US20130251918A1 - Strontium and barium precursors for use in chemical vapor deposition, atomic layer deposition and rapid vapor deposition - Google Patents

Strontium and barium precursors for use in chemical vapor deposition, atomic layer deposition and rapid vapor deposition Download PDF

Info

Publication number
US20130251918A1
US20130251918A1 US13/892,526 US201313892526A US2013251918A1 US 20130251918 A1 US20130251918 A1 US 20130251918A1 US 201313892526 A US201313892526 A US 201313892526A US 2013251918 A1 US2013251918 A1 US 2013251918A1
Authority
US
United States
Prior art keywords
strontium
precursor
precursors
oxidant
solvent
Prior art date
Legal status (The legal status 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 status listed.)
Abandoned
Application number
US13/892,526
Inventor
Thomas M. Cameron
Chongying Xu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Entegris Inc
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
Priority to US13/892,526 priority Critical patent/US20130251918A1/en
Publication of US20130251918A1 publication Critical patent/US20130251918A1/en
Assigned to GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT reassignment GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ADVANCED TECHNOLOGY MATERIALS, INC., ATMI PACKAGING, INC., ATMI, INC., ENTEGRIS, INC., POCO GRAPHITE, INC.
Assigned to GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT reassignment GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ADVANCED TECHNOLOGY MATERIALS, INC., ATMI PACKAGING, INC., ATMI, INC., ENTEGRIS, INC., POCO GRAPHITE, INC.
Assigned to ENTEGRIS, INC. reassignment ENTEGRIS, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ADVANCED TECHNOLOGY MATERIALS, INC.
Assigned to ADVANCED TECHNOLOGY MATERIALS, INC., ATMI, INC., ATMI PACKAGING, INC., ENTEGRIS, INC., POCO GRAPHITE, INC. reassignment ADVANCED TECHNOLOGY MATERIALS, INC. RELEASE BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT
Assigned to POCO GRAPHITE, INC., ATMI PACKAGING, INC., ATMI, INC., ADVANCED TECHNOLOGY MATERIALS, INC., ENTEGRIS, INC. reassignment POCO GRAPHITE, INC. RELEASE BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT
Abandoned legal-status Critical Current

Links

Images

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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD

