WO2022064849A1 - Atomic layer deposition method - Google Patents
Atomic layer deposition method Download PDFInfo
- 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
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- WIPO (PCT)
- Prior art keywords
- gas
- raw material
- film
- chamber
- material gas
- Prior art date
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- 238000000231 atomic layer deposition Methods 0.000 title claims description 110
- 238000000034 method Methods 0.000 title claims description 84
- 239000002994 raw material Substances 0.000 claims abstract description 172
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 127
- 239000007800 oxidant agent Substances 0.000 claims abstract description 47
- 238000010926 purge Methods 0.000 claims abstract description 33
- 239000007789 gas Substances 0.000 claims description 395
- 238000012545 processing Methods 0.000 claims description 85
- 239000011261 inert gas Substances 0.000 claims description 73
- 230000001590 oxidative effect Effects 0.000 claims description 31
- 230000008569 process Effects 0.000 claims description 27
- 238000001179 sorption measurement Methods 0.000 claims description 24
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 claims description 6
- 238000009423 ventilation Methods 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 3
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 claims description 2
- 235000010575 Pueraria lobata Nutrition 0.000 claims description 2
- 241000219781 Pueraria montana var. lobata Species 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 57
- 239000010408 film Substances 0.000 description 177
- 239000010410 layer Substances 0.000 description 23
- 238000010586 diagram Methods 0.000 description 15
- 239000000758 substrate Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
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- 239000002052 molecular layer Substances 0.000 description 8
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- 239000002184 metal Substances 0.000 description 7
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 7
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 6
- 239000011112 polyethylene naphthalate Substances 0.000 description 6
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
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- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
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- 229910018557 Si O Inorganic materials 0.000 description 1
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- 229910052735 hafnium Inorganic materials 0.000 description 1
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- 229910052748 manganese Inorganic materials 0.000 description 1
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- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
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- 238000004544 sputter deposition Methods 0.000 description 1
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- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- 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).
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Abstract
An object (2) subject to film formation is positioned in a chamber (3) of an ALD device (11) and subjected, as appropriate, to a film formation cycle comprising a raw material gas feeding step (S1), a raw material gas purging step (S2), an oxidizing agent feeding step (S3), and an oxidizing agent purging step (S4), whereby an oxide film (21) is formed on a film formation surface (20) of the object (2) subject to film formation. In the oxidizing agent feeding step (S3), 80 vol% or more of ozone gas is fed into the chamber (3), the film formation surface (20) is exposed to the ozone gas at an exposure amount of 1×105 Langmuir or above, and the pressure in the chamber (3) is set to 1000 Pa or below.
Description
本発明は、原子層堆積方法に関するものであって、例えば半導体デバイス等に適用可能な薄膜を形成する技術に係るものである。
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.
半導体デバイス(例えば、CPUの回路)等の先端デバイスの薄膜を形成(以下、単に成膜と適宜称する)する手法としては、蒸着、スパッタリング、化学気相成長法(CVD:Chemical Vapor Deposition)、原子層堆積法(ALD:Atomic Layer Deposition)が代表的である。なかでも、ALDは、段差被覆性と緻密性に最も優れており、最先端デバイスの薄膜形成手段としては必須のものとなっている(例えば、特許文献1)。
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では、主に、被成膜対象物(例えば、シリコンウエハ)が備えられたチャンバ(真空容器等)全体を真空排気する工程、チャンバ内にALDの原料ガス(例えば、TMA(トリメチルアルミニウム))を導入する工程、チャンバから原料ガスを除去する工程、チャンバに原料ガスの酸化剤(例えば、水蒸気)を供給する工程、の4つの工程が繰り返し行われる。チャンバ内に原料ガスを導入し、当該チャンバ内に原料ガスを満たすことで、被成膜対象物の表面に1分子層分の原料ガスが吸着し、当該被成膜対象物の被成膜面に原料ガスの分子層が形成される。
In 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. By introducing the raw material gas into the chamber and filling the chamber with the raw material gas, 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.
そして、チャンバ内に原料ガスの酸化剤を供給することで、被成膜面に形成された原料ガスの分子層が酸化され、当該被成膜面に原料ガスの酸化膜(例えば、酸化アルミニウム)の分子層が形成される。前記4つの工程を繰り返し行うことで、繰り返し回数に応じた膜厚を有する薄膜が形成される。
Then, by supplying the oxidizing agent of the raw material gas into the chamber, 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. Molecular layer is formed. By repeating the above four steps, a thin film having a film thickness corresponding to the number of repetitions is formed.
従来のALDによる成膜工程は、成膜温度が高くなってしまう傾向がある。例えば、TMAと水蒸気を十分に反応させるためには、被成膜対象物を比較的高温(例えば300℃~500℃)まで加熱する必要がある。また、最先端デバイスに用いられるGaN、ZnOのような化合物半導体の場合、被成膜面にヘテロエピタキシーやMBE(Molecular Beam Epitaxy)で組成の微妙に異なる薄膜半導体層が数層重ねて形成されることがある。これらの薄膜半導体層は、加熱により組成ずれが発生してしまうおそれがあるため、低温で成膜することが強く求められる。
In the conventional ALD film formation process, the film formation temperature tends to be high. For example, in order to sufficiently react TMA with water vapor, it is necessary to heat the object to be filmed to a relatively high temperature (for example, 300 ° C. to 500 ° C.). Further, in the case of compound semiconductors such as GaN and ZnO used in cutting-edge devices, several thin film semiconductor layers having slightly different compositions due to heteroepitaxy or MBE (Molecular Beam Epitaxy) are formed on the surface to be filmed. Sometimes. Since these thin film semiconductor layers may have a composition shift due to heating, it is strongly required to form a film at a low temperature.
また、他の最先端デバイスでは、ALDによる成膜温度が、室温~100℃が好ましいという考えがある。よって、酸化剤をオゾン(O3)やプラズマ酸素に置き換え、当該酸化剤により発生するラジカルを利用したALDが検討されている。オゾンは熱分解で強力な酸化剤であるOラジカルを発生でき、低温化が可能であったが、それでも被成膜対象物を数百℃に加熱する必要があった。また、最初からOラジカルを供給可能であって最も低温化が可能とされているプラズマ酸素を用いた場合でも、100℃~150℃程度の低温化であり、さらなる低温化が求められている。
Further, in other state-of-the-art devices, there is an idea that 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.
また、従来のALDによる成膜工程は、成膜時間が長くなる等により成膜効率が低くなってしまう傾向がある。例えば、被成膜面に対し、ALDにより1分子層を成膜するためには、まず当該被成膜面に原料ガスを吸着させ、原料ガスを除去し、当該被成膜面に形成された原料ガス層(吸着層)を酸化する工程を行う必要がある。この工程は、通常数分を要する。例えば、酸化アルミニウムの場合は1分子層の厚みが約0.1nm程度なので、実用的な10nm程度の成膜には約100分子層が必要となり、1分子層あたり30秒としても50分程度もかかってしまう。例えば、CVD等の他の成膜方法であれば、10nm程度の成膜であれば1分以内で成膜可能なことから、他の成膜方法と比較して、ALDの成膜時間の長さは大きなデメリットであり、成膜効率の改善(成膜時間の短縮等)が求められている。
Further, in the conventional ALD film forming process, the film forming efficiency tends to be low due to a long film forming time or the like. For example, in order to form a single molecular layer on the film-deposited surface by ALD, 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. For example, in the case of aluminum oxide, 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. For example, in the case of other film forming methods such as CVD, 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.
本発明は、上記事情に鑑みてなされたものであり、ALDによる成膜工程において成膜温度の低減や成膜効率の改善に貢献する技術を提供することを目的としている。
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.
この発明に係る原子層堆積方法は、前記の課題の解決に貢献できるものであり、その態様としては、原子層堆積装置のチャンバ内における被成膜対象物の被成膜面に酸化膜を形成する方法であって、酸化膜を構成する元素を含む原料ガスをチャンバ内に供給して、被成膜面に当該原料ガスの吸着層を形成する原料ガス供給工程と、原料ガス供給工程で供された原料ガスの余剰ガスと、当該原料ガスが被成膜面に吸着することで生じたガスと、を当該被成膜面から除去する原料ガスパージ工程と、80体積%以上のオゾンガスをチャンバ内に供給し、被成膜面に形成された吸着層を酸化する酸化剤供給工程と、酸化剤供給工程で供されたオゾンガスの余剰ガスと、原料ガスの吸着層を酸化することで生じたガスと、を被成膜面から除去する酸化剤パージ工程と、を有し、酸化剤供給工程は、被成膜面に対するオゾンガスの曝露量を1×105ラングミュア以上とし、チャンバ内の圧力を1000Pa以下とするものである。
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. In 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, and 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.
原子層堆積装置の第1の態様は、被成膜対象物を出し入れ自在に収容可能なチャンバと、被成膜対象物を支持する支持部と、チャンバ内にガスを供給するガス供給部と、チャンバ内のガスを吸気して当該チャンバ外に排出し、当該チャンバ内の減圧状態を維持するガス排出部と、を備え、ガス供給部は、原料ガスをチャンバ内に噴き出す原料ガス噴出口と、オゾンガスをチャンバ内に噴き出すオゾンガス噴出口と、不活性ガスをチャンバ内に噴き出す不活性ガス噴出口と、を有しているものとしても良い。
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.
また、前記各工程は、チャンバ内に不活性ガスを供給することにより、当該チャンバ内のガス流を調整するものとしても良い。
Further, in each of the steps, the gas flow in the chamber may be adjusted by supplying the inert gas into the chamber.
また、チャンバ内の容積または形状に基づいて、不活性ガスの供給量を調整するものとしても良い。
Further, the supply amount of the inert gas may be adjusted based on the volume or shape in the chamber.
また、支持部は、複数個の被成膜対象物を出し入れ自在に収容してチャンバ内に配置可能な筐体状の収容壁を有し、前記収容壁の少なくとも一部には、チャンバ内のガスの通過が可能であって被成膜対象物の通過を遮る通気部が、設けられているものとしても良い。
Further, 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.
原子層堆積装置の第2の態様において、支持部は、被成膜対象物を、被成膜面に沿った四方向のうち相対する二方向において移動自在に支持し、ガス供給部は、チャンバ内において被成膜対象物の被成膜面と対向して配置されたシャワーヘッドを有し、シャワーヘッドは、原料ガス噴出口とオゾンガス噴出口とが、被成膜対象物の被成膜面と対向して前記二方向に所定間隔を隔てて交互に設けられ、原料ガス噴出口とオゾンガス噴出口との両者間に不活性ガス噴出口が設けられており、被成膜対象物の前記二方向の移動に応じて、被成膜面に対し前記各工程を行うものである。
In the second aspect of the atomic layer deposition apparatus, the support unit movably supports the object to be filmed in two of the four directions along the surface to be filmed, and 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. Each of the above steps is performed on the surface to be filmed according to the movement in the direction.
また、シャワーヘッドの各噴出口間のうち少なくとも何れかに、噴出口間排気口が設けられているものとしても良い。
Further, it is also possible that at least one of the outlets of the shower head is provided with an exhaust port between the outlets.
また、支持部は、被成膜対象物の一端側を巻回して支持する一端側ロールと、当該被成膜対象物の他端側を巻回して支持する他端側ロールと、を有し、当該被成膜対象物をロールツーロール方式で移動自在に支持するものとしても良い。
Further, 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.
また、支持部は、被成膜対象物を支持する支持台を有し、当該支持台を被成膜対象物の被成膜面に沿って移動自在であるものとしても良い。
Further, 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.
また、シャワーヘッドは、互いに隣接する原料ガス噴出口およびオゾンガス噴出口による噴出口対が、前記二方向に所定間隔を隔てて複数個配列されているものとしても良い。
Further, 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.
また、シャワーヘッドは、被成膜面に沿った四方向のうち前記二方向と交差している交差方向に、原料ガス噴出口が複数個配列されて原料ガス噴出口群を構成し、前記交差方向に、オゾンガス噴出口が複数個配列されてオゾンガス噴出口群を構成しているものとしても良い。
Further, in the shower head, 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.
また、シャワーヘッドの各噴出口は、前記二方向の寸法が1mm~50mmの範囲内であり、被成膜対象物の被成膜面との間の距離が1mm~20mmの範囲内であるものとしても良い。
Further, 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.
また、シャワーヘッドの各噴出口のうち少なくとも何れかは、被成膜面に沿った四方向のうち前記二方向と交差している交差方向に長いスリット形状であるものとしても良い。
Further, 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.
また、原料ガスのガス供給量は、原料ガス噴出口における前記二方向と垂直方向の単位長さ当たり0.0001~1sccmとし、オゾンガスの供給量は、オゾンガス噴出口における前記二方向と垂直方向の単位長さ当たり0.1sccm~10sccmとするものとしても良い。
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.
