US20050150455A1 - Processing apparatus and processing method - Google Patents
Processing apparatus and processing method Download PDFInfo
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- US20050150455A1 US20050150455A1 US11/002,788 US278804A US2005150455A1 US 20050150455 A1 US20050150455 A1 US 20050150455A1 US 278804 A US278804 A US 278804A US 2005150455 A1 US2005150455 A1 US 2005150455A1
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- processing
- shielding plate
- transparent window
- processing apparatus
- gas
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- 238000003672 processing method Methods 0.000 title claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 45
- 238000009834 vaporization Methods 0.000 claims description 8
- 230000008016 vaporization Effects 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 5
- 230000005855 radiation Effects 0.000 claims 2
- 238000007789 sealing Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 6
- 239000007789 gas Substances 0.000 description 88
- 235000012431 wafers Nutrition 0.000 description 56
- 239000000047 product Substances 0.000 description 30
- 239000002826 coolant Substances 0.000 description 8
- 239000010453 quartz Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 239000011553 magnetic fluid Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 0 C1CC*CC1 Chemical compound C1CC*CC1 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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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
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/3065—Plasma etching; Reactive-ion etching
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
- H01L21/02052—Wet cleaning only
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
- H01J37/32192—Microwave generated discharge
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
- H01L21/02063—Cleaning during device manufacture during, before or after processing of insulating layers the processing being the formation of vias or contact holes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31105—Etching inorganic layers
- H01L21/31111—Etching inorganic layers by chemical means
-
- 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
- H01L21/67115—Apparatus for thermal treatment mainly by radiation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J2237/00—Discharge tubes exposing object to beam, e.g. for analysis treatment, etching, imaging
- H01J2237/20—Positioning, supporting, modifying or maintaining the physical state of objects being observed or treated
- H01J2237/2001—Maintaining constant desired temperature
Definitions
- the present invention relates to a processing apparatus for removing an oxide film from a surface of an object to be processed and also relates to a processing method of removing the oxide film from the surface.
- a mixture of N 2 gas and H 2 gas is activated to produce active gas species.
- NF 3 gas is added to the down flow of the active gas species in order to activate NF 3 gas.
- it is executed to allow the active gas species of NF 3 gas to react with a native oxide film on the surface of the wafer thereby producing a product film.
- the product film is sublimated for its removal.
- a processing apparatus which includes a processing container for accommodating a wafer therein, a NF 3 active gas species generating unit for generating the active gas species of NF 3 gas, heating means positioned outside the processing container in order to heat the wafer and a transparent window arranged between the heating means and the above object to allow heat energy from the heating means through.
- this apparatus it is executed to make the active gas species of NF 3 gas to react with the native oxide film formed on the surface of the wafer, at a low temperature, thereby forming a product film.
- the heating means the product film is heated to a predetermined temperature for its sublimation, removing the native oxide film.
- the object of the present invention is to provide a processing apparatus and a processing method, by which it is possible to prevent the temperature of the object from rising due to residual heat generated in the heating process and also remained in a transparent window, thereby accomplishing the continuous processing for the objects to be processed.
- a processing apparatus for removing an oxide film from a surface of an object to be processed, the processing apparatus comprising: a processing container accommodating the object to be processed therein; an active gas species generating unit for producing active gas species; heater arranged outside the processing container to heat the object to be processed; a transparent window formed in the processing container between the heater and the object to be processed, the transparent window sheltering the interior of the processing container from the outside in an airtight manner and also allowing heating energy from the heater to pass through; and a shielding plate provided in such a way that the shielding plate can be inserted into or extracted from a gap between the object and the transparent window; in the processing apparatus, on condition that the shielding plate is closed to insulate irradiation heat irradiated from the transparent window, the processing apparatus allows the oxide film formed on the surface of the object to react with the active gas species, thereby forming a product film. Subsequently, the processing apparatus opens the shielding plate so as to apply the
- a processing apparatus for removing an oxide film from a surface of an object to be processed, the processing apparatus comprising: a first processing chamber having an active gas species generating unit for producing active gas species and also allowing the oxide film formed on the surface of the object to react with the active gas species under a condition of low temperature, thereby forming a product film; a second processing chamber having heater for heating the object to be processed and allowing the heater to heat the product film formed on the surface of the object to a predetermined temperature for vaporization, thereby removing the product film; and transporter for transporting the object between the first processing chamber and the second processing chamber.
- the active gas species are active gas species of NF 3 gas.
- the shielding plate is provided with cooler for cooling the shielding plate itself.
- the transporter is arranged in a transfer chamber connected to the first processing chamber and the second processing chamber and also filled up with a non-reactive atmosphere inside.
- the active gas species generating unit includes a plasma generating tube having a plasma generating part, a plasma gas introducing part for supplying both N 2 gas and H 2 gas into the plasma generating tube and a NF 3 gas supplying part for adding NF 3 gas to the active gas species flowing down from an interior of the plasma-generating tube.
- the plasma generating part comprises a microwave generating source for generating microwaves and a waveguide for introducing the so-generated microwaves into the plasma generating tube.
- a processing method of removing an oxide film from a surface of an object to be processed while using a processing apparatus which includes a processing container accommodating the object to be processed therein, heater arranged outside the processing container to heat the object to be processed, a transparent window formed in the processing container between the heater and the object to be processed, and a shielding plate provided in such a way that the shielding plate can be inserted into or extracted from a gap between the object and the transparent window
- the processing method comprising the steps of: allowing the oxide film formed on the surface of the object to react with active-gas species under a condition of low temperature on condition that the shielding plate is closed to insulate irradiation heat irradiated from the transparent window, thereby forming a product film; and subsequently, opening the shielding plate and applying the irradiation heat from the heating means to the product film through the transparent window to heat the product film to a predetermined temperature for vaporization, thereby removing the product film.
