WO2007085008A2 - Appareil et procede d’utilisation de chlorure d’indium pour la distribution de vapeur d’indium a une source d’ions - Google Patents

Appareil et procede d’utilisation de chlorure d’indium pour la distribution de vapeur d’indium a une source d’ions Download PDF

Info

Publication number
WO2007085008A2
WO2007085008A2 PCT/US2007/060810 US2007060810W WO2007085008A2 WO 2007085008 A2 WO2007085008 A2 WO 2007085008A2 US 2007060810 W US2007060810 W US 2007060810W WO 2007085008 A2 WO2007085008 A2 WO 2007085008A2
Authority
WO
WIPO (PCT)
Prior art keywords
precursor
indium
vessel
dispensing
vapor
Prior art date
Application number
PCT/US2007/060810
Other languages
English (en)
Other versions
WO2007085008A3 (fr
Inventor
Robert Kaim
Paul J. Marganski
Joseph D. Sweeney
Jose I. Arno
Original Assignee
Advanced Technology Materials, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Advanced Technology Materials, Inc. filed Critical Advanced Technology Materials, Inc.
Publication of WO2007085008A2 publication Critical patent/WO2007085008A2/fr
Publication of WO2007085008A3 publication Critical patent/WO2007085008A3/fr

Links

Classifications

    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • 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
    • C23C16/448—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 generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
    • C23C16/4485—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 generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by evaporation without using carrier gas in contact with the source material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/02—Details
    • H01J37/04—Arrangements of electrodes and associated parts for generating or controlling the discharge, e.g. electron-optical arrangement, ion-optical arrangement
    • H01J37/08—Ion sources; Ion guns
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/30—Electron-beam or ion-beam tubes for localised treatment of objects
    • H01J37/317—Electron-beam or ion-beam tubes for localised treatment of objects for changing properties of the objects or for applying thin layers thereon, e.g. for ion implantation
    • H01J37/3171—Electron-beam or ion-beam tubes for localised treatment of objects for changing properties of the objects or for applying thin layers thereon, e.g. for ion implantation for ion implantation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2237/00—Discharge tubes exposing object to beam, e.g. for analysis treatment, etching, imaging
    • H01J2237/006—Details of gas supplies, e.g. in an ion source, to a beam line, to a specimen or to a workpiece

