. The side roll, the other end roll that winds and supports the other end side of the object to be deposited, the first folded roll arranged in the raw material gas processing furnace, and the first folded roll arranged in the ozone gas processing furnace.
  • the object to be deposited between the and the other end roll is folded back by the first and second folded rolls, and both the inside of the raw material gas processing furnace and the inside of the ozone gas processing furnace are reciprocated and superimposed in a knot.
  • Each time it moves between the raw material gas treatment furnace and the ozone gas treatment furnace it passes through the inside of the inert gas treatment furnace, and the furnace wall of each treatment furnace is formed in the shape of a knot.
  • a processing furnace opening through which the object to be deposited can pass is provided at a position intersecting with the object to be filmed.
  • the position facing the processing furnace opening between the first folding roll and the processing furnace opening in the raw material gas processing furnace and the ozone gas processing furnace may be provided at least one of the positions facing the processing furnace opening between the second folding roll and the processing furnace opening.
  • the cycle of each of the raw material gas supply step, the raw material gas purging step, the oxidant supply step, and the oxidant purging step is performed a plurality of times, and in at least one step and the remaining steps of each raw material gas supply step, the cycle is performed.
  • Different types of raw material gases may be supplied to the object to be deposited.
  • the oxide film adsorbs any of Al 2 O 3 , HfO 2 , TiO 2 , ZnO, Ta 2 O 3 , Ga 2 O 3 , MoO 3 , RuO 2 , SiO 2 , ZrO 2 , and Y 2 O 3 . It may include layers.
  • the object to be filmed may be heated within the range of 100 ° C. or lower, or the object to be filmed may not be heated.
  • the exposure amount of the raw material gas to the surface to be filmed may be 1 ⁇ 10 4 Langmuir or more.
  • the present invention it is possible to contribute to the reduction of the film forming temperature and the improvement of the film forming efficiency in the film forming process by ALD.
  • FIG. 3 is a film forming process diagram relating to the formation of the oxide film 21.
  • the reaction schematic diagram which shows the formation example of the oxide film 21.
  • the pressure change characteristic figure with respect to the elapsed time for explaining an example of the film formation cycle by steps S1 to S4.
  • FIG. 3 is a film thickness characteristic diagram of the oxide film 21 when the film formation cycle is carried out at various temperatures according to Example 1.
  • FIG. The leakage current density characteristic diagram with respect to the applied electric field strength of the oxide film 21 by Example 1.
  • FIG. 1 The schematic block diagram for demonstrating the outline of the ALD apparatus 12 applicable to the ALD method by Example 2.
  • FIG. The schematic block diagram for demonstrating the outline of the ALD apparatus 13 applicable to the ALD method by Example 3.
  • Schematic cross-sectional view for explaining each spout of the shower head 4a (a view when the shower head 4a is viewed from the front of FIG. 9; a view corresponding to a part of FIG. 9).
  • the atomic layer deposition method of the embodiment of the present invention (hereinafter, appropriately referred to as the ALD method) is a conventional ALD method (hereinafter, simply referred to as a conventional method) in which, for example, the film formation temperature is set to a relatively high temperature or radicals generated by an oxidizing agent are used. It is completely different from the ALD method).
  • the ALD method of the present embodiment is a method of forming an oxide film on the surface to be deposited of the object to be deposited located in the chamber of the atomic layer deposition apparatus by ALD (hereinafter, appropriately referred to as the ALD apparatus). Therefore, each step of the raw material gas supply step, the raw material gas purging step, the oxidant supply step, and the oxidant purging step is appropriately performed by the ALD device.
  • the oxidizing agent supply step 80% by volume or more of ozone gas is supplied into the chamber, the exposure amount of the ozone gas to the film-deposited surface is 1 ⁇ 105 Langmuir or more, and the pressure in the chamber is 1000 Pa or less. do.
  • the raw material gas adsorbed on the surface to be formed can be sufficiently oxidized without heating the object to be formed or using radicals as an oxidizing agent. It is possible to form a desired oxide film. Further, in the ALD method using high-concentration ozone gas, it is possible to form an oxide film at a low temperature (for example, 100 ° C. or lower) as compared with the conventional ALD method, so that the heat resistance is as high as that of a Si substrate, for example. It is possible to appropriately form an oxide film not only on a substrate having a relatively high heat resistance but also on a substrate or a film made of a synthetic resin having a relatively low heat resistance.
  • the radicals conventionally used in the ALD method have a relatively short life, so that it is difficult to diffuse widely in the chamber, and the raw material gas adsorbed on the uneven surface to be formed is oxidized. It is possible that things will be difficult. For this reason, the object to be film-formed may be limited to a flat plate-shaped substrate or the like having a flat surface to be filmed, or may be limited to single-wafer processing.
  • the ozone gas can be widely diffused in the chamber, and even if the film-formed surface is uneven, a desired oxide film can be obtained. It is quite possible to form. It is also possible to arrange a plurality of objects to be filmed in the chamber and collectively form an oxide film on each surface to be filmed. From this, it can be seen that it is possible to contribute to the reduction of the film forming temperature and the improvement of the film forming efficiency in the film forming process by ALD. Moreover, since plasma is not used, it can be said that the formed oxide film is plasma damageless.
  • the ALD method of the present embodiment appropriately sets the concentration, exposure amount, and partial pressure of ozone gas in the oxidizing agent supply step, and is desired for the surface to be deposited of the object to be deposited.
  • Any mode may be used as long as it can form an oxide film, and common technical knowledge in various fields (for example, film forming field by ALD, CVD, etc., modification field, chamber field, ozone gas field, unsaturated hydrocarbon gas field, etc.) is appropriately applied.
  • FIG. 1 describes the ALD method according to the first embodiment and shows an outline of the ALD apparatus 11 applicable to the first embodiment.
  • the ALD device 11 of FIG. 1 has a chamber (reaction vessel) 3 capable of freely taking in and out an object 2 to be film-formed, a gas supply unit 4 for supplying various gases into the chamber 3, and gas in the chamber 3. It mainly includes a gas discharge unit 5 that takes in air and discharges it to the outside of the chamber 3.
  • the object to be film-formed 2 housed in the chamber 3 can be appropriately supported by, for example, a support portion (not shown).
  • the gas supply unit 4 includes a raw material gas outlet 41 that ejects the raw material gas into the chamber 3, an ozone gas outlet 42 that ejects ozone gas into the chamber 3, and an inert gas outlet 43 that ejects the inert gas into the chamber 3. , Have.
