WO2009110611A1 - 表面処理装置 - Google Patents
表面処理装置 Download PDFInfo
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- WO2009110611A1 WO2009110611A1 PCT/JP2009/054331 JP2009054331W WO2009110611A1 WO 2009110611 A1 WO2009110611 A1 WO 2009110611A1 JP 2009054331 W JP2009054331 W JP 2009054331W WO 2009110611 A1 WO2009110611 A1 WO 2009110611A1
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- Prior art keywords
- gas
- reactor
- pressure
- surface treatment
- valve
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- H10P72/0462—
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- 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
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67155—Apparatus for manufacturing or treating in a plurality of work-stations
- H01L21/6719—Apparatus for manufacturing or treating in a plurality of work-stations characterized by the construction of the processing chambers, e.g. modular processing chambers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/008—Feed or outlet control devices
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- 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
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67017—Apparatus for fluid treatment
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- 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
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67098—Apparatus for thermal treatment
- H01L21/67109—Apparatus for thermal treatment mainly by convection
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- H10P72/0402—
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- H10P72/0434—
Definitions
- the present invention relates to a surface treatment apparatus that performs surface treatment, surface modification, etc. of a sample using fluorine gas.
- Patent Document 1 Conventionally, surface modification or surface treatment for treating organic substances or the like with fluorine gas has been performed.
- surface treatment apparatuses shown in the following patent documents are known.
- the surface treatment apparatus disclosed in Patent Document 1 is connected by a gas adjustment tank having a supply pipe communicating with a fluorine gas source and an inert gas source, and the gas adjustment tank and a gas conduit.
- the apparatus includes a treatment tank and an exhaust gas treatment apparatus, and is suitable for small-scale surface treatment and surface treatment performed using dilute fluorine gas.
- the reaction is started immediately after the mixed gas introduction is started by the highly reactive fluorine gas contained in the mixed gas, which may cause uneven processing.
- the surface treatment is started from the vicinity of the gas introduction part before the mixed gas is uniformly diffused into the treatment tank and the conditions in the treatment tank become uniform, and uneven processing is caused. May occur.
- a preheated mixed gas is supplied to the treatment tank so that a temperature difference between the object to be treated and the mixed gas is less likely to occur, but in a short flow path to the reactor It is necessary to heat the mixed gas in a short time, and further, it is necessary to heat the mixed gas from the outside of the pipe through which the gas flows at a high temperature added to the desired heating (treatment) temperature by several tens of degrees.
- the temperature of the fluorine gas contained in the mixed gas rises rapidly, and the reactivity of the fluorine gas is further increased to a high temperature, so that a metal member used for a gas conduit or a valve, Even if a resin material used as a packing or the like is formed using a material having high corrosion resistance, the high reactivity may cause local damage such as corrosion.
- the gas in the treatment tank after the surface treatment often contains fluorine gas, and when the treatment tank becomes large, the amount of fluorine gas to be treated may increase. .
- This fluorine gas is known to be a highly reactive, toxic and corrosive gas.
- the fluorine gas is treated.
- the pipes, members, equipment, harmful chemicals, etc. provided downstream from the treatment tank are loaded, resulting in partial heat generation, resulting in corrosion of the pipe, etc.
- some exhaust devices for exhausting gas from the reactor are provided on the downstream side of the reactor, and the pump provided in the exhaust device may be damaged.
- an object of the present invention is to provide a surface treatment apparatus capable of suppressing damages to members constituting the apparatus and processing unevenness of the object to be processed. Moreover, the objective of this invention is providing the surface treatment apparatus which can suppress that an apparatus is damaged with the gas used for surface treatment and modification
- a surface treatment apparatus includes a dilution gas supply device that supplies a dilution gas, a fluorine gas supply device that supplies a fluorine gas, and a mixer that generates a mixed gas by mixing the dilution gas and the fluorine gas.
- a reactor for contacting the object to be processed with the mixed gas further comprising a heating means for heating the dilution gas.
- the heating means heats the dilution gas before mixing the dilution gas and the fluorine gas.
- the diluted gas can be heated with a heater and the heated diluted gas and fluorine gas can be mixed, the fluorine gas is unlikely to be heated to an unnecessarily high temperature. The occurrence of damage such as corrosion can be suppressed. Further, since the heated mixed gas can be supplied to the reactor, it is possible to provide a surface treatment apparatus that can suppress the occurrence of processing unevenness of the object to be processed.
- the surface treatment apparatus of the present invention preferably further includes an ejector that sucks in the fluorine gas using the dilution gas as a drive source.
- the ejector is a device that can draw gas in a reduced pressure state by increasing the flow velocity.
- the ejector can draw the fluorine gas from the fluorine gas supply device by using the dilution gas as a drive source.
- the supply pressure of fluorine gas can be reduced, high-pressure storage of fluorine gas can be suppressed, and fluorine gas can be stored and used more safely.
- the first flow rate adjusting means connected to the dilution gas supply device and the mixer via a pipe, and upstream and downstream of the first flow rate adjusting means.
- a pressure control valve connected via a pipe to the pressure gauge provided and the pressure gauge provided upstream of the dilution gas supply device and the first flow rate adjustment means; Is preferred.
- the reaction The dilution gas can be supplied at a constant flow rate regardless of the influence of pressure such as the internal pressure.
- a mass flow controller etc. can be used, for example.
- the mass flow controller accurately controls the mass flow rate of gas with an electric signal. Therefore, since the mass flow rate of the dilution gas can be controlled, the flow rate of the dilution gas can be controlled more accurately and stably without being affected by the temperature and supply pressure.
- the surface treatment apparatus of the present invention further includes a pressure buffering tank provided between the pressure adjusting valve and the pressure gauge provided on the upstream side of the first flow rate adjusting means. Preferably it is.
- the flow buffer accuracy can be further improved by relaxing the mutual influence between the pressure adjusting valve and the valve provided in the first flow rate adjusting means by the pressure buffering tank.
- the surface treatment apparatus of the present invention preferably further includes a second flow rate adjusting means connected to the fluorine gas supply device and the mixer via a pipe.
- the mass flow rate of the fluorine gas can be accurately controlled by the electric signal by the second flow rate adjusting means, more accurate and stable flow control of the fluorine gas can be performed without being affected by the temperature and supply pressure. It will be possible.
- the second flow rate adjusting means for example, a mass flow controller or the like can be used in the same manner as the first flow rate adjusting means.
- the first communication pipe communicating with the mixer, the back pressure valve provided in the middle of the first communication pipe, and the middle between the first communication, A gas release valve provided on the downstream side of the back pressure valve, a second communication pipe connecting the mixer and the reactor, and a gas provided in the middle of the second communication pipe It is preferable to further include an introduction valve.
- the gas introduction valve is closed and the gas discharge valve is opened until the drive differential pressure for generating sufficient vacuum in the ejector is generated and the flow rate of the dilution gas is stabilized, and the dilution gas is opened through the first communication pipe.
- dilution gas and fluorine gas can be released.
- the gas release valve is closed and the gas introduction valve is opened, so that the mixed gas can be guided to the reactor through the second communication pipe.
- a surface treatment apparatus of the present invention includes a dilution gas supply device that supplies a dilution gas, a fluorine gas supply device that supplies a fluorine gas, a mixer that mixes the dilution gas and the fluorine gas, and generates a mixed gas. And a reactor for bringing the mixed gas into contact with a workpiece, an exhaust device for exhausting exhaust gas from the reactor, and between the reactor and the exhaust device And a plurality of flow paths through which the exhaust gas is circulated, and a plurality of valves provided in each of the plurality of flow paths.
- fluorine gas and hydrogen fluoride gas contained in the gas discharged from the reactor can be removed by the abatement device, adjusted to a desired flow rate, and controlled gas introduced into the abatement device. Therefore, the detoxifying agent filled in the detoxifying apparatus can be consumed and replaced more efficiently and accurately, and the cost for exchanging parts and members of the surface treatment apparatus can be further reduced. From the above, it is possible to provide a surface treatment apparatus that can suppress damage to the apparatus due to gas exhaust after the surface treatment.
- the constituent members from the reactor outlet to the detoxifying device inlet have heating and heat retaining means, and the internal temperature of the constituent members is hydrogen fluoride. It is preferable that it is more than the boiling point of.
- the abatement apparatus has a plurality of abatement towers, and at least one of the plurality of abatement towers is independently connected, It is preferable that at least two towers excluding the independently connected detoxification towers are connected in series.
- the other tower can be replaced or maintained, and can be prepared for the next use. Moreover, since two towers can be used continuously, the detoxification tower can be maintained in a safe state while continuing the operation of the surface treatment apparatus.
- the surface treatment apparatus of the present invention preferably further comprises a heating chamber for heating the object to be treated.
- the object to be processed can be heated in the heating chamber in advance before being brought into contact with the mixed gas, uneven processing and inappropriate processing can be suppressed.
- the heating time of the object to be processed in the reactor can be shortened, the cost can be suppressed, and the processing efficiency can be further improved.
- the surface treatment apparatus further includes a movable member capable of transporting the object to be treated to the reactor and having corrosion resistance to the fluorine gas.
- the object to be processed can be easily transported to and taken out of the reactor, and the influence of generation of impurities from the movable member due to the fluorine gas contained in the mixed gas can be suppressed.
- the reactor further includes a plate-like member provided between the object to be treated and the mixed gas supplied to the reactor. It is preferable.
