WO2013018192A1 - 炭化珪素薄膜の成膜方法 - Google Patents
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- WO2013018192A1 WO2013018192A1 PCT/JP2011/067644 JP2011067644W WO2013018192A1 WO 2013018192 A1 WO2013018192 A1 WO 2013018192A1 JP 2011067644 W JP2011067644 W JP 2011067644W WO 2013018192 A1 WO2013018192 A1 WO 2013018192A1
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
- C23C14/0073—Reactive sputtering by exposing the substrates to reactive gases intermittently
- C23C14/0078—Reactive sputtering by exposing the substrates to reactive gases intermittently by moving the substrates between spatially separate sputtering and reaction stations
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0635—Carbides
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3464—Sputtering using more than one target
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5826—Treatment with charged particles
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
Definitions
- the present invention relates to a method for forming a transparent hard thin film having a SiC composition on a substrate by using a radical-assisted sputtering method.
- a silicon-based thin film (SiO 2 , SiC, Si, etc.) is formed on the substrate by a so-called reactive sputtering method in which a reactive gas (O 2 , N 2 , CH 4, etc.) is flowed together with an inert gas (Ar) during sputtering of the Si target. 3 N 4 etc.) is known (background art of Patent Document 1). While the same SiC thin film formation process is in progress, the hydrocarbon gas species to be supplied are instantaneously applied during the pre-treatment stage (heating process and high-temperature process) of the substrate and the growth stage of the thin film on the substrate, or further in the cooling process.
- a reactive gas O 2 , N 2 , CH 4, etc.
- Ar inert gas
- a SiC (Chemical Vapor Deposition) apparatus configured to be able to supply and supply the optimum type of hydrocarbon gas for each stage is formed, and a SiC single crystal thin film is formed on the substrate using SiH 4 as the Si source gas.
- a method is also known (Patent Document 2). Note that a silicon target and a carbon target are sputtered in a mixed atmosphere of inert gas and hydrogen to form a Si x C 1-x film (where 0 ⁇ x ⁇ 1) on the substrate.
- a method for manufacturing a semiconductor film to be annealed is also known (Patent Document 3).
- JP-A-3-271197 JP 2010-95431 A Japanese Patent No. 3386436
- the reactive sputtering method according to the background art of Patent Document 1 has a disadvantage that it takes a long time to form a thin film and the manufacturing cost increases because the sputtering efficiency is extremely poor.
- the CVD method according to Patent Document 2 has a disadvantage that SiH 4 used as a Si raw material is self-igniting and extremely dangerous in the manufacturing process. Further, the CVD method needs to execute the process after setting the substrate temperature to a high temperature such as 1400 ° C., for example, and is not suitable for processing on a substrate having low heat resistance such as a plastic substrate.
- the semiconductor film obtained by the method according to Patent Document 3 has a low transmittance and cannot be used for applications requiring transparency.
- a silicon carbide thin film that has high transmittance and film strength and can be used for optical applications can be formed in a short time, safely and efficiently even on a substrate having low heat resistance.
- a film forming method Provided is a film forming method.
- a method of forming a silicon carbide thin film on a substrate that is moving in a vacuum state while independently controlling sputtering of a target and exposure of plasma,
- an inert gas atmosphere after sputtering a plurality of different target materials separately and forming an intermediate thin film containing silicon and carbon on the substrate,
- the intermediate thin film is exposed to (or brought into contact with) a plasma generated in an atmosphere of a mixed gas of an inert gas and hydrogen, and is converted into an ultra thin film.
- the intermediate thin film is converted into the intermediate thin film.
- a method for forming a silicon carbide thin film characterized by repeating the formation of a thin film and the film conversion into the ultrathin film.
- a reaction process region and a plurality of film formation process regions are spatially separated from each other in a single vacuum container, and the film formation is configured such that processing in each region can be independently controlled.
- This can be realized by using an apparatus (radical assist sputtering apparatus).
- a method of forming a silicon carbide thin film on a moving substrate using the film forming apparatus as an example Sputtering any one of the plurality of targets in each of the film forming process regions under an inert gas atmosphere, and forming an intermediate thin film containing silicon and carbon on the substrate, In the reaction process region, the intermediate thin film is exposed to plasma generated in an atmosphere of a mixed gas of an inert gas and hydrogen, converted into an ultra thin film, and then converted into the ultra thin film.
- a method for forming a silicon carbide thin film characterized by repeating the formation of an intermediate thin film and the film conversion into the ultra thin film.
- the silicon carbide thin film can be formed in a short time, safely and efficiently even on a low heat resistant substrate by exposing the film to an ultrathin film and then repeating this.
- the silicon carbide thin film formed by the method of the present invention has high transmittance and film strength and is suitable for use in optical applications. That is, according to the method of the present invention, an optical substrate having a silicon carbide thin film on the substrate, having a transmittance of 70% or more at a wavelength of 650 nm to 700 nm, and a Vickers hardness HV of 1300 or more on the thin film side is obtained. Can do.
- FIG. 1 is a partial cross-sectional view showing an example of a film forming apparatus for realizing the method of the present invention.
- FIG. 2 is a partial longitudinal sectional view taken along line II-II in FIG.
- FIG. 3 is a flowchart showing a flow of a film forming method using the film forming apparatus of FIGS.
- SYMBOLS 1 Film-forming apparatus (sputtering apparatus), 11 ... Vacuum container, 13 ... Substrate holder, S ... Substrate, 12, 14, 16 ... Partition wall, 20, 40 ... deposition process region, sputtering source (21a, 21b, 41a, 41b ... magnetron sputtering electrode, 23, 43 ... AC power supply, 24, 44 ... transformer, 29a, 29b, 49a, 49b ... target), for sputtering Gas supply means (26, 46 ... gas cylinder for sputtering, 25, 45 ... mass flow controller), 60 ... reaction process area, 80 ... plasma source (81 ... case body, 83 ... dielectric plate, 85a, 85b ... antenna, 87 ... matching box, 89 ... high frequency power supply), gas supply means for reaction treatment (68 ... reaction treatment) Gas cylinder, 67 ... mass flow controller).