  • These ejection ports 41 to 43 are provided, for example, at positions in the chamber 3 facing the object to be filmed 2 (positions on the upper side in the drawing of the chamber 3 in FIG. 1), via pipes 41a, 42a, and 43a, respectively.
  • the raw material gas supply device 41b, the ozone gas generator 42b, and the inert gas supply device 43b are connected.
  • the pipes 41a and 43a are combined and provided in the chamber 3 as a common spout, and the pipes 41a and 43a are joined and connected to the common spout. It has become.
  • the inert gas of the inert gas supply device 43b can be used as the carrier gas when the raw material gas of the raw material gas supply device 41b is supplied into the chamber 3.
  • the pipe 43c connected to the inert gas supply device 43b is merged with the pipe 42a (merges as shown by a dotted line in FIG. 1) and connected to the ejection port 42, it is inert. It is also possible to eject the inert gas of the gas supply device 43b together with the ozone gas of the ozone gas generator 42b from the ejection port 42 into the chamber 3 (the same applies to FIGS. 8, 9, and 12 described later).
  • the gas discharge unit 5 is provided, for example, at a position in the chamber 3 separated from each of the spouts 41 to 43 (position on the side shown in the figure of the chamber 3 in FIG. 1).
  • the gas discharge unit 5 takes in the gas in the chamber 3 and discharges it to the outside of the chamber 3 to maintain the inside of the chamber 3 in a depressurized state (for example, a state in which the inside of the chamber 3 is in a vacuum environment). Is possible.
  • the gas discharge unit 5 in FIG. 1 has an exhaust pipe 5a, a vacuum pump 5b, and the like.
  • the raw material gas supply step S1 the raw material gas purging step S2, the oxidant supply step S3, and the oxidant purging step S4 shown in FIG. It is possible to form a desired oxide film 21 on the surface to be filmed 20.
  • the raw material gas of the raw material gas supply device 41b (the raw material gas containing the element constituting the target oxide film 21) is supplied into the chamber 3 from the ejection port 41.
  • the raw material gas is adsorbed on the film-formed surface 20 of the film-deposited object 2 in the chamber 3, and the adsorption layer 21a formed by the raw material gas is formed. Will be done.
  • FIG. 3A depicts a state in which a single molecular layer of TMA gas is adsorbed on the film-formed surface 20 of the substrate-shaped object to be film-formed.
  • the film-formed surface 20 is cleaned in the first stage of the raw material gas supply step S1 (for example, the inert gas supply device 43b). It is preferable to supply the inert gas to the chamber 3 and purge it) so that the raw material gas can be easily adsorbed on the film-formed surface 20.
  • the raw material gas supply step S1 for example, the inert gas supply device 43b. It is preferable to supply the inert gas to the chamber 3 and purge it) so that the raw material gas can be easily adsorbed on the film-formed surface 20.
  • the inert gas of the inert gas supply device 43b is supplied into the chamber 3 from the ejection port 43, or the gas in the chamber 3 is taken in by the gas discharge unit 5. And discharge.
  • the surplus gas of the raw material gas supplied in the raw material gas supply step S1 and the gas generated by the adsorption of the raw material gas on the film-formed surface 20 are removed from the film-formed surface 20.
  • the ozone gas of the ozone gas generator 42b is supplied into the chamber 3 from the ejection port 42.
  • the adsorption layer 21a formed on the film-formed surface 20 is oxidized (the methyl group (CH 3 ) is oxidized in FIG. 3), and the film-forming surface 20 is oxidized.
  • An adsorbable region 20a for the next film formation on the surface 20 will be formed.
  • the oxidation reaction as shown in the reaction schematic diagram of FIG. 3 (b) is also possible at room temperature (25 ° C.).
  • the inert gas of the inert gas supply device 43b is supplied from the ejection port 43 into the chamber 3, and the gas in the chamber 3 is discharged into the gas discharge unit. Intake and exhaust by 5.
  • the surplus gas of the ozone gas supplied in the oxidizing agent supply step S3 and the gas generated by oxidizing the adsorption layer 21a of the raw material gas are removed from the film-formed surface 20.
  • a film forming cycle By appropriately repeating the cycle of each of the steps S1 to S4 as described above (hereinafter, simply referred to as a film forming cycle), it is possible to form an oxide film 21 having a desired thickness on the film-deposited surface 20. Obviously, Various film forming conditions in this film forming cycle can be appropriately set according to, for example, the target oxide film 21.
  • each raw material gas supply step S1 when the film forming cycle is performed a plurality of times, for example, at least one step and the remaining steps of each raw material gas supply step S1 are performed by supplying different types of raw material gas to the object to be filmed 2. It is possible to form an oxide film 21 having a multi-layer structure (that is, an oxide film 21 in which a plurality of adsorption layers 21a are laminated) composed of adsorption layers 21a of different raw material gases.
  • the inert gas of the inert gas supply device 43b may be appropriately supplied also in the raw material gas supply step S1 and the oxidant supply step S3.
  • the raw material gas or ozone gas gas supplied from the gas supply unit 4 is used.
  • the inert gas is appropriately supplied as described above (specifically, the supply amount of the inert gas is adjusted based on the volume and shape of the chamber 3 or the inert gas is concerned. By intermittently supplying gas), it becomes possible to promote the gas flow.
  • the gas flow in the chamber 3 can be appropriately adjusted by appropriately supplying the inert gas.
  • the raw material gas and the ozone gas can be easily supplied in a desired supply amount, and the gas in the chamber 3 can be easily discharged.
  • the object to be filmed 2 may be any as long as it can form a desired oxide film 21 on the surface to be filmed 20 by appropriately executing a film forming cycle, and as an example thereof, it may be in the form of a solid, a substrate, or a powder.
  • various particles such as an aggregate of a large number of particles to be filmed (2), a film, a sheet, a cloth, and a fiber can be mentioned.
  • the oxide film can be formed at a relatively low temperature. Therefore, for example, in the case of a substrate or a film.
  • the oxide film is not limited to a substrate having a relatively high heat resistance such as a Si substrate, and an oxide film can be formed on a substrate made of a synthetic resin having a relatively low heat resistance.
  • the object 2 to be deposited is made of a resin
  • examples of the resin include those using a polyester resin, an aramid resin, an olefin resin, polypropylene, PPS (polyphenylene sulfide), PET (polyethylene terephthalate) and the like. Be done.
  • PE polyethylene
  • PEN polyethylene naphthalate
  • POM polyoxymethylene or acetal resin
  • PEEK polyetheretherketone
  • ABS resin acrylonitrile, butadiene, styrene copolymer synthetic resin
  • PA Polyethylene
  • PFA polyethylene tetrafluoride, perfluoroalkoxyethylene copolymer
  • PI polyethylene
  • PVD polyvinyl chloride
  • the surface to be filmed 20 of the object to be filmed 2 is not limited to a mere flat surface, and may have various embodiments.
  • the object to be film-formed 2 shown in FIG. 1 is a solid state in which a plurality of fin-like protrusions are formed, and an uneven step or the like is formed on the surface to be film-formed 20.
