WO2007134183A2 - Système d'alimentation en réactif chimique utilisant un milieu de stockage liquide ionique - Google Patents

Système d'alimentation en réactif chimique utilisant un milieu de stockage liquide ionique Download PDF

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Publication number
WO2007134183A2
WO2007134183A2 PCT/US2007/068693 US2007068693W WO2007134183A2 WO 2007134183 A2 WO2007134183 A2 WO 2007134183A2 US 2007068693 W US2007068693 W US 2007068693W WO 2007134183 A2 WO2007134183 A2 WO 2007134183A2
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Prior art keywords
chemical reagent
storage liquid
reagent
liquid
ultrasonic energy
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PCT/US2007/068693
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English (en)
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WO2007134183A3 (fr
Inventor
Jose I. Arno
Luping Wang
Emanuel I. Cooper
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Advanced Technology Materials, Inc.
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Publication of WO2007134183A2 publication Critical patent/WO2007134183A2/fr
Publication of WO2007134183A3 publication Critical patent/WO2007134183A3/fr

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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C11/00—Use of gas-solvents or gas-sorbents in vessels

Definitions

  • the present invention relates to material storage and delivery systems and methods, and to liquid storage media in which chemical reagents are reversibly storable.
  • the source material is provided in a supply package, also referred to as an ampoule or a vaporizer.
  • the supply package frequently includes a vessel that is externally heated by wrapping of the vessel in heating tape or a heating blanket or thermal jacket. Alternatively, the package may be introduced into a furnace to supply the necessary heat for delivery of the chemical reagent.
  • Examples of such supply packages include the solid source delivery package commercially available from ATMI, Inc. (Danbury, CT, USA) under the trademark ProEvap, conventional bubblers used in the semiconductor manufacturing industry, and ampoules for supplying cluster boron materials for ion implantation.
  • the reagent can be in any of solid, liquid or gaseous forms in specific applications, and may be incorporated in a storage medium from which the reagent is dispensed under appropriate dispensing conditions, for delivery to a process tool or other fluid-utilizing apparatus, process or facility.
  • a primary disadvantage is the time required for the vessel containing the chemical reagent source material to be heated up, along with the associated flow circuitry, including transfer lines, valves, restrictive flow orifice elements, and the like.
  • the supply package therefore has an associated warm-up, heat-up time before the chemical reagent can be dispensed from the package.
  • heating once established, creates a thermal ballast effect, as the heat capacity of the vessel, valve head, and other package components creates a thermal load that must be dissipated when the package is exhausted and must be changed out.
  • the resulting cool-down to ambient temperature for change -out of the package may require significant time, which decreases the efficiency of the manufacturing operation.
  • Another disadvantage entailed in heating of the vessel containing the chemical reagent source material is that the protracted heating of the material may cause thermal decomposition of the material.
  • Such heating may also cause agglomeration of the reagent source material in instances in which the source material is provided in a discontinuous, e.g., finely divided, solid form. As a result, the agglomerated material provides less surface area for volatilization and a reduced delivery rate.
  • a further associated deficiency of heating the chemical reagent supply package is that heat tracing the flow circuitry and delivery system from the package to the downstream process tool can be difficult, time-consuming and susceptible to development of cold spots in the flow circuitry and delivery system that produce condensation of the chemical reagent that can lead to reduced delivery rate or even clogging of the process flow passages and inoperability of the system.
  • ALD pulsed flow atomic layer deposition
  • the pulsing sequence requires rapid opening and closing of valves in the flow circuitry, and such valves over time may clog or fail.
  • the desorption rate of chemical reagent gases dissolved in ionic liquids is typically rather poor, due to the fact that the gases are chemically bound to the fluid media by coordinative or ionic bonds. Chemical bonds are stronger and harder to break as compared to those involved in physical adsorption, and even vacuum desorption of fluid from ionic media may not be sufficient to deliver these fluids at the necessary rates for commercial manufacturing operations. The typical high viscosity of ionic liquid also tends to decrease the desorption rate.
  • ionic liquids as storage media for chemical reagents is also susceptible to the problem of high "heels,” or residual chemical reagent that remains in the supply vessel, bound to the ionic liquid, when the vessel has reached a state where further removal of chemical reagent becomes uneconomic or impractical, and the supply vessel is regarded as being exhausted.
  • the present invention relates to chemical reagent delivery systems and methods.
  • the invention relates to a system comprising a reagent supply container including a vessel holding a composition including a chemical reagent dissolved or dispersed in a storage liquid that is reversibly interactive with the chemical reagent to store the chemical reagent therein, and an ultrasonic energy source arranged to introduce ultrasonic energy into said composition to liberate the chemical reagent therefrom for dispensing from the vessel of the reagent supply container.