- sputtering source 21a, 21b, 41a, 41b ... magnetron
- a film forming apparatus 1 of this example is an apparatus capable of realizing a radical-assisted sputtering (RAS) method, and has a substantially rectangular parallelepiped shape.
- the vacuum vessel 11 is a hollow body.
- An exhaust pipe 15 a is connected to the vacuum container 11, and a vacuum pump 15 for exhausting the inside of the container 11 is connected to this pipe.
- the vacuum pump 15 is composed of, for example, a rotary pump or a turbo molecular pump (TMP).
- TMP turbo molecular pump
- a substrate holder 13 is disposed in the vacuum vessel 11.
- the substrate holder 13 is formed of a cylindrical member that can hold the substrate S as a film formation target in the vacuum vessel 11 on the outer peripheral surface thereof.
- the substrate holder 13 of this example is disposed in the vacuum container 11 so that the rotation axis Z extending in the cylindrical direction is directed in the vertical direction (Y direction) of the vacuum container 11.
- the substrate holder 13 rotates about the axis Z by driving the motor 17.
- two sputtering sources and one plasma source 80 are disposed around the substrate holder 13 disposed in the vacuum vessel 11.
- the film formation process regions 20 and 40 are formed on the front surface of each sputtering source.
- Each region 20, 40 is surrounded on all sides by partition walls 12, 14 projecting from the inner wall surface of the vacuum vessel 11 toward the substrate holder 13, so that each can secure an independent space inside the vacuum vessel 11. It is divided into.
- a reaction process region 60 is formed on the front surface of the plasma source 80.
- the region 60 is surrounded on all sides by a partition wall 16 that protrudes from the inner wall surface of the vacuum vessel 11 toward the substrate holder 13, so that the region 60 is also inside the vacuum vessel 11.
- a space independent of the areas 20 and 40 is secured.
- the processing in each of the regions 20, 40, 60 is configured to be independently controllable.
- Each sputtering source in this example is configured as a dual cathode type including two magnetron sputtering electrodes 21a and 21b (or 41a and 41b).
- targets 29a and 29b (or 49a and 49b) are detachably held on the one end side surfaces of the electrodes 21a and 21b (or 41a and 41b), respectively.
- the other end of each electrode 21a, 21b (or 41a, 41b) is connected to an AC power source 23 (or 43) as power supply means via a transformer 24 (or 44) as power control means for adjusting the amount of power.
- an AC voltage of, for example, about 1 k to 100 kHz is applied to each of the electrodes 21a and 21b (or 41a and 41b).
- the sputtering gas supply means of this example includes a gas cylinder 26 (or 46) for storing the sputtering gas and a mass flow controller 25 (or 45) for adjusting the flow rate of the sputtering gas supplied from the cylinder 26 (or 46).
- the mass flow controller 25 (or 45) is a device that adjusts the flow rate of the sputtering gas.
- the sputtering gas from the cylinder 26 (or 46) is introduced into the region 20 (or 40) with the flow rate adjusted by the mass flow controller 25 (or 45).
- the plasma source 80 of this example includes a case body 81 fixed so as to close an opening formed on the wall surface of the vacuum vessel 11 and a dielectric plate 83 fixed to the case body 81.
- the dielectric plate 83 is fixed to the case body 81 so that an antenna housing chamber is formed in a region surrounded by the case body 81 and the dielectric plate 83.
- the antenna accommodating chamber communicates with the vacuum pump 15 via the pipe 15a, and by evacuating with the vacuum pump 15, the inside of the antenna accommodating chamber can be exhausted to be in a vacuum state.
- the plasma source 80 also includes antennas 85a and 85b in addition to the case body 81 and the dielectric plate 83.
- the antennas 85a and 85b are connected to a high frequency power supply 89 through a matching box 87 that accommodates a matching circuit.
- the antennas 85 a and 85 b are supplied with electric power from the high frequency power supply 89, generate an induction electric field inside the vacuum container 11 (region 60), and generate plasma in the region 60.
- an AC voltage having a frequency of 1 to 27 MHz is applied from the high frequency power supply 89 to the antennas 85a and 85b, and plasma of a reaction processing gas is generated in the region 60.
- a variable capacitor is provided in the matching box 87 so that the power supplied from the high frequency power supply 89 to the antennas 85a and 85b can be changed.
- a reaction processing gas supply means is connected to the plasma source 80.
- the reaction processing gas supply means of this example includes a gas cylinder 68 that stores the reaction processing gas, and a mass flow controller 67 that adjusts the flow rate of the reaction processing gas supplied from the cylinder 68.
- the reaction processing gas is introduced into the region 60 through a pipe.
- the mass flow controller 67 is a device that adjusts the flow rate of the reaction processing gas.
- the reaction processing gas from the cylinder 68 is introduced into the region 60 with the flow rate adjusted by the mass flow controller 67.
- the reaction processing gas supply means is not limited to the above-described configuration (that is, a configuration including one cylinder and one mass flow controller), and includes a configuration including a plurality of cylinders and a mass flow controller (this example to be described later). Further, it is also possible to adopt a configuration including two gas cylinders that store the inert gas and hydrogen separately and two mass flow controllers that adjust the flow rate of each gas supplied from each cylinder.
- a plastic substrate (organic glass substrate), an inorganic substrate (inorganic glass substrate), or a metal substrate such as stainless steel is applicable, and the thickness thereof is, for example, 0.1 to 5 mm.
- the inorganic glass substrate as an example of the substrate S include soda lime glass (6H to 7H), borosilicate glass (6H to 7H), and the like.
- the numbers in parentheses on the inorganic glass substrate are pencil hardness values measured by a method according to JIS-K5600-5-4.
- a plurality of substrates S are intermittently arranged on the outer peripheral surface of the substrate holder 13 along the rotation direction (lateral direction) of the substrate holder 13 and are parallel to the axis Z of the substrate holder 13 (vertical direction, Y direction). Are arranged intermittently along.
