WO2002025713A1 - Gas compositions for cleaning the interiors of reactors as well as for etching films of silicon-containing compounds - Google Patents

Gas compositions for cleaning the interiors of reactors as well as for etching films of silicon-containing compounds Download PDF

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Publication number
WO2002025713A1
WO2002025713A1 PCT/JP2001/008233 JP0108233W WO0225713A1 WO 2002025713 A1 WO2002025713 A1 WO 2002025713A1 JP 0108233 W JP0108233 W JP 0108233W WO 0225713 A1 WO0225713 A1 WO 0225713A1
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WO
WIPO (PCT)
Prior art keywords
gas
mol
cleaning
silicon
etching
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Application number
PCT/JP2001/008233
Other languages
French (fr)
Inventor
Akira Sekiya
Katsuya Fukae
Yuki Mitsui
Ginjiro Tomizawa
Original Assignee
Research Institute Of Innovative Technology For The Earth
National Institute Of Advanced Industrial Science And Technology
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Publication date
Application filed by Research Institute Of Innovative Technology For The Earth, National Institute Of Advanced Industrial Science And Technology filed Critical Research Institute Of Innovative Technology For The Earth
Priority to EP01970182.0A priority Critical patent/EP1320875B1/en
Priority to JP2002529826A priority patent/JP3878972B2/en
Publication of WO2002025713A1 publication Critical patent/WO2002025713A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B7/00—Cleaning by methods not provided for in a single other subclass or a single group in this subclass
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/4401—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber
    • C23C16/4405—Cleaning of reactor or parts inside the reactor by using reactive gases
    • 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
    • H01L21/31116—Etching inorganic layers by chemical means by dry-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
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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

Definitions

  • This invention relates to gas compositions comprising fluorine-containing nitrogen compounds, which compositions are useful for cleaning the interior of reactors such as chambers for CVD (chemical vapor deposition) processes or etch proceses used for manufacturing semiconductor devices on substrates.
  • the invention also relates to such gas compositions capable of efficiently etching films of silicon-containing compounds.
  • the gas compositions have little or no tendency to generate an effluent gas stream containing noxious ingredients, such as CF 4 , NF 3 and the like.
  • thin films have been formed by known techniques such as CVD processes.
  • CVD processes e.g. a thin film for semiconductor devices within a CVD chamber
  • the film-forming material is also deposited, though wastefully, on the remaining surfaces exposed to the interior space of the CVD chamber, including, for example, the surfaces of inner walls of chamber, product- holding jigs, pipings, etc.
  • the material which has accumulated on surface areas other than the target area(s) can be accidentally separated therefrom. Consequently, the peeled-off material or particles thereof can often be carried to the target area where a film is being formed or to be formed, and can cause the film to become contaminated therewith. This would prevent the process operation from producing films of satisfactory quality, and thus would lead to decreased yield. Therefore, it is necessary to remove any undesirably deposited material from the chamber at appropriate intervals and clean the chamber. Removal of the obstructive deposits from the interior of CVD chambers has been carried out manually or chemically, by means of cleaning gases.
  • an etchant typically an etching gas
  • Some fundamental properties are generally required for the chamber cleaning gas and the etching gas which both act to remove the materials deposited in the chamber.
  • the cleaning gas should be able to rapidly clean the interior of the CVD chamber, while the etching gas should be able to selectively and rapidly etch the selected area or areas of deposited film. Further properties commonly required for the cleaning and etching gases include, for example, that they do not generate noxious effluent gases and they are environmentally friendly.
  • a class of perfluorocompounds such as CF 4 , C 2 F 6 , SF 6 , NF 3 and the like have been employed in large amounts in the processes for producing semiconductors and other electronic devices, as a gas for either removing the deposited materials or for etching the deposited films.
  • these conventional perfluorocompound gases are stable substances that can last for a long period of time in the atmosphere and it is difficult to treat a waste gas stream omitting the cleaning step or the etching step in which the above-mentioned conventional cleaning or etching gases are employed.
  • the waste gas stream may contain a high level of the cleaning or etching gas ingredient(s) in an undecomposed or undegraded state and the treatment to reduce these to acceptable levels before discharging to the atmosphere is very expensive.
  • fluorine-containing nitrogen compound o fers improved ability to clean deposits comprising silicon- containing compound(s), while generating, during use in a cleaning process , an effluent gas stream containing no noxious compounds, such as CF 4 , NF 3 or the like, that seriously contribute to global warming; also, improved ability to etch a thin film comprising silicon- containing compound(s), while generating, during use in an etching process, an effluent gas stream containing no noxious compounds, such as CF 4 , NF 3 or the like, that seriously contribute to global warming.
  • an object of the invention is to provide a CVD chamber cleaning gas composition which has excellent performance in cleaning deposits comprising silicon-containing compound(s) and, thus, is useful for cleaning the interior of reactors such as chambers for CVD process used for manufacturing semiconductors, and other electronic devices or the like layered on wafer substrates, and which will generate, during use in a cleaning process, an effluent gas stream containing no noxious compounds, such as CF 4 , NF 3 and the like, that seriously contribute to global warming.
  • a further object of the invention is to provide an etching gas composition which offers excellent performance in etching films comprising silicon-containing compound(s) for manufacturing semiconductors, and other electronic devices or the like layered on substrates, and which will generate, during use in an etching process, an effluent gas stream containing no noxious compounds , such as CF 4 or the like, that seriously contribute to global warming.
  • a gas composition for cleaning the interior of CVD chambers which comprises F 3 NO.
  • This first gas composition may comprise further 0 2 and/or an inert gas or gases.
  • the content of F 3 N0 is preferably in the range of 5 - 70 mol % per 100 mol % of the total quantity of the gas ingredients in the composition.
  • an FNO-containing gas composition for cleaning the interior of CVD chambers which comprises FNO in combination with 0 2 .
  • this second gas composition for cleaning CVD chambers comprises 20 - 50 mol % of FNO per 100 mol % of the total quantity of the gas ingredients in the composition.
  • the content of O z in the second gas composition ranges from 50 to 80 mol %.
  • the second gas composition for cleaning CVD chambers may comprise an inert gas or gases in place of the 0 2 , wherein the content of FNO is desirably in the range of 55 - 95 mol % per 100 mol % of the total quantity of the gas ingredients in the composition. Desirably, the content of said inert gas or gases is in the range of 5 - 45 mol %.
  • the second gas composition for cleaning CVD chambers may comprise an inert gas or gases in addition to the FNO and 0 2 , wherein the content of FNO is desirably in the range of 20 - 90 mol % per 100 mol % of the total quantity of the gas ingredients in the composition.
  • Suitable examples of inert gases which may be used in the above-mentioned CVD chamber cleaning gas composition include N 2 , He, Ne, Ar, Kr, Xe and Rn.