- a processing method of removing an oxide film from a surface of an object to be processed comprising: allowing the oxide film formed on the surface of the object to react with active gas species under a condition of low temperature in a first processing chamber, thereby forming a product film; transporting the object having the product film formed thereon from the first processing chamber to a second processing chamber; and heating the product film formed on the surface of the object in the second processing chamber, to a predetermined temperature for vaporization, thereby removing the product film.
- FIG. 1 is a structural view showing a processing apparatus in accordance with the first embodiment of the present invention
- FIG. 2 is a schematic plan view taken along a line II-II of FIG. 1 , showing a movable shutter of the processing apparatus of FIG. 1 ;
- FIG. 3 is a-schematic sectional view taken along a line III-III of FIG. 2 ;
- FIG. 4 is a schematic plan view showing another movable shutter.
- FIG. 5 is a structural view showing the processing apparatus in accordance with the second embodiment of the present invention.
- FIGS. 1 to 3 are structural views showing the processing apparatus in accordance with the first embodiment of the invention.
- the processing apparatus 12 -includes a plasma generating tube 14 for activating a mixture gas of N 2 gas and H 2 gas by plasma, and a processing container 16 for carrying out a designated surface treatment for removing an oxide film particularly, a native oxide film (i.e. oxide film unintentionally produced by the contact with oxygen in the air, cleaning liquid, etc.) from a semiconductor wafer W as the object to be processed.
- a plasma generating tube 14 for activating a mixture gas of N 2 gas and H 2 gas by plasma
- a processing container 16 for carrying out a designated surface treatment for removing an oxide film particularly, a native oxide film (i.e. oxide film unintentionally produced by the contact with oxygen in the air, cleaning liquid, etc.) from a semiconductor wafer W as the object to be processed.
- a native oxide film i.e. oxide film unintentionally produced by the contact with oxygen in the air, cleaning liquid,
- the processing container 16 is in the form of a cylinder made of aluminum.
- a quartz mount 20 carried by a support member 18 which is movable up and down.
- the processing container 16 is provided, on the margin of a bottom thereof, with an exhaust port 22 allowing the interior of the container 16 to be evacuated.
- an irradiation port 26 is formed on the bottom part of the processing container 16 and a quartz transparent window 28 is fitted to the irradiation port 26 in an airtight manner.
- a number of heating lamps 36 are arranged to heat the mount 20 from the underside, so that heating light emitted from the healing lamps 36 permeates through the transparent window 28 and enters into the back face of the wafer W.
- the plasma generating tube 14 in the form of a tube made of e.g. quartz is fitted to the processing container 16 in an airtight manner. Further, the plasma generating tube 14 is arranged so as to stand on the container 16 while opening into the ceiling part of the container 16 .
- the plasma generating tube 14 is provided, at a top end thereof, with a plasma-gas ejecting part 44 for introducing a plasma gas consisting of N 2 gas and H 2 gas into the tube.
- the plasma-gas ejecting part 44 is equipped with an ejection nozzle 46 inserted into the inside of the plasma generating tube 14 and connected to a gas passage 48 . While, through respective flow control units 50 like mater controllers, the gas passage 48 is connected to a N 2 gas source 52 for storing N 2 gas and a H 2 gas source 54 for storing H 2 gas, respectively.
- a plasma generating part 56 is arranged just below the ejection nozzle 46 .
- the plasma generating part 56 comprises a microwave generating source 58 generating a microwave of 2.45 GHz and a microwave supplier 60 , such as an Ebenson-type waveguide, arranged in the plasma generating tube 14 , so that the microwave generated in the microwave generating source 58 is supplied into the microwave supplier 60 through a rectangular waveguide 62 . Then, the so-supplied microwave allows plasma to be produced in the plasma generating tube 14 and therefore, the nixture of 2 gas and N 2 gas is activated to form a down flowing of the mixture.
- a quartz cover member 66 diverging downward in the form of an umbrella, which covers the upward of the mount 20 thereby to drop a gas on the wafer W effectively.
- a NF 3 gas supplier 68 is arranged to supply NF 3 gas to the wafer.
- the NF 3 gas supplier 68 has an annular shower head 70 made of quartz and provided with numerous gas orifices 72 .
- the shower head 70 is connected to a NF 3 gas source 80 storing NF 3 gas, through a communication tube 74 , a gas passage 76 and a flow controller 78 .
- a movable shutter 101 is disposed between the mount 20 and the transparent window 28 .
- the movable shutter 101 has a shielding plate 103 rotatably arranged so as to cover the transparent window 28 , as shown in FIGS. 2 and 3 .
- the shielding plate 103 is provided with a rotating shaft 105 to penetrate an outer wall 107 of the processing container 16 in order to rotate the plate 103 .
- a magnetic fluid seal 109 is arranged to hold the rotating shaft 105 tightly but rotatably to the outer wall 107 .
- the rotating shaft 105 is equipped with a shaft gear 111 meshing with a motor gear 113 of a drive motor 115 .
- the drive motor 115 With the operation of the drive motor 115 , it allows the shielding plate 103 to rotate through the shaft gear 111 and the motor gear 113 , so that the plate 103 can occupy its opening position of FIG. 2 and the closing position of FIG. 3 .