Definitions

  • the present invention relates to precursors for use in depositing strontium- and barium-containing films on substrates such as wafers or other microelectronic device substrates, as well as associated processes of making and using such precursors, and source packages of such precursors.
  • conformal, high k materials based on barium (Ba) or strontium (Sr), such as strontium titanate (STO) and barium strontium titanate (BST), are deposited on substrates by deposition techniques such as chemical vapor deposition (CVD), atomic layer deposition (ALD) and rapid vapor deposition (RVD).
  • CVD chemical vapor deposition
  • ALD atomic layer deposition
  • RVD rapid vapor deposition
  • Such deposition requires monomeric metal precursors that are transportable (volatile) at temperatures specific to the deposition process.
  • the precursors in liquid form at the delivery temperature used in the deposition process.
  • the precursors should have melting points below the operating temperature of the vaporizer that is used in a liquid delivery deposition process system, to avoid clogging of the vaporizer and to minimize the potential for particle generation by the vaporizer.
  • Such clogging and particle generation issues are particularly common when solutions of solid precursors are used in deposition.
  • the present invention relates to barium and strontium precursors useful in chemical vapor deposition, atomic layer deposition and rapid vapor deposition applications, to form corresponding metal-containing films on substrates, as well as associated processes and packaged forms of such precursors.
  • the invention relates to a metal precursor selected from among:
  • the invention relates to bis(n-propyltetramethyl-cyclopentadienyl)barium and Lewis base adducts thereof.
  • a further aspect of the invention relates to bis(n-propyltetramethyl-cyclopentadienyl)strontium and Lewis base adducts thereof.
  • Yet another aspect of the invention relates to a Lewis base-stabilized strontium cyclopentadienyl complex of the formula:
  • the invention relates to a method of forming a metal-containing film on a substrate, wherein said metal comprises a metal species selected from among barium and strontium, said method comprising volatilizing a metal precursor according to claim 1 , to form a precursor vapor, and contacting said precursor vapor with a substrate to form of said metal-containing film thereon.
  • a further aspect of the invention relates to a precursor composition comprising at least one metal precursor of the invention, and a solvent medium for the metal precursor(s).
  • a still further aspect of the invention relates to a precursor vapor of a metal precursor of the invention.
  • Another aspect of the invention relates to a precursor source package comprising a precursor storage and dispensing vessel containing a metal precursor of the invention.
  • FIG. 1 is a simultaneous thermal analysis (STA) plot of thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) curves for bis(n-propyltetramethyl-cyclopentadienyl)strontium.
  • STA simultaneous thermal analysis
  • TGA thermogravimetric analysis
  • DSC differential scanning calorimetry
  • FIG. 2 is a plot of STA results for Sr(Cp′) 2 and Sr(Cp′) 2 (PMDETA).
  • FIG. 3 is a schematic representation of a material storage and dispensing package containing a precursor of the present invention, in one embodiment thereof.
  • the present invention relates in various aspects to barium and strontium metal precursors having low melting point, characterized by superior stability, and utility for forming highly conformal films.
  • the superior air stability of such precursors also minimizes generation of particles in the CVD/ALD/RVD processes in which such precursors are usefully employed to form barium- and/or strontium-containing films.
  • Metal precursors of the invention include those selected from among:
  • X may in various embodiments comprise specific ligand species described in U.S. Pat. No. 7,108,747, and the complexing species forming adducts may comprise specific ligands described in U.S. Pat. No. 7,108,747.
  • Neutral ligand adducts e.g., of the formula L n , include ligands that bind to the central metal by either one or several of its atoms, where n depicts the number of the ligands being bound.
  • Neutral adduct ligands include ligands as described in such U.S. Pat. No. 7,108,747.
  • the pendant ligands including functional group(s) providing further coordination to the metal center may in various embodiments of the invention include ligands selected from among aminoalkyl, alkoxyalkyl, aryloxyalkyl, imidoalkyl, and acetylalkyl.
  • Ligands may in specific embodiments be selected from among:
  • each of R 1 -R 4 is the same as or different from one another, with each being independently selected from among hydrogen and C 1 -C 6 alkyl and C 6 -C 10 aryl; each of R 5 and R 6 is the same as or different from the other, with each being independently selected from among C 1 -C 6 alkyl; n and m are each selected independently from 0 to 4 with the proviso that m and n cannot be 0 at the same time, and x is selected from 1 to 5;
  • each of R 1 -R 4 is the same as or different from one another, with each being independently selected from among hydrogen, C 1 -C 6 alkyl, and C 6 -C 10 aryl;
  • R 5 is selected from among C 1 -C 6 alkyl, and C 6 -C 10 aryl; and
  • n and m are selected independently from 0 to 4, with the proviso that m and n cannot be 0 at the same time;
  • each of R 1 -R 6 is the same as or different from one another, with each being independently selected from among hydrogen, C 1 -C 6 alkyl, and C 6 -C 10 aryl; and n and m are selected independently from 0 to 4, with the proviso that m and n cannot be 0 at the same time;
  • each of R 1 -R 4 is the same as or different from one another, with each being independently selected from among hydrogen, C 1 -C 6 alkyl, and C 6 -C 10 aryl;
  • R 5 is selected from among C 1 -C 6 alkyl, and C 6 -C 10 aryl; and
  • n and m are selected independently from 0 to 4, with the proviso that m and n cannot be 0 at the same time.
  • Metal precursors of the invention include those selected from among strontium and barium bis(n-propyltetramethylcyclopentadienyl) complexes (I) and strontium and barium isopropylated indenyl complexes (II):
  • M is Ba or Sr
  • THF is tetrahydrofuran
  • Such precursors have low melting points ( ⁇ 130° C.), good transport and deposition properties for forming conformal films on substrates, and good handling characteristics and stability with respect to oxygen and moisture.
  • Bis(n-propyltetramethylcyclopentadienyl)strontium for example, has a melting point of 43.4° C.
  • STA simultaneous thermal analysis
  • TGA thermogravimetric analysis
  • DSC differential scanning calorimetry
  • the invention relates to Lewis-base stabilized strontium and barium cyclopentadienyl complexes that are useful for CVD, ALD and RVD applications, which the metal central atom of the precursor compound is coordinated with one or more Lewis base ligands to form corresponding stabilized complexes of Ba or Sr.
  • the metal central atom of the precursor compound is coordinated with one or more Lewis base ligands to form corresponding stabilized complexes of Ba or Sr.
  • each of the ligands is the same as the other(s).
  • Such Lewis base ligands stabilize the complex against degradation by oxygen and/or moisture in exposure to air, and thus provide more easily handled precursor compositions, relative to various barium and strontium source reagents of the prior art.
  • the invention relates to Lewis base adducts of the dicyclopentadienyl or diindenyl compounds of the invention, wherein the dicyclopentadienyl or diindenyl compound is an oil at standard temperature and pressure (25° C. and 1 atmosphere) conditions.
  • a specific strontium cyclopentadienyl compound of the invention comprises SrCp 2 which can for example be formed from SrCp 2 G adducts, wherein the adducting species G can for example be tetrahydrofuran or ether, e.g., SrCp 2 (THF) 4 where THF is tetrahydrofuran.
  • SrCp 2 can for example be formed from SrCp 2 G adducts, wherein the adducting species G can for example be tetrahydrofuran or ether, e.g., SrCp 2 (THF) 4 where THF is tetrahydrofuran.
  • the Lewis base ligands used to form adducts and complexes of the invention can be of any suitable type, and include, without limitation, multidentate glymes such as dimethoxyethane and tetraglyme, nitrogen-containing multidentate ligands such as PMDETA, and monocoordinate ligands such as pyridine and tetrahydrofuran.
  • multidentate glymes such as dimethoxyethane and tetraglyme
  • nitrogen-containing multidentate ligands such as PMDETA
  • monocoordinate ligands such as pyridine and tetrahydrofuran.
  • the Lewis base ligands enhance compound stability by protecting the metal centers via steric crowding (encapsulation) and by providing electron density to the metal center.
  • Lewis bases such as alkene, diene, cycloalkene, cyclodiene, cyclooctatetraene, alkyne, substituted alkyne (symmetrical or asymmetrical), amine, diamine, triamine, tetraamine, ether, tetrahydrofuran, glyme, diglyme, triglyme, tetraglyme, phosphine, carbonyl, dialkyl sulfide, vinyltrimethylsilane, and allyltrimethylsilane can be used.
  • Lewis bases such as alkene, diene, cycloalkene, cyclodiene, cyclooctatetraene, alkyne, substituted alkyne (symmetrical or asymmetrical), amine, diamine, triamine, tetraamine, ether, tetrahydrofuran, glyme, diglyme, triglyme, tetraglyme, phosphine
  • Precursor compounds stabilized in such fashion exhibit an enhanced robustness and suitability for deposition processes.
  • Precursors in which the central atom in the complex is Sr are particularly useful in ALD processes for forming strontium titanate (STO) films, when such complex and a titanium precursor are employed as the alternating vapor-phase precursors contacted with the substrate.
  • Strontium precursors of the invention e.g., Sr(Cp) 2
  • SrRuOx strontium ruthenium oxide
  • SrRuOx is a conductive oxide and may be employed as an electrode material for STO or barium strontium titanate (BST) devices.
  • the films of the invention can be doped with suitable dopant species, e.g., Nb, Zr, As, etc. and other barium- and/or strontium-containing films can be formed using the Ba and Sr precursors of the invention, including strontium tantalate, barium strontium zirconium titanate, ruthenium strontiate, etc.
  • suitable dopant species e.g., Nb, Zr, As, etc.
  • suitable dopant species e.g., Nb, Zr, As, etc.
  • other barium- and/or strontium-containing films can be formed using the Ba and Sr precursors of the invention, including strontium tantalate, barium strontium zirconium titanate, ruthenium strontiate, etc.
  • the precursors of the invention may also be employed to form BST films, when respective barium and strontium precursors are utilized, in combination with a suitable titanium precursor.
  • a suitable titanium precursor for this purpose, titanium precursors such as those described in U.S. Pat. No. 7,108,747 can be advantageously employed.
  • the Lewis-base ligands will also lower the t 50 of the Ba and Sr compounds with respect to the corresponding compound uncomplexed with the Lewis-base.
  • the lowering of the t 50 value is a result of the Lewis-base ligand disrupting intermolecular interactions.
  • the t 50 value for Sr(Cp′) 2 is 256° C. and the t 50 value for Sr(Cp′) 2 (PMDETA) is 40° C. lower at 216° C.
  • the Lewis-base adducts with lower t 50 values will enable lower transport temperatures to be employed in CVD, ALD and RVD processes.
  • the precursors of the invention can be readily synthesized with the skill of the art, with indenyl precursors being synthesized by a process of a general type as described in J. S. Overby and T. P. Hanusa, Organometallics 1996, 15, 2205, and cyclopentadienyl precursors being synthesized in an analogous manner with respect to corresponding cyclopentadienyl structure in place of the indene structure.
  • the precursors of the invention can be supplied in any suitable form for volatilization to produce the precursor vapor for deposition contacting with the substrate, e.g., in a liquid form that is vaporized or as a solid that is dissolved or suspended in a solvent medium for flash vaporization, as a sublimable solid, or as a solid having sufficient vapor pressure to render it suitable for vapor delivery to the deposition chamber, or in any other suitable form.
  • any suitable solvent medium can be employed in which the precursor can be dissolved or dispersed for delivery.
  • the solvent medium may be a single-component solvent or a multicomponent solvent mixture, including solvent species such as C 3 -C 12 alkanes, C 2 -C 12 ethers, C 6 -C 12 aromatics, C 7 -C 16 arylalkanes, C 10 -C 25 arylcyloalkanes, and further alkyl-substituted forms of aromatic, arylalkane and arylcyloalkane species, wherein the further alkyl substituents in the case of multiple alkyl substituents may be the same as or different from one another and wherein each is independently selected from C 1 -C 8 alkyl.
  • Illustrative solvents include amines, ethers, aromatic solvents, glymes, tetraglymes, alkanes, alkyl-substituted benzene compounds, benzocyclohexane (tetralin), alkyl-substituted benzocyclohexane and ethers, with tetrahydrofuran, xylene, 1,4-tertbutyltoluene, 1,3-diisopropylbenzene, dimethyltetralin, octane and decane being potentially useful solvent species in specific applications.
  • the solvent is selected from among tertiary amines, ethers and aromatic solvent.
  • aromatic solvents such as xylene, 1,4-tertbutyltoluene, 1,3-diisopropylbenzene, tetralin, dimethyltetralin and other alkyl-substituted aromatic solvents.
  • the solvent medium may also comprise a stabilizing solvent, e.g., a Lewis-base ligand.
  • preferred solvents may include amine solvents, neutral amines such as DMAPA, octane or other aliphatic solvents, aromatic solvents such as toluene, ethers such as tetrahydrofuran (THF), and tetraglymes.
  • amine solvents neutral amines such as DMAPA, octane or other aliphatic solvents, aromatic solvents such as toluene, ethers such as tetrahydrofuran (THF), and tetraglymes.
  • the precursors may be supplied in liquid delivery systems as individual precursors or mixtures of precursors, in solvent media that may be comprised of a single component solvent, or alternatively may be constituted by a solvent mixture, as appropriate in a given application.
  • the solvents that may be employed for such purpose can be of any suitable type in which the specific precursor(s) can be dissolved or suspended, and subsequently volatilized to form the precursor vapor for contacting with the substrate on which the metal is to be deposited.
  • the invention also contemplates delivery of the precursor by bubbler delivery techniques, in which the bubbler is arranged to operate at or above the melting point of the precursor.
  • compositions of the invention may alternatively comprise, consist, or consist essentially of any of the components and functional moieties disclosed herein, in specific embodiments of the invention.
  • Precursors of the invention can be utilized in combinations, in which two or more of such precursors are mixed with one another, e.g., in a solution as a precursor cocktail composition for liquid delivery.
  • the precursor species may be individually dissolved in solvent(s) and delivered into vaporizers for volatilization of the precursor solution to form a precursor vapor that then is transported to the deposition chamber of the deposition system to deposit the metal-containing film on a wafer or other microelectronic device substrate.
  • the precursors can be delivered by solid delivery techniques, in which the solid is volatilized to form the precursor vapor that then is transported to the deposition chamber, and with the solid precursor in the first instance being supplied in a packaged form for use, e.g., in a ProE-Vap package (ATMI, Inc., Danbury, Conn., USA).
  • a ProE-Vap package ATMI, Inc., Danbury, Conn., USA.
  • the precursors of the present invention are usefully employed for forming metal-containing thin films of high conformality and uniformity characteristics, by ALD, RVD and CVD processes.
  • the process conditions for the deposition process in a specific application may be readily determined empirically by variation of specific conditions (temperature, pressure, flow rate, concentration, etc.) and characterization of the resulting film deposit.
  • the precursors can be volatilized for the deposition of metal-containing films in any suitable manner and using any suitable vaporizer apparatus or technique.
  • the precursors may be vaporized singly and separately, or they may be volatilized in admixture or solution with one another.
  • any suitable co-reactant or carrier species may be employed, e.g., oxidants, producing agents, inert gases, etc.
  • the oxidant employed in the deposition may be of any suitable type, e.g., nitrous oxide, oxygen, ozone, water, alcohols, combinations of two or more compatible oxidant species selected from such oxidants, or other suitable oxidant.
  • the co-reactants may be supplied simultaneously, e.g., with the precursors entering the deposition chamber concurrently, in a chemical vapor deposition mode, or separately from the precursors, in an atomic layer deposition or digital CVD mode.
  • the precursors can be employed in an ALD mode, in which a purge pulse separates them from the co-reactants, and matched or unmatched precursors may be used.
  • an atomic layer deposition process for forming a layer of strontium titanate on a substrate can be carried out involving pulsing of a titanium source into a deposition reactor, purging the reactor to remove excess titanium precursor, then pulsing water vapor into the reactor, with or without oxidant (such as O 2 , O 3 or N 2 O,) followed by pulsing a strontium source into the reactor and then purging, followed by introduction of water vapor with or without oxidant. This process is repeated until a desired film thickness of the strontium titanate layer is reached.
  • Deposition temperature can for example be in a range of from 250° C. to 500° C. Pulse rates can be on the order from 10 milliseconds to 30 seconds or more.
  • the film may require rapid thermal annealing (RTA) to obtain a crystalline SrTiO 3 film, e.g., by RTA treatment at temperature in a range of from 500° C. to 900° C., for an annealing period of from a few seconds to 30 minutes or more.
  • RTA rapid thermal annealing
  • the oxidant is selected from among oxygen, ozone and oxygen plasma.
  • the use of such oxidant may eliminate the need for a final annealing step, such as rapid thermal annealing. It is noted that formation of the metal-containing film will require oxidant, but in atomic layer deposition processes, when the metal precursor vapor is in contact with the substrate, the presence of an oxidant is not required.
  • the metal films of the invention may be subjected to any suitable post-deposition processing steps, e.g., annealing, oxidizing, reducing, etc., as appropriate to the specific metal film involved.
  • Metal films formed in accordance with the invention may be of any suitable type and include, without limitation, films of metal oxides, metal nitrides, metal hafnates, metal titanates, metal lanthannates, metal ruthenates, metal oxynitrides, metal silicates, and metal silicides, wherein the metal includes barium and/or strontium.
  • the thicknesses of the metal-containing layers in the practice of the present invention can be of any suitable value.
  • the thickness of the metal-containing layer can be in a range of from 2 nm to 500 nm or more.
  • film refers to a layer of deposited material having a thickness below 1000 micrometers, e.g., from such value down to atomic monolayer thickness values.
  • film thicknesses of deposited material layers in the practice of the invention may for example be below 100, 10, or 1 micrometers, or in various thin film regimes below 200, 100, or 50 nanometers, depending on the specific application involved.
  • the term “thin film” means a layer of a material having a thickness below 1 micrometer.
  • a carbon number range e.g., in C 1 -C 12 alkyl
  • identification of a carbon number range is intended to include each of the component carbon number moieties within such range, so that each intervening carbon number and any other stated or intervening carbon number value in that stated range, is encompassed, it being further understood that sub-ranges of carbon number within specified carbon number ranges may independently be included in smaller carbon number ranges, within the scope of the invention, and that ranges of carbon numbers specifically excluding a carbon number or numbers are included in the invention, and sub-ranges excluding either or both of carbon number limits of specified ranges are also included in the invention.
  • C 1 -C 12 alkyl is intended to include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl, including straight chain as well as branched groups of such types. It therefore is to be appreciated that identification of a carbon number range, e.g., C 1 -C 12 , as broadly applicable to a substituent moiety, enables, in specific embodiments of the invention, the carbon number range to be further restricted, as a sub-group of moieties having a carbon number range within the broader specification of the substituent moiety.
  • the carbon number range e.g., C 1 -C 12 alkyl
  • the carbon number range may be more restrictively specified, in particular embodiments of the invention, to encompass sub-ranges such as C 1 -C 4 alkyl, C 2 -C 8 alkyl, C 2 -C 4 alkyl, C 3 -C 5 alkyl, or any other sub-range within the broad carbon number range.
  • compositions may be further specified in specific embodiments by provisos or limitations excluding specific substituents, groups, moieties or structures, in relation to various specifications and exemplifications thereof set forth herein.
  • the invention contemplates restrictively defined compositions, e.g., a composition wherein R i is C 1 -C 12 alkyl, with the proviso that R i ⁇ C 4 alkyl when R j is silyl.
  • Alkyls as used herein include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, pentyl and isopentyl and the like.
  • Aryls as used herein includes hydrocarbons derived from benzene or a benzene derivative that are unsaturated aromatic carbocyclic groups of from 6 to 10 carbon atoms. The aryls may have a single or multiple rings. The term “aryl” as used herein also includes substituted aryls.
  • Examples include, but are not limited to phenyl, naphthyl, xylene, phenylethane, substituted phenyl, substituted naphthyl, substituted xylene, substituted phenylethane and the like.
  • Cycloalkyls as used herein include, but are not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.
  • a range of carbon numbers will be regarded as specifying a sequence of consecutive alternative carbon-containing moieties, including all moieties containing numbers of carbon atoms intermediate the endpoint values of carbon number in the specific range as well as moieties containing numbers of carbon atoms equal to an endpoint value of the specific range, e.g., C 1 -C 6 , is inclusive of C 1 , C 2 , C 3 , C 4 , C 5 and C 6 , and each of such broader ranges may be further limitingly specified with reference to carbon numbers within such ranges, as sub-ranges thereof.
  • the range C 1 -C 6 would be inclusive of and can be further limited by specification of sub-ranges such as C 1 -C 3 , C 1 -C 4 , C 2 -C 6 , C 4 -C 6 , etc. within the scope of the broader range.
  • FIG. 3 is a schematic representation of a material storage and dispensing package 100 containing a barium or strontium precursor, according to one embodiment of the present invention.
  • the material storage and dispensing package 100 includes a vessel 102 that may for example be of generally cylindrical shape as illustrated, defining an interior volume 104 therein.
  • the precursor is a solid at ambient temperature conditions, and such precursor may be supported on surfaces of the trays 106 disposed in the interior volume 104 of the vessel, with the trays having flow passage conduits 108 associated therewith, for flow of vapor upwardly in the vessel to the valve head assembly, for dispensing in use of the vessel.
  • the solid precursor can be coated on interior surfaces in the interior volume of the vessel, e.g., on the surfaces of the trays 106 and conduits 108 .
  • Such coating may be effected by introduction of the precursor into the vessel in a vapor form from which the solid precursor is condensed in a film on the surfaces in the vessel.
  • the precursor solid may be dissolved or suspended in a solvent medium and deposited on surfaces in the interior volume of the vessel by solvent evaporation.
  • the precursor may be melted and poured onto the surfaces in the interior volume of the vessel.
  • the vessel may contain substrate articles or elements that provide additional surface area in the vessel for support of the precursor film thereon.
  • the solid precursor may be provided in granular or finely divided form, which is poured into the vessel to be retained on the top supporting surfaces of the respective trays 106 therein.
  • the vessel 102 has a neck portion 109 to which is joined the valve head assembly 110 .
  • the valve head assembly is equipped with a hand wheel 112 in the embodiment shown.
  • the valve head assembly 110 includes a dispensing port 114 , which may be configured for coupling to a fitting or connection element to join flow circuitry to the vessel.
  • flow circuitry is schematically represented by arrow A in FIG. 1 , and the flow circuitry may be coupled to a downstream ALD or chemical vapor deposition chamber (not shown in FIG. 1 ).
  • the vessel 102 is heated, such input of heat being schematically shown by the reference arrow Q, so that solid precursor in the vessel is at least partially volatilized to provide precursor vapor.
  • the precursor vapor is discharged from the vessel through the valve passages in the valve head assembly 110 when the hand wheel 112 is translated to an open valve position, whereupon vapor deriving from the precursor is dispensed into the flow circuitry schematically indicated by arrow A.
  • the precursor may be provided in a solvent medium, forming a solution or suspension.
  • Such precursor-containing solvent composition then may be delivered by liquid delivery and flash vaporized to produce a precursor vapor.
  • the precursor vapor is contacted with a substrate under deposition conditions, to deposit the metal on the substrate as a film thereon.
  • the precursor is dissolved in an ionic liquid medium, from which precursor vapor is withdrawn from the ionic liquid solution under dispensing conditions.
  • the precursor may be stored in an adsorbed state on a suitable solid-phase physical adsorbent storage medium in the interior volume of the vessel.
  • the precursor vapor is dispensed from the vessel under dispensing conditions involving desorption of the adsorbed precursor from the solid-phase physical adsorbent storage medium.
  • Supply vessels for precursor delivery may be of widely varying type, and may employ vessels such as those commercially available from ATMI, Inc. (Danbury, Conn.) under the trademarks SDS, SAGE, VAC, VACSorb, and ProE-Vap, as may be appropriate in a given storage and dispensing application for a particular precursor of the invention.
  • the precursors of the invention are usefully employed to form precursor vapor for contacting with a substrate to deposit a barium- and/or strontium-containing thin film thereon.
  • Precursors of the invention can be employed to conduct atomic layer deposition, yielding ALD films of superior conformality that are uniformly coated on the substrate with high step coverage and conformality even on high aspect ratio structures.
  • the precursors of the invention enable a wide variety of microelectronic devices, e.g., semiconductor products, flat panel displays, etc., to be fabricated with barium- and/or strontium-containing films of superior quality.