  • both or one of the flat front and back surfaces extending in the longitudinal direction can be the surface to be filmed 20. ..
  • the object to be film-formed 2 may be appropriately heated (for example, heated by a heating mechanism such as a thermocouple or an infrared heater; not shown) for the purpose of improving the film-forming performance.
  • a heating mechanism such as a thermocouple or an infrared heater; not shown
  • heating is performed as necessary so that the film formation temperature of the surface to be filmed 20 is in the range of about room temperature to 100 ° C.
  • the raw material gas applied in the raw material gas supply step S1 is an element forming an oxide film (for example, lithium (Li), magnesium (Mg), silicon (Si), titanium (Ti), vanadium (V), chromium (Cr)).
  • an oxide film for example, lithium (Li), magnesium (Mg), silicon (Si), titanium (Ti), vanadium (V), chromium (Cr)
  • raw material gas containing organic silicon having a Si—O bond or Si—C bond or an organic metal having a metal element-oxygen bond or a metal element-carbon bond, an organic metal complex, or a hydride of silicon or metal can be mentioned.
  • silane generally term for hydrogen silicate
  • TEOS TetraEthyl OrthoSillicate
  • TMS TriMthoxySylane
  • TES TriEthoxySilane
  • TMA TriMethylAlminium
  • TEMAZ Tetrakis 3DAMAS (tri-dimethylaminosilane; SiH [N (CH 3 ) 2 ] 3 ), TDMAT (tetrakis dimethylamino titanium; Ti [N (CH 3 ) 2 ] 4 ), TDHA (tetrakis dimethylamino hafnium) ; Hf [N (CH 3 ) 2 ] 4 ) and the like are used.
  • a complex using a heterogeneous dinuclear complex containing not only one kind of metal element but also a plurality of kinds of metal elements for example, a complex described in JP-A-2016-210742 can be mentioned.
  • the raw material gas may be supplied into the chamber 3 (for example, supplied at 1 LSM or less) by using a carrier gas (N 2 , Ar, He, etc.).
  • a carrier gas N 2 , Ar, He, etc.
  • the inert gas of the inert gas supply device 43b can be used as the carrier gas.
  • ozone gas applied in the oxidant supply step S3 those having various concentrations can be applied, but the higher the ozone concentration, the more preferable.
  • the ozone concentration (volume% concentration) is 80 to 100% by volume.
  • Such a high concentration ozone gas can be obtained by liquefying and separating only ozone from the ozone-containing gas based on the difference in vapor pressure, and then vaporizing the liquefied ozone again.
  • Examples of the ozone gas generator 42b include those disclosed in the patent documents of Japanese Patent Application Laid-Open No. 2001-304756 and Japanese Patent Application Laid-Open No. 2003-20209. Such an ozone gas generator 42b liquefies and separates only ozone based on the difference in vapor pressure between ozone and another gas (for example, oxygen) to generate high-concentration ozone (ozone concentration ⁇ 100% by volume). .. In particular, if a plurality of chambers for liquefying and vaporizing only ozone are provided, high-concentration ozone gas can be continuously supplied by controlling the temperature of these chambers individually.
  • another gas for example, oxygen
  • MPOG-HM1A1 pure ozone generator manufactured by Meidensha.
  • the inert gas may be, for example, any gas that can be applied in the raw material gas purging step S2 and the oxidizing agent purging step S4.
  • An example thereof is an inert gas such as N 2 , Ar, and He.
  • the gas supply unit 4 has ejection ports 41 to 43, and various embodiments may be applied as long as the raw material gas, ozone gas, and inert gas can be supplied to the chamber 3 with a desired supply amount (flow rate, etc.), pressure, or the like. It is possible.
  • the spouts 41 to 43 are not only provided one by one for the chamber 3, but may be provided in a plurality of each. Further, the shapes of the spouts 41 to 43 can be appropriately set, and one example thereof is a circle, a rectangle, an ellipse, a slit shape, or the like.
  • the supply amount and pressure of each gas supplied from the spouts 41 to 43 can be appropriately set by, for example, providing a flow rate variable valve or the like (not shown) in the pipes 41a to 43a.
  • Example of gas supply amount, pressure, etc. The amount of raw material gas, ozone gas, and inert gas supplied to the chamber 3 and the pressure of each gas (for example, the pressure of the ozone gas in the chamber 3 (partial pressure).
  • the pressure between the above and the surface to be deposited 20) can be appropriately controlled and set, and as an example thereof, the type, shape, number of objects to be deposited 2 in the chamber 3 and the like, and The setting may be made in consideration of the type, concentration, etc. of each gas.
  • the process pressure in the chamber 3 due to the film forming cycle is kept within the range of 1000 Pa or less. It is possible to set the supply amount and the like as appropriate. More specifically, the inert gas is supplied from the inert gas outlet 43 into the chamber 3 (for example, intermittently supplied as described later), and the base pressure is within the range of about 1 Pa to 1000 Pa due to the supply. It can be mentioned by appropriately controlling and setting so that it fits in.
  • the time required for one film forming cycle can be appropriately set, and is not particularly limited, but may be set to, for example, several seconds to several tens of seconds (for example, 3 seconds to 60 seconds).
  • the exposure amount of the ozone gas to the film-formed surface 20 is set to 1 ⁇ 105 Langmuir or more, and the pressure due to the ozone gas in the chamber 3 is set. It is possible to appropriately set the supply amount of the ozone gas and the like so that the value is 100 Pa or less.
  • the partial pressure of the ozone gas is set to be 100 Pa or less.
  • the pressure increase due to the supply of ozone gas may be appropriately set to be 100 Pa or less, preferably 50 Pa or less, and more preferably 10 Pa or less.
  • the adsorption layer 21a adsorbed on the film-deposited surface 20 in the raw material gas supply step S1 can be sufficiently oxidized.
  • the raw material gas is adsorbed on the surface to be deposited 20 and sufficiently oxidized (forms an oxide film) in the oxidizing agent supply step S3 in the subsequent stage. It may be set so that it can be set, and it is not particularly limited.
  • the supply amount of the raw material gas and the like may be appropriately set so that the exposure amount of the raw material gas to the film-formed surface 20 is 1 ⁇ 10 4 Langmuir or more. Further, the exposure amount of the raw material gas changes depending on the adsorption rate of the raw material gas. Therefore, for example, even if different types of raw material gases are used, if the adsorption rate with respect to the film-formed surface 20 is about the same, it is conceivable to set the supply amount of each of the raw material gases to be about the same. Examples of the raw material gas having the same adsorption rate include TMA, TDMAT, TDHA and the like.
  • the amount of the inert gas supplied to the chamber 3 may be appropriately set as long as the process pressure is within the range of 1000 Pa or less as described above. Is possible.
  • the inert gas is intermittently supplied to the chamber 3 and appropriately set so as not to excessively dilute the raw material gas and the ozone gas in the chamber 3 (for example, set within 10 times the ozone gas supply amount). ).
  • the exhaust gas by the gas discharge unit 5 is particularly limited as long as the depressurized state in the chamber 3 can be maintained so that the process pressure in the chamber 3 is within the range of 1000 Pa or less as described above. is not it.