  • the F 3 NO-containing and FNO-containing gas compositions for cleaning reactors are, in particular, suitable for use in cleaning the interior of the chambers of CVD equipment.
  • the gas compositions are generally suitable for removing depositions comprising a silicon-containing compound or compounds.
  • Typical examples of the silicon-containing compounds include (1) compounds consisting essentially of silicon; (2) compounds consisting essentially of silicon and at least one of oxygen, nitrogen, fluorine and carbon; and (3) compounds comprising high melting point metal suicides .
  • Etching Gas Compositions include (1) compounds consisting essentially of silicon; (2) compounds consisting essentially of silicon and at least one of oxygen, nitrogen, fluorine and carbon; and (3) compounds comprising high melting point metal suicides .
  • a first etching gas composition suitable for etching films of silicon-containing compounds which is characterized by inclusion of F 3 NO.
  • This first etching gas composition may comprise 0 2 and/or one or more inert gases in addition to the F 3 NO.
  • the content of F 3 NO in the etching gas composition is desirably in the range of 5 - 70 mol % per 100 mol % of the total quantity of the gas ingredients in the composition.
  • a second etching gas composition suitable for etching films of silicon-containing compounds which is characterized by inclusion of FNO and 0 2 and wherein the content of FNO is in the range of 20 - 50 mol % per 100 mol % of the total quantity of the gas ingredients in the composition.
  • the content of the 0 2 is desirably in the range of 50 - 80 mol %.
  • the second etching gas composition may comprise an inert gas or gases in place of the 0 2 , wherein the content of FNO is desirably in the range of 55 - 95 mol % per 100 mol % of the total quantity of the gas ingredients in the composition. Desirably, the content of said inert gas or gases is in the range of 5 - 45 mol %.
  • the second etching gas composition may comprise an inert gas or gases in addition to the FNO and 0 2 , wherein the content of FNO is desirably in the range of 20 - 90 mol % per 100 mol % of the total quantity of the gas ingredients in the composition.
  • Suitable examples of the inert gases which may be used in the above-mentioned etching gas compositions include N 2 , He, Ne, Ar, Kr, Xe and Rn.
  • Typical examples of the silicon-containing compounds which may be etched by the above etching gas compositions include:
  • the gas compositions for removing deposits comprising silicon-containing compounds in CVD chambers and for etching film layers comprising silicon-containing compounds in accordance with the invention comprise specific fluorine- containing nitrogen compounds, or combinations thereof with other gas ingredients. These will be described in more detail.
  • the CVD chamber cleaning gas compositions according to the invention comprise F 3 NO (nitrosyl trifluoride) or mixtures thereof with other gas ingredients, or FNO (nitrosyl fluoride) or mixtures thereof with other gas ingredients . These will be explained below.
  • the first chamber cleaning gas compositions of the invention are characterized by inclusion of F 3 NO, which may include further 0 2 or one or more inert gases, or both.
  • the content of F 3 NO employed in the first chamber cleaning gas compositions desirably ranges from 5 to 70 mol %, preferably from 15 to 60 mol % per 100 mol % of the total quantity of the gas ingredients in the compositions .
  • the content of F 3 NO desirably ranges from 5 to 40 mol %, preferably from 10 to 30 mol %, per 100 mol % of the total quantity of the gas ingredients in the compositions.
  • the content of 0 2 desirably ranges from 60 to 95 mol %, preferably from 70 to 90 mol %.
  • the content of F 3 NO desirably ranges from 10 to 70 mol %, preferably from 20 to 60 mol %, per 100 mol % of the total quantity of the gas ingredients in the compositions .
  • the content of said inert gas or gases desirably ranges from 30 to 90 mol %, preferably from 40 to 80 mol %.
  • the content of F 3 NO desirably ranges from 5 to 70 mol %, preferably from 15 to 60 mol %, per 100 mol % of the total quantity of the gas ingredients in the compositions.
  • the content of 0 2 desirably ranges from 25 to 80 mol %, preferably from 30 to 70 mol %.
  • the content of said inert gas or gases desirably ranges from 5 to 50 mol %, preferably from 5 to 30 mol %.
  • the F 3 NO content used in the first chamber cleaning gas compositions falls within the above-mentioned ranges, it is possible to quickly remove the deposits on the surfaces of the interior of the CVD cambers.
  • the cleaning gas compositions include 0 2 and/or inert gas(es) in the above- mentioned ranges, then the cleaning performance of the compositions are enhanced and improved.
  • F 3 NO used in the chamber cleaning gas compositions of the invention In view of the chemical structure and physical and chemical properties of F 3 NO used in the chamber cleaning gas compositions of the invention, it is believed that the compound would have a short lifetime in the atmosphere and would have less impact on global warming. Therefore, only a very slight adverse effect on environment would be caused even if the chamber cleaning gas compositions were discharged into the atmosphere. Further, even when F 3 NO is decomposed or degraded during or after use in the cleaning process, it would emit little or no noxious gases, such as CF 4 , NF 3 and the like, that have high global warming potential and have adverse environmental effects . Furthermore, since F 3 NO has a low boiling point of -87.6°C, it is present in the gas phase when it is used under the conditions employed in the production of semiconductors and other electronic devices. The gaseous F 3 NO or gaseous mixtures containing it may be handled easily in the chamber cleaning operation .
  • F 3 NO may be prepared, for example, by the below-formulated two-stage route, but the preparation is not limited to this route:
  • the inert gases which may be used in the invention include, for example, N 2 , He, Ne, Ar, Kr, Xe, and Rn.
  • FNO-containing gas mixtures the second cleaning gas compositions
  • the second chamber cleaning gas compositions of the invention are characterized by inclusion of FNO in combination with 0 2 and/or one or more inert gases.
  • the content of FNO is desirably in the range of 20 - 50 mol %,and preferably 30 - 45 mol % per 100 mol % of the total quantity of the ingredients in the composition.
  • the content of 0 2 is desirably in the range of 50 - 80 mol %, and preferably 55 - 70 mol %.
  • the content of FNO is desirably in the range of 55 - 95 mol %, and preferably 60 - 90 mol % per 100 mol % of the total quantity of the ingredients in the composition.
  • the content of inert gas or gases is desirably in the range of 5 - 45 mol %, and preferably 10 - 40 mol %.
  • the second chamber cleaning gas composition of the invention comprises FNO, 0 2 and an inert gas or gases
  • the content of FNO is desirably in the range of 20 - 90 mol %, and preferably 30 - 80 mol % per 100 mol % of the total quantity of the ingredients in the composition.
  • the content of the inert gas or gases is desirably in the range of 5 - 50 mol %, and preferably 10 - 40 mol %.
  • FNO has a low boiling point of -59.9°C, it is present in the gas phase, when it is used under the conditions employed in the production of semiconductors and other electronic devices. Therefore, the gaseous FNO or gaseous mixtures containing it may be handled easily in the chamber cleaning operation.