Abstract

Cyclopentadienyl and indenyl barium/strontium metal precursors and Lewis base adducts thereof are described. Such precursors have utility for forming Ba- and/or Sr-containing films on substrates, in the manufacture of microelectronic devices or structures.

Description

    CROSS-REFERENCE TO RELATED APPLICATIONS
  • This application is a continuation under 35 U.S.C. §120 of U.S. patent application Ser. No. 12/672,684 filed Feb. 8, 2010, which is a U.S. national phase under the provisions of 35 U.S.C. §371 of International Patent Application No. PCT/US08/72045 filed Aug. 3, 2008, which claims the benefit under 35 U.S.C. §119 of U.S. Provisional Patent Application No. 60/954,581 filed Aug. 8, 2007. The disclosures of U.S. patent application Ser. No. 12/672,684, International Patent Application No. PCT/US08/72045, and U.S. Provisional Patent Application No. 60/954,581 are hereby incorporated herein by reference, in their respective entireties, for all purposes.
    • FIELD OF THE INVENTION
  • The present invention relates to precursors for use in depositing strontium- and barium-containing films on substrates such as wafers or other microelectronic device substrates, as well as associated processes of making and using such precursors, and source packages of such precursors.
    • DESCRIPTION OF THE RELATED ART
  • In the manufacture of microelectronic devices, conformal, high k materials based on barium (Ba) or strontium (Sr), such as strontium titanate (STO) and barium strontium titanate (BST), are deposited on substrates by deposition techniques such as chemical vapor deposition (CVD), atomic layer deposition (ALD) and rapid vapor deposition (RVD).
  • Such deposition requires monomeric metal precursors that are transportable (volatile) at temperatures specific to the deposition process.
  • In addition to this requirement, it is advantageous in many applications for the precursors to be in liquid form at the delivery temperature used in the deposition process. For example, the precursors should have melting points below the operating temperature of the vaporizer that is used in a liquid delivery deposition process system, to avoid clogging of the vaporizer and to minimize the potential for particle generation by the vaporizer. Such clogging and particle generation issues are particularly common when solutions of solid precursors are used in deposition.
  • Another problem associated with many conventional barium and strontium precursors is their sensitivity to oxygen and moisture, which cause degradation of these precursors, and increase the handling difficulties of such precursors.
  • It would therefore be a substantial advance in the art to provide barium and strontium precursors having low melting point, e.g., below 130° C., to minimize and preferably avoid the aforementioned clogging and particle generation problems, that have good transport and deposition properties for forming conformal films on substrates, and that have good handling characteristics and stability with respect to oxygen and moisture.
    • SUMMARY OF THE INVENTION
  • The present invention relates to barium and strontium precursors useful in chemical vapor deposition, atomic layer deposition and rapid vapor deposition applications, to form corresponding metal-containing films on substrates, as well as associated processes and packaged forms of such precursors.
  • In one aspect, the invention relates to a metal precursor selected from among:
    • (i) precursors of the formula Cp-M-Cp
      wherein:
    • M is a metal center selected from among Ba or Sr;
    • Cp is cyclopentadienyl having substituents R1, R2, R3, R4 and R5 on respective ring carbon atoms thereof; and
    • each R1, R2, R3, R4, and R5 is the same as or different from one another, with each being independently selected from among H, C1-C12 alkyl, C1-C12 amino, C1-C12 alkylamino, C1-C12 alkoxy, C3-C10 cycloalkyl, C2-C12 alkenyl, C7-C12 aralkyl, C7-C12 alkylaryl, C6-C12 aryl, C5-C12 heteroaryl, C1-C10 perfluoroalkyl, silicon-containing groups selected from the group consisting of silyl, alkylsilyl, perfluoroalkylsilyl, triarylsilyl and alkylsilylsilyl, RaRbRcNNRc, wherein Ra, Rb and Rc may be the same as or different from one another and each is independently selected from hydrogen and C1-C6 alkyl, and pendant ligands including functional group(s) providing further coordination to the metal center;
    • (ii) precursors of the formula Ind-M-Ind
      wherein:
    • M is a metal center selected from among Ba or Sr;
    • Ind is indenyl having substituents R1, R2, R3, R4, R6, R7, R8 and R9 on respective ring carbon atoms thereof; and
    • each R1, R2, R3, R4, R6, R7, R8 and R9 is the same as or different from one another, with each being independently selected from among H, C1-C12 alkyl, C1-C12 amino, C1-C12 alkylamino, C1-C12 alkoxy, C3-C10 cycloalkyl, C2-C12 alkenyl, C7-C12 aralkyl, C7-C12 alkylaryl, C6-C12 aryl, C5-C12 heteroaryl, C1-C10 perfluoroalkyl, silicon-containing groups selected from the group consisting of silyl, alkylsilyl, perfluoroalkylsilyl, triarylsilyl and alkylsilylsilyl, RaRbRcNNRc, wherein Ra, Rb and Rc may be the same as or different from one another and each is independently selected from hydrogen and C1-C6 alkyl, and pendant ligands including functional group(s) providing further coordination to the metal center;
    • (iii) precursors of the formulae MCpX, M(Ind)X and M(Cp)(Ind)
      wherein:
    • M is a metal center selected from among Ba or Sr;
    • Cp is cyclopentadienyl having substituents R1, R2, R3, R4, and R5 on respective ring carbon atoms thereof;
    • Ind is indenyl having substituents R1, R2, R3, R4, R6, R7, R8 and R9 on respective ring carbon atoms thereof;
    • each R1, R2, R3, R4, R6, R7, R8 and R9 is the same as or different from one another, with each being independently selected from among H, C1-C12 alkyl, C1-C12 amino, C1-C12 alkylamino, C1-C12 alkoxy, C3-C10 cycloalkyl, C2-C12 alkenyl, C7-C12 aralkyl, C7-C12 alkylaryl, C6-C12 aryl, C5-C12 heteroaryl, C1-C10 perfluoroalkyl, silicon-containing groups selected from the group consisting of silyl, alkylsilyl, perfluoroalkylsilyl, triarylsilyl and alkylsilylsilyl, RaRbRcNNRc, wherein Ra, Rb and Rc may be the same as or different from one another and each is independently selected from hydrogen and C1-C6 alkyl, and pendant ligands including functional group(s) providing further coordination to the metal center; and
    • X is a coordinating ligand selected from among C1-C12 alkyl, C1-C12 alkylamino, C1-C12 alkoxy, C3-C10 cycloalkyl, C2-C12 alkenyl, C7-C12 aralkyl, C7-C12 alkylaryl, C6-C12 aryl, C5-C12 heteroaryl, C1-C10 perfluoroalkyl, and silicon-containing groups selected from the group consisting of silyl, alkylsilyl, perfluoroalkylsilyl, triarylsilyl and alkylsilylsilyl, beta-diketonate or a corresponding sulfur or nitrogen compound, halide, amide, alkoxide, carboxylate, Schiff base and pendant ligands including functional group(s) providing further coordination to the metal center; and
    • (iv) Lewis-base and neutral ligand adducts of precursors (i), (ii) and (iii).
  • In another aspect, the invention relates to bis(n-propyltetramethyl-cyclopentadienyl)barium and Lewis base adducts thereof.
  • A further aspect of the invention relates to bis(n-propyltetramethyl-cyclopentadienyl)strontium and Lewis base adducts thereof.
  • Yet another aspect of the invention relates to a Lewis base-stabilized strontium cyclopentadienyl complex of the formula:
  • Figure US20130251918A1-20130926-C00001
  • in which:
    • L is a Lewis base ligand;
    • n is the number of Lewis base ligands coordinated to the Sr central atom, and is an integer having a value of from 1 to 4; and
    • each R1, R2, R3, R4 and R5 is the same as or different from one another, with each being independently selected from among H, C1-C12 alkyl, C1-C12 amino, C1-C12 alkylamino, C1-C12 alkoxy, C3-C10 cycloalkyl, C2-C12 alkenyl, C7-C12 aralkyl, C7-C12 alkylaryl, C6-C12 aryl, C5-C12 heteroaryl, C1-C10 perfluoroalkyl, silicon-containing groups selected from the group consisting of silyl, alkylsilyl, perfluoroalkylsilyl, triarylsilyl and alkylsilylsilyl, RaRbRcNNRc, wherein Ra, Rb and Rc may be the same as or different from one another and each is independently selected from hydrogen and C1-C6 alkyl, and pendant ligands including functional group(s) providing further coordination to Sr.
  • In a further aspect, the invention relates to a method of forming a metal-containing film on a substrate, wherein said metal comprises a metal species selected from among barium and strontium, said method comprising volatilizing a metal precursor according to claim 1, to form a precursor vapor, and contacting said precursor vapor with a substrate to form of said metal-containing film thereon.
  • A further aspect of the invention relates to a precursor composition comprising at least one metal precursor of the invention, and a solvent medium for the metal precursor(s).
  • A still further aspect of the invention relates to a precursor vapor of a metal precursor of the invention.
  • Another aspect of the invention relates to a precursor source package comprising a precursor storage and dispensing vessel containing a metal precursor of the invention.
  • Other aspects, features and embodiments of the invention will be more fully apparent from the ensuing disclosure and appended claims.
    • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 1 is a simultaneous thermal analysis (STA) plot of thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) curves for bis(n-propyltetramethyl-cyclopentadienyl)strontium.
  • FIG. 2 is a plot of STA results for Sr(Cp′)2 and Sr(Cp′)2(PMDETA).
  • FIG. 3 is a schematic representation of a material storage and dispensing package containing a precursor of the present invention, in one embodiment thereof.
    •  DETAILED DESCRIPTION OF THE INVENTION, AND PREFERRED EMBODIMENTS THEREOF
  • The present invention relates in various aspects to barium and strontium metal precursors having low melting point, characterized by superior stability, and utility for forming highly conformal films. The superior air stability of such precursors also minimizes generation of particles in the CVD/ALD/RVD processes in which such precursors are usefully employed to form barium- and/or strontium-containing films.
  • Although the ensuing discussion is directed primarily to barium and/or strontium precursors, the invention also contemplates the provision of corresponding precursors with other Group II metal species, such as calcium.
  • Metal precursors of the invention include those selected from among:
    • (i) precursors of the formula Cp-M-Cp
      wherein:
    • M is a metal center selected from among Ba or Sr;
    • Cp is cyclopentadienyl having substituents R1, R2, R3, R4 and R5 on respective ring carbon atoms thereof; and
    • each R1, R2, R3, R4 and R5 is the same as or different from one another, with each being independently selected from among H, C1-C12 alkyl, C1-C12 amino, C1-C12 alkylamino, C1-C12 alkoxy, C3-C10 cycloalkyl, C2-C12 alkenyl (such term being intended to be broadly construed to include substituents containing linear, branched, and/or cyclic moieties containing ethylenic unsaturation, e.g., vinyl, allyl, cyclic -ene species, etc., and substituents containing various types of such moieties therein, e.g., tetramethylpentadienylvinyl), C7-C12 aralkyl, C7-C12 alkylaryl, C6-C12 aryl, C5-C12 heteroaryl, C1-C10 perfluoroalkyl, silicon-containing groups selected from the group consisting of silyl, alkylsilyl, perfluoroalkylsilyl, triarylsilyl and alkylsilylsilyl, RaRbRcNNRc, wherein Ra, Rb and Rc may be the same as or different from one another and each is independently selected from hydrogen and C1-C6 alkyl, and pendant ligands including functional group(s) providing further coordination to the metal center;
    • (ii) precursors of the formula Ind-M-Ind
      wherein:
    • M is a metal center selected from among Ba or Sr;
    • Ind is indenyl having substituents R1, R2, R3, R4, R6, R7, R8 and R9 on respective ring carbon atoms thereof; and
    • each R1, R2, R3, R4, R6, R7, R8 and R9 is the same as or different from one another, with each being independently selected from among H, C1-C12 alkyl, C1-C12 amino, C1-C12 alkylamino, C1-C12 alkoxy, C3-C10 cycloalkyl, C2-C12 alkenyl, C7-C12 aralkyl, C7-C12 alkylaryl, C6-C12 aryl, C5-C12 heteroaryl, C1-C10 perfluoroalkyl, silicon-containing groups selected from the group consisting of silyl, alkylsilyl, perfluoroalkylsilyl, triarylsilyl and alkylsilylsilyl, RaRbRcNNRc, wherein Ra, Rb and Rc may be the same as or different from one another and each is independently selected from hydrogen and C1-C6 alkyl, and pendant ligands including functional group(s) providing further coordination to the metal center;
    • (iii) precursors of the formulae MCpX, M(Ind)X and M(Cp)(Ind)
      wherein:
    • M is a metal center selected from among Ba or Sr;
    • Cp is cyclopentadienyl having substituents R1, R2, R3, R4, and R5 on respective ring carbon atoms thereof;
    • Ind is indenyl having substituents R1, R2, R3, R4, R6, R7, R8 and R9 on respective ring carbon atoms thereof;
    • each R1, R2, R3, R4, R6, R7, R8 and R9 is the same as or different from one another, with each being independently selected from among H, C1-C12 alkyl, C1-C12 amino, C1-C12 alkylamino, C1-C12 alkoxy, C3-C10 cycloalkyl, C2-C12 alkenyl, C7-C12 aralkyl, C7-C12 alkylaryl, C6-C12 aryl, C5-C12 heteroaryl, C1-C10 perfluoroalkyl, silicon-containing groups selected from the group consisting of silyl, alkylsilyl, perfluoroalkylsilyl, triarylsilyl and alkylsilylsilyl, RaRbRcNNRc, wherein Ra, Rb and Rc may be the same as or different from one another and each is independently selected from hydrogen and C1-C6 alkyl, and pendant ligands including functional group(s) providing further coordination to the metal center; and