  • the gas discharge unit 5 in FIG. 1 has an exhaust pipe 5a, a vacuum pump 5b, and the like, but in addition, an ozone killer (abatement equipment such as a detoxification cylinder that decomposes ozone; not shown). It is also possible to have an exhaust valve (a valve whose opening can be adjusted, etc .; not shown) as appropriate. Further, it is preferable to apply an ozone-resistant configuration (for example, a dry pump) to the vacuum pump 5b.
  • an ozone-resistant configuration for example, a dry pump
  • a plurality of exhaust lines may be provided in the gas discharge unit 5, and the exhaust lines may be used properly in each of the steps S1 to S4. This makes it possible to distribute the gas exhausted in each of the steps S1 to S4 to a dedicated abatement facility for processing.
  • the support portion for supporting the object to be filmed 2 housed in the chamber 3 is not particularly limited as long as it can support the film to be filmed so as not to interfere with the film formation on the surface to be filmed 20, for example. Specific examples include the embodiments shown in Examples 2 to 4 described later.
  • Example of film formation by ALD device 11 Based on Example 1 shown above, the film formation cycle by the ALD device 11 is appropriately carried out, and the oxide film 21 of Al 2 O 3 is formed on the film formation surface 20 of the object to be filmed 2 and verified. As a result, the results shown in FIGS. 5 to 7 were obtained.
  • TMA is applied to the raw material gas supplied in the raw material gas supply step S1
  • the pressure increase due to the ozone gas (concentration 80 to 100% by volume) supplied in the oxidizing agent supply step S3 is set to 50 Pa, and the ozone gas is concerned.
  • the exposure time was 3 seconds or less.
  • a PEN film was applied for the film formation shown in FIGS. 5 and 6, and a Si substrate was applied for the film formation shown in FIG. 7.
  • FIG. 5 in which the film-forming temperature is set to about room temperature shows the film thickness characteristics of the oxide film 21 when the film-forming cycle is carried out at various film-forming temperatures. According to FIG.
  • the GPC Rowth Per Cycle
  • the oxide film 21 was formed at a relatively high film formation temperature by the conventional ALD method
  • the GPC was about 1.0 to 1.2 ⁇ / cycle. Therefore, according to the first embodiment, it was confirmed that good film forming speed characteristics can be obtained as compared with the conventional ALD method.
  • FIG. 6 shows a case where an oxide film 21 having a film thickness of 40 nm is formed on the surface to be filmed 20 on one end side in the film thickness direction of the object to be filmed 2, and water vapor with respect to the elapsed time of the object to be filmed 2. It shows the transmittance characteristics. According to FIG. 6, it can be read that the water vapor transmittance converges to about 4.4 ⁇ 10 -4 g / m 2 / day with the passage of time. When the water vapor transmittance of the object to be filmed 2 before forming the oxide film 21 was measured, it was about 10 -1 g / m 2 / day. Therefore, according to this Example 1, it was confirmed that a good barrier property can be obtained in the oxide film 21.
  • FIG. 7 shows the leakage current density characteristics with respect to the applied electric field strength in the oxide film 21. According to FIG. 7, it can be read that the dielectric breakdown strength of 10 MV / cm or more is obtained in the oxide film 21. Therefore, according to the first embodiment, it was confirmed that the leakage current can be sufficiently suppressed and good insulating properties can be obtained in the oxide film 21.
  • Example 2 In the second embodiment, a plurality of objects to be filmed 2, for example, an aggregate of a large number of particles of the object to be filmed 2 as shown in FIG. 8 (b) described later (hereinafter, simply an aggregate to be filmed). 22 is accommodated and supported so that the oxide film 21 can be formed simultaneously on the film-forming surface 20 of each film-forming object 2.
  • a plurality of objects to be filmed 2 for example, an aggregate of a large number of particles of the object to be filmed 2 as shown in FIG. 8 (b) described later (hereinafter, simply an aggregate to be filmed). 22 is accommodated and supported so that the oxide film 21 can be formed simultaneously on the film-forming surface 20 of each film-forming object 2.
  • FIG. 8 describes the ALD method according to the second embodiment and shows an outline of the ALD apparatus 12 applicable to the second embodiment.
  • the ALD device 12 of FIG. 8 includes a support portion 6 having a housing-shaped accommodating wall 61 that can be arranged in the chamber 3, and accommodates a plurality of objects to be deposited 2 in the accommodating wall 61. It has a structure that can be supported.
  • the accommodating wall 61 has a configuration in which a plurality of objects to be film-formed 2 can be freely taken in and out. Further, at least a part of the accommodating wall 61 is provided with a ventilation portion 62 having a plurality of ventilation holes whose pore diameter is smaller than the maximum outer diameter (particle diameter or the like) of the object to be film-formed.
  • a ventilation portion 62 having a plurality of ventilation holes whose pore diameter is smaller than the maximum outer diameter (particle diameter or the like) of the object to be film-formed.
  • the accommodation wall 61 of FIG. 8 it has a cylindrical structure, and ventilation portions 62 are provided at positions on both ends in the axial direction.
  • the accommodating wall 61 is configured to be rotatable (in the case of the accommodating wall 61 of FIG. 8, for example, axially rotatable), so that the film-forming object 2 in the accommodating wall 61 is formed into a film while stirring. be able to. As a result, it may be possible to suppress the formation of oxide film formation spots on the object to be filmed.
  • any gas (raw material gas, ozone gas, inert gas, etc.) that can pass through the chamber 3 and can block the passage of the object to be filmed may be used, and various embodiments are allowed. Can be applied.
  • Example of film formation by ALD device 12 Based on Example 2 shown above, the film formation cycle by the ALD device 12 is appropriately carried out, and Al 2 O is applied to the film-forming surface 20 in the aggregate 22 of the object 2 to be film-formed in the form of a large number of particles.
  • the oxide film 21 of 3 was formed and verified. The verification conditions were the same as in Example 1, and a particle diameter of 1 mm or less was applied to the object to be filmed 2.
  • Example 3 the object to be filmed 2 moves in two directions (hereinafter, simply referred to as two directions of the surface to be filmed) facing each other among the four directions along the surface to be filmed 20 (out of the two directions).
  • the oxide film 21 can be formed on the film-formed surface 20 while moving to one side or reciprocating to both sides.
  • FIG. 9 describes the ALD method according to the third embodiment and shows an outline of the ALD apparatus 13 applicable to the third embodiment.
  • the support portion 7 provided in the chamber 3 allows the ALD device 13 to be formed in the longitudinal direction along the surface to be deposited 20. It is configured to be movably supported in two of the four directions along the film surface (hereinafter, simply referred to as two directions of the surface to be deposited).
