WO2010035522A1 - Procédé et appareil de gravure de film contenant du silicium - Google Patents

Procédé et appareil de gravure de film contenant du silicium Download PDF

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Publication number
WO2010035522A1
WO2010035522A1 PCT/JP2009/054089 JP2009054089W WO2010035522A1 WO 2010035522 A1 WO2010035522 A1 WO 2010035522A1 JP 2009054089 W JP2009054089 W JP 2009054089W WO 2010035522 A1 WO2010035522 A1 WO 2010035522A1
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flow rate
gas
etching
fluorine
silicon
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PCT/JP2009/054089
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English (en)
Japanese (ja)
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俊介 功刀
崇 佐藤
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積水化学工業株式会社
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Priority to KR1020117006861A priority Critical patent/KR101248625B1/ko
Priority to CN2009801327624A priority patent/CN102132386B/zh
Publication of WO2010035522A1 publication Critical patent/WO2010035522A1/fr

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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
    • H01L21/31—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
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
    • H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
    • H01L21/32135—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only
    • H01L21/32136—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only using plasmas
    • H01L21/32137—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only using plasmas of silicon-containing layers
    • 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

Definitions

  • the present invention relates to a method and an apparatus for etching a silicon-containing film containing silicon atoms such as amorphous silicon and silicon oxide.
  • the silicon oxide film can be etched by a processing gas containing a fluorine-based reaction gas such as hydrogen fluoride.
  • a silicon film made of substantially silicon atoms such as amorphous silicon can be etched by a processing gas in which a fluorine-based reaction gas such as hydrogen fluoride and an oxidizing reaction gas such as ozone are mixed.
  • Patent Documents 1 and 2 describe that silicon on a wafer surface is oxidized with ozone to form silicon oxide (Equation 1) and then etched using hydrofluoric acid. The hydrofluoric acid is evaporated by a hydrofluoric acid vapor generator and led to the wafer surface.
  • Patent Document 3 HF, and COF 2, etc.
  • Patent Document 5 describes that CF 4 and O 2 are discharged at atmospheric pressure to obtain radicals, which are led from a plasma space to a substrate at a temperature of 20 ° C. or 100 ° C. to etch single crystal silicon.
  • Patent Document 6 describes that humidified CF 4 or dry CF 4 is discharged at atmospheric pressure, and crystalline silicon is etched at a substrate temperature of 90 ° C.
  • Patent Document 7 in etching silicon in a low-pressure chamber, overetching is performed after substituting an etching gas component with a gas species having a high selection ratio with respect to the substrate at the same time or just before the substrate film is exposed. A method is described.
  • etching a silicon-containing film such as amorphous silicon or silicon oxide
  • water added to a fluorine-based raw material for generating a fluorine-based reaction component see Equation 4
  • water generated by an etching reaction see Equation 3
  • the etching reaction is inhibited where there is a condensed water layer. Therefore, the entire silicon-containing film cannot be etched uniformly, and a part of the silicon-containing film tends to remain in spots.
  • the silicon content remaining in the spot shape can be removed by etching, but the base film is etched more than necessary.
  • the composition of the underlying film it can be considered that the greater the moisture content, the greater the selectivity of the silicon-containing film to the underlying film.
  • the present invention provides a method for etching an object to be processed in which a silicon-containing film is laminated on a base film.
  • a treatment gas containing a fluorine-based reaction component is brought into contact with the object to be treated;
  • the flow rate of the processing gas on the object to be processed is changed according to the progress of etching.
  • Water is generated by etching (see Equation 3).
  • the processing gas may contain moisture (see Formula 4).
  • the flow velocity of the processing gas on the object to be processed is increased, the moisture is likely to be scattered from the surface of the object to be processed due to the momentum of the processing gas. Therefore, the amount of moisture adhering to the surface of the workpiece can be adjusted by adjusting the flow rate of the processing gas.
  • the flow rate of the processing gas is preferably set so that the etching rate of the silicon-containing film has a good moisture content. Thereby, processing time can be shortened.
  • the flow rate of the processing gas may be set so that the etching selection ratio of the silicon-containing film to the base film becomes a large amount of moisture. Thereby, the etching of the base film can be suppressed, and the silicon-containing film can be prevented from remaining in the form of spots.
  • silicon-containing material constituting the silicon-containing film examples include silicon (Si), silicon oxide (SiO 2 ), silicon carbide (SiC), silicon oxide carbide (SiOC), and silicon carbonitride (SiCN).
  • Silicon (Si) may be amorphous silicon, polycrystalline silicon, or single crystal silicon.
  • the processing gas further includes an oxidizing reaction component.
  • the oxidizing reaction component is a gas component having an oxidizing action on a substance such as silicon.
  • the silicon-containing film can be oxidized (see Equation 1) and then etched in the same manner as silicon oxide (see Equation 3).
  • Silicon carbide (SiC) and silicon oxide carbide (SiOC) can be converted into silicon (Si) by heating and then etched in the same manner as silicon (see Equations 1 and 3).
  • the oxidizing reaction component include O 3 , O radical, H 2 O 2 , O 2 , NO 2 , N 2 O, and the like, and preferably O 3 .
  • the underlying film only needs to be composed of a component different from the silicon-containing film to be etched, and may be a silicon-containing material.
  • the base film is, for example, silicon oxide (SiO 2 ), silicon nitride (SiN), or the like.
  • the base film is, for example, silicon nitride (SiN).
  • the base film is, for example, silicon nitride (SiN), silicon oxide (SiO 2 ), or the like.
  • Stepwise means that the change in flow rate is discontinuous or stepped.
  • the flow rate may be continuously changed as etching progresses.
  • the flow rate may be changed at least once.
  • the timing for changing is preferably determined in advance by experiments.
  • the flow rate is preferably increased as etching progresses.
  • the flow rate of the processing gas can be made relatively small, and the amount of water adhering to the surface of the object to be processed can be sufficiently increased. Therefore, the etching rate of the silicon-containing film can be increased.
  • the flow rate of the processing gas is relatively increased to dissipate moisture from the surface of the object to be processed and reduce the amount of moisture adhering to the surface of the object to be processed. Can do.
  • the degree of decrease in the etching rate of the base film due to the decrease in the amount of moisture adhering to the surface of the object to be processed is larger than the silicon-containing film made of silicon or the like. . Therefore, the etching selectivity of the silicon-containing film to the base film can be increased. As a result, overetching of the underlying film can be suppressed, and the occurrence of spotted residues in the silicon-containing film can be reliably prevented.
  • the flow rate is preferably increased stepwise as etching progresses. Thereby, control of the flow rate can be facilitated.
  • the flow rate may be gradually increased as etching progresses.
  • the flow rate may be decreased stepwise or continuously in order to increase the selectivity of the silicon-containing film to the underlying film as etching proceeds.
  • the portion of the silicon-containing film to be etched is relatively reduced by relatively reducing the flow rate during a period (hereinafter referred to as “first etching step”) of etching most (or almost the whole) of the silicon-containing film to be etched.
  • first etching step a period of etching a portion remaining after the first etching step
  • second etching step a portion remaining after the first etching step
  • the base film is made of silicon nitride or the like, the selectivity of the silicon-containing film to the base film can be increased. As a result, overetching of the underlying film can be suppressed, and the occurrence of spotted residues in the silicon-containing film can be reliably prevented.
  • “most” means, for example, 50 to 99.9%, preferably 70 to 99.9%, more preferably 80 to 99.9% of the portion to be etched of the silicon-containing film. More preferably 90 to 99.9%.
  • the “substantially the entire” is the upper limit of the “most” and means, for example, 90 to 99.9% of the portion to be etched of the silicon-containing film.
  • the flow rate may be increased stepwise in the first etching step, and the flow rate in the second etching step may be increased from the final step of the first etching step.
  • the flow rate by changing the flow rate of the processing gas. Thereby, the flow velocity can be changed easily and reliably. It is preferable to increase the flow rate of the processing gas as the etching progresses. It is preferable that the flow rate of the processing gas is relatively small in the first etching step, and the flow rate of the processing gas is relatively large in the second etching step.
  • the flow rate of the processing gas it is preferable to change the flow rate of the processing gas by mixing a flow rate adjusting gas with the processing gas or stopping the mixing. Accordingly, the flow rate of the reaction component in the process gas can be kept from changing much regardless of the change in the flow rate of the process gas, and the change in the etching rate of the silicon-containing film can be suppressed. It is preferable to increase the flow rate of the flow rate adjusting gas as the etching progresses. It is preferable that the flow rate of the flow rate adjusting gas is relatively small in the first etching step, and the flow rate of the flow rate adjusting gas is relatively large in the second etching step. By the mixing, the flow rate adjusting gas becomes a component of the processing gas.