- the plate member may be provided on the movable member between the object to be processed and the mixed gas flowing into the reactor.
- the mixed gas is less likely to come into direct contact with the object to be processed in the vicinity of the mixed gas introduction part in the reactor, it is possible to suppress the processing unevenness of the object to be processed, and to process the object to be processed. Can be performed uniformly.
- the surface treatment apparatus of the present invention it is possible to suppress the fluorine gas from being heated to a high temperature, it is possible to suppress damage to members and the like due to the fluorine gas, and consequently, it is possible to suppress the processing unevenness of the workpiece. . Further, according to the surface treatment apparatus of the present invention, by using a plurality of flow paths, the fluorine gas used for the surface treatment can be exhausted by a desired amount, so that a large amount of fluorine gas is temporarily exhausted. Can be suppressed. This can prevent the apparatus from being damaged by the gas used for the surface treatment or surface modification.
- FIG. 1 is a schematic configuration diagram of a main part of a surface treatment apparatus according to an embodiment of the present invention
- FIG. 2 is a schematic cross-sectional view of the reactor of FIG.
- a surface treatment apparatus 100 includes a dilution gas supply device 1, a fluorine gas supply device 2, a mass flow controller (first flow rate adjusting means) 3a connected to the dilution gas supply device 1 through a pipe, A mass flow controller (second flow rate adjusting means) 3b connected to the fluorine gas supply device 2 via piping, an ejector 4 connected to the mass flow controllers 3a and 3b via piping, and the ejector 4 and piping Are connected to each other through a mixer 5 provided on the downstream side of the ejector 4, a reactor 6 that treats an object to be processed with a mixed gas supplied from the mixer 5, and a gas guided from the reactor 6.
- a detoxification device 7 for detoxifying the fluorine gas and hydrogen fluoride gas contained in the mass flow controller 3 Heaters (heating means) 8 is further provided between the ejector 4 and.
- pressure gauges 9 and 10 are provided on the upstream side and the downstream side of the mass flow controller 3a, respectively, and a pressure adjusting valve 11 and a pressure buffering tank 12 are provided further upstream of the pressure gauge 9. Yes.
- a second communication pipe 16 communicating with the mixer 5 and the reactor 6, a gas introduction valve 17 provided in the middle of the second communication pipe 16, and a branch from the middle of the second communication pipe 16 are branched.
- a back pressure valve 14 and a gas release valve 15 provided in the middle of the first communication pipe 13 are further provided.
- the dilution gas supply device 1 is a device that supplies a gas such as an inert gas that dilutes the fluorine gas.
- a gas such as an inert gas that dilutes the fluorine gas.
- the dilution gas include nitrogen gas, oxygen gas, and argon gas, but are not limited to these gases.
- the fluorine gas supply device 2 supplies fluorine gas.
- a fluorine gas generation device that supplies hydrogen fluoride from a hydrogen fluoride supply device (not shown) or the like to electrolyze and generate fluorine gas, or fluorine Examples thereof include a gas cylinder filled with gas.
- Mass flow controllers (first flow rate adjusting means, second flow rate adjusting means) 3a, 3b are for accurately controlling the mass flow rate of gas with an electric signal. As a result, the dilution gas and fluorine gas flow rates can be controlled more accurately and stably without being affected by temperature and supply pressure.
- the mass flow controllers 3a, 3b require a gas pressure difference of 0.05 to 0.10 MPa in order to control the flow rate. Without this pressure difference, the flow rate cannot be accurately controlled due to the pressure loss inside the mass flow controllers 3a and 3b.
- the dilution gas and the fluorine gas supplied via the mass flow controllers 3a and 3b are used for the treatment pressure (for example, atmospheric pressure) of the reactor 6 provided downstream of the mass flow controllers 3a and 3b, and the mass flow.
- the pressure loss (for example, 0.05 to 0.10 MPa) of the controllers 3a and 3b and the difference necessary for extruding a necessary amount of dilution gas or fluorine gas from the dilution gas supply device 1 or fluorine gas supply device 2 as the supply source If the inlet pressure (for example, atmospheric pressure + 0.10 to 0.20 MPa) equal to or higher than the total pressure (for example, 0.05 to 0.10 MPa) is not generated, normal dilution gas or fluorine gas can be supplied. It will not be possible.
- the outlet pressure of the mass flow controllers 3a and 3b can be lowered by the suction ability of the ejector 4, and the pressure of the reactor 6 does not affect at this time.
- the pressure required for driving the mass flow controllers 3a and 3b can be reduced. Therefore, the holding / supply pressure of fluorine gas can be reduced by the capacity of the ejector. Fluorine gas is a highly reactive gas, and if the holding pressure can be reduced, the risk of corrosion and gas leakage can be reduced accordingly.
- the ejector 4 is an instrument for drawing gas in a reduced pressure state by increasing the flow velocity, and can reliably draw fluorine gas using a dilution gas as a driving source, and the drawn gas is guided to the mixer 5.
- a vacuum generator or the like may be used instead of the ejector 4, for example, a vacuum generator or the like.
- the fluorine gas supply device 2 can supply fluorine gas without any problem even if the pressure upper limit is 200 kPa or less, and the lower limit can be used up to -65 kPa (G).
- the mixer 5 mixes the dilution gas and the fluorine gas drawn by the ejector 4 and introduces them to the reactor 6.
- the mixed gas can also be generated by drawing in the fluorine gas using the diluent gas as a drive source.
- the reactor 6 receives a mixed gas of dilution gas and fluorine gas, and performs surface treatment and modification of the object to be treated.
- the reactor 6 will be described in detail with reference to FIG. 2.
- the reactor 6 has a mixed gas supply port 18 and a mixed gas discharge port 19.
- a processed product 21 and a movable member 22 are disposed.
- a heating chamber 23 is provided in parallel with the reactor 6.
- the plate-like member 20 is erected in the reactor 6 between the mixed gas supply port 18 and the workpiece 21 so as to block the supplied gas.
- the plate-like member 20 may be provided on the movable member 22 or may be removable.
- the plate-like member 20 makes it difficult for the mixed gas to come into direct contact with the workpiece 21 in the vicinity of the mixed gas supply port 18 in the reactor 6, thereby preventing processing unevenness and inappropriate processing from occurring.
- the movable member 22 can move the workpiece 21 into or out of the reactor 6, and is made of a metal material having corrosion resistance against fluorine gas, for example, a mesh or punching metal using stainless steel or the like. Those used are preferred. Moreover, although the wheel is attached to the movable member 22, you may use the thing to which a wheel etc. are not attached as one modification. As another modification, the metal material may have a mesh or punching metal, a metal frame, and a wheel.
- the heating chamber 23 is provided for heating the workpiece 21 in advance before bringing the workpiece 21 into contact with the mixed gas.
- the workpiece 21 is preferably processed in contact with the mixed gas in a heated state, the workpiece 21 is preferably transferred from the heating chamber 23 to the reactor 6 quickly. Therefore, the heating chamber 23 is preferably provided in the vicinity of the reactor 6, and the heating chamber 23 and the reactor 6 may communicate with each other.
- the heating chamber 23 and the reactor 6 may be used.
- the detoxifying device 7 removes hydrogen fluoride gas and fluorine gas generated from the surface of the workpiece 21 in the surface treatment of the reactor 6 to render the gas harmless.
- the gas from which the fluorine gas and the hydrogen fluoride gas have been removed in the detoxifying apparatus 7 is discharged out of the surface treatment apparatus 100.
- one filled with soda lime or the like may be used.
- the heater (heating means) 8 is provided in the middle of a pipe connecting the dilution gas supply device 1 and the ejector 4, and heats the dilution gas supplied from the dilution gas supply device 1. It is. The dilution gas is heated before the dilution gas and the fluorine gas are mixed.
- a heater or the like can be used as the heater (heating means) 8.
- the pressure gauge 9 measures the pressure on the upstream side of the mass flow controller 3a, and is provided on the upstream side of the mass flow controller 3a.
- the pressure gauge 10 measures the pressure on the downstream side of the mass flow controller 3a, and is provided on the downstream side of the mass flow controller 3a.
- the pressure adjusting valve 11 applies a constant driving differential pressure to the mass flow controller 3a in accordance with the difference between the pressure value of the pressure gauge 9 and the pressure value of the pressure gauge 10, and is connected to the dilution gas supply device 1 and the pressure.
- a pipe is provided between the buffer tank 12 and the buffer tank 12.
- the pressure adjusting valve 11 includes the maximum value of the pressure applied to the downstream side from the ejector 4, the drive differential pressure of the ejector 4, the drive differential pressure of the mass flow controller 3 a, and the elements constituting the surface treatment apparatus 100.
- the dilution gas can be supplied at a pressure equal to or higher than the sum of the pressure loss values.
- the dilution gas (flow rate) is supplied by being fixed by the mass flow controller 3a, no differential pressure is generated on the upstream side and the downstream side of the ejector 4, and pressure is generated only when the dilution gas is supplied. .
- the differential pressure on the upstream side and downstream side of the mass flow controller 3a before the dilution gas supply often exceeds the drive differential pressure, and a valve (not shown) provided in the mass flow controller 3a is closed. Gas may not be supplied.
- the dilution gas flow rate can be adjusted by the pressure adjusting valve 11, and the dilution gas can be supplied by applying a constant driving differential pressure to the upstream side and the downstream side of the mass flow controller 3a.
- the hunting phenomenon between the valve provided in the mass flow controller 3a and the pressure adjusting valve 11 will be described in detail.