Definitions

  • the present invention relates to use of indium chloride for delivery of indium vapor to an ion source for implantation of indium ions in a substrate.
  • Indium is a commonly used p-type dopant in the manufacture of microelectronic devices, involving ion implantation in which indium ions (In+ ions) are typically generated from a solid precursor.
  • the solid precursor material is placed in a horizontally mounted vaporizer integrated into the housing of the ion generator unit, such unit in common parlance being referred to as an "ion source.”
  • the most common solid precursor for ion implantation is indium trichloride, InCl 3 .
  • This precursor is a hygroscopic solid (hat entails special handling problems, since it is exposed to atmospheric moisture while being loaded into the vaporizer. As a consequence of the resulting pick-up of moisture, the solid precursor must be "pre-conditioned" to remove the contaminating moisture before implantation can begin.
  • indium trichloride tends to form sticky, corrosive deposits inside the vacuum chambers of the ion implanter, which increases the handling and safety issues accompanying its use.
  • the indium trichloride precursor as a result of its halide constituents entails the potential for in situ reaction with apparatus components in the implanter system. Problems associated with such reactivity include the occurrence of corrosive deposits of chlorides in the ion source and beamline regions of the implanter system. As a result of such corrosive chloride deposits, the implanter system requires extended downtime to accommodate cleaning of vacuum chambers and associated process equipment maintenance.
  • the present invention relates in a primary aspect to ion implantation systems and methods.
  • the invention relates to an ion implantation system including an ion source adapted to ionize a precursor vapor to form ions for implantation in a substrate, a material storage and dispensing apparatus including a vessel adapted to hold precursor, and a dispensing assembly coupled to the vessel for dispensing precursor from the vessel, such dispensing assembly being coupled with the ion source, and a heater adapted for heating of the precursor in the vessel to produce precursor vapor pressure adapted for such dispensing, so that the precursor vapor has sufficient vapor pressure for transport and ionization.
  • the invention in another aspect, relates to method of implanting indium ions in a substrate, such method including ionizing a precursor to form the indium ions, and impinging the indium ions on a substrate, wherein the precursor comprises indium monochloride.
  • the invention relates to a method of implanting ions in a substrate, such method including use of a system of the invention.
  • a further aspect of the invention relates to a method of implanting ions in a substrate, such method including ionizing a precursor to form the ions, and impinging the ions on a substrate, wherein the precursor is supplied for such ionizing from a material storage and dispensing apparatus including a vessel adapted to hold precursor, and a dispensing assembly coupled to the vessel for dispensing precursor vapor from the vessel for such ionizing, with heating of the precursor in the vessel to produce precursor vapor pressure adapted for such dispensing, wherein the precursor is a solid or liquid.
  • a still further aspect of the invention relates to a method of fabricating a microelectronic device including material doped with indium, such method comprising doping the material with indium ions derived from a precursor comprising indium monochloride.
  • Yet another aspect of the invention relates to a method of forming an indium- containing material on a substrate, comprising providing a deposition composition including indium monochloride, and contacting said deposition composition with said substrate under deposition conditions, to form said indium-containing material thereon.
  • the invention in another aspect, relates to a method of implanting indium in a substrate, comprising generating indium ions from an indium precursor comprising indium monochloride, and contacting said ions with the substrate to implant indium therein.
  • a further aspect of the invention relates to a method of depositing indium on a substrate, comprising volatilizing an indium, precursor comprising indium monochloride to form indium monochloride precursor vapor, and contacting said precursor vapor with the substrate to deposit indium thereon.
  • FIG. 1 shows a schematic view of an ion beam apparatus to which the present invention may be adapted.
  • FIG. 2 is a schematic representation of a portion of an ion implantation system including an external vapor delivery cylinder employed for indium vapor delivery, in accordance with one embodiment of the present invention.
  • FIG. 3 is an illustration of an ion implantation system of the invention in one embodiment thereof.
  • FIG. 4 is an illustration of various embodiments of the vessel of the invention.
  • the present invention relates to use of indium chloride for delivery of indium vapor to an ion source for implantation of indium ions in a substrate.
  • indium monochloride precursor indium monochloride precursor
  • indium monochloride precursor in use of the indium monochloride precursor, it will be appreciated that the invention contemplates other material deposition and film-forming techniques in which indium monochloride is used as a source material for indium for corresponding deposition of indium- containing material and indium-containing films.
  • Illustrative of such other techniques are formation of indium-tin-oxide (ITO) films by sputtering, spray pyrolysis, chemical vapor deposition, etc.
  • ITO indium-tin-oxide
  • the invention in one embodiment relates to an ion implantation system including an ion source adapted to ionize a precursor vapor to form ions for implantation in a substrate, a material storage and dispensing apparatus including a vessel adapted to hold precursor, and a dispensing assembly coupled to the vessel for dispensing precursor from the vessel.
  • the system includes a dispensing assembly that is coupled with the ion source, and a heater adapted for heating of the precursor in the vessel to produce precursor vapor pressure adapted for such dispensing, so that the precursor vapor has sufficient vapor pressure for transport and ionization.
  • the material storage and dispensing apparatus can be of any suitable type, including for example the apparatus described in the aforementioned U.S. Provisional Patent Application No. 60/662,515 filed in the names of Paul J. Marganski, et al. for "SYSTEM FOR DELIVERY OF REAGENTS FROM SOLID SOURCES THEREOF' and the fluid storage and dispensing apparatus variously described in U.S. Patent 5,518,528; U.S. Patent 5,704,965; U.S. Patent 5,704,967; U.S. Patent 5,707,424; U.S. Patent 6,101,816; U.S. Patent 6,089,027; U.S. Patent Application Publication 20040206241; U.S. Patent 6,921,062; U.S. Patent Application 10/858,509; and U.S. Patent Application 10/022,298, the disclosures of all of which are hereby incorporated herein by reference, in their respective entireties.