  • FNO may be prepared, for example, by the below-formulated route at a high yield rate, but the preparation is not limited thereto :
  • the inert gases which may be used in the invention include, for example, N 2 , He, Ne, Ar, Kr, Xe, and Rn.
  • Other optional ingredients include, for example, N 2 , He, Ne, Ar, Kr, Xe, and Rn.
  • Other optional ingredients include, for example, N 2 , He, Ne, Ar, Kr, Xe, and Rn.
  • Other optional ingredients include, for example, N 2 , He, Ne, Ar, Kr, Xe, and Rn.
  • the cleaning gas compositions according to the invention may include any other suitable gas or gases unless they behave contrary to the objects of the invention.
  • the optional gases which may be mentioned include 0 3 , H 2 , F 2 , C1F 3 , BrF 3 and the like.
  • the proportions of the optional gases that can be present in the cleaning gas compositions are not critical, provided that the presence thereof in the cleaning gas compositions has no adverse effect on the purpose of the invention.
  • the proportion of a specific optional gas or gases may be determined by some factors , such as the amount , thickness and chemical nature of the deposits on the interior of a reactor of, for example, a CVD apparatus to be cleaned.
  • the expression "to clean a chamber” or any other synonymous expression is intended to mean removal of the films deposited on the surfaces of the inner walls, jigs, pipings, etc. exposed to the inside of chamber for manufacturing semiconductors or other electronic devices.
  • the above-mentioned gas compositions comprising the specific fluorine-containing nitrogen compounds, oxygen and other gases according to the invention may be used advantageously for cleaning CVD chambers, for example CVD equipment .
  • the target substances that are removed from the chamber by the fluorine-containing nitrogen compounds according to the invention may be any deposit comprising the aforementioned silicon-containing compounds that have accumulated on the surfaces of the inner walls of the CVD chamber, jigs, pipings and other parts in the CVD apparatus during operation of the CVD process.
  • Typical examples of the silicon-containing compounds include:
  • Si 3 N 4 and high melting point metal suicides such as WSi, and the like.
  • the material from which the CVD chambers to be cleaned by the chamber cleaning gas compositions of the present invention are prepared is not critical, and may be, for example, stainless steel, aluminum or alloys thereof.
  • the chamber cleaning gas compositions of the present invention can quickly remove the deposits on the surfaces of the inner walls of the CVD chamber, jigs, pipings or other parts in the CVD apparatus, while having no or little adverse effects, such as corrosion, erosion and pitting, on these chamber materials .
  • Removal of the deposits comprising silicon-containing compounds and possibly traces of other substances present in the interior of the CVD chamber using the cleaning gas composition comprised of fluorine-containing nitrogen compounds of the invention may be conducted in any known convenient manner.
  • Various dry cleaning techniques for example, plasma cleaning, remote plasma cleaning and microwave cleaning techniques may be employed.
  • the deposited silicon-containing compounds may be efficiently removed.
  • the gas compositions for etching a thin film of silicon- containing compounds of the invention comprise either (a) F 3 NO or a mixture thereof or (b) FNO or a mixture of FNO. These etching gas compositions will be described below in more detail.
  • the first gas composition for etching a thin film of silicon-containing compounds according to the invention is characterized by inclusion of F 3 NO, which composition may comprise 0 2 and/or one or more inert gases in addition to the F 3 NO.
  • the concentrations of F 3 NO, 0 2 and inert gases in the first etching gas composition are desirably in the same ranges as those for the aforementioned ingredients of the first chamber cleaning gas compositions.
  • the first etching gas compositions containing the ingredients in the specified proportions can rapidly etch a thin film of silicon-containing compounds .
  • the primary ingredient F 3 NO employed in the first etching gas compositions is believed to have a short lifetime in the atmosphere and would contribute less to global warming. Therefore, only a very slight adverse effect on environment would be caused, even if the etching gas compositions were discharged into the atmosphere.
  • the first etching gas compositions can highly selectively attack the films to be processed or etched, it is feasible for them to be employed as substitutes for the conventional etchant gases, such as CF 4 , NF 3 etc.
  • N 2 , He, Ne, Ar, Kr, Xe and Rn may be mentioned.
  • the second gas composition for etching a film layer or layers of silicon-containing compounds according to the invention is characterized by inclusion of FNO, which composition may comprise 0 2 and/or one or more inert gases in addition to the FNO.
  • FNO which composition may comprise 0 2 and/or one or more inert gases in addition to the FNO.
  • the contents of FNO, 0 2 and inert gases in the second etching gas composition are desirably in the same ranges as those for the ingredients of the second chamber cleaning gas compositions that were mentioned hereinbefore.
  • the second etching gas compositions containing the ingredients in the specified proportions can rapidly etch a film layer or layers of silicon-containing compounds.
  • the primary ingredient FNO employed in the second etching gas compositions decomposes or degrades during or after use of the second etching gas composition in the etching process, it would emit little or no noxious gases, such as CF 4 , NF 3 and the like that have high global warming potential and adverse environmental effects.
  • the FNO is believed to have a short lifetime in the atmosphere and contribute less to global warming. Therefore, only a very slight adverse effect on the environment would be caused, even if the etching gas compositions were discharged into the atmosphere .
  • the second etching gas compositions can highly selectively attack the films to be processed or etched, it is feasible for them to be employed as substitutes for the conventional etchant gases, such as CF 4 , NF 3? etc.
  • N 2 He, Ne, Ar, Kr, Xe and Rn may be mentioned.
  • Other optional ingredients may be mentioned.
  • the etching gas compositions according to the invention may include any other suitable gas or gases as long as they behave in accordance with the objects of the invention.
  • optional gases which may be mentioned include 0 3 , H 2 , F 2 , C1F 3 , BrF 3 and the like.
  • the proportions of the optional gases that can be present in the etching gas compositions are not critical, provided that their presence in the etching gas compositions has no adverse effect on the purpose of the invention.
  • the materials to be etched with the etching gas compositions of the invention include a thin film comprising silicon-containing compounds. Typical examples which may be mentioned are at least one of:
  • Etching of the films comprising silicon-containing compounds by means of the etching gas compositions comprising fluorine-containing nitrogen compounds of the invention may be conducted in any known convenient manner.
  • Various dry etching techniques for example, plasma etching, reactive ion etching and microwave etching techniques may be employed.
  • the conditions under which the present etching gas compositions are employed for etching may be similar to those suitable for application of the known etching techniques.
  • Advantages achieved by the Invention The chamber cleaning gas compositions of the invention show little or no tendency towards generation, during or after use in a cleaning step, of an effluent gas stream containing noxious compounds, such as CF 4 , NF 3 or the like, that could have an effect on global warming.
  • the chamber cleaning gas compositions of the present invention has only a limited effect on the environment .