    • X is a coordinating ligand selected from among C1-C12 alkyl, C1-C12 alkylamino, C1-C12 alkoxy, C3-C10 cycloalkyl, C2-C12 alkenyl, C7-C12 aralkyl, C7-C12 alkylaryl, C6-C12 aryl, C5-C12 heteroaryl, C1-C10 perfluoroalkyl, and silicon-containing groups selected from the group consisting of silyl, alkylsilyl, perfluoroalkylsilyl, triarylsilyl and alkylsilylsilyl, beta-diketonate or a corresponding sulfur or nitrogen compound, halide, amide, alkoxide, carboxylate, Schiff base and pendant ligands including functional group(s) providing further coordination to the metal center; and
    • (iv) Lewis-base and neutral ligand adducts of precursors (i), (ii) and (iii).
  • X may in various embodiments comprise specific ligand species described in U.S. Pat. No. 7,108,747, and the complexing species forming adducts may comprise specific ligands described in U.S. Pat. No. 7,108,747. Neutral ligand adducts, e.g., of the formula Ln, include ligands that bind to the central metal by either one or several of its atoms, where n depicts the number of the ligands being bound. Neutral adduct ligands include ligands as described in such U.S. Pat. No. 7,108,747.
  • The pendant ligands including functional group(s) providing further coordination to the metal center may in various embodiments of the invention include ligands selected from among aminoalkyl, alkoxyalkyl, aryloxyalkyl, imidoalkyl, and acetylalkyl. Ligands may in specific embodiments be selected from among:
    • (A) aminoalkyls of the following formulae:
  • Figure US20130251918A1-20130926-C00002
  • wherein each of R1-R4 is the same as or different from one another, with each being independently selected from among hydrogen and C1-C6 alkyl and C6-C10 aryl; each of R5 and R6 is the same as or different from the other, with each being independently selected from among C1-C6 alkyl; n and m are each selected independently from 0 to 4 with the proviso that m and n cannot be 0 at the same time, and x is selected from 1 to 5;
    • (B) alkoxyalkyls and aryloxyalkyls of the following formulae:
  • Figure US20130251918A1-20130926-C00003
  • wherein each of R1-R4 is the same as or different from one another, with each being independently selected from among hydrogen, C1-C6 alkyl, and C6-C10 aryl; R5 is selected from among C1-C6 alkyl, and C6-C10 aryl; and n and m are selected independently from 0 to 4, with the proviso that m and n cannot be 0 at the same time;
    • (C) imidoalkyl of the formula:
  • Figure US20130251918A1-20130926-C00004
  • wherein each of R1-R6 is the same as or different from one another, with each being independently selected from among hydrogen, C1-C6 alkyl, and C6-C10 aryl; and n and m are selected independently from 0 to 4, with the proviso that m and n cannot be 0 at the same time;
    • (D) acetylalkyls of the formula:
  • Figure US20130251918A1-20130926-C00005
  • wherein each of R1-R4 is the same as or different from one another, with each being independently selected from among hydrogen, C1-C6 alkyl, and C6-C10 aryl; R5 is selected from among C1-C6 alkyl, and C6-C10 aryl; and n and m are selected independently from 0 to 4, with the proviso that m and n cannot be 0 at the same time.
  • Metal precursors of the invention, in another aspect thereof, include those selected from among strontium and barium bis(n-propyltetramethylcyclopentadienyl) complexes (I) and strontium and barium isopropylated indenyl complexes (II):
  • Figure US20130251918A1-20130926-C00006
  • wherein M is Ba or Sr, and THF is tetrahydrofuran.
  • Such precursors have low melting points (<130° C.), good transport and deposition properties for forming conformal films on substrates, and good handling characteristics and stability with respect to oxygen and moisture.
  • Bis(n-propyltetramethylcyclopentadienyl)strontium, for example, has a melting point of 43.4° C. The simultaneous thermal analysis (STA) plot of thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) curves for such precursor is shown in FIG. 1 hereof.
  • In another aspect, the invention relates to Lewis-base stabilized strontium and barium cyclopentadienyl complexes that are useful for CVD, ALD and RVD applications, which the metal central atom of the precursor compound is coordinated with one or more Lewis base ligands to form corresponding stabilized complexes of Ba or Sr. Preferably, when more than one Lewis base ligand is present, each of the ligands is the same as the other(s).
  • Such Lewis base ligands stabilize the complex against degradation by oxygen and/or moisture in exposure to air, and thus provide more easily handled precursor compositions, relative to various barium and strontium source reagents of the prior art.
  • In a specific aspect, the invention relates to Lewis base adducts of the dicyclopentadienyl or diindenyl compounds of the invention, wherein the dicyclopentadienyl or diindenyl compound is an oil at standard temperature and pressure (25° C. and 1 atmosphere) conditions. An illustrative adduct of such type is Sr(Cp′)2(PMDETA), wherein Cp′=tetramethyl-n-propylcyclopentadienyl, and PMDETA is pentamethyl diethylene triamine (N-[2-(dimethylamino)ethyl]N,N′,N′-trimethyl-1,2-ethanediamine).
  • A specific strontium cyclopentadienyl compound of the invention comprises SrCp2 which can for example be formed from SrCp2G adducts, wherein the adducting species G can for example be tetrahydrofuran or ether, e.g., SrCp2(THF)4 where THF is tetrahydrofuran.
  • The Lewis base ligands used to form adducts and complexes of the invention can be of any suitable type, and include, without limitation, multidentate glymes such as dimethoxyethane and tetraglyme, nitrogen-containing multidentate ligands such as PMDETA, and monocoordinate ligands such as pyridine and tetrahydrofuran. The Lewis base ligands enhance compound stability by protecting the metal centers via steric crowding (encapsulation) and by providing electron density to the metal center. Lewis bases such as alkene, diene, cycloalkene, cyclodiene, cyclooctatetraene, alkyne, substituted alkyne (symmetrical or asymmetrical), amine, diamine, triamine, tetraamine, ether, tetrahydrofuran, glyme, diglyme, triglyme, tetraglyme, phosphine, carbonyl, dialkyl sulfide, vinyltrimethylsilane, and allyltrimethylsilane can be used.
  • Precursor compounds stabilized in such fashion exhibit an enhanced robustness and suitability for deposition processes. Precursors in which the central atom in the complex is Sr are particularly useful in ALD processes for forming strontium titanate (STO) films, when such complex and a titanium precursor are employed as the alternating vapor-phase precursors contacted with the substrate. Strontium precursors of the invention, e.g., Sr(Cp)2, may also be employed to form strontium ruthenium oxide (SrRuOx) films. SrRuOx is a conductive oxide and may be employed as an electrode material for STO or barium strontium titanate (BST) devices. In various embodiments, the films of the invention can be doped with suitable dopant species, e.g., Nb, Zr, As, etc. and other barium- and/or strontium-containing films can be formed using the Ba and Sr precursors of the invention, including strontium tantalate, barium strontium zirconium titanate, ruthenium strontiate, etc.
  • The precursors of the invention may also be employed to form BST films, when respective barium and strontium precursors are utilized, in combination with a suitable titanium precursor. For this purpose, titanium precursors such as those described in U.S. Pat. No. 7,108,747 can be advantageously employed.
  • An illustrative Lewis base-stabilized strontium cyclopentadienyl complex of the invention is shown below:
  • Figure US20130251918A1-20130926-C00007
  • in which:
    • L is a Lewis base ligand;
    • n is the number of Lewis base ligands coordinated to the Sr central atom, and is an integer having a value of from 1 to 4; and
    • each R1, R2, R3, R4 and R5 is the same as or different from one another, with each being independently selected from among H, C1-C12 alkyl, C1-C12 amino, C1-C12 alkylamino, C1-C12 alkoxy, C3-C10 cycloalkyl, C2-C12 alkenyl, C7-C12 aralkyl, C7-C12 alkylaryl, C6-C12 aryl, C5-C12 heteroaryl, C1-C10 perfluoroalkyl, silicon-containing groups selected from the group consisting of silyl, alkylsilyl, perfluoroalkylsilyl, triarylsilyl and alkylsilylsilyl, RaRbRcNNRc, wherein Ra, Rb and Rc may be the same as or different from one another and each is independently selected from hydrogen and C1-C6 alkyl, and pendant ligands including functional group(s) providing further coordination to the metal center, including for example, aminoalkyl, alkoxyalkyl, aryloxyalkyl, imidoalkyl, and acetylalkyl. Preferred substituent groups among the foregoing include H, C1-C6 alkyl, C1-C6 alkoxy, C6-C10 aryl, C3-C6 alkylsilyl, and pendant ligands including functional group(s) providing further coordination to the metal center, including for example, aminoalkyl, alkoxyalkyl, aryloxyalkyl, imidoalkyl, and acetylalkyl.
  • In addition to enhancing compound stability, the Lewis-base ligands will also lower the t50 of the Ba and Sr compounds with respect to the corresponding compound uncomplexed with the Lewis-base. The lowering of the t50 value is a result of the Lewis-base ligand disrupting intermolecular interactions.
  • The lowering of t50 is evident from analysis of STA results for Sr(Cp′)2 and Sr(Cp′)2(PMDETA), wherein Cp′ is tetramethyl-n-propylcyclopentadienyl, and PMDETA is pentamethyl diethylene triamine. The simultaneous thermal analysis (STA) plot of thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) curves for such precursors is shown in FIG. 2 hereof, wherein the upper TGA curve represents Sr(Cp′)2 and the upper DSC curve represents Sr(Cp′)2(PMDETA).
  • The t50 value for Sr(Cp′)2 is 256° C. and the t50 value for Sr(Cp′)2(PMDETA) is 40° C. lower at 216° C. The Lewis-base adducts with lower t50 values will enable lower transport temperatures to be employed in CVD, ALD and RVD processes.
  • The precursors of the invention can be readily synthesized with the skill of the art, with indenyl precursors being synthesized by a process of a general type as described in J. S. Overby and T. P. Hanusa, Organometallics 1996, 15, 2205, and cyclopentadienyl precursors being synthesized in an analogous manner with respect to corresponding cyclopentadienyl structure in place of the indene structure.
  • The precursors of the invention can be supplied in any suitable form for volatilization to produce the precursor vapor for deposition contacting with the substrate, e.g., in a liquid form that is vaporized or as a solid that is dissolved or suspended in a solvent medium for flash vaporization, as a sublimable solid, or as a solid having sufficient vapor pressure to render it suitable for vapor delivery to the deposition chamber, or in any other suitable form.
  • When solvents are employed for delivery of the precursors of the invention, any suitable solvent medium can be employed in which the precursor can be dissolved or dispersed for delivery. By way of example, the solvent medium may be a single-component solvent or a multicomponent solvent mixture, including solvent species such as C3-C12 alkanes, C2-C12 ethers, C6-C12 aromatics, C7-C16 arylalkanes, C10-C25 arylcyloalkanes, and further alkyl-substituted forms of aromatic, arylalkane and arylcyloalkane species, wherein the further alkyl substituents in the case of multiple alkyl substituents may be the same as or different from one another and wherein each is independently selected from C1-C8 alkyl. Illustrative solvents include amines, ethers, aromatic solvents, glymes, tetraglymes, alkanes, alkyl-substituted benzene compounds, benzocyclohexane (tetralin), alkyl-substituted benzocyclohexane and ethers, with tetrahydrofuran, xylene, 1,4-tertbutyltoluene, 1,3-diisopropylbenzene, dimethyltetralin, octane and decane being potentially useful solvent species in specific applications. In one embodiment, the solvent is selected from among tertiary amines, ethers and aromatic solvent.
  • In various embodiments of the invention, it may be desirable to utilize aromatic solvents such as xylene, 1,4-tertbutyltoluene, 1,3-diisopropylbenzene, tetralin, dimethyltetralin and other alkyl-substituted aromatic solvents. The solvent medium may also comprise a stabilizing solvent, e.g., a Lewis-base ligand.
  • In other applications, preferred solvents may include amine solvents, neutral amines such as DMAPA, octane or other aliphatic solvents, aromatic solvents such as toluene, ethers such as tetrahydrofuran (THF), and tetraglymes.
  • Thus, the precursors may be supplied in liquid delivery systems as individual precursors or mixtures of precursors, in solvent media that may be comprised of a single component solvent, or alternatively may be constituted by a solvent mixture, as appropriate in a given application. The solvents that may be employed for such purpose can be of any suitable type in which the specific precursor(s) can be dissolved or suspended, and subsequently volatilized to form the precursor vapor for contacting with the substrate on which the metal is to be deposited.
  • The invention also contemplates delivery of the precursor by bubbler delivery techniques, in which the bubbler is arranged to operate at or above the melting point of the precursor.
  • In general, the precursor compositions of the invention may alternatively comprise, consist, or consist essentially of any of the components and functional moieties disclosed herein, in specific embodiments of the invention.
  • Precursors of the invention can be utilized in combinations, in which two or more of such precursors are mixed with one another, e.g., in a solution as a precursor cocktail composition for liquid delivery.