原子層堆積装置の第3の態様において、チャンバは、原料ガス噴出口が設けられている原料ガス処理炉と、オゾンガス噴出口が設けられているオゾンガス処理炉と、原料ガス処理炉とオゾンガス処理炉との両者間に介在し、不活性ガス噴出口が設けられている不活性ガス処理炉と、を有して成り、支持部は、被成膜対象物の一端側を巻回して支持する一端側ロールと、当該被成膜対象物の他端側を巻回して支持する他端側ロールと、原料ガス処理炉内に配置された第1折り返しロールと、オゾンガス処理炉内に配置された第2折り返しロールと、を有し、被成膜対象物を、被成膜面に沿った四方向のうち相対する二方向において移動自在に支持するロールツーロール方式の構造であって、一端側ロールと他端側ロールとの間の被成膜対象物は、第1,第2折り返しロールにより折り返されて、原料ガス処理炉内とオゾンガス処理炉内との両者を葛折り状に往復して重畳するように延在し、原料ガス処理炉とオゾンガス処理炉との両者間を移動する毎に、不活性ガス処理炉内を通過し、各処理炉の炉壁は、前記葛折り状の被成膜対象物と交差する位置に、当該被成膜対象物が通過可能な処理炉開口部が設けられているものである。
In the third aspect of the atomic layer deposition apparatus, 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. It is a roll-to-roll type structure that has two folded rolls and movably supports the object to be deposited in two directions opposite to each other in four directions along the surface to be deposited, and is a roll on one end side. 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.
また、前記葛折り状の被成膜対象物の移動経路において、原料ガス処理炉内における第1折り返しロールと処理炉開口部との間で当該処理炉開口部に対向した位置と、オゾンガス処理炉内における第2折り返しロールと処理炉開口部との間で当該処理炉開口部に対向した位置と、のうち少なくとも一方に、位置調整ロールが設けられているものとしても良い。
Further, in the movement path of the object to be deposited in the shape of a knot, 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. A position adjusting roll may be provided at least one of the positions facing the processing furnace opening between the second folding roll and the processing furnace opening.
前記態様においては、原料ガス供給工程、原料ガスパージ工程、酸化剤供給工程、酸化剤パージ工程の各工程によるサイクルを複数回行い、各原料ガス供給工程のうち少なくとも1工程と残りの工程とにおいて、それぞれ異なる種類の原料ガスを被成膜対象物に供給するものとしても良い。
In the above aspect, 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.
また、酸化膜は、Al2O3、HfO2、TiO2、ZnO、Ta2O3、Ga2O3、MoO3、RuO2、SiO2、ZrO2、Y2O3のいずれかの吸着層を含む、としても良い。
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.
また、被成膜対象物を100℃以下の範囲内で加熱、または当該被成膜対象物を加熱しないものとしても良い。
Further, 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.
また、原料ガス供給工程は、被成膜面に対する原料ガスの曝露量を1×104ラングミュア以上とするものとしても良い。
Further, in the raw material gas supply step, the exposure amount of the raw material gas to the surface to be filmed may be 1 × 10 4 Langmuir or more.
以上示したように本発明によれば、ALDによる成膜工程において成膜温度を低減や成膜効率の改善に貢献可能となる。
As shown above, according to 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.
本発明の実施形態の原子層堆積方法(以下、ALD方法と適宜称する)は、例えば成膜温度を比較的高温にしたり、酸化剤により発生するラジカルを利用した従来のALD方法(以下、単に従来ALD方法と適宜称する)とは、全く異なるものである。
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).
すなわち、本実施形態のALD方法は、ALDによる原子層堆積装置(以下、ALD装置と適宜称する)のチャンバ内に位置する被成膜対象物の被成膜面に酸化膜を形成する方法であって、当該ALD装置により、原料ガス供給工程,原料ガスパージ工程,酸化剤供給工程,酸化剤パージ工程の各工程を適宜行うものである。
That is, 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.
そして、酸化剤供給工程においては、チャンバ内に80体積%以上のオゾンガスを供給し、当該オゾンガスの被成膜面に対する曝露量を1×105ラングミュア以上とし、当該チャンバ内の圧力を1000Pa以下とする。
Then, in 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.
このような本実施形態によれば、例えば、被成膜対象物を加熱したり酸化剤としてラジカルを利用しなくても、被成膜面に吸着している原料ガスを十分に酸化することができ、所望の酸化膜を形成することが可能となる。また、高濃度のオゾンガスを用いたALD方法では、従来ALD方法と比較して低温(例えば100℃以下)で酸化膜を形成することも可能であるため、例えばSi基板等のように耐熱性が比較的高い基板だけでなく、当該耐熱性が比較的低い合成樹脂で形成された基板またはフィルム等においても、酸化膜を適宜形成することが可能となる。
According to this embodiment, for example, 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.
例えば、従来ALD方法で利用されているラジカルにおいては、寿命が比較的短いため、チャンバ内で広く拡散することが困難であり、凹凸状の被成膜面に吸着している原料ガスを酸化することが困難となってしまうことも考えられる。このため、被成膜対象物においては、被成膜面が平坦である平板状の基板等に限定されたり、枚葉処理に限定されてしまうおそれがあった。
For example, 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.
一方、本実施形態においては、酸化剤として高濃度のオゾンガスを適用するため、当該オゾンガスをチャンバ内で広く拡散することができ、たとえ被成膜面が凹凸状であっても、所望の酸化膜を形成することが十分可能である。また、複数の被成膜対象物をチャンバ内に配置し、それぞれの被成膜面に対して一括で酸化膜を形成することも可能となる。これにより、ALDによる成膜工程において成膜温度の低減や成膜効率の改善に貢献可能であることが判る。また、プラズマを用いないため、成膜した酸化膜がプラズマダメージレスであると言える。
On the other hand, in the present embodiment, since high-concentration ozone gas is applied as an oxidizing agent, 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.
本実施形態のALD方法は、前述のように酸化剤供給工程におけるオゾンガスの濃度,曝露量,分圧を適宜設定したものであって、被成膜対象物の被成膜面に対して所望の酸化膜を形成できる態様であれば良く、種々の分野(例えば、ALD,CVD等による成膜分野,改質分野,チャンバ分野,オゾンガス分野,不飽和炭化水素ガス分野等)の技術常識を適宜適用し、必要に応じて先行技術文献等を適宜参照して設計変形することが可能であり、その一例として以下に示す実施例1~4が挙げられる。
As described above, 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. However, it is possible to modify the design by appropriately referring to the prior art documents and the like as necessary, and Examples 1 to 4 shown below can be mentioned as an example thereof.
なお、以下の実施例1~4は、例えば互いに同様の内容について同一符号を引用する等により、詳細な説明を適宜省略しているものとする。
In the following Examples 1 to 4, detailed description will be omitted as appropriate, for example, by quoting the same reference numerals for the same contents.
≪実施例1≫
<ALD装置11の主な構成>
図1は、実施例1によるALD方法を説明するものであって、当該実施例1で適用可能なALD装置11の概略を示すものである。図1のALD装置11は、被成膜対象物2を出し入れ自在に収容可能なチャンバ(反応容器)3と、チャンバ3内に各種ガスを供給するガス供給部4と、チャンバ3内のガスを吸気して当該チャンバ3外に排出するガス排出部5と、を主として備えている。チャンバ3内に収容した被成膜対象物2は、例えば図外の支持部により適宜支持することが可能である。 << Example 1 >>
<Main configuration ofALD device 11>
FIG. 1 describes the ALD method according to the first embodiment and shows an outline of theALD 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).
<ALD装置11の主な構成>
図1は、実施例1によるALD方法を説明するものであって、当該実施例1で適用可能なALD装置11の概略を示すものである。図1のALD装置11は、被成膜対象物2を出し入れ自在に収容可能なチャンバ(反応容器)3と、チャンバ3内に各種ガスを供給するガス供給部4と、チャンバ3内のガスを吸気して当該チャンバ3外に排出するガス排出部5と、を主として備えている。チャンバ3内に収容した被成膜対象物2は、例えば図外の支持部により適宜支持することが可能である。 << Example 1 >>
<Main configuration of
FIG. 1 describes the ALD method according to the first embodiment and shows an outline of the
ガス供給部4は、原料ガスをチャンバ3内に噴き出す原料ガス噴出口41と、オゾンガスをチャンバ3内に噴き出すオゾンガス噴出口42と、不活性ガスをチャンバ3内に噴き出す不活性ガス噴出口43と、有している。これら噴出口41~43においては、例えばチャンバ3における被成膜対象物2と対向する位置(図1ではチャンバ3の図示上方側の位置)に設けられ、それぞれ配管41a,42a,43aを介して、原料ガス供給装置41b,オゾンガス発生装置42b,不活性ガス供給装置43bが接続されている。
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.
図1の噴出口41,43の場合、一つに纏められて共通の噴出口としてチャンバ3に設けられており、当該共通の噴出口に対し、配管41a,43aが合流して接続された構成となっている。このような構成によれば、原料ガス供給装置41bの原料ガスをチャンバ3内に供給する場合のキャリアガスとして、不活性ガス供給装置43bの不活性ガスを利用することができる。
In the case of the spouts 41 and 43 of FIG. 1, 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. According to such a configuration, 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.
また、例えば、不活性ガス供給装置43bに接続されている配管43cを、配管42aと合流(図1では点線で描写するように合流)して噴出口42に接続した構成によれば、不活性ガス供給装置43bの不活性ガスを、オゾンガス発生装置42bのオゾンガスと共に噴出口42からチャンバ3内に噴き出すことも可能(後述の図8,図9,図12も同様に可能)となる。
Further, for example, according to the configuration in which 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).
ガス排出部5は、例えばチャンバ3における各噴出口41~43から距離を隔てた位置(図1ではチャンバ3の図示側方側の位置)に設けられる。このガス排出部5は、チャンバ3内のガスを吸気して当該チャンバ3外に排出し、当該チャンバ3内を減圧状態(例えばチャンバ3内が真空環境下となるような状態)に維持することが可能な構成とする。図1のガス排出部5の場合、排気管5a,真空ポンプ5b等を有した構成となっている。
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.
<ALD装置を用いる場合の成膜工程>
ALD装置11においては、図2に示す原料ガス供給工程S1,原料ガスパージ工程S2,酸化剤供給工程S3,酸化剤パージ工程S4を順次実行することにより、チャンバ3内の被成膜対象物2の被成膜面20に所望の酸化膜21を形成することが可能となる。 <Deposition process when using ALD device>
In theALD apparatus 11, 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.
ALD装置11においては、図2に示す原料ガス供給工程S1,原料ガスパージ工程S2,酸化剤供給工程S3,酸化剤パージ工程S4を順次実行することにより、チャンバ3内の被成膜対象物2の被成膜面20に所望の酸化膜21を形成することが可能となる。 <Deposition process when using ALD device>
In the
図2において、まず原料ガス供給工程S1では、原料ガス供給装置41bの原料ガス(目的とする酸化膜21を構成する元素を含む原料ガス)を噴出口41からチャンバ3内に供給する。これにより、図3(a)の反応模式図のように、チャンバ3内の被成膜対象物2の被成膜面20に対して原料ガスが吸着し、当該原料ガスによる吸着層21aが形成される。図3(a)では、基板状の被成膜対象物2における被成膜面20に対し、1分子層のTMAガスが吸着されている状態を描写するものとなっている。
In FIG. 2, first, in the raw material gas supply step S1, 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. As a result, as shown in the reaction schematic diagram of FIG. 3A, 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.
なお、被成膜対象物2の被成膜面20に例えば不純物等が付着している場合には、原料ガス供給工程S1の前段において被成膜面20を清浄(例えば不活性ガス供給装置43bの不活性ガスをチャンバ3に供給してパージ)し、当該被成膜面20に対して原料ガスを吸着し易くしておくことが好ましい。
When impurities or the like are attached to the film-formed surface 20 of the object to be film-formed, for example, 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.
原料ガス供給工程S1の後、原料ガスパージ工程S2では、不活性ガス供給装置43bの不活性ガスを噴出口43からチャンバ3内に供給したり、当該チャンバ3内のガスをガス排出部5により吸気して排出する。これにより、前記原料ガス供給工程S1で供された原料ガスの余剰ガスと、当該原料ガスが被成膜面20に吸着することで生じたガスと、を当該被成膜面20から除去する。
After the raw material gas supply step S1, in the raw material gas purging step S2, 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. As a result, 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.
次に、酸化剤供給工程S3では、オゾンガス発生装置42bのオゾンガスを噴出口42からチャンバ3内に供給する。これにより、図3(b)の反応模式図のように、被成膜面20に形成されている吸着層21aが酸化(図3ではメチル基(CH3)が酸化)され、当該被成膜面20における次の成膜のための吸着可能領域20aが形成されることとなる。この図3(b)の反応模式図に示すような酸化反応は、室温(25℃)でも可能である。
Next, in the oxidant supply step S3, the ozone gas of the ozone gas generator 42b is supplied into the chamber 3 from the ejection port 42. As a result, as shown in the reaction schematic diagram of FIG. 3B, 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.).
そして、酸化剤パージ工程S4では、原料ガスパージ工程S2と同様に、不活性ガス供給装置43bの不活性ガスを噴出口43からチャンバ3内に供給したり、当該チャンバ3内のガスをガス排出部5により吸気して排出する。これにより、前記酸化剤供給工程S3で供されたオゾンガスの余剰ガスと、前記原料ガスの吸着層21aを酸化することで生じたガスと、を被成膜面20から除去する。
Then, in the oxidant purging step S4, as in the raw material gas purging step S2, 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. As a result, 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.
以上のような各工程S1~S4によるサイクル(以下、単に成膜サイクルと適宜称する)を適宜繰り返すことにより、被成膜面20に対して所望厚さの酸化膜21を形成することが可能となる。この成膜サイクルにおける各種成膜条件は、例えば目的とする酸化膜21に応じて、適宜設定することが可能である。
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. Become. Various film forming conditions in this film forming cycle can be appropriately set according to, for example, the target oxide film 21.