  • the invention in another aspect, relates to a chemical reagent delivery system comprising a chemical reagent package including a vessel to which a dispensing assembly is coupled, wherein the vessel contains an ionic liquid in which the chemical reagent is stored, and from which it is disengaged and dispensed through the dispensing assembly under dispensing conditions involving ultrasonic energy impingement on the ionic liquid, and an ultrasonic energy source adapted to impinge ultrasonic energy on the ionic liquid to disengage the chemical reagent therefrom for dispensing thereof through the dispensing assembly.
  • a further aspect of the invention relates to a method of chemical reagent delivery, comprising dissolving or dispersing a chemical reagent in a storage liquid to form a composition in which the chemical reagent is reversibly stored, applying ultrasonic energy to the composition to disengage the chemical reagent from the storage liquid in a volatilized form, and delivering the chemical reagent in the volatilized form to a locus of use of said chemical reagent.
  • Another aspect of the invention relates to a chemical reagent delivery method comprising providing a chemical reagent package including a vessel to which a dispensing assembly is coupled, wherein the vessel contains an ionic liquid in which the chemical reagent is stored, and from which it is disengaged and dispensed through the dispensing assembly under dispensing conditions involving ultrasonic energy impingement on the ionic liquid, and impinging ultrasonic energy on the ionic liquid to disengage the chemical reagent therefrom, and dispensing the disengaged chemical reagent through the dispensing assembly.
  • the invention in another aspect, relates to a system comprising a reagent supply container including a vessel holding a composition including a chemical reagent dissolved or dispersed in a storage liquid that is reversibly interactive with the chemical reagent to store the chemical reagent therein in a storage state, and to release the chemical reagent from the storage liquid for dispensing from the vessel of the reagent supply container in a dispensing state, wherein the storage liquid has solid particles therein that are adapted to prevent supersaturation of the storage liquid.
  • a further aspect of the invention relates to a method of chemical reagent delivery, comprising dissolving or dispersing a chemical reagent in a storage liquid to form a composition in which the chemical reagent is reversibly stored in a storage mode of operation, releasing the chemical reagent from the storage liquid in a dispensing mode of operation, and delivering the released chemical reagent in a volatilized form to a locus of use of said chemical reagent, wherein the storage liquid has solid particles therein that are adapted to prevent supersaturation of the storage liquid.
  • a reagent supply container including a vessel holding a composition including a chemical reagent dissolved or dispersed in a storage liquid that is reversibly interactive with the chemical reagent to store the chemical reagent therein in a storage state, and to release the chemical reagent from the storage liquid for dispensing from the vessel of the reagent supply container in a dispensing state, wherein the storage liquid has solid particles therein that are adapted to remove impurities from the storage liquid.
  • the invention in another aspect relates to a method of chemical reagent delivery, comprising dissolving or dispersing a chemical reagent in a storage liquid to form a composition in which the chemical reagent is reversibly stored in a storage mode of operation, releasing the chemical reagent from the storage liquid in a dispensing mode of operation, and delivering the released chemical reagent in a volatilized form to a locus of use of said chemical reagent, wherein the storage liquid has solid particles therein that are adapted to remove impurities from the storage liquid.
  • FIG. 1 is a schematic representation of a chemical reagent delivery system according to one embodiment of the invention.
  • FIG. 2 is a schematic representation of a chemical reagent delivery system according to one embodiment of the invention.
  • the present invention relates to a material storage and dispensing system, involving use of an ionic liquid storage medium.
  • chemical reagent is vaporized or nebulized for delivery, using ultrasonic energy.
  • Ultrasonic vaporizers convert electrical energy to rapid-rate mechanical vibrations, typically on the order of thousands to hundreds of thousands of Hertz. The resulting high frequency vibrations produce intense cavitation in fluids exposed to the ultrasonic energy.
  • Cavitation bubbles develop in the fluid. Such bubbles exhibit high temperature and pressure that produce vaporization or atomization of the fluid.
  • An illustrative ultrasonic vaporizer exhibiting the aforementioned characteristics is the Omron Model NE-U22 mesh type nebulizer commercially available from Omron
  • Nebulizers of such type generate a high throughput vapor without heating the bulk volume of the source liquid.
  • liquid reagents can be readily vaporized by nebulizers.
  • the resulting atomized material can be transported to the microelectronic device manufacturing tool using a carrier gas, or by use of vacuum, involving vacuum pumps, ejectors, eductors or the like.
  • Solids delivery can be correspondingly carried out, by dissolving the solid reagent in a low vapor pressure liquid, such as an ionic liquid, mineral oil, silicon-based oil, fluorocarbon-based oil, etc.
  • the invention relates to a system comprising a reagent supply container including a vessel holding a composition including a chemical reagent dissolved or dispersed in a storage liquid that is reversibly interactive with the chemical reagent to store the chemical reagent therein, and an ultrasonic energy source arranged to introduce ultrasonic energy into said composition to liberate the chemical reagent therefrom for dispensing from the vessel of the reagent supply container.