- the valve provided in the mass flow controller 3a is opened, and the flow rate increases while the drive differential pressure decreases.
- the pressure adjusting valve 11 is opened to secure the pressure and the pressure increases, but the flow rate of the dilution gas exceeds the set value, and the valve (not shown) provided in the mass flow controller 3a is closed.
- the drive differential pressure increases and the pressure adjusting valve 11 is closed.
- the drive differential pressure decreases, but the dilution gas flow rate also decreases.
- the pressure buffer tank 12 is provided between the pressure adjusting valve 11 and the pressure gauge 9 via a pipe, and can store the dilution gas supplied from the dilution gas supply device 1.
- a valve (not shown) provided in the mass flow controller 3a and the pressure adjusting valve 11 cause hunting due to a combination of a set flow rate, a piping system, a supply pressure, a response speed of a selected device, and the like, It is possible to suppress a decrease in flow rate accuracy.
- this pressure buffering tank 12 the mutual influence between a valve (not shown) provided in the mass flow controller 3a and the pressure adjusting valve 11 is alleviated, and the flow rate accuracy of the dilution gas can be further improved.
- the first communication pipe 13 is a pipe through which the dilution gas drawn by the ejector 4 and passed through the mixer, or the dilution gas and the fluorine gas passes, and is branched from the second communication pipe 16. Further, in the middle of the first communication pipe 13, a back pressure valve 14 and a gas release valve 15 are provided further downstream of the back pressure valve 14. In the first communication pipe 13, the further downstream side of the gas release valve 15 is led to the abatement apparatus 7.
- the back pressure valve 14 is a valve for keeping the pressure of the fluid passing through the valve (fluid before passing through the valve) constant, and the gas whose pressure is adjusted by the back pressure valve 14 passes through the gas release valve 15.
- the pressure of the dilution gas and / or fluorine gas drawn by the ejector 4 and passing through the mixer 5 is adjusted to be constant by the back pressure valve 14.
- the set pressure value of the back pressure valve 14 is preferably measured in advance as a pressure stable value on the downstream side of the ejector 4 when the flow rate of the dilution gas set by the mass flow controller 3a is introduced into the reactor 6. Value.
- this value when supplying the mixed gas to the reactor 6, the mixed gas whose flow rate and concentration are controlled to be constant can be supplied to the reactor 6 immediately after the start of supply. More preferably, it is a value obtained by measuring in advance the pressure stable value on the downstream side of the ejector 4 when the set flow rate of the mixed gas is introduced into the reactor 6. If this value is set, the flow and concentration management accuracy can be further improved.
- the back pressure valve 14 may be provided in a pipe upstream of the mixer 5.
- the back pressure valve 14 may be provided in a pipe connecting the heater 8 and the ejector 4 or a pipe connecting the ejector 4 and the mixer 5.
- the gas release valve 15 is opened until the flow rate of the dilution gas is stabilized, and is closed when the flow rate of the dilution gas is stabilized. This is because the drive differential pressure is required to generate a sufficient vacuum in the ejector 4, and immediately after the dilution gas is supplied, the pressure increase gradually occurs until the drive differential pressure is reached, so that the flow rate of the dilution gas is stabilized. This is because it takes time. Since the pressure fluctuation of the fluorine gas is small in the fluorine gas supply device 2, the flow rate is instantaneously stabilized when the supply is started.
- the gas release valve 15 is opened, the dilution gas and / or the mixed gas are guided to the abatement apparatus 7. On the other hand, when the gas release valve 15 is closed, the dilution gas and / or the mixed gas are guided to the reactor 6 through the second communication pipe 16.
- the second communication pipe 16 is a pipe that guides the dilution gas and the fluorine gas to the reactor 6 after the flow rate of the dilution gas is stabilized.
- the gas introduction valve 17 is opened after the flow rate of the dilution gas is stabilized and a sufficient degree of vacuum is obtained, and is opened at the same time as the gas release valve 15 is closed. It is closed until the flow rate of the dilution gas is stabilized.
- the gas release valve 15 and the gas introduction valve 17 instantaneously close the gas release valve 15 and open the gas introduction valve 17 when the flow rate of the dilution gas is stabilized and a sufficient degree of vacuum is obtained in the ejector 4.
- Dilution gas and fluorine gas change the path from the first communication pipe 13 to the second communication pipe 16 and are led to the reactor 6.
- the switching between the gas release valve 15 and the gas introduction valve 17 is performed instantaneously, the flow rate and the degree of vacuum of the dilution gas and fluorine gas are extremely small.
- the fluorine gas supply device 2 since the pressure fluctuation is small, when the supply is started, the flow rate of the fluorine gas is instantaneously stabilized.
- the back pressure valve 14 is set so that the pressure stable value on the downstream side of the ejector 4 when the flow rate of the dilution gas set by the mass flow controller 3a is introduced into the reactor 6 is measured in advance. It is preferable. Further, only the dilution gas is supplied first, and the fluorine gas is supplied before switching between the gas release valve 15 and the gas introduction valve 17, and the mixed gas whose flow rate and concentration are controlled to be constant is supplied to the first communication pipe. Then, the gas release valve 15 may be closed and the gas introduction valve 17 may be opened.
- concentration was managed better can be supplied to the reactor 6.
- the dilution gas supplied from the dilution gas supply device 1 is guided to the pressure buffer tank 12 through the pressure adjustment valve 11 when the pressure adjustment valve 11 is opened.
- a part of the dilution gas is stored in the pressure buffer tank 12, and the other dilution gas is guided to the mass flow controller 3 a via the pressure gauge 9.
- the mass flow controller 3 a the mass flow rate is controlled, and the diluted gas whose flow rate is adjusted is led to the heater 8 via the pressure gauge 10.
- the pressure adjusting valve 11 when the pressure adjusting valve 11 is open, the difference in pressure value between the pressure gauge 9 on the upstream side of the mass flow controller 3a and the pressure gauge 10 on the downstream side is low, that is, the mass flow controller 3a. This is a case where no driving differential pressure is generated.
- the pressure adjustment valve 11 when the pressure adjustment valve 11 is closed, the dilution gas supplied from the dilution gas supply device 1 is blocked by the pressure adjustment valve 11 and is not led to the pressure buffer tank 12.
- the pressure adjusting valve 11 When the pressure adjusting valve 11 is closed, the pressure difference between the pressure gauge 9 on the upstream side of the mass flow controller 3a and the pressure gauge 10 on the downstream side is high, that is, the driving difference of the mass flow controller 3a. This is the case when pressure is generated. In this case, the dilution gas stored in the pressure buffer tank 12 is guided to the mass flow controller 3a.
- the fluorine gas passes through the mass flow controller 3 b using the dilution gas as a drive source and is drawn by the ejector 4.
- the mass flow controller 3b controls the mass flow rate of the fluorine gas, and the diluted gas whose flow rate is adjusted is drawn by the ejector 4.
- the dilution gas and fluorine gas heated in the heater 8 are guide
- the mixed gas is guided to the second communication pipe 16.
- the gas introduction valve 17 is closed and the gas release valve 15 is opened until the flow rate of the dilution gas is stabilized, and the dilution gas and / or the fluorine gas is guided to the first communication pipe 13.
- the pressure of the dilution gas and / or the fluorine gas guided to the first communication pipe 13 is adjusted by the back pressure valve 14, and then passes through the gas release valve 15 and is guided to the abatement apparatus 7.
- the gas release valve 15 is instantaneously closed and the gas introduction valve 17 is opened.
- the flow path is changed from the communication pipe 13 to pass through the second communication pipe 16 and led to the reactor 6.
- an object 21 (see the dotted line in FIG. 2) heated in advance in the heating chamber 23 is transported and arranged by the movable member 22. Then, the mixed gas supplied from the mixed gas supply port 18 collides with the plate-like member 20 in the reactor 6 and comes into contact with the object 21 to be subjected to surface treatment or surface modification. Thereafter, when a predetermined processing time elapses, the gas in the reactor 6 is discharged from the mixed gas discharge port 19 and guided to the detoxifying device 7, and the detoxifying device 7 detoxifies the fluorine gas and the hydrogen fluoride gas. And discharged to the outside of the surface treatment apparatus 100.
- the dilution gas is heated in advance by the heater 8, and the heated dilution gas and the fluorine gas can be mixed.
- the heated mixed gas can be supplied to the reactor 6, it can suppress that the process nonuniformity of the to-be-processed object 21 arises.
- the ejector 4 can draw in the fluorine gas from the fluorine gas supply device 2 using the dilution gas as a drive source. Thereby, since the supply pressure of fluorine gas can be reduced, high-pressure storage of fluorine gas can be suppressed, and fluorine gas can be stored and used more safely. In addition, it is possible to supply fluorine gas in a more accurate amount, which is less supplied than the dilution gas.
- a constant driving differential pressure can be applied to the mass flow controller 3a by the pressure adjusting valve 11, piping provided on the downstream side of the dilution gas supply device 1 and the mass flow controller 3a, the internal pressure of the reactor 6, etc. Regardless of the influence of pressure, the dilution gas can be supplied at a constant flow rate.
- the pressure buffering tank 12 can further reduce the mutual influence between the pressure adjusting valve 11 and a valve (not shown) provided in the mass flow controller 3a, thereby further improving the flow rate accuracy.