  • Alternatively, the precursor species may be individually dissolved in solvent(s) and delivered into vaporizers for volatilization of the precursor solution to form a precursor vapor that then is transported to the deposition chamber of the deposition system to deposit the metal-containing film on a wafer or other microelectronic device substrate.
  • As a still further alternative, the precursors can be delivered by solid delivery techniques, in which the solid is volatilized to form the precursor vapor that then is transported to the deposition chamber, and with the solid precursor in the first instance being supplied in a packaged form for use, e.g., in a ProE-Vap package (ATMI, Inc., Danbury, Conn., USA).
  • The precursors of the present invention are usefully employed for forming metal-containing thin films of high conformality and uniformity characteristics, by ALD, RVD and CVD processes. The process conditions for the deposition process in a specific application may be readily determined empirically by variation of specific conditions (temperature, pressure, flow rate, concentration, etc.) and characterization of the resulting film deposit.
  • The precursors can be volatilized for the deposition of metal-containing films in any suitable manner and using any suitable vaporizer apparatus or technique. The precursors may be vaporized singly and separately, or they may be volatilized in admixture or solution with one another.
  • In the formation of metal-containing films, any suitable co-reactant or carrier species may be employed, e.g., oxidants, producing agents, inert gases, etc. In a specific embodiment in which an oxidant is used, the oxidant employed in the deposition may be of any suitable type, e.g., nitrous oxide, oxygen, ozone, water, alcohols, combinations of two or more compatible oxidant species selected from such oxidants, or other suitable oxidant. The co-reactants may be supplied simultaneously, e.g., with the precursors entering the deposition chamber concurrently, in a chemical vapor deposition mode, or separately from the precursors, in an atomic layer deposition or digital CVD mode. The precursors can be employed in an ALD mode, in which a purge pulse separates them from the co-reactants, and matched or unmatched precursors may be used.
  • By way of specific example, an atomic layer deposition process for forming a layer of strontium titanate on a substrate can be carried out involving pulsing of a titanium source into a deposition reactor, purging the reactor to remove excess titanium precursor, then pulsing water vapor into the reactor, with or without oxidant (such as O2, O3 or N2O,) followed by pulsing a strontium source into the reactor and then purging, followed by introduction of water vapor with or without oxidant. This process is repeated until a desired film thickness of the strontium titanate layer is reached. Deposition temperature can for example be in a range of from 250° C. to 500° C. Pulse rates can be on the order from 10 milliseconds to 30 seconds or more. After deposition, the film may require rapid thermal annealing (RTA) to obtain a crystalline SrTiO3 film, e.g., by RTA treatment at temperature in a range of from 500° C. to 900° C., for an annealing period of from a few seconds to 30 minutes or more.
  • In one embodiment of the above-described process, the oxidant is selected from among oxygen, ozone and oxygen plasma. The use of such oxidant may eliminate the need for a final annealing step, such as rapid thermal annealing. It is noted that formation of the metal-containing film will require oxidant, but in atomic layer deposition processes, when the metal precursor vapor is in contact with the substrate, the presence of an oxidant is not required.
  • The metal films of the invention may be subjected to any suitable post-deposition processing steps, e.g., annealing, oxidizing, reducing, etc., as appropriate to the specific metal film involved.
  • Metal films formed in accordance with the invention may be of any suitable type and include, without limitation, films of metal oxides, metal nitrides, metal hafnates, metal titanates, metal lanthannates, metal ruthenates, metal oxynitrides, metal silicates, and metal silicides, wherein the metal includes barium and/or strontium.
  • In general, the thicknesses of the metal-containing layers in the practice of the present invention can be of any suitable value. In a specific embodiment of the invention, the thickness of the metal-containing layer can be in a range of from 2 nm to 500 nm or more.
  • As used herein, the term “film” refers to a layer of deposited material having a thickness below 1000 micrometers, e.g., from such value down to atomic monolayer thickness values. In various embodiments, film thicknesses of deposited material layers in the practice of the invention may for example be below 100, 10, or 1 micrometers, or in various thin film regimes below 200, 100, or 50 nanometers, depending on the specific application involved. As used herein, the term “thin film” means a layer of a material having a thickness below 1 micrometer.
  • As used herein, the singular forms “a”, “and”, and “the” include plural referents unless the context clearly dictates otherwise.
  • As used herein, the identification of a carbon number range, e.g., in C1-C12 alkyl, is intended to include each of the component carbon number moieties within such range, so that each intervening carbon number and any other stated or intervening carbon number value in that stated range, is encompassed, it being further understood that sub-ranges of carbon number within specified carbon number ranges may independently be included in smaller carbon number ranges, within the scope of the invention, and that ranges of carbon numbers specifically excluding a carbon number or numbers are included in the invention, and sub-ranges excluding either or both of carbon number limits of specified ranges are also included in the invention. Accordingly, C1-C12 alkyl is intended to include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl, including straight chain as well as branched groups of such types. It therefore is to be appreciated that identification of a carbon number range, e.g., C1-C12, as broadly applicable to a substituent moiety, enables, in specific embodiments of the invention, the carbon number range to be further restricted, as a sub-group of moieties having a carbon number range within the broader specification of the substituent moiety. By way of example, the carbon number range e.g., C1-C12 alkyl, may be more restrictively specified, in particular embodiments of the invention, to encompass sub-ranges such as C1-C4 alkyl, C2-C8 alkyl, C2-C4 alkyl, C3-C5 alkyl, or any other sub-range within the broad carbon number range.
  • The precursors of the invention may be further specified in specific embodiments by provisos or limitations excluding specific substituents, groups, moieties or structures, in relation to various specifications and exemplifications thereof set forth herein. Thus, the invention contemplates restrictively defined compositions, e.g., a composition wherein Ri is C1-C12 alkyl, with the proviso that Ri≠C4 alkyl when Rj is silyl.
  • “Alkyls” as used herein include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, pentyl and isopentyl and the like. “Aryls” as used herein includes hydrocarbons derived from benzene or a benzene derivative that are unsaturated aromatic carbocyclic groups of from 6 to 10 carbon atoms. The aryls may have a single or multiple rings. The term “aryl” as used herein also includes substituted aryls. Examples include, but are not limited to phenyl, naphthyl, xylene, phenylethane, substituted phenyl, substituted naphthyl, substituted xylene, substituted phenylethane and the like. “Cycloalkyls” as used herein include, but are not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. In all chemical formulae herein, a range of carbon numbers will be regarded as specifying a sequence of consecutive alternative carbon-containing moieties, including all moieties containing numbers of carbon atoms intermediate the endpoint values of carbon number in the specific range as well as moieties containing numbers of carbon atoms equal to an endpoint value of the specific range, e.g., C1-C6, is inclusive of C1, C2, C3, C4, C5 and C6, and each of such broader ranges may be further limitingly specified with reference to carbon numbers within such ranges, as sub-ranges thereof. Thus, for example, the range C1-C6 would be inclusive of and can be further limited by specification of sub-ranges such as C1-C3, C1-C4, C2-C6, C4-C6, etc. within the scope of the broader range.
  • The invention, as variously described herein in respect of features, aspects and embodiments thereof, may in particular implementations be constituted as comprising, consisting, or consisting essentially of, some or all of such features, aspects and embodiments, as well as elements and components thereof being aggregated to constitute various further implementations of the invention.
  • FIG. 3 is a schematic representation of a material storage and dispensing package 100 containing a barium or strontium precursor, according to one embodiment of the present invention.
  • The material storage and dispensing package 100 includes a vessel 102 that may for example be of generally cylindrical shape as illustrated, defining an interior volume 104 therein. In this specific embodiment, the precursor is a solid at ambient temperature conditions, and such precursor may be supported on surfaces of the trays 106 disposed in the interior volume 104 of the vessel, with the trays having flow passage conduits 108 associated therewith, for flow of vapor upwardly in the vessel to the valve head assembly, for dispensing in use of the vessel.
  • The solid precursor can be coated on interior surfaces in the interior volume of the vessel, e.g., on the surfaces of the trays 106 and conduits 108. Such coating may be effected by introduction of the precursor into the vessel in a vapor form from which the solid precursor is condensed in a film on the surfaces in the vessel. Alternatively, the precursor solid may be dissolved or suspended in a solvent medium and deposited on surfaces in the interior volume of the vessel by solvent evaporation. In yet another method the precursor may be melted and poured onto the surfaces in the interior volume of the vessel. For such purpose, the vessel may contain substrate articles or elements that provide additional surface area in the vessel for support of the precursor film thereon.
  • As a still further alternative, the solid precursor may be provided in granular or finely divided form, which is poured into the vessel to be retained on the top supporting surfaces of the respective trays 106 therein.
  • The vessel 102 has a neck portion 109 to which is joined the valve head assembly 110. The valve head assembly is equipped with a hand wheel 112 in the embodiment shown. The valve head assembly 110 includes a dispensing port 114, which may be configured for coupling to a fitting or connection element to join flow circuitry to the vessel. Such flow circuitry is schematically represented by arrow A in FIG. 1, and the flow circuitry may be coupled to a downstream ALD or chemical vapor deposition chamber (not shown in FIG. 1).
  • In use, the vessel 102 is heated, such input of heat being schematically shown by the reference arrow Q, so that solid precursor in the vessel is at least partially volatilized to provide precursor vapor. The precursor vapor is discharged from the vessel through the valve passages in the valve head assembly 110 when the hand wheel 112 is translated to an open valve position, whereupon vapor deriving from the precursor is dispensed into the flow circuitry schematically indicated by arrow A.
  • In lieu of solid delivery of the precursor, the precursor may be provided in a solvent medium, forming a solution or suspension. Such precursor-containing solvent composition then may be delivered by liquid delivery and flash vaporized to produce a precursor vapor. The precursor vapor is contacted with a substrate under deposition conditions, to deposit the metal on the substrate as a film thereon.
  • In one embodiment, the precursor is dissolved in an ionic liquid medium, from which precursor vapor is withdrawn from the ionic liquid solution under dispensing conditions.
  • As a still further alternative, the precursor may be stored in an adsorbed state on a suitable solid-phase physical adsorbent storage medium in the interior volume of the vessel. In use, the precursor vapor is dispensed from the vessel under dispensing conditions involving desorption of the adsorbed precursor from the solid-phase physical adsorbent storage medium.
  • Supply vessels for precursor delivery may be of widely varying type, and may employ vessels such as those commercially available from ATMI, Inc. (Danbury, Conn.) under the trademarks SDS, SAGE, VAC, VACSorb, and ProE-Vap, as may be appropriate in a given storage and dispensing application for a particular precursor of the invention.
    • INDUSTRIAL APPLICABILITY
  • The precursors of the invention are usefully employed to form precursor vapor for contacting with a substrate to deposit a barium- and/or strontium-containing thin film thereon. Precursors of the invention can be employed to conduct atomic layer deposition, yielding ALD films of superior conformality that are uniformly coated on the substrate with high step coverage and conformality even on high aspect ratio structures. The precursors of the invention enable a wide variety of microelectronic devices, e.g., semiconductor products, flat panel displays, etc., to be fabricated with barium- and/or strontium-containing films of superior quality.