- the targets 29a and 29b are obtained by forming a film raw material into a flat plate shape, the longitudinal direction of which is parallel to the rotation axis Z of the substrate holder 13, and the plane in the parallel direction is the substrate holder. 13 is held on the surface of each electrode 21a, 21b (or 41a, 41b) so as to oppose the side surface of 13.
- targets 29a and 29b are made of silicon (Si)
- targets 49a and 49b are made of carbon (C).
- SiC silicon carbide
- SiC silicon carbide
- the silicon carbide target for example, one obtained by the following method can be used. First, a SiC slurry prepared by adding a dispersant, a binder (for example, an organic binder), and water and stirring to silicon carbide powder is molded (for example, cast molding, press molding, extrusion molding, etc.) to form a molded body. obtain.
- the obtained molded body is fired and sintered at a temperature of about 1450 to 2300 ° C. (preferably 1500 to 2200 ° C., more preferably 1600 to 1800 ° C.), for example, in a vacuum or non-oxidizing atmosphere.
- the obtained sintered body is impregnated with molten Si at about 1450 to 2200 ° C. (preferably 1500 to 2200 ° C., more preferably 1500 to 1800 ° C.) in a vacuum or a reduced pressure non-oxidizing atmosphere.
- the pores of the sintered body are filled with Si.
- a SiC target having a density of 3 g / cm 3 or more thus obtained can be used. With such a high-density and uniform SiC target, stable discharge can be performed with high input during sputtering film formation, which can contribute to an increase in film formation speed.
- the inside of the vacuum vessel 11 is sealed with the door between the load lock chamber and the vacuum vessel 11 being used.
- the inside is brought to a high vacuum state of about 10 ⁇ 5 to 0.1 Pa.
- the valve is opened and the antenna accommodating chamber of the plasma source 80 is exhausted at the same time.
- the driving of the motor 17 is started, and the substrate holder 13 is rotated about the axis Z. Then, the substrate S held on the outer peripheral surface of the substrate holder 13 revolves around the axis Z that is the rotation axis of the substrate holder 13, and between the position facing the regions 20 and 40 and the position facing the region 60. Move repeatedly.
- the rotation speed of the substrate holder 13 may be 10 rpm or more, but is preferably 50 rpm or more, more preferably 80 rpm or more. By setting it to 50 rpm or more, the effect of introducing hydrogen at the time of plasma exposure can be suitably exhibited, and it becomes easy to promote the improvement of the transmittance and film strength of the silicon carbide thin film formed on the substrate S. .
- the upper limit of the rotation speed of the substrate holder 13 is, for example, about 150 rpm, preferably 100 rpm. The above is the preparation before film formation in step (hereinafter abbreviated as “S”) 1 in FIG.
- the sputtering process performed in the regions 20 and 40 and the plasma exposure process performed in the region 60 are sequentially repeated to generate a thin film made of silicon carbide as a final thin film having a predetermined thickness on the surface of the substrate S.
- an intermediate thin film is formed on the surface of the substrate S by two successive sputtering processes, and the intermediate thin film is converted into an ultrathin film by a subsequent plasma exposure process. Then, by repeating the two sputtering processes and the plasma exposure process, the next ultrathin film is deposited on the ultrathin film, and this operation is repeated until the final thin film is obtained.
- the “intermediate thin film” is a thin film formed by passing through both the region 20 and the region 40.
- “Ultra-thin film” is a term used to prevent confusion with this final “thin film” because an ultra-thin film is deposited multiple times to form a final thin film (thin film with a target thickness). In the sense that it is sufficiently thinner than the final “thin film”.
- the sputtering process of this example is performed as follows. First, after confirming the stability of the pressure in the vacuum vessel 11, the pressure in the region 20 is adjusted to, for example, 0.05 to 0.2 Pa, and then a sputtering gas having a predetermined flow rate from the gas cylinder 26 via the mass flow controller 25. Is introduced into region 20.
- an inert gas is used alone as a sputtering gas, and no reactive gas such as nitrogen or oxygen is used in combination. Therefore, the deposition rate does not decrease as compared with the reactive sputtering method in which such reactive gases are introduced simultaneously.
- the flow rate of the inert gas introduced in this example is, for example, about 100 to 600 sccm, preferably about 150 to 500 sccm.
- the sputtering power density is 1.5 W / cm 2 to 2.0 W / cm 2 , preferably 1.6 W / cm 2 to 1.8 W / cm 2 , particularly preferably 1 with respect to the targets 29a and 29b.
- Power (sputtering power) is supplied so as to be about 7 W / cm 2 .
- Power density means power (W) supplied per unit area (cm 2 ) of the targets 29a, 29b (or 49a, 49b) (the same applies hereinafter).
- the target 29a becomes a cathode (minus pole) at a certain point in time, and the target 29b always becomes an anode (plus pole).
- the target 29b becomes the cathode (minus pole) and the target 29a becomes the anode (plus pole).
- the pair of targets 29a and 29b alternately become an anode and a cathode, so that a part of the sputtering gas (inert gas) around each target 29a and 29b emits electrons and is ionized.
- a leakage magnetic field is formed on the surfaces of the targets 29a and 29b by the magnets disposed on the electrodes 21a and 21b, so that the electrons draw a toroidal curve in the magnetic field generated near the surfaces of the targets 29a and 29b. Go around. Strong plasma is generated along the trajectory of the electrons, and ions of the sputtering gas in the plasma are accelerated toward the target in the negative potential state (cathode side) and collide with the targets 29a and 29b. Atoms and particles (Si atoms and Si particles) on the surfaces of 29a and 29b are knocked out (sputtering). These atoms and particles are film raw material that is a raw material of the thin film, and adhere to the surface of the substrate S. The above is the sputtering of the silicon target (or carbon target) in the region 20 in S21 of FIG.
