US20060207504A1 - Film formation method and apparatus for semiconductor process - Google Patents

Film formation method and apparatus for semiconductor process Download PDF

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US20060207504A1
US20060207504A1 US11/367,339 US36733906A US2006207504A1 US 20060207504 A1 US20060207504 A1 US 20060207504A1 US 36733906 A US36733906 A US 36733906A US 2006207504 A1 US2006207504 A1 US 2006207504A1
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gas
mixture
process gas
supply
field
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Kazuhide Hasebe
Mitsuhiro Okada
Chaeho Kim
Byounghoon Lee
Pao-Hwa Chou
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Tokyo Electron Ltd
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Tokyo Electron Ltd
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Publication of US20060207504A1 publication Critical patent/US20060207504A1/en
Priority to US12/167,270 priority Critical patent/US8343594B2/en
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • C23C16/455—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 characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45512—Premixing before introduction in the reaction chamber
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C23C16/22—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 deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • C23C16/345—Silicon nitride
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C23C16/455—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 characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
    • C23C16/45531—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations specially adapted for making ternary or higher compositions
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C23C16/455—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 characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
    • C23C16/45536—Use of plasma, radiation or electromagnetic fields
    • C23C16/45542—Plasma being used non-continuously during the ALD reactions
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C23C16/455—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 characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C23C16/455—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 characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45563—Gas nozzles
    • C23C16/45578—Elongated nozzles, tubes with holes
    • 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
    • C23C16/50—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 using electric discharges
    • C23C16/505—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 using electric discharges using radio frequency discharges
    • C23C16/509—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 using electric discharges using radio frequency discharges using internal electrodes
    • 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
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/0217—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz
    • 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
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    • H01L21/02107—Forming insulating materials on a substrate
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    • H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
    • H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
    • H01L21/02211—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound being a silane, e.g. disilane, methylsilane or chlorosilane
    • 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
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
    • H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
    • H01L21/02219—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and nitrogen
    • 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
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    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H01L21/02274—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]
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Definitions

  • the present invention relates to a film formation apparatus and method for a semiconductor process for forming a thin film on a target substrate, such as a semiconductor wafer.
  • semiconductor process used herein includes various kinds of processes which are performed to manufacture a semiconductor device or a structure having wiring layers, electrodes, and the like to be connected to a semiconductor device, on a target substrate, such as a semiconductor wafer or a glass substrate used for an LCD (Liquid Crystal Display) or FPD (Flat Panel Display), by forming semiconductor layers, insulating layers, and conductive layers in predetermined patterns on the target substrate.
  • a target substrate such as a semiconductor wafer
  • various processes such as film formation, etching, oxidation, diffusion, reformation, annealing, and natural oxide film removal.
  • Jpn. Pat. Appln. KOKAI Publication No. 6-34974 discloses a semiconductor processing method of this kind performed in a vertical heat-processing apparatus (of the so-called batch type).
  • semiconductor wafers are first transferred from a wafer cassette onto a vertical wafer boat and supported thereon at intervals in the vertical direction.
  • the wafer cassette can store, e.g., 25 wafers, while the wafer boat can support 30 to 150 wafers.
  • the wafer boat is loaded into a process container from below, and the process container is airtightly closed.
  • a predetermined heat process is performed, while the process conditions, such as process gas flow rate, process pressure, and process temperature, are controlled.
  • silicon oxide films are mainly used as insulating films for semiconductor devices.
  • silicon nitride films Si 3 N 4 films
  • silicon nitride films are disposed as films resistant to oxidation, films for preventing impurity diffusion, and sidewall films of gate electrode structures. Since silicon nitride films provide a low coefficient of impurity diffusion and a good barrier property against oxidation, they are very suitable as insulating films for the purpose described above. Further, boron nitride films (BN films) have also attracted attention for the same reasons.
  • DCS and NH 3 are supplied as a silane family gas and a nitriding gas, respectively, to form a silicon nitride film (SiN)
  • the process is performed, as follows. Specifically, DCS and NH 3 gas are alternately and intermittently supplied into a process container with purge periods interposed therebetween.
  • an RF radio frequency
  • DCS is supplied into the process container
  • a layer with a thickness of one molecule or more of DCS is adsorbed onto the surface of wafers.
  • the superfluous DCS is removed during the purge period.
  • NH 3 is supplied and plasma is generated, thereby performing low temperature nitridation to form a silicon nitride film.
  • silicon nitride films have a relatively high dielectric constant, which increases parasitic capacitance and thus is problematic. Specifically, with an increase in parasitic capacitance, the mobility of electrons is suppressed, so the device operation speed decreases. Further, where a silicon nitride film is used for a sensor of the charge storage type, there is a problem in that parasitic capacitance increases a background level.
  • Jpn. Pat. Appln. KOKAI Publication No. 2004-6801 discloses a method of forming a silicon nitride film doped with boron (B) as an impurity, by CVD (Chemical Vapor Deposition). Silicon nitride films doped with boron (SiBN) have not only a low coefficient of impurity diffusion and a good barrier property against oxidation, but also a very low dielectric constant, so they are very useful as insulating films.
  • An object of the present invention is to provide an apparatus and method for a semiconductor process, which can uniformly supply a process gas in a small amount, such as a doping gas, into a process container in the vertical direction, thereby improving the inter-substrate uniformity in the composition of deposited films.
  • a film formation apparatus for a semiconductor process comprising:
  • a process container having a process field configured to accommodate a plurality of target substrates stacked at intervals;
  • a support member configured to support the target substrates inside the process field
  • a heater configured to heat the target substrates inside the process field
  • an exhaust system configured to exhaust gas inside the process field
  • a process gas supply system configured to supply process gases to the process field so as to deposit a thin film on the target substrates, wherein the process gases include a first process gas for providing a main material of the thin film, a second process gas for reacting with the first process gas, and a third process gas for providing a sub-material of the thin film;
  • control section configured to control an operation of the apparatus including the process gas supply system
  • process gas supply system comprises
  • a gas mixture tank disposed outside the process container and configured to mix the first and third process gases to form a mixture gas
  • a mixture gas supply line configured to supply the mixture gas from the gas mixture tank to the process field
  • first and third process gas supply circuits configured to supply the first and third process gases to the gas mixture tank, respectively
  • a second process gas supply circuit having a second process gas supply line configured to supply the second process gas to the process field without passing through the gas mixture tank
  • first and second switching valves disposed on the mixture gas supply line and the second process gas supply line, respectively, and
  • control section controls the first and second switching valves to be opened and closed so as to alternately and pulse-wise supply the mixture gas from the gas mixture tank and the second process gas from the second process gas supply circuit to the process field.
  • a film formation apparatus for a semiconductor process comprising:
  • a process container having a process field configured to accommodate a plurality of target substrates stacked at intervals;
  • a support member configured to support the target substrates inside the process field
  • a heater configured to heat the target substrates inside the process field
  • an exhaust system configured to exhaust gas inside the process field
  • a process gas supply system configured to supply process gases to the process field so as to deposit a thin film on the target substrates, wherein the process gases include a first process gas for providing a main material of the thin film, a second process gas for reacting with the first process gas, and a third process gas for providing a sub-material of the thin film, and the third process gas is supplied to the process field in an amount smaller than that of the first process gas;
  • control section configured to control an operation of the apparatus including the process gas supply system
  • process gas supply system comprises
  • a mixture gas supply line configured to mix the first and third process gases to form a mixture gas and supply the mixture gas to the process field
  • first and third process gas supply circuits having first and third process gas supply lines configured to supply the first and third process gases to the mixture gas supply line, respectively,
  • a second process gas supply circuit having a second process gas supply line configured to supply the second process gas to the process field without passing through the mixture gas supply line
  • a first tank disposed on the first process gas supply line immediately before the first switching valve to temporarily store the first process gas
  • control section controls the first, second, and third switching valves to be opened and closed so as to alternately and pulse-wise supply the mixture gas from the mixture gas supply line and the second process gas from the second process gas supply circuit to the process field.
  • a film formation method for a semiconductor process comprising:
  • process gases include a first process gas for providing a main material of the thin film, a second process gas for reacting with the first process gas, and a third process gas for providing a sub-material of the thin film,
  • a film formation method for a semiconductor process comprising:
  • process gases include a first process gas for providing a main material of the thin film, a second process gas for reacting with the first process gas, and a third process gas for providing a sub-material of the thin film, and the third process gas is supplied to the process field in an amount smaller than that of the first process gas,
  • a computer readable medium containing program instructions for execution on a processor, which, when executed by the processor, cause a film formation apparatus for a semiconductor process to execute
  • process gases include a first process gas for providing a main material of the thin film, a second process gas for reacting with the first process gas, and a third process gas for providing a sub-material of the thin film,
  • a computer readable medium containing program instructions for execution on a processor, which, when executed by the processor, cause a film formation apparatus for a semiconductor process to execute
  • process gases include a first process gas for providing a main material of the thin film, a second process gas for reacting with the first process gas, and a third process gas for providing a sub-material of the thin film, and the third process gas is supplied to the process field in an amount smaller than that of the first process gas,
  • FIG. 1 is a sectional view showing a film formation apparatus (vertical CVD apparatus) according to a first embodiment of the present invention
  • FIG. 2 is a sectional plan view showing part of the apparatus shown in FIG. 1 ;
  • FIG. 3 is a timing chart of the gas supply and RF (radio frequency) application of a film formation method according to a first embodiment
  • FIG. 4 is a sectional view showing a film formation apparatus (vertical CVD apparatus) according to a second embodiment of the present invention
  • FIG. 5 is a view showing part of a gas supply system used in a film formation apparatus according to a modification of the second embodiment.
  • FIG. 6 is a block diagram schematically showing the structure of a main control section.
  • the inventors studied problems caused in conventional film formation apparatuses for a semiconductor process, where a plurality of source gases were used to perform a film formation process, such as a process for forming a thin film doped with an impurity. As a result, the inventors have arrived at the findings given below.
  • the source gases includes a main source gas containing a main component element of a deposition film and a doping gas
  • the supply amount of the doping gas is far smaller than the supply amount of the main source gas, in general.
  • the supply amount of the doping gas supplied into a vertical process container is small, a problem arises such that an element derived from the doping gas is taken into deposited films on wafers in varying amounts, depending on the wafer position in the vertical direction. Consequently, the inter-substrate uniformity in the composition of the deposited films tends to be lower. This problem is caused due to differences in the adsorptivity of the source gas relative to the wafer surface and in the flow rate of the source gases.
  • a gas such as a doping gas
  • countermeasures are required to supply the gas at a uniform supply amount in the vertical direction.
  • a gas nozzle having a number of gas spouting holes at predetermined intervals is disposed to extend in the longitudinal direction of the vertical process container, and the doping gas is delivered from the holes.
  • the supply time of the doping gas is shortened to increase the flow rate of the gas per unit time.
  • the flow rate from gas spouting holes at the upstream side tends to be higher than the flow rate from gas spouting holes at the downstream side. In this respect, it is not easy to optimize the dimensions and so forth of gas spouting holes, so as to uniformize the flow rate from the gas spouting holes, for a small gas supply amount.
  • the gas can be mixed with an inactive carrier gas to increase the total flow rate, as a countermeasure.
  • the partial pressure of the doping gas decreases and thus the adsorption rate of the doping gas decreases by that much.
  • FIG. 1 is a sectional view showing a film formation apparatus (vertical CVD apparatus) according to a first embodiment of the present invention.
  • FIG. 2 is a sectional plan view showing part of the apparatus shown in FIG. 1 .
  • the film formation apparatus 2 has a process field configured to be selectively supplied with a first process gas containing dichlorosilane (DCS) gas as a silane family gas, a second process gas containing ammonia (NH 3 ) gas as a nitriding gas, and a third process gas containing BCl 3 gas as a boron-containing gas.
  • the film formation apparatus 2 is configured to form an SIBN (boron doped silicon nitride) film on target substrates by CVD in the process field. Accordingly, the boron-containing gas is used as a doping gas.
  • the process field is further configured to be selectively supplied with a fourth process gas containing C 2 H 4 gas (ethylene gas) as a carbon hydride gas, as needed.