また、前記成膜サイクルを複数回行う場合、例えば各原料ガス供給工程S1のうち少なくとも1工程と残りの工程とを、それぞれ異なる種類の原料ガスを被成膜対象物2に供給することにより、それぞれ異なる原料ガスの吸着層21aからなる多層構造の酸化膜21(すなわち、複数の吸着層21aが積層された酸化膜21)を、構成できることとなる。
Further, 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.
<各工程S1~S4における不活性ガス>
原料ガスパージ工程S2や酸化剤パージ工程S4においては、チャンバ3内のガスをガス排出部5により吸気すると同時に、不活性ガス供給装置43bの不活性ガスをチャンバ3内に適宜供給することにより、当該チャンバ3内のガスのガス流が促進され、余剰ガス等の除去(パージ)に要する時間の短縮化を図ることが可能となる。 <Inert gas in each process S1 to S4>
In the raw material gas purging step S2 and the oxidant purging step S4, the gas in thechamber 3 is taken in by the gas discharge unit 5, and at the same time, the inert gas of the inert gas supply device 43b is appropriately supplied into the chamber 3. The gas flow of the gas in the chamber 3 is promoted, and it becomes possible to shorten the time required for removing (purging) excess gas and the like.
原料ガスパージ工程S2や酸化剤パージ工程S4においては、チャンバ3内のガスをガス排出部5により吸気すると同時に、不活性ガス供給装置43bの不活性ガスをチャンバ3内に適宜供給することにより、当該チャンバ3内のガスのガス流が促進され、余剰ガス等の除去(パージ)に要する時間の短縮化を図ることが可能となる。 <Inert gas in each process S1 to S4>
In the raw material gas purging step S2 and the oxidant purging step S4, the gas in the
また、不活性ガス供給装置43bの不活性ガスは、原料ガス供給工程S1や酸化剤供給工程S3においても、適宜供給しても良い。
Further, 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.
例えば、チャンバ3内のガスがガス供給部4に逆流すると、当該逆流したガスによりガス供給部4(後述の実施例3ではシャワーヘッド4a)にパーティクルの付着や成膜が起こったり、当該ガス供給部4から供給する原料ガスやオゾンガスのガス流が妨げられることが考えられるが、前記のように不活性ガスを適宜供給することにより、当該逆流の抑制が可能となる。
For example, when the gas in the chamber 3 flows back to the gas supply unit 4, particles adhere to or form a film on the gas supply unit 4 (shower head 4a in Example 3 described later) due to the backflow gas, or the gas is supplied. It is conceivable that the gas flow of the raw material gas or ozone gas supplied from the unit 4 is obstructed, but the backflow can be suppressed by appropriately supplying the inert gas as described above.
また、チャンバ3内の容積・形状等によっては(例えば容積が大きい場合(例えば容積1m3超の場合)や形状が複雑な場合には)、ガス供給部4から供給する原料ガスやオゾンガスのガス流が低くなってしまう場合があるが、前記のように不活性ガスを適宜供給(具体的には、チャンバ3の容積・形状に基づいて不活性ガスの供給量を調整したり、当該不活性ガスを断続的に供給)することにより、当該ガス流を促進することが可能となる。
Further, depending on the volume and shape of the chamber 3 (for example, when the volume is large (for example, when the volume exceeds 1 m 3 ) or when the shape is complicated), the raw material gas or ozone gas gas supplied from the gas supply unit 4 is used. Although the flow may be low, 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.
したがって、各工程S1~S4においては、それぞれ不活性ガスを適宜供給することにより、チャンバ3内におけるガス流を適宜調整できる。これにより、原料ガスやオゾンガスを所望の供給量で供給することが容易になったり、チャンバ3内のガスの排出が容易となることが判る。
Therefore, in each of the steps S1 to S4, the gas flow in the chamber 3 can be appropriately adjusted by appropriately supplying the inert gas. As a result, it can be seen that 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.
<被成膜対象物2の一例>
被成膜対象物2においては、成膜サイクルを適宜実行して被成膜面20に所望の酸化膜21を形成できるものであれば良く、その一例として固形状,基板状,粉体状(例えば多数の粒子状の被成膜対象物2の集合体),フィルム状,シート状,布状,繊維状等の種々のものが挙げられる。 <Example of the object to be filmed 2>
The object to be filmed 2 may be any as long as it can form a desiredoxide 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. For example, 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.
被成膜対象物2においては、成膜サイクルを適宜実行して被成膜面20に所望の酸化膜21を形成できるものであれば良く、その一例として固形状,基板状,粉体状(例えば多数の粒子状の被成膜対象物2の集合体),フィルム状,シート状,布状,繊維状等の種々のものが挙げられる。 <Example of the object to be filmed 2>
The object to be filmed 2 may be any as long as it can form a desired
また、原料ガスと80体積%以上の高濃度のオゾンガスとを用いて酸化膜を形成する手法では、当該酸化膜を比較的低温で形成することが可能であるため、例えば基板またはフィルム等の場合、Si基板等の比較的耐熱性が高い基板等に限定されることはなく、耐熱性が比較的低い合成樹脂で形成された基板等に酸化膜を形成することもできる。
Further, in the method of forming an oxide film using a raw material gas and a high concentration ozone gas of 80% by volume or more, 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.
被成膜対象物2が樹脂を用いてなる場合、当該樹脂としては、例えば、ポリエステル樹脂、アラミド樹脂、オレフィン樹脂、ポリプロピレン、PPS(ポリフェニレンサルファイド)、PET(ポリエチレンテレフタレート)等を用いたものが挙げられる。
When 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.
その他、PE(ポリエチレン)、PEN(ポリエチレンナフタレート)、POM(ポリオキシメチレン、または、アセタール樹脂)、PEEK(ポリエーテルエーテルケトン)、ABS樹脂(アクリロニトリル、ブタジエン、スチレン共重合合成樹脂)、PA(ポリアミド)、PFA(4フッ化エチレン、パーフルオロアルコキシエチレン共重合体)、PI(ポリイミド)、PVD(ポリ二塩化ビニル)等を用いたものも挙げられる。
In addition, 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) and the like are also used.
被成膜対象物2の被成膜面20においては、単なる平坦状に形成されたものに限定されず、種々の態様であっても良い。例えば図1に示す被成膜対象物2は、複数個のフィン状突起が形成された固形状であり、被成膜面20において凹凸状の段差等が形成されたものとなっている。
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. For example, 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.
例えば後述の実施例3,4のように被成膜対象物2が長尺フィルム状の場合、長手方向に延在する平坦な表裏面の両方または片方を被成膜面20とすることができる。
For example, when the object to be filmed 2 is in the form of a long film as in Examples 3 and 4 described later, both or one of the flat front and back surfaces extending in the longitudinal direction can be the surface to be filmed 20. ..
また、被成膜対象物2は、例えば成膜性能の向上を図る目的で、適宜加熱(例えば熱電対や赤外線ヒータ等の加熱機構により加熱;図示省略)しても良い。具体例としては、被成膜面20の成膜温度が室温程度~100℃の範囲内となるように、必要に応じて加熱することが挙げられる。
Further, 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. As a specific example, 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.
<原料ガスの一例>
原料ガス供給工程S1で適用する原料ガスは、酸化膜を形成する元素(例えば、リチウム(Li)、マグネシウム(Mg)、ケイ素(Si)、チタン(Ti)、バナジウム(V)、クロム(Cr)、マンガン(Mn)、鉄(Fe)、コバルト(Co)、ニッケル(Ni)、銅(Cu)、亜鉛(Zn)、ガリウム(Ga)、ゲルマニウム(Ge)、イットリウム(Y)、ジルコニウム(Zr)、モリブデン(Mo)、ルテニウム(Ru)、ロジウム(Rh)、インジウム(In)、錫(Sn)、ハフニウム(Hf)、タンタル(Ta)、タングステン(W)、イリジウム(Ir)、白金(Pt)、鉛(Pb)等;以下これらの元素を金属または金属元素という)を構成元素として含む態様が挙げられる。 <Example of raw material gas>
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)). , Manganese (Mn), Iron (Fe), Cobalt (Co), Nickel (Ni), Copper (Cu), Zinc (Zn), Gallium (Ga), Germanium (Ge), Ittrium (Y), Zirconium (Zr) , Molybdenum (Mo), Ruthenium (Ru), Rodium (Rh), Indium (In), Tin (Sn), Hafnium (Hf), Tantal (Ta), Tungsten (W), Iridium (Ir), Platinum (Pt) , Lead (Pb), etc .; hereinafter, these elements are referred to as a metal or a metal element) as a constituent element.
原料ガス供給工程S1で適用する原料ガスは、酸化膜を形成する元素(例えば、リチウム(Li)、マグネシウム(Mg)、ケイ素(Si)、チタン(Ti)、バナジウム(V)、クロム(Cr)、マンガン(Mn)、鉄(Fe)、コバルト(Co)、ニッケル(Ni)、銅(Cu)、亜鉛(Zn)、ガリウム(Ga)、ゲルマニウム(Ge)、イットリウム(Y)、ジルコニウム(Zr)、モリブデン(Mo)、ルテニウム(Ru)、ロジウム(Rh)、インジウム(In)、錫(Sn)、ハフニウム(Hf)、タンタル(Ta)、タングステン(W)、イリジウム(Ir)、白金(Pt)、鉛(Pb)等;以下これらの元素を金属または金属元素という)を構成元素として含む態様が挙げられる。 <Example of raw material gas>
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)). , Manganese (Mn), Iron (Fe), Cobalt (Co), Nickel (Ni), Copper (Cu), Zinc (Zn), Gallium (Ga), Germanium (Ge), Ittrium (Y), Zirconium (Zr) , Molybdenum (Mo), Ruthenium (Ru), Rodium (Rh), Indium (In), Tin (Sn), Hafnium (Hf), Tantal (Ta), Tungsten (W), Iridium (Ir), Platinum (Pt) , Lead (Pb), etc .; hereinafter, these elements are referred to as a metal or a metal element) as a constituent element.
例えば、Si-O結合若しくはSi-C結合を有する有機シリコンまたは金属元素-酸素結合若しくは金属元素-炭素結合を有する有機金属を含有する原料ガスや、有機金属錯体またはケイ素や金属の水素化物等の原料ガスが挙げられる。
For example, 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. Raw material gas can be mentioned.
より具体的には、原料ガスとして、シラン(ケイ化水素の総称)、TEOS(TetraEthyl OrthoSillicate)、TMS(TriMthoxySilane)、TES(TriEthoxySilane)、TMA(TriMethyl Alminium)、TEMAZ(Tetrakis(ethylmethylamino)zirconium)、3DAMAS(トリ・ジメチルアミノ・シラン;SiH[N(CH3)2]3)、TDMAT(テトラキス・ジメチルアミノ・チタニウム;Ti[N(CH3)2]4)、TDMAH(テトラキス・ジメチルアミノ・ハフニウム;Hf[N(CH3)2]4)等を用いたものが挙げられる。また、金属元素1種類だけでなく複数種類の金属元素を含む異種複核錯体(例えば、特開2016-210742等に記載の錯体)を用いたものも挙げられる。
More specifically, as the raw material gas, silane (general 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. Further, 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.
また、原料ガスは、例えばキャリアガス(N2,Ar,He等)を用いてチャンバ3内に供給(例えば1LSM以下で供給)するようにしても良い。図1の場合には、不活性ガス供給装置43bの不活性ガスをキャリアガスとして用いることが可能である。
Further, 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.). In the case of FIG. 1, the inert gas of the inert gas supply device 43b can be used as the carrier gas.
<オゾンガスの一例>
酸化剤供給工程S3で適用するオゾンガスは、種々の濃度のものを適用することが可能であるが、オゾン濃度が高いほど好ましい。具体的には、高濃度のオゾンガスにおいて、オゾン濃度(体積%濃度)を80~100体積%とすること好ましい。このような高濃度のオゾンガスは、オゾン含有ガスから蒸気圧の差に基づいてオゾンのみを液化分離した後、再び液化したオゾンを気化させて得ることができる。 <Example of ozone gas>
As the 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. Specifically, in a high concentration ozone gas, it is preferable that 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.
酸化剤供給工程S3で適用するオゾンガスは、種々の濃度のものを適用することが可能であるが、オゾン濃度が高いほど好ましい。具体的には、高濃度のオゾンガスにおいて、オゾン濃度(体積%濃度)を80~100体積%とすること好ましい。このような高濃度のオゾンガスは、オゾン含有ガスから蒸気圧の差に基づいてオゾンのみを液化分離した後、再び液化したオゾンを気化させて得ることができる。 <Example of ozone gas>
As the 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. Specifically, in a high concentration ozone gas, it is preferable that 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.
オゾンガス発生装置42bとしては、例えば、特開2001-304756号公報や特開2003-20209号公報の特許文献に開示されているものが挙げられる。このようなオゾンガス発生装置42bは、オゾンと他のガス(例えば、酸素)の蒸気圧の差に基づきオゾンのみを液化分離して高濃度のオゾン(オゾン濃度≒100体積%)を生成している。特に、オゾンのみを液化および気化させるチャンバを複数備えると、これらのチャンバを個別に温度制御することにより、連続的に高濃度のオゾンガスを供給することができる。
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.
なお、高濃度のオゾンガスを生成する市販の装置として、例えば、明電舎製のピュアオゾンジェネレータ(MPOG-HM1A1)がある。
As a commercially available device that generates high-concentration ozone gas, for example, there is a pure ozone generator (MPOG-HM1A1) manufactured by Meidensha.