  • the chamber cleaning gas compositions of the invention may be handled with ease, can quickly remove the films adhering to the interior of the CVD chamber, and have improved cleaning qualities compared to those of conventional cleaning gases.
  • the present gas compositions for etching silicon-containing films show little or no tendency towards generation, during use in an etching process, of an effluent gas stream containing noxious compounds, such as CF 4 , NF 3 or the like, that would have an effect on global warming.
  • Use of the etching gas compositions of the present invention has only a limited effect on the environment.
  • the etching gas compositions according to the invention can efficiently etch silicon-containing films while ensuring high dimensional accuracy of the product semiconductor patterns; they also demonstrate excellent etching capabilities compared to those of conventional etchant gases .
  • EXAMPLE The invention will be further illustrated in detail with reference to the following Examples which are not intended to be restrictive in any way to the scope of the invention.
  • PREPARATION 1 SYNTHESIS OF F 3 NO A dried 200 ml "HASTELLOY"* reactor vessel was charged with 26 g (0.12 mol) of antimony pentafluoride(SbF 5 ) followed by 14.2 g (0.2 mol) of nitrogen trifluoride(NF 3 ) and 8.8 g (0.2 mol) of nitrous oxide(N 2 0) . The mixture was allowed to react at 150°C for a period of 60 hours. The resulting product NF 2 0 + Sb 2 F 1:L ⁇ was treated with 10 g (0.24 mol) of sodium fluoride (NaF) and, then the mixture was allowed to react at 210°C for a period of 20 hours.

Abstract

This invention relates to gas compositions comprising fluorine-containing nitrogen compounds, which compositions are useful for cleaning the interior of reactors, such as those of CVD (chemical vapor deposition) equipment and also for etching films of silicon-containing compounds. Advantageously, the gas compositions are environmentally friendly and have little or no tendency to generate an effluent gas stream containing noxious ingredients, such as CF4, NF3 and the like. There are provided: a gas composition for cleaning the interior of film deposition chambers contaminated with silicic deposition, which comprises F3NO or combinations of F3NO with O2 and/or inert gas(es) or which comprises FNO or a combination of FNO with O2 and/or inert gas(es); and also a similar gas composition for etching films of silicon-containing compounds, e.g. films of semiconductive materials.

Description

DESCRIPTION
GAS COMPOSITIONS FOR CLEANING THE INTERIORS OF REACTORS AS WELL AS FOR ETCHING FILMS OF SILICON-CONTAINING COMPOUNDS
Field of the Invention
This invention relates to gas compositions comprising fluorine-containing nitrogen compounds, which compositions are useful for cleaning the interior of reactors such as chambers for CVD (chemical vapor deposition) processes or etch proceses used for manufacturing semiconductor devices on substrates. The invention also relates to such gas compositions capable of efficiently etching films of silicon-containing compounds. Advantageously, the gas compositions have little or no tendency to generate an effluent gas stream containing noxious ingredients, such as CF4, NF3 and the like. Background of the Invention
To date, in processes for producing thin-film devices, such as for the production of semiconductors , thin films have been formed by known techniques such as CVD processes. In the formation of such a film, e.g. a thin film for semiconductor devices within a CVD chamber, though it is desirable to allow or permit a film-forming material to deposit preferentially over the target area or areas of the wafer substrate or substrates held in the CVD chamber, the film-forming material is also deposited, though wastefully, on the remaining surfaces exposed to the interior space of the CVD chamber, including, for example, the surfaces of inner walls of chamber, product- holding jigs, pipings, etc. Furthermore, during the deposition process, the material which has accumulated on surface areas other than the target area(s) can be accidentally separated therefrom. Consequently, the peeled-off material or particles thereof can often be carried to the target area where a film is being formed or to be formed, and can cause the film to become contaminated therewith. This would prevent the process operation from producing films of satisfactory quality, and thus would lead to decreased yield. Therefore, it is necessary to remove any undesirably deposited material from the chamber at appropriate intervals and clean the chamber. Removal of the obstructive deposits from the interior of CVD chambers has been carried out manually or chemically, by means of cleaning gases. In the production of semiconductors and other electronic devices, it is also necessary to partially remove a layer or layers of various semiconductive materials deposited on a wafer substrate by means of an etchant, typically an etching gas, so as to leave a semiconductor circuit in a pre-determined pattern on the wafer substrate. Some fundamental properties are generally required for the chamber cleaning gas and the etching gas which both act to remove the materials deposited in the chamber. The cleaning gas should be able to rapidly clean the interior of the CVD chamber, while the etching gas should be able to selectively and rapidly etch the selected area or areas of deposited film. Further properties commonly required for the cleaning and etching gases include, for example, that they do not generate noxious effluent gases and they are environmentally friendly. Heretofore, a class of perfluorocompounds, such as CF4, C2F6, SF6, NF3 and the like have been employed in large amounts in the processes for producing semiconductors and other electronic devices, as a gas for either removing the deposited materials or for etching the deposited films.
However, these conventional perfluorocompound gases are stable substances that can last for a long period of time in the atmosphere and it is difficult to treat a waste gas stream omitting the cleaning step or the etching step in which the above-mentioned conventional cleaning or etching gases are employed. The waste gas stream may contain a high level of the cleaning or etching gas ingredient(s) in an undecomposed or undegraded state and the treatment to reduce these to acceptable levels before discharging to the atmosphere is very expensive. These aforementioned problems have been presented by the conventional cleaning and etching gases. Furthermore, it is known that the conventional perfluorocompound gases have very high global warming potential (ITH; 100 years): when compared with carbon dioxide (C02), CF4 exhibits a factor 6,500 times; C2F6 exhibits a factor 9,200 times; SF6 exhibits a factor 23,900 times; and NF3 exhibits a factor 8,000 times, respectively, that of C02. There is a concern that these substances could have a serious effect on the environment .
Under the circumstances, there has been a strong need for a substitute etching or cleaning gas that has a low global warming potential, one which exhibits excellent performance in cleaning deposits of silicon-containing compounds as well as excellent etching performance for the silicon-containing compound films .
Even if a gas itself as used in the cleaning or etching process has no or little effect on the environment, the gas could be subject to decomposition during the cleaning or etching process, at the same time generating noxious gases, such as CF4 and NF3, which last for a long period of time in the atmosphere. Therefore, it is desired to provide a substitute etching or cleaning gas that will not decompose to produce any noxious gas or gases having an adverse effect on the environment.
Thus, the inventors, having focused their efforts on research into the amelioration or elimination of the above- mentioned prior art problems, have now discovered that a particular kind of fluorine-containing nitrogen compound o fers : improved ability to clean deposits comprising silicon- containing compound(s), while generating, during use in a cleaning process , an effluent gas stream containing no noxious compounds, such as CF4, NF3 or the like, that seriously contribute to global warming; also, improved ability to etch a thin film comprising silicon- containing compound(s), while generating, during use in an etching process, an effluent gas stream containing no noxious compounds, such as CF4, NF3 or the like, that seriously contribute to global warming.
