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US20010003271A1 - Processing apparatus with a chamber having therein a high-corrosion-resistant sprayed film - Google Patents

Processing apparatus with a chamber having therein a high-corrosion-resistant sprayed film Download PDF

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Publication number
US20010003271A1
US20010003271A1 US09/731,722 US73172200A US2001003271A1 US 20010003271 A1 US20010003271 A1 US 20010003271A1 US 73172200 A US73172200 A US 73172200A US 2001003271 A1 US2001003271 A1 US 2001003271A1
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Prior art keywords
gas
chamber
film
processing apparatus
substrate
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US09/731,722
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English (en)
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Hayashi Otsuki
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Tokyo Electron Ltd
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Tokyo Electron Ltd
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Assigned to TOKYO ELECTRON LIMITED reassignment TOKYO ELECTRON LIMITED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: OTSUKI, HAYASHI
Publication of US20010003271A1 publication Critical patent/US20010003271A1/en
Priority to US10/444,957 priority Critical patent/US7846291B2/en
Priority to US11/980,596 priority patent/US7879179B2/en
Priority to US11/980,570 priority patent/US20080069966A1/en
Abandoned legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical 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
    • C23C16/455Chemical 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
    • C23C16/45563Gas nozzles
    • C23C16/45565Shower nozzles
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical 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
    • C23C16/4401Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber
    • C23C16/4404Coatings or surface treatment on the inside of the reaction chamber or on parts thereof
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical 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
    • C23C16/455Chemical 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
    • C23C16/45514Mixing in close vicinity to the substrate
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical 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
    • C23C16/455Chemical 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
    • C23C16/45561Gas plumbing upstream of the reaction chamber
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical 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
    • C23C16/455Chemical 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
    • C23C16/45563Gas nozzles
    • C23C16/45574Nozzles for more than one gas
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical 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
    • C23C16/455Chemical 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
    • C23C16/45563Gas nozzles
    • C23C16/4558Perforated rings
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical 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
    • C23C16/50Chemical 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
    • C23C16/505Chemical 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
    • C23C16/507Chemical 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 external electrodes, e.g. in tunnel type reactors
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/10Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
    • C23C4/11Oxides
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32Gas-filled discharge tubes
    • H01J37/32009Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
    • H01J37/32082Radio frequency generated discharge
    • H01J37/321Radio frequency generated discharge the radio frequency energy being inductively coupled to the plasma
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32Gas-filled discharge tubes
    • H01J37/32431Constructional details of the reactor
    • H01J37/32458Vessel
    • H01J37/32477Vessel characterised by the means for protecting vessels or internal parts, e.g. coatings
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32Gas-filled discharge tubes
    • H01J37/32431Constructional details of the reactor
    • H01J37/32458Vessel
    • H01J37/32477Vessel characterised by the means for protecting vessels or internal parts, e.g. coatings
    • H01J37/32495Means for protecting the vessel against plasma
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/26Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension

Definitions

  • a present invention relates to a processing chamber having a mounted chamber having a high-corrosion-resistant film and applied to a film forming apparatus, heat processing apparatus and etching apparatus as used in a CVD (Chemical Vapor Deposition), etc.
  • CVD Chemical Vapor Deposition
  • a barrier layer is formed on the bottom and inner wall of the hole before forming a buried layer in the contact hole or via hole and then such a buried layer is formed.
  • a TiN film is known as a barrier layer.
  • a high dielectric constant material such as Ta 2 O 5 is used as a capacitor gate material to obtain a higher capacitance without changing its scale.
  • a higher dielectric constant material is not stabler in characteristic than SiO 2 conventionally used as the capacitor gate material. If a poly-Si is used on the overlying electrode, it is oxidized due to the chemical reaction after the formation of the capacitance, thus failing to manufacture a device element of stable characteristics. It is, therefore, necessary that a less-oxidized TiN film be used as an overlying electrode.
  • the TiN film has been formed by using a physical vapor deposition (PVD) technique and a demand has been made for a finer and higher integration device in particular.
  • PVD physical vapor deposition
  • the design rules are particularly stringent.