  • the apparatus 2 includes a process container 4 shaped as a cylindrical column with a ceiling and an opened bottom, in which a process field 5 is defined to accommodate and process a plurality of semiconductor wafers (target substrates) stacked at intervals in the vertical direction.
  • the entirety of the process container 4 is made of, e.g., quartz.
  • the top of the process container 4 is provided with a quartz ceiling plate 6 to airtightly seal the top.
  • the bottom of the process container 4 is connected through a seal member 10 , such as an O-ring, to a cylindrical manifold 8 .
  • the process container may be entirely formed of a cylindrical quartz column without a manifold 8 separately formed.
  • the manifold 8 is made of, e.g., stainless steel, and supports the bottom of the process container 4 .
  • a wafer boat 12 made of quartz is moved up and down through the bottom port of the manifold 8 , so that the wafer boat 12 is loaded/unloaded into and from the process container 4 .
  • a number of target substrates or semiconductor wafers W are stacked on a wafer boat 12 .
  • the wafer boat 12 has struts 12 A that can support, e.g., about 50 to 100 wafers having a diameter of 300 mm at essentially regular intervals in the vertical direction.
  • the wafer boat 12 is placed on a table 16 through a heat-insulating cylinder 14 made of quartz.
  • the table 16 is supported by a rotary shaft 20 , which penetrates a lid 18 made of, e.g., stainless steel, and is used for opening/closing the bottom port of the manifold 8 .
  • the portion of the lid 18 where the rotary shaft 20 penetrates is provided with, e.g., a magnetic-fluid seal 22 , so that the rotary shaft 20 is rotatably supported in an airtightly sealed state.
  • a seal member 24 such as an O-ring, is interposed between the periphery of the lid 18 and the bottom of the manifold 8 , so that the interior of the process container 4 can be kept sealed.
  • the rotary shaft 20 is attached at the distal end of an arm 26 supported by an elevating mechanism 25 , such as a boat elevator.
  • the elevating mechanism 25 moves the wafer boat 12 and lid 18 up and down integratedly.
  • the table 16 may be fixed to the lid 18 , so that wafers W are processed without rotation of the wafer boat 12 .
  • a gas supply system is connected to the side of the manifold 8 to supply predetermined process gases to the process field 5 within the process container 4 .
  • the gas supply system includes a second process gas supply circuit 28 , a first process gas supply circuit 30 , a third process gas supply circuit 32 , and a purge gas supply circuit 36 , and, as needed, a fourth process gas supply circuit 34 .
  • the first process gas supply circuit 30 is arranged to supply a first process gas containing a silane family gas, such as DCS (dichlorosilane) gas.
  • the second process gas supply circuit 28 is arranged to supply a second process gas containing a nitriding gas, such as ammonia (NH 3 ) gas.
  • the third process gas supply circuit 32 is arranged to supply a third process gas containing a boron-containing gas (doping gas), such as BC 1 3 gas.
  • the fourth process gas supply circuit 34 is arranged to supply a fourth process gas containing a carbon hydride gas, such as C 2 H 4 gas (ethylene gas).
  • the purge gas supply circuit 36 is arranged to supply an inactive gas, such as N 2 gas, as a purge gas.
  • Each of the first, second, and fourth process gases is mixed with a suitable amount of carrier gas, as needed. However, such a carrier gas will not be mentioned, hereinafter, for the sake of simplicity of explanation.
  • the first, third, and fourth process gas supply circuits 30 , 32 , and 34 are connected to a common mixture gas supply circuit 35 .
  • the mixture gas supply circuit 35 has a gas mixture tank configured to mix the first and third process gases, and further the fourth process gas in addition thereto, as needed.
  • the gas mixture tank 42 is designed to have a volume for uniformly mixing the gases and temporarily store a sufficient supply amount of the mixture gas, such as a volume of, e.g., about four liters (to be changed depending on the gas flow rate).
  • the gas mixture tank 52 is connected to a gas distribution nozzle 40 formed of a quartz pipe through a mixture gas supply line 44 provided with a switching valve 44 A.
  • the second process gas supply circuit 28 is connected to a gas distribution nozzle 38 formed of a quartz pipe.
  • the gas distribution nozzles 38 and 40 penetrate the sidewall of the manifold 8 from the outside and then turn and extend upward.
  • the gas distribution nozzles 38 and 40 respectively have a plurality of gas spouting holes 38 A and 40 A, each set of holes being formed at predetermined intervals in the longitudinal direction (the vertical direction) over all the wafers W on the wafer boat 12 .
  • Each of the gas spouting holes 38 A and 40 A delivers the corresponding process gas almost uniformly in the horizontal direction, so as to form gas flows parallel with the wafers W on the wafer boat 12 .
  • the purge gas supply circuit 36 includes a short gas nozzle 46 , which penetrates the sidewall of the manifold 8 from the outside.
  • the gas mixture tank 52 is connected to gas sources 30 S, 32 S, and 34 S of DCS gas, BC 1 3 gas, and C 2 H 4 gas, respectively, through gas supply lines (gas passages) 50 , 52 , and 54 of the first, third, and fourth process gas supply circuits 30 , 32 , and 34 , respectively.
  • the gas distribution nozzle 38 of the second process gas supply circuit 28 is connected to a gas source 28 S of NH 3 gas through a gas supply line (gas passage) 48 .
  • the nozzle 46 of the purge gas supply circuit 36 is connected to a gas source 36 S of N 2 gas through gas supply lines (gas passage) 56 .
  • the gas supply lines 48 , 50 , 52 , 54 , and 56 are provided with switching valves 48 A, 50 A, 52 A, 54 A, and 56 A and flow rate controllers 48 B, 50 B, 52 B, 54 B, and 56 B, such as mass flow controllers, respectively.
  • NH 3 gas, DCS gas, BCl 3 gas, C 2 H 4 gas, and N 2 gas can be supplied at controlled flow rates.
  • a gas exciting section 66 is formed at the sidewall of the process container 4 in the vertical direction.
  • a long and thin exhaust port 68 for vacuum-exhausting the inner atmosphere is formed by cutting the sidewall of the process container 4 in, e.g., the vertical direction.
  • the gas exciting section 66 has a vertically long and thin opening 70 formed by cutting a predetermined width of the sidewall of the process container 4 , in the vertical direction.
  • the opening 70 is covered with a quartz cover 72 airtightly connected to the outer surface of the process container 4 by welding.
  • the cover 72 has a vertical long and thin shape with a concave cross-section, so that it projects outward from the process container 4 .
  • the gas exciting section 66 is formed such that it projects outward from the sidewall of the process container 4 and is opened on the other side to the interior of the process container 4 .
  • the inner space of the gas exciting section 66 communicates with the process field 5 within the process container 4 .
  • the opening 70 has a vertical length sufficient to cover all the wafers W on the wafer boat 12 in the vertical direction.
  • a pair of long and thin electrodes 74 are disposed on the opposite outer surfaces of the cover 72 , and face each other along the longitudinal direction (the vertical direction).
  • the electrodes 74 are connected to an RF (Radio Frequency) power supply 76 for plasma generation, through feed lines 78 .
  • An RF voltage of, e.g., 13.56 MHz is applied to the electrodes 74 to form an RF electric field for exciting plasma between the electrodes 74 .
  • the frequency of the RF voltage is not limited to 13.56 MHz, and it may be set at another frequency, e.g., 400 kHz.
  • the gas distribution nozzle 38 of the second process gas is bent outward in the radial direction of the process container 4 , at a position lower than the lowermost wafer W on the wafer boat 12 . Then, the gas distribution nozzle 38 vertically extends at the deepest position (the farthest position from the center of the process container 4 ) in the gas exciting section 66 . As shown also in FIG. 2 , the gas distribution nozzle 38 is separated outward from an area sandwiched between the pair of electrodes 74 (a position where the RF electric field is most intense), i.e., a plasma generation area PS where the main plasma is actually generated.
  • the second process gas containing NH 3 gas is spouted from the gas spouting holes 38 A of the gas distribution nozzle 38 toward the plasma generation area PS. Then, the second process gas is excited (decomposed or activated) in the plasma generation area PS, and is supplied in this state onto the wafers W on the wafer boat 12 .
  • An insulating protection cover 80 made of, e.g., quartz is attached on and covers the outer surface of the cover 72 .
  • a cooling mechanism (not shown) is disposed in the insulating protection cover 80 and comprises coolant passages respectively facing the electrodes 74 .
  • the coolant passages are supplied with a coolant, such as cooled nitrogen gas, to cool the electrodes 74 .
  • the insulating protection cover 80 is covered with a shield (not shown) disposed on the outer surface to prevent RF leakage.
  • the gas distribution nozzle 40 of the mixture gas supply circuit 35 is disposed to vertically extend upward.
  • the mixture gas (a mixture gas of the first and third process gases, and further the fourth process gas in addition thereto, as needed) is spouted from the gas spouting holes 40 A of the gas distribution nozzle 40 toward the center of the process container 4 .
  • the exhaust port 68 which is formed opposite the gas exciting section 66 , is covered with an exhaust port cover member 82 .
  • the exhaust port cover member 82 is made of quartz with a U-shape cross-section, and attached by welding.
  • the exhaust cover member 82 extends upward along the sidewall of the process container 4 , and has a gas outlet 84 at the top of the process container 4 .
  • the gas outlet 84 is connected to a vacuum-exhaust system GE including a vacuum pump and so forth.
  • the process container 4 is surrounded by a heater 86 , which is used for heating the atmosphere within the process container 4 and the wafers W.
  • a thermocouple (not shown) is disposed near the exhaust port 68 in the process container 4 to control the heater 86 .
  • the film formation apparatus 2 further includes a main control section 60 formed of, e.g., a computer, to control the entire apparatus.
  • the main control section 60 can control the film formation process described below in accordance with the process recipe of the film formation process concerning, e.g., the film thickness and composition of a film to be formed, stored in the memory 212 thereof in advance.
  • the relationship between the process gas flow rates and the thickness and composition of the film is also stored as control data in advance.
  • the main control section 60 can control the elevating mechanism 25 , gas supply circuits 28 , 30 , 32 , 34 , 35 and 36 , exhaust system GE, gas exciting section 66 , heater 86 , and so forth, based on the stored process recipe and control data.
  • ALD Advanced Layer Deposition
  • a film formation method such as ALD (Atomic Layer Deposition) film formation
  • a third process gas containing BC 1 3 gas as a boron-containing gas are selectively supplied into the process field 5 accommodating wafers W.
  • this film formation method is an example where a fourth process gas containing C 2 H 4 gas (ethylene gas) as a carbon hydride gas is not supplied.
  • the wafer boat 12 at room temperature which supports a number of, e.g., 50 to 100, wafers having a diameter of 300 mm, is loaded into the process container 4 heated at a predetermined temperature, and the process container 4 is airtightly closed. Then, the interior of the process container 4 is vacuum-exhausted and kept at a predetermined process pressure, and the wafer temperature is increased to a process temperature for film formation. At this time, the apparatus is in a waiting state until the temperature becomes stable. Then, while the wafer boat 12 is rotated, the first to third process gases are intermittently supplied from the respective gas distribution nozzles 38 and 40 at controlled flow rates.
  • the first process gas containing DCS gas and the third process gas containing BCl 3 gas are supplied into the gas mixture tank 42 to form a mixture gas.
  • the mixture gas is supplied from the gas spouting holes 40 A of the gas distribution nozzle 40 to form gas flows parallel with the wafers W on the wafer boat 12 . While being supplied, molecules of DCS gas and BC 1 3 gas and molecules and atoms of decomposition products generated by their decomposition are adsorbed on the wafers W.
  • the second process gas containing NH 3 gas is supplied from the gas spouting holes 38 A of the gas distribution nozzle 38 to form gas flows parallel with the wafers W on the wafer boat 12 .
  • the second process gas is selectively excited and partly turned into plasma when it passes through the plasma generation area PS between the pair of electrodes 74 .
  • radicals activated species
  • the symbol ⁇ * ⁇ denotes that it is a radical.
  • the radicals flow out from the opening 70 of the gas exciting section 66 toward the center of the process container 4 , and are supplied into gaps between the wafers W in a laminar flow state.