Claims (20)

What is claimed is:
1. A method of depositing a strontium ruthenium oxide film on a substrate, comprising carrying out an atomic layer deposition (ALD) process with strontium and ruthenium precursors, wherein the strontium precursor is bis(n-propyltetramethylcyclopentadienyl)strontium.
2. The method of claim 1, wherein the precursor is dissolved in a solvent medium.
3. The method of claim 2, wherein the solvent in the solvent medium is a single-component solvent or a multicomponent solvent mixture.
4. The method of claim 2, wherein the solvent medium is selected from the group consisting of C3-C12 alkanes, C2-C12 ethers, C6-C12 aromatics, C7-C16 arylalkanes, C10-C25 arylcyloalkanes, and further alkyl-substituted forms of the aromatic, arylalkane and arylcyloalkane species, wherein the further alkyl substituents in the case of multiple alkyl substituents may be the same as or different from one another and wherein each is independently selected from C1-C8 alkyl.
5. The method of claim 2, wherein the solvent medium is selected from the group consisting of xylene, 1,4-tertbutyltoluene, 1,3-diisopropylbenzene, tetralin and dimethyltetralin.
6. The method of claim 1, wherein the strontium precursor is in liquid form and is vaporized for vapor delivery in the atomic layer deposition process.
7. The method of claim 1, wherein the method is conducted in the presence of an oxidant.
8. The method of claim 7, wherein the oxidant is nitrous oxide, oxygen, ozone, water, alcohols, or combinations of two or more compatible oxidant species selected therefrom.
9. The method of claim 7, wherein the oxidant is oxygen, oxygen plasma, ozone or nitrous oxide.
10. The method of claim 7, wherein the oxidant is nitrous oxide.
11. A method of depositing a film comprising strontium and ruthenium on a substrate, comprising carrying out an atomic layer deposition (ALD) process with strontium and ruthenium precursors, wherein the strontium precursor is bis(n-propyltetramethylcyclopentadienyl)strontium.
12. The method of claim 11, wherein the precursor is dissolved in a solvent medium.
13. The method of claim 12, wherein the solvent in the solvent medium is a single-component solvent or a multicomponent solvent mixture.
14. The method of claim 12, wherein the solvent medium is selected from the group consisting of C3-C12 alkanes, C2-C12 ethers, C6-C12 aromatics, C7-C16 arylalkanes, C10-C25 arylcyloalkanes, and further alkyl-substituted forms of the aromatic, arylalkane and arylcyloalkane species, wherein the further alkyl substituents in the case of multiple alkyl substituents may be the same as or different from one another and wherein each is independently selected from C1-C8 alkyl.
15. The method of claim 12, wherein the solvent medium is selected from the group consisting of xylene, 1,4-tertbutyltoluene, 1,3-diisopropylbenzene, tetralin and dimethyltetralin.
16. The method of claim 11, wherein the strontium precursor is in liquid form and is vaporized for vapor delivery in the atomic layer deposition process.
17. The method of claim 11, wherein the method is conducted in the presence of an oxidant.
18. The method of claim 17, wherein the oxidant is nitrous oxide, oxygen, ozone, water, alcohols, or combinations of two or more compatible oxidant species selected therefrom.
19. The method of claim 17, wherein the oxidant is oxygen, oxygen plasma, ozone or nitrous oxide.
20. The method of claim 17, wherein the oxidant is nitrous oxide.
US13/892,526 2007-08-08 2013-05-13 Strontium and barium precursors for use in chemical vapor deposition, atomic layer deposition and rapid vapor deposition Abandoned US20130251918A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US13/892,526 US20130251918A1 (en) 2007-08-08 2013-05-13 Strontium and barium precursors for use in chemical vapor deposition, atomic layer deposition and rapid vapor deposition