  • CVD chemical vapor deposition
  • a thermal CVD is used, in which TiCl 4 and NH 3 (ammonia) or MMH (monomethylhydrazine) is applied, as a reaction gas, to a heated substrate.
  • the TiN film being a columnar crystal, is liable to be boundary-diffused and involves a lower barrier characteristic.
  • the lower barrier characteristic presents a problem in the case where the TiN film is used as a barrier layer for a Cu connection line or an oxygen diffusion barrier for Ta 2 O 5 connection line of an electrode overlying the capacitor. That is, a problem occurs due to the corrosion of the Cu connection line by the residual chlorine or a lowering of a capacitance of Ta 2 O 5 by the diffusion of oxygen.
  • An amount of Cl in the formed film can be indeed reduced by making a film formation temperature higher.
  • a high temperature process is not preferable due to a problem, such as thermal resistance and the corrosion, of a connection line material such as Cu and Al.
  • ICP Inductively Coupled Plasma
  • an antenna member such as a coil is provided around a bell jar (chamber).
  • an inductive electromagnetic field is created to provide plasma.
  • the TiN film becomes low-resistance and low in chlorine, and even a film formed at a relatively low temperature is made low in an amount of residual chlorine.
  • a deposit is formed on the inner wall of the chamber due to the introduction of a process gas from above the chamber and a foreign deposit is liable to be formed.
  • the plasma created is attenuated due to the deposit of a conductive film on the inner wall of the upper chamber, thus making it difficult to form a film.
  • An object of the present invention is to provide a processing apparatus having a chamber applied to a film forming apparatus, heat processing apparatus and etching apparatus and having a high-corrosion-resistant property and less liable to deposit a product by a process gas or a product, such as an etching product, on its inner wall thereof.
  • the thus constructed processing apparatus has a mounted chamber holding a to-be-processed substrate and having members for work-processing the substrate by any of heating, plasma, process gas or a combination thereof, in which a film of Al 2 O 3 and Y 2 O 3 is formed on the inner wall surface of the chamber and on the exposed surfaces of the members within the chamber, the Al 2 O 3 /Y 2 O 3 weight ratio being above 0.5.
  • the Al 2 O 3 /Y 2 O 3 weight ratio is in a range above 0.5 but below 4.
  • the thickness of the formed film is above 50 ⁇ m.
  • FIG. 1 is a view showing a practical structure of a plasma CVD apparatus according to a first embodiment of the present invention
  • FIGS. 2A and 2B are views showing a sample of a test by etching and evaluation standard
  • FIG. 3 is a view showing a relation of members in an etching time to an etched amount
  • FIG. 7 is a view showing a rate of a composite oxide when the Al 2 O 3 /Y 2 O 3 weight ratio of a sprayed film varies;
  • FIG. 8 is a view showing a relation of an Al 2 O 3 /Y 2 O 3 weight ratio of a sprayed film to an etched amount
  • FIG. 9 is a view showing an X-ray diffraction pattern of a sprayed film when sprayed is made using a YAG;
  • FIG. 10 is a view showing a practical form of a plasma CVD apparatus according to a second embodiment
  • FIG. 11 is a view showing a practical form of a plasma CVD apparatus according to a third embodiment
  • FIG. 12 is a view showing a practical structure of a plasma CVD apparatus according to a fourth embodiment
  • FIGS. 13A and 13B show a practical structure of a shower head in the fourth embodiment
  • FIGS. 14A and 14B are a view showing a modified structure of the shower head in the fourth embodiment
  • FIG. 15 is a view showing practical structures of head section
  • FIG. 16 is a perspective view showing a first modified structure of a gas discharge member
  • FIG. 17 is a perspective view showing a second modified structure of a gas discharge member
  • FIG. 18 is a view showing one form of a lower-height thin type chamber
  • FIG. 19 is a view showing one form of a semi-spherical type chamber
  • FIG. 20 is a view showing one form of a dome-type chamber
  • FIG. 21 is a view showing a practical structure of a heat processing apparatus
  • FIG. 22 is a view showing a practical structure of an ashing apparatus
  • FIG. 23 is a view showing a practical structure of an etching apparatus.