- non-conductive or poorly conductive incomplete reactants may adhere on the anode, but when this anode is converted to a cathode by an alternating electric field, these Incomplete reactants and the like are sputtered, and the target surface becomes the original clean state. Then, by repeating the pair of targets 29a and 29b alternately becoming an anode and a cathode, a stable anode potential state is always obtained, and a change in the plasma potential (almost equal to the normal anode potential) is prevented, and the substrate The film raw material adheres stably to the surface of S.
- the region 40 is also operated together with the operation of the region 20 (sputtering gas supply, power supply from the AC power supply 23). Specifically, the pressure in the region 40 is adjusted to, for example, 0.05 to 0.2 Pa, and then a sputtering gas having a predetermined flow rate is introduced into the region 40 from the gas cylinder 46 via the mass flow controller 45.
- an inert gas is used alone as the sputtering gas, and the flow rate of the inert gas is, for example, about 100 to 600 sccm, preferably about 150 to 500. Then, the surroundings of the targets 49a and 49b are similarly in an inert gas atmosphere. In this state, an AC voltage is applied from the AC power supply 43 to the electrodes 41a and 41b via the transformer 42 so that an alternating electric field is applied to the targets 49a and 49b.
- the target 49a, 49b has a predetermined power density (for example, 4.5 times to 5.5 times, preferably 4.8 times to 5.2 times, particularly preferably) of the power density for sputtering the targets 29a, 29b. It is important to supply electric power at a sputtering power density of about 5 times. By doing so, there is an advantage that it is possible to efficiently form a silicon carbide thin film having high transmittance and high film strength.
- Power density on the target 49a, 49b is the target 29a, when the power density for the 29b of 1.5W / cm 2 ⁇ 2.0W / cm 2, for example, 8.5W / cm 2 ⁇ 9.0W / cm 2, preferably Is 8.5 W / cm 2 to 8.7 W / cm 2 , particularly preferably around 8.6 W / cm 2 .
- the targets 29a and 49b It is possible to supply power with a sputtering power density of a predetermined power density (for example, 2 to 3 times, preferably 2.3 to 2.8 times, particularly preferably about 2.5 times) of the power density for sputtering 29b.
- the power density for the targets 49a and 49b is 3.0 to 4.0 W / cm 2 (preferably 3.3 to 3.7 W / cm 2 , particularly preferably 3.
- the target 49a is compared to the targets 29a and 29b.
- 49b is supplied with electric power at a sputtering power density that is a predetermined multiple of the power density for sputtering (for example, 0.5 to 1.2 times, preferably 0.7 to 1.0 times, particularly preferably about 0.8 times). can do.
- the power density for the targets 29a and 29b is 10 to 18 W / cm 2 (preferably 13 to 15 W / cm 2 , particularly preferably around 14 W / cm 2 ) when the power density for the targets 49a and 49b is, for example, It can be 7 to 15 W / cm 2 , preferably 9 to 13 W / cm 2 , and particularly preferably about 11 W / cm 2 .
- the target 49a By supplying power to the targets 49a and 49b, the target 49a becomes a cathode (negative pole) at a certain point in time as described above, and at that time, the target 49b always becomes an anode (positive pole). If the direction of the alternating current changes at the next time point, the target 49b becomes the cathode and the target 49a becomes the anode. In this way, the pair of targets 49a and 49b alternately become an anode and a cathode, so that a part of the sputtering gas (inert gas) around each target 49a and 49b emits electrons and is ionized.
- the sputtering gas inert gas
- a leakage magnetic field is formed on the surfaces of the targets 49a and 49b by the magnets arranged on the electrodes 41a and 41b, so that the electrons draw a toroidal curve in the magnetic field generated near the surfaces of the targets 49a and 49b. Go around.
- a strong plasma is generated along the trajectory of the electrons, and ions of the sputtering gas in the plasma are accelerated toward the target in the negative potential state (cathode side) and collide with the targets 49a and 49b.
- Atoms and particles (C atoms, C particles, etc.) on the surfaces of 49a and 49b are knocked out. These atoms and particles are film raw material that is a raw material of the thin film. In this example, these atoms and particles adhere to the Si atoms and Si particles already attached on the substrate S to form an intermediate thin film.
- the above is the sputtering of the carbon target (or silicon carbide target) in the region 40 in S22 of FIG.
- the intermediate thin film of this example is composed of a mixture of each element (Si atom or Si particle and C atom or C particle) and is not in a strong chemical bond state.
- Plasma treatment is performed as follows.
- the operation of the region 60 is started together with the operation of the regions 20 and 40.
- a predetermined amount of reaction processing gas is introduced into the region 60 from the gas cylinder 68 via the mass flow controller 67, and the surroundings of the antennas 85a and 85b are set to a predetermined gas atmosphere.
- the pressure in the region 60 is maintained at 0.07 to 1 Pa, for example. Further, at least during the generation of plasma in the region 60, the internal pressure of the antenna housing chamber is maintained at 0.001 Pa or less.
- a voltage of 100 k to 50 MHz (preferably 1 M to 27 MHz) is applied to the antennas 85 a and 85 b from the high frequency power supply 89 with the reaction processing gas introduced from the cylinder 68, the antennas 85 a and 85 b in the region 60 are applied to the antennas 85 a and 85 b. Plasma is generated in the facing area.
- the power (plasma processing power) supplied from the high-frequency power source 89 is, for example, 3 kW or more, preferably 4 kW or more, more preferably 4.5 kW or more.
- Is made of a resin material for example, a small power of 1 kW or less, preferably 0.8 kW or less, more preferably 0.5 kW or less can be obtained.
- each process of S21 to S23 in FIG. Sputtering treatment and plasma exposure treatment are repeated (No in S3; thin film deposition step).
- a final thin film (SiC thin film) having a desired film thickness is generated on the substrate S.
- the present inventors contacted the intermediate thin film with plasma generated in an atmosphere of a mixed gas of inert gas and hydrogen, converted the film into an ultra thin film, and then stacked the ultra thin film to a predetermined thickness.