  • the ultrasonic energy source can include any suitable type of source, such as an ultrasonic nebulizer, a piezoelectric ultrasonic nozzle, etc.
  • the chemical reagent likewise can be of any suitable type, such as a reagent species selected from the group consisting of photoresists, etching agents, organometallic compounds, dielectric materials, and dopants.
  • the reagent supply container contains the ultrasonic energy source at least partially disposed in an interior volume of the vessel.
  • the ultrasonic energy source can be located exteriorly of the reagent supply container.
  • the chemical reagent can be used for manufacturing a microelectronic device, such as a semiconductor structure, flat-panel display, or subassemblies for precursor structures therefor.
  • the reagent supply container can be arranged in chemical reagent feed relationship to a microelectronic device manufacturing tool or other locus of use of the chemical reagent.
  • the reagent supply container can be coupled with the locus of use of the chemical reagent by flow circuitry, including typing, conduits, valving, manifolds, and associated process monitoring and control devices.
  • the reagent supply container is unheated other than by the ultrasonic energy source.
  • the reagent supply container of such type can for example be arranged in chemical reagent feed relationship to a vapor deposition chamber in which the chemical reagent is contacted with a substrate for deposition of a film- forming material thereon, with the ultrasonic energy source being constituted by an ultrasonic vaporizer.
  • the chemical reagent delivery system of the convention permits delivery of the chemical reagent from the vessel of the reagent supply container at sub -atmospheric pressure, or other suitable pressure, appropriate to the process and end use of the chemical reagent.
  • the chemical reagent is flowed from the reagent supply container to a locus of use of the chemical reagent, wherein the locus of use comprises a chamber that is maintained at sub -atmospheric pressure.
  • the storage liquid comprises a low vapor pressure liquid, e.g., a liquid selected from among ionic liquids, mineral oils, silicon-based oils and fluorocarbon-based oils.
  • the ultrasonic energy source can be constituted by an ultrasonic vaporizer that is adapted for on-off switched operation for pulsed dispensing of the chemical reagent for atomic layer deposition.
  • the storage liquid utilized in the practice of the present invention can for example comprise a Lewis acid or Lewis base.
  • the storage liquid can include a reactive ionic liquid, or any other liquid medium in which the chemical reagent of interest is storable in a reversible manner, including the ability to be stored in the liquid storage medium without degradation or decomposition, and to be extractable from the liquid storage medium under dispensing conditions, including ultrasonic energy exposure of the liquid storage medium containing the stored chemical reagent.
  • a further aspect of the invention relates to a method of chemical reagent delivery, comprising dissolving or dispersing a chemical reagent in a storage liquid to form a composition in which the chemical reagent is reversibly stored, applying ultrasonic energy to the composition to disengage the chemical reagent from the storage liquid in a volatilized form, and delivering the chemical reagent in the volatilized form to a locus of use of said chemical reagent.
  • Another aspect of the invention relates to a chemical reagent delivery method comprising providing a chemical reagent package including a vessel to which a dispensing assembly is coupled, wherein the vessel contains an ionic liquid in which the chemical reagent is stored, and from which it is disengaged and dispensed through the dispensing assembly under dispensing conditions involving ultrasonic energy impingement on the ionic liquid, and impinging ultrasonic energy on the ionic liquid to disengage the chemical reagent therefrom, and dispensing the disengaged chemical reagent through the dispensing assembly.
  • the localized vaporization involved in nebulization obviates decomposition issues that occur in conventional reagent delivery in microelectronic device manufacturing operations.
  • Ultrasonic generation of volatilized reagent also entails the advantage that material delivery rates can be controlled in a simple and ready manner, by changing the intensity and/or frequency of the ultrasonic vibration.
  • the invention contemplates dissolution of chemical reagent material in an ionic liquid, and the extraction of such chemical reagent from the ionic liquid for dispensing, using ultrasonic energy that is impinged on such liquid to effect disengagement of the chemical reagent from the liquid storage medium.
  • the invention in one embodiment relates to a chemical reagent package including a vessel to which a dispensing assembly is coupled, wherein the vessel contains an ionic liquid in which the chemical reagent is stored, and from which it is disengaged and dispensed under dispensing conditions involving ultrasonic energy impingement on the ionic liquid.
  • the invention also contemplates chemical reagent package arrangements in which an ultrasonic vaporizer is interiorly disposed in the vessel of the package, to generate piezoelectric vibration therein for liberation of the chemical reagent from the ionic liquid storage medium, for discharge from the package through the dispensing assembly.
  • the ionic fluid containing the chemical reagent dissolved therein can be transferred from the vessel of the chemical reagent package, into an external ultrasonic device to effect extraction of the chemical reagent from the liquid, so that the thus- separated chemical reagent in fluid form can be flowed to the downstream locus of use.