  • the fluorine reaction components may be a fluorine-based raw material containing H 2 O and fluorine-based source gas added to be generated through the plasma space of approximately atmospheric pressure.
  • the flow rate adjusting gas may be mixed with the fluorine-based source gas upstream of the plasma space, or the mixing may be stopped, and the flow rate may be adjusted by the flow rate of the flow rate adjusting gas. Since the flow rate of the fluorine-based raw material can be maintained constant, fluctuations in the amount of fluorine-based reaction components generated can be suppressed, and fluctuations in the etching rate of the silicon-containing film can be suppressed.
  • the flow rate adjusting gas may be a dilution gas for the fluorine-based raw material, or may be a gas different from the dilution gas.
  • a flow rate adjusting gas is mixed with the processing gas downstream from the plasma space, or mixing is stopped, and the flow rate is adjusted by the flow rate of the flow rate adjusting gas.
  • the flow rate ratio and flow rate of each component of the gas introduced into the plasma space can be maintained constant regardless of the change in the flow velocity. Thereby, the discharge in the plasma space can be stabilized. Therefore, fluctuations in the etching rate of the silicon-containing film can be more reliably suppressed.
  • the flow rate of the flow rate adjusting gas in the first etching step may be zero.
  • the present invention provides an apparatus for etching an object to be processed in which a silicon-containing film is laminated on a base film.
  • a processing gas supply system for supplying a processing gas containing a fluorine-based reaction component to the object to be processed;
  • a flow rate adjusting means for changing the flow rate of the process gas on the workpiece according to the progress of etching;
  • the amount of water adhesion on the surface of the workpiece can be adjusted by adjusting the flow rate.
  • the etching rate of the silicon-containing film can be adjusted to be good at a stage that does not affect the base film. Therefore, the processing time can be shortened.
  • the silicon-containing film can be adjusted to have a good selectivity with respect to the base film. Therefore, etching of the base film can be suppressed, and the occurrence of spotted residues in the silicon-containing film can be reliably prevented.
  • the flow rate adjusting means preferably changes the flow rate stepwise as etching progresses. Thereby, the control of the flow rate adjusting means can be facilitated.
  • the flow rate adjusting means may continuously change the flow rate as etching progresses.
  • the flow rate adjusting means increase the flow rate as etching progresses.
  • the flow rate of the processing gas is relatively reduced, the amount of moisture attached to the surface of the object to be processed is increased, and the etching rate of the silicon-containing film can be increased. Therefore, the processing time can be reliably shortened.
  • the flow rate of the processing gas is relatively increased to dissipate moisture from the surface of the object to be processed and reduce the amount of moisture adhering to the surface of the object to be processed. Can do.
  • the base film is made of silicon nitride or the like, the selectivity of the silicon-containing film to the base film can be increased. As a result, overetching of the underlying film can be suppressed, and the occurrence of spotted residues in the silicon-containing film can be reliably prevented.
  • the flow rate adjusting means increase the flow rate stepwise as etching progresses. Thereby, the control of the flow rate adjusting means can be facilitated.
  • the flow rate adjusting means may gradually increase the flow rate continuously as etching progresses.
  • the flow rate adjusting means may decrease the flow rate stepwise or continuously in order to increase the selectivity of the silicon-containing film to the underlying film as etching proceeds.
  • the flow rate adjusting means reduces the flow rate relatively until most of the portion to be etched of the silicon-containing film is etched, and relatively increases the flow rate when etching the remaining silicon-containing film. It is preferable. Thus, when most of the portion to be etched of the silicon-containing film is etched, the amount of moisture attached to the surface of the object to be processed can be increased to reliably increase the etching rate. Therefore, the processing time can be reliably shortened. Thereafter, when the remaining silicon-containing film is etched, moisture is scattered from the surface of the object to be processed, and the amount of moisture adhering to the surface of the object to be processed can be reduced.
  • the base film is made of silicon nitride or the like, the selectivity of the silicon-containing film to the base film can be increased. As a result, overetching of the underlying film can be suppressed, and the occurrence of spotted residues in the silicon-containing film can be reliably prevented.
  • the flow rate adjusting means is a flow rate adjusting means for adjusting the flow rate of the processing gas.
  • the flow rate adjusting means can have a simple structure, and the flow rate can be reliably changed.
  • the flow rate adjusting means increases the flow rate of the processing gas as etching progresses.
  • the flow rate adjusting means may reduce the flow rate of the processing gas as etching progresses.
  • the processing gas supply system introduces into the plasma space a plasma generation unit that forms a plasma space near atmospheric pressure, and a fluorine-based source gas that includes a fluorine-based material that serves as the fluorine-based reaction component and to which H 2 O is added. And a raw material supply line.
  • the flow rate adjusting means may mix the flow rate adjusting gas into the raw material supply line or stop mixing, and adjust the flow rate according to the flow rate of the flow rate adjusting gas.
  • the flow rate of the fluorine-based raw material can be kept constant, so that fluctuations in the amount of fluorine-based reaction components generated can be suppressed, and fluctuations in the etching rate of the silicon-containing film can be suppressed.
  • the flow rate adjusting gas constitutes one component of the processing gas.
  • the flow rate adjusting unit mix or stop mixing the flow rate adjusting gas into the processing gas supply system downstream of the plasma space, and adjust the flow rate according to the flow rate of the flow rate adjusting gas. Accordingly, the flow rate ratio and flow rate of each component of the gas introduced into the plasma space can be maintained constant regardless of the change in the flow velocity. Therefore, the discharge in the plasma space can be stabilized. Therefore, fluctuations in the etching rate of the silicon-containing film can be more reliably suppressed.
  • the present invention provides an apparatus for etching an object to be processed in which a silicon-containing film is laminated on a base film.
  • a plurality of processing gas supply systems for blowing out a processing gas containing a fluorine-based reaction component;
  • a switching means for selectively switching a processing gas supply system in which a processing gas is sprayed onto the object to be processed according to the progress of etching; And having different flow rates on the object to be processed when the process gases from at least two of the plurality of process gas supply systems are sprayed on the object to be processed. .
  • the flow rate of the processing gas sprayed on the workpiece can be adjusted by selecting the processing gas supply system.
  • the amount of moisture adhering to the surface of the workpiece can be adjusted by the difference in flow rate.
  • the etching rate of the silicon-containing film can be adjusted to be good at a stage that does not affect the base film. Therefore, the processing time can be shortened.
  • the silicon-containing film can be adjusted to have a good selectivity with respect to the base film. Therefore, etching of the base film can be suppressed, and the occurrence of spotted residues in the silicon-containing film can be reliably prevented.
  • the switching unit selects a processing gas supply system having a relatively high flow rate as etching progresses.
  • the treatment gas from the supply system with a low flow rate is blown onto the object to be processed, so that the amount of moisture adhering to the surface of the object to be processed can be increased, and the etching rate of the silicon-containing film can be ensured.
  • the processing gas from the supply system with a high flow rate is blown onto the object to be processed, so that the water is scattered from the surface of the object to be processed and the water adheres to the surface of the object to be processed.
  • the amount can be reduced. Therefore, when the base film is made of silicon nitride or the like, the selectivity of the silicon-containing film to the base film can be increased. As a result, overetching of the underlying film can be suppressed, and the occurrence of spotted residues in the silicon-containing film can be reliably prevented.
  • the switching means selects a processing gas supply system having a relatively low flow rate until most of the portion to be etched of the silicon-containing film is etched, and when the remaining silicon-containing film is etched, the flow rate is It is preferable to select a relatively large process gas supply system.
  • a processing gas supply system having a relatively low flow rate until most of the portion to be etched of the silicon-containing film is etched, and when the remaining silicon-containing film is etched, the flow rate is It is preferable to select a relatively large process gas supply system.
  • the base film is made of silicon nitride or the like, the selection ratio of the silicon-containing film to the base film can be increased. As a result, over-etching of the base film can be suppressed, and the occurrence of spotted residues in the silicon-containing film can be reliably prevented.
  • the flow rates of the processing gases of at least two processing gas supply systems among the plurality of processing gas supply systems are different from each other. Thereby, the flow rate of the processing gas on the workpiece can be changed by switching the processing gas supply system and changing the flow rate of the processing gas sprayed on the workpiece.
  • the switching unit selects a processing gas supply system in which the flow rate of the processing gas is relatively large as etching progresses.
  • the switching means may select a processing gas supply system in which the flow rate of the processing gas is relatively small as etching progresses.
  • Each processing gas supply system introduces into the plasma space a plasma generation unit that forms a plasma space near atmospheric pressure, and a fluorine-based source gas that includes a fluorine-based material that serves as the fluorine-based reaction component and to which H 2 O is added.