  • the support portion 7 of FIG. 9 is of a so-called roll-to-roll method, and has a one-sided roll 71, which is a winding shaft on which one end side of a long film-shaped object to be film-formed is wound, and the covering. It has a roll 72 on the other end, which is a winding shaft on which the other end of the film object 2 is wound, and transport rolls 73a, 73b arranged between the roll 71 on the one end and the roll 72 on the other end. However, each roll is configured to rotate appropriately.
  • the object to be film-formed 2 sent out from one of the one end side roll 71 and the other end side roll 72 is taken up by the other via the transport rolls 73a and 73b.
  • the support portion 7 it is possible to appropriately move the object to be filmed 2 in the two directions of the surface to be filmed.
  • both the transport rolls 73a and 73b are arranged on the upper side in the chamber 3 at predetermined intervals, and the film-forming object 2 moving between the two is covered.
  • the film forming surface 20 faces the upper side in the chamber 3 (facing the shower head 4a described later).
  • a gas supply unit 4 having a shower head 4a is provided on the upper side of the chamber 3.
  • the shower head 4a has a structure having a plurality of ejection ports 41 to 43, respectively, and is located at a position facing the film-forming surface 20 of the film-forming object 2 moving between the transport rolls 73a and 73b. , Is provided.
  • the raw material gas supply device 41b, the ozone gas generator 42b, and the inert gas supply device 43b are connected to the spouts 41 to 43 of the shower head 4a via pipes 41a, 42a, and 43a, respectively.
  • the gas from each of the devices 41b to 43b can be appropriately supplied into the chamber 3 from the ejection ports 41 to 43, respectively.
  • the support portion 7 may be in a manner as long as it can movably support the object to be filmed 2 housed in the chamber 3 in two directions on the surface to be filmed, and is based on the roll-to-roll method as shown in FIG. Not limited to.
  • a method having a support base for example, a support base as shown by reference numeral 7 in FIG. 1 of Japanese Patent No. 602470
  • a support base method that supports the object to be film-formed
  • FIG. 10 shows an example of the shower head 4a.
  • the unmarked solid line arrow indicates an example of the supply direction of each gas
  • the dotted line arrow indicates an example of the exhaust direction of each gas.
  • a plurality of ejection ports 41 and 42 are provided on the portions 4b facing the film-deposited surface 20 of the film-deposited object 2 moving between the transport rolls 73a and 73b, respectively. ing.
  • Both of these spouts 41 and 42 are alternately located in the two directions of the film-deposited surface at predetermined intervals, and a pair of spouts by the spouts 41 and 42 adjacent to each other (for example, a jet indicated by reference numeral T in FIG. 10).
  • a plurality of outlet pairs) are arranged in two directions of the film-deposited surface at predetermined intervals.
  • a spout 43 is provided between the spouts 41 and 42. Further, an exhaust port 44 between the spouts is provided between the spouts 41 to 43.
  • the exhaust port 44 has a configuration in which gas or the like between the exhaust port 44 and the surface to be filmed 20 can be taken in and discharged to the outside of the chamber 3.
  • a plurality of the ejection ports 41 to 43 and the exhaust port 44 (hereinafter, collectively referred to simply as an ejection port or the like) in the shower head 4a are not only provided in a plurality of arrangements along the two directions of the film-formed surface, but also the said.
  • a plurality of layers may be arranged in an intersecting direction (hereinafter, simply referred to as an intersecting direction) that intersects the two directions of the film-deposited surface.
  • a plurality of spouts 41 may be arranged in the crossing direction to form a raw material gas spout group, or a plurality of spouts 42 may be arranged in the crossing direction to form an ozone gas spout group.
  • the mode (shape, size, etc.) of the ejection port and the like and the distance between the film-deposited object 2 and the film-deposited surface 20 are not limited to the same, and may be different. good.
  • the dimensions (slit width in the case of a slit-shaped spout having a long slit in the crossing direction) V1 to V8 in the two directions of the surface to be filmed such as the spout are 10 -1 mm to several hundred mm. It is possible to set it within the range of, preferably within the range of 1 mm to 100 mm. Further, the distance h1 to h8 between each ejection port and the like and the surface to be filmed surface 20 of the object to be filmed 2 is in the range of several mm to several hundred mm, preferably in the range of 1 mm to 100 mm, more preferably.
  • the ejection port 42 may be set within the range of 1 mm to 20 mm.
  • the distance h8 related to the spout 42 is set to be larger than the distances h1 to h7 related to other spouts and the like.
  • the pitch between the spouts and the like may be appropriately set in consideration of the opening dimensions of the spouts and the like.
  • the object to be filmed 2 is movablely supported by the support portion 7 (for example, can be supported by a roll-to-roll method or a support base method), and the object to be filmed 2 is to be filmed.
  • the film is not particularly limited as long as it can form the oxide film 21 on the surface to be filmed 20 while moving in two directions.
  • a long film-like flat front and back surface extending in the longitudinal direction is the film-forming surface 20 (in FIG. 9, one of the front and back surfaces is film-deposited). It becomes a surface 20) and is movably supported by the support portion 7 in the longitudinal direction (two directions of the surface to be filmed).
  • the exposure amount of ozone gas to the surface to be filmed 20 is 1 ⁇ 10 5 Langmuir or more, and the ozone gas is concerned.
  • the pressure is 100 Pa or less, and the exposure amount of the raw material gas to the film-formed surface 20 can be 1 ⁇ 10 4 Langmuir or more.
  • the adsorption layer 21a adsorbed on the film-formed surface 20 in the raw material gas supply step S1 can be sufficiently oxidized in the oxidizing agent supply step S3.
  • the flow rate of ozone gas may be 0.1 sccm to 10 sccm per unit length in the direction perpendicular to the two directions of the surface to be filmed at the ejection port 42.
  • the flow rate of the raw material gas may be 0.0001 sccm to 1 sccm per unit length in the direction perpendicular to the two directions of the surface to be filmed at the ejection port 41.
  • the flow rate of the inert gas may be set relatively large (for example, set higher than the flow rate of ozone gas) within the range where the process pressure does not exceed 1000 Pa.
  • the moving speed of the object to be filmed 2 in two directions on the surface to be filmed may be appropriately set in consideration of the pitch between each ejection port and the like. Convection occurs between each ejection port and the like and the surface to be filmed 20 according to the magnitude of the moving speed set in this way, for example, the reaction of each gas to the surface to be filmed 20 is promoted, and the film is formed. There is a possibility that it can contribute to ease of use.
  • the film-formed surface 20 passes through the regions A1 to A4 in this order as shown in FIG. 10, and the steps S1 to S4 are carried out in the regions A1 to A4 as shown below.
  • the raw material gas is ejected from the ejection port 41 by the raw material gas supply step S1.
  • the raw material gas is adsorbed on the film-deposited surface 20 to form the adsorption layer 21a by the raw material gas.
