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WO2008018861A1 - Complexes de cuivre(i) et procédés de dépôt de films de cuivre au moyen d'un dépôt par couche atomique - Google Patents

Complexes de cuivre(i) et procédés de dépôt de films de cuivre au moyen d'un dépôt par couche atomique Download PDF

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Publication number
WO2008018861A1
WO2008018861A1 PCT/US2006/030707 US2006030707W WO2008018861A1 WO 2008018861 A1 WO2008018861 A1 WO 2008018861A1 US 2006030707 W US2006030707 W US 2006030707W WO 2008018861 A1 WO2008018861 A1 WO 2008018861A1
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WO
WIPO (PCT)
Prior art keywords
alkyl
copper
independently selected
substrate
fluorine
Prior art date
Application number
PCT/US2006/030707
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English (en)
Inventor
Kyung-Ho Park
Original Assignee
E. I. Du Pont De Nemours And Company
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 E. I. Du Pont De Nemours And Company filed Critical E. I. Du Pont De Nemours And Company
Priority to PCT/US2006/030707 priority Critical patent/WO2008018861A1/fr
Publication of WO2008018861A1 publication Critical patent/WO2008018861A1/fr

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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
    • C23C16/44—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]
    • 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
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
    • 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
    • C23C16/06—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 metallic material
    • C23C16/18—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 metallic material from metallo-organic compounds
    • 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 novel 1 ,3-diimine copper complexes.
  • the invention also relates to processes for forming copper deposits on substrates or in or on porous solids, using the 1 ,3-diimine copper complexes.
  • ALD Atomic layer deposition
  • a copper precursor and a reducing agent are alternatively introduced into a reaction chamber. After the copper precursor is introduced into the reaction chamber and allowed to adsorb onto a substrate, the excess (unadsorbed) precursor vapor is pumped or purged from the chamber. The removal of excess precursor vapor is followed by introduction of a reducing agent that reacts with the copper precursor on the substrate surface to form copper metal and a free form of the ligand. This cycle can be repeated if needed to achieve the desired film thickness.
  • the ALD process differs from chemical vapor deposition (CVD) in the decomposition chemistry of the metal complex.
  • the complex undergoes pyrolytic decomposition on contact with the surface to give the desired film.
  • the complex is not completely decomposed to metal on contact with the surface. Rather, formation of the metal film takes place on introduction of a second reagent, which reacts with the deposited metal complex.
  • the second reagent is a reducing agent.
  • Advantages of an ALD process include the ability to control the film thickness and improved conformality of coverage because of the self-limiting adsorption of the precursor to the substrate surface in the first step of the process.
  • the ligands used in the ALD processes are desirably stable with respect to decomposition and should be able to desorb from the complex in a metal-free form. Following reduction of the copper, the ligand is liberated and must be removed from the surface to prevent its incorporation into the metal layer being formed.
  • US 2003/0135061 discloses a dimeric copper(l) precursor which can be used to deposit metal or metal-containing films on a substrate under ALD or CVD conditions.
  • One aspect of this invention is a process for forming copper deposits on a substrate comprising: a. contacting a substrate with a copper complex, (I), to form a deposit of a copper complex on the substrate; and
  • L is selected from the group consisting of C 2 - C 15 olefins, C 2 - Ci 5 alkynes, nitriles, aromatic heterocycles, and phosphines; n is 1 or 2; R 1 and R 2 are independently selected from the group consisting of H, C 1 - C 4 alkyl, fluorine-substituted CrC 4 alkyl, and Si(R 4 J 3 , where each R 4 is independently C-1-C4 alkyl;
  • Another aspect of the present invention is an article comprising a 1,3-diimine copper complex, (I), deposited on a substrate.
  • a further aspect of the present invention is a composition corresponding to copper complex, (I).
  • a further aspect of the invention is a composition corresponding to ligand, (II),
  • R 1 and R 2 are independently selected from the group consisting of H, C 1 - C 4 alkyl, fluorine-substituted C 1 -C 4 alkyl, and Si(R 4 ) 3 , where each R 4 is independently C 1 -C 4 alkyl; and R 3 is independently selected from CrC 4 alkyl, fluorine-substituted d-C 4 alkyl, and Si(R 4 ) 3 , where each R 4 is independently C 1 -C 4 alkyl.