- a silicon carbide thin film having high transmittance and high film strength can be formed on the substrate S was found by experiments.
- the reason why an excellent film quality silicon carbide thin film can be obtained by such treatment is not necessarily clear.
- the composition of the intermediate thin film and the exposure to the plasma are independent from each other in terms of time, and the structure is greatly different from that of normal continuous film formation (such as vacuum deposition) in that this is periodically repeated. .
- the deposited intermediate thin film is exposed to specific plasma generated in a mixed gas atmosphere containing hydrogen as an inert gas.
- a mixed gas atmosphere containing hydrogen as an inert gas containing hydrogen as an inert gas.
- the intermediate thin film is converted into ions (H 2 + ) of hydrogen molecules and hydrogen in the plasma.
- the transmittance and the film strength of the silicon carbide thin film as the final thin film are increased by efficiently taking in energy from the active species and, as a result, achieving a high-strength interatomic bond.
- the present inventors speculate that hydrogen molecule ions (H 2 + ) in the plasma have a function of promoting the bonding of atoms in the intermediate thin film.
- the mixing ratio of the inert gas and hydrogen is preferably 97: 3 to 80:20 (that is, hydrogen concentration 3 to 20%), more preferably 97: 3 to 90:10 (hydrogen concentration) in terms of volume. 3 to 10%), more preferably 97: 3 to 94: 6 (hydrogen concentration 3 to 6%), and particularly preferably around 95: 5 (hydrogen concentration around 5%).
- the transmittance of the resulting silicon carbide thin film tends to increase as the hydrogen concentration increases, if the concentration is too high (for example, exceeding 20%), safety management is hindered in the manufacturing process. In addition, there is a tendency that the balance between the transmittance and film strength of the formed silicon carbide thin film is deteriorated. On the other hand, if the hydrogen concentration is too low, the transmittance of the resulting silicon carbide thin film is lowered.
- the flow rate of the mixed gas is, for example, about 300 to 1000 sccm, preferably about 400 to 600 sccm.
- the introduction flow rate of the mixed gas is small, both the transmittance and film strength of the formed silicon carbide thin film tend to decrease. Conversely, if the flow rate of introduction is too large, there is a safety problem.
- argon helium, etc.
- the inert gas In this example, the case where argon is used as the inert gas is illustrated.
- the silicon carbide thin film formed on the substrate S in this example has high transmittance and film strength. Specifically, with a silicon carbide thin film on the substrate S, the transmittance at a wavelength of 650 nm to 700 nm is 70% or more, preferably 75% or more, and the Vickers hardness HV on the thin film side is 1300 or more, preferably Is 1500 or more, more preferably 1700 or more, and still more preferably 1800 or more. Further, the dynamic friction coefficient ⁇ k can be set to 0.5 or less.
- An optical substrate in which such a silicon carbide thin film is formed on the substrate S can be used, for example, as a window material for a sandblasting apparatus.
- Vickers hardness HV is one type of indentation hardness, and is generally used as one of numerical values representing the hardness of an object.
- the measuring method uses a regular square pyramid of diamond having a face angle of 136 ° as an indenter, and obtains the length of the diagonal line of the square recess generated when the indenter is pushed into the sample with a constant load.
- the surface area of the dent is obtained from the length of the diagonal line, and a value obtained by dividing the load by the surface area is obtained as the Vickers hardness. This Vickers hardness is expressed only by a numerical value without a unit.
- plasma post-treatment may be further performed. Specifically, first, the rotation of the substrate holder 13 is temporarily stopped, and the operations in the regions 20 and 40 (supply of sputtering gas and supply of power from the AC power sources 23 and 43) are stopped. On the other hand, the operation of the region 60 is continued as it is. That is, in the region 60, the supply of the reaction processing gas and the supply of power from the high frequency power supply 89 are continued to continue generating plasma.
- the silicon carbide thin film formed on the substrate S is subjected to plasma processing (post-processing) while passing through the region 60.
- plasma processing post-processing
- the plasma exposure treatment when forming the silicon carbide thin film and the plasma post-treatment after formation of the silicon carbide thin film may be performed under the same conditions or different conditions. Can also be done.
- the hydrogen gas concentration in the mixed gas may be varied.
- the hydrogen concentration in the latter is set to 93: 7 in the plasma post-treatment and the latter is more than the former. It may be raised or vice versa.
- the transmittance can be expected to be further improved.
- the plasma processing power (power supplied from the high-frequency power supply 89) may be varied with respect to the plasma exposure processing when forming the silicon carbide thin film.
- the matching box 87 can be used for adjustment.
- the plasma post-treatment time is set to an appropriate time within a range of about 1 to 60 minutes, for example.
- the silicon carbide thin film is formed using the sputtering apparatus 1 capable of realizing the radical-assisted sputtering method that performs magnetron sputtering, which is an example of sputtering.
- the present invention is not limited to this. It is also possible to form a film by another sputtering method using a film forming apparatus that performs other known sputtering such as bipolar sputtering without using electric discharge.
- the atmosphere during sputtering is an inert gas atmosphere in any case.
- ⁇ Sputtering in region 20 >> ⁇ Sputtering gas: Ar, ⁇ Gas pressure for sputtering: 0.1 Pa -Sputtering gas introduction flow rate: 150 sccm, Targets 29a and 29b: silicon (Si) Sputtering power density: 1.7 W / cm 2 -Frequency of the alternating voltage applied to the electrodes 21a and 21b: 40 kHz.
- ⁇ Sputtering in region 40 >> ⁇ Sputtering gas: Ar, ⁇ Gas pressure for sputtering: 0.1 Pa -Sputtering gas introduction flow rate: 150 sccm, Target 49a, 49b: carbon (C), Sputtering power density: 8.6 W / cm 2 (Equivalent to about 5 times the power density for sputtering the targets 29a and 29b made of silicon (Si)) -Frequency of the alternating voltage applied to the electrodes 41a and 41b: 40 kHz.