  • FIG. 24 is a view showing a relation of a breakdown voltage to the thickness of the sprayed film in the respective embodiment of the present invention.
  • FIG. 1 is a cross-sectional view showing a practical example applied to a CVD film forming apparatus as a first embodiment of the present invention in a processing apparatus having a mounted chamber having a high corrosion-resistant thermal sprayed film.
  • the film forming apparatus of the present invention is directed to forming, for example, a TiN thin film.
  • the film forming apparatus 10 includes a chamber 11 having a lower chamber 11 a and upper chamber 11 formed as an integral unit in a hermetically sealable way.
  • the upper chamber 11 b is made smaller in diameter than the lower chamber 11 a .
  • the lower chamber 11 a is comprised of an electric conductor 12 , such as aluminum, whose surface is anadigation processed for example.
  • the upper chamber 11 b comprises a base material 13 of, for example, a ceramic material and a sprayed film 14 .
  • the film 14 may contain oxide of Y, Sc, La, Ce, Eu, Dy or the like, or fluoride of one of these metals.
  • the film 14 may be made of a compound of a III-a element of the periodic table, such as Y 2 O 3 . Needless to say, the film 14 may be made of such a compound and any other material.
  • the film 14 containing a compound of a III-a element is a sprayed film that substantially comprises Al2O3 and Y 2 O 3 .
  • the material of the chamber use can be made of ceramic (Al 2 O 3 , SiO 2 , AlN etc.,), aluminum or stainless steel, metal or metal alloy.
  • a weight ratio of Al 2 O 3 /Y 2 O 3 of the sprayed film 14 is preferably 0.5 to 4. It is to be noted that FIG. 8 simply shows data of the weight ratio of up to 1.5.
  • the sprayed film 14 it may be possible to spray an Al 2 O 3 and Y 2 O 3 compound or to spray, for example, yttrium-aluminum-garnet (YAG) in a composite oxide state of the above-mentioned composition range.
  • the thickness of the sprayed film is based on the insulation withstand characteristic for plasma generation and, from the standpoint of the breakdown voltage characteristic shown in, for example, FIG. 2, may be of the order of at least 50 ⁇ m and preferably of the order of 50 ⁇ m but not above 300 ⁇ m from the standpoint of a manufacturing process and cost.
  • the ceramics of the base material 13 may be Al 2 O 3 , SiO 2 , such as silica glass and quartz, AlN, alternatively, rigid plastic may be used, and, here, the sprayed film as set out above is not formed on the inner wall of the upper chamber 11 b but it may be formed there.
  • an insulating plate 15 of ceramic, etc., and support base 16 are provided and a substantially cylindrical susceptor 17 is provided on the support base 16 to place a semiconductor wafer (hereinafter referred to as a wafer) as a to-be-processed object on it.
  • a wafer semiconductor wafer
  • a coolant chamber 18 is provided in the interior of the support base 16 to receive the coolant via a coolant introducing tube 19 .
  • the coolant is discharged out of a discharge tube 20 .
  • a cold is conducted through the susceptor 17 to the wafer W.
  • a heating element 21 is buried in the susceptor 17 to heat the wafer W to a predetermined temperature by supplying power from a power source 22 .
  • a controller 23 is connected to the power source 22 . And the temperature of the wafer W is controlled by a cold of the coolant and heat of the heating element.
  • an electrostatic chuck 24 is provided which is substantially the same in configuration as the wafer W.
  • the electrostatic chuck 24 is so formed as to have an electrode 26 buried in an insulating material 25 .
  • the wafer W is electrostatically attracted by a Coulomb force, etc., generated by applying a DC voltage from a DC power source 27 to the electrode 26 .
  • a focusing ring 28 is provided at the outer peripheral portion of an upper surface of the electrostatic chuck 24 to surround the wafer W.
  • the above-mentioned sprayed film 14 is formed on those exposed surfaces of the support base 16 , susceptor 17 , electrostatic chuck 24 and focusing ring 28 within the chamber.
  • a shower head member 30 is provided above the chamber 11 b .
  • many gas discharge holes 30 a (Ar, ClF 3 ), 30 b (Ar, TiCl 4 ) and 30 c (NH 3 ) are alternately formed to discharge gases in a down direction within the chamber.