The present invention has been developed and accomplished on the basis of the above finding. Accordingly, an object of the invention is to provide a CVD chamber cleaning gas composition which has excellent performance in cleaning deposits comprising silicon-containing compound(s) and, thus, is useful for cleaning the interior of reactors such as chambers for CVD process used for manufacturing semiconductors, and other electronic devices or the like layered on wafer substrates, and which will generate, during use in a cleaning process, an effluent gas stream containing no noxious compounds, such as CF4, NF3 and the like, that seriously contribute to global warming.
A further object of the invention is to provide an etching gas composition which offers excellent performance in etching films comprising silicon-containing compound(s) for manufacturing semiconductors, and other electronic devices or the like layered on substrates, and which will generate, during use in an etching process, an effluent gas stream containing no noxious compounds , such as CF4 or the like, that seriously contribute to global warming. Summary of the Invention CVD Chamber Cleaning Gas Compositions:
In accordance with the first aspect of the invention, there is provided a gas composition for cleaning the interior of CVD chambers, which comprises F3NO. This first gas composition may comprise further 02 and/or an inert gas or gases. The content of F3N0 is preferably in the range of 5 - 70 mol % per 100 mol % of the total quantity of the gas ingredients in the composition. In accordance with the second aspect of the invention, there is provided an FNO-containing gas composition for cleaning the interior of CVD chambers, which comprises FNO in combination with 02. Preferably, this second gas composition for cleaning CVD chambers comprises 20 - 50 mol % of FNO per 100 mol % of the total quantity of the gas ingredients in the composition. Desirably, the content of Oz in the second gas composition ranges from 50 to 80 mol %.
The second gas composition for cleaning CVD chambers may comprise an inert gas or gases in place of the 02, wherein the content of FNO is desirably in the range of 55 - 95 mol % per 100 mol % of the total quantity of the gas ingredients in the composition. Desirably, the content of said inert gas or gases is in the range of 5 - 45 mol %. Alternatively, the second gas composition for cleaning CVD chambers may comprise an inert gas or gases in addition to the FNO and 02, wherein the content of FNO is desirably in the range of 20 - 90 mol % per 100 mol % of the total quantity of the gas ingredients in the composition. Suitable examples of inert gases which may be used in the above-mentioned CVD chamber cleaning gas composition include N2, He, Ne, Ar, Kr, Xe and Rn.
The F3NO-containing and FNO-containing gas compositions for cleaning reactors are, in particular, suitable for use in cleaning the interior of the chambers of CVD equipment. The gas compositions are generally suitable for removing depositions comprising a silicon-containing compound or compounds. Typical examples of the silicon-containing compounds include (1) compounds consisting essentially of silicon; (2) compounds consisting essentially of silicon and at least one of oxygen, nitrogen, fluorine and carbon; and (3) compounds comprising high melting point metal suicides . Etching Gas Compositions :
Further according to the third aspect of the invention, there is provided a first etching gas composition suitable for etching films of silicon-containing compounds, which is characterized by inclusion of F3NO. This first etching gas composition may comprise 02 and/or one or more inert gases in addition to the F3NO. The content of F3NO in the etching gas composition is desirably in the range of 5 - 70 mol % per 100 mol % of the total quantity of the gas ingredients in the composition. According to the fourth aspect of the invention, there is further provided a second etching gas composition suitable for etching films of silicon-containing compounds, which is characterized by inclusion of FNO and 02 and wherein the content of FNO is in the range of 20 - 50 mol % per 100 mol % of the total quantity of the gas ingredients in the composition. The content of the 02 is desirably in the range of 50 - 80 mol %.
The second etching gas composition may comprise an inert gas or gases in place of the 02, wherein the content of FNO is desirably in the range of 55 - 95 mol % per 100 mol % of the total quantity of the gas ingredients in the composition. Desirably, the content of said inert gas or gases is in the range of 5 - 45 mol %. Alternatively, the second etching gas composition may comprise an inert gas or gases in addition to the FNO and 02, wherein the content of FNO is desirably in the range of 20 - 90 mol % per 100 mol % of the total quantity of the gas ingredients in the composition.
Suitable examples of the inert gases which may be used in the above-mentioned etching gas compositions include N2, He, Ne, Ar, Kr, Xe and Rn.
Typical examples of the silicon-containing compounds which may be etched by the above etching gas compositions include:
(1) compounds consisting essentially of silicon; (2) compounds consisting essentially of silicon and at least one of oxygen, nitrogen, fluorine and carbon; and (3) compounds comprising high melting point metal suicides . Embodiments of the Invention
The gas compositions for removing deposits comprising silicon-containing compounds in CVD chambers and for etching film layers comprising silicon-containing compounds in accordance with the invention comprise specific fluorine- containing nitrogen compounds, or combinations thereof with other gas ingredients. These will be described in more detail.
CVD CHAMBER CLEANING GAS COMPOSITIONS:
The CVD chamber cleaning gas compositions according to the invention comprise F3NO (nitrosyl trifluoride) or mixtures thereof with other gas ingredients, or FNO (nitrosyl fluoride) or mixtures thereof with other gas ingredients . These will be explained below.
FaNO and mixtures thereof (the first cleaning gas compositions) The first chamber cleaning gas compositions of the invention are characterized by inclusion of F3NO, which may include further 02 or one or more inert gases, or both. The content of F3NO employed in the first chamber cleaning gas compositions desirably ranges from 5 to 70 mol %, preferably from 15 to 60 mol % per 100 mol % of the total quantity of the gas ingredients in the compositions .
In the case where the first chamber cleaning gas compositions comprise F3NO and 02, the content of F3NO desirably ranges from 5 to 40 mol %, preferably from 10 to 30 mol %, per 100 mol % of the total quantity of the gas ingredients in the compositions. The content of 02 desirably ranges from 60 to 95 mol %, preferably from 70 to 90 mol %.
In the case where the first chamber cleaning gas compositions comprise F3NO and one or more inert gases, the content of F3NO desirably ranges from 10 to 70 mol %, preferably from 20 to 60 mol %, per 100 mol % of the total quantity of the gas ingredients in the compositions . The content of said inert gas or gases desirably ranges from 30 to 90 mol %, preferably from 40 to 80 mol %. Further, in the case where the first chamber cleaning gas compositions comprise F3NO, 02 and one or more inert gases, the content of F3NO desirably ranges from 5 to 70 mol %, preferably from 15 to 60 mol %, per 100 mol % of the total quantity of the gas ingredients in the compositions. The content of 02 desirably ranges from 25 to 80 mol %, preferably from 30 to 70 mol %. The content of said inert gas or gases desirably ranges from 5 to 50 mol %, preferably from 5 to 30 mol %. Where the F3NO content used in the first chamber cleaning gas compositions falls within the above-mentioned ranges, it is possible to quickly remove the deposits on the surfaces of the interior of the CVD cambers. Where the cleaning gas compositions include 02 and/or inert gas(es) in the above- mentioned ranges, then the cleaning performance of the compositions are enhanced and improved.