- a coolant passage 117 is formed inside the shielding plate 103 and also the rotating shaft 105 . Extending from the lower end of the rotating shaft 105 to the exterior of the processing container 16 , the coolant passage 117 is connected to a coolant circulating means 119 arranged outside the processing container 16 .
- the coolant circulating means 119 supplies the coolant passage 117 with a coolant, such as water, the shielding plate 103 can be cooled down.
- FIG. 4 is a view of an example of another movable shutter 121 .
- the movable shutter 121 includes a shielding plate 123 for covering the transparent window 28 .
- Connected with he shielding plate 123 are two drive shafts 125 , 125 which has their other ends connected to a piston rod of a hydraulic cylinder 127 .
- respective magnetic fluid seals 131 are arranged between the drive shafts 125 , 125 and the outer wall 129 , allowing the shafts 125 , 125 to move in relation to the outer wall 129 while maintaining respective gaps between the shafts 125 , 125 and the outer wall 129 in airtight manner.
- the operation of the hydraulic cylinder 127 allows the shielding plate 123 to occupy its opening position and the closing position.
- the shielding plate 123 and the drive shafts 125 may be provided, inside thereof, with coolant passages while their ends outside the processing container 16 are connected with a coolant circulating means arranged outside the processing container 16 to allow the shielding plate 123 to be cooled.
- a coolant circulating means arranged outside the processing container 16 to allow the shielding plate 123 to be cooled.
- NF 3 gas supplied from the NF 3 gas source 80 is added to the down flowing active gas species of the mixture gas composed of N 2 gas and H 2 gas, through the annular shower head 70 .
- the so-added NF 3 gas is also activated by the down flowing active gas species.
- NF 3 gas is activated to react with the native oxide film on the surface of the wafer W in combination with the above-mentioned down flowing active gas species, thereby producing a product film having elements Si, N, H, F mixed therein.
- the movable shutter 101 is under the closed condition.
- the reason why the shutter closes is to prevent the temperature of the wafer from being elevated since the radiant heat from the transparent window 28 heated in the previous heating process reached the wafer W.
- the respective flow rates of H 2 gas, NF 3 gas and N 2 gas are equal to 10 sccm, 150 sccm, 1400 sccm, respectively.
- the other conditions are respectively 4 Torr in processing pressure, 400 W in plasma voltage, and 1 minute in processing time. In this way, it is carried out to form the product film reacting with the native oxide film on the wafer surface.
- the upside of the mount 20 is covered with the cover member 66 in the form of an umbrella, the down flowing active gas species flow down on the wafer surface effectively without dispersing to the circumference, so that the product film can be completed effectively.
- the processing container 16 When the formation of the product film is completed in this way, stop respective supplies of H 2 gas, NF 3 gas and N 2 gas and likewise the driving of the microwave generating source 58 and thereupon, the processing container 16 is evacuated to discharge residual gas. Subsequently, bring the movable shutter 101 to the opening position and light the heating lamp 36 to heat the wafer W into a predetermined temperature, for example, more than 100° C. Owing to this heating, the above product film is sublimated for its vaporization. Thus, the native oxide film on the wafer W is eliminated, so that a Si-surface appears on the wafer surface. Then, the processing conditions are 1 mTorr in processing pressure and the order of 2 minutes in processing time.
- the processing apparatus is provided, between the wafer W and the transparent window 28 , with the movable shutter 101 capable of entering and withdrawing. Therefore, when the active NF 3 gas reacts with the native oxide film on the wafer surface to produce the product film having elements Si, N, H, F mixed therein, namely, at the processing at low temperature, it is possible to prevent the wafer W from being heated by the radiant heat emitted from the transparent window 28 heated in the previous heating process. Accordingly, in case of repeating the above “low temperature” treatment and the heating treatment against a plurality of wafers by turns, it is possible to prevent the wafer during the low temperature treatment from being heated by the radiant heat due to the previous heating treatment. Therefore, the low temperature treatment and the heating treatment can be successively carried out with no interval, accomplishing the removal operation of the oxide film effectively.
- Such operation and effect are similar to the reciprocating movable shutter 121 of FIG. 4 .
- FIG. 5 shows the second embodiment of the present invention.
- a processing apparatus 201 is characterized to have a low-temperature processing chamber and a heating chamber independently.
- the processing apparatus 201 is provided, at a center thereof, with a transfer chamber 203 .
- a transfer chamber 203 there is a transfer device for transporting the wafer.
- a non-reactive atmosphere for example, vacuum which can prevent the occurrence of native oxide film on the wafer W during the transportation of wafer W.
- a load locking chamber 205 is provided in order to load the wafer to be processed into the transfer chamber 203 .
- each low-temperature processing chamber 207 substantially corresponds to the processing apparatus 12 of FIG. 1 while removing the movable shutter 101 and the heating lamp 36 . Then, although it is necessary that the processing container 16 has its bottom closed tightly, a member for closing the bottom of the container 16 doesn't have to be provided with such light-permeability as the transparent window 18 of FIG. 1 . Thus, for example, an aluminum plate in place of the transparent window 28 of FIG. 1 may close the bottom of the processing container 16 .
- the active NF 3 gas reacts with the native oxide film on the wafer surface to produce the product film having elements Si, N, H, F mixed therein.
- the transfer chamber 203 is provided with a heating chamber 209 .
- heating means for example, a well-known stage heater of resistance heating type, which allows the wafer W to be heated.
- the wafer W after the low-temperature treatment is heated to a predetermined temperature, for example, more than 100° C. Owing to this heating, the above product film is sublimated for its vaporization. Thus, the native oxide film on the wafer W is eliminated.