- the mass flow rate of the fluorine gas can be accurately controlled by the electric signal by the mass flow controller 3b, the flow rate of the fluorine gas can be accurately and stably controlled without being influenced by the temperature and the supply pressure.
- the gas introduction valve 17 is closed and the gas release valve 15 is opened until the drive differential pressure for generating a sufficient vacuum in the ejector 4 is generated and the flow rate of the dilution gas is stabilized, and dilution is performed through the first communication pipe 13. Gas and / or fluorine gas can be released to the abatement device 7 or the like. Then, after the flow rate of the dilution gas is stabilized, the gas release valve 15 is closed and the gas introduction valve 17 is opened so that the mixed gas can be guided to the reactor 6 through the second communication pipe 16. Thereby, when supplying mixed gas to the reactor 6, the mixed gas by which the flow volume and density
- the workpiece 21 can be heated in advance in the heating chamber 23 before being brought into contact with the mixed gas, processing unevenness and inappropriate processing can be suppressed. Moreover, by heating the to-be-processed object 21 beforehand, the heating time of the to-be-processed object 21 in the reactor 6 can be shortened, cost can be held down, and processing efficiency can further be improved.
- the movable member 22 using a metal material having corrosion resistance for the fluorine gas since the movable member 22 using a metal material having corrosion resistance for the fluorine gas is used, the workpiece 21 can be easily transported and carried out to the reactor 6, and the fluorine contained in the mixed gas can be used. It is possible to prevent the gas from causing an influence such as generation of impurities from the movable member 22.
- the plate-like member 20 is provided between the workpiece 21 and the mixed gas supplied to the reactor 6, the mixed gas is treated in the vicinity of the mixed gas introduction part in the reactor 6. It becomes difficult to come into direct contact with the object 21, it is possible to suppress the processing unevenness of the object 21 to be processed, and the object 21 can be uniformly processed.
- FIG. 3 is a schematic configuration diagram of a main part of the surface treatment apparatus according to the second embodiment.
- symbol as 1st Embodiment is a thing substantially the same as 1st Embodiment, description may be abbreviate
- the surface treatment apparatus 200 includes a dilution gas supply apparatus 1, a fluorine gas supply apparatus 2, a mass flow controller (first flow rate adjusting means) 3a connected to the dilution gas supply apparatus 1 via a pipe, A mass flow controller (second flow rate adjusting means) 3b connected to the fluorine gas supply device 2 via piping, an ejector 4 connected to the mass flow controllers 3a and 3b via piping, and the ejector 4 and piping Are connected to each other, and a mixer 5 provided on the downstream side of the ejector 4, a reactor 6 that treats an object to be processed with a mixed gas supplied from the mixer 5, and gas is exhausted from the reactor 6.
- pressure gauges 9 and 10 are provided on the upstream side and the downstream side of the mass flow controller 3a, respectively, and a pressure adjusting valve 11 and a pressure buffering tank 12 are provided further upstream of the pressure gauge 9. Yes.
- a second communication pipe 16 communicating with the mixer 5 and the reactor 6, a gas introduction valve 17 provided in the middle of the second communication pipe 16, and a branch from the middle of the second communication pipe 16 are branched.
- a back pressure valve 14 and a gas release valve 15 provided in the middle of the first communication pipe 214.
- the piping and components from the outlet of the reactor 6 to the inlet of the abatement device 208 have a heating / heat-retaining device 250, and the internal temperature of the piping and components is maintained above the boiling point of hydrogen fluoride. Yes.
- the dilution gas supply device 1 is a device that supplies an inert gas for diluting the fluorine gas.
- the dilution gas include nitrogen gas, oxygen gas, and argon gas, but are not limited to these gases.
- the fluorine gas supply device 2 supplies fluorine gas, and examples thereof include a device that supplies hydrogen fluoride from a hydrogen fluoride supply device (not shown) and the like, and generates fluorine gas, a gas cylinder, and the like. .
- Mass flow controllers (first flow rate adjusting means, second flow rate adjusting means) 3a, 3b are for accurately controlling the mass flow rate of gas with an electric signal. As a result, the dilution gas and fluorine gas flow rates can be controlled more accurately and stably without being affected by temperature and supply pressure.
- the mass flow controllers 3a, 3b require a gas pressure difference of 0.05 to 0.10 MPa in order to control the flow rate. Without this pressure difference, the flow rate cannot be accurately controlled due to the pressure loss inside the mass flow controllers 3a and 3b.
- the dilution gas and the fluorine gas supplied via the mass flow controllers 3a and 3b are used for the treatment pressure (for example, atmospheric pressure) of the reactor 6 provided downstream of the mass flow controllers 3a and 3b, and the mass flow.
- Pressure loss for example, 0.05 to 0.10 MPa
- the controllers 3a and 3b and necessary for pushing out a necessary amount of dilution gas or fluorine gas from the dilution gas supply device 1 or the fluorine gas supply device 2 as the supply source If the inlet pressure (for example, atmospheric pressure +0.10 to 0.20 MPa) equal to or higher than the total pressure of the differential pressure (for example, 0.05 to 0.10 MPa) is not generated, normal dilution gas or fluorine gas is supplied.
- the outlet pressure of the mass flow controllers 3a and 3b can be lowered by the suction ability of the ejector 4, and the pressure of the reactor 6 does not affect at this time.
- the pressure required for driving the mass flow controllers 3a and 3b can be reduced. Therefore, the holding / supply pressure of fluorine gas can be reduced by the capacity of the ejector. Fluorine gas is a highly reactive gas, and if the holding pressure can be reduced, the risk of corrosion and gas leakage can be reduced accordingly.
- the ejector 4 is an instrument for drawing gas in a reduced pressure state by increasing the flow velocity, and can reliably draw fluorine gas using a dilution gas as a driving source, and the drawn gas is guided to the mixer 5.
- a vacuum generator or the like may be used instead of the ejector 4, for example, a vacuum generator or the like.
- the fluorine gas supply device 2 can supply fluorine gas without any problem even if the pressure upper limit is 200 kPa or less, and the lower limit can be used up to -65 kPa (G).
- the mixer 5 mixes the dilution gas and the fluorine gas drawn by the ejector 4 and guides the generated mixed gas to the reactor 6.
- the mixed gas can also be generated by drawing in the fluorine gas using the diluent gas as a drive source.
- the reactor 6 receives a mixed gas of dilution gas and fluorine gas, and performs surface treatment and surface modification of the object to be treated.
- the reactor 6 will be described in detail with reference to FIG. 2.
- the reactor 6 has a mixed gas supply port 18 and a mixed gas discharge port 19.
- a processed product 21 and a movable member 22 are disposed.
- a heating chamber 23 is provided in parallel with the reactor 6.
- the plate-like member 20 is erected in the reactor 6 between the mixed gas supply port 18 and the workpiece 21 so as to block the supplied gas.
- the plate-like member 20 may be provided on the movable member 22 or may be removable.
- the plate-like member 20 makes it difficult for the mixed gas to come into direct contact with the workpiece 21 in the vicinity of the mixed gas supply port 18 in the reactor 6, thereby preventing processing unevenness and inappropriate processing from occurring.
- the movable member 22 can move the workpiece 21 into or out of the reactor 6, and is a metal or metal mesh having corrosion resistance to fluorine gas, such as stainless steel or punching metal Are preferably used.
- fluorine gas such as stainless steel or punching metal
- the wheel is attached to the movable member 22, you may use the thing to which a wheel etc. are not attached as one modification.
- the metal material may have a mesh or punching metal, a metal frame, and a wheel.
- the heating chamber 23 is provided for heating the workpiece 21 in advance before bringing the workpiece 21 into contact with the mixed gas.
- 2 are a workpiece 21 heated in the heating chamber 23 and a movable member 22 that can move the workpiece 21 to the reactor 6.
- the heating chamber 23 is preferably provided in the vicinity of the reactor 6, and the heating chamber 23 and the reactor 6 may communicate with each other.
- one in which the heating chamber 23 and the reactor 6 are provided adjacent to each other, or one in which the heating chamber 23 is provided in the reactor 6 may be used.
- the exhaust device 207 exhausts the gas in the reactor 6 to the detoxification device 208 after the surface treatment or surface modification of the object to be processed in the reactor 6 is completed, and has a pump. Yes.
- the gas discharged from the reactor 6 includes fluorine gas and hydrogen fluoride gas. It is.
- the detoxifying device 208 removes hydrogen fluoride gas and fluorine gas generated from the surface of the workpiece 21 in the surface treatment of the reactor 6 to detoxify the gas exhausted from the reactor,
- Three towers 208a, 208b and 208c are provided.
- the detoxification towers 208a, 208b and 208c are filled with a detoxifying agent.
- the detoxifying agent include sodium fluoride which adsorbs hydrogen fluoride gas as a main component, fluorine gas and fluoride.
- Examples include soda lime (soda lime) that adsorbs hydrogen gas.
- any one of the three towers 208a, 208b, 208c is connected independently of the other two towers by opening and closing the valve, and the other two towers are connected in series. ing.
- the surface treatment apparatus 200 When the surface treatment apparatus 200 is operated, one of the two towers connected in series is used, and the other tower is connected to the first tower, The first column can be supplemented by continuously removing the fluorine gas and hydrogen fluoride gas that could not be removed in the first column in the second column.
- maintenance and replacement of a detoxifying agent are performed for one tower connected independently while the other two towers are used.
- the connection is made by switching (opening and closing) the valve, and which one of the towers is independent or the other two towers is appropriately changed according to the state of use of the harmful agent. It is something that can be done.