  • a flow rate adjusting gas supply unit that joins the flow rate adjusting gas to the source supply line of at least one processing gas supply system.
  • Each processing gas supply system introduces into the plasma space a plasma generation unit that forms a plasma space near atmospheric pressure, and a fluorine-based source gas that includes a fluorine-based material that serves as the fluorine-based reaction component and to which H 2 O is added.
  • a flow rate adjusting gas supply unit that joins the flow rate adjusting gas to the processing gas supply system downstream of the plasma space of the at least one processing gas supply system. .
  • the processing gas supply system to which the flow rate adjusting gas supply unit is connected it is possible to easily increase the flow rate of the processing gas from the processing gas supply system to which the flow rate adjusting gas supply unit is not connected, and as a result The gas flow rate at can be easily increased.
  • the flow rate adjusting gas is not introduced into the plasma space, the discharge can be stabilized, and the reaction components can be generated stably. it can.
  • Examples of the fluorine-based raw material include perfluorocarbon (PFC), hydrofluorocarbon (HFC), SF 6 , NF 3 , and XeF 2 .
  • Examples of the PFC include CF 4 , C 2 F 6 , C 3 F 6 , C 3 F 8 and the like.
  • Examples of the HFC include CHF 3 , C 2 H 2 F 2 , and CH 3 F.
  • An OH-containing compound may be used in place of H 2 O.
  • Examples of the OH group-containing compound include hydrogen peroxide water and alcohol.
  • Examples of the dilution gas for the fluorine-based material include N 2 and the like in addition to rare gases such as Ar and He.
  • Examples of the fluorine-based reaction component include HF, COF 2 and the like.
  • a dilution gas may be used as the flow rate adjusting gas, and the flow rate of the dilution gas may be changed.
  • the processing gas supply system supplies a processing gas containing a fluorine-based reaction component and an oxidizing reaction component to the object to be processed. It is preferable to do. Thereby, the silicon-containing material can be oxidized with an oxidizing reaction component (Equation 1), and then etched with a fluorine-based reaction component (Equation 3).
  • the silicon-containing material is silicon carbide, silicon oxide carbide, or the like, it is preferable to further include a heating unit.
  • silicon carbide, silicon oxide silicon carbide, or the like can be siliconized, and then etched in the same manner as when the silicon-containing material is silicon.
  • the oxygen-based source gas in which the source supply line becomes the fluorine-based source gas and an oxidizing reaction component (O 3 , O radical, etc.) It is preferable to introduce at least a fluorine source gas into the plasma space.
  • the flow rate adjusting gas is preferably an inert gas or an oxidizing reaction gas.
  • the inert gas include nitrogen (N 2 ) in addition to noble gases such as Ar and He. From the viewpoint of reducing the running cost, it is preferable to use nitrogen as the inert gas serving as the flow rate adjusting gas.
  • the oxidizing reaction gas contains the oxidizing reaction component (ozone (O 3 ), hydrogen peroxide (H 2 O 2 ), oxygen (O 2 ), etc.), and preferably contains ozone (O 3 ).
  • the oxidizing reaction gas may contain a plurality of kinds of oxidizing reaction components, or may contain raw material components of the oxidizing reaction components.
  • the oxidizing reaction gas may be a mixed gas of ozone (O 3 ) and oxygen (O 2 ).
  • the oxidizing reaction gas may contain an inert gas such as nitrogen or Ar.
  • a processing gas is Contains an oxidizing reactive gas for causing an oxidation reaction.
  • the flow rate of the oxidizing gas may be changed to change the flow rate of the processing gas, and thus the flow rate may be changed.
  • the oxidizing reaction gas can be used as a flow rate adjusting gas. Therefore, it is not necessary to separately prepare a gas dedicated for adjusting the flow rate, and the type of gas used can be reduced.
  • the flow rate of the fluorine-based source gas or the fluorine-based reaction gas can be maintained constant regardless of the flow rate change of the entire processing gas. Therefore, fluctuations in the etching rate of the silicon-containing film can be suppressed. Even when no oxidizing reaction component is required to etch the silicon-containing film, an oxidizing reaction gas may be used as the flow rate adjusting gas.
  • the process gas supply system supplies a fluorine-based reaction gas containing the fluorine-based reaction component to the object to be processed, and a fluorine-based reaction gas supply system that supplies the reaction object.
  • the flow rate adjusting means may adjust the flow rate of the supply gas of the oxidizing reaction gas supply system.
  • the supply flow rate of the oxidizing reaction gas can be changed according to the progress of etching, and the supply flow rate of the entire process gas can be changed.
  • the flow rate of the processing gas can be adjusted.
  • the oxidizing reaction gas can be used for etching (oxidation reaction) of the silicon-containing film and also as a flow rate adjusting gas. Therefore, a gas dedicated to the flow rate adjustment is not necessary, and the required gas species can be reduced.
  • the flow rate of the fluorine-based reactive gas by the fluorine-based reactive gas supply system is maintained constant regardless of the flow rate control of the oxidizing reactive gas. be able to. Thereby, fluctuations in the etching rate of the silicon-containing film can be suppressed.
  • the oxidizing reaction gas can be generated by a gas excitation device such as a plasma generation unit or an ozonizer using an oxygen-based source gas as a raw material.
  • a gas excitation device such as a plasma generation unit or an ozonizer using an oxygen-based source gas as a raw material.
  • oxygen gas (O 2 ) as an oxygen-based source gas into the plasma generation unit to generate plasma
  • an oxidizing reaction gas containing an oxidizing reaction component such as oxygen radicals
  • oxygen gas (O 2 ) as an oxygen-based source gas into the ozonizer
  • an oxidizing reaction gas composed of an ozone-containing gas can be generated.
  • the oxidizing reaction gas is used as a flow rate adjusting gas, the supply flow rate of the oxygen-based source gas to the plasma discharge unit or the ozonizer may be adjusted. As a result, the flow rate of the oxidizing reaction gas can be adjusted, and consequently the flow rate of the processing gas can be adjusted.
  • the oxygen-based source gas is a gas that is a raw material for the oxidizing reaction gas.
  • examples of the oxygen-based source gas include O 2 , NO, NO 2 , N 2 O and the like, preferably O 2 . These oxygen-based source gases themselves have some oxidizing action and function as oxidizing reaction gases.
  • the raw material supply line may be configured to mix and introduce the fluorine-based source gas and the oxygen-based source gas into the plasma space.
  • the oxidizing reaction component may be obtained by converting the oxygen-based source gas into plasma, excitation activation, or ozonization on a line different from the source supply line.
  • the fluorine-based reaction component from the raw material supply line and the oxidizing reaction component from the other line may be mixed and supplied to the object to be processed, or supplied to the object to be processed from separate outlets. You may decide to do it.
  • the oxidizing reaction gas is preferably generated in the separate line.
  • the production efficiency of the fluorine-based reaction gas can be reliably maintained constant regardless of the flow rate change of the oxidizing reaction gas.
  • the etching rate of the silicon-containing film can be stabilized.
  • the processing gas supply system may include a container such as a cylinder storing the oxidizing reaction gas.
  • the oxidizing reaction gas may be supplied as it is from the container to the object to be processed. Thereby, the plasma discharge part and the ozonizer for generating the oxidizing reaction gas can be omitted.
  • the oxidizing reaction gas is used as the flow rate adjusting gas, the supply flow rate of the oxidizing reaction gas from the container may be adjusted.
  • the oxidizing reaction gas supply path from the vessel is preferably joined to the fluorine-based reaction gas supply path downstream from the plasma generation unit for generating the fluorine-based reaction gas.
  • the vicinity of atmospheric pressure refers to a range of 1.013 ⁇ 10 4 to 50.663 ⁇ 10 4 Pa, and 1.333 ⁇ 10 4 to 10.664 considering the ease of pressure adjustment and the simplification of the apparatus configuration.
  • ⁇ 10 4 Pa is preferable, and 9.331 ⁇ 10 4 to 10.397 ⁇ 10 4 Pa is more preferable.
  • the silicon-containing film can be etched without residue and at a high rate, and etching of the base film can be suppressed.
  • FIG. 1 is an explanatory diagram showing a schematic configuration of the first embodiment of the present invention.
  • 2A is a cross-sectional view of the workpiece before etching
  • FIG. 2B is a plan view of the workpiece at the end of the first etching step
  • FIG. It is sectional drawing of FIG.2 (b)
  • FIG.2 (d) is a top view of the to-be-processed object at the time of completion
  • FIG. 3 is an explanatory diagram showing a schematic configuration of the second embodiment of the present invention.
  • FIG. 4 is an explanatory diagram showing a schematic configuration of the third embodiment of the present invention.