- the transfer chamber 203 further includes a cooling chamber 211 .
- This cooling chamber 211 serves to cool the wafer after the heating treatment. Despite that the processed wafer is unloaded while being accommodated in a resinous cassette, there is the possibility of the resin cassette being damaged by the wafer of high temperature. Therefore, the apparatus is constructed so as to cool the wafer before it is accommodated in the cassette.
- the wafer having the native oxide film formed thereon is transported from the load locking chamber 205 into the transfer chamber- 203 .
- the wafer is transported to the low-temperature processing chamber 207 where the so-called low-temperature treatment is carried out. Since the processing apparatus 201 has the heating chamber 209 arranged independently of the low-temperature processing chamber 207 , it is possible to prevent the residual heat in the previous heating process from exerting a bad influence on the low-temperature treatment.
- the wafer to be processed is fed to the heating chamber 209 .
- the wafer W after the low-temperature treatment is heated to a designated temperature, for example, more than 100° C.
- the so-heated wafer is fed to the cooling chamber 211 . After being cooled, the wafer is accommodated in the cassette and discharged from the chamber 211 . Accordingly, it is possible to prevent the wafer of high temperature from damaging the resinous cassette.
- the processing apparatus 201 since the processing apparatus 201 has the low-temperature chamber 207 and the heating chamber 209 arranged independently of each other, it is possible to prevent the wafer from being heated due to the influence of heating process when the active NF 3 gas reacts with the native oxide film on the wafer to produce the product film having Si, N, H, F mixed therein, in other words, at the low-temperature treatment.
- the low-temperature treatment and the heating process can be continuously performed with no interval, so that it is possible to accomplish the oxide film removing operation effectively.
- the shielding plate which is adapted so as to enter the gap between the object and the transparent window and also withdraw from the gap. Therefore, the closing of the shielding plate makes it possible to insulate the heat irradiated from the transparent window and also allows the active gas species to react with the oxide film under the low-temperature condition.
- the low-temperature treatment allowing the active gas species to react with the oxide film is carried out in a different chamber from that of the subsequent heating process., Accordingly, the low-temperature treatment and the heating process can be continuously performed with no interval, so that it is possible to accomplish the oxide film removing operation effectively.
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- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
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Abstract
The present invention provides a processing apparatus and a processing method, both of which can carry out a low-temperature process to allow active gas species to react with an oxide film on an object to be processed to form a product film and a heating process to heat the object to a predetermined temperature to evaporate the product film, in succession. This processing apparatus 12 is provided with a shielding plate 103 capable of entering a gap between the object W and a transparent window 28 and also withdrawing from the gap. On condition that the shielding plate 103 is closed to cut off irradiation heat from the transparent window 28, the product film is formed by allowing the active gas species of NF3 gas to react with a native oxide film on the object under the low-temperature condition. After that, upon closing the shielding plate 103, the native oxide film is removed by applying heat irradiated from a heating lamp 36 to the product film through the transparent window 28. Additionally, the apparatus includes a low-temperature processing chamber 207 allowing NF3 gas to react with the native oxide film at a low temperature and a heating chamber 209 for heating the product film, independently.
Description
- 1. Field of the Invention
- The present invention relates to a processing apparatus for removing an oxide film from a surface of an object to be processed and also relates to a processing method of removing the oxide film from the surface.
- 2. Description of the Related Art
- Hitherto, as the method of removing native oxide films in fine holes formed in a wafer effectively, there is a surface treatment method as follows.
- At first, by using of plasma technique, a mixture of N2 gas and H2 gas is activated to produce active gas species. Second, NF3 gas is added to the down flow of the active gas species in order to activate NF3 gas. Next, it is executed to allow the active gas species of NF3 gas to react with a native oxide film on the surface of the wafer thereby producing a product film. By heating the wafer to a designated temperature subsequently, the product film is sublimated for its removal.
- As the apparatus used in such a method, there is known a processing apparatus which includes a processing container for accommodating a wafer therein, a NF3 active gas species generating unit for generating the active gas species of NF3 gas, heating means positioned outside the processing container in order to heat the wafer and a transparent window arranged between the heating means and the above object to allow heat energy from the heating means through. In this apparatus, it is executed to make the active gas species of NF3 gas to react with the native oxide film formed on the surface of the wafer, at a low temperature, thereby forming a product film. Next, by the heating means, the product film is heated to a predetermined temperature for its sublimation, removing the native oxide film.
- In the above processing apparatus, however, if the heating process of the wafer has been completed and subsequently, a new wafer is loaded into the processing container for the low-temperature treatment, then the new wafer is undesirably heated due to heat radiated from the transparent window heated in the previous heating process. Therefore, it is necessary to wait for the transparent window to be cooled to a designated temperature, thereby causing the processing efficiency to be deteriorated remarkably.
- In order to solve the above problem, the object of the present invention is to provide a processing apparatus and a processing method, by which it is possible to prevent the temperature of the object from rising due to residual heat generated in the heating process and also remained in a transparent window, thereby accomplishing the continuous processing for the objects to be processed.
- In accordance with the first feature of the invention, there is provided a processing apparatus for removing an oxide film from a surface of an object to be processed, the processing apparatus comprising: a processing container accommodating the object to be processed therein; an active gas species generating unit for producing active gas species; heater arranged outside the processing container to heat the object to be processed; a transparent window formed in the processing container between the heater and the object to be processed, the transparent window sheltering the interior of the processing container from the outside in an airtight manner and also allowing heating energy from the heater to pass through; and a shielding plate provided in such a way that the shielding plate can be inserted into or extracted from a gap between the object and the transparent window; in the processing apparatus, on condition that the shielding plate is closed to insulate irradiation heat irradiated from the transparent window, the processing apparatus allows the oxide film formed on the surface of the object to react with the active gas species, thereby forming a product film. Subsequently, the processing apparatus opens the shielding plate so as to apply the irradiation heat from the heater to the product film through the transparent window and further heats the product film to a predetermined temperature for vaporization, thereby removing the product film.