- Plasma exposure in region 60 >> Reaction reaction gas: Ar + H 2 ⁇ Hydrogen concentration in reaction gas: See Table 1.
- the Vickers hardness HV on the surface of the silicon carbide thin film tends to increase as the value of the hydrogen concentration in the mixed gas increases from 0% to 10%.
- the hydrogen concentration exceeds 10%, there is a tendency to decrease as the value increases.
- the transmittance of the experimental example sample this tends to increase as the hydrogen concentration in the mixed gas increases.
- the targets 49a and 49b in the region 40 were changed to those composed of silicon carbide (SiC). Moreover, the sputtering power density for the targets 29a and 29b made of silicon (Si) in the region 20 was changed to 3.5 W / cm 2 . Furthermore, the sputtering power density for the targets 49a and 49b was changed to 8.8 W / cm 2 (corresponding to about 2.5 times the power density for sputtering the targets 29a and 29b). Except for these, samples were formed under the same conditions as in Experimental Examples 1 to 5, and samples of each experimental example in which a silicon carbide thin film having a thickness of 4 ⁇ m was formed on the substrate S were obtained. Each sample obtained was subjected to the same evaluation as in Experimental Examples 1 to 5, and it was confirmed that the same tendency was observed.
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Abstract
Description
不活性ガスの雰囲気下で、材質が異なる複数のターゲットを別々にスパッタリングし、珪素と炭素を含む中間薄膜を基板上に形成した後、
前記中間薄膜に対して、不活性ガスと水素の混合ガスの雰囲気下で発生させたプラズマを曝露し(または接触させ)、超薄膜に膜変換させ、その後、該超薄膜に対して、前記中間薄膜の形成と前記超薄膜への膜変換を繰り返すことを特徴とする炭化珪素薄膜の成膜方法が提供される。
不活性ガスの雰囲気の下、各成膜プロセス領域のそれぞれで、前記複数のターゲットのうちのいずれかをスパッタリングし、珪素と炭素を含む中間薄膜を基板上に形成した後、
前記反応プロセス領域で、前記中間薄膜に対して、不活性ガスと水素の混合ガスの雰囲気下で発生させたプラズマを曝露し、超薄膜に膜変換させ、その後、該超薄膜に対して、前記中間薄膜の形成と前記超薄膜への膜変換を繰り返すことを特徴とする炭化珪素薄膜の成膜方法が提供される。
20,40…成膜プロセス領域、スパッタ源(21a,21b,41a,41b…マグネトロンスパッタ電極、23,43…交流電源、24,44…トランス、29a,29b,49a,49b…ターゲット)、スパッタ用ガス供給手段(26,46…スパッタ用ガスボンベ、25,45…マスフローコントローラ)、
60…反応プロセス領域、80…プラズマ源(81…ケース体、83…誘電体板、85a,85b…アンテナ、87…マッチングボックス、89…高周波電源)、反応処理用ガス供給手段(68…反応処理用ガスボンベ、67…マスフローコントローラ)。
まず、本発明方法を実現することができる成膜装置の一構成例を説明する。
なお、反応処理用ガス供給手段は、上記構成(つまり、1つのボンベと1つのマスフローコントローラを含む構成)に限らず、複数のボンベとマスフローコントローラを含む構成(後述する本例を例に取ると、不活性ガスと水素を別々に貯蔵する2つのガスボンベと、各ボンベから供給される各ガスの流量を調整する2つのマスフローコントローラを含む構成)とすることもできる。
(1)まず、成膜の前準備をする。具体的には、まず電極21a,21b(又は41a,41b)の上にターゲット29a,29b(又は49a,49b)をセットする。これとともに、真空容器11の外で基板ホルダ13に成膜対象としての基板Sをセットし、真空容器11のロードロック室内に収容する。
基板Sは、基板ホルダ13の外周面に、基板ホルダ13の回転方向(横方向)に沿って断続的に複数配列され、かつ基板ホルダ13の軸線Zと平行な方向(縦方向、Y方向)に沿って断続的に複数配列される。
炭化珪素ターゲットとしては、例えば以下の方法で得られるものを用いることができる。まず、炭化珪素粉末に、分散剤、結合剤(例えば有機質バインダ)、水を添加して撹拌して調製したSiCのスラリーを成形(例えば鋳込み成形、プレス成形、押出成形など)して成形体を得る。次に、得られた成形体を、例えば真空中又は非酸化性雰囲気中で1450~2300℃程度(好ましくは1500~2200℃、より好ましくは1600~1800℃)の温度で焼成して焼結させる。次に、得られた焼結体に、溶融したSiを、真空中又は減圧非酸化性雰囲気中、1450~2200℃程度(好ましくは1500~2200℃、より好ましくは1500~1800℃)で含浸させ、焼結体の気孔をSiで満たすようにする。本例では、こうして得られる密度3g/cm3 以上のSiCターゲットを用いることができる。このような高密度かつ均一なSiCターゲットであれば、スパッタリング成膜時に高入力で安定した放電をおこなうことができ、成膜速度を高めることに寄与しうる。
以上が、図3のステップ(以下「S」と略記する。)1での成膜の前準備である。
まず、真空容器11内の圧力の安定を確認した後、領域20内の圧力を例えば0.05~0.2Paに調整し、その後、マスフローコントローラ25を介してガスボンベ26から所定流量のスパッタ用ガスを領域20に導入する。
以上が、図3のS21における、領域20での珪素ターゲット(または炭素ターゲット)のスパッタリングである。