In view of the chemical structure and physical and chemical properties of F3NO used in the chamber cleaning gas compositions of the invention, it is believed that the compound would have a short lifetime in the atmosphere and would have less impact on global warming. Therefore, only a very slight adverse effect on environment would be caused even if the chamber cleaning gas compositions were discharged into the atmosphere. Further, even when F3NO is decomposed or degraded during or after use in the cleaning process, it would emit little or no noxious gases, such as CF4, NF3 and the like, that have high global warming potential and have adverse environmental effects . Furthermore, since F3NO has a low boiling point of -87.6°C, it is present in the gas phase when it is used under the conditions employed in the production of semiconductors and other electronic devices. The gaseous F3NO or gaseous mixtures containing it may be handled easily in the chamber cleaning operation .
F3NO may be prepared, for example, by the below-formulated two-stage route, but the preparation is not limited to this route:
NF3 + N20 + 2SbF5 → NF20+Sb2F1:J + N2 NF20+Sb2Fxl " + 2NaF → F3N0 + 2NaSbF6 The inert gases which may be used in the invention include, for example, N2, He, Ne, Ar, Kr, Xe, and Rn. FNO-containing gas mixtures (the second cleaning gas compositions)
The second chamber cleaning gas compositions of the invention are characterized by inclusion of FNO in combination with 02 and/or one or more inert gases. In the case where the second chamber cleaning gas composition of the invention comprises FNO and 02, the content of FNO is desirably in the range of 20 - 50 mol %,and preferably 30 - 45 mol % per 100 mol % of the total quantity of the ingredients in the composition. The content of 02 is desirably in the range of 50 - 80 mol %, and preferably 55 - 70 mol %.
Further, in the case where the second chamber cleaning gas composition of the invention comprises FNO and an inert gas or gases, the content of FNO is desirably in the range of 55 - 95 mol %, and preferably 60 - 90 mol % per 100 mol % of the total quantity of the ingredients in the composition. The content of inert gas or gases is desirably in the range of 5 - 45 mol %, and preferably 10 - 40 mol %. Furthermore, in the case where the second chamber cleaning gas composition of the invention comprises FNO, 02 and an inert gas or gases , the content of FNO is desirably in the range of 20 - 90 mol %, and preferably 30 - 80 mol % per 100 mol % of the total quantity of the ingredients in the composition. The content of the inert gas or gases is desirably in the range of 5 - 50 mol %, and preferably 10 - 40 mol %.
Where the content of FNO, 02 and inert gas(es) used in the second chamber cleaning gas compositions falls within the above-mentioned ranges, it is possible to quickly remove the deposits on the surfaces of the interior of the CVD chambers.
In view of the chemical structure and physical and chemical properties of FNO, it is believed that the compound would have a short lifetime in the atmosphere and contribute less to global warming. Therefore, only a very slight adverse effect on environment would be caused if the chamber cleaning gas compositions were discharged into the atmosphere.
Further, even when FNO decomposes during use of the second cleaning gas composition in the cleaning step, it would emit little or no noxious gases, such as CF4, NF3 and the like, that have high global warming potential and have an adverse effect on the environment.
Furthermore, since FNO has a low boiling point of -59.9°C, it is present in the gas phase, when it is used under the conditions employed in the production of semiconductors and other electronic devices. Therefore, the gaseous FNO or gaseous mixtures containing it may be handled easily in the chamber cleaning operation. FNO may be prepared, for example, by the below-formulated route at a high yield rate, but the preparation is not limited thereto :
F2 + 2NO → 2FNO The inert gases which may be used in the invention include, for example, N2, He, Ne, Ar, Kr, Xe, and Rn. Other optional ingredients :
The cleaning gas compositions according to the invention may include any other suitable gas or gases unless they behave contrary to the objects of the invention. Examples of the optional gases which may be mentioned include 03, H2, F2, C1F3, BrF3 and the like. The proportions of the optional gases that can be present in the cleaning gas compositions are not critical, provided that the presence thereof in the cleaning gas compositions has no adverse effect on the purpose of the invention. The proportion of a specific optional gas or gases may be determined by some factors , such as the amount , thickness and chemical nature of the deposits on the interior of a reactor of, for example, a CVD apparatus to be cleaned. As used herein, the expression "to clean a chamber" or any other synonymous expression is intended to mean removal of the films deposited on the surfaces of the inner walls, jigs, pipings, etc. exposed to the inside of chamber for manufacturing semiconductors or other electronic devices. The above-mentioned gas compositions comprising the specific fluorine-containing nitrogen compounds, oxygen and other gases according to the invention may be used advantageously for cleaning CVD chambers, for example CVD equipment .
The target substances that are removed from the chamber by the fluorine-containing nitrogen compounds according to the invention may be any deposit comprising the aforementioned silicon-containing compounds that have accumulated on the surfaces of the inner walls of the CVD chamber, jigs, pipings and other parts in the CVD apparatus during operation of the CVD process. Typical examples of the silicon-containing compounds include:
(1) compounds consisting essentially of silicon,
(2) compounds consisting essentially of silicon and at least one of oxygen, nitrogen, fluorine and carbon, and
(3) compounds comprising high melting point metal suicides. Particular examples that may be mentioned include Si, Si02,
Si3N4 and high melting point metal suicides, such as WSi, and the like.
The material from which the CVD chambers to be cleaned by the chamber cleaning gas compositions of the present invention are prepared is not critical, and may be, for example, stainless steel, aluminum or alloys thereof.
The chamber cleaning gas compositions of the present invention can quickly remove the deposits on the surfaces of the inner walls of the CVD chamber, jigs, pipings or other parts in the CVD apparatus, while having no or little adverse effects, such as corrosion, erosion and pitting, on these chamber materials . Removal of the deposits comprising silicon-containing compounds and possibly traces of other substances present in the interior of the CVD chamber using the cleaning gas composition comprised of fluorine-containing nitrogen compounds of the invention may be conducted in any known convenient manner. Various dry cleaning techniques, for example, plasma cleaning, remote plasma cleaning and microwave cleaning techniques may be employed. Thus, by means of the chamber cleaning gas compositions according to the invention, the deposited silicon-containing compounds may be efficiently removed.
GAS COMPOSITIONS FOR ETCHING FILMS OF SILICON-CONTAINING COMPOUNDS :
The gas compositions for etching a thin film of silicon- containing compounds of the invention comprise either (a) F3NO or a mixture thereof or (b) FNO or a mixture of FNO. These etching gas compositions will be described below in more detail.