  • the radicals react with molecules of DCS gas adsorbed on the surface of the wafers W, so that a thin film is formed on the wafers W. Further, at this time, B atoms generated by decomposition of BC 1 3 gas are taken into the thin film, so a film of SiBN doped with boron as an impurity is formed. Alternatively, when DCS gas and BC 1 3 gas flow onto radicals adsorbed on the surface of the wafers W, the same reaction is caused, so an SIBN film doped with boron is formed on the wafers W.
  • FIG. 3 is a timing chart of the gas supply and RF (radio frequency) application of a film formation method according to the first embodiment.
  • the film formation method according to this embodiment is arranged to alternately repeat first to fourth steps T 1 to T 4 .
  • a cycle comprising the first to fourth steps T 1 to T 4 is repeated a number of times, and thin films of SiBN formed by respective cycles are laminated, thereby arriving at an SiBN film having a target thickness.
  • the first step T 1 is arranged to perform supply of the mixture gas of the first process gas (denoted as DCS in FIG. 3 ) and the third process gas (denoted as BCl 3 in FIG. 3 ) to the process field 5 , while stopping supply of the second process gas (denoted as NH 3 in FIG. 3 ) to the process field 5 .
  • the second step T 2 is arranged to stop supply of the mixture gas of the first and third process gases and the second process gas to the process field 5 .
  • the third step T 3 is arranged to perform supply of the second process gas to the process field 5 , while stopping supply of the mixture gas of the first and third process gases to the process field 5 .
  • the RF power supply 76 is set in the ON state to turn the second process gas into plasma by the gas exciting section 66 , so as to supply the second process gas in an activated state to the process field 5 during a sub-step T 3 b.
  • the fourth step T 4 is arranged to stop supply of the mixture gas of the first and third process gases and the second process gas to the process field 5 .
  • the RF power supply 76 is turned on after a predetermined time ⁇ t passes, to turn the second process gas into plasma by the gas exciting section 66 , so as to supply the second process gas in an activated state to the process field 5 during the sub-step T 3 b.
  • the predetermined time ⁇ t is defined as the time necessary for stabilizing the flow rate of NH 3 gas, which is set at, e.g., about 5 seconds.
  • the second process gas may be turned into plasma by the gas exciting section 66 over the entire period of supplying the second process gas. Since the RF power supply is turned on to generate plasma after the flow rate of the second process gas is stabilized, the uniformity of radical concentration among the wafers W (uniformity in the vertical direction) is improved.
  • Each of the second and fourth steps T 2 and T 4 is used as a purge step to remove the residual gas within the process container 4 .
  • the term “purge” means removal of the residual gas within the process container 4 by vacuum-exhausting the interior of the process container 4 while supplying an inactive gas, such as N 2 gas, into the process container 4 , or by vacuum-exhausting the interior of the process container 4 while stopping supply of all the gases.
  • the second and fourth steps T 2 and T 4 may be arranged such that the first half utilizes only vacuum-exhaust and the second half utilizes both vacuum-exhaust and inactive gas supply.
  • first and third steps T 1 and T 3 may be arranged to stop vacuum-exhausting the process container 4 while supplying each of the first to third process gases.
  • the interior of the process container 4 can be continuously vacuum-exhausted over the entirety of the first to fourth steps T 1 to T 4 .
  • the first step T 1 is set to be within a range of about 1 to 20 seconds, and, for example, at about 10 seconds, the second step T 2 is set to be within a range of about 5 to 15 seconds, and, for example, at about 10 seconds, the third step T 3 is set to be within a range of about 1 to 30 seconds, and, for example, at about 20 seconds, the sub-step T 3 b is set to be within a range of about 1 to 25 seconds, and, for example, at about 10 seconds, and the fourth step T 4 is set to be within a range of about 5 to 15 seconds, and, for example, at about 10 seconds.
  • the film thickness obtained by one cycle of the first to fourth steps T 1 to T 4 is about 0.11 to 0.13 nm. Accordingly, for example, where the target film thickness is 70 nm, the cycle is repeated about 600 times.
  • these values of time and thickness are merely examples and thus are not limiting.
  • the process conditions of the film formation process are as follows.
  • the flow rate of DCS gas is set to be within a range of 50 to 2,000 sccm, e.g., at 1,000 sccm (1 slm).
  • the flow rate of NH 3 gas is set to be within a range of 500 to 5,000 sccm, e.g., at 1,000 sccm.
  • the flow rate of BC 1 3 gas is set to be within a range of 1 to 15 sccm, e.g., at 2 sccm. Accordingly, the flow rate of BC 1 3 gas is far smaller than the flow rate of DCS gas.
  • the process temperature is lower than ordinary CVD processes, and is set to be within a range of 300 to 700° C., and preferably a range of 550 to 630° C. If the process temperature is lower than 300° C., essentially no film is deposited because hardly any reaction is caused. If the process temperature is higher than 700° C., a low quality CVD film is deposited, and existing films, such as a metal film, suffer thermal damage.
  • the process pressure is set to be within a range of 13 Pa (0.1 Torr) to 1,330 Pa (10 Torr), and preferably a range of 40 Pa (0.3 Torr) to 266 Pa (2 Torr).
  • the process pressure is set at 1 Torr during the first step (adsorption step) T 1 , and at 0.3 Torr during the third step (nitridation step using plasma) T 3 . If the process pressure is lower than 13 Pa, the film formation rate becomes lower than the practical level. If the process pressure is higher than 1,330 Pa, it becomes difficult to generate plasma.
  • the first process gas containing DCS gas for providing the main material of a thin film, and the third process gas containing BCl 3 gas for providing a sub-material of the thin film are uniformly mixed at first in the gas mixture tank 42 to form a mixture gas.
  • the mixture gas is then intermittently supplied into the process field 5 through a plurality of gas spouting holes 40 A arrayed at intervals in the vertical direction.
  • the amount of BCl 3 gas is small, it can be essentially uniformly distributed within the process container 4 in the vertical direction without using a carrier gas. Consequently, the ratio of the composition elements in SiBN thin films to be formed becomes more uniform, regardless of wafer position.
  • the supply amount of the third process gas is far smaller than the supply amount of the first process gas.
  • the third process gas in a smaller supply amount is made to accompany the first process gas in a larger supply amount, so that it can be uniformly distributed within the process container 4 in the vertical direction.
  • the supply amount of one source gas is 1/100 or less of the supply amount of the other source gas, the above-described effect of uniformizing the ratio of the composition elements in films is more influential.
  • BCl 3 gas When BC 1 3 gas is adsorbed on the wafer surface, the adsorption amount depends on the partial pressure of BC 1 3 gas.
  • BCl 3 gas is supplied into the process container 4 uniformly in the vertical direction without using a carrier gas.
  • the partial pressure of BC 1 3 gas can be higher than that in the case of a carrier gas being used, so adsorption of BCl 3 gas on the wafer surface is promoted. Consequently, while the film formation rate per unit cycle is maintained, the time necessary for one cycle is shortened, so the throughput is improved.
  • a conventional film formation method took about 15 seconds until BCl 3 gas was sufficiently adsorbed on a wafer surface.
  • the present embodiment took only two or three seconds for the same. Accordingly, the conventional method took about 30 seconds for one cycle, while the present embodiment shortened this period to only 8 seconds.
  • the mixture gas may be formed and supplied by either of the following two methods.
  • the first method comprises continuously supplying the first and third process gases from the first and third process gas supply circuits 30 and 32 into the gas mixture tank 42 , while supplying the mixture gas pulse-wise from the gas mixture tank 42 into the process field 5 .
  • the second method comprises simultaneously supplying the first and third process gases pulse-wise in a first phase from the first and third process gas supply circuits 30 and 32 into the gas mixture tank 42 , while supplying the mixture gas pulse-wise in a second phase reverse to the first phase from the gas mixture tank 42 into the process field 5 .
  • the switching valves 50 A and 52 A of the first and third process gas supply circuits 30 and 32 and the switching valve 44 A of the mixture gas supply circuit 35 are opened and closed in accordance with instructions from the main control section 60 , as follows.
  • the switching valves 50 A and 52 A are kept opened and the switching valve 44 A is opened and closed pulse-wise.
  • the switching valves 50 A and 52 A are opened and closed pulse-wise while the switching valve 44 A is closed and opened pulse-wise in the reverse phase.
  • the fourth process gas containing C 2 H 4 gas (ethylene gas) as a carbon hydride gas is not supplied, but the fourth process gas may be supplied, as needed.
  • the fourth process gas is supplied into the gas mixture tank 42 at a controlled flow rate, simultaneously with the first and third process gases.
  • a thin film to be formed is an insulating film of SiBCN (boron doped silicon carbon nitride) containing carbon.
  • FIG. 4 is a sectional view showing a film formation apparatus (vertical CVD apparatus) according to a second embodiment of the present invention.
  • This film formation apparatus 2 X has the same structure as the film formation apparatus 2 shown in FIG. 1 except for the first, third, and fourth process gas supply circuits 30 , 32 , and 34 and the mixture gas supply circuit 35 . Accordingly, an explanation will be give of the film formation apparatus 2 X, focusing on the difference from the film formation apparatus 2 .
  • the first, third, and fourth process gas supply circuits 30 , 32 , and 34 are connected to a common mixture gas supply circuit 35 X.
  • the mixture gas supply circuit 35 X includes a mixture gas supply pipe 40 X configured to mix the first and third process gases, and further the fourth process gas in addition thereto, as needed.
  • the mixture gas supply pipe 40 X is formed of a quartz pipe, which is a proximal end portion of a gas distribution nozzle 40 .
  • the first, third, and fourth process gas supply circuits 30 , 32 , and 34 have tanks 102 , 104 , and 106 , respectively, disposed immediately before the mixture gas supply pipe 40 X to temporarily store the corresponding process gases. Since the tanks 102 and 106 need to handle a large gas flow rate, they are larger than the tank 104 . For example, each of the tanks 102 and 106 has a volume of about four liters, while the tank 104 has a volume of about 0.05 liters (both to be changed depending on the gas flow rate).
  • the tanks 102 , 104 , and 106 are connected to the mixture gas supply pipe 40 X through gas supply lines 103 , 105 , and 107 provided with switching valves 103 A, 105 A, and 107 A, respectively.
  • the tanks 102 , 104 , and 106 of the first, third, and fourth process gas supply circuits 30 , 32 , and 34 are connected to gas sources 30 S, 32 S, and 34 S of DCS gas, BC 1 3 gas, and C 2 H 4 gas, respectively, through gas supply lines (gas passages) 50 , 52 , and 54 .
  • the gas supply lines 50 , 52 , and 54 are provided with switching valves 50 A, 52 A, and 54 A and flow rate controllers 50 B, 52 B, and 54 B, such as mass flow controllers, respectively. With this arrangement, DCS gas, BC 1 3 gas, and C 2 H 4 gas can be supplied at controlled flow rates.
  • ALD Advanced Deposition
  • this film formation method is also an example where a fourth process gas containing C 2 H 4 gas (ethylene gas) as a carbon hydride gas is not supplied.
  • the gas supply and RF (radio frequency) application of this film formation method are performed in accordance with the timing chart shown in FIG. 3 .
  • a mixture gas denoted as DCS+BC 1 3 in FIG.
  • the switching valves 103 A and 105 A are simultaneously opened and closed to supply first and third process gases temporarily stored in the tanks 102 and 104 into the mixture gas supply pipe 40 X and mix them in the pipe 40 X.
  • the mixture gas is supplied from the gas spouting holes 40 A of the gas distribution nozzle 40 to form gas flows parallel with the wafers W on the wafer boat 12 .
  • the mixture gas may be formed and supplied by either of the following two methods (also in the following explanation, the fourth process gas is not supplied).
  • the first method comprises continuously supplying the first and third process gases into the respective tanks 102 and 104 of the first and third process gas supply circuits 30 and 32 , while supplying the gases pulse-wise from the respective tanks 102 and 104 into the mixture gas supply pipe 40 X.
  • the second method comprises simultaneously supplying the first and third process gases pulse-wise in a first phase into the respective tanks 102 and 104 of the first and third process gas supply circuits 30 and 32 , while supplying the gases pulse-wise in a second phase reverse to the first phase from the respective tanks 102 and 104 into the mixture gas supply pipe 40 X.