  • the surplus gas of the raw material gas supplied in the step S1 and the gas (CH 4 gas) generated by the adsorption of the raw material gas on the surface to be deposited surface 20 are present. It is removed by the exhaust port 44 or the gas discharge unit 5, or is removed by the raw material gas purging step S2.
  • the inert gas is ejected from the ejection port 43, and the surplus gas and the like are removed from the region A1.
  • ozone gas is sprayed from the ejection port 42 by the oxidizing agent supply step S3.
  • the adsorption layer 21a due to the raw material gas adsorbed on the film-formed surface 20 is oxidized to form the oxide film 21.
  • an adsorbable region 20a for the next film formation is formed on the surface of the oxide film 21, an adsorbable region 20a for the next film formation is formed.
  • the surplus gas of the ozone gas supplied in the step S3 and the gas generated by oxidizing the adsorption layer 21a are generated by the exhaust port 44 between the ejection ports and the gas discharge unit 5. It is removed or removed by the oxidant purging step S4.
  • the inert gas is ejected from the inert gas outlet 43, and the excess gas and the like are removed from the region A2.
  • the film formation cycles of the steps S1 to S4 in the regions A1 and A2 shown above are similarly carried out in the regions after the A1 and A2 (for example, the regions A3 and A4 in FIG. 10).
  • the desired oxide film 21 can be formed on the surface to be filmed 20 by appropriately performing the film forming cycle. Further, by performing the film forming cycle a plurality of times, it is possible to form a desired film thickness in the oxide film 21.
  • the film forming object 2 is moved to one side or reciprocated in both directions in the two directions of the film forming surface, so that the film forming cycle of the regions A1 to A4 is appropriately performed a plurality of times. There is something to do.
  • Example of film formation by ALD device 13 Based on Example 3 shown above, the film formation cycle by the ALD apparatus 13 is appropriately carried out, and the oxide film of Al 2 O 3 is formed on the film-forming surface 20 of the object 2 to be film-formed in the form of a long film. 21 was formed and verified. The verification conditions were the same as in Example 1, and a PEN film was applied to the object to be filmed 2.
  • Example 1 As a result, as in Example 1, good film formation rate characteristics, barrier properties (water vapor transmittance is about 4.0 ⁇ 10 -4 g / m 2 / day in Example 3), and insulating properties in the oxide film 21. In addition to the above, it was confirmed that the following is obtained.
  • the steps S1 to S4 of the film forming cycle can be appropriately advanced at the same time while moving the object to be filmed 2 in two directions on the surface to be filmed. By comparison, it may be easier to shorten the film formation time.
  • the inert gas outlet 43 and the exhaust port 44 between the outlets are provided between the raw material gas outlet 41 and the ozone gas outlet 42, for example, the raw material gas and the ozone gas are dispersed in the chamber 3. Can be suppressed. As a result, for example, on the inner wall surface of the chamber 3, it is possible to suppress the adhesion and film formation of particles due to the raw material gas and ozone gas, and it is possible to reduce the burden of maintenance of the chamber 3 and the like (cleaning process in the chamber 3 and the like). There is.
  • Example 4 is an application of the roll-to-roll method shown in Example 3, in which the chamber 3 has a structure divided into a plurality of gas treatment furnaces, and each step S1 to S4 of the film forming cycle is the same. It is designed so that it can be shared and implemented for each gas treatment furnace as appropriate.
  • FIG. 12 describes the ALD method according to the fourth embodiment and shows an outline of the ALD apparatus 14 applicable to the fourth embodiment.
  • the ALD device 14 of FIG. 12 includes a chamber 30 having a divided structure and a support portion 8, and the support portion 8 allows a long film-shaped object to be deposited 2 to be deposited in two directions on the surface to be deposited. On the other hand, it is configured so that it can be moved and supported.
  • the chamber 30 includes a raw material gas processing furnace 31 provided with a raw material gas ejection port 41, an ozone gas processing furnace 32 provided with an ozone gas ejection port 42, and both the raw material gas processing furnace 31 and the ozone gas processing furnace 32. It has an inert gas processing furnace 33 provided with an inert gas outlet 43 interposed between the two.
  • the inert gas treatment furnace 34 having the same structure as the inert gas treatment furnace 33 is provided at the position opposite to the inert gas treatment furnace 33 sandwiching the raw material gas treatment furnace 31. Has been done.
  • the inert gas treatment furnace 34 can be applied, for example, to clean the film-formed surface 20 between the one-side roll 71 and the other-end roll 72 and the raw material gas treatment furnace 31, which will be described later. , Can be omitted as appropriate.
  • processing furnace openings 31a to 34a through which the film-forming object 2 can pass are provided at positions intersecting the movement path of the film-forming object 2 on the road wall. Each is provided.
  • the processing furnace openings 31a to 34a are configured to allow the object to be film-formed 2 to pass through the processing furnaces 31 to 34 so as not to interfere with the depressurized state (for example, a parallel seal type slit valve for a vacuum chamber). Etc.).
  • the support portion 8 is of a so-called roll-to-roll system, in which one end-side roll 71, which is a winding shaft on which one end side of the object to be film-formed is wound, and the other end side of the object to be film-formed 2 are formed. It has a roll 72 on the other end, which is a wound winding shaft, a first folded roll 74 arranged in the raw material gas processing furnace 31, and a second folded roll 75 arranged in the ozone gas processing furnace 32. However, each roll is configured to rotate appropriately.
  • one end side roll 71 and the other end side roll 72 are on the outer peripheral side of the chamber 30, and the inert gas sandwiching the raw material gas processing furnace 31 (and the inert gas processing furnace 34) is interposed. It is provided so as to be located on the opposite side of the processing furnace 33.
  • the object to be film-formed 2 between the one end side roll 71 and the other end side roll 72 is placed at each position (inside the processing furnaces 31 and 32). I support it to fold back.
  • the object to be film-formed 2 between the one-side roll 71 and the other-end roll 72 can be placed in both the raw material gas processing furnace 31 and the ozone gas processing furnace 32, as depicted in FIG. 12, for example. It reciprocates in a kudzu shape and is extended and supported so as to overlap. Further, each time the raw material gas processing furnace 31 and the ozone gas processing furnace 32 move between the two (hereinafter, simply referred to as “movement between the two)), the gas passes through the inert gas processing furnace 33.
  • a plurality of the first folded rolls 74 and the second folded rolls 75 are arranged in the overlapping direction of the object to be filmed 2. By appropriately changing the number of sequences, it is possible to set the number of movements between the objects to be filmed 2 as desired.
  • pipes 41a to 43a, devices 41b to 43b, etc. similar to those of the ALD devices 11 to 13 are connected to each of the spouts 41 to 43, respectively. It is supposed to be.