- the detoxification tower 208a is connected independently to the two detoxification towers 208b and 208c to perform maintenance, exchange of the detoxifying agent, and the like.
- Two towers 208b and 208c are connected in series, and fluorine gas and hydrogen fluoride gas contained in the gas discharged from the reactor 6 are removed in the towers 208a and 208b.
- the valves 261, 262, 263, 264, 265, 275, 276, 277, 281 are closed, and the valves 271, 272, 273, 274, 282, 283, 285, 286 are opened.
- the abatement tower 208b is connected to the two abatement towers 208a and 208c independently to perform maintenance, exchange of the abatement agent, and the like.
- Two towers 208a and 208c are connected in series, and the fluorine gas and hydrogen fluoride gas contained in the gas discharged from the reactor 6 are removed in the towers 208a and 208c.
- the valves 261, 272, 273, 274, 277, 281 and 286 are closed, and the valves 262, 263, 264, 265, 271, 275, 276, 282, 283 and 284 are opened.
- the abatement tower 208c is connected to the two abatement towers 208a and 208b independently to perform maintenance, exchange of the abatement agent, and the like.
- Two towers 208a and 208b are connected in series, and fluorine gas and hydrogen fluoride gas contained in the gas discharged from the reactor 6 are removed in the two towers 208a and 208b.
- the valves 265, 271, 277, 281, 282, 283, 284, 285, 286 are closed, and the valves 261, 262, 263, 264, 272, 273, 274, 275, 276 are opened.
- the gas detoxified with the fluorine gas and the hydrogen fluoride gas in the detoxification device 208 is discharged out of the surface treatment device 200, but may be used again for the surface treatment.
- a detoxification tower is not restricted to 3 towers, You may have 4 or more towers.
- the heater (heating means) 8 heats the dilution gas supplied from the dilution gas supply device 1 before mixing with the fluorine gas, and is in the middle of the pipe connecting the ejector 4 and the pressure gauge 10. Is provided.
- the heater (heating means) 8 for example, a heater or the like can be used.
- the pressure gauge 9 measures the pressure on the upstream side of the mass flow controller 3a, and is provided on the upstream side of the mass flow controller 3a.
- the pressure gauge 10 measures the pressure on the downstream side of the mass flow controller 3a, and is provided on the downstream side of the mass flow controller 3a.
- the pressure adjusting valve 11 applies a constant driving differential pressure to the mass flow controller 3a in accordance with the difference between the pressure value of the pressure gauge 9 and the pressure value of the pressure gauge 10, and is connected to the dilution gas supply device 1 and the pressure.
- a pipe is provided between the buffer tank 12 and the buffer tank 12.
- the pressure adjusting valve 11 includes the maximum value of the pressure applied to the downstream side from the ejector 4, the drive differential pressure of the ejector 4, the drive differential pressure of the mass flow controller 3 a, and the elements constituting the surface treatment apparatus 100.
- the dilution gas can be supplied at a pressure equal to or higher than the sum of the pressure loss values.
- the dilution gas when the dilution gas is supplied by being fixed by the mass flow controller 3a, no differential pressure is generated on the upstream side and the downstream side of the ejector 4, and pressure is generated only when the dilution gas is supplied. For this reason, the differential pressure on the upstream side and downstream side of the mass flow controller 3a before the dilution gas supply often exceeds the drive differential pressure, and a valve (not shown) provided in the mass flow controller 3a is closed. Gas may not be supplied. In this case, the dilution gas flow rate can be adjusted by the pressure adjusting valve 11, and the dilution gas can be supplied by applying a constant driving differential pressure to the upstream side and the downstream side of the mass flow controller 3a.
- the hunting phenomenon between the valve provided in the mass flow controller 3a and the pressure adjusting valve 11 will be described in detail.
- the valve provided in the mass flow controller 3a is opened, and the flow rate increases while the drive differential pressure decreases.
- the pressure adjusting valve 11 is opened to secure the pressure and the pressure increases, but the flow rate of the dilution gas exceeds the set value, and the valve (not shown) provided in the mass flow controller 3a is closed.
- the drive differential pressure increases and the pressure adjusting valve 11 is closed.
- the drive differential pressure decreases, but the dilution gas flow rate also decreases.
- the pressure buffer tank 12 is provided between the pressure adjusting valve 11 and the pressure gauge 9 via a pipe, and can store the dilution gas supplied from the dilution gas supply device 1.
- a valve (not shown) provided in the mass flow controller 3a and the pressure adjusting valve 11 cause hunting due to a combination of a set flow rate, a piping system, a supply pressure, a response speed of a selected device, and the like, It is possible to suppress a decrease in flow rate accuracy.
- this pressure buffering tank 12 the mutual influence between a valve (not shown) provided in the mass flow controller 3a and the pressure adjusting valve 11 is alleviated, and the flow rate accuracy of the dilution gas can be further improved.
- the first communication pipe 214 is a pipe through which dilution gas drawn by the ejector 4 and passed through the mixer, or through which dilution gas and fluorine gas pass, is provided to branch to the second communication pipe 16. Further, in the middle of the first communication pipe 214, a back pressure valve 14 and a gas release valve 15 are provided further downstream of the back pressure valve 14. In the first communication pipe 214, the further downstream side of the gas release valve 15 is led to the exhaust device 207 and the abatement device 208.
- the back pressure valve 14 is a valve for keeping the pressure of the fluid passing through the valve constant, and the gas whose pressure is adjusted by the back pressure valve 14 passes through the gas release valve 15 and is guided to the abatement device 208.
- the pressure of the dilution gas and / or fluorine gas drawn by the ejector 4 and passing through the mixer 5 is adjusted to be constant by the back pressure valve 14.
- the set pressure value of the back pressure valve 14 is preferably measured in advance as a pressure stable value on the downstream side of the ejector 4 when the flow rate of the dilution gas set by the mass flow controller 3a is introduced into the reactor 6. Value.
- this value when supplying the mixed gas to the reactor 6, the mixed gas whose flow rate and concentration are controlled to be constant can be supplied to the reactor 6 immediately after the start of supply. More preferably, it is a value obtained by measuring in advance the pressure stable value on the downstream side of the ejector 4 when the set flow rate of the mixed gas is introduced into the reactor 6. If this value is set, the flow and concentration management accuracy can be further improved.
- the gas release valve 15 is opened until the flow rate of the dilution gas is stabilized, and is closed when the flow rate of the dilution gas is stabilized. This is because the drive differential pressure is required to generate a sufficient vacuum in the ejector 4, and immediately after the dilution gas is supplied, the pressure increase gradually occurs until the drive differential pressure is reached, so that the flow rate of the dilution gas is stabilized. This is because it takes time. Since the pressure fluctuation of the fluorine gas is small in the fluorine gas supply device 2, the flow rate is instantaneously stabilized when the supply is started.
- the gas release valve 15 is opened, the dilution gas and / or the mixed gas are guided to the exhaust device 207 through the first communication pipe 214.
- the gas release valve 15 is closed, the dilution gas and / or the mixed gas are guided to the reactor 6 through the second communication pipe 16.
- the second communication pipe 16 is a pipe that guides the dilution gas and the fluorine gas to the reactor 6 after the flow rate of the dilution gas is stabilized.
- the gas introduction valve 17 is opened after the flow rate of the dilution gas is stabilized and a sufficient degree of vacuum is obtained, and is opened at the same time as the gas release valve 15 is closed. It is closed until the flow rate of the dilution gas is stabilized.
- the gas release valve 15 and the gas introduction valve 17 instantaneously close the gas release valve 15 and open the gas introduction valve 17 when the flow rate of the dilution gas is stabilized and a sufficient degree of vacuum is obtained in the ejector 4.
- the dilution gas and the fluorine gas are guided to the reactor 6 by changing the flow path from the first communication pipe 214 to the second communication pipe 16.
- the switching between the gas release valve 15 and the gas introduction valve 17 is performed instantaneously, the flow rate and the degree of vacuum of the dilution gas and the fluorine gas are extremely small.
- the fluorine gas supply device 2 since the pressure fluctuation is small, when the supply is started, the flow rate of the fluorine gas is instantaneously stabilized.
- the back pressure valve 14 is set so that the pressure stable value on the downstream side of the ejector 4 when the flow rate of the dilution gas set by the mass flow controller 3a is introduced into the reactor 6 is measured in advance. It is preferable. Further, only the dilution gas is supplied first, and the fluorine gas is supplied before switching between the gas release valve 15 and the gas introduction valve 17, and the mixed gas whose flow rate and concentration are controlled to be constant is supplied to the first communication pipe. Then, the gas release valve 15 may be closed and the gas introduction valve 17 may be opened.
- concentration was managed better can be supplied to the reactor 6.
- the flow paths 219, 220, 221, and 222 are branched between the reactor 6 and the exhaust device 207, and are flow paths through which exhaust gas discharged from the reactor 6 passes. .
- the flow paths 219, 220, 221, and 222 those having different piping systems may be used, or plural or all having the same piping diameter may be used.
- a small flow path in the piping system can be used first, and gradually changed to a larger flow path in the piping system according to the progress of gas exhaust. .
- only one flow path is used first, and the number of flow paths used is gradually increased according to the progress of gas exhaustion. be able to.
- the channels 219, 220, 221, and 222 are not limited to four channels, but may be five or more channels, or two or three channels.