  • ALD atomic layer deposition
  • the complexes decompose to metal on addition of a suitable reducing agent.
  • the ligands are further chosen so that they will desorb without decomposition upon exposure of the copper complex to a reducing agent.
  • the reduction of these copper complexes to copper metal by commercially available reducing agents has been demonstrated to proceed cleanly at moderate temperatures.
  • copper is deposited on a substrate by: a. contacting a substrate with a copper complex, (I), to form a deposit of a copper complex on the substrate; and
  • L is selected from the group consisting of C 2 - C15 olefins, C 2 - C15 alkynes, nitriles, aromatic heterocycles, and phosphines; n is 1 or 2;
  • the present deposition processes allow the use of relatively low temperatures (e.g., about 0 to 200 0 C) and produce high quality, uniform films. Desirable films are continuous and conductive. The processes also provide a direct route to a copper film, avoiding the need for formation of an intermediate oxide film.
  • the copper can be deposited on the surface, or in and/or on porosity, of the substrate.
  • Suitable substrates include conducting, semiconducting and insulating substrates, including copper, silicon wafers, wafers used in the manufacture of ultra large scale integrated circuits, wafers prepared with dielectric material having a lower dielectric constant than silicon dioxide, and silicon dioxide and low k substrates coated with a barrier layer.
  • Barrier layers to prevent the migration of copper include tantalum, tantalum nitride, titanium, titanium nitride, tantalum silicon nitride, titanium silicon nitride, tantalum carbon nitride, and niobium nitride.
  • the processes can be conducted in solution, i.e., by contacting a solution of the copper complex with the reducing agent.
  • the free form of the ligand can be removed, for example, via vacuum, purging, heating, rinsing with a suitable solvent, or a combination of such methods. This process can be repeated to build up thicker layers of copper, or to eliminate pin-holes.
  • the deposition of the copper complex is typically conducted at 0 to 200 0 C.
  • the reduction of the copper complex is typically carried out at similar temperatures, 0 to 200 0 C, more preferably 50 to 150 0 C.
  • a copper complex is deposited on the substrate.
  • the formation of a metallic copper film does not occur until the copper complex is exposed to the reducing agent.
  • Aggressive reducing agents are preferred to reduce the copper complex rapidly and completely. Suitable reducing agents are volatile and do not decompose on heating. "Aggressive reducing agents" are of sufficient reducing power to react rapidly on contact with the copper complex deposited on the substrate surface. Suitable reducing agents have been identified that have been used for copper(l) reduction in an ALD process, as disclosed, for example, in patent publication WO 2004/094689. One feature of these reagents is the presence of a proton donor. The reducing agent is desirably able to transfer at least one electron to reduce the copper ion of the complex and at least one proton to protonate the ligand.
  • the oxidized reducing agent and the protonated ligand be able to be easily removed from the surface of the newly formed copper deposit.
  • the protonated ligand is removed by vacuum, by purging or by flushing the surface with a suitable solvent.
  • Suitable reducing agents for the copper deposition processes include 9-BBN, borane, diborane, dihydrobenzofuran, pyrazoline, germanes, diethylsilane, dimethylsilane, ethylsilane, phenylsilane, silane and disilane. Diethylsilane and silane are preferred.
  • the copper complexes are admitted to a reactor chamber containing the substrate under conditions of temperature, time and pressure to attain a suitable fluence of vaporized complex to the surface of the substrate.
  • time, T, P The selection of these variables (time, T, P) will depend on individual chamber and system design, and the desired process rate, but as a general guideline, temperatures within the range of about O to 200 0 C; pressures within the range of about 100 to 180 mTorr; and a time period of at least 30 seconds to 1 minute can be used.
  • the undeposited complex vapor is removed from the chamber (e.g., by pumping or purging) and the reducing agent is introduced into the chamber at a pressure of about 50 to 760 mTorr to reduce the adsorbed copper complex.
  • the substrate is held at a temperature of about 0 to 200 0 C during reduction.
  • this reduction is rapid (i.e., can generally be completed within a time range of one second to several minutes for most complexes) and substantially complete (e.g., about 95% complete or more).