- In accordance with the second feature of the invention, there is also provided a processing apparatus for removing an oxide film from a surface of an object to be processed, the processing apparatus comprising: a first processing chamber having an active gas species generating unit for producing active gas species and also allowing the oxide film formed on the surface of the object to react with the active gas species under a condition of low temperature, thereby forming a product film; a second processing chamber having heater for heating the object to be processed and allowing the heater to heat the product film formed on the surface of the object to a predetermined temperature for vaporization, thereby removing the product film; and transporter for transporting the object between the first processing chamber and the second processing chamber.
- In accordance with the third feature of the invention, the active gas species are active gas species of NF3 gas.
- In accordance with the fourth feature of the invention, the shielding plate is provided with cooler for cooling the shielding plate itself.
- In accordance with the fifth feature of the invention, the transporter is arranged in a transfer chamber connected to the first processing chamber and the second processing chamber and also filled up with a non-reactive atmosphere inside.
- In accordance with the sixth feature of the invention, the active gas species generating unit includes a plasma generating tube having a plasma generating part, a plasma gas introducing part for supplying both N2 gas and H2 gas into the plasma generating tube and a NF3 gas supplying part for adding NF3 gas to the active gas species flowing down from an interior of the plasma-generating tube.
- In accordance with the seventh feature of the invention, the plasma generating part comprises a microwave generating source for generating microwaves and a waveguide for introducing the so-generated microwaves into the plasma generating tube.
- In accordance with the eighth feature of the invention, there is also provided a processing method of removing an oxide film from a surface of an object to be processed while using a processing apparatus which includes a processing container accommodating the object to be processed therein, heater arranged outside the processing container to heat the object to be processed, a transparent window formed in the processing container between the heater and the object to be processed, and a shielding plate provided in such a way that the shielding plate can be inserted into or extracted from a gap between the object and the transparent window, the processing method comprising the steps of: allowing the oxide film formed on the surface of the object to react with active-gas species under a condition of low temperature on condition that the shielding plate is closed to insulate irradiation heat irradiated from the transparent window, thereby forming a product film; and subsequently, opening the shielding plate and applying the irradiation heat from the heating means to the product film through the transparent window to heat the product film to a predetermined temperature for vaporization, thereby removing the product film.
- In accordance with the nineth feature of the invention, there is also provided a processing method of removing an oxide film from a surface of an object to be processed, the processing apparatus comprising: allowing the oxide film formed on the surface of the object to react with active gas species under a condition of low temperature in a first processing chamber, thereby forming a product film; transporting the object having the product film formed thereon from the first processing chamber to a second processing chamber; and heating the product film formed on the surface of the object in the second processing chamber, to a predetermined temperature for vaporization, thereby removing the product film.
-
FIG. 1 is a structural view showing a processing apparatus in accordance with the first embodiment of the present invention; -
FIG. 2 is a schematic plan view taken along a line II-II ofFIG. 1 , showing a movable shutter of the processing apparatus ofFIG. 1 ; -
FIG. 3 is a-schematic sectional view taken along a line III-III ofFIG. 2 ; -
FIG. 4 is a schematic plan view showing another movable shutter; and -
FIG. 5 is a structural view showing the processing apparatus in accordance with the second embodiment of the present invention. - Preferred embodiments for embodying the processing apparatus of the present invention will be described with reference to figures, below.
- FIGS. 1 to 3 are structural views showing the processing apparatus in accordance with the first embodiment of the invention. In
FIG. 1 , the processing apparatus 12-includes aplasma generating tube 14 for activating a mixture gas of N2 gas and H2 gas by plasma, and aprocessing container 16 for carrying out a designated surface treatment for removing an oxide film particularly, a native oxide film (i.e. oxide film unintentionally produced by the contact with oxygen in the air, cleaning liquid, etc.) from a semiconductor wafer W as the object to be processed. - The
processing container 16 is in the form of a cylinder made of aluminum. In theprocessing container 16, there is aquartz mount 20 carried by asupport member 18 which is movable up and down. Theprocessing container 16 is provided, on the margin of a bottom thereof, with anexhaust port 22 allowing the interior of thecontainer 16 to be evacuated. Below themount 20, anirradiation port 26 is formed on the bottom part of theprocessing container 16 and a quartztransparent window 28 is fitted to theirradiation port 26 in an airtight manner. Below thetransparent window 28, a number ofheating lamps 36, such as halogen lamps, are arranged to heat themount 20 from the underside, so that heating light emitted from thehealing lamps 36 permeates through thetransparent window 28 and enters into the back face of the wafer W. - On the other hand, the
plasma generating tube 14 in the form of a tube made of e.g. quartz is fitted to theprocessing container 16 in an airtight manner. Further, theplasma generating tube 14 is arranged so as to stand on thecontainer 16 while opening into the ceiling part of thecontainer 16. Theplasma generating tube 14 is provided, at a top end thereof, with a plasma-gas ejecting part 44 for introducing a plasma gas consisting of N2 gas and H2 gas into the tube. The plasma-gas ejecting part 44 is equipped with anejection nozzle 46 inserted into the inside of theplasma generating tube 14 and connected to agas passage 48. While, through respectiveflow control units 50 like mater controllers, thegas passage 48 is connected to a N2 gas source 52 for storing N2 gas and a H2 gas source 54 for storing H2 gas, respectively. - A