<不活性ガスの一例>
不活性ガスは、例えば原料ガスパージ工程S2や酸化剤パージ工程S4において適用可能なものであれば良い。その一例としては、N2,Ar,He等の不活性ガスが挙げられる。 <Example of inert gas>
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.
不活性ガスは、例えば原料ガスパージ工程S2や酸化剤パージ工程S4において適用可能なものであれば良い。その一例としては、N2,Ar,He等の不活性ガスが挙げられる。 <Example of inert gas>
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.
<ガス供給部4の一例>
ガス供給部4は、噴出口41~43を有し、原料ガス,オゾンガス,不活性ガスを例えば所望の供給量(流量等),圧力等でチャンバ3に供給できれば良く、種々の態様を適用することが可能である。 <Example ofgas supply unit 4>
Thegas 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.
ガス供給部4は、噴出口41~43を有し、原料ガス,オゾンガス,不活性ガスを例えば所望の供給量(流量等),圧力等でチャンバ3に供給できれば良く、種々の態様を適用することが可能である。 <Example of
The
噴出口41~43は、チャンバ3に対して単に1個ずつ設けるだけでなく、それぞれ複数個設けても良い。また、噴出口41~43の形状は、適宜設定することが可能であり、その一例として円形,矩形,楕円,スリット状等にすることが挙げられる。
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.
噴出口41~43から供給される各ガスの供給量や圧力においては、例えば配管41a~43aに図外の流量可変バルブ等を設けることにより、適宜設定することが可能である。
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.
<ガス供給量,圧力等の一例>
チャンバ3に供給する原料ガス,オゾンガス,不活性ガスの供給量や、当該各ガスによる圧力(例えばチャンバ3内のオゾンガスによる圧力(分圧)。後述の実施例3では、例えば噴出口41~43等と被成膜面20との間の圧力)等は、適宜制御して設定することが可能であり、その一例としてはチャンバ3内の被成膜対象物2の種類,形状,個数や、当該各ガスの種類,濃度等を考慮して設定することが挙げられる。 <Example of gas supply amount, pressure, etc.>
The amount of raw material gas, ozone gas, and inert gas supplied to thechamber 3 and the pressure of each gas (for example, the pressure of the ozone gas in the chamber 3 (partial pressure). In Example 3 described later, for example, the ejection ports 41 to 43. 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.
チャンバ3に供給する原料ガス,オゾンガス,不活性ガスの供給量や、当該各ガスによる圧力(例えばチャンバ3内のオゾンガスによる圧力(分圧)。後述の実施例3では、例えば噴出口41~43等と被成膜面20との間の圧力)等は、適宜制御して設定することが可能であり、その一例としてはチャンバ3内の被成膜対象物2の種類,形状,個数や、当該各ガスの種類,濃度等を考慮して設定することが挙げられる。 <Example of gas supply amount, pressure, etc.>
The amount of raw material gas, ozone gas, and inert gas supplied to the
具体例としては、図4に示すように各工程S1~S4による成膜サイクルを実施する場合において、成膜サイクルによるチャンバ3内のプロセス圧力が1000Pa以下の範囲内に収まるように、各ガスの供給量等を適宜設定することが挙げられる。より具体的には、不活性ガス噴出口43からチャンバ3内に対して不活性ガスを供給(例えば後述のように断続的に供給)し、当該供給によりベース圧力が1Pa~1000Pa程度の範囲内に収まるように適宜制御して設定することが挙げられる。成膜サイクル1回に要する時間は適宜設定することが可能であり、特に限定されるものではないが、例えば数秒~数十秒(例えば3秒~60秒)程度に設定することが挙げられる。
As a specific example, as shown in FIG. 4, when the film forming cycle according to each step S1 to S4 is carried out, 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).
また、酸化剤供給工程S3において80体積%以上のオゾンガスをチャンバ3に供給する場合、当該オゾンガスの被成膜面20に対する曝露量を1×105ラングミュア以上とし、当該チャンバ3内のオゾンガスによる圧力が100Pa以下となるように、当該オゾンガスの供給量等を適宜設定することが挙げられる。
When 80% by volume or more of ozone gas is supplied to the chamber 3 in the oxidant supply step S3, 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.
例えば、チャンバ3内に、オゾンガスの他に不活性ガスが存在している場合には、当該オゾンガスの分圧が100Pa以下となるように設定することとなる。また、オゾンガスの供給による圧力上昇においては、100Pa以下、好ましくは50Pa以下、より好ましく10Pa以下となるように適宜設定することが挙げられる。
For example, when an inert gas other than the ozone gas is present in the chamber 3, the partial pressure of the ozone gas is set to be 100 Pa or less. Further, 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.
このような酸化剤供給工程S3によれば、原料ガス供給工程S1において被成膜面20に吸着した吸着層21aを、十分に酸化することが可能となる。
According to such an oxidizing agent supply step S3, the adsorption layer 21a adsorbed on the film-deposited surface 20 in the raw material gas supply step S1 can be sufficiently oxidized.
原料ガス供給工程S1においてチャンバ3に供給する原料ガスの供給量等は、例えば当該原料ガスを被成膜面20に吸着させ、後段の酸化剤供給工程S3において十分に酸化(酸化膜を形成)できるように設定すれば良く、特に限定されるものではない。
Regarding the supply amount of the raw material gas supplied to the chamber 3 in the raw material gas supply step S1, for example, 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.
具体例としては、被成膜面20に対する原料ガスの曝露量が1×104ラングミュア以上となるように、当該原料ガスの供給量等を適宜設定することが挙げられる。また、原料ガスの曝露量は、当該原料ガスの吸着率によって変化する。このため、例えば異なる種類の原料ガスであっても、被成膜面20に対する吸着率が同程度の場合には、当該各原料ガスの供給量はそれぞれ同程度に設定することが考えられる。この吸着率が同程度の原料ガスの一例としては、TMA,TDMAT,TDMAH等が挙げられる。
As a specific example, 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.
原料ガスパージ工程S2,酸化剤パージ工程S4において、チャンバ3に供給する不活性ガスの供給量等は、前記のようにプロセス圧力が1000Pa以下の範囲内に収まる態様であれば良く、適宜設定することが可能である。例えば、ガス排出部5によってパージしている状態の場合には、当該パージをアシストできる程度に設定することが挙げられる。具体例としては、チャンバ3に対して不活性ガスを断続的に供給し、当該チャンバ3内における原料ガスやオゾンガスを希釈し過ぎないように適宜設定(例えば、オゾンガス供給量の10倍以内に設定)することが挙げられる。
In the raw material gas purging step S2 and the oxidant purging step S4, 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. For example, in the case of a state of purging by the gas discharge unit 5, it may be set to such that the purging can be assisted. As a specific example, 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). ).
<ガス排出部5の一例>
ガス排出部5による排気は、前記のようにチャンバ3内のプロセス圧力が1000Pa以下の範囲内に収まるように、当該チャンバ3内の減圧状態を維持できる態様であれば良く、特に限定されるものではない。 <Example ofgas discharge unit 5>
The exhaust gas by thegas 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.
ガス排出部5による排気は、前記のようにチャンバ3内のプロセス圧力が1000Pa以下の範囲内に収まるように、当該チャンバ3内の減圧状態を維持できる態様であれば良く、特に限定されるものではない。 <Example of
The exhaust gas by the
図1のガス排出部5の場合、排気管5a,真空ポンプ5b等を有した構成となっているが、その他にオゾンキラー(オゾンを分解する除害筒等の除害設備;図示省略),排気バルブ(開度調整可能なバルブ等;図示省略)等を適宜有した構成とすることも挙げられる。また、真空ポンプ5bは、オゾンに耐性のある構成(例えば、ドライポンプ)を適用することが好ましい。
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.
また、ガス排出部5において複数の排気ラインを設けておき、各工程S1~S4において当該各排気ラインを使い分けるようにしても良い。これにより、各工程S1~S4において排気するガスをそれぞれ専用の除害設備に振り分けて処理することが可能となる。
Further, 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.
<支持部の一例>
チャンバ3内に収容した被成膜対象物2を支持する支持部は、例えば被成膜面20に対する成膜を妨げないように支持できる態様であれば良く、特に限定されるものではない。具体例としては後述の実施例2~4に示す態様が挙げられる。 <Example of support>
The support portion for supporting the object to be filmed 2 housed in thechamber 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.
チャンバ3内に収容した被成膜対象物2を支持する支持部は、例えば被成膜面20に対する成膜を妨げないように支持できる態様であれば良く、特に限定されるものではない。具体例としては後述の実施例2~4に示す態様が挙げられる。 <Example of support>
The support portion for supporting the object to be filmed 2 housed in the
<ALD装置11による成膜例>
以上示した実施例1に基づいて、ALD装置11による成膜サイクルを適宜実施し、被成膜対象物2における被成膜面20に対してAl2O3の酸化膜21を形成して検証したところ、図5~図7に示すような結果が得られた。 <Example of film formation byALD device 11>
Based on Example 1 shown above, the film formation cycle by theALD 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.
以上示した実施例1に基づいて、ALD装置11による成膜サイクルを適宜実施し、被成膜対象物2における被成膜面20に対してAl2O3の酸化膜21を形成して検証したところ、図5~図7に示すような結果が得られた。 <Example of film formation by
Based on Example 1 shown above, the film formation cycle by the
なお、この検証条件として、原料ガス供給工程S1で供給する原料ガスにはTMAを適用し、酸化剤供給工程S3で供給するオゾンガス(濃度80~100体積%)による圧力上昇を50Paとし、当該オゾンガスの暴露時間は3秒以下とした。また、被成膜対象物2において、図5,図6に示す成膜ではPEN製フィルムを適用し、図7に示す成膜ではSi基板を適用した。また、成膜温度は、室温程度となるように設定した
図5は、種々の成膜温度で成膜サイクルを実施した場合の酸化膜21の膜厚特性を示すものである。この図5によると、成膜温度が室温(25℃)程度の場合に、GPC(Growth Per Cycle)が1.7Å/cycleであることが読み取れる。なお、比較例として、従来ALD方法により比較的高温の成膜温度で酸化膜21を形成したところ、GPCは1.0~1.2Å/cycle程度であった。したがって、本実施例1によれば、従来ALD方法と比較して、良好な成膜速度特性が得られることを確認できた。 As this verification condition, 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. Further, in the film-formingobject 2, 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. Further, 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. 5, it can be read that the GPC (Growth Per Cycle) is 1.7 Å / cycle when the film formation temperature is about room temperature (25 ° C.). As a comparative example, when 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 Å / 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.
図5は、種々の成膜温度で成膜サイクルを実施した場合の酸化膜21の膜厚特性を示すものである。この図5によると、成膜温度が室温(25℃)程度の場合に、GPC(Growth Per Cycle)が1.7Å/cycleであることが読み取れる。なお、比較例として、従来ALD方法により比較的高温の成膜温度で酸化膜21を形成したところ、GPCは1.0~1.2Å/cycle程度であった。したがって、本実施例1によれば、従来ALD方法と比較して、良好な成膜速度特性が得られることを確認できた。 As this verification condition, 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. Further, in the film-forming
図6は、被成膜対象物2の膜厚方向一端側の被成膜面20に膜厚40nmの酸化膜21を形成した場合であって、当該被成膜対象物2の経過時間に対する水蒸気透過率特性を示すものである。この図6によると、時間経過と共に、水蒸気透過率が4.4×10-4g/m2/day程度に収束していくことが読み取れる。なお、酸化膜21を形成する前の被成膜対象物2の水蒸気透過率を測定したところ、10-1g/m2/day程度であった。したがって、本実施例1によれば、酸化膜21において、良好なバリア性が得られることを確認できた。
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.
図7は、酸化膜21における印加電界強度に対するリーク電流密度特性を示すものである。この図7によると、酸化膜21において10MV/cm以上の絶縁破壊強度が得られていることを読み取れる。したがって、本実施例1によれば、酸化膜21において、リーク電流を十分抑制でき、良好な絶縁性が得られることを確認できた。
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.
なお、この検証において、被成膜面20に対するオゾンガスの曝露量を確認したところ、1.1×106ラングミュア程度(すなわち、1×105ラングミュアの1桁上回る程度)に至っていた。
In this verification, when the exposure amount of ozone gas to the film-formed surface 20 was confirmed, it reached about 1.1 × 10 6 Langmuir (that is, about an order of magnitude higher than 1 × 10 5 Langmuir).
≪実施例2≫
実施例2は、複数個の被成膜対象物2、例えば後述図8(b)に示すような多数の粒子状の被成膜対象物2の集合体(以下、単に被成膜対象集合体と適宜称する)22を収容して支持し、各被成膜対象物2の被成膜面20に対して同時に酸化膜21を形成できるようにしたものである。 << 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 theoxide film 21 can be formed simultaneously on the film-forming surface 20 of each film-forming object 2.
実施例2は、複数個の被成膜対象物2、例えば後述図8(b)に示すような多数の粒子状の被成膜対象物2の集合体(以下、単に被成膜対象集合体と適宜称する)22を収容して支持し、各被成膜対象物2の被成膜面20に対して同時に酸化膜21を形成できるようにしたものである。 << 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
<ALD装置12の主な構成>
図8は、実施例2によるALD方法を説明するものであって、当該実施例2で適用可能なALD装置12の概略を示すものである。図8のALD装置12は、チャンバ3内に配置可能な筐体状の収容壁61を有した支持部6を備えており、当該収容壁61内に複数個の被成膜対象物2を収容して支持できる構成となっている。 <Main configuration ofALD device 12>
FIG. 8 describes the ALD method according to the second embodiment and shows an outline of theALD 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.