  • FIG. 5 is an explanatory diagram showing a schematic configuration of the fourth embodiment of the present invention.
  • FIG. 1 is an explanatory diagram showing a schematic configuration of the first embodiment of the present invention.
  • 2A is a cross-sectional view of the workpiece before etching
  • FIG. 2B is a plan
  • FIG. 6 is an explanatory diagram showing a schematic configuration of the fifth embodiment of the present invention.
  • FIG. 7 is an explanatory diagram showing a schematic configuration of the sixth embodiment of the present invention.
  • FIG. 8 is an explanatory diagram showing a schematic configuration of the seventh embodiment of the present invention.
  • FIG. 9 is an explanatory diagram showing a schematic configuration of the eighth embodiment of the present invention.
  • FIG. 10 is a graph showing the results of Example 2.
  • FIG. 11 is a graph showing the results of Example 3.
  • FIG. 2A shows an example of the workpiece 90 before etching.
  • the object 90 to be processed includes, for example, glass for flat panel display as a substrate 91, a base film 92 is formed on the glass substrate 91, and a silicon-containing film 93 to be etched is laminated on the base film 92.
  • the base film 92 is made of, for example, silicon nitride (SiNx).
  • the silicon-containing film 93 to be etched is made of, for example, amorphous silicon (a-Si).
  • a portion of the silicon-containing film 93 of the workpiece 90 that should not be etched is covered with a mask such as a resist.
  • a portion of the silicon-containing film 93 that is not masked becomes a portion to be etched.
  • FIG. 1 shows an example of an etching apparatus 1 used for etching the silicon-containing film 93.
  • the etching apparatus 1 includes a processing gas supply system 10 and a support unit 20.
  • the workpiece 90 is supported by the support unit 20.
  • the support part 20 is composed of a stage, for example.
  • a heating unit 21 is provided inside the support unit 20. The workpiece 90 can be heated by the heating unit 21.
  • the processing gas supply system 10 includes a raw material supply line 30 and a plasma generation unit 40.
  • a fluorine-based material supply unit 31 is provided at the upstream end of the material supply line 30.
  • the fluorine-based material supply unit 31 sends a fluorine-based material gas to the material supply line 30.
  • the fluorine-based raw material include CF 4 , CHF 3 , C 2 F 6 , C 3 F 8 , SF 6 , NF 3 , and XeF 2 .
  • CF 4 is used as the fluorine-based material.
  • the fluorine-based raw material may be diluted with a diluent gas such as Ar, He, N 2 or the like, or may not be diluted.
  • CF 4 diluted with Ar is used as the fluorine-based source gas.
  • An addition unit 32 is connected to the raw material supply line 30.
  • the addition unit 32 is configured by a humidifier that stores liquid water (H 2 O), vaporizes the liquid water, and adds it to the fluorine-based source gas (CF 4 + Ar) in the source supply line 30. ing.
  • a part of the fluorine-based raw material gas flowing through the raw material supply line 30 is diverted to the addition unit 32, and this diverted gas is brought into contact with the liquid surface of the addition unit 32 to vaporize water into the diversion gas.
  • the diverted gas may be bubbled in the water of the addition unit 32 to vaporize the water. Water may be vaporized by heating with a heater and supplied to the raw material supply line 30.
  • An oxygen-based raw material supply unit 34 is connected downstream from the addition unit 32 of the raw material supply line 30.
  • the raw material supply unit 34 supplies an oxygen-based raw material gas to the raw material supply line 30.
  • the fluorine-based source gas and the oxygen-based source gas are mixed in the source supply line 30.
  • the oxygen-based raw material include O 2 , NO, NO 2 , and N 2 O.
  • O 2 gas is used as the oxygen-based source gas.
  • the connection point of the oxygen-based material supply unit 34 to the material supply line 30 may be upstream of the addition unit 32.
  • the raw material supply line 30 is connected to a flow rate adjusting gas supply unit 60 (flow rate adjusting means).
  • the connection point of the flow rate adjusting gas supply unit 60 to the raw material supply line 30 is on the downstream side of the water addition unit 32 and on the downstream side of the connection unit with the oxygen-based raw material supply unit 34, but is not limited thereto. It may be upstream from the oxygen-based raw material supply unit 34, or may be upstream from the water addition unit 32.
  • the flow rate adjusting gas supply unit 60 stores a flow rate adjusting gas.
  • the flow rate adjusting gas is preferably an inert gas.
  • the inert gas include N 2 in addition to noble gases such as Ar and He.
  • N 2 is used as the flow rate adjusting gas.
  • the flow rate adjusting gas supply unit 60 can take two states: a mixing mode in which the flow rate adjusting gas is mixed in the raw material supply line 30 and a stop mode in which mixing is stopped. Although detailed illustration is omitted, the flow rate adjusting gas supply unit 60 is provided with an on-off valve and a flow rate control valve. With these valves, either the mixing mode or the stop mode is selected, and the flow rate of the flow rate adjusting gas (N 2 ) in the mixing mode is adjusted.
  • the downstream end of the raw material supply line 30 extends to the plasma generation unit 40.
  • the plasma generation unit 40 has a pair of electrodes 41 and 41 facing each other.
  • a solid dielectric layer (not shown) is provided on the facing surface of at least one of the electrodes 41.
  • One of these electrodes 41, 41 is connected to a power source 42, and the other is electrically grounded.
  • a raw material supply line 30 is connected to the upstream end of the plasma space 43.
  • an ejection portion 59 made of a nozzle is provided at the downstream end of the plasma space 43.
  • the ejection part 59 faces the workpiece 90 on the support part 20.
  • the ejection part 59 may be relatively moved (scanned) with respect to the support part 20 so as to reciprocate between both ends of the support part 20.
  • the bottom surface of the ejection portion 59 has a certain area, and defines a gas path between the workpiece 90 and the workpiece.
  • the processing gas ejected from the opening of the ejection part 59 flows in a direction away from the opening of the ejection part 59 along the surface of the workpiece 90 in the gas path.
  • the etching process is divided into a first etching process from the initial stage to the middle stage (before reaching the final stage) of etching and a second etching process performed at the final stage of etching.
  • a fluorine-based source gas (CF 4 + Ar) is sent from the fluorine-based source supply unit 31 to the source supply line 30.
  • Water (H 2 O) is added to the fluorine-based source gas by the addition unit 32.
  • the addition amount of water is adjusted by the addition unit 32.
  • the amount of water added is increased as much as possible without causing condensation.
  • the fluorine source gas contains water having a dew point temperature of 10 to 50 ° C.
  • the dew point temperature of the fluorine-based source gas is preferably lower than the ambient temperature or the temperature of the workpiece 90. Thereby, dew condensation can be prevented in the piping constituting the raw material supply line 30 and on the surface of the workpiece 90.
  • the dew point of the fluorine-based source gas is 15 to 20 ° C.
  • the oxygen-based material gas (O 2 ) from the oxygen-based material supply unit 34 is mixed with the fluorine-based material gas (CF 4 + Ar + H 2 O) after adding water to generate a mixed material gas.
  • volume ratio of water is sufficiently small with respect to the fluorine-based source gas and the oxygen-based source gas, the volume ratio between the fluorine-based source gas and the oxygen-based source gas before adding water and the fluorine after adding water
  • the volume ratio of the system material gas and the oxygen system material gas is almost the same.
  • the flow rate adjusting gas supply unit 60 is set to a stop mode, and mixing of the flow rate adjusting gas (N 2 ) into the raw material supply line 30 is stopped.
  • the mixed raw material gas (CF 4 + Ar + O 2 + H 2 O) is introduced as it is into the inter-electrode space 43 from the downstream end of the raw material supply line 30 without being mixed with the flow rate adjusting gas (N 2 ).
  • the first processing gas is a recipe that can etch the silicon 93 at a high rate.
  • the fluorine-based reaction component include HF, COF 2 and the like. These fluorine-based reaction components are mainly produced by the decomposition of CF 4 and H 2 O.
  • the oxidizing reaction component include O 3 and O radicals. These oxidizing reaction components are mainly produced using O 2 as a raw material.
  • the first processing gas is ejected from the plasma generation unit 40 and sprayed onto the workpiece 90 on the support unit 20.
  • the first processing gas flows on the surface of the workpiece 90.
  • the gas flow rate on the surface of the workpiece 90 is smaller than the second etching step described later.
  • the oxidizing reaction component in the first processing gas comes into contact with the silicon-containing film 93 made of amorphous silicon, and an oxidation reaction of silicon occurs to generate silicon oxide (Formula 1).
  • a fluorine-based reaction component comes into contact with this silicon oxide (formula 3), and volatile SiF 4 is generated.
  • the silicon-containing film 93 is etched at a good etching rate.