  • the material storage and dispensing apparatus of the invention should be fabricated of a suitable high thermal conductivity material such as, for example, silver, silver alloys, copper, copper alloys, aluminum, aluminum alloys, lead, nickel clad, stainless steel, graphite and/or ceramic material.
  • a suitable high thermal conductivity material such as, for example, silver, silver alloys, copper, copper alloys, aluminum, aluminum alloys, lead, nickel clad, stainless steel, graphite and/or ceramic material.
  • the material should also be fabricated from a material that is compatible with the precursor.
  • aluminum is not generally considered to be compatible with chlorides, due to their high reactivity. Therefore, and in consequence of such fact, the vessel of the precursor material storage and dispensing apparatus may be formed of a more compatible material such as stainless steel.
  • a passivation layer may be utilized, such as by anodizing the material, to prevent the material and precursor from contacting one another.
  • the vessel can be subjected to appropriate cleaning and renewal operations, to restore the vessel for resumption of operation, by recharging the vessel with new solid source material. Necessary levels of cleaning and renewal operations will vary, dependent on the vessel material and tfie precursor material.
  • the minimization of down-time for such transitional cleanup and recharging operations may be effected by use of a disposable liner that is dropped into the vessel with a fresh inventory of solids, after a prior inventory of solid is volatilized, and the disposable liner previously containing the original charge of solid source material is simply removed from the vessel, and discarded. Therefore, in another embodiment, the vessel may contain a removable liner inside which the precursor is contained. Such a liner may be inserted into and removed from the vessel.
  • a liner therefore facilitates the refilling of the vessel.
  • a non-volatile residue may form. This residue, when present on internal wall surfaces of a vessel holding the solid source material, is extremely difficult to remove. Therefore, the use of a disposable liner or bag can greatly enhance the reusability of the solid source vessel.
  • the vessel may in fact be supplied to a user by the manufacturer or distributor in a closed state, and the vessel, although connected to valves and dispensing lines, may otherwise remain in a closed condition for return to the manufacturer for refurbishing.
  • the manufacturer then may open the vessel for cleaning. If a liner or bag is used, the manufacturer can simply open the vessel, remove and discard the bag, insert a new bag containing a charge of the solid source material, or a bag that is installed in the vessel in an empty state, and thereafter charged with the solid source material.
  • die liner instead of being disposable, may be formed of a material that is readily cleaned, whereby a liner bag, rather than being discarded, may be simply placed into a volume of cleaning solution, whereby deposited solids, etc. are solubilized or chemically reacted by the cleaning solution, to regenerate the bag for reuse.
  • the disposable or otherwise reusable liner can be formed of any suitable material of construction, e.g., a polymer such as polyimide, polysulfone, etc. that possesses good structural integrity and retention of properties under elevated temperature volatilization conditions to which the solid source material must be subjected to form the desired vapor.
  • a polymer such as polyimide, polysulfone, etc. that possesses good structural integrity and retention of properties under elevated temperature volatilization conditions to which the solid source material must be subjected to form the desired vapor.
  • the vessel may include enhanced surface area structures therein, such as trays, as described in U.S. Patent 6,921,062, or porous inert foam inserts to provide a consistent rate of evaporation of the precursor material and to provide sufficient vapor pressure for the dispensing and ionizing steps of the associated implantation process.
  • enhanced surface area structures therein such as trays, as described in U.S. Patent 6,921,062, or porous inert foam inserts to provide a consistent rate of evaporation of the precursor material and to provide sufficient vapor pressure for the dispensing and ionizing steps of the associated implantation process.
  • the foam may in fact be usefully employed in combination with the trays, or alone, as a monolithic body, or bed of monolithic articles, that can be deployed in the interior volume of the vaporizer vessel, in place of a tray assembly or other support structure.
  • the foam being a porous solid structural body, can also enable a substantially increased surface area to be provided, in relation to a planar tray surface, with the specific magnitude of increase in surface area depending on the porosity and pore size characteristics of the foam.
  • the foam also enables greater metal to chemistry contact to be achieved, in relation to a tray structure alone. This in turn enables more uniform heating of the chemistry itself to be realized, when heat is inputted to the vessel.
  • Such porous foam inserts may comprise anodized aluminum or nickel foam, stainless steel, nickel, bronze, etc. As set forth above with respect to liners and bags, the porous foam inserts may be reusable or may be disposable.
  • the precursor advantageously is a solid or liquid.
  • reference to the precursor as a solid or liquid is to be understood as referring to such precursor material as having a vapor pressure associated with the solid or liquid material, wherein such vapor pressure may vary as a function of temperature of the solid or liquid.
  • the dispensing assembly of die ion implantation system of the invention is coupled with the ion source by flow circuitry, and such flow circuitry may be heated by the heater.
  • the vessel in such system can hold a suitable precursor, such as a normally (at standard temperature of 25 0 C and standard pressure of 1 atmosphere) solid or liquid precursor that is heated to provide appropriate vapor pressure of the vapor phase of such precursor in the vessel, with the heater optionally heating the flow circuitry, e.g., by a same or distinct heating unit of a heating system, such as a separate heating tape wrapped around the conduit of the flow circuit, or a steam tracing line on such conduit.