  • the processing furnaces 31 to 34 are provided with the same gas discharge unit 5 as the ALD devices 11 to 13, and are configured to be able to maintain the depressurized state in the processing furnaces 31 to 34, respectively, but they are omitted as appropriate in FIG. It is a depiction of the fire.
  • the film forming cycle By appropriately carrying out such a film forming cycle, it becomes possible to form a desired oxide film 21 on the surface to be filmed 20.
  • the film forming cycle may be appropriately performed a plurality of times. Be done.
  • the supply amount (filling amount) of the raw material gas, ozone gas, and inert gas supplied from the ejection ports 41 to 43 to the chamber 30, the pressure due to each gas, and the like can be appropriately set in the same manner as in Examples 1 and 2. However, it may be set in consideration of the moving speed of the object to be filmed 2 in two directions on the surface to be filmed.
  • the raw material gas, the ozone gas, and the inert gas are appropriately supplied to the processing furnaces 31 to 34 (for example, the raw material gas, Ozone gas and inert gas can be supplied to different processing furnaces 31 to 34 for filling, and after the filling, the treatment furnaces 31 to 34 do not mix with each other.
  • a state that can contribute to the formation of the oxide film 21 (exposure of the ozone gas and the raw material gas to the surface to be formed 20). If the amount is 1 ⁇ 10 5 Langmuir or more, 1 ⁇ 10 4 Langmuir or more), there is no need to newly supply or replace.
  • the high concentration ozone gas is in the range of room temperature to about 400 ° C., the thermal decomposition reaction due to collision between ozone and the like is suppressed, and it is possible to contribute to the film formation of the oxide film 21 for a sufficiently long time. Become.
  • the inert gas may be appropriately supplied.
  • the gas flow in the processing furnaces 31 and 32 can be appropriately adjusted, and it becomes easy to supply the raw material gas and ozone gas in a desired supply amount or diffuse them in the processing furnaces 31 and 32. It can be seen that the gas in 31 and 32 can be easily discharged.
  • each processing furnace 31 to 34 may be different.
  • the pressure of the processing furnaces 31 and 32 may be set within a range in which gas leakage from the processing furnaces 31 and 32 does not occur.
  • the inert gas in the processing furnaces 33 and 34 since the inert gas in the processing furnaces 33 and 34 is relatively safe even if it leaks (safer than the raw material gas and ozone gas), it is safer than the processing furnaces 31 and 32. It may be set high.
  • the moving speed of the object to be filmed 2 in two directions on the surface to be filmed may be appropriately set in consideration of the concentration and pressure of each gas in the chamber 30. Convection occurs on the surface to be filmed 20 according to the magnitude of the moving speed set in this way, and for example, it is possible to promote the reaction of each gas with the surface to be filmed 20 and contribute to the ease of film formation. There is sex.
  • the passage time (stay time) of the processing furnaces 31 and 32 each time the film-deposited object 2 moves between the two is set to 0.1 seconds or more and 1 second or more, respectively.
  • first folded roll 74 and the second folded roll 75 ⁇ Example of the first folded roll 74 and the second folded roll 75>
  • the shapes and arrangements of the first folded roll 74 and the second folded roll 75 can be appropriately set and are not particularly limited.
  • the large size in the direction in which the object to be filmed 2 is superimposed (hereinafter, simply referred to as the overlapping direction). It is also conceivable that this may lead to an increase in the amount of gas supplied to the chamber 30. Further, the formation region of the processing furnace openings 31a to 33a is expanded, and the penetration angle of the object to be filmed 2 with respect to the processing furnace openings 31a to 33a is increased, so that the processing furnace openings 31a to 33a and the film to be filmed are formed. If a gap is created between the object 2 and the object 2, gas leakage may occur.
  • the process is performed between the first folded roll 74 in the processing furnace 31 and the processing furnace opening 31a in the movement path of the knot-folded object to be film-formed.
  • a position adjusting roll 76 may be provided at a position facing the furnace opening 31a.
  • a position adjusting roll 77 may be provided between the second folding roll 75 and the processing furnace opening 32a at a position facing the processing furnace opening 32a.
  • the arrangement dimensions in the overlapping directions are arranged so as to be narrower than the arrangement dimensions in the overlapping directions of the first and second folded rolls 74 and 75, respectively.
  • the knot-folded object to be film-formed 2 is supported so as to converge in the superimposing direction.
  • Example of film formation by ALD device 14 Based on Example 4 shown above, the film formation cycle by the ALD apparatus 14 is appropriately carried out, and the oxide film of Al 2 O 3 is formed on the film-forming surface 20 of the object 2 to be film-formed in the form of a long film. An attempt was made to form 21.
  • the verification conditions were the same as in Example 1, and a PEN film was applied to the object to be filmed 2.
  • Example 3 As a result, as in Example 1, good film formation rate characteristics, barrier properties (water vapor transmittance is about 4.0 ⁇ 10 -4 g / m 2 / day in Example 4), and insulating properties in the oxide film 21. Further, as in Example 3, it is possible that the film formation time can be easily shortened and the burden related to maintenance can be reduced, and the following can be confirmed.
  • Example 4 since it is not always necessary to replace each gas filled in each of the processing furnaces 31 to 34 of the chamber 30, the gas is used more efficiently (reduced supply amount) as compared with Example 3. There is a possibility that it can be done.
  • the ALD method of the present invention has been described above by showing a specific embodiment, the ALD method is not limited to the present embodiment, and the design can be appropriately changed as long as the characteristics are not impaired. The redesigned one also belongs to the technical scope of the present invention.
  • a multi-layered film having an ALD film and a CVD film is formed on the film-deposited surface 20 of the same object to be deposited 2. It is also possible to do. For example, if a SiO 2 film that can be formed at high speed by CVD and has high elastic resistance is formed by CVD and an Al 2 O 3 film with high water vapor permeability is formed by ALD between the SiO 2 films, it is realized as a single-layer film. It is possible to form a multi-layered film having multi-functionality at a low temperature.
  • each component of the ALD devices 11 to 14 it may be omitted as appropriate as long as a desired oxide film 21 can be formed on the surface to be deposited 20.
  • the raw material gas purging step S2 the oxidant purging step S4, and the like can be sufficiently realized by the intake of gas in the chamber 3 by the gas discharging unit 5, the inert gas outlet 43 and the like may be omitted as appropriate. ..
  • the exhaust port between outlets 44 and the like may be omitted as appropriate (for example, the exhaust port between outlets is provided only in a part of each outlet).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Chemical Vapour Deposition (AREA)
  • Formation Of Insulating Films (AREA)