  • the reaction is at least 95% complete within an exposure time of from less than one second to several minutes. It is desired that the products from this reaction are readily removed from the surface of the substrate under the reducing conditions.
  • This invention also provides novel 1 ,3-diimine copper complexes,
  • L is selected from the group consisting of C 2 - Ci 5 olefins, C 2 - Ci 5 alkynes, nitriles, aromatic heterocycles, and phosphines; n is 1 or 2;
  • R 1 and R 2 are independently selected from the group consisting of H, Ci-
  • L is a linear, terminal olefin.
  • L can also be an internal olefin of cis- or trans-configuration; cis-configuration is preferred.
  • L can be a cyclic or bicyclic olefin.
  • L can also be substituted, for example with fluorine or silyl groups.
  • Suitable olefins include, but are not limited to, vinyltrimethylsilane, allyltrimethylsilane, 1-hexene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene, and norbomene.
  • L can also be alkyne, nitrile, or an aromatic nitrogen heterocycle such as pyridine, pyrazine, triazine, or ⁇ /-substituted imidazole, pyrazole, ortriazole.
  • L can also be a phosphine. This invention also provides ligands of Formula (II)
  • R 1 and R 2 are independently selected from the group consisting of H, Cr C 4 alkyl, fluorine-substituted CrC 4 alkyl, and Si(R 4 ) 3 , where each R 4 is independently CrC 4 alkyl;
  • R 3 is independently selected from CrC 4 alkyl, fluorine-substituted CrC 4 alkyl, and Si(R 4 ) 3 , where each R 4 is independently CrC 4 alkyl.
  • R 3 is a C 2 -C 4 alkyl group, it can also contain a silylene group in the alkyl chain, e.g., -CH 2 SiH 2 CH 3 or -CH 2 Si(H)(CH 3 )CH 3 or -CH 2 Si(CHg) 2 CH 3 .
  • 1-aza-1- cycloalkylidenealkane can be depronated by strong base, then treated with an electrophile such as an ester or acid halide derivative to provide the corresponding keto exocyclic enamine as an intermediate.
  • Treatment of this intermediate with an alkylating agent such as dimethylsulfate, followed by the addition of a primary amine affords the desired exocyclic diketimine.
  • the exocyclic ketimine after deprotonation by strong base, can be directly coupled with an imidoyl derivative to provide the desired ⁇ -diketimine.
  • Other ligands can be prepared similarly.
  • this invention provides an article comprising a 1 ,3-diimine copper complex of structure (I), deposited on a substrate.
  • Suitable substrates include: copper, silicon wafers, wafers used in the manufacture of ultra-large scale integrated circuits, wafers prepared with dielectric material having a lower dielectric constant than silicon dioxide, and silicon dioxide and low k substrates coated with a barrier layer.
  • Barrier layers can be used to prevent the migration of copper into the substrate.
  • Suitable barrier layers include: tantalum, tantalum nitride, titanium, titanium nitride, tantalum silicon nitride, titanium silicon nitride, tantalum carbon nitride, and niobium nitride.
  • the viscous oil was used as a copper precursor to create a copper film on a substrate.
  • the substrate consisted of a silicon dioxide wafer with 250-Angstrom layer of tantalum and a 100 Angstrom layer of copper.
  • Approximately 0.04 g of copper precursor was loaded in the dry box into a porcelain boat.
  • the boat and wafer ( ⁇ 1 cm 2 ) were placed in a glass tube approximately 3.5 inches apart.
  • the glass tube was removed from the dry box and attached to a vacuum line. Heating coils were attached to the glass tube surrounding both the area around the porcelain boat and the area around the wafer chip. This configuration allows the two areas to be maintained at different temperatures.
  • an argon flow was created through the tube, passing first over the sample in the boat and then over the wafer.
  • the pressure inside the tube was maintained at 100-180 mTorr.
  • the region around the wafer was warmed to 120 0 C. After approximately an hour, the temperature of the region around the sample boat was raised to 60 0 C.
  • the area around the sample boat was then cooled to room temperature.
  • the tube was evacuated to a pressure of -10 mTorr and was back-filled with diethylsilane.
  • the area of the tube at 110 0 C quickly turned a copper color.
  • the apparatus was cooled and returned to the dry box. The copper color was perceptibly darker. The process was repeated to yield a wafer with a smooth copper film.
  • methyl ⁇ /-methylthioacetimidate (5.3 g, 51.5 mmol) was added dropwise over 30 min at -78 0 C.
  • the reaction mixture was stirred as the temperature was allowed to gradually rise to room temperature, and was then continuously stirred at room temperature overnight.
  • THF solvent was removed under reduced pressure, then 30 mL of methanol was added dropwise to the residue.
  • pentane 50 mL x 2 was added to the residue, and the mixture was filtered.