plasma generating part 56 is arranged just below theejection nozzle 46. Theplasma generating part 56 comprises amicrowave generating source 58 generating a microwave of 2.45 GHz and amicrowave supplier 60, such as an Ebenson-type waveguide, arranged in theplasma generating tube 14, so that the microwave generated in themicrowave generating source 58 is supplied into themicrowave supplier 60 through arectangular waveguide 62. Then, the so-supplied microwave allows plasma to be produced in theplasma generating tube 14 and therefore, the nixture of 2 gas and N2 gas is activated to form a down flowing of the mixture. - At an
outlet 64 identical to the lowermost end of theplasma generating tube 14, there is communicably provided aquartz cover member 66 diverging downward in the form of an umbrella, which covers the upward of themount 20 thereby to drop a gas on the wafer W effectively. Just below theoutlet 64, a NF3 gas supplier 68 is arranged to supply NF3 gas to the wafer. The NF3gas supplier 68 has anannular shower head 70 made of quartz and provided withnumerous gas orifices 72. Theshower head 70 is connected to a NF3 gas source 80 storing NF3 gas, through acommunication tube 74, agas passage 76 and aflow controller 78. - In the structure mentioned above, a
movable shutter 101 is disposed between themount 20 and thetransparent window 28. Themovable shutter 101 has ashielding plate 103 rotatably arranged so as to cover thetransparent window 28, as shown inFIGS. 2 and 3 . Theshielding plate 103 is provided with a rotatingshaft 105 to penetrate anouter wall 107 of theprocessing container 16 in order to rotate theplate 103. Between the rotatingshaft 105 and theouter wall 107, amagnetic fluid seal 109 is arranged to hold the rotatingshaft 105 tightly but rotatably to theouter wall 107. The rotatingshaft 105 is equipped with a shaft gear 111 meshing with amotor gear 113 of adrive motor 115. - With the operation of the
drive motor 115, it allows theshielding plate 103 to rotate through the shaft gear 111 and themotor gear 113, so that theplate 103 can occupy its opening position ofFIG. 2 and the closing position ofFIG. 3 . - A
coolant passage 117 is formed inside theshielding plate 103 and also the rotatingshaft 105. Extending from the lower end of the rotatingshaft 105 to the exterior of theprocessing container 16, thecoolant passage 117 is connected to acoolant circulating means 119 arranged outside theprocessing container 16. When the coolant circulating means 119 supplies thecoolant passage 117 with a coolant, such as water, theshielding plate 103 can be cooled down. With the arrangement mentioned above, it is possible to prevent the temperature of theshielding plate 103 from being elevated by radiant heat irradiated from thetransparent window 28. Accordingly, the radiant heat from the shieldingplate 103 can be prevented from reaching the wafer W thereby to avoid rising the temperature of the wafer W. - Meanwhile,
FIG. 4 is a view of an example of anothermovable shutter 121. Themovable shutter 121 includes ashielding plate 123 for covering thetransparent window 28. Connected with he shieldingplate 123 are twodrive shafts hydraulic cylinder 127. Further, in theprocessing container 16 where thedrive shafts outer wall 129, respective magnetic fluid seals 131 are arranged between thedrive shafts outer wall 129, allowing theshafts outer wall 129 while maintaining respective gaps between theshafts outer wall 129 in airtight manner. In this way, the operation of thehydraulic cylinder 127 allows the shieldingplate 123 to occupy its opening position and the closing position. - Also in this case, similarly to the case of
FIG. 3 , the shieldingplate 123 and thedrive shafts 125 may be provided, inside thereof, with coolant passages while their ends outside theprocessing container 16 are connected with a coolant circulating means arranged outside theprocessing container 16 to allow theshielding plate 123 to be cooled. With this structure, it is possible to restrain the temperature of the wafer W from be elevated by the radiant heat from the shieldingplate 123. - Next, we explain a removing method of the native oxide film, which is performed by the apparatus constructed above. First, load the semiconductor wafer W as an object to be processed into the
processing container 16 via a not-shown gate valve and put the wafer W on themount 20. In this wafer W there exist contact holes etc. formed in e.g. the preceding stage, while the native oxide film is generated on each bottom of the contact holes. - After loading the wafer W in the
processing container 16, close up thechamber 16 tightly and subsequently evacuate it. Then, introduce N2 gas and H2 gas, which have been fed from the N2 gas source 52 and the H2 gas source 54 respectively, into theplasma generating tube 14 through the plasma-gas ejecting part 44, at predetermined flow rates. Simultaneously, generate the microwave of 2.45 GHz by themicrowave generating source 58 of theplasma generating part 56 and introduce the microwave into theplasma generating tube 14 via themicrowave supplier 60. Consequently, by the microwave, both N2 gas and H2 gas are activated and changed into plasmatic gases to form active gas species. These active gas species form their down flow by the evacuation in theprocessing container 16 and fall in theplasma generating tube 14 toward theoutlet 64. - On the other hand, NF3 gas supplied from the NF3 gas source 80 is added to the down flowing active gas species of the mixture gas composed of N2 gas and H2 gas, through the
annular shower head 70. As a result, the so-added NF3 gas is also activated by the down flowing active gas species. In this way, NF3 gas is activated to react with the native oxide film on the surface of the wafer W in combination with the above-mentioned down flowing active gas species, thereby producing a product film having elements Si, N, H, F mixed therein. - Since this processing is accelerated at low temperature, the wafer W does not have to be heated during the processing and the product film is produced at room temperature.