  • the vessel heater can be of any suitable type, e.g., a heating jacket at least partially surrounding the vessel, such as an electrical resistance heating jacket, or a heat exchange jacket through which a heating fluid is flowed.
  • the heater may include an infrared light source for infrared heating of the vessel, or radiant heating with a heat lamp disposed in close proximity to the vessel may be employed.
  • additional heating methods may be employed, including, but not limited to microwave heating, conductive heating, convective heating, electrical resistance heating, etc.
  • the heater includes cartridge heater element(s), with corresponding holes being drilled or otherwise formed in a wall of the vessel, and electric cartridge heaters being inserted into the respective openings.
  • electric cartridge heaters when coupled with a source of electrical power, serve to supply heat to the wall of the vessel.
  • the holes drilled in the vessel wall can be tapped to provide threading in the opening that is complementary to threading on the electric cartridge heater or an associated fitting or coupling. Heating can also be carried out by clamping matable pieces to the vessel, in the form of an oven.
  • the vessel may be at least partially surrounded by an insulating jacket. A jacket around the vessel may insulate and/or heat the vessel.
  • the vessel is formed of a high thermal conductivity material, for heating of the precursor material.
  • a high thermal conductivity material ensures good thermal uniformity of the vessel contents.
  • Such high thermal conductivity materials may include, but are not limited to aluminum, nickel, copper and stainless steel.
  • a vortex cooler can be employed to rapidly cool a vessel at elevated temperature.
  • the vessel In order to remove the vessel after use, the vessel must be cool enough for an operator to handle, and a vortex cooler can be used to reduce the temperature of the vessel to a handleable condition.
  • Other cooling methods may include, but are not limited to, use of a water jacket on the vessel and a thermoelectric cooler. Any method may be utilized to cool the vessel sufficient for handling.
  • the vessel contains a temperature sensor and/or a pressure sensor as part of a monitor and control scheme to modulate heating of the precursor material through heating of the vessel and the dispensing assembly.
  • the monitor and control scheme is utilized to achieve a predetermined temperature and pressure of the flow of precursor vapor into the ion source.
  • the sensor is a temperature sensor which provides over- temperature protection.
  • the sensor may be coupled to a switch, in series with the heat source. When the temperature is sensed to be at or above the limit of a maximum temperature, the switch will be activated, controlling further heating.
  • the vessel defines an enclosed interior volume in which the precursor is retained.
  • the vessel is equipped with a valve assembly at its upper end that is enveloped by a block of high thermal conductivity material that can be detachably secured to the valve assembly.
  • high thermal conductivity materials may include, but are not limited to aluminum, nickel and copper.
  • the block is separable into component parts, which cooperatively mate with one another to form the enveloping block structure around the valve.
  • the block in one embodiment is formed of two half-sections that envelope the valve assembly, in thermal conduction contact with the valve structure, so that the block when heated thermally conducts heat to the valve, to avoid condensation of the precursor vapor in the valve assembly.
  • the respective parts of the block may be coupled with one another in any suitable manner.
  • the block may be formed as half-sections that are hinged with respect to one another, to be opened and fitted around the valve head assembly, being thereafter closed so that the half-sections mate with one another and are secureable in position by a suitable securement structure.
  • This securement structure may be of any suitable type, including coupling elements, lock structures, latches, keyed structures, etc.
  • the block may be equipped with a passage therethrough to permit flow of precursor vapor from the valve in the valve assembly through the block to the ion source and/or associated flow circuitry.
  • the flow circuitry can in turn be coupled with a downstream process facility in which the dispensed vapor is utilized.
  • the block may be equipped with fittings, couplings, or the like that matably engage the port of the valve in the valve assembly, and permit coupling of the block with the associated flow circuitry, e.g., a discharge conduit with a fitting that engages the block.
  • the associated flow circuitry e.g., a discharge conduit with a fitting that engages the block.
  • the block may be heated by any suitable heating arrangement, including radiant heat, resistive heating of the block itself when coupled with a suitable electrical power supply, impingement of microwave or ultrasonic energy on the block causing heating thereof, jacketing of the block with a heating and/or insulating jacket operatively arranged to heat the block to elevated temperature, or other suitable heating arrangement by which the temperature of the block may be elevated to conduct heat to the valve passages in the valve assembly of the material storage and dispensing apparatus, so as to prevent condensation of precursor vapor in the passages of the valve, the ion source and associated flow circuitry.
  • any suitable heating arrangement including radiant heat, resistive heating of the block itself when coupled with a suitable electrical power supply, impingement of microwave or ultrasonic energy on the block causing heating thereof, jacketing of the block with a heating and/or insulating jacket operatively arranged to heat the block to elevated temperature, or other suitable heating arrangement by which the temperature of the block may be elevated to conduct heat to the valve passages in the valve assembly of the material storage and dispensing apparatus
  • the system contains one or more sections in which the temperature is independently controlled. Such sections are referred to herein as "temperature control zones.”
  • the valve and block may be within a single temperature control zone, different from the temperature control zone in which the vessel is present.
  • the temperature of the block may be monitored and controlled separately from the temperature of the vessel. Over- temperature protection may also be provided to the valve and block assembly.
  • High conductance valves useful in the invention may include those commercially available from Swagelok Company (Solon, Ohio, USA), in particular the ELD8 series valves.
  • Other examples of valves useful in the invention include those disclosed in International Patent Application Publication WO/2006/101767 published September 28, 2006 and entitled "SYSTEM FOR DELIVERY OF REAGENTS FROM SOLED SOURCES THEREOF," the contents of which are hereby incorporated by reference in their entirety.