  • the pipes of a gas supply system 40 are connected to the shower head member 30 .
  • a pipe 55 for supplying a gas (Ar, ClF 3 ) is connected to the gas discharge holes 30 a
  • a pipe 56 for supplying a gas (Ar, TiCl 4 ) is connected to the gas discharge holes 30 b
  • a pipe 57 for supplying a gas (NH 3 ) is connected to the gas discharge holes 30 c .
  • the shower head member 30 is comprised of, for example, a three-layers-stacked structure of three gas dispersion plate and has discharge plate having the gas discharge holes.
  • the respective gas discharge plate has a groove and holes for allowing one kind of gas to be dispersed evenness to a whole gas discharge surface area in the head.
  • the discharge holes of the gas dispersion plate are so formed as not be overlapped with the discharge holes of the other gas dispersion plate.
  • the gas discharge holes are arranged in a matrix array upon viewing the gas discharge hole surface side from below. And a post-mixing system is adopted according to which TiCl 4 gas and NH 3 gas are discharged from the alternately formed different discharge holes and these gases are mixed as a process gas after being discharged.
  • the gas supply system 40 has a ClF 3 supply source 41 for supplying ClF 3 as a cleaning gas, Ar supply sources 42 and 43 for supplying Ar, a TiCl 4 supply source 44 for supplying TiCl 4 as a process gas and an NH 3 supply source 45 for supplying NH 3 as a process gas.
  • a gas line 46 is connected to the ClF 3 supply source 41
  • gas lines 47 and 48 are connected to the Ar supply sources 42 and 43 , respectively
  • a gas line 49 is connected to the TiCl 4 supply source 44 and a gas line 50 is connected to the NH 3 supply source 45 .
  • a valve 51 ( 51 a , 51 b ) and mass flow controller 52 are provided at these gas lines.
  • the gas line 46 extending from the ClF 3 supply source 41 is joined and the gas line 46 extending form the ClF 3 supply source 41 is joined.
  • the gas line 46 extending form the ClF 3 supply source 41 is joined into a gas line 53 .
  • ClF 3 serving as a cleaning gas is passed through the gas line 46 and pipe 53 and reaches the shower head 30 to allow it to be introduced via the gas discharge holes 30 a into the upper chamber 11 b .
  • Ar alone is supplied from the Ar supply source 42 .
  • the gas line 49 extending from the TiCl 4 supply source 44 is joined.
  • TiCl 4 gas passed through the gas line 49 and pipe 54 is carried by the argon gas and reaches the shower head 30 .
  • the TiCl 4 gas is introduced from the gas discharge holes 30 b into the chamber 11 .
  • the NH 3 gas is supplied from the NH 3 supply source 45 past the gas line 50 and pipe 55 to the shower head 30 and introduced from the gas discharge holes 30 c into the upper chamber 11 b .
  • monomethylhydrazine MMH may be used.
  • the exhaust tube 61 is provided which is connected to an exhaust apparatus 62 including a vacuum pump. By operating the exhaust apparatus 62 it is possible to reduce pressure in the chamber 11 to a predetermined vacuum level.
  • a gate valve 63 is provided at the sidewall of the lower chamber 11 a and, in its open state, allows the wafer W to be passed into and out of an outside, for example, an adjacent load lock chamber, not shown.
  • a coil 65 as an antenna member is wound around the upper chamber 11 b and a high frequency power source 66 is connected to the coil 65 .
  • the high frequency power source 66 has a frequency of, for example, 13.65 MHz.
  • a cooling mechanism 67 using a cooling medium such as a coolant and a cooling source 68 for driving this are provided.
  • the gate valve 63 is opened and, in its open state, a wafer W is loaded into the chamber 11 and placed onto the electrostatic chuck 24 .
  • the wafer W is attracted to the electrostatic chuck 24 by applying a voltage to the electrode 26 .
  • the gate valve 63 is closed, and the interior of the chamber 11 is evacuated by the exhaust system 62 to a predetermined vacuum level.
  • a high frequency power is supplied from the high frequency power source 66 to the coil 65 to create an inductive electromagnetic field within the upper chamber 11 b . Plasma is generated under this high frequency electric field.