- Hereat, during the processing, the
movable shutter 101 is under the closed condition. The reason why the shutter closes is to prevent the temperature of the wafer from being elevated since the radiant heat from thetransparent window 28 heated in the previous heating process reached the wafer W. - As to the processing conditions, the respective flow rates of H2 gas, NF3 gas and N2 gas are equal to 10 sccm, 150 sccm, 1400 sccm, respectively. The other conditions are respectively 4 Torr in processing pressure, 400 W in plasma voltage, and 1 minute in processing time. In this way, it is carried out to form the product film reacting with the native oxide film on the wafer surface. In this case, since the upside of the
mount 20 is covered with thecover member 66 in the form of an umbrella, the down flowing active gas species flow down on the wafer surface effectively without dispersing to the circumference, so that the product film can be completed effectively. - When the formation of the product film is completed in this way, stop respective supplies of H2 gas, NF3 gas and N2 gas and likewise the driving of the
microwave generating source 58 and thereupon, theprocessing container 16 is evacuated to discharge residual gas. Subsequently, bring themovable shutter 101 to the opening position and light theheating lamp 36 to heat the wafer W into a predetermined temperature, for example, more than 100° C. Owing to this heating, the above product film is sublimated for its vaporization. Thus, the native oxide film on the wafer W is eliminated, so that a Si-surface appears on the wafer surface. Then, the processing conditions are 1 mTorr in processing pressure and the order of 2 minutes in processing time. - As mentioned above, the processing apparatus is provided, between the wafer W and the
transparent window 28, with themovable shutter 101 capable of entering and withdrawing. Therefore, when the active NF3 gas reacts with the native oxide film on the wafer surface to produce the product film having elements Si, N, H, F mixed therein, namely, at the processing at low temperature, it is possible to prevent the wafer W from being heated by the radiant heat emitted from thetransparent window 28 heated in the previous heating process. Accordingly, in case of repeating the above “low temperature” treatment and the heating treatment against a plurality of wafers by turns, it is possible to prevent the wafer during the low temperature treatment from being heated by the radiant heat due to the previous heating treatment. Therefore, the low temperature treatment and the heating treatment can be successively carried out with no interval, accomplishing the removal operation of the oxide film effectively. - In the movable shutter of the processing apparatus, since the
motor 115 outside the processing container and theshielding plate 103 inside the container are connected with each other by therotating shaft 105 sealed by themagnetic fluid seal 109, there is no need to provide any driving means in the processing container, whereby it can be small-sized with the prevention of contamination. - Such operation and effect are similar to the reciprocating
movable shutter 121 ofFIG. 4 . -
FIG. 5 shows the second embodiment of the present invention. Aprocessing apparatus 201 is characterized to have a low-temperature processing chamber and a heating chamber independently. Theprocessing apparatus 201 is provided, at a center thereof, with atransfer chamber 203. In thetransfer chamber 203, there is a transfer device for transporting the wafer. At the interior of thetransfer chamber 203, there is established a non-reactive atmosphere, for example, vacuum which can prevent the occurrence of native oxide film on the wafer W during the transportation of wafer W. In thetransfer chamber 203, aload locking chamber 205 is provided in order to load the wafer to be processed into thetransfer chamber 203. - While, on the opposite side of the
transfer chamber 203 to theload locking chamber 205, there are provided two low-temperature processing chambers temperature processing chamber 207 substantially corresponds to theprocessing apparatus 12 ofFIG. 1 while removing themovable shutter 101 and theheating lamp 36. Then, although it is necessary that theprocessing container 16 has its bottom closed tightly, a member for closing the bottom of thecontainer 16 doesn't have to be provided with such light-permeability as thetransparent window 18 ofFIG. 1 . Thus, for example, an aluminum plate in place of thetransparent window 28 ofFIG. 1 may close the bottom of theprocessing container 16. In this low-temperature processing chamber 207, the active NF3 gas reacts with the native oxide film on the wafer surface to produce the product film having elements Si, N, H, F mixed therein. - Again, the
transfer chamber 203 is provided with aheating chamber 209. In theheating chamber 209, there is provided heating means, for example, a well-known stage heater of resistance heating type, which allows the wafer W to be heated. In theheating chamber 209, the wafer W after the low-temperature treatment is heated to a predetermined temperature, for example, more than 100° C. Owing to this heating, the above product film is sublimated for its vaporization. Thus, the native oxide film on the wafer W is eliminated. - The
transfer chamber 203 further includes acooling chamber 211. Thiscooling chamber 211 serves to cool the wafer after the heating treatment. Despite that the processed wafer is unloaded while being accommodated in a resinous cassette, there is the possibility of the resin cassette being damaged by the wafer of high temperature. Therefore, the apparatus is constructed so as to cool the wafer before it is accommodated in the cassette. - In the so-constructed
processing apparatus 201, the wafer having the native oxide film formed thereon is transported from theload locking chamber 205 into the transfer chamber-203. Next, the wafer is transported to the low-temperature processing chamber 207 where the so-called low-temperature treatment is carried out. Since theprocessing apparatus 201 has theheating chamber 209 arranged independently of the low-temperature processing chamber 207, it is possible to prevent the residual heat in the previous heating process from exerting a bad influence on the low-temperature treatment. After that, the wafer to be processed is fed to theheating chamber 209. In theheating chamber 209, the wafer W after the low-temperature treatment is heated to a designated temperature, for example, more than 100° C. to sublimate (evaporate) the above product film. Consequently, the native oxide film on the wafer W is removed. Thereafter, the so-heated wafer is fed to thecooling chamber 211. After being cooled, the wafer is accommodated in the cassette and discharged from thechamber 211. Accordingly, it is possible to prevent the wafer of high temperature from damaging the resinous cassette. - As mentioned above, since the
processing apparatus 201 has the low-temperature chamber 207 and theheating chamber 209 arranged independently of each other, it is possible to prevent the wafer from being heated due to the influence of heating process when the active NF3 gas reacts with the native oxide film on the wafer to produce the product film having Si, N, H, F mixed therein, in other words, at the low-temperature treatment. Thus, the low-temperature treatment and the heating process can be continuously performed with no interval, so that it is possible to accomplish the oxide film removing operation effectively. - According to the invention, there is provided the shielding plate which is adapted so as to enter the gap between the object and the transparent window and also withdraw from the gap. Therefore, the closing of the shielding plate makes it possible to insulate the heat irradiated from the transparent window and also allows the active gas species to react with the oxide film under the low-temperature condition. Further in the present invention, the low-temperature treatment allowing the active gas species to react with the oxide film is carried out in a different chamber from that of the subsequent heating process., Accordingly, the low-temperature treatment and the heating process can be continuously performed with no interval, so that it is possible to accomplish the oxide film removing operation effectively.