図8は、実施例2によるALD方法を説明するものであって、当該実施例2で適用可能なALD装置12の概略を示すものである。図8のALD装置12は、チャンバ3内に配置可能な筐体状の収容壁61を有した支持部6を備えており、当該収容壁61内に複数個の被成膜対象物2を収容して支持できる構成となっている。 <Main configuration of
FIG. 8 describes the ALD method according to the second embodiment and shows an outline of the
収容壁61は、複数個の被成膜対象物2を出し入れ自在に収容可能な構成となっている。また、収容壁61の少なくとも一部には、孔径が被成膜対象物2の最大外径(粒子径等)よりも小さい通気孔を複数有した通気部62が、設けられている。図8の収容壁61の場合、円筒状の構造であって、軸心方向両端側の位置に通気部62が設けられている。
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. In the case of 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.
支持部6においては、前記のように複数個の被成膜対象物2を出し入れ自在に収容して被成膜面20に酸化膜21を形成できれば良く、種々の態様を適用することが可能である。
In the support portion 6, as described above, it is sufficient that a plurality of objects to be filmed 2 can be freely taken in and out to form the oxide film 21 on the surface to be filmed 20, and various embodiments can be applied. be.
例えば、収容壁61において、回転自在(図8の収容壁61の場合、例えば軸回転自在)な構成とすることにより、当該収容壁61内の被成膜対象物2を撹拌しながら成膜することができる。これにより、被成膜対象物に対する酸化膜の形成斑が生じないように抑制できる可能がある。
For example, 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.
通気部62においては、チャンバ3内のガス(原料ガス,オゾンガス,不活性ガス等)の通過が可能であって被成膜対象物の通過を遮ることができるものであれば良く、種々の態様を適用することが可能である。その一例としては、集合体22の各被成膜対象物2の粒子径よりも小さい通気孔を複数有したメッシュ構造のものが挙げられる。
In the ventilation unit 62, 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. As an example thereof, there is a mesh structure having a plurality of vent holes smaller than the particle size of each object to be filmed 2 of the aggregate 22.
<ALD装置12による成膜例>
以上示した実施例2に基づいて、ALD装置12による成膜サイクルを適宜実施し、多数の粒子状の被成膜対象物2の集合体22における被成膜面20に対して、Al2O3の酸化膜21を形成して検証した。なお、この検証条件は、実施例1と同様とし、被成膜対象物2には粒子径が1mm以下のものを適用した。 <Example of film formation byALD device 12>
Based on Example 2 shown above, the film formation cycle by theALD 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.
以上示した実施例2に基づいて、ALD装置12による成膜サイクルを適宜実施し、多数の粒子状の被成膜対象物2の集合体22における被成膜面20に対して、Al2O3の酸化膜21を形成して検証した。なお、この検証条件は、実施例1と同様とし、被成膜対象物2には粒子径が1mm以下のものを適用した。 <Example of film formation by
Based on Example 2 shown above, the film formation cycle by the
その結果、実施例1と同様に、酸化膜21において良好な成膜速度特性,バリア性,絶縁性が得られることを確認できた。
As a result, it was confirmed that good film formation rate characteristics, barrier properties, and insulating properties can be obtained in the oxide film 21 as in Example 1.
≪実施例3≫
実施例3は、被成膜対象物2において、被成膜面20に沿った四方向のうち相対する二方向(以下、単に被成膜面二方向と適宜称する)で移動(二方向のうち一方に移動、または双方に往復動)させながら、当該被成膜面20に酸化膜21を形成できるようにしたものである。 << Example 3 >>
In the third embodiment, 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). Theoxide film 21 can be formed on the film-formed surface 20 while moving to one side or reciprocating to both sides.
実施例3は、被成膜対象物2において、被成膜面20に沿った四方向のうち相対する二方向(以下、単に被成膜面二方向と適宜称する)で移動(二方向のうち一方に移動、または双方に往復動)させながら、当該被成膜面20に酸化膜21を形成できるようにしたものである。 << Example 3 >>
In the third embodiment, 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
<ALD装置13の主な構成>
図9は、実施例3によるALD方法を説明するものであって、当該実施例3で適用可能なALD装置13の概略を示すものである。図9のALD装置13は、チャンバ3内に収容された被成膜対象物2において、当該チャンバ3内に設けられている支持部7により、被成膜面20に沿った長手方向(被成膜面に沿った四方向のうち相対する二方向(以下、単に被成膜面二方向と適宜称する))に対し移動自在に支持できるように構成されている。 <Main configuration ofALD device 13>
FIG. 9 describes the ALD method according to the third embodiment and shows an outline of theALD apparatus 13 applicable to the third embodiment. In the ALD device 13 of FIG. 9, in the object to be deposited 2 housed in the chamber 3, 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).
図9は、実施例3によるALD方法を説明するものであって、当該実施例3で適用可能なALD装置13の概略を示すものである。図9のALD装置13は、チャンバ3内に収容された被成膜対象物2において、当該チャンバ3内に設けられている支持部7により、被成膜面20に沿った長手方向(被成膜面に沿った四方向のうち相対する二方向(以下、単に被成膜面二方向と適宜称する))に対し移動自在に支持できるように構成されている。 <Main configuration of
FIG. 9 describes the ALD method according to the third embodiment and shows an outline of the
図9の支持部7は、いわゆるロール to ロール方式のものであって、長尺フィルム状の被成膜対象物2の一端側が巻回された巻き軸である一端側ロール71と、当該被成膜対象物2の他端側が巻回された巻き軸である他端側ロール72と、当該一端側ロール71と他端側ロール72との間に配置された搬送ロール73a,73bと、を有し、各ロールが適宜回動する構成となっている。
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.
このような支持部7により、一端側ロール71,他端側ロール72のうち一方から送り出された被成膜対象物2は、搬送ロール73a,73bを経由して、他方に巻き取られることとなる。すなわち、支持部7によれば、被成膜対象物2を被成膜面二方向において適宜移動させることが可能となる。また、図9の支持部7の場合、搬送ロール73a,73bの両者がチャンバ3内の上方側において所定間隔を隔てて配置されており、当該両者間を移動する被成膜対象物2の被成膜面20が、当該チャンバ3内の上方側に対向(後述のシャワーヘッド4aと対向)するようになっている。
By such a support portion 7, 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. Become. That is, according to 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. Further, in the case of the support portion 7 of FIG. 9, 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).
チャンバ3における上方側には、シャワーヘッド4aを有したガス供給部4が設けられている。このシャワーヘッド4aは、噴出口41~43をそれぞれ複数個有した構造であって、搬送ロール73a,73bの両者間を移動する被成膜対象物2の被成膜面20と対向する位置に、設けられている。
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.
シャワーヘッド4aの噴出口41~43には、原料ガス供給装置41b,オゾンガス発生装置42b,不活性ガス供給装置43bが、それぞれ配管41a,42a,43aを介して接続されている。これにより、当該各装置41b~43bからのガスを、それぞれ噴出口41~43からチャンバ3内に適宜供給できる構成となっている。
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. As a result, 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.
<支持部7の他例>
支持部7においては、チャンバ3内に収容された被成膜対象物2を被成膜面二方向において移動自在に支持できる態様であれば良く、図9に示すようなロール to ロール方式によるものに限定されるものではない。例えば、被成膜対象物2を支持する支持台(例えば、特許6052470号公報の図1中の符号7で示すような支持台)を有した方式(以下、単に支持台方式と適宜称する)であって、当該支持台を被成膜面二方向に移動自在(被成膜面20がシャワーヘッド4aと対向するように移動自在)にした構成が挙げられる。 <Other examples ofsupport 7>
Thesupport 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. For example, 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) that supports the object to be film-formed (hereinafter, simply referred to as a support base method). Therefore, there is a configuration in which the support base is movable in two directions on the surface to be filmed (movable so that the surface 20 to be filmed faces the shower head 4a).
支持部7においては、チャンバ3内に収容された被成膜対象物2を被成膜面二方向において移動自在に支持できる態様であれば良く、図9に示すようなロール to ロール方式によるものに限定されるものではない。例えば、被成膜対象物2を支持する支持台(例えば、特許6052470号公報の図1中の符号7で示すような支持台)を有した方式(以下、単に支持台方式と適宜称する)であって、当該支持台を被成膜面二方向に移動自在(被成膜面20がシャワーヘッド4aと対向するように移動自在)にした構成が挙げられる。 <Other examples of
The
<シャワーヘッド4aの一例>
図10は、シャワーヘッド4aの一例を示すものである。なお、図10(および後述の図11)中において、符号を付していない実線矢印は各ガスの供給方向の一例、点線矢印は各ガスの排気方向の一例を示すものである。 <Example ofshower head 4a>
FIG. 10 shows an example of theshower head 4a. In FIG. 10 (and FIG. 11 described later), the unmarked solid line arrow indicates an example of the supply direction of each gas, and the dotted line arrow indicates an example of the exhaust direction of each gas.
図10は、シャワーヘッド4aの一例を示すものである。なお、図10(および後述の図11)中において、符号を付していない実線矢印は各ガスの供給方向の一例、点線矢印は各ガスの排気方向の一例を示すものである。 <Example of
FIG. 10 shows an example of the
図10のシャワーヘッド4aにおいては、搬送ロール73a,73bの両者間を移動する被成膜対象物2の被成膜面20と対向する部位4bに、噴出口41,42がそれぞれ複数個設けられている。
In the shower head 4a of FIG. 10, 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.
これら噴出口41,42の両者は、被成膜面二方向に所定間隔を隔てて交互に位置し、互いに隣接する噴出口41,42による噴出口対(例えば図10中の符号Tで示す噴出口対)が、被成膜面二方向に所定間隔を隔てて複数個配列された構成となっている。
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.
また、噴出口41,42との両者間に、噴出口43が設けられている。また、噴出口41~43の各噴出口間には、噴出口間排気口44が設けられている。この排気口44は、当該排気口44と被成膜面20との間のガス等を吸気して、チャンバ3外に排出できる構成となっている。
Further, 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.
<シャワーヘッド4aにおける噴出口41~43,排気口44の一例>
シャワーヘッド4aにおける噴出口41~43,排気口44それぞれ(以下、纏めて単に噴出口等と適宜称する)は、単に被成膜面二方向に沿って複数個配列して設けるだけでなく、当該被成膜面二方向と交差している交差方向(以下、単に交差方向と適宜称する)にも複数個配列して設けても良い。例えば、噴出口41を交差方向に複数個配列して原料ガス噴出口群を構成したり、噴出口42を交差方向に複数個配列してオゾンガス噴出口群を構成することが挙げられる。 <Example ofoutlets 41 to 43 and exhaust port 44 in the shower head 4a>
A plurality of theejection 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. For example, 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.
シャワーヘッド4aにおける噴出口41~43,排気口44それぞれ(以下、纏めて単に噴出口等と適宜称する)は、単に被成膜面二方向に沿って複数個配列して設けるだけでなく、当該被成膜面二方向と交差している交差方向(以下、単に交差方向と適宜称する)にも複数個配列して設けても良い。例えば、噴出口41を交差方向に複数個配列して原料ガス噴出口群を構成したり、噴出口42を交差方向に複数個配列してオゾンガス噴出口群を構成することが挙げられる。 <Example of
A plurality of the
また、噴出口等の態様(形状、大きさ等)や、被成膜対象物2の被成膜面20との間の距離は、それぞれ同一にすることに限定されず、それぞれ異なっていても良い。
Further, 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.
例えば図11に示すように、噴出口等の被成膜面二方向の寸法(交差方向に長いスリット状の噴出口等の場合、スリット幅)V1~V8は、10-1mm~数百mmの範囲内、好ましくは1mm~100mmの範囲内に設定することが挙げられる。また、各噴出口等と被成膜対象物2の被成膜面20との間の距離h1~h8は、数mm~数百mmの範囲内、好ましくは1mm~100mmの範囲内、より好ましく(特に噴出口42)は1mm~20mmの範囲内に設定することが挙げられる。図11の場合、噴出口42に係る距離h8が、他の噴出口等に係る距離h1~h7よりも大きく設定された描写となっている。
For example, as shown in FIG. 11, 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. (In particular, the ejection port 42) may be set within the range of 1 mm to 20 mm. In the case of FIG. 11, 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.
各噴出口等間のピッチ(図11ではW1~W8)は、例えば、それぞれ当該噴出口等の開口寸法を考慮して適宜設定することが挙げられる。
The pitch between the spouts and the like (W1 to W8 in FIG. 11) may be appropriately set in consideration of the opening dimensions of the spouts and the like.
<被成膜対象物2の一例>
被成膜対象物2においては、支持部7により移動自在に支持可能(例えば、ロール to ロール方式や支持台方式により支持可能)なものであって、当該被成膜対象物2を被成膜面二方向において移動させながら被成膜面20に酸化膜21を形成できるものであれば、特に限定されるものではない。 <Example of the object to be filmed 2>
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 theoxide film 21 on the surface to be filmed 20 while moving in two directions.