  • a carrier gas may be employed for improving the delivery rate of the indium material, including a suitable carrier gas, e.g., helium, nitrogen, argon, xenon, etc.
  • a suitable carrier gas e.g., helium, nitrogen, argon, xenon, etc.
  • Such carrier gas may be at suitable elevated temperature to provide an appropriate vapor pressure to the precursor vapor being transported to the ion source by the carrier gas.
  • the use of a carrier gas for transport of the indium precursor vapor may in specific applications provide additional benefit in disassociating the indium precursor molecules.
  • the vessel may contain a level sensing apparatus, which is a device that is in contact with the precursor in the vessel, whether in liquid or solid form, and a spring that allows the device to remain in contact with the precursor as Ihe amount in the vessel fluctuates.
  • a level sensing apparatus which is a device that is in contact with the precursor in the vessel, whether in liquid or solid form, and a spring that allows the device to remain in contact with the precursor as Ihe amount in the vessel fluctuates.
  • Actual level sensing may be effected by use of electrical contact(s) or magnetic, optical, pressure or other sensors that provide an output indicative of the level of the device in contact with the upper surface of the precursor, thereby producing an output reflecting the amount of precursor that remains in the vessel.
  • the precursor comprises an indium precursor, and in a specifically further preferred embodiment, the indium precursor comprises indium monochloride.
  • the ion source in the system in another preferred embodiment includes a housing that is devoid of any vaporizer integrated into such housing.
  • the invention in one method embodiment relates to a method of implanting indium ions in a substrate, by ionizing a precursor to form the indium ions, and impinging the indium ions on a substrate, wherein the precursor comprises indium monochloride.
  • the precursor is advantageously supplied to an ion source for such ionizing from a material storage and dispensing source that is heated so that precursor vapor is delivered from the material storage and dispensing source at suitable vapor pressure for such ionizing.
  • the material storage and dispensing apparatus includes a vessel adapted to hold precursor, and a dispensing assembly coupled to the vessel for dispensing precursor from the vessel, with the dispensing assembly being coupled with an ion source adapted for the ionizing, and a heater adapted for heating of the precursor in the vessel so that precursor has sufficient vapor pressure for transport from the vessel and associated dispensing assembly, and subsequent ionization.
  • the use of a positive thermal gradient within the system may be employed to combat such re-deposition. In a specific implementation, this is accomplished by ensuring that as the precursor material moves from the vessel through the dispensing assembly and into the ionization chamber, the environment of the precursor is maintained at a temperature that exceeds that of the vaporizer, so that re-deposition is precluded.
  • any suitable temperature gradient may be employed for such purpose, it is generally preferable that the temperature of the vessel is 1-10 0 C cooler than any part of the rest of the system. In one embodiment the temperature of the vessel is about 1° to about 2 0 C cooler than any part of the remainder of the system. In another embodiment the temperature of the vessel is about 5° to about 10 0 C cooler than any part of the remainder of the system.
  • the material storage and dispensing apparatus in one preferred embodiment, is of a size ihat is manually transportable, e.g., being able to be physically carried by an individual from an inventory or supply point, either with or without the dispensing assembly, to the point of installation and use of the material storage and dispensing apparatus.
  • the material storage and dispensing apparatus of the invention can be constructed and configured in any suitable manner, and may utilize any of the various elements, features, components and sub-assemblies described herein, with inclusion or exclusion of any one or more of specific elements, features, components and sub-assemblies, as may be appropriate in a specific implementation of the invention.
  • the system in various embodiments may comprise indium monochloride or other indium precursor as a component material in the system, as initially commercially supplied for use in an ion implantation or indium film deposition application.
  • the supply vessel in the storage and dispensing system of the invention in one embodiment thereof contains indium monochloride precursor in an amount of from about 20 to about 500 grams. In another embodiment, the vessel contains from about 50 to about 250 grams of indium monochloride, and in still another embodiment, the vessel contains from about 100 to about 200 grams of indium chloride. In such ranges, the term "about” refers to amounts that may vary by up to 5% of the specific numeric values.
  • the invention contemplates a method of implanting ions in a substrate, involving use of a system as described hereinabove.
  • the method of implanting ions in a substrate can therefore include ionizing a precursor to form the ions, and impinging the ions on a substrate, wherein the precursor is supplied for the ionizing from a material storage and dispensing apparatus including a vessel adapted to hold precursor, and a dispensing assembly coupled to the vessel for dispensing precursor from the vessel, with heating of the precursor in the vessel so that precursor vapor dispensed from the apparatus has sufficient vapor pressure for transport and ionizing, with the precursor being of solid or liquid form in the vessel as a source of vapor for such dispensing.
  • the solid or liquid precursor forms a two-phase equilibrium with its own vapor, in which the vapor pressure depends on temperature.
  • the dispensed precursor vapor can be flowed from the dispensing assembly by flow circuitry to an ionization zone for the ionizing, and such flow circuitry can be heated in the aforementioned heating step, which can also involve operation of a heating and/or insulating jacket at least partially surrounding the vessel, e.g., of a type as previously described.
  • the precursor preferably comprises an indium precursor such as indium monochloride.
  • the ionization zone preferably includes a housing that is devoid of any vaporizer integrated into the housing.
  • the flow circuitry can be controlled, as necessary, using any known method.
  • the system comprises a temperature control loop and a flow restrictor.