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US95458107P 2007-08-08 2007-08-08
PCT/US2008/072045 WO2009020888A1 (en) 2007-08-08 2008-08-03 Strontium and barium precursors for use in chemical vapor deposition, atomic layer deposition and rapid vapor deposition
US67268410A 2010-07-26 2010-07-26
US13/892,526 US20130251918A1 (en) 2007-08-08 2013-05-13 Strontium and barium precursors for use in chemical vapor deposition, atomic layer deposition and rapid vapor deposition

Related Parent Applications (2)

Application Number Title Priority Date Filing Date
PCT/US2008/072045 Continuation WO2009020888A1 (en) 2007-08-08 2008-08-03 Strontium and barium precursors for use in chemical vapor deposition, atomic layer deposition and rapid vapor deposition
US67268410A Continuation 2007-08-08 2010-07-26

Publications (1)

Publication Number Publication Date
US20130251918A1 true US20130251918A1 (en) 2013-09-26

Family

ID=40341670

Family Applications (2)

Application Number Title Priority Date Filing Date
US12/672,684 Active 2029-03-11 US8455049B2 (en) 2007-08-08 2008-08-03 Strontium precursor for use in chemical vapor deposition, atomic layer deposition and rapid vapor deposition
US13/892,526 Abandoned US20130251918A1 (en) 2007-08-08 2013-05-13 Strontium and barium precursors for use in chemical vapor deposition, atomic layer deposition and rapid vapor deposition

Family Applications Before (1)

Application Number Title Priority Date Filing Date
US12/672,684 Active 2029-03-11 US8455049B2 (en) 2007-08-08 2008-08-03 Strontium precursor for use in chemical vapor deposition, atomic layer deposition and rapid vapor deposition

Country Status (3)

Country Link
US (2) US8455049B2 (en)
TW (1) TW200925161A (en)
WO (1) WO2009020888A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9443736B2 (en) 2012-05-25 2016-09-13 Entegris, Inc. Silylene compositions and methods of use thereof
US9534285B2 (en) 2006-03-10 2017-01-03 Entegris, Inc. Precursor compositions for atomic layer deposition and chemical vapor deposition of titanate, lanthanate, and tantalate dielectric films
US10186570B2 (en) 2013-02-08 2019-01-22 Entegris, Inc. ALD processes for low leakage current and low equivalent oxide thickness BiTaO films

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008088563A2 (en) 2007-01-17 2008-07-24 Advanced Technology Materials, Inc. Precursor compositions for ald/cvd of group ii ruthenate thin films
JP5248025B2 (en) * 2007-03-01 2013-07-31 東京エレクトロン株式会社 Method for forming SrTiO3 film and computer-readable storage medium
KR101498732B1 (en) * 2007-06-26 2015-03-04 가부시키가이샤 코준도카가쿠 켄큐쇼 Process for forming the strontium-containing thin film
WO2009057058A1 (en) * 2007-10-29 2009-05-07 L'air Liquide-Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Alkaline earth metal containing precursor solutions
WO2010065874A2 (en) 2008-12-05 2010-06-10 Atmi High concentration nitrogen-containing germanium telluride based memory devices and processes of making
US8663735B2 (en) 2009-02-13 2014-03-04 Advanced Technology Materials, Inc. In situ generation of RuO4 for ALD of Ru and Ru related materials
WO2010107878A2 (en) 2009-03-17 2010-09-23 Advanced Technology Materials, Inc. Method and composition for depositing ruthenium with assistive metal species
TW201132787A (en) 2010-03-26 2011-10-01 Advanced Tech Materials Germanium antimony telluride materials and devices incorporating same
WO2011146913A2 (en) 2010-05-21 2011-11-24 Advanced Technology Materials, Inc. Germanium antimony telluride materials and devices incorporating same
US20120196449A1 (en) * 2011-01-27 2012-08-02 Advanced Technology Materials, Inc. Zirconium, hafnium and titanium precursors for atomic layer deposition of corresponding metal-containing films
KR101399552B1 (en) 2012-05-04 2014-05-27 한국화학연구원 Strontium precursors, preparation method thereof and process for the formation of thin films using the same
WO2013165212A1 (en) * 2012-05-04 2013-11-07 한국화학연구원 Strontium precursor, method for preparing same, and method for forming thin film by using same
WO2014070682A1 (en) 2012-10-30 2014-05-08 Advaned Technology Materials, Inc. Double self-aligned phase change memory device structure
US9245742B2 (en) 2013-12-18 2016-01-26 Asm Ip Holding B.V. Sulfur-containing thin films
US9711350B2 (en) 2015-06-03 2017-07-18 Asm Ip Holding B.V. Methods for semiconductor passivation by nitridation
US9711396B2 (en) * 2015-06-16 2017-07-18 Asm Ip Holding B.V. Method for forming metal chalcogenide thin films on a semiconductor device
US9741815B2 (en) 2015-06-16 2017-08-22 Asm Ip Holding B.V. Metal selenide and metal telluride thin films for semiconductor device applications
CN109477214A (en) 2016-07-19 2019-03-15 应用材料公司 The deposition of flowable silicon-containing film

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5204314A (en) * 1990-07-06 1993-04-20 Advanced Technology Materials, Inc. Method for delivering an involatile reagent in vapor form to a CVD reactor
US6110531A (en) * 1991-02-25 2000-08-29 Symetrix Corporation Method and apparatus for preparing integrated circuit thin films by chemical vapor deposition
US20030032238A1 (en) * 2001-08-08 2003-02-13 Wan-Don Kim Methods for manufacturing storage nodes of stacked capacitors
US20030038594A1 (en) * 2001-08-24 2003-02-27 Semiconductor Energy Laboratory Co., Ltd. Luminous device
US20080242111A1 (en) * 2007-02-15 2008-10-02 Holme Timothy P Atomic layer deposition of strontium oxide via n-propyltetramethyl cyclopentadiendyl precursor