  • the ionic liquid in which the chemical reagent is stored, and from which the chemical reagent is liberated under dispensing conditions involving ultrasonic energy impingement on the ionic liquid may be of any suitable type. Illustrative ionic liquids includes those described in the aforementioned U.S. Patent Application Publication No. 20040206241 published October 21, 2004 in the names of Daniel Joseph Tempel, et al.
  • the ionic liquid can serve as a reactive liquid, e.g., as a Lewis acid or Lewis base, to effect reversible reaction with the chemical reagent to be stored.
  • Reactive ionic liquids include cationic and anionic components, in which the acidity or basicity of the reactive ionic liquid is governed by the acid or base strength of the cation, the anion, or by a combination of the two.
  • Ionic liquids potentially useful in the broad practice of the present invention include, without limitation, salts of alkylphosphonium, alkylammonium, N-alkylpyridinium and N,N'- dialkylimidazolium cations.
  • Common cations contain d- Ci 8 alkyl groups, and include the ethyl, butyl and hexyl derivatives of N-alkyl-N'-methylimidazolium and N-alkylpyridinium.
  • Other cations include pyridazinium, pyrimidinium, pyrazinium, pyrazolium, triazolium, thiazolium, and oxazolium, as well as ethylammonium and piperidinium.
  • Also potentially useful in the broad practice of the present invention are "task- specific" ionic liquids bearing reactive functional groups on the cation. Such ionic liquids can be prepared using functionalized cations containing a Lewis base or Lewis acid functional group.
  • Task specific ionic liquids include aminoalkyl, such as aminopropyl; ureidopropyl, and thioureido derivatives of the above cations.
  • Specific examples of task-specific ionic liquids containing functionalized cations include salts of l-alkyl-3-(3-aminopropyl)imidazolium, 1- alkyl-3-(3-ureidopropyl)- imidazolium, l-alkyl-3-(3-thioureidopropyl)imidazolium, l-alkyl-4- (2-diphenylphosphanylethyl)pyridinium, l-alkyl-3-(3-sulfopropyl- )imidazolium, and trialkyl- (3-sulfopropyl)phosphonium.
  • alkyl groups that can be added in place of alkyl groups include alkoxyalkyl and alkylthioalkyl, e.g., methoxyethyl or ethoxyethyl, and methylthiotethyl or ethylthioethyl. These latter groups provide a mild basic reactivity toward metal compounds, while keeping melting points and viscosities relatively low.
  • anions can be matched with the cation component of such ionic liquids for achieving Lewis acidity.
  • One type of anion is derived from a metal halide.
  • the halide most often used is chloride although other halides may also be used.
  • Preferred metals for supplying the anion component, e.g. the metal halide include copper, aluminum, iron, zinc, tin, antimony, titanium, niobium, tantalum, gallium, and indium.
  • Bismuth halides are also advantageous for providing low melting points combined with mild Lewis acidity.
  • metal chloride anions examples include CuCl 2 " , Cu2Cl 3 ⁇ AlCl 4 " , A12C1 7 “ , ZnCl 3 “ , ZnCl 4 2” , Zn 2 Cl 5 “ , FeCl 3 “ , FeCl 4 “ , Fe 2 Cl 7 “ , TiCl 5 “ , TiCl 6 2” , SnCl 5 “ , SnCl 6 2” , etc.
  • species derived from SbF 5 and SbF 3 are notable, e.g. Sb 2 F 11 " as an acidic entity.
  • bi- or multinuclear halide ions which include halide atoms shared by two metals, e.g., Al- -Cl- -Al or Sb- F-- Sb, have Lewis acid activity.
  • the type of metal halide and the amount of the metal halide employed has an effect on the acidity of the ionic liquid.
  • the resulting anion may be in the form AlCl 4 " or Al 2 Cl 7 " .
  • the two anions derived from aluminum trichloride have different acidity characteristics, and these differing acidity characteristics affect the type of gases that can be reactively stored.
  • Room temperature ionic liquids, or low melting temperature ionic liquids typically melting below 100 0 C
  • halide compounds from which Lewis acidic or Lewis basic ionic liquids can be prepared include:
  • a preferred reactive liquid is an ionic liquid and the anion component of the reactive liquid is a cuprate or aluminate and the cation component is derived from a dialkylimidazolium salt.
  • Another anion component that may be useful in connection with phosphine and arsine is Ga 2 Cl 7 " .
  • Many low-melting, low vapor pressure reactive liquids having Lewis acid character can also be formed around oxygen-containing functional groups.
  • mixtures of phosphoric acid with pyrophosphoric or metaphosphoric acid have very low vapor pressure and are highly acidic.
  • Some alkylammonium salts display a moderate acidity through their protonated ammonium entity, e.g., ethylammonium nitrate.
  • Single-charged ions of bi- or multiprotic acids, such as HSCV or H 3 P 2 O 7 " can form relatively low melting salts and have substantial acidic activity due to their remaining protons.
  • low-melting salts of organic acids containing a weakly basic anion and a strongly acidic cation can be used as Lewis acids.