FaNO and mixtures thereof (the first etching gas compositions)
As mentioned hereinbefore, the first gas composition for etching a thin film of silicon-containing compounds according to the invention is characterized by inclusion of F3NO, which composition may comprise 02 and/or one or more inert gases in addition to the F3NO. The concentrations of F3NO, 02 and inert gases in the first etching gas composition are desirably in the same ranges as those for the aforementioned ingredients of the first chamber cleaning gas compositions. The first etching gas compositions containing the ingredients in the specified proportions can rapidly etch a thin film of silicon-containing compounds .
In view of its chemical structure and chemical and physical properties , the primary ingredient F3NO employed in the first etching gas compositions is believed to have a short lifetime in the atmosphere and would contribute less to global warming. Therefore, only a very slight adverse effect on environment would be caused, even if the etching gas compositions were discharged into the atmosphere.
Further, even when F3NO decomposes during use of the first etching gas composition in the etching process, it would emit little or no noxious gases, such as CF4, NF3 and the like, that have high global warming potential and adverse environmental effects.
Furthermore, because the first etching gas compositions can highly selectively attack the films to be processed or etched, it is feasible for them to be employed as substitutes for the conventional etchant gases, such as CF4, NF3 etc.
As inert gases that may be incorporated into the first etching gas compositions according to the invention, N2, He, Ne, Ar, Kr, Xe and Rn may be mentioned. FNO and mixtures thereof (the second etching gas compositions)
As mentioned hereinbefore, the second gas composition for etching a film layer or layers of silicon-containing compounds according to the invention is characterized by inclusion of FNO, which composition may comprise 02 and/or one or more inert gases in addition to the FNO. The contents of FNO, 02 and inert gases in the second etching gas composition are desirably in the same ranges as those for the ingredients of the second chamber cleaning gas compositions that were mentioned hereinbefore. The second etching gas compositions containing the ingredients in the specified proportions can rapidly etch a film layer or layers of silicon-containing compounds. Even when the primary ingredient FNO employed in the second etching gas compositions decomposes or degrades during or after use of the second etching gas composition in the etching process, it would emit little or no noxious gases, such as CF4, NF3 and the like that have high global warming potential and adverse environmental effects. In view of its chemical structure and chemical and physical properties, the FNO is believed to have a short lifetime in the atmosphere and contribute less to global warming. Therefore, only a very slight adverse effect on the environment would be caused, even if the etching gas compositions were discharged into the atmosphere .
Furthermore, because the second etching gas compositions can highly selectively attack the films to be processed or etched, it is feasible for them to be employed as substitutes for the conventional etchant gases, such as CF4, NF3? etc.
As inert gases that may be incorporated into the second etching gas compositions according to the invention, N2, He, Ne, Ar, Kr, Xe and Rn may be mentioned. Other optional ingredients :
The etching gas compositions according to the invention may include any other suitable gas or gases as long as they behave in accordance with the objects of the invention. Examples of optional gases which may be mentioned include 03, H2, F2, C1F3, BrF3 and the like. The proportions of the optional gases that can be present in the etching gas compositions are not critical, provided that their presence in the etching gas compositions has no adverse effect on the purpose of the invention.
The materials to be etched:
The materials to be etched with the etching gas compositions of the invention include a thin film comprising silicon-containing compounds. Typical examples which may be mentioned are at least one of:
(1) compounds consisting essentially of silicon,
(2) compounds consisting essentially of silicon and at least one of oxygen, nitrogen, fluorine and carbon, and
(3) compounds comprising high melting point metal suicides. Particular examples that may be mentioned include Si film, Si02 film, Si3N4 film and films of high melting point metal suicides, such as WSi, and the like.
Etching of the films comprising silicon-containing compounds by means of the etching gas compositions comprising fluorine-containing nitrogen compounds of the invention may be conducted in any known convenient manner. Various dry etching techniques, for example, plasma etching, reactive ion etching and microwave etching techniques may be employed. The conditions under which the present etching gas compositions are employed for etching may be similar to those suitable for application of the known etching techniques. Advantages achieved by the Invention: The chamber cleaning gas compositions of the invention show little or no tendency towards generation, during or after use in a cleaning step, of an effluent gas stream containing noxious compounds, such as CF4, NF3 or the like, that could have an effect on global warming. Use of the chamber cleaning gas compositions of the present invention has only a limited effect on the environment . The chamber cleaning gas compositions of the invention may be handled with ease, can quickly remove the films adhering to the interior of the CVD chamber, and have improved cleaning qualities compared to those of conventional cleaning gases.
Furthermore, the present gas compositions for etching silicon-containing films show little or no tendency towards generation, during use in an etching process, of an effluent gas stream containing noxious compounds, such as CF4, NF3 or the like, that would have an effect on global warming. Use of the etching gas compositions of the present invention has only a limited effect on the environment. The etching gas compositions according to the invention can efficiently etch silicon-containing films while ensuring high dimensional accuracy of the product semiconductor patterns; they also demonstrate excellent etching capabilities compared to those of conventional etchant gases . EXAMPLE The invention will be further illustrated in detail with reference to the following Examples which are not intended to be restrictive in any way to the scope of the invention. PREPARATION 1: SYNTHESIS OF F3NO A dried 200 ml "HASTELLOY"* reactor vessel was charged with 26 g (0.12 mol) of antimony pentafluoride(SbF5) followed by 14.2 g (0.2 mol) of nitrogen trifluoride(NF3) and 8.8 g (0.2 mol) of nitrous oxide(N20) . The mixture was allowed to react at 150°C for a period of 60 hours. The resulting product NF20+Sb2F1:L ~ was treated with 10 g (0.24 mol) of sodium fluoride (NaF) and, then the mixture was allowed to react at 210°C for a period of 20 hours. The reaction product was subjected to isolation and purification to yield 3.5 g (0.04 mol) of F3NO. The resulting product was analyzed by gas chromatography and FT-IR and identified to be F3NO thereby. The yield was 20% on the basis of the starting nitrogen trifluoride. (* a trade name of an alloy commercially available from Hayness Stellite Co.) PREPARATION 2: SYNTHESIS OF FNO A dried, 100 ml nickel reactor vessel was charged with 6.0 g (0.20 mol) of nitrogen monoxide followed with 1.34 liters of fluorine gas that had been diluted to 20 mol % (equal to 0.12 mol of F2) . The mixture was allowed to react at 30°C for one hour. The reaction products were subjected to isolation and purification to yield 8.8 g (0.18 mol) of FNO. The resulting product was analyzed by gas chromatography and FT-IR. The product compound was identified to be FNO thereby. The yield was 90% on the basis of the starting nitrogen monoxide. EXAMPLES 1 - 7 Chamber cleaning test :
Samples of F3NO as produced in the above PREPARATION 1 were mixed with oxygen or argon (Ar) in various proportions as shown in TABLE 1.