Abstract

La présente invention concerne un objet (2) soumis à une formation de film qui est positionné dans une chambre (3) d'un dispositif ALD (11) et soumis, selon le cas, à un cycle de formation de film comprenant une étape d'alimentation en matière première gazeuse (S1), une étape de purge de matière première gazeuse (S2), une étape d'alimentation en oxydant (S3) et une étape de purge d'oxydant (S4), un film d'oxyde (21) étant formé sur une surface de formation de film (20) de l'objet (2) soumis à une formation de film. Dans l'étape d'alimentation en oxydant (S3), au moins 80 % en volume d'ozone gazeux sont introduits dans la chambre (3), la surface de formation de film (20) est exposée l'ozone gazeux selon une quantité d'exposition supérieure ou égale à 1 × 105 Langmuir et la pression dans la chambre (3) est réglée à 1 000 Pa ou moins.
PCT/JP2021/028526 2020-09-25 2021-08-02 Dispositif de dépôt de couche atomique WO2022064849A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202180065452.6A CN116209786B (zh) 2020-09-25 2021-08-02 原子层沉积方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020160603A JP7056710B2 (ja) 2020-09-25 2020-09-25 原子層堆積方法
JP2020-160603 2020-09-25

Publications (1)

Publication Number Publication Date
WO2022064849A1 true WO2022064849A1 (fr) 2022-03-31

Family

ID=80845042

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/028526 WO2022064849A1 (fr) 2020-09-25 2021-08-02 Dispositif de dépôt de couche atomique

Country Status (3)

Country Link
JP (1) JP7056710B2 (fr)
CN (1) CN116209786B (fr)
WO (1) WO2022064849A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7431897B2 (ja) * 2022-07-20 2024-02-15 明電ナノプロセス・イノベーション株式会社 酸化膜形成方法
CN117568780A (zh) * 2023-11-16 2024-02-20 无锡松煜科技有限公司 一种利用ald法制备氧化铝钝化膜的方法及装置

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006324284A (ja) * 2005-05-17 2006-11-30 Tdk Corp 電気化学キャパシタの製造方法
JP2009044093A (ja) * 2007-08-10 2009-02-26 Tokyo Electron Ltd 成膜方法、成膜装置及び記憶媒体
JP5206908B2 (ja) * 2011-03-29 2013-06-12 凸版印刷株式会社 巻き取り成膜装置
JP2015525302A (ja) * 2012-06-20 2015-09-03 エムティーエスナノテック株式会社Ｍｔｓ Ｎａｎｏｔｅｃｈ Ｉｎｃ． 原子層蒸着装置及びその方法
JP2016005900A (ja) * 2014-05-27 2016-01-14 パナソニックＩｐマネジメント株式会社 ガスバリア膜、ガスバリア膜付きフィルム基板およびこれを備えた電子デバイス。
JP6052470B1 (ja) * 2015-03-12 2016-12-27 株式会社明電舎 樹脂の改質方法
WO2020170482A1 (fr) * 2019-02-19 2020-08-27 株式会社明電舎 Procédé de dépôt par couche atomique et dispositif de dépôt par couche atomique
WO2021038958A1 (fr) * 2019-08-30 2021-03-04 株式会社明電舎 Appareil de dépôt de couche atomique et procédé de dépôt de couche atomique

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100555582C (zh) * 2004-08-11 2009-10-28 株式会社明电舍 用于形成氧化物膜的方法和设备
JP4613587B2 (ja) * 2004-08-11 2011-01-19 株式会社明電舎 酸化膜形成方法とその装置
JP4849863B2 (ja) 2005-10-14 2012-01-11 株式会社明電舎 酸化膜形成方法
KR101435100B1 (ko) * 2012-06-20 2014-08-29 주식회사 엠티에스나노테크 원자층 증착 장치

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006324284A (ja) * 2005-05-17 2006-11-30 Tdk Corp 電気化学キャパシタの製造方法
JP2009044093A (ja) * 2007-08-10 2009-02-26 Tokyo Electron Ltd 成膜方法、成膜装置及び記憶媒体
JP5206908B2 (ja) * 2011-03-29 2013-06-12 凸版印刷株式会社 巻き取り成膜装置
JP2015525302A (ja) * 2012-06-20 2015-09-03 エムティーエスナノテック株式会社Ｍｔｓ Ｎａｎｏｔｅｃｈ Ｉｎｃ． 原子層蒸着装置及びその方法
JP2016005900A (ja) * 2014-05-27 2016-01-14 パナソニックＩｐマネジメント株式会社 ガスバリア膜、ガスバリア膜付きフィルム基板およびこれを備えた電子デバイス。
JP6052470B1 (ja) * 2015-03-12 2016-12-27 株式会社明電舎 樹脂の改質方法
WO2020170482A1 (fr) * 2019-02-19 2020-08-27 株式会社明電舎 Procédé de dépôt par couche atomique et dispositif de dépôt par couche atomique
WO2021038958A1 (fr) * 2019-08-30 2021-03-04 株式会社明電舎 Appareil de dépôt de couche atomique et procédé de dépôt de couche atomique

Also Published As

Publication number Publication date
JP2022053787A (ja) 2022-04-06
CN116209786B (zh) 2024-04-30
CN116209786A (zh) 2023-06-02
JP7056710B2 (ja) 2022-04-19

Similar Documents

Publication Publication Date Title
WO2022064849A1 (fr) Dispositif de dépôt de couche atomique
KR101686029B1 (ko) 기판 처리 장치, 반도체 장치의 제조 방법 및 기록 매체
WO2020170482A1 (fr) Procédé de dépôt par couche atomique et dispositif de dépôt par couche atomique
KR102268455B1 (ko) 산화막 형성 방법
JP2013153143A (ja) 成膜方法
WO2021038958A1 (fr) Appareil de dépôt de couche atomique et procédé de dépôt de couche atomique
JPWO2019187337A1 (ja) 酸化膜形成方法
US20220364235A1 (en) Atomic layer deposition method and atomic layer deposition device
WO2021053904A1 (fr) Dispositif de formation de film d'oxyde
WO2022118879A1 (fr) Dispositif de dépôt de couche atomique et procédé de dépôt de couche atomique
WO2024018811A1 (fr) Procédé de formation d'un film d'oxyde
JP2022087800A (ja) 原子層堆積装置および原子層堆積方法
JP2022087554A (ja) 原子層堆積装置および原子層堆積方法
JP6702514B1 (ja) 酸化膜形成装置
JP2023137315A (ja) 表面改質方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21871981

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21871981

Country of ref document: EP

Kind code of ref document: A1