  • die invention provides a high temperature pressure control valve and a transducer in combination with a flow restrictor.
  • the flow circuitry is controlled by a flow control assembly including at least a valve, a feedback control circuit and an associated proportional solenoid or the like so that the valve can be electronically controlled remotely by a microprocessor (CPU).
  • the output flow control means may comprise a rotameter/needle valve assembly for controlling the flow of vaporized precursor from an outlet port of the vessel to the ion source.
  • the needle valve is an air-operated device, designed to apply precise and repeatable amounts of vaporized precursor, dependent on specific variables such as valve open time, fluid pressure, flow control adjustment, dispense tip diameter and fluid viscosity.
  • Various needle flow valves for this purpose are readily commercially available.
  • the flow circuitry is controlled by a flow control assembly including a constant flow control valve equipped with an orifice sized to deliver a specific flow rate ranging from about micromillilters to about liters per minute.
  • the constant flow control valve is in fluid communication with an outlet port of the vessel.
  • the orifice of the constant flow control valve is sized to provide a controlled and constant flow of vaporized precursor to the ion source via the connecting dispensing assembly.
  • the constant flow control valve may further include a diaphragm which is resiliently biased into a normally open position, and which shifts to a closed position when exposed to a fluid pressure above a predetermined maximum level.
  • the constant flow valve automatically closes when the fluid delivery pressure is above the predetermined maximum level and automatically opens when the fluid delivery pressures falls below that maximum level thereby maintaining a substantially constant flow of the vaporized precursor through the connecting dispensing assembly to the ion source.
  • the use of a constant flow control valve with any of the vessels described above, provides for a flow rate that will remain essentially constant, even with varying pressures and varying fluid viscosities.
  • Various constant flow control valves for this purpose are readily commercially available.
  • the output flow control means may include a mass flow controller (MFC) in fluid communication with an output port of the vessel to control the flow of vaporized precursor to the ion source.
  • MFC mass flow controller
  • the flow of material through the mass flow controller may, for example be in a range of from about 0.5 seem to 5 seem, and more preferably, from about 1 to about 2 seem, in various embodiments of the invention.
  • the mass flow controller having a variable valve and positioned in fluid communication with the dispensing assembly, can accommodate different flow rates, set points and pressures.
  • the MFC is communicatively connected to a CPU for adjusting the valve positioning, thereby compensating for the pressure and density of the gas that actually is flowing through the MFC, in order to maintain sufficient flow into die ion source.
  • the invention in one aspect thereof contemplates a method for fabricating a microelectronic device including material doped with indium, in which such method includes doping the material with indium ions derived from a precursor comprising indium monochloride.
  • an indium precursor material is disposed in a container that is external to the ion source in the implanter system.
  • the apparatus and method of the present invention have the following advantages: (i) the precursor is able to be supplied in die first instance in a sealed container that is conveniently used at the implanter site or other end-use environment of the precursor vapor, e.g., a chemical vapor deposition tool, plasma etch tool, or semiconductor manufacturing facility, whereby precursor purity is assured and the absence of moisture (since atmospheric exposure of the precursor is avoided) reduces or eliminates requirements for preconditioning of the precursor material; (ii) the user/operator of the implantation system (or of other precursor vapor-using process equipment) avoids (he requirement of manually loading the vaporizer with toxic or otherwise hazardous material; (iii) the external cylinder can be constructed and arranged to hold many more times the amount of precursor than is able to be held by the conventional vaporizer unit (e.g., 10 times or more, such as 100-200 grams versus 10 grams for a conventional vaporizer unit), so that a single charge of precursor will last for many source lifetimes, avoiding the source rebuild maintenance
  • an external supply vessel for the precursor in accordance with the present invention, also has the advantage that it permits use of precursors that heretofore have not been able to be utilized in the prior art procedure of disposing the precursor in the vaporizer unit.
  • liquid source materials can be employed in place of solid source materials, as precursors for vapor-phase processes.
  • indium trichloride As a specific example, the most commonly employed indium precursor for ion implantation is indium trichloride, as discussed earlier herein. Indium trichloride has a melting point of about 58O 0 C. Indium monochloride, having a melting point of about 22O 0 C, is not known as an indium precursor in conventional vaporizers, as a consequence of the fact that such material would be in liquid form at the delivery temperatures on the order of 300 0 C that are typically utilized for indium implantation.
  • Indium monochloride has a number of advantages over indium trichloride, as a precursor for ion implantation of indium ions: (i) indium monochloride has a higher vapor pressure at temperature below 350 0 C, than does indium trichloride; (ii) indium monochloride has a higher indium content than indium trichloride, yielding a more favorable formation of In + relative to chlorine ions in the ion source, (iii) indium monochloride has a lower chlorine content than indium trichloride, so that the amount of chlorine available to form sticky, corrosive deposits is substantially reduced.
  • the invention thus contemplates the use of indium monochloride as an indium precursor for use in ion implantation of indium, in which the indium monochloride is supplied from a material storage and dispensing apparatus including a vessel holding such precursor and a dispenser assembly coupled to the vessel.
  • the material storage and dispensing apparatus further includes a heater adapted to heat the vessel.
  • the heater can be in the form of a heating and/or insulating jacket disposed about the container, embedded heat transfer passages in the vessel, electrical resistance heating elements disposed in the vessel, or other device and/or structure effecting heating of the contents of the vessel.