  • the first processing gas also contains a component of the mixed raw material gas that has not been decomposed in the plasma space 43, and thus also contains water.
  • a part of this water reacts with the fluorine-based reaction component COF 2 to generate HF (Equation 2) and contributes to the etching of silicon.
  • a part of the remaining water adheres to the surface of the workpiece 90 and condenses.
  • water is generated by the etching reaction (formula 3) by HF, and a part of this water adheres to the surface of the workpiece 90 and condenses.
  • a condensed layer of water is formed on the surface of the workpiece 90.
  • the flow rate of the first processing gas on the workpiece 90 is large enough to prevent the moisture on the surface of the workpiece 90 from scattering too much. Therefore, the condensed layer can be made to an appropriate thickness, and the silicon etching rate can be made sufficiently high.
  • the water condensate layer may become thicker than necessary at the surface of the workpiece 90.
  • the etching reaction is hindered where the condensed layer is thick. Therefore, as shown in FIGS. 2B and 2C, the surface of the workpiece 90 just before the etching reaches the final stage, the portion where the base film 92 is exposed, and the silicon-containing film 93 to be etched. Can still be left.
  • the remaining silicon-containing film 93 is referred to as a remaining film 93a.
  • the remaining film 93a has a spotted shape (a mottled shape).
  • the flow rate adjusting gas supply unit 60 is set to the mixed mode.
  • Other operations and processing conditions are preferably the same as those in the first etching step. Therefore, the flow rate adjusting gas (N 2 ) is mixed from the flow rate adjusting gas supply unit 60 to the mixed source gas (CF 4 + Ar + O 2 + H 2 O) having the same component and the same flow rate as the first etching step. Thereby, the flow volume of source gas increases.
  • the mixed raw material gas (CF 4 + Ar + O 2 + H 2 O + N 2 ) is introduced into the plasma space 43 to be converted into plasma.
  • a processing gas containing a fluorine-based reaction component such as HF or COF 2 and an oxidizing reaction component such as O 3 or O radical is generated.
  • the processing gas in the second etching step is appropriately referred to as “second processing gas”.
  • the flow rate of the second processing gas is larger than the flow rate of the first processing gas in the first etching step by the amount of the mixed flow rate adjusting gas (N 2 ).
  • the amounts of the fluorine-based reaction component (such as HF) and the oxidizing reaction component (such as O 3 ) in the second processing gas are substantially equal to those in the first etching step.
  • the second processing gas is ejected from the ejection part 59 and sprayed onto the workpiece 90.
  • the opening degree of the ejection part 59 is constant, so that the blowing speed of the second processing gas from the ejection part 59 is larger than the blowing speed of the first processing gas in the first etching step.
  • the second processing gas flows on the surface of the workpiece 90. While the gas flow rate has increased, the distance (working distance) between the ejection portion 59 and the object to be processed 90 is constant, so the flow rate of the second processing gas on the surface of the object to be processed 90 is It becomes larger than the flow velocity of the first processing gas in one etching process.
  • the amount of moisture adhering to the surface of the workpiece 90 is smaller than that in the first etching step, and the thickness of the condensed layer is smaller than that in the first etching step.
  • the etching rate of the underlying silicon nitride film 92 decreases.
  • the degree of decrease in the etching rate of silicon nitride is greater than the degree of decrease in the etching rate associated with the decrease in the silicon condensation layer. Therefore, the selection ratio of the etching target film 93 to the base film 92 can be increased.
  • the amount of the fluorine-based reaction component (HF or the like) and the oxidizing reaction component (O 3 or the like) in the second processing gas is substantially equal to that in the first etching step, it is possible to suppress a decrease in the etching rate of silicon.
  • the spot-like residual film 93a can be selectively etched and removed at a good etching rate, and the overetching amount d of the base film 92 can be reduced.
  • Switching from the first etching step to the second etching step can be easily performed only by switching the flow rate adjusting gas supply unit 60 from the stop mode to the mixing mode.
  • the addition unit 32 changes the water addition rate. Is also responsive.
  • Second Embodiment As shown in FIG. 3, the second embodiment is different from the first embodiment (FIG. 1) in the mixing location of the flow rate adjusting gas into the processing gas supply system 10.
  • the flow rate adjusting gas supply unit 60 is connected not to the raw material supply line 30 upstream of the plasma generation unit 40 but to the ejection line 50 downstream of the plasma generation unit 40.
  • the ejection line 50 extends from the plasma space 43.
  • a jet part 59 is provided at the downstream end of the jet line 50.
  • a flow rate adjusting gas supply unit 60 is connected to an intermediate portion of the ejection line 50.
  • the flow rate adjusting gas supply unit 60 is in a stop mode in the first etching step. Therefore, the operation of the first etching process is the same as that of the first embodiment.
  • the flow rate adjusting gas supply unit 60 is in a mixed mode.
  • a mixed raw material gas (CF 4 + Ar + O 2 + H 2 O) having the same component and the same flow rate as the first etching step is generated and introduced into the plasma generation unit 40.
  • the flow rate adjusting gas is not mixed with the mixed raw material gas before being introduced into the plasma generating unit 40. Therefore, even when the first etching process is switched to the second etching process, the gas state in the plasma space 43 does not change, and the discharge can be stabilized.
  • a processing gas containing a fluorine-based reaction component (HF or the like) and an oxidizing reaction component (O 3 or the like) is obtained.
  • the amount of these reaction components generated can be the same as in the first etching step.
  • This processing gas is led out to the ejection line 50.
  • the processing gas is mixed with a flow rate adjusting gas (N 2 ) from the supply unit 60.
  • N 2 flow rate adjusting gas
  • the processing gas supply system 10 of the third embodiment generates a fluorine-based reaction component and an oxidizing reaction component separately.
  • the processing gas supply system 10 has a fluorine-based reaction gas supply system 33 and an oxidizing reaction gas supply system 35 separately.
  • the fluorine-based reactive gas supply system 33 includes a raw material supply line 30, a plasma generation unit 40, and a fluorine-based ejection path 51.
  • the raw material supply line 30 is the same as that of the second embodiment (FIG. 3) except that the oxygen-based raw material supply unit 34 is not connected.
  • a flow rate adjusting gas supply unit 60 is connected to the fluorine-based jet passage 51.
  • the material supply line 30 introduces only the fluorine-based material gas (CF 4 + Ar + H 2 O) into the plasma generation unit 40.
  • the oxygen-based source gas is not introduced into the plasma generation unit 40.
  • a fluorine-based ejection path 51 extends from the downstream end of the plasma space 43 of the plasma generation unit 40.
  • the oxidizing reaction gas supply system 35 includes an oxygen-based material supply unit 34, a plasma generation unit 44 different from the plasma generation unit 40, and an oxygen-based ejection path 52.
  • the plasma generation unit 44 has a pair of electrodes 45 and 45 facing each other.
  • a solid dielectric layer (not shown) is provided on the opposing surface of at least one of the electrodes 45.
  • One of these electrodes 45, 45 is connected to a power source 46, and the other is electrically grounded.
  • An oxygen-based material supply unit 34 is connected to the upstream end of the plasma space 47.
  • An oxygen-based ejection path 52 extends from the downstream end of the plasma space 47 of the plasma generation unit 44.
  • the ejection path 51 of the fluorine-based reaction gas supply system 33 and the ejection path 52 of the oxidizing reaction gas supply system 35 are joined together.
  • the common jet part 53 is continued to this merge part.
  • the common ejection part 53 faces the workpiece 90 on the support part 20.
  • the common ejection part 53 may be moved relative to the support part 20 so as to reciprocate between both ends of the support part 20.
  • the fluorine-based source gas (CF 4 + Ar + H 2 O) is converted into plasma by the plasma generation unit 40, and a fluorine-based reaction gas containing a fluorine-based reaction component (HF or the like). Is generated and led to the ejection path 51.
  • the oxygen-based source gas (O 2 ) from the oxygen-based source supply unit 34 is introduced into the plasma space 47 of the plasma generation unit 44 to be converted into plasma, and the oxidation reaction occurs.
  • An oxidizing reaction gas containing components (such as O 3 ) is generated.
  • This oxidizing reaction gas is led out from the plasma generation unit 44 to the ejection path 52 and mixed with the fluorine-based reaction gas from the ejection path 51.
  • the fluorine-based source gas and the oxygen-based source gas are converted into plasma by separate plasma generation units 40 and 44, the generation amount of the fluorine-based reaction component and the generation amount of the oxidizing reaction component are sufficiently large. can do. Thereby, the etching rate of the silicon-containing film 93 in each of the first and second etching steps can be increased, and the processing time can be further shortened.