A sample of silicon wafer having an Si02 film deposited over the surface thereof was placed in a CVD chamber and subjected to a cleaning test using one of the gas mixtures shown in TABLE 1 , under the following cleaning conditions : a pressure of 110 Pa; an input Rf power of 290 W; and a total gas flow rate of 60 seem. The cleaning procedure under these conditions was performed for a period of 2 minutes . The results of cleaning performance for each of the test cleaning gas compositions are shown in TABLE 1 below. TABLE 1
Figure imgf000022_0001
EXAMPLES 8 - 13
Chamber cleaning test :
Samples of FNO as produced in the above PREPARATION 2 were mixed with oxygen or argon (Ar) in various proportions as shown in TABLE 2 and subjected to the Si02 film cleaning test under the same conditions as used in the previous Examples. The results are set forth in TABLE 2 below. TABLE 2
Figure imgf000023_0001
COMPARATIVE EXAMPLES 1 - 3
Chamber cleaning test with conventional cleaning gas compositions :
The cleaning test procedure in the previous EXAMPLES was substantially repeated using some conventional cleaning gas compositions as shown in TABLE 3. The results are set forth in TABLE 3.
TABLE 3
Figure imgf000023_0002
From the cleaning test results of the above Examples, the feasibility of the present etching gas compositions is proved beyond doubt.

Claims

1. A gas composition for cleaning the interior of CVD chambers, which comprises F3NO.
2. A gas composition for cleaning the interior of CVD chambers, which comprises F3NO and 02.
3. A gas composition for cleaning the interior of CVD chambers, which comprises F3NO, 02 and one or more inert gases.
4. A gas composition for cleaning the interior of CVD chambers, which comprises F3NO and one or more inert gases .
5. The gas composition for cleaning the interior of CVD chambers according to any one of the preceding claims 1 - 4, in which the content of said F3NO is in the range of 5 - 70 mol % per 100 mol % of the total content of the gas ingredients in said composition. .
6. A gas composition for cleaning the interior of CVD chambers, which comprises FNO and 02, the content of said FNO being in the range of 20 - 50 mol % per 100 mol % of the total quantity of the gas ingredients in said composition.
7. The gas composition for cleaning the interior of CVD chambers according to claim 6, in which the content of said 02 is in the range of 50 - 80 mol %.
8. A gas composition for cleaning the interior of CVD chambers, which comprises FNO and one or more inert gases, the content of said FNO being in the range of 55 - 95 mol % per 100 mol % of the total quantity of the gas ingredients in said composition.
9. The gas composition for cleaning the interior of CVD chambers according to claim 8, in which the content of said inert gas or gases is in the range of 5 - 45 mol % per 100 mol % of the total quantity of the gas ingredients in said composition.
10. A gas composition for cleaning the interior of CVD chambers, which comprises FNO, 02 and one or more inert gases, the content of said FNO being in the range of 20 - 90 mol % per 100 mol % of the total quantity of the gas ingredients in said composition.
11. The gas composition for cleaning the interior of CVD chambers according to any one of claims 3, 4, 5, 8, 9 and 10, in which said inert gas or gases are selected from the group consisting of N2, He, Ne, Ar, Kr, Xe and Rn.
12. The gas composition for cleaning the interior of CVD chambers according to any one of claims 1 - 11, in which the chamber to be cleaned is the CVD chamber.
13. The gas composition for cleaning the interior of CVD chambers according to any one of claims 1 - 12, which is to be used for removing a deposit consisting of a silicon containing- compound or compounds in the interior of said chambers .
14. The gas composition for cleaning the interior of CVD chambers according to claim 13, in which said silicon containing-compound or compounds are at least one selected from the group consisting of: (1) compounds consisting essentially of silicon, (2) compounds consisting essentially of silicon and at least one of oxygen, nitrogen, fluorine and carbon, and (3) compounds comprising high melting point metal suicides.
15. A gas composition for etching a thin film comprising a silicon-containing compound or compounds, which gas composition comprises F3NO.
16. A gas composition for etching a thin film comprising a silicon-containing compound or compounds, which gas composition comprises F3NO and 02.
17. A gas composition for etching a thin film comprising a silicon-containing compound or compounds, which gas composition comprises F3NO, 02 and an inert gas or gases.
18. A gas composition for etching a thin film comprising a silicon-containing compound or compounds, which gas composition comprises F3NO and an inert gas or gases .
19. The gas composition for etching a thin film comprising a silicon-containing compound or compounds according to any one of claims 15 - 18, in which the content of said F3NO is in the range of 5 - 70 mol % per 100 mol % of the total quantity of the gas ingredients in said composition.
20. A gas composition for etching a thin film comprising a silicon-containing compound or compounds, which gas composition comprises FNO and 02, the content of said FNO being in the range of 20 - 50 mol % per 100 mol % of the total quantity of the gas ingredients in said composition.
21. The gas composition for etching a thin film comprising a silicon-containing compound or compounds according to claim 20 in which the content of said Oz is in the range of 50 - 80 mol % .
22. A gas composition for etching a thin film comprising a silicon-containing compound or compounds which gas composition comprises FNO and one or more inert gases , the content of said FNO being in the range of 55 - 95 mol % per 100 mol % of the total quantity of the gas ingredients in said composition.
23. The gas composition for etching a thin film comprising a silicon-containing compound or compounds according to claim
22, in which the content of said inert gas or gases is in the range of 5 - 45 mol % per 100 mol % of the total quantity of the gas ingredients in said composition.
24. A gas composition for etching a thin film comprising a silicon-containing compound or compounds, which gas composition comprises FNO, 02 and one or more inert gases, the content of said FNO being in the range of 20 - 90 mol % per 100 mol % of the total quantity of the gas ingredients in said composition.
25. The gas composition for etching a thin film comprising a silicon-containing compound or compounds according to any one of claims 17, 18, 19, 22, 23 and 24, in which said inert gas or gases are selected from the group consisting of N2, He, Ne, Ar, Kr, Xe and Rn.
26. The gas composition for etching a thin film comprising a silicon-containing compound or compounds according to any one of claims 15 - 25, in which said silicon containing-compound or compounds are at least one selected from the group consisting of:
(1) compounds consisting essentially of silicon, (2) compounds consisting essentially of silicon and at least one of oxygen, nitrogen, fluorine and carbon, and (3) compounds comprising high melting point metal suicides.
PCT/JP2001/008233 2000-09-25 2001-09-21 Gas compositions for cleaning the interiors of reactors as well as for etching films of silicon-containing compounds WO2002025713A1 (en)

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EP1320875A4 (en) 2008-01-23
US20030143846A1 (en) 2003-07-31
JP2004511088A (en) 2004-04-08
EP1320875B1 (en) 2015-08-12
EP1320875A1 (en) 2003-06-25
EP2372753A1 (en) 2011-10-05
EP2372753B1 (en) 2013-01-16

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