  • the invention contemplates the use of indium monochloride as a precursor for deposition of indium-containing material, e.g., formation of indium-containing thin ( ⁇ 1000 ⁇ m) films, on substrates, such as in the manufacture of microelectronic devices, including semiconductor products and flat-panel displays.
  • deposition of indium- containing material may be carried out in any suitable manner, including for example vapor deposition techniques such as chemical vapor deposition, plasma-assisted chemical vapor deposition, plasma spray coating, pyrolytic deposition, sputter deposition, etc.
  • the invention also contemplates other indium halides, including indium bromides and indium chlorides in addition to indium monochloride and indium trichloride.
  • the precursor of the invention may be present in the vessel in solid or liquid form, as discussed previously.
  • Such precursor form may include precursor dissolved into or adsorbed onto an ionic liquid, or precursor adsorbed onto a solid phase sorbent material, i.e. carbon and/or other solid structure or material.
  • Use of the precursor in such dissolved or adsorbed forms may provide improved heat transfer and vaporization efficiency within the vessel, e.g., by the specific heat, conductivity, etc., of the ionic liquid or sorbent material.
  • the invention further contemplates such material storage and dispensing apparatus as including the precursor, optionally with other reagents, as a stand-alone package of the precursor that can be coupled in material dispensing relationship to a vaporizer of an ion implantation system, to supply precursor to the vaporizer, without precursor being loaded in the first instance into a vaporizer.
  • the invention also contemplates an indium ion implantation process, in which indium is ionized from a precursor comprising indium monochloride, to generate the indium implantation ions.
  • the invention additionally contemplates a method of forming an indium-containing material on a substrate, including providing a deposition composition comprising indium monochloride, and contacting such deposition composition with the substrate under deposition conditions, to form the indium-containing material thereon.
  • the deposition composition comprises indium monochloride vapor.
  • the method may for example involve vapor deposition contacting of the deposition composition with the substrate, e.g., involving chemical vapor deposition, or such method may include ion implantation.
  • the material storage and dispensing apparatus is portable and removably connected to the ion source.
  • the vessel in such apparatus in a specific embodiment may be sized to contain indium monochloride as the precursor, in an amount in a range of from about 50 to about 500 grams, preferably from about 100 to about 200 grams, and the the material storage and dispensing apparatus may be portable and removably connected or connectable to the ion source.
  • FIG. 1 shows a schematic view of an ion beam apparatus to which the present invention may be adapted.
  • the ion beam apparatus includes an ion source 10 and employs an accelerating voltage to inject an ion beam 24 into an evacuated enclosure 12.
  • the beam then enters a magnetic analyzer 14 which is adjusted to select particles with a particular mass and charge for the beam 25 exiting the magnetic analyzer.
  • the ion beam 25 exits the magnetic analyzer 14 and then is directed through a voltage accelerator/decelerator 16 where the selected beam energy is imparted to the ion beam 25.
  • the ion beam 26 exiting the voltage accelerator/decelerator 16 passes through a scanning system 18 which scans the ion beam over the surface of a wafer 30.
  • the ion beam exiting the scanning system 18 passes through an energy filter 52, to provide improved energy uniformity, and a plasma flood gun 54, to neutralize any charge buildup on the wafer during ion implantation.
  • the ion beam 27 exiting the plasma flood gun 54 is directed, by the scanning system 18, to the proper location on an integrated circuit wafer 30 which is disposed on a wafer holder 20.
  • a coupling mechanism 22 attaches the wafer holder 20 to the evacuated enclosure 12. In this manner the ion beam 27 exiting the scanning system can be used to implant dopant into the wafer substrate.
  • FIG. 2 is a schematic representation of a portion of an ion implantation system including an external solid delivery cylinder employed for indium vapor delivery, in accordance with one embodiment of the present invention.
  • the implanter system 100 includes a cylindrical container 102 with a heater jacket 106 and shutoff valve 108 on valve body 104, mounted externally but in close proximity to the ion source (e.g., with a spacing of 10 to 100 centimeters therebetween).
  • the cylindrical container (“cylinder”) holds precursor.
  • the heater jacket 106 can be an electrical resistance heating jacket, equipped with electrical connections 116 and 118, for connection with electrical cables and suitable power supply, to effect electrical resistance heating by the resistance element(s) in the jacket.
  • the heater jacket 106 can be a jacket adapted for flow therethrough of a heated fluid, with the connections 116 and 118 being fluid coupling connections adapted for connection with flow circuitry supplying heat transfer fluid from a suitable supply of heat exchange medium.
  • a heated tube 110 passes from the shutoff valve 108 into the source vacuum chamber 122 through the source flange 112, having source bushing 114 associated therewith, and to the source arc chamber (not shown). This tube is heated to an appropriate temperature for maintaining the precursor at appropriate temperature so that the vapor pressure of its vapor phase is appropriate for delivery to the source arc chamber for ionization and generation of die implant species.
  • FIG. 3 is an illustration of an ion implantation system of the invention.
  • This illustration includes a material storage and dispensing apparatus including a vessel 201 adapted to hold precursor 202 and a dispensing apparatus 203 coupled to the vessel for dispensing precursor.
  • the illustration also includes a vessel heater 205 and a heater of the flow circuitry 206.
  • the illustration also sets forth an ion source 204.
  • FIG. 4 is an illustration of various embodiments of the vessel of the invention.
  • Figure 4A shows a vessel with a removable liner 207. Such a liner may be removable, disposable and/or capable of being cleaned.
  • Figure 4B shows a vessel containing trays 208 as enhanced surface areas of the vessel.
  • Figure 4C shows a vessel with a porous, inert foam insert 209.
  • Figure 4D shows a vessel containing a level sensor 210 attached via a spring 211.
  • Figure 4E shows a vessel containing a valve assembly 212 enveloped by a block 213 of high thermal conductivity material