  • the flow rate adjusting gas supply unit 60 is in the stop mode in the first etching step, and the flow rate adjusting gas supply unit 60 is in the mixed mode in the second etching step. It is the same. Therefore, in the second etching step, the flow rate adjusting gas (N 2 ) from the supply unit 60 is introduced into the ejection path 51 and mixed with the fluorine-based reaction gas.
  • an ozonizer 48 is used in place of the plasma generation unit 44 as an oxidizing reaction gas generating device in the oxidizing reaction gas supply system 35.
  • Oxygen gas (O 2 ) from the oxygen-based raw material supply unit 34 is introduced into the ozonizer 48 to generate an oxidizing reaction gas containing O 3 , and this oxidizing reaction gas is led out to the ejection path 52. Yes.
  • Other configurations and operations are the same as those of the third embodiment (FIG. 4).
  • the etching apparatus 1 of the fifth embodiment includes a plurality (two) of processing gas supply systems 10.
  • Each processing gas supply system 10 has substantially the same configuration as the processing gas supply system 10 of the first and second embodiments (FIGS. 1 and 3).
  • each component of the first process gas supply system 10 ⁇ / b> A is denoted by the same reference numeral as the corresponding component in the process gas supply system 10 of the above-described embodiment.
  • the constituent elements of the second processing gas supply system 10B are denoted by the same reference numerals as those of the corresponding constituent elements in the processing gas supply system 10 of the above-described embodiment.
  • the first processing gas supply system 10A is different from the processing gas supply system 10 of the first and second embodiments (FIGS. 1 and 3) in that the flow rate adjusting gas supply unit 60 is not connected. . Therefore, the first processing gas that does not contain the flow rate adjusting gas (N 2 ) is constantly ejected from the first processing gas supply system 10A.
  • the component and flow rate of the first processing gas from the supply system 10A are the same as the first processing gas in the first etching step of the first and second embodiments.
  • the second processing gas supply system 10B has the same configuration as the processing gas supply system 10 of the second embodiment (FIG. 3). However, the flow rate adjusting gas supply unit 60B of the second processing gas supply system 10B is always operated in the mixed mode. Therefore, the second processing gas including the flow rate adjusting gas (N 2 ) is constantly ejected from the second processing gas supply system 10B. The component and flow rate of the second processing gas from the supply system 10B are the same as the second processing gas in the second etching process of the first and second embodiments.
  • the ejection flow rate of the first processing gas supply system 10A is relatively small by the amount not mixed with the flow rate adjusting gas, and the ejection flow rate of the second processing gas supply system 10B is relatively large by the mixing amount of the flow rate adjusting gas. .
  • the opening degree of the ejection part 59A of the first processing gas supply system 10A and the opening degree of the ejection part 59A of the second processing gas supply system 10B are equal to each other. Therefore, the blow-off flow rate from the first processing gas supply system 10A is relatively small.
  • the blowing flow rate from the second processing gas supply system 10A is relatively large.
  • the moving means 22 is connected to the support part 20.
  • the moving means 22 includes, for example, a drive unit such as a motor and a slide unit that is advanced and retracted by the drive unit, and the support unit 20 is connected to the slide unit.
  • the moving unit 22 causes the support unit 20 to have a first position (solid line in FIG. 6) facing the first processing gas ejection part 59A and a second position (in FIG. 6) facing the second processing gas ejection part 59A. It is designed to move between the two-dot chain line).
  • the support unit 20 is positioned at the first position by the moving means 22.
  • the first processing gas ejected from the first processing gas supply system 10 ⁇ / b> A contacts the workpiece 90.
  • the flow rate of the first processing gas is relatively low, and the flow rate on the workpiece 90 is relatively small. Therefore, a condensed layer of water having an appropriate thickness is easily formed on the surface of the workpiece 90, and the etching rate of the silicon-containing film 93 can be increased.
  • the support unit 20 When most of the silicon-containing film 93 is etched, the support unit 20 is moved from the first position to the second position by the moving means 22. Thereby, it is possible to shift from the first etching process to the second etching process with little time.
  • the second processing gas ejected from the second processing gas supply system 10 ⁇ / b> B comes into contact with the workpiece 90.
  • the flow rate of the second process gas is higher than the gas flow rate of the first process gas supply system 10A. Therefore, moisture can be scattered from the surface of the object to be processed 90, and formation of a condensed layer of water on the surface of the object to be processed 90 can be suppressed.
  • the moving unit 22 constitutes a switching unit that selectively switches between the processing gas supply systems 10 ⁇ / b> A and 10 ⁇ / b> B through which the processing gas is blown onto the workpiece 90.
  • the moving speed of the support part 20 and the number of the processing gas supply systems 10 used in the first etching step are determined in advance so that the base film 92 is exposed in the first etching step or is left on the base film 92 by experiments.
  • the thickness of the silicon-containing film 93 is determined to be extremely small.
  • the moving means 22 may be connected to the ejection parts 59A, 59B instead of the support part 20, and instead of moving the support part 20 between the first position and the second position, the ejection parts 59A, By moving 59B, the ejection part 59A may be opposed to the support part 20 in the first etching process, and the ejection part 59B may be opposed to the support part 20 in the second etching process.
  • the workpiece 94 is a continuous sheet.
  • the continuous sheet-like workpiece 94 is fed from the feed roll 23 and taken up by the take-up roll 24.
  • a heating unit 21 is provided on the back side of the workpiece 94 between the rolls 23 and 24.
  • the ejection part 59A of the first processing gas supply system 10A is disposed at a position between the rolls 23 and 24 near the feeding roll 23.
  • An ejection portion 59B of the second processing gas supply system 10B is disposed at a position near the take-up roll 24 between the rolls 23 and 24.
  • the workpiece 94 fed out from the feed roll 23 comes into contact with the low-flow first processing gas at a low flow rate from the first processing gas supply system 10A. Thereafter, the second process gas is brought into contact with the second process gas at a high flow rate and high speed from the second process gas supply system 10B. Thereby, it can transfer to a 2nd etching process continuously from a 1st etching process.
  • the feeding roll 23 and the take-up roll 24 function as a workpiece support section that replaces the stage-shaped support section 20.
  • the feed roll 23 and the take-up roll 24 constitute a switching unit that selectively switches between the processing gas supply systems 10A and 10B in which the processing gas is blown to the workpiece 90.
  • the change of the flow rate of the processing gas and thus the flow velocity is not limited to two steps, and may be performed in three or more steps.
  • the gas flow rate and thus the flow rate may be changed over two or more stages.
  • the gas flow rate and thus the flow rate may be changed over two or more stages.
  • FIG. 8 shows an embodiment in which the flow rate of the processing gas, and hence the flow rate, is changed over three stages in the first etching process and the second etching process.
  • the etching apparatus 1 includes three processing gas supply systems 10. When these three process gas supply systems 10 are distinguished from each other, X is added to the reference numerals of the first stage (left side in FIG. 8) of the process gas supply system 10 and its components, and the second stage (center in FIG. 8). ) Is attached to the reference numerals of the processing gas supply system 10 and its constituent elements, and Z is attached to the reference numerals of the third stage (right side in FIG. 8) of the processing gas supply system 10 and its constituent elements.
  • the first-stage and second-stage process gas supply systems 10X and 10Y become the first process gas supply system for executing the first etching process.
  • the processing gas supply system 10Z at the final stage (third stage) becomes the second processing gas supply system for executing the second etching process.
  • the first stage processing gas supply system 10X has the same configuration as the first processing gas supply system 10A of the fifth embodiment (FIG. 6) and the sixth embodiment (FIG. 7). That is, the flow rate adjusting gas supply unit 60 is not connected to the processing gas supply system 10X.
  • the processing gas ejected from the first processing gas supply system 10A does not include the flow rate adjusting gas (N 2 ) and has a small flow rate.
  • the second stage processing gas supply system 10Y has the same configuration as the second processing gas supply system 10B of the fifth and sixth embodiments (FIGS. 6 and 7). It is always operated in mixed mode. However, the mixing flow rate of the flow rate adjusting gas is smaller than the mixing flow rate of the flow rate adjusting gas in the second processing gas supply system 10B.
  • the third stage (final stage) processing gas supply system 10Z has the same configuration as the second processing gas supply system 10B of the fifth and sixth embodiments (FIGS. 6 and 7), and the flow rate adjusting gas.
  • Supply unit 60Y is always operated in the mixed mode.
  • the mixed flow rate of the flow rate adjusting gas is also the same as that of the second processing gas supply system 10B.
  • the mixed flow rate of the flow rate adjusting gas by the third stage flow rate adjusting gas supply unit 60Z is preferably 1 to 4 times the mixed flow rate of the flow rate adjusting gas by the second stage flow rate adjusting gas supply unit 60Y. More preferably, it is 2 to 3 times.