一方で、ターゲット29a,29bとして炭化珪素(SiC)で構成されたものを用い、かつターゲット49a,49bとして炭素(C)で構成されたものを用いる場合、ターゲット29a,29bに対して、ターゲット49a,49bをスパッタリングするパワー密度の所定倍(例えば0.5~1.2倍、好ましくは0.7~1.0倍、特に好ましくは0.8倍前後)のスパッタリングパワー密度となる電力を供給することができる。この場合、ターゲット29a,29bに対するパワー密度は、上記ターゲット49a,49bに対するパワー密度が10~18W/cm2 (好ましくは13~15W/cm2 、特に好ましくは14W/cm2 前後)の場合、例えば7~15W/cm2 、好ましくは9~13W/cm2 、特に好ましくは11W/cm2 前後とすることができる。
以上が、図3のS22における、領域40での炭素ターゲット(または炭化珪素ターゲット)のスパッタリングである。
以上が、図3のS23における、領域60での中間薄膜へのプラズマ曝露である。
図1及び図2に示すスパッタ装置1を用い、基板Sとしてガラス性基板であるBK7を基板ホルダ13に複数枚セットし、下記の条件で、領域20でのスパッタリング、領域40でのスパッタリング、及び領域60でのプラズマ曝露を繰り返し(薄膜堆積工程)、厚み4μmの炭化珪素薄膜を基板S上に成膜した各実験例サンプルを得た。
・基板温度:室温。
・スパッタ用ガス:Ar、
・スパッタ用ガス圧:0.1Pa、
・スパッタ用ガスの導入流量:150sccm、
・ターゲット29a,29b:珪素(Si)、
・スパッタリングパワー密度:1.7W/cm2 、
・電極21a,21bに印加する交流電圧の周波数:40kHz。
・スパッタ用ガス:Ar、
・スパッタ用ガス圧:0.1Pa、
・スパッタ用ガスの導入流量:150sccm、
・ターゲット49a,49b:炭素(C)、
・スパッタリングパワー密度:8.6W/cm2 、
(珪素(Si)で構成されるターゲット29a,29bをスパッタリングするパワー密度の約5倍に相当)
・電極41a,41bに印加する交流電圧の周波数:40kHz。
・反応処理用ガス:Ar+H2 、
・反応処理用ガス中の水素濃度:表1を参照、
・反応処理得用ガス圧:0.3Pa、
・反応処理用ガスの導入流量:500sccm、
・高周波電源89からアンテナ85a,85bに供給される電力(プラズマ処理電力):2kW、
・アンテナ85a,85bに印加する交流電圧の周波数:13.56MHz。
得られた各サンプルについて、下記の方法で物性の評価をし、その結果を表1に示した。
微小硬さ試験機(MMT-X7、マツザワ社製)を用い、下記の測定条件で、実験例サンプルの炭化珪素薄膜表面の硬さを測定した。
・圧子形状:ビッカース圧子(a=136°)、
・測定環境:温度20℃・相対湿度60%、
・試験荷重:25gf、
・荷重速度:10μ/s、
・最大荷重クリープ時間:15秒。
分光光度計(商品名:U-4000、日立社製)を用いて波長650nm~700nmにおける透過率を測定した。
水平直線往復摺動方式による自動摩擦摩耗解析装置(Triboster TS501:協和界面科学社製)を用い、荷重:50g、速度:60mm/分、測定回数:10往復の条件で、サンプルの炭化珪素薄膜側の動摩擦係数(μk)を測定した。
領域40でのターゲット49a,49bを炭化珪素(SiC)で構成したものに変更した。また、領域20での珪素(Si)で構成されるターゲット29a,29bに対するスパッタリングパワー密度を3.5W/cm2 に変更した。さらに、ターゲット49a,49bに対するスパッタリングパワー密度を8.8W/cm2 (ターゲット29a,29bをスパッタリングするパワー密度の約2.5倍に相当)に変更した。
これら以外は、実験例1~5と同じ条件で成膜し、厚み4μmの炭化珪素薄膜を基板S上に成膜した各実験例サンプルを得た。得られた各サンプルについて、実験例1~5と同じ評価を行ったところ、同様の傾向が見られることを確認した。
領域40での炭素(C)で構成されるターゲット49a,49bに対するスパッタリングパワー密度を14W/cm2 に変更した。また、ターゲット29a,29bを炭化珪素(SiC)で構成したものに変更した。さらに、このターゲット29a,29bに対するスパッタリングパワー密度を11W/cm2 (炭素(C)で構成されるターゲット49a,49bをスパッタリングするパワー密度の約0.8倍に相当)に変更した。
これら以外は、実験例1~5と同じ条件で成膜し、厚み4μmの炭化珪素薄膜を基板S上に成膜した各実験例サンプルを得た。そして得られた各サンプルについて、実験例1~5と同じ評価を行ったところ、同様の傾向が見られることを確認した。
Claims (11)
- 真空状態の中、ターゲットのスパッタリングとプラズマの曝露とを独立して制御しながら移動している基板上に炭化珪素の薄膜を成膜する方法であって、
不活性ガスの雰囲気下で、材質が異なる複数のターゲットを別々にスパッタリングし、珪素と炭素を含む中間薄膜を基板上に形成した後、
前記中間薄膜に対して、不活性ガスと水素の混合ガスの雰囲気下で発生させたプラズマを曝露し、超薄膜に膜変換させ、その後、該超薄膜に対して、前記中間薄膜の形成と前記超薄膜への膜変換を繰り返すことを特徴とする炭化珪素薄膜の成膜方法。 - 請求項1記載の成膜方法において、単一の真空容器内で反応プロセス領域と複数の成膜プロセス領域とがそれぞれ空間的に分離して配置され、各領域での処理が独立して制御可能に構成された成膜装置を用い、移動している基板上に炭化珪素の薄膜を成膜する方法であって、
不活性ガスの雰囲気の下、各成膜プロセス領域のそれぞれで、前記複数のターゲットのうちのいずれかをスパッタリングし、珪素と炭素を含む中間薄膜を基板上に形成した後、
前記反応プロセス領域で、前記中間薄膜に対して、不活性ガスと水素の混合ガスの雰囲気下で発生させたプラズマを曝露し、超薄膜に膜変換させ、その後、該超薄膜に対して、前記中間薄膜の形成と前記超薄膜への膜変換を繰り返すことを特徴とする炭化珪素薄膜の成膜方法。 - 請求項1又は2記載の成膜方法において、前記混合ガスは水素を3~20%の濃度で含有する成膜方法。
- 請求項1~3の何れか一項記載の成膜方法において、珪素ターゲット、炭素ターゲット及び炭化珪素ターゲットから選ばれる2つのターゲットを用いる成膜方法。
- 請求項4記載の成膜方法において、珪素ターゲットと炭素ターゲットを用いる場合に、前記珪素ターゲットをスパッタリングするパワー密度の5倍前後のパワー密度で前記炭素ターゲットをスパッタリングすることを特徴とする成膜方法。
- 請求項5記載の成膜方法において、1.7W/cm2 前後のパワー密度で前記珪素ターゲットをスパッタリングすることを特徴とする成膜方法。
- 請求項4記載の成膜方法において、珪素ターゲットと炭化珪素ターゲットを用いる場合に、前記珪素ターゲットをスパッタリングするパワー密度の2.5倍前後のパワー密度で前記炭化珪素ターゲットをスパッタリングすることを特徴とする成膜方法。
- 請求項7記載の成膜方法において、3.5W/cm2 前後のパワー密度で前記珪素ターゲットをスパッタリングすることを特徴とする成膜方法。
- 請求項4記載の成膜方法において、炭素ターゲットと炭化珪素ターゲットを用いる場合に、前記炭素ターゲットをスパッタリングするパワー密度の0.8倍前後のパワー密度で前記炭化珪素ターゲットをスパッタリングすることを特徴とする成膜方法。