  • a predetermined amount of NH 2 gas and TiCl 4 gas are introduced into the upper chamber 11 b from the NH 3 supply source 45 and TiCl 4 supply source 44 to generate plasma and are brought to the lower chamber 11 a side.
  • a TiN thin film is formed onto the wafer W.
  • the formation of the TiN thin film is effected at a temperature of about 300 to 450° C. by controlling an output to the heating element 21 and an amount of flow of a coolant.
  • the wafer W is unloaded out of the chamber 11 and the ClF 3 gas serving as a cleaning gas is introduced into the chamber 11 to clean the interior of the chamber.
  • the inner wall of the upper chamber 11 b is attacked by the plasma generated in the upper chamber 11 b and exposed to the ClF 3 gas (etching gas) at a cleaning time.
  • ClF 3 gas etching gas
  • no adequate corrosion resistance was not obtained in a conventional chamber made of quartz and Al 2 O 3 with the resultant disadvantage of a short life.
  • the sprayed film 14 has insulating property because it contains 6 a III-a group element of the periodic table. Use can be made of, as the basic material, various kinds of materials such as ceramic herein used, aluminum, stainless steel, rigid plastic (engineering plastic) etc. Further, the sprayed film 14 is lower in cost than a sintered product and has a greater merit of forming a film for a short period of time. It is to be noted that such sprayed film may be formed on the inner wall of the lower chamber 11 a and can enhance a corrosion resistance of the lower chamber 11 a.
  • Eight types of samples were used, each comprised a 20 ⁇ 20 ⁇ 2 mm aluminum base, a 200 ⁇ m-thick first sprayed film made of Al 2 O 3 and Y 2 O 3 and formed on the aluminum base, and a 200 ⁇ m-thick second sprayed film formed on the first sprayed film.
  • the first sprayed film is made of Y 2 O 3 in the first type sample, Sc 2 O 3 in the second type sample, Sc 2 F 3 in the third type sample, YF 3 in the fourth type sample, La 2 O 3 in the fifth fifty type sample, CeO 2 in the sixth type sample, Eu 2 O 3 in the seventh type sample, and DyO 3 in the eighth type sample.
  • the sample was, while leaving a central area of 10 mm square, masked at its outer peripheral area with a polyimide film and irradiated with plasma.
  • a plasma-resistant property was evaluated with an etched amount.
  • the etched amount was evaluated with its depth, as shown in FIG. 2B, with the use of a surface roughness meter.
  • samples of other materials were also evaluated in terms of the corrosion-resistant property.
  • the result of evaluation is as shown in FIG. 3.
  • the etched amount is shown with the etched amount of alumina standardized as “1”.
  • the films containing a III-a element of the periodic table had higher corrosion resistance to plasma than the other materials.
  • the sprayed film made of Al 2 O 3 and Y 2 O 3 exhibited a particularly high corrosion resistance since it was of YAG composition.
  • FIGS. 4, 5 and 6 show and X-ray diffraction pattern each. As shown in these figures, for any of the sprayed films, diffraction peaks corresponding to the Al 2 O 3 and Y 2 O 3 crystals are dominant but the diffraction peaks of composite oxides, such as YAlO 3 and Y 4 Al 2 O 9 were also confirmed. It is found that the producing rate of these composite oxides is increased with an increase in the weight ratio of Al 2 O 3 /Y 2 O 3 as shown in FIG. 7.
  • FIG. 10 is a cross-sectional view showing a CVD apparatus according to the second embodiment.
  • a chamber, shower head and gas supply system are different in structure from those of the first embodiment.
  • the same reference numerals are employed to designate parts or elements corresponding in structure to those shown in FIG. 1 and any further explanation is, therefore, omitted.
  • the pipes of the gas supply system 40 are connected to the shower head member 70 .
  • a pipe 81 for supplying an Ar gas and ClF 2 gas is connected to the gas discharge holes 70 a
  • a pipe 82 for supplying a TiCl 4 gas and Ar gas is connected to the gas discharge holes 70 b
  • a pipe 83 for supplying an NH 3 gas is connected to the gas discharge holes 70 c .