  • many metal salts of 2-ethylhexanoic acid also known as octoates
  • 2-ethylhexanoic acid also known as octoates
  • zinc 2-ethylhexanoate is one of several octoates that are liquids at room temperature, and can be used as a Lewis acid due to the acidity of the zinc ion.
  • Some organic sulfonate and phosphonate salts may be used in similar fashion.
  • Gases having Lewis basicity to be stored in and delivered from Lewis acidic reactive liquids may comprise one or more of phosphine, pentaborane, arsine, stibene, ammonia, hydrogen sulfide, hydrogen selenide, hydrogen telluride, isotopically- enriched analogs, basic organic or organo metallic compounds, etc.
  • nongaseous materials may be stored in and delivered from the liquid storage medium.
  • the material stored in and delivered from the liquid storage medium can itself be a liquid.
  • Such stored and subsequently delivered liquid may for example be a liquid that under storage conditions is miscible with the liquid storage medium, and that under dispensing conditions is immiscible with the liquid storage medium, e.g., forming a phase-separated liquid volume from which the phase-separated liquid is discharged from the associated storage and dispensing vessel.
  • the material stored in and delivered from the liquid storage medium can be a solid that is solubilized or suspended in the liquid storage medium, and subsequently released from the liquid storage medium under dispensing conditions.
  • both the anion and cation are Lewis basic.
  • Lewis basic anions include carboxylates, e.g., 2-ethylhexanoate, fluorinated carboxylates, sulfonates, fluorinated sulfonates, imides, borates, sulfates, phosphates, chloride, partially protonated ions derived from polyprotic acids, etc.
  • Common anion forms include BF 4 " , PF 6 “ , AsF 6 “ , SbF 6 “ , CH3COO “ , CF3COO “ , CF 3 SO 3 “ , P-CH 3 -C 6 H 4 SO 3 “ , (CF 3 SO 2 ) 2 N ⁇ (NC) 2 N “ , (CF 3 SO 2 ) 3 C ⁇ chloride, and F(HF) n " .
  • Other anions include organo metallic compounds such as alkylaluminates, and alkyl- or arylborates.
  • Preferred anions include BF 4 " , p-CH 3 -C 6 H 4 SO 3 " , CF 3 SO 3 " , (CF 3 SOz) 2 N “ , (NC) 2 N-(CF 3 SO 2 ) 3 C ⁇ CH 3 COO " and CF 3 COO " .
  • Other useful anions include: R-O-SO 3 " (alkyl sulfates), e.g. ethyl sulfate, CH 3 CH 2 -O-SO 3 " (the respective salts are easily made); and (RO) 2 P(O)O " (dialkylphosphate) as moderately weak bases, e.g., dibutylphosphate, and wherein R in the foregoing formulae is alkyl.
  • Ionic liquids comprising cations that contain Lewis basic groups may also be used in storing gases having Lewis acidity.
  • Lewis basic cations include rings with multiple heteroatoms.
  • a Lewis basic group may also be part of a substituent on either the anion or cation.
  • Potentially useful Lewis basic substituent groups include amine, phosphine, ether, carbonyl, nitrile, thioether, alcohol, thiol, etc.
  • Gases having Lewis acidity to be stored in and delivered from Lewis basic reactive liquids may comprise one or more of diborane, boron trifluoride, boron trichloride, SiF 4 , germane, hydrogen cyanide, HF, HCl, Hl, HBr, GeF 4 , isotopically-enriched analogs, acidic organic or organometallic compounds, etc.
  • Lewis basic reactive liquids e.g., ionic liquids
  • Gases having Lewis acidity to be stored in and delivered from Lewis basic reactive liquids may comprise one or more of diborane, boron trifluoride, boron trichloride, SiF 4 , germane, hydrogen cyanide, HF, HCl, Hl, HBr, GeF 4 , isotopically-enriched analogs, acidic organic or organometallic compounds, etc.
  • boron trifluoride boron trichloride
  • SiF 4 germane
  • hydrogen cyanide HF
  • ionic liquids in halide form can be used for safe storage and controlled delivery of bromine in Br 3 " form, of iodine in I 3 " or I 5 " or I 7 " form, and of chlorine in ICl 4 " form.
  • the two-electron oxidation of some main-group metals and metalloids by halogens from their intermediate to their highest oxidation state can also be viewed as a Lewis acid-base reaction, and some of these oxidation systems are candidates for storage and delivery of halogens through a halide- containing anion.
  • Nonvolatile covalent liquids containing Lewis acidic or Lewis basic functional groups are also useful as reactive liquids for chemically complexing gases.
  • Such liquids may include discrete organic or organometallic compounds, oligomers, low molecular weight polymers, branched amorphous polymers, natural and synthetic oils, etc.
  • liquids bearing Lewis acid functional groups include substituted boranes, borates, aluminums, or alumoxanes; protic acids such as carboxylic and sulfonic acids, and complexes of metals such as titanium, nickel, copper, etc.