Family Cites Families (62)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU768457A1 (en) 1976-01-04 1980-10-07 Всесоюзный научно-исследовательский и проектно-конструкторский институт добычи угля гидравлическим способом Catalyst for removing nitrogen oxides from exhaust gases
US4948623A (en) 1987-06-30 1990-08-14 International Business Machines Corporation Method of chemical vapor deposition of copper, silver, and gold using a cyclopentadienyl/metal complex
US4962214A (en) 1988-05-11 1990-10-09 Massachusettes Institute Of Technology Catalytic enantioselective addition of hydrocarbon equivalents to alpha, beta-unsaturated carbonyl compounds
US4915988A (en) 1988-06-22 1990-04-10 Georgia Tech Research Corporation Chemical vapor deposition of group IIA metals and precursors therefor
US4927670A (en) 1988-06-22 1990-05-22 Georgia Tech Research Corporation Chemical vapor deposition of mixed metal oxide coatings
US4960916A (en) 1989-09-29 1990-10-02 United States Of America As Represented By The Secretary Of The Navy Organometallic antimony compounds useful in chemical vapor deposition processes
US6110529A (en) 1990-07-06 2000-08-29 Advanced Tech Materials Method of forming metal films on a substrate by chemical vapor deposition
US5711816A (en) 1990-07-06 1998-01-27 Advanced Technolgy Materials, Inc. Source reagent liquid delivery apparatus, and chemical vapor deposition system comprising same
US5453494A (en) 1990-07-06 1995-09-26 Advanced Technology Materials, Inc. Metal complex source reagents for MOCVD
US5225561A (en) * 1990-07-06 1993-07-06 Advanced Technology Materials, Inc. Source reagent compounds for MOCVD of refractory films containing group IIA elements
US5362328A (en) 1990-07-06 1994-11-08 Advanced Technology Materials, Inc. Apparatus and method for delivering reagents in vapor form to a CVD reactor, incorporating a cleaning subsystem
US5840897A (en) 1990-07-06 1998-11-24 Advanced Technology Materials, Inc. Metal complex source reagents for chemical vapor deposition
US6111124A (en) 1997-10-30 2000-08-29 Advanced Technology Materials, Inc. Lewis base adducts of anhydrous mononuclear tris(β-diketonate) bismuth compositions for deposition of bismuth-containing films, and method of making the same
US6511706B1 (en) 1990-07-06 2003-01-28 Advanced Technology Materials, Inc. MOCVD of SBT using tetrahydrofuran-based solvent system for precursor delivery
US5280012A (en) 1990-07-06 1994-01-18 Advanced Technology Materials Inc. Method of forming a superconducting oxide layer by MOCVD
US6218518B1 (en) 1990-07-06 2001-04-17 Advanced Technology Materials, Inc. Tetrahydrofuran-adducted group II β-diketonate complexes as source reagents for chemical vapor deposition
JP2799134B2 (en) 1992-09-22 1998-09-17 三菱電機株式会社 Barium strontium titanate-based dielectric thin film CVD material and memory capacitor
US20030152813A1 (en) 1992-10-23 2003-08-14 Symetrix Corporation Lanthanide series layered superlattice materials for integrated circuit appalications
US5919522A (en) * 1995-03-31 1999-07-06 Advanced Technology Materials, Inc. Growth of BaSrTiO3 using polyamine-based precursors
JPH10273779A (en) 1997-03-28 1998-10-13 Nippon Sanso Kk Cvd device
US6177558B1 (en) 1997-11-13 2001-01-23 Protogene Laboratories, Inc. Method and composition for chemical synthesis using high boiling point organic solvents to control evaporation
US6277436B1 (en) 1997-11-26 2001-08-21 Advanced Technology Materials, Inc. Liquid delivery MOCVD process for deposition of high frequency dielectric materials
US6787186B1 (en) 1997-12-18 2004-09-07 Advanced Technology Materials, Inc. Method of controlled chemical vapor deposition of a metal oxide ceramic layer
US6111122A (en) 1998-04-28 2000-08-29 Advanced Technology Materials, Inc. Group II MOCVD source reagents, and method of forming Group II metal-containing films utilizing same
US7098163B2 (en) 1998-08-27 2006-08-29 Cabot Corporation Method of producing membrane electrode assemblies for use in proton exchange membrane and direct methanol fuel cells
FI108375B (en) 1998-09-11 2002-01-15 Asm Microchemistry Oy Still for producing insulating oxide thin films
GB0004852D0 (en) 2000-02-29 2000-04-19 Unilever Plc Ligand and complex for catalytically bleaching a substrate
US6562678B1 (en) 2000-03-07 2003-05-13 Symetrix Corporation Chemical vapor deposition process for fabricating layered superlattice materials
US6984591B1 (en) 2000-04-20 2006-01-10 International Business Machines Corporation Precursor source mixtures
US6342445B1 (en) * 2000-05-15 2002-01-29 Micron Technology, Inc. Method for fabricating an SrRuO3 film
JP4621333B2 (en) 2000-06-01 2011-01-26 ホーチキ株式会社 Thin film formation method
US20020090815A1 (en) 2000-10-31 2002-07-11 Atsushi Koike Method for forming a deposited film by plasma chemical vapor deposition
US6599447B2 (en) 2000-11-29 2003-07-29 Advanced Technology Materials, Inc. Zirconium-doped BST materials and MOCVD process forming same
US6669990B2 (en) 2001-06-25 2003-12-30 Samsung Electronics Co., Ltd. Atomic layer deposition method using a novel group IV metal precursor
JP4921652B2 (en) 2001-08-03 2012-04-25 エイエスエム インターナショナル エヌ．ヴェー． Method for depositing yttrium oxide and lanthanum oxide thin films
US6730164B2 (en) 2002-08-28 2004-05-04 Micron Technology, Inc. Systems and methods for forming strontium- and/or barium-containing layers
CN1726303B (en) 2002-11-15 2011-08-24 哈佛学院院长等 Atomic layer deposition using metal amidinates
US6989457B2 (en) 2003-01-16 2006-01-24 Advanced Technology Materials, Inc. Chemical vapor deposition precursors for deposition of tantalum-based materials
KR20060079144A (en) 2003-06-18 2006-07-05 어플라이드 머티어리얼스, 인코포레이티드 Atomic layer deposition of barrier materials
US7005665B2 (en) 2004-03-18 2006-02-28 International Business Machines Corporation Phase change memory cell on silicon-on insulator substrate
US7584942B2 (en) 2004-03-31 2009-09-08 Micron Technology, Inc. Ampoules for producing a reaction gas and systems for depositing materials onto microfeature workpieces in reaction chambers
WO2006012052A2 (en) 2004-06-25 2006-02-02 Arkema, Inc. Amidinate ligand containing chemical vapor deposition precursors
KR100642635B1 (en) 2004-07-06 2006-11-10 삼성전자주식회사 Semiconductor integrated circuit devices having a hybrid dielectric layer and methods of fabricating the same
JP2006037123A (en) 2004-07-22 2006-02-09 Toyoshima Seisakusho:Kk Cvd raw material for thin film, and thin film obtained by using the same
KR100632948B1 (en) 2004-08-06 2006-10-11 삼성전자주식회사 Sputtering method for forming a chalcogen compound and method for fabricating phase-changeable memory device using the same
US7300873B2 (en) * 2004-08-13 2007-11-27 Micron Technology, Inc. Systems and methods for forming metal-containing layers using vapor deposition processes
US7250367B2 (en) 2004-09-01 2007-07-31 Micron Technology, Inc. Deposition methods using heteroleptic precursors
KR100652378B1 (en) 2004-09-08 2006-12-01 삼성전자주식회사 Sb Precursor and Manufacturing Method of Phase-Change Memory Device using the Same
US7390360B2 (en) 2004-10-05 2008-06-24 Rohm And Haas Electronic Materials Llc Organometallic compounds
KR100618879B1 (en) 2004-12-27 2006-09-01 삼성전자주식회사 A Ge precursor, a thin layer prepared by using the Ge precursor, a method for preparing the thin layer and a phase-change memory device
US20060172067A1 (en) 2005-01-28 2006-08-03 Energy Conversion Devices, Inc Chemical vapor deposition of chalcogenide materials
KR100585175B1 (en) 2005-01-31 2006-05-30 삼성전자주식회사 Fabrication method of gesbte thin film by chemical vapor deposition process
KR100688532B1 (en) 2005-02-14 2007-03-02 삼성전자주식회사 A Te precursor, a Te-including chalcogenide thin layer prepared by using the Te precursor, a method for preparing the thin layer and a phase-change memory device
US20070154637A1 (en) 2005-12-19 2007-07-05 Rohm And Haas Electronic Materials Llc Organometallic composition
KR20160027244A (en) 2006-03-10 2016-03-09 인티그리스, 인코포레이티드 Precursor compositions for atomic layer deposition and chemical vapor deposition of titanate, lanthanate, and tantalate dielectric films
US20080254218A1 (en) 2007-04-16 2008-10-16 Air Products And Chemicals, Inc. Metal Precursor Solutions For Chemical Vapor Deposition
TWI398541B (en) 2007-06-05 2013-06-11 羅門哈斯電子材料有限公司 Organometallic compounds
KR101498732B1 (en) 2007-06-26 2015-03-04 가부시키가이샤 코준도카가쿠 켄큐쇼 Process for forming the strontium-containing thin film
US20090087561A1 (en) 2007-09-28 2009-04-02 Advanced Technology Materials, Inc. Metal and metalloid silylamides, ketimates, tetraalkylguanidinates and dianionic guanidinates useful for cvd/ald of thin films
US20090215225A1 (en) 2008-02-24 2009-08-27 Advanced Technology Materials, Inc. Tellurium compounds useful for deposition of tellurium containing materials
US20090275164A1 (en) 2008-05-02 2009-11-05 Advanced Technology Materials, Inc. Bicyclic guanidinates and bridging diamides as cvd/ald precursors
US8636845B2 (en) 2008-06-25 2014-01-28 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Metal heterocyclic compounds for deposition of thin films

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5204314A (en) * 1990-07-06 1993-04-20 Advanced Technology Materials, Inc. Method for delivering an involatile reagent in vapor form to a CVD reactor
US6110531A (en) * 1991-02-25 2000-08-29 Symetrix Corporation Method and apparatus for preparing integrated circuit thin films by chemical vapor deposition
US20030032238A1 (en) * 2001-08-08 2003-02-13 Wan-Don Kim Methods for manufacturing storage nodes of stacked capacitors
US20030038594A1 (en) * 2001-08-24 2003-02-27 Semiconductor Energy Laboratory Co., Ltd. Luminous device
US20080242111A1 (en) * 2007-02-15 2008-10-02 Holme Timothy P Atomic layer deposition of strontium oxide via n-propyltetramethyl cyclopentadiendyl precursor

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9534285B2 (en) 2006-03-10 2017-01-03 Entegris, Inc. Precursor compositions for atomic layer deposition and chemical vapor deposition of titanate, lanthanate, and tantalate dielectric films
US9443736B2 (en) 2012-05-25 2016-09-13 Entegris, Inc. Silylene compositions and methods of use thereof
US10186570B2 (en) 2013-02-08 2019-01-22 Entegris, Inc. ALD processes for low leakage current and low equivalent oxide thickness BiTaO films

Also Published As

Publication number Publication date
US20100291299A1 (en) 2010-11-18
TW200925161A (en) 2009-06-16
WO2009020888A1 (en) 2009-02-12
US8455049B2 (en) 2013-06-04

Similar Documents

Publication Publication Date Title
US8455049B2 (en) Strontium precursor for use in chemical vapor deposition, atomic layer deposition and rapid vapor deposition
US8524931B2 (en) Precursor compositions for ALD/CVD of group II ruthenate thin films
US8784936B2 (en) Precursor compositions for atomic layer deposition and chemical vapor deposition of titanate, lanthanate, and tantalate dielectric films
US8168811B2 (en) Precursors for CVD/ALD of metal-containing films
EP2644741B1 (en) Methods of preparing titanium containing thin films by atomic layer deposition using monocyclopentadienyl titanium-based precursors
JP5873494B2 (en) Molybdenum (IV) amide precursors and their use in atomic layer deposition methods
US8039062B2 (en) Methods of atomic layer deposition using hafnium and zirconium-based precursors
US7709384B2 (en) Tantalum amide complexes for depositing tantalum-containing films, and method of making same
US7750173B2 (en) Tantalum amido-complexes with chelate ligands useful for CVD and ALD of TaN and Ta205 thin films
US20100209610A1 (en) Group iv complexes as cvd and ald precursors for forming metal-containing thin films
WO2008128141A2 (en) Zirconium, hafnuim, titanium, and silicon precursors for ald/cvd
TW201833123A (en) Zirconium, hafnium, titanium precursors and deposition of group 4 containing films using the same
US10870921B2 (en) Cyclopentadienyl titanium alkoxides with ozone activated ligands for ALD of TiO2

Legal Events

Date Code Title Description
AS Assignment

Owner name: GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT, NEW YORK

Free format text: SECURITY INTEREST;ASSIGNORS:ENTEGRIS, INC.;POCO GRAPHITE, INC.;ATMI, INC.;AND OTHERS;REEL/FRAME:032815/0852

Effective date: 20140430

Owner name: GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT, NEW Y

Free format text: SECURITY INTEREST;ASSIGNORS:ENTEGRIS, INC.;POCO GRAPHITE, INC.;ATMI, INC.;AND OTHERS;REEL/FRAME:032815/0852

Effective date: 20140430

AS Assignment

Owner name: GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT, NEW YORK

Free format text: SECURITY INTEREST;ASSIGNORS:ENTEGRIS, INC.;POCO GRAPHITE, INC.;ATMI, INC.;AND OTHERS;REEL/FRAME:032812/0192

Effective date: 20140430

Owner name: GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT, NEW Y

Free format text: SECURITY INTEREST;ASSIGNORS:ENTEGRIS, INC.;POCO GRAPHITE, INC.;ATMI, INC.;AND OTHERS;REEL/FRAME:032812/0192

Effective date: 20140430

AS Assignment

Owner name: ENTEGRIS, INC., MASSACHUSETTS

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:ADVANCED TECHNOLOGY MATERIALS, INC.;REEL/FRAME:034894/0025

Effective date: 20150204

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION

AS Assignment

Owner name: ADVANCED TECHNOLOGY MATERIALS, INC., CONNECTICUT

Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT;REEL/FRAME:047477/0032

Effective date: 20181106

Owner name: ENTEGRIS, INC., MASSACHUSETTS

Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT;REEL/FRAME:047477/0032

Effective date: 20181106

Owner name: ATMI, INC., CONNECTICUT

Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT;REEL/FRAME:047477/0032

Effective date: 20181106

Owner name: ATMI PACKAGING, INC., CONNECTICUT

Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT;REEL/FRAME:047477/0032

Effective date: 20181106

Owner name: POCO GRAPHITE, INC., MASSACHUSETTS

Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT;REEL/FRAME:047477/0032

Effective date: 20181106

Owner name: POCO GRAPHITE, INC., MASSACHUSETTS

Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT;REEL/FRAME:047477/0151

Effective date: 20181106

Owner name: ADVANCED TECHNOLOGY MATERIALS, INC., CONNECTICUT

Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT;REEL/FRAME:047477/0151

Effective date: 20181106

Owner name: ENTEGRIS, INC., MASSACHUSETTS

Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT;REEL/FRAME:047477/0151

Effective date: 20181106

Owner name: ATMI, INC., CONNECTICUT

Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT;REEL/FRAME:047477/0151

Effective date: 20181106

Owner name: ATMI PACKAGING, INC., CONNECTICUT

Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT;REEL/FRAME:047477/0151

Effective date: 20181106