- the valves 223, 224, 225, and 226 are provided in the middle of the flow paths 219, 220, 221, and 222, respectively.
- the valves 223, 224, 225, and 226 may be, for example, automatic valves or manual valves.
- valve 224 provided in the flow path 220 having the second smallest pipe diameter is opened and the valve 223 is closed to change the gas flow path from the flow path 219 to the flow path 220.
- both the flow paths 219 and 220 are used while the valve 223 is opened, or the valve 224 is also opened after a while after only the valve 223 is opened. You may use it in order of the path 219-> channel 220-> channel 219,220. Then, in accordance with the progress of the subsequent gas exhaust, the flow is changed to the next large flow path 221 of the piping system in the same manner as described above.
- valves 223 and 224 are closed, the valves 225 and 226 are sequentially opened, and the gas flow paths are sequentially changed to the flow paths 221 and 222.
- a plurality of valves may be opened so that gas can pass through the plurality of flow paths.
- valves for example, the valve 223 is opened, and the other valves 224, 225, and 226 are closed. Then, the gas is exhausted, and then the number of gas flow paths is gradually changed from one to two, three, and four according to the progress of the gas exhaust. That is, without closing the valve 223 that is already open, the other valves 224, 225, and 226 are opened to increase the gas flow path.
- any two flow paths have the same pipe diameter, and the other two flow paths use the same pipe diameter, or the other two flow paths Even in the case where the flow paths have different pipe diameters, the gas flow paths can be changed in the same manner as described above according to the progress of gas exhaust.
- piping and components in particular, metal members constituting the piping and components have a heating / heat insulation device 250.
- the internal temperature of the outer tube and the component members is maintained above the boiling point of hydrogen fluoride, that is, about 19 degrees or more.
- a heater or the like may be used as the heating device.
- the heating / warming device 250 is attached to the pipe, but it is preferable that the heating / warming device 250 is also attached to the valves 223, 224, 225, 226 and the exhaust device 207.
- the dilution gas supplied from the dilution gas supply device 1 is guided to the pressure buffer tank 12 through the pressure adjustment valve 11 when the pressure adjustment valve 11 is opened.
- a part of the dilution gas is stored in the pressure buffer tank 12, and the other dilution gas is guided to the mass flow controller 3 a via the pressure gauge 9.
- the mass flow controller 3 a the mass flow rate is controlled, and the diluted gas whose flow rate is adjusted is led to the heater 8 via the pressure gauge 10.
- the pressure adjusting valve 11 when the pressure adjusting valve 11 is open, the difference in pressure value between the pressure gauge 9 on the upstream side of the mass flow controller 3a and the pressure gauge 10 on the downstream side is low, that is, the mass flow controller 3a. This is a case where no driving differential pressure is generated.
- the pressure adjustment valve 11 when the pressure adjustment valve 11 is closed, the dilution gas supplied from the dilution gas supply device 1 is blocked by the pressure adjustment valve 11 and is not led to the pressure buffer tank 12.
- the pressure adjusting valve 11 When the pressure adjusting valve 11 is closed, the pressure difference between the pressure gauge 9 on the upstream side of the mass flow controller 3a and the pressure gauge 10 on the downstream side is high, that is, the driving difference of the mass flow controller 3a. This is the case when pressure is generated. In this case, the dilution gas stored in the pressure buffer tank 12 is guided to the mass flow controller 3a.
- the fluorine gas passes through the mass flow controller 3 b using the dilution gas as a drive source and is drawn by the ejector 4.
- the mass flow controller 3b controls the mass flow rate of the fluorine gas, and the diluted gas whose flow rate is adjusted is drawn by the ejector 4.
- the mixed gas is guided to the second communication pipe 16.
- the gas introduction valve 17 is closed and the gas discharge valve 15 is opened until the flow rate of the dilution gas is stabilized, and the dilution gas and / or the fluorine gas is guided to the first communication pipe 214.
- the pressure of the dilution gas and / or the fluorine gas guided to the first communication pipe 214 is adjusted by the back pressure valve 14, and then passes through the gas release valve 15 and is guided to the exhaust device 207.
- the gas release valve 15 is instantaneously closed and the gas introduction valve 17 is opened.
- the flow path is changed from the communication pipe 214, passes through the second communication pipe 16, and is guided to the reactor 6.
- an object to be processed 21 (refer to a dotted line part in FIG. 2) preliminarily heated in the heating chamber 23 is conveyed and arranged by the movable member 22. Then, the mixed gas supplied from the mixed gas supply port 18 collides with the plate-like member 20 in the reactor 6 and comes into contact with the object 21 to be subjected to surface treatment or surface modification. Thereafter, when a predetermined processing time has elapsed, the gas in the reactor 6 is discharged from the mixed gas discharge port 19 by the exhaust device 207.
- the gas discharged from the mixed gas discharge port 19 passes through one or more of the flow paths 219, 220, 221 and 222 and is guided to the exhaust device 207.
- the valve 223 is opened and the valves 224, 225, and 226 are closed, and the gas flows only in the flow path 219.
- the exhaust device 207 gradually change the valves to be opened or increase the number of valves to be opened according to the progress of the exhaust of the gas.
- the number of channels is increased or the number of channels is increased. In this way, the gas that has passed through the valves 223, 224, 225, 226 and the flow paths 219, 220, 221, 222 passes through the exhaust device 207 and is guided to the abatement device 208.
- the piping and components from the outlet of the reactor 6 to the inlet of the abatement device 208 have heating and heat retaining means, so that the fluorine contained in the gas discharged from the mixed gas outlet 19 The gas or hydrogen fluoride gas is guided to the abatement device 208 without being liquefied.
- Fluorine gas and hydrogen fluoride gas are removed from the gas guided to the abatement apparatus 208 in the abatement towers 208a, 208b, and 208c.
- the gas guided to the abatement apparatus 208 will be described.
- the gas guided to the abatement tower 208b is a fluorine gas by soda lime filled in the abatement tower 208b.
- the component of hydrogen fluoride gas is adsorbed and removed, and is discharged out of the surface treatment apparatus 200.
- the detoxification apparatus is provided. Using piping and valves (not shown), the gas is guided to the abatement tower 208c, and the components of fluorine gas and hydrogen fluoride gas are adsorbed and removed by soda lime filled in the abatement tower 208c. And discharged to the outside of the surface treatment apparatus 200. Note that the gas from which the fluorine gas and the hydrogen fluoride gas have been removed may be used again for the surface treatment.
- the dilution gas is heated in advance by the heater 8, and the heated dilution gas and the fluorine gas can be mixed.
- the fluorine gas can be indirectly heated with the dilution gas, the fluorine gas is unlikely to become a high temperature, and it is possible to prevent the surface treatment apparatus 200 from being damaged by the fluorine gas.
- the heated mixed gas can be supplied to the reactor 6, it can suppress that the process nonuniformity of the to-be-processed object 21 arises.
- the ejector 4 can draw in the fluorine gas from the fluorine gas supply device 2 using the dilution gas as a drive source. Thereby, since the supply pressure of fluorine gas can be reduced, high-pressure storage of fluorine gas can be suppressed, and fluorine gas can be stored more safely. Further, it is possible to supply a more accurate amount of fluorine gas which is less supplied than the dilution gas.
- a constant driving differential pressure can be applied to the mass flow controller 3a by the pressure adjusting valve 11, piping provided on the downstream side of the dilution gas supply device 1 and the mass flow controller 3a, the internal pressure of the reactor 6, etc. Regardless of the influence of pressure, the dilution gas can be supplied at a constant flow rate.
- the pressure buffering tank 12 can further reduce the mutual influence between the pressure adjusting valve 11 and a valve (not shown) provided in the mass flow controller 3a, thereby further improving the flow rate accuracy.
- accurate and stable gas flow rate control is possible without being affected by temperature and supply pressure.
- the mass flow rate of the fluorine gas can be accurately controlled by the electric signal by the mass flow controller 3b, the flow rate of the fluorine gas can be accurately and stably controlled without being influenced by the temperature and the supply pressure.
- the gas introduction valve 17 is closed and the gas release valve 15 is opened until the drive differential pressure for generating a sufficient vacuum in the ejector 4 is generated and the flow rate of the dilution gas is stabilized, and dilution is performed through the first communication pipe 214.
- Gas and / or fluorine gas can be discharged to the exhaust device 207, the abatement device 208, and the like.
- the gas release valve 15 is closed and the gas introduction valve 17 is opened so that the mixed gas can be guided to the reactor 6 through the second communication pipe 16.
- the workpiece 21 can be heated in advance in the heating chamber 23 before being brought into contact with the mixed gas, processing unevenness and inappropriate processing can be suppressed. Moreover, by heating the to-be-processed object 21 beforehand, the heating time of the to-be-processed object 21 in the reactor 6 can be shortened, cost can be held down, and processing efficiency can further be improved.
- the movable member 22 using a metal material having corrosion resistance is used for the fluorine gas, the workpiece 21 can be easily transported and carried out to the reactor 6, and the fluorine gas contained in the mixed gas can be used. It is possible to suppress the occurrence of an influence such as generation of impurities from the movable member 22.
- the plate-like member 20 is provided between the workpiece 21 and the mixed gas supplied to the reactor 6, the mixed gas is to be treated in the vicinity of the mixed gas introduction portion in the reactor 6. It becomes difficult to contact 21 directly, it can suppress that the processing non-uniformity of the to-be-processed object 21 arises, and the process to the to-be-processed object 21 can be performed uniformly.