  • the switching valves 50 A and 52 A of the first and third process gas supply circuits 30 and 32 and the switching valves 103 A and 105 A downstream from the tanks are opened and closed in accordance with instructions from the main control section 60 , as follows.
  • the switching valves 50 A and 52 A are kept opened and the switching valves 103 A and 105 A are opened and closed pulse-wise.
  • the switching valves 50 A and 52 A are opened and closed pulse-wise while the switching valves 103 A and 105 A are closed and opened pulse-wise in the reverse phase.
  • FIG. 5 is a view showing part of a gas supply system used in a film formation apparatus according to a modification of the second embodiment (the fourth process gas supply circuit is not shown).
  • the tank 104 of the third process gas supply circuit 32 is omitted because the flow rate of the third process gas containing BCl 3 gas is far smaller than the flow rate of the first process gas containing DCS gas.
  • the third process gas in a smaller amount is made to be uniformly mixed with the first process gas in a larger amount within the mixture gas supply pipe 40 X, so that the third process gas is uniformly supplied.
  • FIG. 6 is a block diagram schematically showing the structure of the main control section 60 .
  • the main control section 60 includes a CPU 210 , which is connected to a storage section 212 , an input section 214 , and an output section 216 .
  • the storage section 212 stores process programs and process recipes.
  • the input section 214 includes input devices, such as a keyboard, a pointing device, and a storage media drive, to interact with an operator.
  • the output section 216 outputs control signals for controlling components of the processing apparatus.
  • FIG. 6 also shows a storage medium 218 attached to the computer in a removable state.
  • Each of the methods according to the first and second embodiments may be written as program instructions for execution on a processor, into a computer readable storage medium or media to be applied to a semiconductor processing apparatus.
  • program instructions of this kind may be transmitted by a communication medium or media and thereby applied to a semiconductor processing apparatus.
  • the storage medium or media are a magnetic disk (flexible disk, hard disk (a representative of which is a hard disk included in the storage section 212 ), etc.), an optical disk (CD, DVD, etc.), a magneto-optical disk (MO, etc.), and a semiconductor memory.
  • a computer for controlling the operation of the semiconductor processing apparatus reads program instructions stored in the storage medium or media, and executes them on a processor, thereby performing a corresponding method, as described above.
  • the exciting section 66 for generating plasma of the film formation apparatus 2 is integrally combined with the process container 4 .
  • the exciting section 66 may be separately disposed from the process container 4 , so as to excite NH 3 gas outside the process container 4 (so called remote plasma), and then supply the excited NH 3 gas into the process container 4 .
  • NH 3 gas may be supplied without being activated, and, in this case, the members associating with the gas exciting section 66 are not necessary.
  • the process temperature needs to be increased to some extent to compensate for energy decrease due to no plasma being used.
  • the distribution nozzle 40 having a number of gas spouting holes 40 A is used as a nozzle for supplying the mixture gas.
  • a linear or straight pipe similar to the gas nozzle 46 , or a bent or L-shaped pipe may be used for the same purpose.
  • the mixture gas is supplied from below or above the process field 5 .
  • an exhaust port 68 is formed at the top or bottom of the process container 4 to cause the mixture gas to sufficiently flow within the process field 5 in the vertical direction.
  • the first process gas contains DCS gas as a silane family gas.
  • the silane family gas may be one or more gases selected from the group consisting of dichlorosilane (DCS), hexachlorodisilane (HCD), monosilane (SiH 4 ), disilane (Si 2 Cl 6 ), hexamethyl-disilazane (HMDS), tetrachlorosilane (TCS), disilylamine (DSA), trisilylamine (TSA), bistertial-butylaminosilane (BTBAS).
  • DCS dichlorosilane
  • HCD hexachlorodisilane
  • H 4 monosilane
  • Si 2 Cl 6 hexamethyl-disilazane
  • HMDS tetrachlorosilane
  • DSA disilylamine
  • TSA trisilylamine
  • BBAS bistertial-butylaminosilane
  • the second process gas contains a nitriding gas, which may be NH 3 gas or N 2 gas.
  • a nitriding gas such as dinitrogen oxide (N 2 O) or nitrogen oxide (NO)
  • N 2 O dinitrogen oxide
  • NO nitrogen oxide
  • a film to be formed is a film based on silicon oxynitride that contains oxygen (O).
  • the third process gas contains BC 1 3 gas as a boron-containing gas.
  • the boron-containing gas may be one or more gases selected from the group consisting of BC 1 3 , B 2 H 6 , BF 3 , and B(CH 3 ) 3 .
  • the fourth process gas contains ethylene gas as a carbon hydride gas.
  • the carbon hydride gas may be one or more gases selected from the group consisting of acetylene, ethylene, methane, ethane, propane, and butane.
  • an SiBN film or SiBCN film is formed.
  • the present invention may be applied to a process for forming a BCN film (carbon-containing boron nitride film).
  • a boron-containing gas and a carbon hydride gas are used as source gases and mixed.
  • the present invention can be applied to various film formation processes which use a plurality of source gases that does not cause any problem if they are mixed before being supplied into a process container.
  • the present invention may be applied to a film formation process using an oxidizing gas, such as O 2 gas, as a reaction gas.
  • a target substrate is not limited to a semiconductor wafer, and it may be another substrate, such as an LCD substrate or glass substrate.

Abstract

A film formation apparatus for a semiconductor process includes a process gas supply system configured to supply process gases. The process gas supply system includes a gas mixture tank configured to mix first and third process gases to form a mixture gas, a mixture gas supply line configured to supply the mixture gas from the gas mixture tank to a process field, a second process gas supply circuit having a second process gas supply line configured to supply a second process gas to the process field without passing through the gas mixture tank, and first and second switching valves disposed on the mixture gas supply line and the second process gas supply line, respectively. A control section controls the first and second switching valves to be opened and closed so as to alternately and pulse-wise supply the mixture gas and the second process gas to the process field.

Description

    CROSS-REFERENCE TO RELATED APPLICATIONS
  • This application is based upon and claims the benefit of priority from prior Japanese Patent Applications No. 2005-070034, filed Mar. 11, 2005; and No. 2006-004192, filed Jan. 11, 2006, the entire contents of both of which are incorporated herein by reference.
    • BACKGROUND OF THE INVENTION
  • 1. Field of the Invention
  • The present invention relates to a film formation apparatus and method for a semiconductor process for forming a thin film on a target substrate, such as a semiconductor wafer. The term “semiconductor process” used herein includes various kinds of processes which are performed to manufacture a semiconductor device or a structure having wiring layers, electrodes, and the like to be connected to a semiconductor device, on a target substrate, such as a semiconductor wafer or a glass substrate used for an LCD (Liquid Crystal Display) or FPD (Flat Panel Display), by forming semiconductor layers, insulating layers, and conductive layers in predetermined patterns on the target substrate.
  • 2. Description of the Related Art
  • In manufacturing semiconductor devices for constituting semiconductor integrated circuits, a target substrate, such as a semiconductor wafer, is subjected to various processes, such as film formation, etching, oxidation, diffusion, reformation, annealing, and natural oxide film removal. Jpn. Pat. Appln. KOKAI Publication No. 6-34974 discloses a semiconductor processing method of this kind performed in a vertical heat-processing apparatus (of the so-called batch type). According to this method, semiconductor wafers are first transferred from a wafer cassette onto a vertical wafer boat and supported thereon at intervals in the vertical direction. The wafer cassette can store, e.g., 25 wafers, while the wafer boat can support 30 to 150 wafers. Then, the wafer boat is loaded into a process container from below, and the process container is airtightly closed. Then, a predetermined heat process is performed, while the process conditions, such as process gas flow rate, process pressure, and process temperature, are controlled.
  • Conventionally, silicon oxide films (SiO2 films) are mainly used as insulating films for semiconductor devices. However, in recent years, owing to the demands of increased integration and miniaturization of semiconductor integrated circuits, silicon nitride films (Si3N4 films) are used in place of silicon oxide films, as needed (Jpn. Pat. Appln. KOKAI Publication No. 6-34974). For example, silicon nitride films are disposed as films resistant to oxidation, films for preventing impurity diffusion, and sidewall films of gate electrode structures. Since silicon nitride films provide a low coefficient of impurity diffusion and a good barrier property against oxidation, they are very suitable as insulating films for the purpose described above. Further, boron nitride films (BN films) have also attracted attention for the same reasons.
  • For example, where dichlorosilane (DCS) and NH3 are supplied as a silane family gas and a nitriding gas, respectively, to form a silicon nitride film (SiN), the process is performed, as follows. Specifically, DCS and NH3 gas are alternately and intermittently supplied into a process container with purge periods interposed therebetween. When NH3 gas is supplied, an RF (radio frequency) is applied to generate plasma within the process container so as to promote a nitridation reaction. More specifically, when DCS is supplied into the process container, a layer with a thickness of one molecule or more of DCS is adsorbed onto the surface of wafers. The superfluous DCS is removed during the purge period. Then, NH3 is supplied and plasma is generated, thereby performing low temperature nitridation to form a silicon nitride film. These sequential steps are repeated to complete a film having a predetermined thickness.
  • On the other hand, in recent years, increasing the operation speed of semiconductor devices is also an important factor. In this respect, silicon nitride films have a relatively high dielectric constant, which increases parasitic capacitance and thus is problematic. Specifically, with an increase in parasitic capacitance, the mobility of electrons is suppressed, so the device operation speed decreases. Further, where a silicon nitride film is used for a sensor of the charge storage type, there is a problem in that parasitic capacitance increases a background level.
  • Under the circumstances, it has been proposed to dope a silicon nitride film with an impurity, so as to decrease the dielectric constant while maintaining the impurity diffusion coefficient and oxidation barrier property. Jpn. Pat. Appln. KOKAI Publication No. 2004-6801 discloses a method of forming a silicon nitride film doped with boron (B) as an impurity, by CVD (Chemical Vapor Deposition). Silicon nitride films doped with boron (SiBN) have not only a low coefficient of impurity diffusion and a good barrier property against oxidation, but also a very low dielectric constant, so they are very useful as insulating films.
  • However, as described later, the present inventors have found that, where a process gas in a small amount, such as a doping gas, is used in conventional vertical heat-processing apparatuses (of the so-called batch type), the inter-substrate uniformity in the composition of deposited films tends to be deteriorated.
    • BRIEF SUMMARY OF THE INVENTION
  • An object of the present invention is to provide an apparatus and method for a semiconductor process, which can uniformly supply a process gas in a small amount, such as a doping gas, into a process container in the vertical direction, thereby improving the inter-substrate uniformity in the composition of deposited films.
  • According to a first aspect of the present invention, there is provided a film formation apparatus for a semiconductor process, comprising:
  • a process container having a process field configured to accommodate a plurality of target substrates stacked at intervals;
  • a support member configured to support the target substrates inside the process field;
  • a heater configured to heat the target substrates inside the process field;
  • an exhaust system configured to exhaust gas inside the process field;
  • a process gas supply system configured to supply process gases to the process field so as to deposit a thin film on the target substrates, wherein the process gases include a first process gas for providing a main material of the thin film, a second process gas for reacting with the first process gas, and a third process gas for providing a sub-material of the thin film;
  • a control section configured to control an operation of the apparatus including the process gas supply system,
  • wherein the process gas supply system comprises
  • a gas mixture tank disposed outside the process container and configured to mix the first and third process gases to form a mixture gas,
  • a mixture gas supply line configured to supply the mixture gas from the gas mixture tank to the process field,
  • first and third process gas supply circuits configured to supply the first and third process gases to the gas mixture tank, respectively,
  • a second process gas supply circuit having a second process gas supply line configured to supply the second process gas to the process field without passing through the gas mixture tank,
  • first and second switching valves disposed on the mixture gas supply line and the second process gas supply line, respectively, and
  • wherein the control section controls the first and second switching valves to be opened and closed so as to alternately and pulse-wise supply the mixture gas from the gas mixture tank and the second process gas from the second process gas supply circuit to the process field.