  • Pipe-like gas discharge members 71 and 72 extending from the upper chamber 11 c toward the upper zone of the lower chamber 11 a are connected to the gas discharge holes 70 b and 70 c .
  • a gas discharge hole 71 a is formed in the gas discharge member 71 and a gas discharge hole 72 a is formed in the gas discharge member 72 .
  • a gas line 47 extending from an Ar supply source 42 and gas line 46 extending from a ClF 3 supply source 41 are connected to the pipe 81 .
  • the Ar gas and ClF 3 gas are introduced from the pipe 81 into the upper chamber 11 c via the gas discharge hole 70 a , noting that the Ar gas alone is sometimes supplied there.
  • a gas line 49 extending from a TiCl 4 supply source 44 and gas line 48 extending from an Ar supply source 43 are connected to the pipe 82 .
  • the TiCl 4 gas using an Ar gas as a carrier gas is introduced from the pipe 82 through the gas discharge hole 70 b and gas discharge hole 71 a in the gas discharge member 71 into the upper zone of the lower chamber 11 a .
  • a gas line 50 extending from an NH 3 supply source 43 is connected to the pipe 83 and the NH 3 gas is introduced from the pipe 83 through a gas discharge hole 70 c and gas discharge hole 72 a in the gas discharge member 72 into the upper zone of the lower chamber 11 a.
  • the TiCl 4 gas and NH 3 gas are supplied directly into the upper zone of the lower chamber 11 a without passing through the upper chamber 11 c . After so discharged, these gases are mixed within the lower chamber 11 a .
  • the gas line 46 extending from the ClF 3 supply source 41 is joined into the gas line 81 and, by opening a valve 51 on the gas line 46 , the ClF 3 as a cleaning gas is supplied past the gas line 46 and then the pipe 81 to the shower head 70 to allow the ClF 3 gas to be introduced via the discharge hole 70 a into the upper chamber 11 c.
  • a wafer W is loaded into the chamber 11 and the Ar gas as a plasma generation gas is introduced via the gas discharge holes 70 a in the shower head into the upper chamber 11 c .
  • the Ar gas as a plasma generation gas is introduced via the gas discharge holes 70 a in the shower head into the upper chamber 11 c .
  • the film-formed semiconductor wafer is externally unloaded out of the chamber 11 and a ClF 3 gas serving as a cleaning gas is introduced into the chamber 11 to clean the inner wall of the chamber.
  • the Ar gas alone for plasma generation is supplied into the upper chamber 11 c and the TiCl 4 gas and NH 3 gas, serving as a process gas, are supplied directly into the lower chamber 11 a via the gas discharge members 71 and 72 , so that the process gas almost never reaches the inner wall of the upper chamber 11 c . As a result, almost no deposit resulting from the process gas is formed on the inner wall of the upper chamber 11 c.
  • FIG. 11 is a cross-sectional view showing a CVD apparatus according to a third embodiment of the present invention.
  • This embodiment constitutes a combined structure of a lower chamber 11 a similar to that in the first embodiment shown in FIG. 1 and an upper chamber 11 c similar to that of the second embodiment shown in FIG. 10.
  • a sprayed film 14 of mainly Al 2 O 3 and Y 2 O 3 having an insulating property and high corrosion resistance as set out above is formed on the inner wall of the upper chamber 11 b .
  • the same reference numerals are employed to designate parts or elements corresponding in structure to those shown in FIGS. 1 and 10 and any further explanation is, therefore, omitted.
  • a high-corrosion-resistant sprayed film 14 is formed on the inner wall of the upper chamber 11 c and, even if plasma and cleaning gas are contacted with the inner wall, is hard to be etched to provide a longer service life to the chamber. In addition, almost no deposit resulting from the process gas is formed on the upper chamber 11 b . As a result, unlike the prior art technique, there is no inconvenience of the plasma being attenuated by a conductive film deposited on the inner wall of the chamber and hence no difficulty is encountered in the formation of a film.
  • a sprayed film may be formed on the inner wall of the lower chamber 11 a and, by forming such a sprayed film, it is possible to improve a high corrosion resistance to the lower chamber 11 a.