- each valve 223, 224, 225, 226 By appropriately opening and closing each valve 223, 224, 225, 226, the flow paths 219, 220, 221, 222 having different pipe diameters can be appropriately changed and used, or the flow paths 219, 220, 221 used.
- a gas having a desired flow rate can be guided to the exhaust device 207 and the abatement device 208.
- a large amount of gas containing fluorine gas is discharged from the reactor 6, a large amount of gas is obtained using the flow paths 219, 220, 221 and 222 and the valves 223, 224, 225, and 226.
- the exhaust device 207 and the detoxifying device 208 can be prevented from being temporarily led to the exhaust device 207 and the detoxifying device 208, and the calorific value of the detoxifying agent is increased by a large amount of fluorine gas. It is possible to suppress degradation due to partial corrosion or rapid wear by applying a load to equipment, a pesticide and the like. Further, since the exhaust device 207 is provided, the gas can be easily exhausted from the reactor 6. Further, the fluorine gas and hydrogen fluoride gas contained in the gas discharged from the reactor 6 can be removed by the abatement device 208 and adjusted to a desired flow rate, and the controlled gas is supplied to the abatement device 208.
- the detoxifying agent filled in the detoxifying apparatus 208 can be consumed and replaced more efficiently and accurately, and the cost for replacing parts, members, etc. of the surface treatment apparatus 200 can be further reduced. be able to. From the above, it is possible to suppress damage to the apparatus due to gas exhaust after the surface treatment.
- the abatement device 208 two towers 208b and 208c are connected in series and the other tower 208a is connected independently, so two towers are used continuously. In the meantime, it is possible to replace or maintain the other tower of the detoxifying agent and to prepare for the next use. Further, since the two towers 208b and 208c can be used continuously, the towers 208a, 208b and 208c can be maintained in a safe state while the operation of the surface treatment apparatus 200 is continued.
- FIG. 4 is a view showing a modification of the reactor of FIG.
- a plate-like member 343 is further provided in the reactor 336, and the reaction chamber 336a and the heating chamber 336b are formed by the plate-like member 343.
- the mixed gas supply port 338, the mixed gas discharge port 339, the plate member 340, the workpiece 341, and the movable member 342 are the mixed gas supply port 18 and the mixed gas discharge port according to the above embodiment. 19, the plate-like member 20, the workpiece 21, and the movable member 22.
- the reactor 336 having the above configuration is used in place of the reactor 6 and the heating chamber 23 in the surface treatment apparatuses 100 and 200, the same effects as those of the surface treatment apparatuses 100 and 200 can be obtained, and the reaction chamber 336a and the heating chamber can be heated. Since the chamber 336b is provided adjacent to the chamber 336b, the object to be processed can be moved to the reaction chamber 336a earlier after being heated in the heating chamber 336b. Here, if the plate-like member 343 can be removed, it can be moved to the reaction chamber 336a more easily.
- the plate-like member 343 may be removable or may not be removable. Further, for example, an openable and closable opening that communicates between the reaction chamber 336a and the heating chamber 336b may be provided. With such a structure, the workpiece 341 can be moved from the heating chamber 336b to the reaction chamber 336a using the opening.
- FIG. 5 is a schematic view of the main part of the surface treatment apparatus according to this modification.
- FIG. 5 shows with the same code
- the surface treatment apparatus 400 in the present modification is further provided with a dilution gas discharge pipe 410 branched from a pipe connecting the heater 8 and the ejector 4.
- a fluorine gas purge gas line 420 branched from the middle of the pipe connecting the dilution gas supply device 1 and the pressure adjusting tank 12 is provided.
- the downstream of the fluorine gas purge gas line 420 is connected to a pipe connecting the heater 8 and the ejector 4.
- a pressure control device (pressure control means) 430 for controlling the primary pressure applied to the mass flow controller 3a based on the pressure in the pipe measured by the pressure gauges 9 and 10 is provided.
- the back pressure valve 414 is provided in the dilution gas discharge pipe 410 instead of the back pressure valve 14 in 1st Embodiment.
- the dilution gas discharge pipe 410 is connected upstream of a valve provided in the pipe connecting the heater 8 and the ejector 4 in the pipe connecting the heater 8 and the ejector 4.
- the dilution gas discharge pipe 410 is provided with a back pressure valve 414 and a dilution gas discharge valve 415 in this order from upstream to downstream. Similar to the back pressure valve 14 in the first embodiment, the back pressure valve 414 keeps the pressure of the dilution gas before entering the back pressure valve 414 constant.
- the back pressure valve 414 measures in advance the pressure stable value downstream of the ejector 4 when the flow rate of the dilution gas set by the mass flow controller 3a is introduced into the reactor 6 as in the back pressure valve 14 in the first embodiment.
- the mixed gas can be supplied to the reactor 6.
- the dilution gas discharge valve 415 is introduced into the dilution gas discharge pipe 410 and discharges the dilution gas whose pressure is adjusted by the back pressure valve 14 to the downstream side of the dilution gas discharge pipe 410.
- the dilution gas discharge pipe 410 may be provided with a thermometer (not shown). The temperature of the dilution gas passing through the dilution gas discharge pipe 410 is measured by this thermometer, and the opening / closing of the back pressure valve 414 and the dilution gas discharge valve 415 is adjusted.
- the valve provided in the pipe connecting the heater 8 and the ejector 4 is closed, and the back pressure valve 414 and the dilution gas discharge valve 415 are opened. .
- the dilution gas that has not been sufficiently heated by the heater 8 is introduced into the dilution gas discharge pipe 410, passes through the back pressure valve 414 and the dilution gas discharge valve 415, and is discharged outside the surface treatment apparatus 400.
- the back pressure valve 414 and the dilution gas discharge valve 415 are closed, and the heater 8 and the ejector 4 are connected. Open the valve on the pipe.
- the dilution gas passes through the ejector 4 and is guided to the mixer 5 in a state where it reaches a predetermined temperature.
- the dilution gas discharge pipe 410, the back pressure valve 414, and the dilution gas discharge valve 415 can be used as described above.
- the heater 8 is Can cool quickly.
- the diluent gas released from the diluent gas discharge pipe 410 can be used again for the fluorine gas dilution gas or for cooling the heater.
- the fluorine gas purge gas line 420 is connected upstream of the pressure adjusting valve 11 in a pipe connecting the dilution gas supply device 1 and the pressure adjusting tank 12.
- the downstream side of the fluorine gas purge gas line 420 is connected downstream of a valve provided in the middle of the pipe connecting the heater 8 and the ejector 4 in the pipe connecting the heater 8 and the ejector 4.
- the fluorine gas purge gas line 420 is provided with a valve, through which the unheated dilution gas supplied from the dilution gas supply device 1 passes.
- the dilution gas that has passed through the fluorine gas purge gas line 420 is guided to the ejector 4.
- connection between the dilution gas supply device 1 and the ejector 4 is made by two kinds of methods by providing a gas line 420 for purging fluorine gas.
- the two types of connection methods are a method in which the dilution gas supply device 1 and the ejector 4 are connected via the pressure buffering tank 12, the mass flow controller 3a, and the heater 8, and the dilution gas supply device 1 and the ejector 4 Is a method in which the pressure buffer tank 12, the mass flow controller 3a, and the heater 8 are not connected.
- the pressure control device (pressure control means) 430 reads the pressure on the upstream side (inlet) and the downstream side (outlet) of the mass flow controller 3a from the measurement results of the pressure gauges 9 and 10, and calculates the indicated values of the pressure gauges 9 and 10. Then, the primary pressure applied to the mass flow controller 3a is calculated. This result is commanded to the pressure adjusting valve 11. Upon receiving the command, the pressure adjusting valve 11 adjusts the open / closed state of the valve. As a result, the primary pressure applied to the mass flow controller 3a is controlled.
- the same effect as that of the first embodiment can be obtained.
- the dilution gas discharge pipe 410, the back pressure valve 414, and the dilution gas discharge valve 415 the dilution gas is prevented from coming into contact with the fluorine gas until it reaches a desired temperature by the heater 8. Can be released. Accordingly, the dilution gas can be supplied to the mixer 5 at a desired temperature from the initial supply to the mixer 5.
- the dilution gas used is arbitrarily discharged by exhausting the used dilution gas by using the dilution gas discharge pipe 410, the back pressure valve 414 and the dilution gas discharge valve 415. And the heater 8 can be cooled quickly.
- the fluorine gas existing in the piping, equipment and apparatus provided downstream of the ejector 4 is to be purged with the dilution gas after completion of the reaction of the workpiece in the reactor 6, the dilution gas to be used needs to be heated. There is no. For this reason, by introducing the dilution gas supplied from the dilution gas supply device 1 to the ejector 4 using the fluorine gas purge gas line 420, the unheated dilution gas can be quickly and efficiently fluorinated at an arbitrary flow rate. The gas can be purged.
- the heat insulating material may be provided in the middle of the communication pipe between the ejector and the mixer or in the pipe on the downstream side of the mixer.
- the heat insulating material it becomes difficult to be affected by the outside air temperature, and the mixed gas can be supplied to the reactor at a high temperature. As a result, it is possible to suppress the occurrence of processing unevenness and the like, and to further improve the processing efficiency.
- two or more reactors may be provided.
- at least one reactor may be used as a reactor, and another reactor may be used as a heating chamber.
- a valve capable of shutting off the devices constituting the surface treatment apparatus may be further provided.