  • the ejection portions 59 of the three processing gas supply systems 10 are arranged in a line at intervals.
  • a roller conveyor 25 is installed below these ejection portions 59.
  • the roller conveyor 25 is extended in the arrangement direction of the ejection parts 59.
  • the workpiece 90 is conveyed by the roller conveyor 25 in the order below the first stage ejection part 59X, below the second stage ejection part 59Y, and below the third stage ejection part 59Z.
  • the roller conveyor 25 constitutes a conveying unit and a supporting unit for the workpiece 90.
  • the roller conveyor 25 comprises the switching means which selectively switches the process gas supply system 10 with which process gas is sprayed on the to-be-processed object 90.
  • FIG. The moving speed of the roller conveyor 25 and the number of processing gas supply systems 10 are determined in advance by experiments.
  • the workpiece 90 comes into contact with the processing gas from the second stage processing gas supply system 10Y and is etched.
  • a flow rate adjusting gas (N 2 ) is mixed with the second stage processing gas. Therefore, the flow rate of the second stage processing gas is larger than that of the first stage, and the gas flow rate on the workpiece 90 is larger than that of the first stage.
  • moisture is scattered from the surface of the workpiece 90, and the thickness of the condensed layer on the surface of the workpiece 90 can be made smaller than in the first stage. Therefore, the selection ratio of the silicon-containing film 93 to the base film 92 can be increased. Therefore, when the concave portion of the uneven surface of the silicon-containing film 93 reaches the interface with the base film 92, the base film 92 can be prevented from being scraped.
  • FIG. 9 shows an eighth embodiment of the present invention.
  • the oxidizing reaction gas is used as a flow rate adjusting gas.
  • the processing gas supply system 10 of the eighth embodiment includes a fluorine-based reaction gas supply system 33 and an oxidizing reaction gas supply system 35 having an ozonizer 48, as in the fourth embodiment (FIG. 5). Including.
  • the fluorine-based reactive gas supply system 33 is not connected to a flow rate adjusting gas supply unit 60 as a flow rate adjusting means.
  • an oxidizing reactive gas flow rate adjusting unit 61 is provided as a flow rate adjusting unit on a line connecting the oxygen-based raw material supplying unit 34 and the ozonizer 48 of the oxidizing reactive gas supply system 35.
  • the flow rate adjusting unit 61 includes a flow rate control valve and a mass flow controller.
  • the flow rate adjusting unit 61 adjusts the flow rate of the oxygen-based source gas (O 2 ) supplied from the oxygen-based source supply unit 34 to the ozonizer 48, and as a result, the oxidizing reaction gas (O 2 + O 3 ) from the ozonizer 48. Adjust the supply gas flow rate.
  • the flow rate adjusting unit 61 may be provided in the ejection path 52 downstream from the ozonizer 48.
  • the first etching process of the eighth embodiment is substantially the same as the first etching process of the third and fourth embodiments.
  • the humidified fluorine-based source gas (CF 4 + Ar + H 2 O) is turned into plasma to generate a fluorine-based reaction gas.
  • oxygen-based source gas (O 2 ) is supplied from the oxygen-based source supply unit 34 of the oxidizing reaction gas supply system 35 to the ozonizer 48, and the oxidizing reaction gas (O 2 + O 3 ) is generated by the ozonizer 48.
  • a processing gas is obtained by mixing these fluorine-based reaction gas and oxidizing reaction gas.
  • This processing gas is ejected from the ejection part 53 and brought into contact with the workpiece 90.
  • the supply flow rate of the oxygen-based source gas (O 2 ) and, therefore, the oxidizing reaction gas (O 2 + O 3 ) is increased by the flow rate adjusting unit 61 compared to the first etching process.
  • the supply flow rate of the fluorine-based reaction gas is preferably the same as that in the first etching step.
  • the selection ratio of the silicon film 93 to the base film 92 can be increased.
  • silicone can be suppressed by setting it as the same flow rate as a 1st etching process.
  • the silicon residual film 93a can be selectively etched and removed at a good etching rate, and the overetching amount d of the base film 92 can be reduced.
  • the oxidizing reaction gas also serves as the flow rate adjusting gas, a gas dedicated to the flow rate adjustment (for example, N 2 ) is unnecessary. Therefore, the required gas species can be reduced.
  • the silicon-containing film 93 to be etched is not limited to amorphous silicon, but may be polysilicon or single crystal silicon.
  • the silicon-containing film 93 to be etched is not limited to silicon, and may be silicon oxide, silicon carbide, silicon oxide carbide, or the like.
  • the processing gas does not need to contain an oxidizing reaction component. Therefore, the oxygen-based raw material supply unit 34 can be omitted.
  • the silicon-containing film 93 to be etched is silicon carbide or silicon oxide carbide, it can be converted into silicon by a heating operation, and then etched in the same manner as in the above embodiment.
  • the base film 92 is not limited to silicon nitride, and may be any component different from the silicon-containing film 93 to be etched.
  • the base film 92 may be silicon oxide.
  • the base film may be, for example, silicon nitride.
  • the base film 92 may be, for example, silicon nitride or silicon oxide.
  • the processing gas flow rate on the workpiece 90 may be reduced in order to increase the selectivity of silicon to the underlying film as etching proceeds.
  • the processing gas flow rate in the second etching step may be smaller than that in the first etching step.
  • the processing gas flow rate may be reduced and then increased.
  • the processing gas flow rate may be increased and then decreased.
  • the process gas flow rate is not limited to being changed stepwise, but may be continuously changed (gradual decrease or increase).
  • the mixing flow rate of the flow rate adjusting gas (N 2 ) may be changed stepwise or continuously.
  • Flow rate adjusting means for changing the flow rate of the processing gas, instead of mixing the flow rate adjusting gas (N 2) to the processing gas supply system 10, or to mix the flow rate adjusting gas (N 2)
  • the flow rate of the fluorine-based source gas (CF 4 + Ar) may be changed
  • the flow rate of the dilution gas (Ar) in the fluorine-based source gas may be changed
  • the oxygen-based source material (O 2 ) The flow rate may be changed.
  • the flow rate adjusting means may adjust the opening degree of the ejection portion 59 instead of adjusting the gas flow rate or in addition to adjusting the gas flow rate. You may adjust the thickness (distance between the ejection part 59 and the to-be-processed object 90) of the gas path defined between the ejection part 59 and the to-be-processed object 90.
  • fluorine-based raw material such as C 2 F 6 , C 3 F 6 , and C 3 F 8 may be used as the fluorine-based raw material.
  • CHF 3 , CH 2 F 2 , and CH 3 HFC (hydrofluorocarbon) such as F may be used, and fluorine-containing compounds other than PFC and HFC such as SF 6 , NF 3 , and XeF 2 may be used.
  • fluorine-containing compounds other than PFC and HFC such as SF 6 , NF 3 , and XeF 2 may be used.
  • As a dilution gas other inert gas such as He, Ne, N 2 may be used instead of Ar.
  • oxygen-based raw material oxygen-containing compounds such as NO, NO 2 , and N 2 O may be used instead of O 2 .
  • an OH group-containing compound may be used instead of water (H 2 O).
  • the OH group-containing compound include hydrogen peroxide water (H 2 O 2 ) and alcohols such as ethanol and methanol.
  • H 2 O 2 hydrogen peroxide water
  • alcohols such as ethanol and methanol.
  • H 2 O 2 the reactivity is high and it is difficult to stably add it to the gas of the fluorine-based reaction component.
  • the carbon component (C) reacts when it is introduced into the plasma, and an organic polymer is produced. Therefore, it is necessary to decompose and remove it. Therefore, H 2 O that can be supplied simply and stably is preferable.
  • the oxidizing reaction component itself such as O 3 is stored in a tank or the like, and the oxidizing reaction component is taken out from the tank to remove fluorine. You may mix with a system reaction component.
  • the fluorine-based reaction gas and the oxidizing reaction gas are not mixed and blown out from different jetting parts toward the object to be processed. Also good.
  • the timing of switching from the first etching process to the second etching process is not limited to the stage where the base film 92 is exposed, and may be set to a stage just before the base film 92 is exposed.
  • two processing gas supply systems 10X may be provided side by side, and four processing gas supply systems 10 may be provided in the entire apparatus 1.
  • This structure is suitable when the thickness of the silicon-containing film 93 is large and the amount that can be etched by one processing gas supply system 10X is less than half the thickness of the silicon-containing film 93. That is, by providing two processing gas supply systems 10X, more than half or most of the silicon-containing film 93 can be etched at a good etching rate. Thereafter, etching is performed by increasing the silicon selection ratio in the processing gas supply system 10Y, and then etching is performed by further increasing the silicon selection ratio in the processing gas supply system 10Z.