被成膜対象物2においては、支持部7により移動自在に支持可能(例えば、ロール to ロール方式や支持台方式により支持可能)なものであって、当該被成膜対象物2を被成膜面二方向において移動させながら被成膜面20に酸化膜21を形成できるものであれば、特に限定されるものではない。 <Example of the object to be filmed 2>
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
図9に示す被成膜対象物2の場合、長尺フィルム状であって、長手方向に延在する平坦な表裏面が被成膜面20(図9では表裏面のうち一方が被成膜面20)となり、支持部7により、当該長手方向(被成膜面二方向)において移動自在に支持されている。
In the case of the object to be film-formed 2 shown in FIG. 9, 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).
<ガス供給量,圧力等>
シャワーヘッド4aにおける噴出口41~43からチャンバ3に供給する原料ガス,オゾンガス,不活性ガスの流量(供給量)や、当該各ガスによる圧力等は、実施例1,2と同様に適宜設定することが可能であるが、各噴出口等間のピッチ、被成膜対象物2の被成膜面二方向への移動速度,各噴出口等の排気速度(成膜箇所の圧力)等を考慮して、設定することが挙げられる。 <Gas supply amount, pressure, etc.>
The flow rate (supply amount) of the raw material gas, ozone gas, and inert gas supplied from theejection ports 41 to 43 in the shower head 4a to the chamber 3, the pressure due to each gas, and the like are appropriately set in the same manner as in Examples 1 and 2. However, the pitch between each ejection port, etc., the moving speed of the object to be deposited 2 in two directions on the surface to be deposited, the exhaust speed of each ejection port, etc. (pressure at the film forming location), etc. are taken into consideration. Then, setting is mentioned.
シャワーヘッド4aにおける噴出口41~43からチャンバ3に供給する原料ガス,オゾンガス,不活性ガスの流量(供給量)や、当該各ガスによる圧力等は、実施例1,2と同様に適宜設定することが可能であるが、各噴出口等間のピッチ、被成膜対象物2の被成膜面二方向への移動速度,各噴出口等の排気速度(成膜箇所の圧力)等を考慮して、設定することが挙げられる。 <Gas supply amount, pressure, etc.>
The flow rate (supply amount) of the raw material gas, ozone gas, and inert gas supplied from the
前記のように被成膜対象物2の被成膜面二方向への移動速度等を考慮した設定により、例えば、オゾンガスの被成膜面20に対する曝露量を1×105ラングミュア以上、当該オゾンガスによる圧力を100Pa以下、被成膜面20に対する原料ガスの曝露量を1×104ラングミュア以上にすることが可能となる。これにより、原料ガス供給工程S1において被成膜面20に吸着した吸着層21aを、酸化剤供給工程S3において十分に酸化することが可能となる。
By setting in consideration of the moving speed of the object to be filmed 2 in two directions on the surface to be filmed as described above, for example, 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. As a result, 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.
具体例としては、オゾンガスの流量において、噴出口42における被成膜面二方向と垂直方向の単位長さ当たり、0.1sccm~10sccmとすることが挙げられる。
As a specific example, 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.
原料ガスの流量においては、噴出口41における被成膜面二方向と垂直方向の単位長さ当たり、0.0001sccm~1sccmとすることが挙げられる。
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.
不活性ガスの流量においては、プロセス圧力が1000Paを超えない範囲で、比較的多く設定(例えばオゾンガス流量よりも多く設定)することが挙げられる。
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.
被成膜対象物2の被成膜面二方向への移動速度は、各噴出口等間のピッチ等を考慮して、適宜設定することが挙げられる。このように設定した移動速度の大きさ等に応じて、各噴出口等と被成膜面20との間に対流が生じ、例えば当該被成膜面20に対する各ガスの反応を促し、成膜し易さ等に貢献できる可能性がある。
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.
<ALD装置13を用いる場合の成膜工程の一例>
ALD装置13により成膜を行う場合、例えば、支持部7に支持された被成膜対象物2を一端側ロール71から他端側ロール72に対して移動(図9では、図示左側から図示右側へ移動)させることにより、当該被成膜対象物2を被成膜面二方向に移動ながら成膜サイクルを適宜実施することとなる。 <Example of film formation process whenALD device 13 is used>
When film formation is performed by theALD device 13, for example, the object to be filmed 2 supported by the support portion 7 is moved from one end side roll 71 to the other end side roll 72 (in FIG. 9, from the left side in the drawing to the right side in the drawing). By moving the object to be filmed 2 in two directions on the surface to be filmed, the film forming cycle is appropriately carried out.
ALD装置13により成膜を行う場合、例えば、支持部7に支持された被成膜対象物2を一端側ロール71から他端側ロール72に対して移動(図9では、図示左側から図示右側へ移動)させることにより、当該被成膜対象物2を被成膜面二方向に移動ながら成膜サイクルを適宜実施することとなる。 <Example of film formation process when
When film formation is performed by the
この場合、被成膜面20は、例えば図10に示すように領域A1~A4の順に通過し、当該領域A1~A4において以下に示すように各工程S1~S4が実施されることとなる。
In this case, 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.
まず、領域A1においては、原料ガス供給工程S1により、噴出口41から原料ガスが噴き出される。これにより、図3(a)に示した反応模式図のように、原料ガスが被成膜面20に吸着して、当該原料ガスによる吸着層21aが形成される。
First, in the region A1, the raw material gas is ejected from the ejection port 41 by the raw material gas supply step S1. As a result, as shown in the reaction schematic diagram shown in FIG. 3A, the raw material gas is adsorbed on the film-deposited surface 20 to form the adsorption layer 21a by the raw material gas.
この領域A1における原料ガス供給工程S1の後、当該工程S1で供された原料ガスの余剰ガスと、当該原料ガスが被成膜面20に吸着することで生じたガス(CH4ガス)は、排気口44やガス排出部5により除去、または原料ガスパージ工程S2により除去される。この原料ガスパージ工程S2では、噴出口43から不活性ガスが噴き出され、余剰ガス等が領域A1から除去されることとなる。
After the raw material gas supply step S1 in this region A1, 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. In this 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.
次に、領域A2においては、酸化剤供給工程S3により、噴出口42からオゾンガスが噴き付けられる。これにより、図3(b)に示した反応模式図のように、被成膜面20に吸着した原料ガスによる吸着層21aが酸化して、酸化膜21が形成される。そして、酸化膜21の表面においては、次の成膜のための吸着可能領域20aが形成されることとなる。
Next, in the region A2, ozone gas is sprayed from the ejection port 42 by the oxidizing agent supply step S3. As a result, as shown in the reaction schematic diagram shown in FIG. 3B, 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. Then, on the surface of the oxide film 21, an adsorbable region 20a for the next film formation is formed.
この領域A2における酸化剤供給工程S3の後、当該工程S3で供されたオゾンガスの余剰ガスと、吸着層21aを酸化することで生じたガスは、噴出口間排気口44やガス排出部5により除去、または酸化剤パージ工程S4により除去される。この酸化剤パージ工程S4では、不活性ガス噴出口43から不活性ガスが噴き出され、余剰ガス等が領域A2から除去されることとなる。
After the oxidant supply step S3 in this region A2, 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. In this 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.
以上示した領域A1,A2における各工程S1~S4の成膜サイクルは、当該A1,A2より後段の領域(例えば図10の領域A3,A4)においても同様に実施されることとなる。
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).
以上示したように、成膜サイクルを適宜実施することにより、被成膜面20に対して所望の酸化膜21を形成できることが判る。また、成膜サイクルを複数回行うことにより、酸化膜21において所望の膜厚に形成することも可能となる。
As shown above, it can be seen that 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.
成膜サイクルを複数回行う手法としては、例えば被成膜対象物2を被成膜面二方向において一方に移動または双方に往復動させることにより、領域A1~A4の成膜サイクルを複数回適宜行うことが挙げられる。
As a method of performing the film forming cycle a plurality of times, for example, 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.
<ALD装置13による成膜例>
以上示した実施例3に基づいて、ALD装置13による成膜サイクルを適宜実施し、長尺フィルム状の被成膜対象物2の被成膜面20に対して、Al2O3の酸化膜21を形成して検証した。なお、この検証条件は、実施例1と同様とし、被成膜対象物2にはPEN製フィルムを適用した。 <Example of film formation byALD device 13>
Based on Example 3 shown above, the film formation cycle by theALD 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.
以上示した実施例3に基づいて、ALD装置13による成膜サイクルを適宜実施し、長尺フィルム状の被成膜対象物2の被成膜面20に対して、Al2O3の酸化膜21を形成して検証した。なお、この検証条件は、実施例1と同様とし、被成膜対象物2にはPEN製フィルムを適用した。 <Example of film formation by
Based on Example 3 shown above, the film formation cycle by the
その結果、実施例1と同様に、酸化膜21において良好な成膜速度特性,バリア性(実施例3では水蒸気透過率が4.0×10-4g/m2/day程度),絶縁性が得られる他に、以下に示すことを確認できた。
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.
すなわち、実施例3によれば、当該被成膜対象物2を被成膜面二方向に移動させながら、成膜サイクルの各工程S1~S4を同時に適宜進行できるため、実施例1,2と比較すると、成膜時間を短縮化し易くなる可能性がある。
That is, according to the third embodiment, 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.
また、原料ガス噴出口41とオゾンガス噴出口42との間に、不活性ガス噴出口43や噴出口間排気口44が設けられているため、例えば原料ガスやオゾンガスがチャンバ3内で分散することを抑制できる。これにより、例えばチャンバ3の内壁面等において、原料ガスやオゾンガスによるパーティクルの付着や成膜を抑制でき、当該チャンバ3等のメンテナンス(チャンバ3内の洗浄処理等)に係る負担を軽減できる可能性がある。
Further, since 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.
≪実施例4≫
実施例4は、実施例3に示したロール to ロール方式を応用したものであって、チャンバ3を複数個のガス処理炉に分割された構造とし、成膜サイクルの各工程S1~S4を当該各ガス処理炉に適宜分担して実施できるようにしたものである。 << Example 4 >>
Example 4 is an application of the roll-to-roll method shown in Example 3, in which thechamber 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.
実施例4は、実施例3に示したロール to ロール方式を応用したものであって、チャンバ3を複数個のガス処理炉に分割された構造とし、成膜サイクルの各工程S1~S4を当該各ガス処理炉に適宜分担して実施できるようにしたものである。 << Example 4 >>
Example 4 is an application of the roll-to-roll method shown in Example 3, in which the
<ALD装置14の主な構成>
図12は、実施例4によるALD方法を説明するものであって、当該実施例4で適用可能なALD装置14の概略を示すものである。図12のALD装置14は、分割構造のチャンバ30と、支持部8と、を備えており、当該支持部8により、長尺フィルム状の被成膜対象物2を被成膜面二方向に対して移動自在に支持できるように構成されている。 <Main configuration ofALD device 14>
FIG. 12 describes the ALD method according to the fourth embodiment and shows an outline of theALD 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.
図12は、実施例4によるALD方法を説明するものであって、当該実施例4で適用可能なALD装置14の概略を示すものである。図12のALD装置14は、分割構造のチャンバ30と、支持部8と、を備えており、当該支持部8により、長尺フィルム状の被成膜対象物2を被成膜面二方向に対して移動自在に支持できるように構成されている。 <Main configuration of
FIG. 12 describes the ALD method according to the fourth embodiment and shows an outline of the
チャンバ30は、原料ガス噴出口41が設けられている原料ガス処理炉31と、オゾンガス噴出口42が設けられているオゾンガス処理炉32と、当該原料ガス処理炉31とオゾンガス処理炉32との両者間に介在し不活性ガス噴出口43が設けられている不活性ガス処理炉33と、を有して成る。
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.
図12のチャンバ30の場合、原料ガス処理炉31を挟んだ不活性ガス処理炉33の反対側の位置にも、当該不活性ガス処理炉33と同様の構造の不活性ガス処理炉34が設けられている。この不活性ガス処理炉34は、例えば後述の一端側ロール71,他端側ロール72と原料ガス処理炉31との間において被成膜面20を清浄するために適用することが可能であるが、適宜省略することも可能である。
In the case of the chamber 30 of FIG. 12, 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.
各処理炉31~34の炉壁には、当該路壁における被成膜対象物2の移動経路と交差する位置に、当該被成膜対象物2が通過可能な処理炉開口部31a~34aがそれぞれ設けられている。これら処理炉開口部31a~34aは、それぞれ処理炉31~34内の減圧状態を妨げないように被成膜対象物2を通過させることが可能な構成(例えば真空チャンバ用の平行シール型スリットバルブ等を用いた構成)とする。
On the furnace walls of the processing furnaces 31 to 34, 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.).
支持部8は、いわゆるロール to ロール方式のものであって、被成膜対象物2の一端側が巻回された巻き軸である一端側ロール71と、当該被成膜対象物2の他端側が巻回された巻き軸である他端側ロール72と、原料ガス処理炉31内に配置された第1折り返しロール74と、オゾンガス処理炉32内に配置された第2折り返しロール75と、を有し、各ロールが適宜回動する構成となっている。
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.
図12の支持部8の場合、一端側ロール71および他端側ロール72が、チャンバ30の外周側であって、原料ガス処理炉31(および不活性ガス処理炉34)を挟んだ不活性ガス処理炉33の反対側に位置するように、設けられている。
In the case of the support portion 8 of FIG. 12, 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.
第1折り返しロール74および第2折り返しロール75は、それぞれ一端側ロール71と他端側ロール72との間の被成膜対象物2を、各々の位置(各処理炉31,32内)にて折り返すように支持している。
In the first folded roll 74 and the second folded roll 75, 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.