  • a gas supplied from the gas supply system 40 is discharged and directed toward a central area at the upper zone of the lower chamber 11 a and diffused onto a wafer W.
  • a deposit resulting from a process gas is almost hardly formed on the inner wall of the upper chamber 11 d .
  • a sprayed film 14 is formed on the inner wall of the upper chamber and, even if plasma and cleaning gas are contacted with the inner wall, etching is less liable to occur and it is possible to extend the service life of the chamber.
  • FIGS. 13A and 13B each shows a practical structure of a shower head 81 in this embodiment.
  • the shower head 81 is comprised of a ring-type three-layered structure and so designed as to collect gases in the respective outer head sections into a middle-layer head section. That is, ring-like diffusion channels 84 a , 85 a and 86 a are provided in the head sections 84 , 85 and 86 to allow the process gas to be introduced into the chamber.
  • a plurality of discharge holes 84 b (NH 3 gas), discharge holes 85 b (Ar gas) and discharge holes 86 b (TiCl 4 gas or ClF 3 gas) leading to the diffusion channels 84 a , 85 a and 86 a are provided in a middle layer of the head section 85 in one array to allow a corresponding gas to be discharged in a horizontal direction.
  • these discharge holes are so arranged as to allow different kinds of process gases to be sequentially discharged with an argon gas in between.
  • the discharge holes 85 b , 86 b , 85 b , 84 b , 85 b , 86 b , . . . that is, an Ar gas, TiCl 4 gas or ClF 3 gas, Ar gas, NH 3 gas, Ar gas, TiCl 4 gas or ClF 3 gas, . . . are used.
  • FIG. 15 Various practical structures as shown in FIG. 15 are realized depending upon the order in which these head sections are stacked. In these structures, six cases are shown in FIG. 15. It is to be noted that the TiCl 4 gas and ClF 3 gas are switchingly used at a film forming time and cleaning time but that independent corresponding discharge holes may be provided for these gases.
  • the shower heads for introducing the gases into the chamber can be variously changed or modified in the embodiment of the present invention.
  • a shower head is so configured as to have one gas introducing member 95 for allowing a process gas to be supplied from the top side of an upper bell jar onto a wafer W within a lower chamber and a gas discharge section 96 connected to the lower end of the gas introducing member 95 and having a plurality of discharge holes to allow a gas to be spirally supplied down toward the wafer W.
  • a shower head comprises one gas introducing member 97 similar to the gas introducing member 95 and a plurality of gas discharge sections 98 connected to the lower end of the gas introducing member 97 , provided in an outwardly branched fashion and having a plurality of discharge holes so provided as to allow a gas to be discharged down onto a wafer W.
  • two kinds of process gases are separately individually introduced into the chamber, these gases may be introduced together.
  • the present invention is not restricted thereto and other films may be formed.
  • a Cl-containing gas is used as a feed gas and the present invention is effective to the formation of a film using these materials.
  • TiN, Ti, TiSiN, SiN, Ta, TaN, Ta 2 O 5 , PZT, BST, RuO and ZrO As such materials, use is made of, for example, TiN, Ti, TiSiN, SiN, Ta, TaN, Ta 2 O 5 , PZT, BST, RuO and ZrO; a LOWK material, such as SiOF recently used as an insulating interlayer of a low dielectric constant; and Ta, TaN used as a barrier of Cu and SiN used as a etching stop.
  • FIGS. 18, 19 and 20 Those applied forms of chambers provided in the processing apparatus according to the above-mentioned embodiments will be explained below with reference to FIGS. 18, 19 and 20 .
  • the lower chamber 11 a shown in FIG. 1 is taken as an example and, as a gas supply system, a gas supply system for supplying a gas from the sidewall of the chamber shown in FIG. 12 is taken as an example.
  • a gas supply system for supplying a gas from the sidewall of the chamber shown in FIG. 12 is taken as an example.
  • FIG. 18 is one example of a lower-height thin type chamber.
  • This thin type chamber 11 e is thin and has a height (depth) H of, for example, about 0.65 to 10 cm and, preferably, 0.65 to 5 cm.