  • processing gas supply systems 10X may be arranged in parallel.
  • the flow rate adjusting gas supply unit 60 may also be provided in the first stage process gas supply system 10X.
  • a plurality of embodiments may be combined with each other.
  • the flow rate adjusting gas supply unit 60 of the third to seventh embodiments (FIGS. 4 to 8) may be connected to the raw material supply line 30 as in the first embodiment (FIG. 1).
  • Each of the processing gas supply systems 10 of the fifth to seventh embodiments (FIGS. 6 to 8) is similar to that of the third and fourth embodiments (FIGS. 4 and 5). May be generated by different routes.
  • the plasma generator 44 of the third embodiment (FIG. 4) may be used instead of the ozonizer 48.
  • the first and second embodiments (FIGS.
  • the flow rate adjusting gas supply unit 60 is omitted, and instead, the material supply line of the oxygen-based material supply unit 34 is used.
  • the flow rate adjusting unit 61 may be provided on the connection path to the No. 30, and the oxygen-based source gas and thus the oxidizing reaction component may be substituted for the flow rate adjusting gas. In this case, attention is paid to the influence on the stability of the discharge in the plasma generation unit 40 and the generation efficiency of the fluorine-based reaction gas due to the change in the flow rate of the oxygen-based source gas.
  • the flow rate adjusting gas supply unit 60B of the processing gas supply system 10B is omitted, and instead, an oxygen-based material supply is provided.
  • the flow rate adjusting unit 61 may be provided on the connection path of the unit 34B to the raw material supply line 30B, and the oxygen-based raw material gas, and thus the oxidizing reaction component, may be used as the flow rate adjusting gas. In this case, attention is paid to the influence on the stability of the discharge in the plasma generation unit 40B and the generation efficiency of the fluorine-based reactive gas accompanying the change in the flow rate of the oxygen-based source gas.
  • FIG. 1 In the seventh embodiment (FIG.
  • the flow rate adjusting gas supply units 60Y and 60Z of the processing gas supply systems 10Y and 10Z are omitted, and instead, the oxygen-based material supply unit 34Y. , 34Z may be provided on each connection path to the raw material supply lines 30Y, 30Z, and the oxygen-based raw material gas, and thus the oxidizing reaction component, may be substituted for the flow rate adjusting gas.
  • the processing gas supply systems 10 of the fifth to seventh embodiments FIGS.
  • the etching method and the etching apparatus according to the present invention are designed to remove contaminants including silicon adhering to the surface of an object to be processed, and to remove a roughened portion of a silicon wafer or glass in addition to pattern etching of an object to be processed patterned with a resist or the like. It can also be applied to planarization, roughening of the front or back surface of a silicon wafer or glass.
  • the amorphous silicon film was etched in two stages, a first etching process and a second etching process.
  • the base film was silicon nitride, and a sample in which amorphous silicon was laminated on the base film was used.
  • the first etching process was performed.
  • CF 4 was used as a fluorine-based raw material.
  • Ar was used as a dilution gas.
  • CF 4 was diluted with Ar to obtain a fluorine-based source gas (CF 4 + Ar).
  • the fluorine-based source gas (CF 4 + Ar) was added to the fluorine-based source gas (CF 4 + Ar) with a commercially available water addition device. The amount of water was controlled so that the dew point temperature was 18 ° C. The flow rate adjusting gas supply unit 60 was set to the stop mode.
  • the fluorine-based source gas (CF 4 + Ar + H 2 O) after the addition of water was turned into plasma by the plasma generation unit 40 to obtain a fluorine-based reaction gas.
  • the plasma discharge conditions are as follows. Distance between electrodes: 1mm Voltage between electrodes: 12kV Power frequency: 40 kHz (pulse wave)
  • O 2 gas as an oxygen-based source gas was introduced into the ozonizer 48 to obtain an oxidizing reaction gas (O 2 + O 3 ).
  • the ozone concentration of the oxidizing reaction gas was about 8%.
  • the fluorine-based reaction gas from the plasma generation unit 40 and the oxidizing reaction gas from the plasma generation unit 44 were mixed to obtain a first processing gas.
  • the volume mixing ratio of the fluorine-based reaction gas and the oxidizing reaction gas was 1: 1.
  • the workpiece 90 was placed on the stage 20, and the ejection portion 53 was disposed above the workpiece. While the first processing gas was blown out from the ejection portion 53, the ejection portion 53 was moved (scanned) so as to reciprocate from one end to the other end of the workpiece 90. The moving speed was 4 m / min. The one-way movement in the forward direction or the backward direction was set as one scan, the scan was performed 18 times, and the first etching process was completed. At this time, spot-like amorphous silicon 93a having a thickness of 0.1 to 10 ⁇ m remained on the surface of the workpiece 90 (see FIGS. 2B and 2C). The etching rate of the amorphous silicon film in the first etching step was 10.1 nm / scan, and the selectivity of the amorphous silicon film to the silicon nitride film was about 1.3.
  • a second etching step was performed.
  • the flow rate adjusting gas supply unit 60 was set to the mixed mode.
  • the number of scans of the ejection part 53 was four.
  • Other processing conditions in the second etching step were the same as those in the first etching step.
  • the remaining amorphous silicon 93a could be completely removed by the second etching process.
  • the etching rate of the amorphous silicon film in the second etching process was 8.6 nm / scan, and the selection ratio of the amorphous silicon film to the silicon nitride film was higher than that in the first etching process and was about 2.3. Therefore, it was confirmed that the overetching of the underlying silicon nitride film 92 can be reduced.
  • Example 1 The relationship between the mixing ratio of the flow rate adjusting gas to the processing gas and the selectivity of amorphous silicon to silicon nitride was investigated.
  • the etching apparatus shown in FIG. The raw material components and generation conditions of the processing gas were the same as those in Example 1. Nitrogen (N 2 ) was mixed with this processing gas as a flow rate adjusting gas, and the mixed flow rate of nitrogen was changed.
  • the etching rate of amorphous silicon (a-Si) and silicon nitride (SiNx) was measured, and the selection ratio of amorphous silicon (a-Si) to silicon nitride (SiNx) was calculated.
  • Example 3 does not use N 2 gas as a flow rate adjusting gas.
  • an oxidizing reaction gas composed of an ozone-containing gas (O 2 + O 3 ) was generated by the ozonizer 48 as in Example 1.
  • the flow rate of the oxidizing reaction gas was changed so that the volume mixing ratio of the fluorine-based reaction gas and the oxidizing reaction gas was 2: 1 to 1: 2.
  • the flow rate of the fluorine-based reaction gas was constant.
  • the etching rate of amorphous silicon (a-Si) and silicon nitride (SiNx) was measured, and the selection ratio of amorphous silicon (a-Si) to silicon nitride (SiNx) was calculated.
  • the present invention is applicable, for example, to the manufacture of flat panel displays (FPD) and semiconductor wafers.
  • FPD flat panel displays
  • semiconductor wafers semiconductor wafers

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Abstract

L'invention porte sur un procédé et un appareil de gravure d'un film contenant du silicium tel qu'un film de silicium ou un film d'oxyde de silicium à une vitesse élevée sans laisser de résidus, tout en supprimant une gravure d'un film de base. Un film contenant du silicium (93) sur un film de base (92) est gravé en amenant un gaz de traitement, qui contient un composant réactionnel à base de fluor et un composant réactionnel oxydant, en contact avec un objet (90) devant être traité. Le débit du gaz de traitement sur l'objet (90) devant être traité est modifié par un moyen de régulation de débit (60) en fonction de la progression de la gravure. De préférence, le débit de gaz est modifié par régulation de la quantité du flux de gaz de traitement. Plus préférablement, la quantité du flux de gaz de traitement est régulée par mélange d'un gaz de régulation de débit dans un système d'alimentation en gaz de traitement (10) ou par arrêt du mélange.
PCT/JP2009/054089 2008-09-25 2009-03-04 Procédé et appareil de gravure de film contenant du silicium WO2010035522A1 (fr)

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CN2009801327624A CN102132386B (zh) 2008-09-25 2009-03-04 含硅膜的蚀刻方法以及装置

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KR101660831B1 (ko) * 2014-11-28 2016-09-29 피에스케이 주식회사 기판 처리 장치 및 방법
JP6978265B2 (ja) * 2017-09-29 2021-12-08 積水化学工業株式会社 表面処理装置及び表面処理方法

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CN102132386A (zh) 2011-07-20
TW201013775A (en) 2010-04-01
KR101248625B1 (ko) 2013-04-02
KR20110050530A (ko) 2011-05-13
CN103035516A (zh) 2013-04-10

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