- An automatic valve, a manual valve, or the like may be used for part or all of this valve.
- the plate member provided between the mixed gas and the object to be processed may be removable or may be fixed to the reactor or the movable member.
- an exhaust device or the like may be further provided between the reactor and the abatement device.
- the exhaust device facilitates exhaust of the mixed gas from the reactor.
- a pipe for guiding the gas discharged from the reactor to the fluorine supply device and the dilution gas supply device may be further provided.
- the abatement apparatus has three abatement towers, but is not limited to three towers, and may have four or more towers.
- the removal tower connected in series is not restricted to two towers, Three towers or more may be sufficient.
- the abatement towers connected independently are not limited to one tower and may be two or more towers.
- the pressure control device 430 in the surface treatment apparatus 400 according to the present modification may be provided in the surface treatment apparatuses 100 and 200 in the present embodiment.
- the primary pressure (inlet pressure) applied to the mass flow controller 3a can be controlled, so that the dilution gas can be supplied stably.
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Abstract
Description
2 フッ素ガス供給装置
3a、3b マスフローコントローラー
4 エジェクター
5 混合器
6、36 反応器
7 除害装置
8 加熱器
9、10 圧力計
11 圧力調節用バルブ
12 圧力緩衝用タンク
13、214 第1連通管
14、414 背圧弁
15 ガス放出弁
16 第2連通管
17 ガス導入弁
18、38 混合ガス供給口
19、39 混合ガス排出口
20、40、343 板状部材
21、341 被処理物
22、342 可動部材
23、336b 加熱室
336a 反応室
100,200 表面処理装置
207 排気装置
208 除害装置
208a、208b、208c 除害塔
219、220、221、222 流路
223、224、225、226 弁
250 加熱・保温装置
ここでは、本発明に係る表面処理装置の第1実施形態に関して説明する。図1は、本発明の実施形態に係る表面処理装置の主要部の概略構成図であり、図2は、図1の反応器の断面模式図である。
ここでは、本発明に係る表面処理装置の第2実施形態に関して説明する。図3は、第2実施形態に係る表面処理装置の主要部の概略構成図である。なお、第1実施形態と同符号のものは、第1実施形態とほぼ同様なものであるので説明を省略することがある。
Claims (15)
- 希釈ガスを供給する希釈ガス供給装置と、
フッ素ガスを供給するフッ素ガス供給装置と、
前記希釈ガスと、前記フッ素ガスとを混合して混合ガスを生成させる混合器と、
前記混合ガスに被処理物を接触させる反応器とを備えた表面処理装置であって、
前記希釈ガスを加熱する加熱手段をさらに備えていることを特徴とする表面処理装置。 - 前記加熱手段が、前記希釈ガスと前記フッ素ガスとを混合する前に、前記希釈ガスを加熱するものであることを特徴とする請求項1に記載の表面処理装置。
- 前記希釈ガスを駆動源として、前記フッ素ガスを吸い込むエジェクターをさらに備えていることを特徴とする請求項1又は2に記載の表面処理装置。
- 前記希釈ガス供給装置と前記混合器とに接続されている第1流量調整手段と、
前記第1流量調整手段の上流側及び下流側に設けられている圧力計と、
前記希釈ガス供給装置と前記第1流量調整手段の上流側に設けられている圧力計とに配管を介して接続されている圧力調節用バルブをさらに備えていることを特徴とする請求項1~3のいずれか1項に記載の表面処理装置。 - 前記圧力調節用バルブと前記第1流量調整手段の上流側に設けられている前記圧力計との間に設けられている圧力緩衝用タンクをさらに備えていることを特徴とする請求項1~4のいずれか1項に記載の表面処理装置。
- 前記フッ素ガス供給装置と前記混合器とに接続されている第2流量調整手段をさらに備えていることを特徴とする請求項1~5のいずれか1項に記載の表面処理装置。
- 前記混合器に連通している第1連通管と、
前記第1連通管の途中に設けられている背圧弁と、
前記第1連通間の途中に、前記背圧弁の下流側に設けられているガス放出弁と、
前記混合器と前記反応器との間を連結している第2連通管と、
前記第2連通管の途中に設けられているガス導入弁とをさらに備えていることを特徴とする請求項1~6のいずれか1項に記載の表面処理装置。 - 希釈ガスを供給する希釈ガス供給装置と、
フッ素ガスを供給するフッ素ガス供給装置と、
前記希釈ガスと、前記フッ素ガスとを混合し、混合ガスを発生させる混合器と、
前記混合ガスを被処理物に接触させる反応器とを備えた表面処理装置であって、
前記反応器内から排気ガスを排出する排気装置と、
前記反応器と前記排気装置との間に設けられており、前記排気ガスを流通させる複数の流路と、
前記複数の流路の各々に設けられている複数の弁とをさらに備えていることを特徴とする表面処理装置。 - 前記排気装置と接続されている除害装置を備えていることを特徴とする請求項8に記載の表面処理装置。
- 前記反応器出口から前記除害装置入口までの構成部材が、加熱・保温手段を有しているものであり、
前記構成部材の内部温度がフッ化水素の沸点以上であることを特徴とする請求項8又は9に記載の表面処理装置。 - 前記除害装置が、複数の除害塔を有するものであり、
前記複数の除害塔のうち、少なくとも1塔が独立して接続されていると共に、前記独立して接続されている除害塔を除く少なくとも2塔が直列に接続されていることを特徴とする請求項8~10のいずれか1項に記載の表面処理装置。 - 前記被処理物を加熱する加熱室をさらに備えていることを特徴とする請求項1~11のいずれか1項に記載の表面処理装置。
- 前記被処理物を前記反応器へ搬送できる、前記フッ素ガスに対する耐食性を有する可動部材をさらに備えていることを特徴とする請求項1~12のいずれか1項に記載の表面処理装置。
- 前記反応器内において、前記被処理物と前記反応器に供給された前記混合ガスとの間に設けられている板状部材をさらに備えていることを特徴とする請求項1~13のいずれか1項に記載の表面処理装置。
- 前記可動部材の上に、前記被処理物と前記反応器に流入した前記混合ガスとの間に設けられている板状部材をさらに備えていることを特徴とする請求項13に記載の表面処理装置。
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12/921,305 US20110020187A1 (en) | 2008-03-06 | 2008-03-06 | Surface treatment apparatus |
| EP09718093A EP2263792A1 (en) | 2008-03-06 | 2009-03-06 | Surface treatment apparatus |
| CN200980107772.2A CN101959594B (zh) | 2008-03-06 | 2009-03-06 | 表面处理装置 |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008-056952 | 2008-03-06 | ||
| JP2008056952A JP2009213947A (ja) | 2008-03-06 | 2008-03-06 | 表面処理装置 |
| JP2008-056951 | 2008-03-06 | ||
| JP2008056951A JP5679139B2 (ja) | 2008-03-06 | 2008-03-06 | 表面処理装置 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2009110611A1 true WO2009110611A1 (ja) | 2009-09-11 |
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| Application Number | Title | Priority Date | Filing Date |
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| PCT/JP2009/054331 Ceased WO2009110611A1 (ja) | 2008-03-06 | 2009-03-06 | 表面処理装置 |
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| Country | Link |
|---|---|
| US (1) | US20110020187A1 (ja) |
| EP (1) | EP2263792A1 (ja) |
| KR (1) | KR101608097B1 (ja) |
| CN (1) | CN101959594B (ja) |
| TW (1) | TWI515242B (ja) |
| WO (1) | WO2009110611A1 (ja) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130255784A1 (en) * | 2012-03-30 | 2013-10-03 | Applied Materials, Inc. | Gas delivery systems and methods of use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP6370684B2 (ja) * | 2014-11-14 | 2018-08-08 | エドワーズ株式会社 | 除害装置 |
| CN104630690A (zh) * | 2015-01-30 | 2015-05-20 | 柳州市同进汽车零部件制造有限公司 | 汽车配件表面处理方法 |
| JP6752447B2 (ja) * | 2016-12-21 | 2020-09-09 | 日本電気硝子株式会社 | ガラス基板の製造装置及び製造方法 |
| SG10202101458WA (en) * | 2020-02-25 | 2021-09-29 | Kc Co Ltd | Gas mixing supply device, supply system, and gas mixing supply method |
| SG10202101459XA (en) * | 2020-02-25 | 2021-09-29 | Kc Co Ltd | Gas mixing supply device, mixing system, and gas mixing supply method |
| CN113912013B (zh) * | 2021-10-13 | 2022-12-27 | 中船(邯郸)派瑞特种气体股份有限公司 | 一种安全性高的高纯三氟化氯反应制备装置 |
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- 2009-03-06 TW TW098107504A patent/TWI515242B/zh not_active IP Right Cessation
- 2009-03-06 CN CN200980107772.2A patent/CN101959594B/zh not_active Expired - Fee Related
- 2009-03-06 KR KR1020107020109A patent/KR101608097B1/ko not_active Expired - Fee Related
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| Publication number | Publication date |
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| US20110020187A1 (en) | 2011-01-27 |
| KR20100130191A (ko) | 2010-12-10 |
| KR101608097B1 (ko) | 2016-03-31 |
| CN101959594B (zh) | 2014-11-05 |
| EP2263792A1 (en) | 2010-12-22 |
| TWI515242B (zh) | 2016-01-01 |
| TW200946572A (en) | 2009-11-16 |
| CN101959594A (zh) | 2011-01-26 |
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