  • liquids bearing Lewis basic functional groups include ethers, amines, phosphines, ketones, aldehydes, nitrites, thioethers, alcohols, thiols, amides, esters, ureas, carbamates, etc.
  • reactive covalent liquids include tributylborane, tributyl borate, triethylaluminum, methanesulfonic acid, trifluoromethanesulfonic acid, titanium tetrachloride, tetraethyleneglycol dimethylether, trialkylphosphine, trialkylphosphine oxide, polytetramethyleneglycol, polyester, polycaprolactone, poly(olefin-alt-carbon monoxide), oligomers, polymers or copolymers of acrylates, methacrylates, or acrylonitrile, etc. In many cases, these liquids suffer from excessive volatility at elevated temperatures and are not suited for thermal-mediated evolution.
  • Supersaturation can be minimized by promoting gas nucleation. This goal is best achieved by adding to the liquid an amount of high surface area solid particles that are insoluble and inert under the operating conditions.
  • Typical examples include microporous carbon particles, silica particles, ceramic honeycombs, and alumina granules.
  • the particles are made of a material with relatively high thermal conductivity and low reactivity, such as carbon, alumina or silicon carbide.
  • the solid phase and the liquid phase may both be interconnected, with the solid phase in effect serving as a "support” and the liquid being an "affinity medium" in the manner described in U.S. Patent 6,027,547, and with gas bubbles percolating through the liquid between the solid support particles.
  • a small amount of solid "boiling chips" may be sufficient.
  • the delivery system therefore is preferably designed to filter out any aerosol droplets of the ionic liquid that are formed by the "boiling" process involving the extraction of the chemical reagent from the ionic liquid.
  • the filtration can be accomplished in any suitable manner, e.g., using conventional filtration equipment and techniques applicable to filtering of aerosols.
  • ionic liquids While some ionic liquids are in liquid state at room temperature, e.g., 25°C, there are many ionic liquid species that are not. Furthermore, some ionic liquids may freeze during transit. Loading the reactive liquid with gaseous chemical reagent can also increase the melting temperature of the mixture, especially when a stoichiometric composition is approached. The ionic liquid system may therefore often be below its equilibrium freezing point. Nonetheless, whether or not the material inside the supply vessel actually freezes is difficult to predict, because of the tendency of viscous liquids to supercool.
  • the system may be maintained for a reasonable period of time above the highest melting point in the relevant part of the phase diagram of the reactive liquid and reactive gas; however, such approach is time-consuming and restricts the operating temperature range.
  • electrode probes can be supplied for impedance measurements, since typically the resistivity of ionic solids is many orders of magnitude above that of the corresponding liquids.
  • the impedance across the canister at several points can then be monitored, e.g., after transit, during refilling, and periodically during use.
  • Such approach has the added benefit that it can also diagnose poorly controlled bubbling, by having a pair of electrodes positioned at the level of the upper layer of the liquid.
  • Yet another approach, which avoids any necessity of inserting electrical leads into the vessel for impedance measurement is the use of acoustic sensing techniques.
  • a high surface area solid capable of acting as a strong adsorbent for the impurities in the reactive liquid.
  • microporous carbon beads can be used, both to nucleate gas bubbles as needed and to strongly adsorb residual unsaturated nitrogen compounds such as imidazoles and pyridines which often constitute the main residual impurities in ionic liquids.
  • thoroughly dried alumina or silica can be added to the ionic liquid in order to remove residual water and other impurity species having affinity for the alumina or silica.
  • the invention in another aspect, relates to a system comprising a reagent supply container including a vessel holding a composition including a chemical reagent dissolved or dispersed in a storage liquid that is reversibly interactive with the chemical reagent to store the chemical reagent therein in a storage state, and to release the chemical reagent from the storage liquid for dispensing from the vessel of the reagent supply container in a dispensing state, wherein the storage liquid has solid particles therein that are adapted to prevent supersaturation of the storage liquid.
  • the solid particles may be of any type, e.g., carbon particles, silica particles, ceramic honeycombs, silicon carbide particles and alumina particles.
  • the system optionally can further comprise a phase monitor arranged to monitor storage liquid in the reagent supply container to verify phase state thereof.
  • the phase monitor can include at least one impedance sensor arranged to sense impedance of the storage liquid.
  • the phase monitor comprises an acoustic sensor.
  • the storage liquid contains porous carbon beads.
  • the reagent supply system is provided as part of a microelectronic device manufacturing facility.
  • the system in a further embodiment includes a storage liquid that comprises an ionic liquid.
  • a further aspect of the invention relates to a method of chemical reagent delivery, comprising dissolving or dispersing a chemical reagent in a storage liquid to form a composition in which the chemical reagent is reversibly stored in a storage mode of operation, releasing the chemical reagent from the storage liquid in a dispensing mode of operation, and delivering the released chemical reagent in a volatilized form to a locus of use of said chemical reagent, wherein the storage liquid has solid particles therein that are adapted to prevent supersaturation of the storage liquid.