これにより、一端側ロール71と他端側ロール72との間の被成膜対象物2は、例えば図12で描写するように、原料ガス処理炉31内とオゾンガス処理炉32内との両者を葛折り状に往復し、重畳するように延在して支持されている。また、原料ガス処理炉31とオゾンガス処理炉32との両者間を移動(以下、単に両者間移動と適宜称する)する毎に、不活性ガス処理炉33内を通過することとなっている。
As a result, 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.
第1折り返しロール74および第2折り返しロール75は、それぞれ被成膜対象物2の重畳方向に複数個配列されている。この配列数を適宜変化させることにより、被成膜対象物2の両者間移動数を所望通りに設定することが可能となる。
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.
ALD装置14においては、各噴出口41~43に対し、ALD装置11~13と同様の配管41a~43a,装置41b~43b等がそれぞれ接続されることとなるが、図12では適宜省略した描写としている。また、処理炉31~34には、ALD装置11~13と同様のガス排出部5が設けられ、当該処理炉31~34内の減圧状態をそれぞれ維持できる構成となるが、図12では適宜省略した描写としている。
In the ALD device 14, 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. Further, 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.
<ALD装置14を用いる場合の成膜工程の一例>
ALD装置14により成膜を行う場合、まず、支持部8に支持された被成膜対象物2を一端側ロール71から他端側ロール72に対して移動させる。そして、被成膜対象物2が両者間移動して往復する毎に、各工程S1~S4の成膜サイクルが実施されることとなる。 <Example of film formation process whenALD device 14 is used>
When film formation is performed by theALD device 14, first, the object to be deposited 2 supported by the support portion 8 is moved from the one end side roll 71 to the other end side roll 72. Then, each time the film-forming object 2 moves between the two and reciprocates, the film-forming cycle of each step S1 to S4 is carried out.
ALD装置14により成膜を行う場合、まず、支持部8に支持された被成膜対象物2を一端側ロール71から他端側ロール72に対して移動させる。そして、被成膜対象物2が両者間移動して往復する毎に、各工程S1~S4の成膜サイクルが実施されることとなる。 <Example of film formation process when
When film formation is performed by the
このような成膜サイクルを適宜実施することにより、被成膜面20に対して所望の酸化膜21を形成できることが可能となる。成膜サイクルを複数回行う手法としては、例えば被成膜対象物2を被成膜面二方向において一方に移動または双方に往復動させることにより、当該成膜サイクルを複数回適宜行うことが挙げられる。
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. As a method of performing the film forming cycle a plurality of times, for example, by moving the object to be filmed 2 in one direction or reciprocating in both directions in the two directions of the film forming surface, the film forming cycle may be appropriately performed a plurality of times. Be done.
<ガス供給量,圧力等>
噴出口41~43からチャンバ30に供給する原料ガス,オゾンガス,不活性ガスの供給量(充填量)や、当該各ガスによる圧力等は、実施例1,2と同様に適宜設定することが可能であるが、被成膜対象物2の被成膜面二方向への移動速度等を考慮して、設定することが挙げられる。 <Gas supply amount, pressure, etc.>
The supply amount (filling amount) of the raw material gas, ozone gas, and inert gas supplied from theejection 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.
噴出口41~43からチャンバ30に供給する原料ガス,オゾンガス,不活性ガスの供給量(充填量)や、当該各ガスによる圧力等は、実施例1,2と同様に適宜設定することが可能であるが、被成膜対象物2の被成膜面二方向への移動速度等を考慮して、設定することが挙げられる。 <Gas supply amount, pressure, etc.>
The supply amount (filling amount) of the raw material gas, ozone gas, and inert gas supplied from the
本実施例4のように複数個の処理炉31~34を有した構造のチャンバ30によれば、当該処理炉31~34に原料ガス,オゾンガス,不活性ガスを適宜供給(例えば、原料ガス,オゾンガス,不活性ガスをそれぞれ異なる処理炉31~34に供給)して充填でき、当該充填後においては、各処理炉31~34間で互いに混合されることがない。
According to the chamber 30 having a structure having a plurality of processing furnaces 31 to 34 as in the fourth embodiment, 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.
このため、例えば処理炉31,32それぞれに所定量の原料ガス,オゾンガスを供給して充填した後は、酸化膜21の成膜に寄与できる状態(被成膜面20に対するオゾンガス,原料ガスの曝露量がそれぞれ1×105ラングミュア以上,1×104ラングミュア以上)であれば、新たに追加して供給したり入れ替える必要はない。例えば、高濃度のオゾンガスは、室温~400℃程度の範囲内であれば、オゾン同士の衝突等による熱分解反応が抑制され、酸化膜21の成膜に対して十分長く寄与することが可能となる。
Therefore, for example, after supplying and filling predetermined amounts of raw material gas and ozone gas to each of the processing furnaces 31 and 32, 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. For example, if 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.
したがって、処理炉31~34に供給して充填した各ガスは、常に供給する必要はなく、定期的(例えば1時間毎)に入れ替えれば良い。
Therefore, it is not always necessary to supply each gas supplied and filled in the processing furnaces 31 to 34, and it may be replaced regularly (for example, every hour).
また、チャンバ30においても、処理炉31,32それぞれに原料ガス,オゾンガスを供給する場合には、不活性ガスを適宜供給しても良い。これにより、処理炉31,32内におけるガス流を適宜調整でき、原料ガスやオゾンガスを所望の供給量で供給したり当該処理炉31,32内で拡散させることが容易になったり、当該処理炉31,32内のガスの排出が容易となることが判る。
Further, also in the chamber 30, when the raw material gas and the ozone gas are supplied to the processing furnaces 31 and 32, respectively, the inert gas may be appropriately supplied. As a result, 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.
また、各処理炉31~34の圧力はそれぞれ異なっていても良い。例えば、処理炉31,32の圧力においては、当該処理炉31,32からのガス漏れが起こらない範囲で設定することが挙げられる。一方、処理炉33,34の場合、当該処理炉33,34内の不活性ガスは漏れても比較的安全(原料ガス,オゾンガスと比較して安全)であるため、処理炉31,32よりも高く設定しても良い。
Further, the pressure of each processing furnace 31 to 34 may be different. For example, 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. On the other hand, in the case of 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.
被成膜対象物2の被成膜面二方向への移動速度は、チャンバ30内の各ガスの濃度や圧力等を考慮して、適宜設定することが挙げられる。このように設定した移動速度の大きさ等に応じて、被成膜面20において対流が生じ、例えば当該被成膜面20に対する各ガスの反応を促し、成膜し易さ等に貢献できる可能性がある。
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.
具体例としては、被成膜対象物2が両者間移動する毎の処理炉31,32の通過時間(滞在時間)をそれぞれ0.1秒以上,1秒以上に設定することが挙げられる。
As a specific example, 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.
<第1折り返しロール74,第2折り返しロール75の一例>
第1折り返しロール74および第2折り返しロール75の形状や配列等は、適宜設定することが可能であり、特に限定されるものではない。 <Example of the first foldedroll 74 and the second folded roll 75>
The shapes and arrangements of the first foldedroll 74 and the second folded roll 75 can be appropriately set and are not particularly limited.
第1折り返しロール74および第2折り返しロール75の形状や配列等は、適宜設定することが可能であり、特に限定されるものではない。 <Example of the first folded
The shapes and arrangements of the first folded
第1折り返しロール74や第2折り返しロール75の配列数が多くなると、例えばALD装置14のチャンバ30において、被成膜対象物2が重畳する方向(以下、単に重畳方向と適宜称する)への大型化を招いたり、当該チャンバ30に対するガスの供給量が増えてしまうことも考えられる。また、処理炉開口部31a~33aの形成領域が拡大したり当該処理炉開口部31a~33aに対する被成膜対象物2の侵入角度が大きくなり、当該処理炉開口部31a~33aと被成膜対象物2との間に隙間が生じた場合には、ガス漏れが起こることも考えられる。
When the number of arrangements of the first folded roll 74 and the second folded roll 75 increases, for example, in the chamber 30 of the ALD device 14, 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.
このような場合、例えば図12に示すように前記葛折り状の被成膜対象物2の移動経路において、処理炉31内における第1折り返しロール74と処理炉開口部31aとの間で当該処理炉開口部31aに対向した位置に、位置調整ロール76を設けることが挙げられる。また、処理炉32内においても同様に、第2折り返しロール75と処理炉開口部32aとの間で当該処理炉開口部32aと対向した位置に、位置調整ロール77を設けることが挙げられる。
In such a case, for example, as shown in FIG. 12, 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. Similarly, in the processing furnace 32, 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.
図12の位置調整ロール76,77の場合、それぞれの重畳方向の配列寸法が、第1,第2折り返しロール74,75それぞれの重畳方向の配列寸法よりも狭くなるように、配列されている。これにより、前記葛折り状の被成膜対象物2が、前記重畳方向に収束するように支持されている。
In the case of the position adjusting rolls 76 and 77 in FIG. 12, 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. As a result, the knot-folded object to be film-formed 2 is supported so as to converge in the superimposing direction.
以上のように位置調整ロール76,77を配置することにより、ALD装置14の小型化や、各ガスの供給量の縮小に貢献することが可能となる。また、処理炉開口部31a~33aに対する被成膜対象物2の侵入角度を小さくし、ガス漏れを抑制することも可能となる。
By arranging the position adjusting rolls 76 and 77 as described above, it is possible to contribute to the miniaturization of the ALD device 14 and the reduction of the supply amount of each gas. Further, it is possible to reduce the penetration angle of the object to be film-formed 2 with respect to the processing furnace openings 31a to 33a and suppress gas leakage.
<ALD装置14による成膜例>
以上示した実施例4に基づいて、ALD装置14による成膜サイクルを適宜実施し、長尺フィルム状の被成膜対象物2の被成膜面20に対して、Al2O3の酸化膜21の形成を試みた。なお、この検証条件は、実施例1と同様とし、被成膜対象物2にはPEN製フィルムを適用した。 <Example of film formation byALD device 14>
Based on Example 4 shown above, the film formation cycle by theALD 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.
以上示した実施例4に基づいて、ALD装置14による成膜サイクルを適宜実施し、長尺フィルム状の被成膜対象物2の被成膜面20に対して、Al2O3の酸化膜21の形成を試みた。なお、この検証条件は、実施例1と同様とし、被成膜対象物2にはPEN製フィルムを適用した。 <Example of film formation by
Based on Example 4 shown above, the film formation cycle by the
その結果、実施例1と同様に、酸化膜21において良好な成膜速度特性,バリア性(実施例4では水蒸気透過率が4.0×10-4g/m2/day程度),絶縁性が得られ、さらに実施例3と同様に、成膜時間を短縮化し易くしたりメンテナンスに係る負担を軽減できる可能性がある他に、以下に示すことを確認できた。
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.
すなわち、実施例4は、チャンバ30の各処理炉31~34に充填する各ガスにおいて、常に入れ替える必要がないため、実施例3と比較すると、当該各ガスを効率良く使用(供給量を減少)できる可能性がある。
That is, in 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.
以上、具体的な実施形態を示して本発明のALD方法について説明したが、当該ALD方法は本実施形態に限定されるものではなく、その特徴を損なわない範囲で適宜設計変更が可能であり、その設計変更されたものも、本発明の技術的範囲に属する。
Although 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.
例えば、本実施形態のALD方法の成膜プロセスの前後にCVDプロセスを行うことで、同一の被成膜対象物2の被成膜面20にALD膜とCVD膜を備える多層構造の膜を形成することも可能である。例えば、CVDで高速成膜が可能で弾性耐力の高いSiO2膜をCVD成膜し、SiO2膜の間に水蒸気透過性の高いAl2O3膜をALD成膜すると、単層膜では実現しない多機能性を有する多層構造の膜を低温で成膜可能となる。
For example, by performing a CVD process before and after the film formation process of the ALD method of the present embodiment, 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.
また、ALD装置11~14の各構成要素においては、被成膜面20に対して所望の酸化膜21を形成できる範囲で、適宜省略しても良い。例えば、ガス排出部5によるチャンバ3内のガスの吸気により、原料ガスパージ工程S2,酸化剤パージ工程S4等を十分実現できる場合には、不活性ガス噴出口43等を適宜省略することが挙げられる。ALD装置13の場合は、噴出口間排気口44等を適宜省略(例えば、各噴出口間のうち一部のみに噴出口間排気口を設ける等)することも挙げられる。
Further, in 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. For example, when 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. .. In the case of the ALD device 13, 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).
Claims (20)
- 原子層堆積装置のチャンバ内における被成膜対象物の被成膜面に酸化膜を形成する方法であって、
酸化膜を構成する元素を含む原料ガスをチャンバ内に供給して、被成膜面に当該原料ガスの吸着層を形成する原料ガス供給工程と、
原料ガス供給工程で供された原料ガスの余剰ガスと、当該原料ガスが被成膜面に吸着することで生じたガスと、を当該被成膜面から除去する原料ガスパージ工程と、
80体積%以上のオゾンガスをチャンバ内に供給し、被成膜面に形成された吸着層を酸化する酸化剤供給工程と、
酸化剤供給工程で供されたオゾンガスの余剰ガスと、原料ガスの吸着層を酸化することで生じたガスと、を被成膜面から除去する酸化剤パージ工程と、を有し、
酸化剤供給工程は、被成膜面に対するオゾンガスの曝露量を1×105ラングミュア以上とし、チャンバ内の圧力を1000Pa以下とする、原子層堆積方法。 A method of forming an oxide film on the surface of an object to be deposited in the chamber of an atomic layer deposition apparatus.