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

Abstract

La présente invention concerne des nouveaux complexes de cuivre de 1,3-diimine et l'utilisation de ces complexes pour le dépôt de cuivre sur des substrats ou dans ou sur des solides poreux au moyen d'un procédé de dépôt par couche atomique.
PCT/US2006/030707 2006-08-07 2006-08-07 Complexes de cuivre(i) et procédés de dépôt de films de cuivre au moyen d'un dépôt par couche atomique WO2008018861A1 (fr)

Priority Applications (1)

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PCT/US2006/030707 WO2008018861A1 (fr) 2006-08-07 2006-08-07 Complexes de cuivre(i) et procédés de dépôt de films de cuivre au moyen d'un dépôt par couche atomique

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PCT/US2006/030707 WO2008018861A1 (fr) 2006-08-07 2006-08-07 Complexes de cuivre(i) et procédés de dépôt de films de cuivre au moyen d'un dépôt par couche atomique

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7488435B2 (en) * 2006-08-07 2009-02-10 E. I. Du Pont De Nemours And Company Copper(I) complexes and processes for deposition of copper films by atomic layer deposition

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003095701A1 (fr) * 2002-01-18 2003-11-20 E.I. Du Pont De Nemours And Company Complexes de cuivre (ii) volatils destines au depot de films de cuivre par depot par couche atomique
WO2004094689A2 (fr) * 2003-04-16 2004-11-04 E. I. Du Pont De Nemours And Company Complexes de cuivre (i) volatils permettant le depot de films de cuivre par depot de couches atomiques
US20050227007A1 (en) * 2004-04-08 2005-10-13 Bradley Alexander Z Volatile copper(I) complexes for deposition of copper films by atomic layer deposition
WO2006015200A1 (fr) * 2004-07-30 2006-02-09 E.I. Dupont De Nemours And Company complexes de cuivre (II) en vue du dépôt de films de cuivre par dépôt de couche atomique
WO2006033731A2 (fr) * 2004-08-16 2006-03-30 E.I. Dupont De Nemours And Company Depot de cuivre en couche atomique au moyen de tensioactifs

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003095701A1 (fr) * 2002-01-18 2003-11-20 E.I. Du Pont De Nemours And Company Complexes de cuivre (ii) volatils destines au depot de films de cuivre par depot par couche atomique
WO2004094689A2 (fr) * 2003-04-16 2004-11-04 E. I. Du Pont De Nemours And Company Complexes de cuivre (i) volatils permettant le depot de films de cuivre par depot de couches atomiques
US20050227007A1 (en) * 2004-04-08 2005-10-13 Bradley Alexander Z Volatile copper(I) complexes for deposition of copper films by atomic layer deposition
WO2006015200A1 (fr) * 2004-07-30 2006-02-09 E.I. Dupont De Nemours And Company complexes de cuivre (II) en vue du dépôt de films de cuivre par dépôt de couche atomique
WO2006033731A2 (fr) * 2004-08-16 2006-03-30 E.I. Dupont De Nemours And Company Depot de cuivre en couche atomique au moyen de tensioactifs

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7488435B2 (en) * 2006-08-07 2009-02-10 E. I. Du Pont De Nemours And Company Copper(I) complexes and processes for deposition of copper films by atomic layer deposition

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