  • According to a second aspect of the present invention, there is provided a film formation apparatus for a semiconductor process, comprising:
  • a process container having a process field configured to accommodate a plurality of target substrates stacked at intervals;
  • a support member configured to support the target substrates inside the process field;
  • a heater configured to heat the target substrates inside the process field;
  • an exhaust system configured to exhaust gas inside the process field;
  • a process gas supply system configured to supply process gases to the process field so as to deposit a thin film on the target substrates, wherein the process gases include a first process gas for providing a main material of the thin film, a second process gas for reacting with the first process gas, and a third process gas for providing a sub-material of the thin film, and the third process gas is supplied to the process field in an amount smaller than that of the first process gas;
  • a control section configured to control an operation of the apparatus including the process gas supply system,
  • wherein the process gas supply system comprises
  • a mixture gas supply line configured to mix the first and third process gases to form a mixture gas and supply the mixture gas to the process field,
  • first and third process gas supply circuits having first and third process gas supply lines configured to supply the first and third process gases to the mixture gas supply line, respectively,
  • a second process gas supply circuit having a second process gas supply line configured to supply the second process gas to the process field without passing through the mixture gas supply line,
  • first, second, and third switching valves disposed on the first, second, and third process gas supply lines, respectively,
  • a first tank disposed on the first process gas supply line immediately before the first switching valve to temporarily store the first process gas, and
  • wherein the control section controls the first, second, and third switching valves to be opened and closed so as to alternately and pulse-wise supply the mixture gas from the mixture gas supply line and the second process gas from the second process gas supply circuit to the process field.
  • According to a third aspect of the present invention, there is provided a film formation method for a semiconductor process, comprising:
  • heating a plurality of target substrates stacked at intervals within a process field in a process container; and
  • supplying process gases to the process field to deposit a thin film on the target substrates, wherein the process gases include a first process gas for providing a main material of the thin film, a second process gas for reacting with the first process gas, and a third process gas for providing a sub-material of the thin film,
  • wherein said supplying the process gases comprises
  • supplying the first and third process gases to a gas mixture tank disposed outside the process container to form a mixture gas,
  • supplying the mixture gas from the gas mixture tank to the process field, and
  • supplying the second process gas to the process field without passing through the gas mixture tank,
  • so as to alternately and pulse-wise supply the mixture gas and the second process gas to the process field.
  • According to a fourth aspect of the present invention, there is provided a film formation method for a semiconductor process, comprising:
  • heating a plurality of target substrates stacked at intervals within a process field in a process container; and
  • supplying process gases to the process field to deposit a thin film on the target substrates, wherein the process gases include a first process gas for providing a main material of the thin film, a second process gas for reacting with the first process gas, and a third process gas for providing a sub-material of the thin film, and the third process gas is supplied to the process field in an amount smaller than that of the first process gas,
  • wherein said supplying the process gases comprises
  • supplying the first and third process gases to a mixture gas supply line to form a mixture gas and supply the mixture gas to the process field, while temporarily storing the first process gas in a first tank disposed immediately before the mixture gas supply line, and
  • supplying the second process gas to the process field without passing through the mixture gas supply line,
  • so as to alternately and pulse-wise supply the mixture gas and the second process gas to the process field.
  • According to a fifth aspect of the present invention, there is provided a computer readable medium containing program instructions for execution on a processor, which, when executed by the processor, cause a film formation apparatus for a semiconductor process to execute
  • heating a plurality of target substrates stacked at intervals within a process field in a process container; and
  • supplying process gases to the process field to deposit a thin film on the target substrates, wherein the process gases include a first process gas for providing a main material of the thin film, a second process gas for reacting with the first process gas, and a third process gas for providing a sub-material of the thin film,
  • wherein said supplying the process gases comprises
  • supplying the first and third process gases to a gas mixture tank disposed outside the process container to form a mixture gas,
  • supplying the mixture gas from the gas mixture tank to the process field, and
  • supplying the second process gas to the process field without passing through the gas mixture tank,
  • so as to alternately and pulse-wise supply the mixture gas and the second process gas to the process field.
  • According to a sixth aspect of the present invention, there is provided a computer readable medium containing program instructions for execution on a processor, which, when executed by the processor, cause a film formation apparatus for a semiconductor process to execute
  • heating a plurality of target substrates stacked at intervals within a process field in a process container; and
  • supplying process gases to the process field to deposit a thin film on the target substrates, wherein the process gases include a first process gas for providing a main material of the thin film, a second process gas for reacting with the first process gas, and a third process gas for providing a sub-material of the thin film, and the third process gas is supplied to the process field in an amount smaller than that of the first process gas,
  • wherein said supplying the process gases comprises
  • supplying the first and third process gases to a mixture gas supply line to form a mixture gas and supply the mixture gas to the process field, while temporarily storing the first process gas in a first tank disposed immediately before the mixture gas supply line, and
  • supplying the second process gas to the process field without passing through the mixture gas supply line,
  • so as to alternately and pulse-wise supply the mixture gas and the second process gas to the process field.
  • Additional objects and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objects and advantages of the invention may be realized and obtained by means of the instrumentalities and combinations particularly pointed out hereinafter.
    • BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
  • The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate embodiments of the invention, and together with the general description given above and the detailed description of the embodiments given below, serve to explain the principles of the invention.
  • FIG. 1 is a sectional view showing a film formation apparatus (vertical CVD apparatus) according to a first embodiment of the present invention;
  • FIG. 2 is a sectional plan view showing part of the apparatus shown in FIG. 1;
  • FIG. 3 is a timing chart of the gas supply and RF (radio frequency) application of a film formation method according to a first embodiment;
  • FIG. 4 is a sectional view showing a film formation apparatus (vertical CVD apparatus) according to a second embodiment of the present invention;
  • FIG. 5 is a view showing part of a gas supply system used in a film formation apparatus according to a modification of the second embodiment; and
  • FIG. 6 is a block diagram schematically showing the structure of a main control section.
    • DETAILED DESCRIPTION OF THE INVENTION
  • In the process of developing the present invention, the inventors studied problems caused in conventional film formation apparatuses for a semiconductor process, where a plurality of source gases were used to perform a film formation process, such as a process for forming a thin film doped with an impurity. As a result, the inventors have arrived at the findings given below.
  • Specifically, where a plurality of source gases are used to perform a film formation process, it is important to control the ratio of film composition elements of to be a predetermined value, so as to attain high film quality. However, for example, where the source gases includes a main source gas containing a main component element of a deposition film and a doping gas, the supply amount of the doping gas is far smaller than the supply amount of the main source gas, in general. In this case, since the supply amount of the doping gas supplied into a vertical process container is small, a problem arises such that an element derived from the doping gas is taken into deposited films on wafers in varying amounts, depending on the wafer position in the vertical direction. Consequently, the inter-substrate uniformity in the composition of the deposited films tends to be lower. This problem is caused due to differences in the adsorptivity of the source gas relative to the wafer surface and in the flow rate of the source gases.
  • For this reason, where the supply amount of a gas, such as a doping gas, supplied into a vertical process container is small, countermeasures are required to supply the gas at a uniform supply amount in the vertical direction. For example, a gas nozzle having a number of gas spouting holes at predetermined intervals is disposed to extend in the longitudinal direction of the vertical process container, and the doping gas is delivered from the holes. Alternatively, the supply time of the doping gas is shortened to increase the flow rate of the gas per unit time. However, even with the former countermeasure, where a very small gas supply amount is handled, the flow rate from gas spouting holes at the upstream side tends to be higher than the flow rate from gas spouting holes at the downstream side. In this respect, it is not easy to optimize the dimensions and so forth of gas spouting holes, so as to uniformize the flow rate from the gas spouting holes, for a small gas supply amount.
  • Further, where the supply amount of a gas, such as a doping gas, is very small, the gas can be mixed with an inactive carrier gas to increase the total flow rate, as a countermeasure. In this case, however, due to the presence of the carrier gas, the partial pressure of the doping gas decreases and thus the adsorption rate of the doping gas decreases by that much.
  • Embodiments of the present invention achieved on the basis of the findings given above will now be described with reference to the accompanying drawings. In the following description, the constituent elements having substantially the same function and arrangement are denoted by the same reference numerals, and a repetitive description will be made only when necessary.
  • <First Embodiment>
  • FIG. 1 is a sectional view showing a film formation apparatus (vertical CVD apparatus) according to a first embodiment of the present invention. FIG. 2 is a sectional plan view showing part of the apparatus shown in FIG. 1. The film formation apparatus 2 has a process field configured to be selectively supplied with a first process gas containing dichlorosilane (DCS) gas as a silane family gas, a second process gas containing ammonia (NH3) gas as a nitriding gas, and a third process gas containing BCl3 gas as a boron-containing gas. The film formation apparatus 2 is configured to form an SIBN (boron doped silicon nitride) film on target substrates by CVD in the process field. Accordingly, the boron-containing gas is used as a doping gas. The process field is further configured to be selectively supplied with a fourth process gas containing C2H4 gas (ethylene gas) as a carbon hydride gas, as needed.
  • The apparatus 2 includes a process container 4 shaped as a cylindrical column with a ceiling and an opened bottom, in which a process field 5 is defined to accommodate and process a plurality of semiconductor wafers (target substrates) stacked at intervals in the vertical direction. The entirety of the process container 4 is made of, e.g., quartz. The top of the process container 4 is provided with a quartz ceiling plate 6 to airtightly seal the top. The bottom of the process container 4 is connected through a seal member 10, such as an O-ring, to a cylindrical manifold 8. The process container may be entirely formed of a cylindrical quartz column without a manifold 8 separately formed.
  • The manifold 8 is made of, e.g., stainless steel, and supports the bottom of the process container 4. A wafer boat 12 made of quartz is moved up and down through the bottom port of the manifold 8, so that the wafer boat 12 is loaded/unloaded into and from the process container 4. A number of target substrates or semiconductor wafers W are stacked on a wafer boat 12. For example, in this embodiment, the wafer boat 12 has struts 12A that can support, e.g., about 50 to 100 wafers having a diameter of 300 mm at essentially regular intervals in the vertical direction.
  • The wafer boat 12 is placed on a table 16 through a heat-insulating cylinder 14 made of quartz. The table 16 is supported by a rotary shaft 20, which penetrates a lid 18 made of, e.g., stainless steel, and is used for opening/closing the bottom port of the manifold 8.
  • The portion of the lid 18 where the rotary shaft 20 penetrates is provided with, e.g., a magnetic-fluid seal 22, so that the rotary shaft 20 is rotatably supported in an airtightly sealed state. A seal member 24, such as an O-ring, is interposed between the periphery of the lid 18 and the bottom of the manifold 8, so that the interior of the process container 4 can be kept sealed.
  • The rotary shaft 20 is attached at the distal end of an arm 26 supported by an elevating mechanism 25, such as a boat elevator. The elevating mechanism 25 moves the wafer boat 12 and lid 18 up and down integratedly. The table 16 may be fixed to the lid 18, so that wafers W are processed without rotation of the wafer boat 12.
  • A gas supply system is connected to the side of the manifold 8 to supply predetermined process gases to the process field 5 within the process container 4. Specifically, the gas supply system includes a second process gas supply circuit 28, a first process gas supply circuit 30, a third process gas supply circuit 32, and a purge gas supply circuit 36, and, as needed, a fourth process gas supply circuit 34. The first process gas supply circuit 30 is arranged to supply a first process gas containing a silane family gas, such as DCS (dichlorosilane) gas. The second process gas supply circuit 28 is arranged to supply a second process gas containing a nitriding gas, such as ammonia (NH3) gas. The third process gas supply circuit 32 is arranged to supply a third process gas containing a boron-containing gas (doping gas), such as BC1 3 gas. The fourth process gas supply circuit 34 is arranged to supply a fourth process gas containing a carbon hydride gas, such as C2H4 gas (ethylene gas). The purge gas supply circuit 36 is arranged to supply an inactive gas, such as N2 gas, as a purge gas. Each of the first, second, and fourth process gases is mixed with a suitable amount of carrier gas, as needed. However, such a carrier gas will not be mentioned, hereinafter, for the sake of simplicity of explanation.