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

La présente invention concerne un système d’implantation ionique (100) comprenant une source d’ions conçue pour ioniser une vapeur de précurseur et former ainsi des ions à implanter dans un substrat (30), un appareil de stockage et de distribution de matériau comprenant une cuve (102) conçue pour contenir le précurseur, ainsi qu’un ensemble de distribution (104, 108) couplé à la cuve pour distribuer le précurseur à partir de la cuve. L’ensemble de distribution est couplé à la source d’ions (10) et un réchauffeur (106) est conçu pour chauffer le précurseur dans la cuve de telle sorte que le précurseur distribué à partir dudit appareil à la source d’ions est maintenu en phase vapeur pour l’implantation des ions dérivés de celui-ci. Un tel système peut être adapté pour la distribution de monochlorure d’indium, par exemple, à partir d’un appareil portatif de stockage et de distribution de matériau, sans qu’il soit nécessaire d’intégrer un vaporisateur dans le logement de la source d’ions et sans que se posent les problèmes de manipulation et de traitement relatifs à l’utilisation de trichlorure d’indium.
PCT/US2007/060810 2006-01-20 2007-01-20 Appareil et procede d’utilisation de chlorure d’indium pour la distribution de vapeur d’indium a une source d’ions WO2007085008A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US76046406P 2006-01-20 2006-01-20
US60/760,464 2006-01-20

Publications (2)

Publication Number Publication Date
WO2007085008A2 true WO2007085008A2 (fr) 2007-07-26
WO2007085008A3 WO2007085008A3 (fr) 2008-01-03

Family

ID=38288417

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2007/060810 WO2007085008A2 (fr) 2006-01-20 2007-01-20 Appareil et procede d’utilisation de chlorure d’indium pour la distribution de vapeur d’indium a une source d’ions

Country Status (1)

Country Link
WO (1) WO2007085008A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2023520933A (ja) * 2020-05-11 2023-05-22 プラクスエア・テクノロジー・インコーポレイテッド イオン注入器へのアンチモン含有材料の貯蔵及び送達

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5209952A (en) * 1989-03-09 1993-05-11 Merck Patent Gesellschaft Mit Beschraenkter Haftung Use of organometallic compounds to deposit thin films from the gas phase
US20050064637A1 (en) * 2003-09-23 2005-03-24 Wen-Yuan Yeh [method of manufacturing nmos transistor with p-type gate]
US20050269520A1 (en) * 1999-12-13 2005-12-08 Semequip Inc. Icon implantation ion source, system and method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5209952A (en) * 1989-03-09 1993-05-11 Merck Patent Gesellschaft Mit Beschraenkter Haftung Use of organometallic compounds to deposit thin films from the gas phase
US20050269520A1 (en) * 1999-12-13 2005-12-08 Semequip Inc. Icon implantation ion source, system and method
US20050064637A1 (en) * 2003-09-23 2005-03-24 Wen-Yuan Yeh [method of manufacturing nmos transistor with p-type gate]

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2023520933A (ja) * 2020-05-11 2023-05-22 プラクスエア・テクノロジー・インコーポレイテッド イオン注入器へのアンチモン含有材料の貯蔵及び送達

Also Published As

Publication number Publication date
WO2007085008A3 (fr) 2008-01-03

Similar Documents

Publication Publication Date Title
JP6639580B2 (ja) 蒸発器、堆積アレンジメント、堆積装置及びこれらを操作する方法
TWI303461B (en) Vaporizer delivery ampoule
US20030111014A1 (en) Vaporizer/delivery vessel for volatile/thermally sensitive solid and liquid compounds
JP5020407B2 (ja) アンプルのための加熱式バルブマニホールド
JP6647202B2 (ja) 堆積アレンジメント、堆積装置、及びこれらの操作方法
WO2009010468A1 (fr) Appareil d'évaporation sous vide pour substances solides
KR100767296B1 (ko) 화학기상증착장치의 소스파우더 공급장치
US6001172A (en) Apparatus and method for the in-situ generation of dopants
JP2011054789A (ja) 基板処理装置
TW201842224A (zh) 鍍膜裝置以及用於在真空下於基板上進行反應性氣相沉積的方法
EP2053070A1 (fr) Appareil et procédé de dépôt chimique en phase vapeur
US20120111374A1 (en) Ion implantation tool cleaning apparatus and method
WO2007085008A2 (fr) Appareil et procede d’utilisation de chlorure d’indium pour la distribution de vapeur d’indium a une source d’ions
WO2012168924A1 (fr) Appareil et procédé d'alimentation en gaz de matériau solide
KR100518147B1 (ko) 증착장치,유기증발원및유기박막제조방법
JP2020150046A (ja) 基板処理装置および半導体装置の製造方法
JPH05283340A (ja) 液体原料気化供給装置

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
NENP Non-entry into the national phase in:

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 07717331

Country of ref document: EP

Kind code of ref document: A2

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)