  • Such method may constitute part of a process of microelectronic device manufacturing.
  • the liquid employed as storage liquid in such method may include an ionic liquid.
  • a reagent supply container including a vessel holding a composition including a chemical reagent dissolved or dispersed in a storage liquid that is reversibly interactive with the chemical reagent to store the chemical reagent therein in a storage state, and to release the chemical reagent from the storage liquid for dispensing from the vessel of the reagent supply container in a dispensing state, wherein the storage liquid has solid particles therein that are adapted to remove impurities from the storage liquid.
  • the solid particles in such a system can be of any suitable type, e.g., carbon particles, silica particles, ceramic honeycombs, silicon carbide particles and alumina particles.
  • the system may employ solid particles comprising porous carbon beads, and the system may be part of a microelectronic device manufacturing facility.
  • the storage liquid in such system can comprise an ionic liquid.
  • the invention in another aspect relates to a method of chemical reagent delivery, comprising dissolving or dispersing a chemical reagent in a storage liquid to form a composition in which the chemical reagent is reversibly stored in a storage mode of operation, releasing the chemical reagent from the storage liquid in a dispensing mode of operation, and delivering the released chemical reagent in a volatilized form to a locus of use of said chemical reagent, wherein the storage liquid has solid particles therein that are adapted to remove impurities from the storage liquid.
  • the solid particles can be of any suitable type, including, for example, carbon particles, silica particles, ceramic honeycombs, silicon carbide particles and alumina particles.
  • the foregoing method may be part of a process of microelectronic device manufacturing.
  • the storage liquid in such method can comprise an ionic liquid.
  • FIG. 1 is a schematic representation of a chemical reagent delivery system 10 according to one embodiment of the invention.
  • the chemical reagent delivery system 10 includes a chemical reagent storage and delivery container 12 including a vessel 14 defining an interior volume 16 therein. In the interior volume 16 is contained a volume of an ionic liquid 18 having a chemical reagent dissolved or dispersed therein.
  • the chemical reagent storage and delivery container 12 includes a nebulization and dispensing head assembly 22 coupled to the upper end of the vessel 14, e.g., by welding, brazing, mechanical coupling, or the like.
  • the head assembly 22 includes a fill port 24 for introducing the ionic fluid storage medium and chemical reagent into the interior volume 16 of the vessel 14.
  • the ionic fluid storage medium and the chemical reagent can be introduced into the vessel in sequential fashion, with the ionic liquid being introduced first, followed by introduction of the chemical reagent to the interior volume for solubilization in the ionic liquid therein.
  • the chemical reagent may be mixed with the ionic liquid in a mixing chamber or container, to form the solution or dispersion of the chemical reagent and ionic liquid, and the resulting solution or dispersion can then be introduced into the vessel interior volume through the fill port 24.
  • the head assembly 22 further includes a dispensing tube 17 extending downwardly into the interior volume of the vessel, for flow of the chemical reagent vapor 30 through the dispensing tube 17 and an associated interior passage (not shown) in the head assembly main body portion to the discharge line 36 joined in closed flow communication with such interior passage.
  • the head assembly 22 also includes an ultrasonic nebulizer 19 disposed at least partially in the interior volume 16 of the vessel 14, and arranged to impinge ultrasonic waves 28 on the ionic liquid 18 containing the chemical reagent, to effect disengagement of the chemical reagent from the ionic liquid, producing the liberated vapor 30.
  • the ultrasonic nebulizer 19 is powered by a power supply 34 coupled with the head assembly 22 by power supply line 32.
  • the liberated chemical reagent vapor then flows in discharge line 36 to the process tool 38, which in this illustrative embodiment comprises a vapor deposition chamber defining an interior volume 40 containing wafer 44 mounted on substrate support 46.
  • the wafer 44 is mounted on the support 46 so that it is contacted by the nebulized vapor 42, to form a film on the wafer from the active deposition species in the chemical reagent.
  • the process tool 38 is coupled to pump 50 by exhaust line 48.
  • the pump 50 is arranged to impose a vacuum on the process tool, and thereby to draw the chemical reagent vapor into the process tool chamber.
  • the system could use another type of fluid driver, such as an eductor, ejector, blower, fan, compressor, or the like.
  • the chemical reagent is able to be dispensed at sub- atmospheric pressure, thereby increasing the safety of the system in relation to a conventional system utilizing high pressure gas cylinders for supply of pressurized gas to the process tool.
  • FIG. 1 is a schematic representation of a chemical reagent delivery system 100 according to another embodiment of the invention.
  • the chemical reagent delivery system 100 includes a reactive liquid storage container 102 joined to feed line 104 and feeding pump 106 with reactive liquid containing chemical reagent dispersed or dissolved therein.