  • More specifically, the first, third, and fourth process gas supply circuits 30, 32, and 34 are connected to a common mixture gas supply circuit 35. The mixture gas supply circuit 35 has a gas mixture tank configured to mix the first and third process gases, and further the fourth process gas in addition thereto, as needed. The gas mixture tank 42 is designed to have a volume for uniformly mixing the gases and temporarily store a sufficient supply amount of the mixture gas, such as a volume of, e.g., about four liters (to be changed depending on the gas flow rate). The gas mixture tank 52 is connected to a gas distribution nozzle 40 formed of a quartz pipe through a mixture gas supply line 44 provided with a switching valve 44A. On the other hand, the second process gas supply circuit 28 is connected to a gas distribution nozzle 38 formed of a quartz pipe.
  • The gas distribution nozzles 38 and 40 penetrate the sidewall of the manifold 8 from the outside and then turn and extend upward. The gas distribution nozzles 38 and 40 respectively have a plurality of gas spouting holes 38A and 40A, each set of holes being formed at predetermined intervals in the longitudinal direction (the vertical direction) over all the wafers W on the wafer boat 12. Each of the gas spouting holes 38A and 40A delivers the corresponding process gas almost uniformly in the horizontal direction, so as to form gas flows parallel with the wafers W on the wafer boat 12. The purge gas supply circuit 36 includes a short gas nozzle 46, which penetrates the sidewall of the manifold 8 from the outside.
  • The gas mixture tank 52 is connected to gas sources 30S, 32S, and 34S of DCS gas, BC1 3 gas, and C2H4 gas, respectively, through gas supply lines (gas passages) 50, 52, and 54 of the first, third, and fourth process gas supply circuits 30, 32, and 34, respectively. The gas distribution nozzle 38 of the second process gas supply circuit 28 is connected to a gas source 28S of NH3 gas through a gas supply line (gas passage) 48. The nozzle 46 of the purge gas supply circuit 36 is connected to a gas source 36S of N2 gas through gas supply lines (gas passage) 56. The gas supply lines 48, 50, 52, 54, and 56 are provided with switching valves 48A, 50A, 52A, 54A, and 56A and flow rate controllers 48B, 50B, 52B, 54B, and 56B, such as mass flow controllers, respectively. With this arrangement, NH3 gas, DCS gas, BCl3 gas, C2H4 gas, and N2 gas can be supplied at controlled flow rates.
  • A gas exciting section 66 is formed at the sidewall of the process container 4 in the vertical direction. On the side of the process container 4 opposite to the gas exciting section 66, a long and thin exhaust port 68 for vacuum-exhausting the inner atmosphere is formed by cutting the sidewall of the process container 4 in, e.g., the vertical direction.
  • Specifically, the gas exciting section 66 has a vertically long and thin opening 70 formed by cutting a predetermined width of the sidewall of the process container 4, in the vertical direction. The opening 70 is covered with a quartz cover 72 airtightly connected to the outer surface of the process container 4 by welding. The cover 72 has a vertical long and thin shape with a concave cross-section, so that it projects outward from the process container 4.
  • With this arrangement, the gas exciting section 66 is formed such that it projects outward from the sidewall of the process container 4 and is opened on the other side to the interior of the process container 4. In other words, the inner space of the gas exciting section 66 communicates with the process field 5 within the process container 4. The opening 70 has a vertical length sufficient to cover all the wafers W on the wafer boat 12 in the vertical direction.
  • A pair of long and thin electrodes 74 are disposed on the opposite outer surfaces of the cover 72, and face each other along the longitudinal direction (the vertical direction). The electrodes 74 are connected to an RF (Radio Frequency) power supply 76 for plasma generation, through feed lines 78. An RF voltage of, e.g., 13.56 MHz is applied to the electrodes 74 to form an RF electric field for exciting plasma between the electrodes 74. The frequency of the RF voltage is not limited to 13.56 MHz, and it may be set at another frequency, e.g., 400 kHz.
  • The gas distribution nozzle 38 of the second process gas is bent outward in the radial direction of the process container 4, at a position lower than the lowermost wafer W on the wafer boat 12. Then, the gas distribution nozzle 38 vertically extends at the deepest position (the farthest position from the center of the process container 4) in the gas exciting section 66. As shown also in FIG. 2, the gas distribution nozzle 38 is separated outward from an area sandwiched between the pair of electrodes 74 (a position where the RF electric field is most intense), i.e., a plasma generation area PS where the main plasma is actually generated. The second process gas containing NH3 gas is spouted from the gas spouting holes 38A of the gas distribution nozzle 38 toward the plasma generation area PS. Then, the second process gas is excited (decomposed or activated) in the plasma generation area PS, and is supplied in this state onto the wafers W on the wafer boat 12.
  • An insulating protection cover 80 made of, e.g., quartz is attached on and covers the outer surface of the cover 72. A cooling mechanism (not shown) is disposed in the insulating protection cover 80 and comprises coolant passages respectively facing the electrodes 74. The coolant passages are supplied with a coolant, such as cooled nitrogen gas, to cool the electrodes 74. The insulating protection cover 80 is covered with a shield (not shown) disposed on the outer surface to prevent RF leakage.
  • At a position near and outside the opening 70 of the gas exciting section 66, the gas distribution nozzle 40 of the mixture gas supply circuit 35 is disposed to vertically extend upward. The mixture gas (a mixture gas of the first and third process gases, and further the fourth process gas in addition thereto, as needed) is spouted from the gas spouting holes 40A of the gas distribution nozzle 40 toward the center of the process container 4.
  • On the other hand, the exhaust port 68, which is formed opposite the gas exciting section 66, is covered with an exhaust port cover member 82. The exhaust port cover member 82 is made of quartz with a U-shape cross-section, and attached by welding. The exhaust cover member 82 extends upward along the sidewall of the process container 4, and has a gas outlet 84 at the top of the process container 4. The gas outlet 84 is connected to a vacuum-exhaust system GE including a vacuum pump and so forth.
  • The process container 4 is surrounded by a heater 86, which is used for heating the atmosphere within the process container 4 and the wafers W. A thermocouple (not shown) is disposed near the exhaust port 68 in the process container 4 to control the heater 86.
  • The film formation apparatus 2 further includes a main control section 60 formed of, e.g., a computer, to control the entire apparatus. The main control section 60 can control the film formation process described below in accordance with the process recipe of the film formation process concerning, e.g., the film thickness and composition of a film to be formed, stored in the memory 212 thereof in advance. In the memory 212, the relationship between the process gas flow rates and the thickness and composition of the film is also stored as control data in advance. Accordingly, the main control section 60 can control the elevating mechanism 25, gas supply circuits 28, 30, 32, 34, 35 and 36, exhaust system GE, gas exciting section 66, heater 86, and so forth, based on the stored process recipe and control data.
  • Next, an explanation will be given of a film formation method (so called ALD (Atomic Layer Deposition) film formation) performed in the apparatus shown in FIG. 1. In this film formation method, an insulating film of SiBN is formed on semiconductor wafers by CVD. In order to achieve this, a first process gas containing dichlorosilane (DCS) gas as a silane family gas, a second process gas containing ammonia (NH3) gas as a nitriding gas, and a third process gas containing BC1 3 gas as a boron-containing gas are selectively supplied into the process field 5 accommodating wafers W. At this time, the first process gas and third process gas are mixed in the gas mixture tank 42, and the mixture gas thus formed is supplied into the process field. It should be noted that this film formation method is an example where a fourth process gas containing C2H4 gas (ethylene gas) as a carbon hydride gas is not supplied.
  • At first, the wafer boat 12 at room temperature, which supports a number of, e.g., 50 to 100, wafers having a diameter of 300 mm, is loaded into the process container 4 heated at a predetermined temperature, and the process container 4 is airtightly closed. Then, the interior of the process container 4 is vacuum-exhausted and kept at a predetermined process pressure, and the wafer temperature is increased to a process temperature for film formation. At this time, the apparatus is in a waiting state until the temperature becomes stable. Then, while the wafer boat 12 is rotated, the first to third process gases are intermittently supplied from the respective gas distribution nozzles 38 and 40 at controlled flow rates.
  • Specifically, the first process gas containing DCS gas and the third process gas containing BCl3 gas are supplied into the gas mixture tank 42 to form a mixture gas. The mixture gas is supplied from the gas spouting holes 40A of the gas distribution nozzle 40 to form gas flows parallel with the wafers W on the wafer boat 12. While being supplied, molecules of DCS gas and BC1 3 gas and molecules and atoms of decomposition products generated by their decomposition are adsorbed on the wafers W.
  • On the other hand, the second process gas containing NH3 gas is supplied from the gas spouting holes 38A of the gas distribution nozzle 38 to form gas flows parallel with the wafers W on the wafer boat 12. The second process gas is selectively excited and partly turned into plasma when it passes through the plasma generation area PS between the pair of electrodes 74. At this time, for example, radicals (activated species), such as N*, NH*, NH2*, and NH3*, are produced (the symbol ┌*┐ denotes that it is a radical). The radicals flow out from the opening 70 of the gas exciting section 66 toward the center of the process container 4, and are supplied into gaps between the wafers W in a laminar flow state.
  • The radicals react with molecules of DCS gas adsorbed on the surface of the wafers W, so that a thin film is formed on the wafers W. Further, at this time, B atoms generated by decomposition of BC1 3 gas are taken into the thin film, so a film of SiBN doped with boron as an impurity is formed. Alternatively, when DCS gas and BC1 3 gas flow onto radicals adsorbed on the surface of the wafers W, the same reaction is caused, so an SIBN film doped with boron is formed on the wafers W.
  • FIG. 3 is a timing chart of the gas supply and RF (radio frequency) application of a film formation method according to the first embodiment. As shown in FIG. 3, the film formation method according to this embodiment is arranged to alternately repeat first to fourth steps T1 to T4. A cycle comprising the first to fourth steps T1 to T4 is repeated a number of times, and thin films of SiBN formed by respective cycles are laminated, thereby arriving at an SiBN film having a target thickness.
  • Specifically, the first step T1 is arranged to perform supply of the mixture gas of the first process gas (denoted as DCS in FIG. 3) and the third process gas (denoted as BCl3 in FIG. 3) to the process field 5, while stopping supply of the second process gas (denoted as NH3 in FIG. 3) to the process field 5. The second step T2 is arranged to stop supply of the mixture gas of the first and third process gases and the second process gas to the process field 5. The third step T3 is arranged to perform supply of the second process gas to the process field 5, while stopping supply of the mixture gas of the first and third process gases to the process field 5. Further, halfway through the third step T3, the RF power supply 76 is set in the ON state to turn the second process gas into plasma by the gas exciting section 66, so as to supply the second process gas in an activated state to the process field 5 during a sub-step T3 b. The fourth step T4 is arranged to stop supply of the mixture gas of the first and third process gases and the second process gas to the process field 5.
  • In the third step T3, the RF power supply 76 is turned on after a predetermined time Δt passes, to turn the second process gas into plasma by the gas exciting section 66, so as to supply the second process gas in an activated state to the process field 5 during the sub-step T3 b. The predetermined time Δt is defined as the time necessary for stabilizing the flow rate of NH3 gas, which is set at, e.g., about 5 seconds. However, the second process gas may be turned into plasma by the gas exciting section 66 over the entire period of supplying the second process gas. Since the RF power supply is turned on to generate plasma after the flow rate of the second process gas is stabilized, the uniformity of radical concentration among the wafers W (uniformity in the vertical direction) is improved.
  • Each of the second and fourth steps T2 and T4 is used as a purge step to remove the residual gas within the process container 4. The term “purge” means removal of the residual gas within the process container 4 by vacuum-exhausting the interior of the process container 4 while supplying an inactive gas, such as N2 gas, into the process container 4, or by vacuum-exhausting the interior of the process container 4 while stopping supply of all the gases. In this respect, the second and fourth steps T2 and T4 may be arranged such that the first half utilizes only vacuum-exhaust and the second half utilizes both vacuum-exhaust and inactive gas supply. Further, the first and third steps T1 and T3 may be arranged to stop vacuum-exhausting the process container 4 while supplying each of the first to third process gases. However, where supplying each of the first to third process gases is performed along with vacuum-exhausting the process container 4, the interior of the process container 4 can be continuously vacuum-exhausted over the entirety of the first to fourth steps T1 to T4.