  • the distance from the inner top surface of the chamber to a wafer W is about 3.8 to 30 cm and, preferably, 3.8 to 20 cm. Since, in this way, the chamber has a lower-volume shape, an exposed area within the chamber is smaller and hence the apparatus is smaller and ensures an easier maintenance. It is, therefore, possible to alleviate an evacuation load on the system 62 .
  • An upper chamber 11 f shown in FIG. 19 is of a semi-spherical type, that is, a bell jar type and an upper chamber 11 g shown in FIG. 20 is of a dome-shaped type. According to these upper chambers, the distribution of an electric field by an antenna relative to the wafer W is made uniform compared with that of a box-type chamber and hence the thickness profile of a formed film, etching, etc., are made uniform.
  • FIG. 21 is a view showing a practical structure applied to a heat processing apparatus as a fifth embodiment in a processing apparatus with a mounted chamber having a high-corrosion-resistant sprayed film according to the present invention.
  • the heat processing apparatus 101 can perform an anneal process for promoting recrystallization of a formed film and a thermal oxidation process.
  • This heat processing apparatus 101 has a susceptor 103 located within a chamber 102 to support a wafer W, a wafer lifting mechanism 105 provided below the susceptor 103 to allow the wafer W to be lifted up by a plurality of lift pins 104 at a transfer of the wafer W, a heater 106 provided in the susceptor 103 and a gas flow chamber 107 for hermetically supplying a gas such as an Ar gas and oxygen gas onto the wafer W.
  • a gas flow chamber 107 for hermetically supplying a gas such as an Ar gas and oxygen gas onto the wafer W.
  • a sprayed film 14 of Al 2 O 3 /Y 2 O 3 is formed on the inner surface of the gas flow chamber 107 and on the surface of a guide section 108 provided on the susceptor 103 to guide a wafer mounting position and, by doing so, it is possible to obtain the same effect as in the above-mentioned respective embodiments.
  • FIG. 22 is a view showing a practical structure applied to an ashing apparatus as a sixth embodiment in a processing apparatus with a mounted chamber having a high-corrosion-resistant sprayed film according to the present invention.
  • the ashing apparatus comprises a hermetically sealable chamber 111 having a lower chamber 111 a and upper chamber 111 b , a susceptor 112 on which a wafer W is placed, a heater 113 provided in the susceptor 112 to heat the wafer W, a gas supply system, not shown, for supplying a process gas such as oxygen, and an evacuation apparatus for evacuating the interior of the chamber 111 .
  • a high-corrosion-resistant sprayed film is formed on the whole inner surface of the upper chamber 111 b and on the sidewall of the lower chamber 111 a except the inner bottom surface and, by doing so, it is possible to obtain the same effect as in the above-mentioned respective embodiment.
  • FIG. 23 is a view showing a practical structure applied to an etching apparatus as a seventh embodiment in a processing apparatus with a mounted chamber having a high-corrosion-resistant sprayed film according to the present invention.
  • a sprayed film 14 is formed, as the above-mentioned case, on exposed surfaces of the susceptor 123 , focusing ring 130 , shower head 122 and shield ring 128 within the chamber and further on the inner upper surface and inner bottom surface of the chamber 121 .
  • a sprayed film of substantially Al 2 O 3 /Y 2 O 3 whose weight ratio is above 0.5 is formed on the inner wall of the chamber and, by doing so, the chamber is less liable to be etched under a plasma and cleaning gas due to the presence of the high-corrosion resistant sprayed film.
  • the present invention can be preferably applied to the film formation, etching, ashing and heat treatment on a less-etching thermal sprayed film of the chamber.
  • the gas supply system supplies a process gas near the upper zone of a wafer within the chamber, the gas hardly reaches the inner wall of the chamber and almost no product is deposited on the wall.
  • a material for the chamber use can be made of a ceramic (Al 2 O 3 , SiO 2 , AlN, etc.), aluminum, stainless steel, metal or alloy.

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US11/980,596 Expired - Fee Related US7879179B2 (en) 1999-12-10 2007-10-31 Processing apparatus with a chamber having therein a high-corrosion-resistant sprayed film
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US7846291B2 (en) 2010-12-07
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US7879179B2 (en) 2011-02-01
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