Claims (12)
1-9. (canceled)
10. A processing apparatus for removing an oxide film from a surface of an object to be processed, the processing apparatus comprising:
a processing container accommodating the object to be processed therein;
an active gas species generating unit for producing active gas species;
a heater arranged outside the processing container to heat the object to be processed;
a transparent window formed in the processing container between the heater and the object to be processed, the transparent window sheltering the interior of the processing container from the outside in an airtight manner and also allowing heating energy from the heater to pass through; and
a movable shielding plate provided in a gap between the transparent window and the object configured to shield the object from heat radiation from the transparent window, the shielding plate being extractable from and insertable into the gap.
11. A processing apparatus as claimed in claim 10 wherein the movable shielding plate is located adjacent to and along the transparent window and configured to obstruct a heat radiation from the transparent window to the object.
12. A processing apparatus as claimed in claim 10 or 11, wherein the active gas species generating unit is configured to produce NF3 gas.
13. A processing apparatus as claimed in claim 10 or 11, wherein the shielding plate is provided with a cooler for cooling the shielding plate itself.
14. A processing apparatus as claimed in claim 10 or 11, wherein the active gas species generating unit includes:
a plasma generating tube having a plasma generating part;
a plasma gas introducing part for supplying both N2 gas and H2 gas into the plasma generating tube; and
a NF3 gas supplying part for adding NF3 gas to the active gas species flowing down from an interior of the plasma generating tube.
15. A processing apparatus as claimed in claim 14 , wherein
the plasma generating part comprises a microwave generating source for generating microwaves and a waveguide for introducing the so-generated microwaves into the plasma generating tube.
16. A processing apparatus as claimed in claim 10 , wherein the heater is configured to be actuated after finishing the step of forming the product film.
17. A processing apparatus as claimed in claim 10 , further comprising:
a shaft connected with the shielding plate;
a driver arranged outside the processing container for driving the shaft; and
a seal for airtight sealing between the shaft and a wall of the processing container;
wherein the shielding plate is inserted into or extracted from a gap between the object and the transparent window by actuating the driver.
18. A processing method of removing an oxide film from a surface of an object to be processed while using a processing apparatus which includes a processing container accommodating the object to be processed therein, a heater arranged outside the processing container to heat the object to be processed, a transparent window formed in the processing container between the heater and the object to be processed, and a shielding plate provided in such a way that the shielding plate can be inserted into or extracted from a gap between the object and the transparent window, the processing method comprising the steps of:
allowing the oxide film formed on the surface of the object to react with active gas species under a condition of low temperature oil condition that the shielding plate is closed to insulate irradiation heat irradiated from the transparent window, thereby forming a product film; and subsequently,
opening the shielding plate and applying irradiation heat irradiated from the heater to the product film through the transparent window to heat the product film to a
predetermined temperature for vaporization, thereby removing the product film.
19. A processing method as claimed in claim 18 , wherein the heater is actuated after finishing the step of forming the product.
20. A processing method of removing an oxide film from a surface of an object to be processed, the processing method comprising:
allowing the oxide film formed on the surface of the object to react with active gas species under a condition of low temperature in a first processing chamber, thereby forming a product film;
transporting the object having the product film formed thereon from the first processing chamber to a second processing chamber; and
heating the product film formed on the surface of the object in the second processing chamber, to a predetermined temperature of vaporization, thereby removing the product film.
Priority Applications (3)
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US11/980,613 US8398813B2 (en) | 1999-08-13 | 2007-10-31 | Processing apparatus and processing method |
US11/980,612 US20080113104A1 (en) | 1999-08-13 | 2007-10-31 | Processing apparatus and processing method |
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US66776800A | 2000-09-22 | 2000-09-22 | |
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Also Published As
Publication number | Publication date |
---|---|
US20080113104A1 (en) | 2008-05-15 |
US20080067147A1 (en) | 2008-03-20 |
KR100666018B1 (en) | 2007-01-10 |
JP4057198B2 (en) | 2008-03-05 |
KR20020027529A (en) | 2002-04-13 |
JP2001053055A (en) | 2001-02-23 |
US8398813B2 (en) | 2013-03-19 |
WO2001013419A1 (en) | 2001-02-22 |
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