  • In FIG. 3, the first step T1 is set to be within a range of about 1 to 20 seconds, and, for example, at about 10 seconds, the second step T2 is set to be within a range of about 5 to 15 seconds, and, for example, at about 10 seconds, the third step T3 is set to be within a range of about 1 to 30 seconds, and, for example, at about 20 seconds, the sub-step T3 b is set to be within a range of about 1 to 25 seconds, and, for example, at about 10 seconds, and the fourth step T4 is set to be within a range of about 5 to 15 seconds, and, for example, at about 10 seconds. In general, the film thickness obtained by one cycle of the first to fourth steps T1 to T4 is about 0.11 to 0.13 nm. Accordingly, for example, where the target film thickness is 70 nm, the cycle is repeated about 600 times. However, these values of time and thickness are merely examples and thus are not limiting.
  • The process conditions of the film formation process are as follows. The flow rate of DCS gas is set to be within a range of 50 to 2,000 sccm, e.g., at 1,000 sccm (1 slm). The flow rate of NH3 gas is set to be within a range of 500 to 5,000 sccm, e.g., at 1,000 sccm. The flow rate of BC1 3 gas is set to be within a range of 1 to 15 sccm, e.g., at 2 sccm. Accordingly, the flow rate of BC1 3 gas is far smaller than the flow rate of DCS gas.
  • The process temperature is lower than ordinary CVD processes, and is set to be within a range of 300 to 700° C., and preferably a range of 550 to 630° C. If the process temperature is lower than 300° C., essentially no film is deposited because hardly any reaction is caused. If the process temperature is higher than 700° C., a low quality CVD film is deposited, and existing films, such as a metal film, suffer thermal damage.
  • The process pressure is set to be within a range of 13 Pa (0.1 Torr) to 1,330 Pa (10 Torr), and preferably a range of 40 Pa (0.3 Torr) to 266 Pa (2 Torr). For example, the process pressure is set at 1 Torr during the first step (adsorption step) T1, and at 0.3 Torr during the third step (nitridation step using plasma) T3. If the process pressure is lower than 13 Pa, the film formation rate becomes lower than the practical level. If the process pressure is higher than 1,330 Pa, it becomes difficult to generate plasma.
  • As described above, the first process gas containing DCS gas for providing the main material of a thin film, and the third process gas containing BCl3 gas for providing a sub-material of the thin film are uniformly mixed at first in the gas mixture tank 42 to form a mixture gas. The mixture gas is then intermittently supplied into the process field 5 through a plurality of gas spouting holes 40A arrayed at intervals in the vertical direction. In this case, although the amount of BCl3 gas is small, it can be essentially uniformly distributed within the process container 4 in the vertical direction without using a carrier gas. Consequently, the ratio of the composition elements in SiBN thin films to be formed becomes more uniform, regardless of wafer position.
  • In other words, the supply amount of the third process gas is far smaller than the supply amount of the first process gas. In this case, the third process gas in a smaller supply amount is made to accompany the first process gas in a larger supply amount, so that it can be uniformly distributed within the process container 4 in the vertical direction. Particularly, where the supply amount of one source gas is 1/100 or less of the supply amount of the other source gas, the above-described effect of uniformizing the ratio of the composition elements in films is more influential.
  • When BC1 3 gas is adsorbed on the wafer surface, the adsorption amount depends on the partial pressure of BC1 3 gas. According to this embodiment, BCl3 gas is supplied into the process container 4 uniformly in the vertical direction without using a carrier gas. In this case, the partial pressure of BC1 3 gas can be higher than that in the case of a carrier gas being used, so adsorption of BCl3 gas on the wafer surface is promoted. Consequently, while the film formation rate per unit cycle is maintained, the time necessary for one cycle is shortened, so the throughput is improved.
  • For example, in an experiment, a conventional film formation method took about 15 seconds until BCl3 gas was sufficiently adsorbed on a wafer surface. On the other hand, the present embodiment took only two or three seconds for the same. Accordingly, the conventional method took about 30 seconds for one cycle, while the present embodiment shortened this period to only 8 seconds.
  • Typically, the mixture gas may be formed and supplied by either of the following two methods. The first method comprises continuously supplying the first and third process gases from the first and third process gas supply circuits 30 and 32 into the gas mixture tank 42, while supplying the mixture gas pulse-wise from the gas mixture tank 42 into the process field 5. The second method comprises simultaneously supplying the first and third process gases pulse-wise in a first phase from the first and third process gas supply circuits 30 and 32 into the gas mixture tank 42, while supplying the mixture gas pulse-wise in a second phase reverse to the first phase from the gas mixture tank 42 into the process field 5.
  • In order to realize these methods, the switching valves 50A and 52A of the first and third process gas supply circuits 30 and 32 and the switching valve 44A of the mixture gas supply circuit 35 are opened and closed in accordance with instructions from the main control section 60, as follows. In the first method, over a plurality of cycles from the start to the end of the film formation process, the switching valves 50A and 52A are kept opened and the switching valve 44A is opened and closed pulse-wise. In the second method, over a plurality of cycles from the start to the end of the film formation process, the switching valves 50A and 52A are opened and closed pulse-wise while the switching valve 44A is closed and opened pulse-wise in the reverse phase.
  • In the film formation method described above, the fourth process gas containing C2H4 gas (ethylene gas) as a carbon hydride gas is not supplied, but the fourth process gas may be supplied, as needed. In this case, the fourth process gas is supplied into the gas mixture tank 42 at a controlled flow rate, simultaneously with the first and third process gases. Where a mixture gas of the first, third, and fourth process gases is used, a thin film to be formed is an insulating film of SiBCN (boron doped silicon carbon nitride) containing carbon.
  • <Second Embodiment>
  • FIG. 4 is a sectional view showing a film formation apparatus (vertical CVD apparatus) according to a second embodiment of the present invention. This film formation apparatus 2X has the same structure as the film formation apparatus 2 shown in FIG. 1 except for the first, third, and fourth process gas supply circuits 30, 32, and 34 and the mixture gas supply circuit 35. Accordingly, an explanation will be give of the film formation apparatus 2X, focusing on the difference from the film formation apparatus 2.
  • In the film formation apparatus 2X, the first, third, and fourth process gas supply circuits 30, 32, and 34 are connected to a common mixture gas supply circuit 35X. The mixture gas supply circuit 35X includes a mixture gas supply pipe 40X configured to mix the first and third process gases, and further the fourth process gas in addition thereto, as needed. The mixture gas supply pipe 40X is formed of a quartz pipe, which is a proximal end portion of a gas distribution nozzle 40.
  • The first, third, and fourth process gas supply circuits 30, 32, and 34 have tanks 102, 104, and 106, respectively, disposed immediately before the mixture gas supply pipe 40X to temporarily store the corresponding process gases. Since the tanks 102 and 106 need to handle a large gas flow rate, they are larger than the tank 104. For example, each of the tanks 102 and 106 has a volume of about four liters, while the tank 104 has a volume of about 0.05 liters (both to be changed depending on the gas flow rate). The tanks 102, 104, and 106 are connected to the mixture gas supply pipe 40X through gas supply lines 103, 105, and 107 provided with switching valves 103A, 105A, and 107A, respectively.
  • The tanks 102, 104, and 106 of the first, third, and fourth process gas supply circuits 30, 32, and 34 are connected to gas sources 30S, 32S, and 34S of DCS gas, BC1 3 gas, and C2H4 gas, respectively, through gas supply lines (gas passages) 50, 52, and 54. The gas supply lines 50, 52, and 54 are provided with switching valves 50A, 52A, and 54A and flow rate controllers 50B, 52B, and 54B, such as mass flow controllers, respectively. With this arrangement, DCS gas, BC1 3 gas, and C2H4 gas can be supplied at controlled flow rates.
  • Next, an explanation will be given of a film formation method (so called ALD (Atomic Layer Deposition) film formation) performed in the apparatus shown in FIG. 4. It should be noted that this film formation method is also an example where a fourth process gas containing C2H4 gas (ethylene gas) as a carbon hydride gas is not supplied. The gas supply and RF (radio frequency) application of this film formation method are performed in accordance with the timing chart shown in FIG. 3. At this time, in order to form and supply a mixture gas (denoted as DCS+BC1 3 in FIG. 3), the switching valves 103A and 105A are simultaneously opened and closed to supply first and third process gases temporarily stored in the tanks 102 and 104 into the mixture gas supply pipe 40X and mix them in the pipe 40X. The mixture gas is supplied from the gas spouting holes 40A of the gas distribution nozzle 40 to form gas flows parallel with the wafers W on the wafer boat 12. As a consequence, this apparatus can provide the same operation and effect as those obtained in the apparatus shown in FIG. 1.
  • Typically, the mixture gas may be formed and supplied by either of the following two methods (also in the following explanation, the fourth process gas is not supplied). The first method comprises continuously supplying the first and third process gases into the respective tanks 102 and 104 of the first and third process gas supply circuits 30 and 32, while supplying the gases pulse-wise from the respective tanks 102 and 104 into the mixture gas supply pipe 40X. The second method comprises simultaneously supplying the first and third process gases pulse-wise in a first phase into the respective tanks 102 and 104 of the first and third process gas supply circuits 30 and 32, while supplying the gases pulse-wise in a second phase reverse to the first phase from the respective tanks 102 and 104 into the mixture gas supply pipe 40X.
  • In order to realize these methods, the switching valves 50A and 52A of the first and third process gas supply circuits 30 and 32 and the switching valves 103A and 105A downstream from the tanks are opened and closed in accordance with instructions from the main control section 60, as follows. In the first method, over a plurality of cycles from the start to the end of the film formation process, the switching valves 50A and 52A are kept opened and the switching valves 103A and 105A are opened and closed pulse-wise. In the second method, over a plurality of cycles from the start to the end of the film formation process, the switching valves 50A and 52A are opened and closed pulse-wise while the switching valves 103A and 105A are closed and opened pulse-wise in the reverse phase.
  • FIG. 5 is a view showing part of a gas supply system used in a film formation apparatus according to a modification of the second embodiment (the fourth process gas supply circuit is not shown). In this modification, the tank 104 of the third process gas supply circuit 32 is omitted because the flow rate of the third process gas containing BCl3 gas is far smaller than the flow rate of the first process gas containing DCS gas. Even with this arrangement, the third process gas in a smaller amount is made to be uniformly mixed with the first process gas in a larger amount within the mixture gas supply pipe 40X, so that the third process gas is uniformly supplied.
  • <Common Matters to First and Second Embodiments>
  • Each of the methods according to the first and second embodiments is performed under the control of the main control section 60 in accordance with a process program, as described above. FIG. 6 is a block diagram schematically showing the structure of the main control section 60. The main control section 60 includes a CPU 210, which is connected to a storage section 212, an input section 214, and an output section 216. The storage section 212 stores process programs and process recipes. The input section 214 includes input devices, such as a keyboard, a pointing device, and a storage media drive, to interact with an operator. The output section 216 outputs control signals for controlling components of the processing apparatus. FIG. 6 also shows a storage medium 218 attached to the computer in a removable state.
  • Each of the methods according to the first and second embodiments may be written as program instructions for execution on a processor, into a computer readable storage medium or media to be applied to a semiconductor processing apparatus. Alternately, program instructions of this kind may be transmitted by a communication medium or media and thereby applied to a semiconductor processing apparatus. Examples of the storage medium or media are a magnetic disk (flexible disk, hard disk (a representative of which is a hard disk included in the storage section 212), etc.), an optical disk (CD, DVD, etc.), a magneto-optical disk (MO, etc.), and a semiconductor memory. A computer for controlling the operation of the semiconductor processing apparatus reads program instructions stored in the storage medium or media, and executes them on a processor, thereby performing a corresponding method, as described above.
  • In the embodiments described above, for example, the exciting section 66 for generating plasma of the film formation apparatus 2 is integrally combined with the process container 4. Alternatively, the exciting section 66 may be separately disposed from the process container 4, so as to excite NH3 gas outside the process container 4 (so called remote plasma), and then supply the excited NH3 gas into the process container 4. Further, NH3 gas may be supplied without being activated, and, in this case, the members associating with the gas exciting section 66 are not necessary. However, in this case, the process temperature needs to be increased to some extent to compensate for energy decrease due to no plasma being used.