  • the pump flows the reactive liquid dispersion or solution to the disengagement chamber 110, in which the liquid dispersion or solution may pass through an ultrasonic nozzle (not shown in FIG. 2).
  • the chamber 110 may be arranged with an ultrasonic energy source 112 that is actuated to generate ultrasonic waves 114 that are impinged on the liquid dispersion or solution, to cause such dispersion or solution to release the chemical reagent therefrom, as a consequence of the input of the ultrasonic energy to the dispersion or solution.
  • the chemical reagent thereby is volatilized and flows from the disengagement chamber 110 in line 116 to the process tool 122 or other fluid-utilizing process equipment.
  • the unused volatilized chemical reagent is flowed in effluent line 124 to effluent abatement facility 126, which may for example comprise wet and/or dry scrubbing, neutralization, oxidation treatment, chemical reaction abatement, or the like, serving to abate hazardous gas species in the effluent stream from the process tool 122.
  • the present invention provides a simple and efficient alternative to the prior art approach of bulk heating of the reagent supply vessel and associated piping, valves, manifolds, etc.
  • the chemical reagent is not exposed to sustained elevated temperature conditions that can degrade and decompose the reagent.
  • the ultrasonic volatilization of the chemical reagent in the system of the invention facilitates change-out of chemical reagent containers without the need to await cool- down of a hot vessel before a fresh container can be installed, and avoids the need for warm- up/heat-up of the vessel that is a major deficiency of prior art chemical reagent vapor generation systems.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)
  • Automatic Analysis And Handling Materials Therefor (AREA)

Abstract

La présente invention concerne un système (10) comprenant un contenant d'alimentation en réactif (12) dans lequel un récipient (14) contient une composition comprenant un réactif chimique dissout ou dispersé dans un liquide de stockage (18) qui est interactif de manière réversible avec le réactif chimique de façon à stocker le réactif chimique dans celui-ci, et une source d'énergie ultrasonique (19, 32, 34) adaptée de façon à introduire une énergie ultrasonique dans la composition afin de libérer le réactif chimique provenant de celle-ci de façon à le distribuer à partir du récipient du contenant d'alimentation en réactif. La source d'énergie ultrasonique peut être fournie à l'intérieur du contenant, ou peut être fournie sous la forme d'une partie d'une unité d'impact à énergie ultrasonique externe (112), dans laquelle le réactif chimique stocké, par exemple, un réactif de fabrication de dispositif microélectronique, est extrait du milieu de stockage liquide pour le transport dans un procédé ou dispositif utilisant le réactif (38). Le milieu de stockage liquide peut par exemple comprendre un liquide ionique avec lequel le réactif chimique est extrait de manière réversible, et ultérieurement libéré dans des conditions présentant une exposition à une énergie ultrasonique.
PCT/US2007/068693 2006-05-13 2007-05-10 Système d'alimentation en réactif chimique utilisant un milieu de stockage liquide ionique WO2007134183A2 (fr)

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WO2014179585A1 (fr) * 2013-05-02 2014-11-06 Praxair Technology, Inc. Source d'alimentation et procédé pour une implantation d'ion sélénium enrichi
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US10497569B2 (en) 2009-07-23 2019-12-03 Entegris, Inc. Carbon materials for carbon implantation
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US9142387B2 (en) 2009-10-27 2015-09-22 Entegris, Inc. Isotopically-enriched boron-containing compounds, and methods of making and using same
US9171725B2 (en) 2010-02-26 2015-10-27 Entegris, Inc. Enriched silicon precursor compositions and apparatus and processes for utilizing same
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US9754786B2 (en) 2010-02-26 2017-09-05 Entegris, Inc. Method and apparatus for enhanced lifetime and performance of ion source in an ion implantation system
US10354877B2 (en) 2012-02-14 2019-07-16 Entegris, Inc. Carbon dopant gas and co-flow for implant beam and source life performance improvement
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WO2014137872A1 (fr) * 2013-03-05 2014-09-12 Advanced Technology Materials, Inc. Compositions, systèmes et procédés d'implantation d'ions
EP2965347A4 (fr) * 2013-03-05 2017-02-15 Entegris, Inc. Compositions, systèmes et procédés d'implantation d'ions
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CN105190826A (zh) * 2013-05-02 2015-12-23 普莱克斯技术有限公司 用于富硒离子注入的供应源和方法
CN105190826B (zh) * 2013-05-02 2019-02-15 普莱克斯技术有限公司 用于富硒离子注入的供应源和方法
US9257286B2 (en) 2013-05-02 2016-02-09 Praxair Technology, Inc. Supply source and method for enriched selenium ion implantation
WO2014179585A1 (fr) * 2013-05-02 2014-11-06 Praxair Technology, Inc. Source d'alimentation et procédé pour une implantation d'ion sélénium enrichi
US11062906B2 (en) 2013-08-16 2021-07-13 Entegris, Inc. Silicon implantation in substrates and provision of silicon precursor compositions therefor

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