A raw material gas supply process in which a raw material gas containing an element constituting an oxide film is supplied into the chamber to form an adsorption layer of the raw material gas on the surface to be filmed.
A raw material gas purging step of removing the surplus gas of the raw material gas supplied in the raw material gas supply step and the gas generated by the adsorption of the raw material gas on the film-formed surface to be formed.
An oxidant supply step of supplying 80% by volume or more of ozone gas into the chamber to oxidize the adsorption layer formed on the surface to be filmed, and
It has an oxidant purging step of removing the surplus gas of ozone gas provided in the oxidant supply step and the gas generated by oxidizing the adsorption layer of the raw material gas from the surface to be deposited.
The oxidant supply step is an atomic layer deposition method in which the exposure amount of ozone gas to the surface to be filmed is 1 × 105 Langmuir or more and the pressure in the chamber is 1000 Pa or less. - 原子層堆積装置は、
被成膜対象物を出し入れ自在に収容可能なチャンバと、
被成膜対象物を支持する支持部と、
チャンバ内にガスを供給するガス供給部と、
チャンバ内のガスを吸気して当該チャンバ外に排出し、当該チャンバ内の減圧状態を維持するガス排出部と、を備え、
ガス供給部は、
原料ガスをチャンバ内に噴き出す原料ガス噴出口と、
オゾンガスをチャンバ内に噴き出すオゾンガス噴出口と、
不活性ガスをチャンバ内に噴き出す不活性ガス噴出口と、を有している、請求項1記載の原子層堆積方法。 Atomic layer deposition equipment
A chamber that can freely put in and take out the object to be filmed,
A support part that supports the object to be filmed and
A gas supply unit that supplies gas into the chamber,
It is provided with a gas discharge unit that takes in gas in the chamber and discharges it to the outside of the chamber to maintain a decompressed state in the chamber.
The gas supply section
A raw material gas outlet that ejects the raw material gas into the chamber,
An ozone gas outlet that ejects ozone gas into the chamber,
The atomic layer deposition method according to claim 1, further comprising an inert gas outlet that ejects the inert gas into the chamber. - 前記各工程は、チャンバ内に不活性ガスを供給することにより、当該チャンバ内のガス流を調整する、請求項1または2記載の原子層堆積方法。 The atomic layer deposition method according to claim 1 or 2, wherein each step adjusts the gas flow in the chamber by supplying an inert gas into the chamber.
- チャンバ内の容積または形状に基づいて、不活性ガスの供給量を調整する、請求項3記載の原子層堆積方法。 The atomic layer deposition method according to claim 3, wherein the supply amount of the inert gas is adjusted based on the volume or shape in the chamber.
- 支持部は、複数個の被成膜対象物を出し入れ自在に収容してチャンバ内に配置可能な筐体状の収容壁を有し、
前記収容壁の少なくとも一部には、チャンバ内のガスの通過が可能であって被成膜対象物の通過を遮る通気部が、設けられている、請求項2~4の何れかに記載の原子層堆積方法。 The support portion has a housing-like accommodating wall capable of accommodating a plurality of objects to be filmed in and out freely and arranging them in the chamber.
The invention according to any one of claims 2 to 4, wherein at least a part of the accommodating wall is provided with a ventilation portion that allows the passage of gas in the chamber and blocks the passage of the object to be deposited. Atomic layer deposition method. - 支持部は、被成膜対象物を、被成膜面に沿った四方向のうち相対する二方向において移動自在に支持し、
ガス供給部は、チャンバ内において被成膜対象物の被成膜面と対向して配置されたシャワーヘッドを有し、
シャワーヘッドは、
原料ガス噴出口とオゾンガス噴出口とが、被成膜対象物の被成膜面と対向して前記二方向に所定間隔を隔てて交互に設けられ、
原料ガス噴出口とオゾンガス噴出口との両者間に不活性ガス噴出口が設けられており、
被成膜対象物の前記二方向の移動に応じて、被成膜面に対し前記各工程を行う、請求項2~4の何れかに記載の原子層堆積方法。 The support portion movably supports the object to be filmed in two of the four directions along the surface to be filmed, which are opposite to each other.
The gas supply unit has a shower head arranged in the chamber so as to face the surface of the object to be filmed.
Shower head
The raw material gas outlet and the ozone gas outlet are alternately provided in the two directions at predetermined intervals so as to face the film-forming surface of the object to be film-formed.
An inert gas outlet is provided between both the raw material gas outlet and the ozone gas outlet.
The atomic layer deposition method according to any one of claims 2 to 4, wherein each of the above steps is performed on the surface to be deposited according to the movement of the object to be deposited in the two directions. - シャワーヘッドの各噴出口間のうち少なくとも何れかに、噴出口間排気口が設けられている、請求項6記載の原子層堆積方法。 The atomic layer deposition method according to claim 6, wherein an exhaust port between the outlets is provided at least between the outlets of the shower head.
- 支持部は、被成膜対象物の一端側を巻回して支持する一端側ロールと、当該被成膜対象物の他端側を巻回して支持する他端側ロールと、を有し、当該被成膜対象物をロールツーロール方式で移動自在に支持する、請求項6または7記載の原子層堆積方法。 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 roll that winds and supports the other end side of the object to be deposited. The atomic layer deposition method according to claim 6 or 7, wherein the object to be film-formed is movably supported by a roll-to-roll method.
- 支持部は、被成膜対象物を支持する支持台を有し、当該支持台を被成膜対象物の被成膜面に沿って移動自在である、請求項6または7記載の原子層堆積方法。 The atomic layer deposition according to claim 6 or 7, wherein the support portion has a support base for supporting the object to be formed, and the support can be moved along the surface to be formed of the object to be formed. Method.
- シャワーヘッドは、互いに隣接する原料ガス噴出口およびオゾンガス噴出口による噴出口対が、前記二方向に所定間隔を隔てて複数個配列されている、請求項6~9の何れかに記載の原子層堆積方法。 The atomic layer according to any one of claims 6 to 9, wherein the shower head has a plurality of spout pairs of raw material gas spouts and ozone gas spouts adjacent to each other arranged at predetermined intervals in the two directions. Deposition method.
- シャワーヘッドは、
被成膜面に沿った四方向のうち前記二方向と交差している交差方向に、原料ガス噴出口が複数個配列されて原料ガス噴出口群を構成し、
前記交差方向に、オゾンガス噴出口が複数個配列されてオゾンガス噴出口群を構成している、請求項6~10の何れかに記載の原子層堆積方法。 Shower head
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-deposited surface to form a raw material gas ejection group.
The atomic layer deposition method according to any one of claims 6 to 10, wherein a plurality of ozone gas ejection ports are arranged in the crossing direction to form an ozone gas ejection port group. - シャワーヘッドの各噴出口は、前記二方向の寸法が1mm~50mmの範囲内であり、被成膜対象物の被成膜面との間の距離が1mm~20mmの範囲内である、請求項6~11の何れかに記載の原子層堆積方法。 Claimed that 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 deposited and the surface to be deposited is in the range of 1 mm to 20 mm. The atomic layer deposition method according to any one of 6 to 11.
- シャワーヘッドの各噴出口のうち少なくとも何れかは、被成膜面に沿った四方向のうち前記二方向と交差している交差方向に長いスリット形状である、請求項6~12の何れかに記載の原子層堆積方法。 According to any one of claims 6 to 12, at least one of the outlets of the shower head has a slit shape that is long in the intersecting direction intersecting the two directions among the four directions along the surface to be deposited. The atomic layer deposition method described.
- 原料ガスのガス供給量は、原料ガス噴出口における前記二方向と垂直方向の単位長さ当たり0.0001~1sccmとし、
オゾンガスの供給量は、オゾンガス噴出口における前記二方向と垂直方向の単位長さ当たり0.1sccm~10sccmとする、請求項6~13の何れかに記載の原子層堆積方法。 The gas supply amount of the raw material gas shall be 0.0001 to 1 sccm per unit length in the two directions and the vertical direction at the raw material gas outlet.
The atomic layer deposition method according to any one of claims 6 to 13, wherein the amount of ozone gas supplied is 0.1 sccm to 10 sccm per unit length in the two directions and the vertical direction at the ozone gas outlet. - チャンバは、
原料ガス噴出口が設けられている原料ガス処理炉と、
オゾンガス噴出口が設けられているオゾンガス処理炉と、
原料ガス処理炉とオゾンガス処理炉との両者間に介在し、不活性ガス噴出口が設けられている不活性ガス処理炉と、
を有して成り、
支持部は、
被成膜対象物の一端側を巻回して支持する一端側ロールと、
当該被成膜対象物の他端側を巻回して支持する他端側ロールと、
原料ガス処理炉内に配置された第1折り返しロールと、
オゾンガス処理炉内に配置された第2折り返しロールと、
を有し、被成膜対象物を、被成膜面に沿った四方向のうち相対する二方向において移動自在に支持するロールツーロール方式の構造であって、
一端側ロールと他端側ロールとの間の被成膜対象物は、
第1,第2折り返しロールにより折り返されて、原料ガス処理炉内とオゾンガス処理炉内との両者を葛折り状に往復して重畳するように延在し、
原料ガス処理炉とオゾンガス処理炉との両者間を移動する毎に、不活性ガス処理炉内を通過し、
各処理炉の炉壁は、前記葛折り状の被成膜対象物と交差する位置に、当該被成膜対象物が通過可能な処理炉開口部が設けられている、請求項2~4の何れかに記載の原子層堆積方法。 The chamber is
A raw material gas processing furnace equipped with a raw material gas outlet,
An ozone gas processing furnace equipped with an ozone gas outlet and
An inert gas processing furnace, which is located between the raw material gas processing furnace and the ozone gas processing furnace and is provided with an inert gas outlet,
Made up of
The support part
One-sided roll that winds and supports one-sided side of the object to be film-formed,
The other end roll that winds and supports the other end of the object to be film-formed,
The first folding roll placed in the raw material gas processing furnace,
The second folding roll placed in the ozone gas processing furnace and
It is a roll-to-roll structure that movably supports the object to be filmed in two of the four directions along the surface to be filmed.
The object to be film-formed between the roll on one end side and the roll on the other end side is
It is folded back by the first and second folding rolls, and extends so as to reciprocate and overlap both the inside of the raw material gas processing furnace and the inside of the ozone gas processing furnace in a kudzu-folded manner.
Each time it moves between the raw material gas processing furnace and the ozone gas processing furnace, it passes through the inert gas processing furnace.
Claims 2 to 4, wherein the furnace wall of each processing furnace is provided with a processing furnace opening through which the object to be deposited can pass at a position intersecting the knot-shaped object to be deposited. The atomic layer deposition method according to any one. - 前記葛折り状の被成膜対象物の移動経路において、
原料ガス処理炉内における第1折り返しロールと処理炉開口部との間で当該処理炉開口部に対向した位置と、
オゾンガス処理炉内における第2折り返しロールと処理炉開口部との間で当該処理炉開口部に対向した位置と、
のうち少なくとも一方に、位置調整ロールが設けられている、請求項15記載の原子層堆積方法。 In the movement path of the object to be film-formed in the shape of a kudzu fold,
The position facing the processing furnace opening between the first folding roll and the processing furnace opening in the raw material gas processing furnace,
The position facing the processing furnace opening between the second folding roll and the processing furnace opening in the ozone gas processing furnace, and
The atomic layer deposition method according to claim 15, wherein a position adjusting roll is provided on at least one of them. - 原料ガス供給工程、原料ガスパージ工程、酸化剤供給工程、酸化剤パージ工程の各工程によるサイクルを複数回行い、各原料ガス供給工程のうち少なくとも1工程と残りの工程とにおいて、それぞれ異なる種類の原料ガスを被成膜対象物に供給する、請求項1~16の何れかに記載の原子層堆積方法。 The raw material gas supply process, the raw material gas purging process, the oxidant supply process, and the oxidant purging process are repeated multiple times, and at least one of the raw material gas supply processes and the remaining process have different types of raw materials. The atomic layer deposition method according to any one of claims 1 to 16, wherein gas is supplied to the object to be deposited.
- 酸化膜は、Al2O3、HfO2、TiO2、ZnO、Ta2O3、Ga2O3、MoO3、RuO2、SiO2、ZrO2、Y2O3のいずれかの吸着層を含む、請求項1~17の何れかに記載の原子層堆積方法。 The oxide film is an adsorption layer of 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 . The atomic layer deposition method according to any one of claims 1 to 17, which comprises.
- 被成膜対象物を100℃以下の範囲内で加熱、または当該被成膜対象物を加熱しない、請求項1~18の何れかに記載の原子層堆積方法。 The atomic layer deposition method according to any one of claims 1 to 18, wherein the object to be filmed is heated within a range of 100 ° C. or less, or the object to be filmed is not heated.
- 原料ガス供給工程は、被成膜面に対する原料ガスの曝露量を1×104ラングミュア以上とする、請求項1~19の何れかに記載の原子層堆積方法。 The atomic layer deposition method according to any one of claims 1 to 19, wherein the raw material gas supply step is such that the exposure amount of the raw material gas to the film-deposited surface is 1 × 10 4 Langmuir or more.
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