- 請求項9記載の成膜方法において、14W/cm2 前後のパワー密度で前記炭素ターゲットをスパッタリングすることを特徴とする成膜方法。
- 基板上に炭化珪素の薄膜を有する光学基板において、前記炭化珪素の薄膜は、請求項1~10の何れかの方法で基板上に形成され、波長650nm~700nmでの透過率が70%以上であり、薄膜側のビッカーズ硬度HVが1300以上である光学基板。
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JP2011546349A JP4919367B1 (ja) | 2011-08-02 | 2011-08-02 | 炭化珪素薄膜の成膜方法 |
CN201180019967.9A CN103038387B (zh) | 2011-08-02 | 2011-08-02 | 碳化硅薄膜的成膜方法 |
PCT/JP2011/067644 WO2013018192A1 (ja) | 2011-08-02 | 2011-08-02 | 炭化珪素薄膜の成膜方法 |
US13/700,695 US9157146B2 (en) | 2011-08-02 | 2011-08-02 | Method for depositing silicon carbide film |
KR1020127016689A KR20130071415A (ko) | 2011-08-02 | 2011-08-02 | 탄화규소 박막의 성막방법 |
EP11855264.5A EP2740815B1 (en) | 2011-08-02 | 2011-08-02 | Method for forming silicon carbide thin film |
HK13106615.7A HK1179664A1 (en) | 2011-08-02 | 2013-06-05 | Method for forming silicon carbide thin film |
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EP (1) | EP2740815B1 (ja) |
JP (1) | JP4919367B1 (ja) |
KR (1) | KR20130071415A (ja) |
CN (1) | CN103038387B (ja) |
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US9663374B2 (en) * | 2011-04-21 | 2017-05-30 | The United States Of America, As Represented By The Secretary Of The Navy | Situ grown SiC coatings on carbon materials |
JP2016148098A (ja) * | 2015-02-13 | 2016-08-18 | 株式会社神戸製鋼所 | 降伏比と加工性に優れた超高強度鋼板 |
KR20190017956A (ko) * | 2016-06-13 | 2019-02-20 | 비아비 솔루션즈 아이엔씨. | 보호용 코팅을 포함하는 보호 물품 |
WO2019202729A1 (ja) * | 2018-04-20 | 2019-10-24 | 株式会社シンクロン | 反応性スパッタ装置及びこれを用いた複合金属化合物又は混合膜の成膜方法 |
CN109830419B (zh) * | 2019-01-24 | 2020-05-19 | 中国原子能科学研究院 | 一种微型潘宁离子源 |
US11505866B2 (en) * | 2019-04-25 | 2022-11-22 | Shibaura Mechatronics Corporation | Film formation apparatus and film formation method |
JP7313308B2 (ja) * | 2019-04-25 | 2023-07-24 | 芝浦メカトロニクス株式会社 | 成膜装置及び成膜方法 |
DE102020202567A1 (de) * | 2020-02-28 | 2021-09-02 | Robert Bosch Gesellschaft mit beschränkter Haftung | Verfahren und Vorrichtung zum Beschichten einer tribologisch hochbelasteten Oberfläche eines metallischen Bauteils |
JP7111380B2 (ja) * | 2020-04-01 | 2022-08-02 | 株式会社シンクロン | スパッタ装置及びこれを用いた成膜方法 |
US20240263298A1 (en) * | 2023-02-08 | 2024-08-08 | Innolux Corporation | Deposition apparatus and deposition method |
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- 2011-08-02 CN CN201180019967.9A patent/CN103038387B/zh active Active
- 2011-08-02 JP JP2011546349A patent/JP4919367B1/ja active Active
- 2011-08-02 WO PCT/JP2011/067644 patent/WO2013018192A1/ja active Application Filing
- 2011-08-02 EP EP11855264.5A patent/EP2740815B1/en active Active
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Also Published As
Publication number | Publication date |
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EP2740815A1 (en) | 2014-06-11 |
CN103038387A (zh) | 2013-04-10 |
EP2740815A4 (en) | 2015-06-03 |
KR20130071415A (ko) | 2013-06-28 |
EP2740815B1 (en) | 2016-04-13 |
JP4919367B1 (ja) | 2012-04-18 |
JPWO2013018192A1 (ja) | 2015-03-02 |
US9157146B2 (en) | 2015-10-13 |
HK1179664A1 (en) | 2013-10-04 |
CN103038387B (zh) | 2015-05-27 |
US20140205844A1 (en) | 2014-07-24 |
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