  • In the embodiments described above, for example, the distribution nozzle 40 having a number of gas spouting holes 40A is used as a nozzle for supplying the mixture gas. Alternatively, a linear or straight pipe similar to the gas nozzle 46, or a bent or L-shaped pipe may be used for the same purpose. Where the straight pipe or L-shaped pipe is used, the mixture gas is supplied from below or above the process field 5. In this case, an exhaust port 68 is formed at the top or bottom of the process container 4 to cause the mixture gas to sufficiently flow within the process field 5 in the vertical direction.
  • In the embodiments described above, for example, the first process gas contains DCS gas as a silane family gas. In this respect, the silane family gas may be one or more gases selected from the group consisting of dichlorosilane (DCS), hexachlorodisilane (HCD), monosilane (SiH4), disilane (Si2Cl6), hexamethyl-disilazane (HMDS), tetrachlorosilane (TCS), disilylamine (DSA), trisilylamine (TSA), bistertial-butylaminosilane (BTBAS).
  • In the embodiments described above, the second process gas contains a nitriding gas, which may be NH3 gas or N2 gas. Where the present invention is applied to formation of a film based on silicon oxynitride, an oxynitriding gas, such as dinitrogen oxide (N2O) or nitrogen oxide (NO), may be used in place of the nitriding gas. In this case, a film to be formed is a film based on silicon oxynitride that contains oxygen (O).
  • In the embodiments described above, for example, the third process gas contains BC1 3 gas as a boron-containing gas. In this respect, the boron-containing gas may be one or more gases selected from the group consisting of BC1 3, B2H6, BF3, and B(CH3)3.
  • In the embodiments described above, for example, the fourth process gas contains ethylene gas as a carbon hydride gas. In this respect, the carbon hydride gas may be one or more gases selected from the group consisting of acetylene, ethylene, methane, ethane, propane, and butane.
  • In the embodiments described above, for example, an SiBN film or SiBCN film is formed. Alternatively, for example, the present invention may be applied to a process for forming a BCN film (carbon-containing boron nitride film). In this case, a boron-containing gas and a carbon hydride gas are used as source gases and mixed. The present invention can be applied to various film formation processes which use a plurality of source gases that does not cause any problem if they are mixed before being supplied into a process container. For example, the present invention may be applied to a film formation process using an oxidizing gas, such as O2 gas, as a reaction gas.
  • A target substrate is not limited to a semiconductor wafer, and it may be another substrate, such as an LCD substrate or glass substrate.
  • Additional advantages and modifications will readily occur to those skilled in the art. Therefore, the invention in its broader aspects is not limited to the specific details and representative embodiments shown and described herein. Accordingly, various modifications may be made without departing from the spirit or scope of the general inventive concept as defined by the appended claims and their equivalents.

Claims (24)

1. A film formation apparatus for a semiconductor process, comprising:
a process container having a process field configured to accommodate a plurality of target substrates stacked at intervals;
a support member configured to support the target substrates inside the process field;
a heater configured to heat the target substrates inside the process field;
an exhaust system configured to exhaust gas inside the process field;
a process gas supply system configured to supply process gases to the process field so as to deposit a thin film on the target substrates, wherein the process gases include a first process gas for providing a main material of the thin film, a second process gas for reacting with the first process gas, and a third process gas for providing a sub-material of the thin film;
a control section configured to control an operation of the apparatus including the process gas supply system,
wherein the process gas supply system comprises
a gas mixture tank disposed outside the process container and configured to mix the first and third process gases to form a mixture gas,
a mixture gas supply line configured to supply the mixture gas from the gas mixture tank to the process field,
first and third process gas supply circuits configured to supply the first and third process gases to the gas mixture tank, respectively,
a second process gas supply circuit having a second process gas supply line configured to supply the second process gas to the process field without passing through the gas mixture tank,
first and second switching valves disposed on the mixture gas supply line and the second process gas supply line, respectively, and
wherein the control section controls the first and second switching valves to be opened and closed so as to alternately and pulse-wise supply the mixture gas from the gas mixture tank and the second process gas from the second process gas supply circuit to the process field.
2. The apparatus according to claim 1, wherein the control section performs control to continuously supply the first and third process gases from the first and third process gas supply circuits to the gas mixture tank, while supplying the mixture gas pulse-wise from the gas mixture tank to the process field.
3. The apparatus according to claim 1, wherein the control section performs control to simultaneously supply the first and third process gases pulse-wise in a first phase from the first and third process gas supply circuits to the gas mixture tank, while supplying the mixture gas pulse-wise in a second phase reverse to the first phase from the gas mixture tank to the process field.
4. The apparatus according to claim 1, wherein the mixture gas supply line and the second process gas supply line comprise first and second supply ports, respectively, each of which comprises a plurality of gas spouting holes arrayed over the target substrates in a vertical direction to form gas flows parallel with the target substrates.
5. The apparatus according to claim 1, wherein the third process gas is supplied to the process field in an amount 1/100 or less of the first process gas.
6. The apparatus according to claim 1, wherein the first process gas contains a silane family gas, the second process gas contains a nitriding gas or oxynitriding gas, and the third process gas contains a doping gas.
7. The apparatus according to claim 6, wherein the process gas supply system further comprises a fourth process gas supply circuit configured to supply a fourth process gas containing a carbon hydride gas to the gas mixture tank.
8. The apparatus according to claim 6, wherein the first process gas contains at least one gas selected from the group consisting of dichlorosilane, hexachlorodisilane, monosilane, disilane, hexamethyldisilazane, tetrachlorosilane, disilylamine, trisilylamine, and bistertialbutylaminosilane, the second process gas contains at least one gas selected from the group consisting of ammonia, nitrogen, dinitrogen oxide, and nitrogen oxide, and the third process gas contains at least one gas selected from the group consisting of BCl3, B2H6, BF3, and B(CH3)3.
9. The apparatus according to claim 1, further comprises an exciting mechanism configured to activate the second process gas by generating plasma.
10. The apparatus according to claim 9, wherein the exciting mechanism comprises a plasma generation area disposed in a space communicating with the process field and between a supply port of the second process gas and the target substrates.
11. A film formation apparatus for a semiconductor process, comprising:
a process container having a process field configured to accommodate a plurality of target substrates stacked at intervals;
a support member configured to support the target substrates inside the process field;
a heater configured to heat the target substrates inside the process field;
an exhaust system configured to exhaust gas inside the process field;
a process gas supply system configured to supply process gases to the process field so as to deposit a thin film on the target substrates, wherein the process gases include a first process gas for providing a main material of the thin film, a second process gas for reacting with the first process gas, and a third process gas for providing a sub-material of the thin film, and the third process gas is supplied to the process field in an amount smaller than that of the first process gas;
a control section configured to control an operation of the apparatus including the process gas supply system,
wherein the process gas supply system comprises
a mixture gas supply line configured to mix the first and third process gases to form a mixture gas and supply the mixture gas to the process field,
first and third process gas supply circuits having first and third process gas supply lines configured to supply the first and third process gases to the mixture gas supply line, respectively,
a second process gas supply circuit having a second process gas supply line configured to supply the second process gas to the process field without passing through the mixture gas supply line,
first, second, and third switching valves disposed on the first, second, and third process gas supply lines, respectively,
a first tank disposed on the first process gas supply line immediately before the first switching valve to temporarily store the first process gas, and
wherein the control section controls the first, second, and third switching valves to be opened and closed so as to alternately and pulse-wise supply the mixture gas from the mixture gas supply line and the second process gas from the second process gas supply circuit to the process field.
12. The apparatus according to claim 11, wherein the control section controls the first and third switching valve to be simultaneously opened and closed.
13. The apparatus according to claim 11, wherein the process gas supply system further comprises a second tank disposed on the third process gas supply line immediately before the third switching valve to temporarily store the third process gas
14. The apparatus according to claim 11, wherein the mixture gas supply line and the second process gas supply line comprise first and second supply ports, respectively, each of which comprises a plurality of gas spouting holes arrayed over the target substrates in a vertical direction to form gas flows parallel with the target substrates.
15. The apparatus according to claim 11, wherein the third process gas is supplied to the process field in an amount 1/100 or less of the first process gas.
16. The apparatus according to claim 11, wherein the first process gas contains a silane family gas, the second process gas contains a nitriding gas or oxynitriding gas, and the third process gas contains a doping gas.
17. The apparatus according to claim 16, wherein the process gas supply system further comprises a fourth process gas supply circuit configured to supply a fourth process gas containing a carbon hydride gas to the mixture gas supply line.
18. The apparatus according to claim 16, wherein the first process gas contains at least one gas selected from the group consisting of dichlorosilane, hexachlorodisilane, monosilane, disilane, hexamethyldisilazane, tetrachlorosilane, disilylamine, trisilylamine, and bistertialbutylaminosilane, the second process gas contains at least one gas selected from the group consisting of ammonia, nitrogen, dinitrogen oxide, and nitrogen oxide, and the third process gas contains at least one gas selected from the group consisting of BCl3, B2H6, BF3, and B(CH3)3.
19. The apparatus according to claim 11, further comprises an exciting mechanism configured to activate the second process gas by generating plasma.
20. The apparatus according to claim 19, wherein the exciting mechanism comprises a plasma generation area disposed in a space communicating with the process field and between a supply port of the second process gas and the target substrates.
21. A film formation method for a semiconductor process, comprising:
heating a plurality of target substrates stacked at intervals within a process field in a process container; and
supplying process gases to the process field to deposit a thin film on the target substrates, wherein the process gases include a first process gas for providing a main material of the thin film, a second process gas for reacting with the first process gas, and a third process gas for providing a sub-material of the thin film,
wherein said supplying the process gases comprises
supplying the first and third process gases to a gas mixture tank disposed outside the process container to form a mixture gas,
supplying the mixture gas from the gas mixture tank to the process field, and
supplying the second process gas to the process field without passing through the gas mixture tank,
so as to alternately and pulse-wise supply the mixture gas and the second process gas to the process field.
22. A film formation method for a semiconductor process, comprising:
heating a plurality of target substrates stacked at intervals within a process field in a process container; and
supplying process gases to the process field to deposit a thin film on the target substrates, wherein the process gases include a first process gas for providing a main material of the thin film, a second process gas for reacting with the first process gas, and a third process gas for providing a sub-material of the thin film, and the third process gas is supplied to the process field in an amount smaller than that of the first process gas,
wherein said supplying the process gases comprises
supplying the first and third process gases to a mixture gas supply line to form a mixture gas and supply the mixture gas to the process field, while temporarily storing the first process gas in a first tank disposed immediately before the mixture gas supply line, and
supplying the second process gas to the process field without passing through the mixture gas supply line,
so as to alternately and pulse-wise supply the mixture gas and the second process gas to the process field.
23. A computer readable medium containing program instructions for execution on a processor, which, when executed by the processor, cause a film formation apparatus for a semiconductor process to execute
heating a plurality of target substrates stacked at intervals within a process field in a process container; and
supplying process gases to the process field to deposit a thin film on the target substrates, wherein the process gases include a first process gas for providing a main material of the thin film, a second process gas for reacting with the first process gas, and a third process gas for providing a sub-material of the thin film,
wherein said supplying the process gases comprises
supplying the first and third process gases to a gas mixture tank disposed outside the process container to form a mixture gas,
supplying the mixture gas from the gas mixture tank to the process field, and
supplying the second process gas to the process field without passing through the gas mixture tank,
so as to alternately and pulse-wise supply the mixture gas and the second process gas to the process field.
24. A computer readable medium containing program instructions for execution on a processor, which, when executed by the processor, cause a film formation apparatus for a semiconductor process to execute
heating a plurality of target substrates stacked at intervals within a process field in a process container; and
supplying process gases to the process field to deposit a thin film on the target substrates, wherein the process gases include a first process gas for providing a main material of the thin film, a second process gas for reacting with the first process gas, and a third process gas for providing a sub-material of the thin film, and the third process gas is supplied to the process field in an amount smaller than that of the first process gas,
wherein said supplying the process gases comprises
supplying the first and third process gases to a mixture gas supply line to form a mixture gas and supply the mixture gas to the process field, while temporarily storing the first process gas in a first tank disposed immediately before the mixture gas supply line, and
supplying the second process gas to the process field without passing through the mixture gas supply line,
so as to alternately and pulse-wise supply the mixture gas and the second process gas to the process field.
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US8343594B2 (en) 2013-01-01
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