WO2008085426A1 - Précurseurs de cuivre liquide volatile pour des applications de film fin - Google Patents

Précurseurs de cuivre liquide volatile pour des applications de film fin Download PDF

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Publication number
WO2008085426A1
WO2008085426A1 PCT/US2007/026215 US2007026215W WO2008085426A1 WO 2008085426 A1 WO2008085426 A1 WO 2008085426A1 US 2007026215 W US2007026215 W US 2007026215W WO 2008085426 A1 WO2008085426 A1 WO 2008085426A1
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Prior art keywords
copper
metal complex
metal
group
cvd
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Application number
PCT/US2007/026215
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English (en)
Inventor
John Anthony Thomas Norman
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Air Products And Chemicals, Inc.
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Publication of WO2008085426A1 publication Critical patent/WO2008085426A1/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]
    • C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for 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
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C 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

Definitions

  • Figure 1 is the TGA/DSC, respectively, for copper precursor Cu-1
  • Figure 2 is the TGA/DSC for copper precursor Cu-2
  • Figure 3 is a graph comparing the vapor pressures of Cu-1 and Cu-2
  • Figure 4 shows the molecular structure of Cu-3 as determined by X-ray Crystallography.
  • Figure 5 is the TGA for Cu-3 (here named Kl 4).
  • Figure 6 is an Arrenhius Graph of the several experimental deposition runs of Example 9.
  • the present invention is copper +1 compounds that retain the low tempertaure processing advantages typical for copper +1 compounds, but the compounds of the present invention have the thermal stability normally associated with copper +2 compounds, which always have higher process temperatures. Also, the compounds of the present invention are easy to handle for the process engineer, using simple bubbler delivery. In the semiconductor industry, there continues to be an ongoing interest in the development of volatile copper precursor compounds for the growth of thin copper films for various interconnect applications by Chemical Vapor Deposition (CVD) or Atomic Layer Deposition (ALD).
  • CVD Chemical Vapor Deposition
  • ALD Atomic Layer Deposition
  • copper precursors to be useful for these processes it is preferred that they are liquid at ALD or CVD source temperatures, highly volatile, thermally stable, and yet, chemically reactive towards reducing agents, to yield pure copper films. It is well known that incorporation of the element fluorine into the chemical structure of a copper precursor will increase its volatility. This is especially highly advantageous if the precursor is thermally stable, because it can then be safely heated to a high vapor pressure without fear of the precursor decomposing. A high deposition rate of copper is then achieved, when this high vapor pressure of precursor is flowed through the CVD or ALD reactor and reacted with a reducing agent. High thermal stability also offers other processing advantages, one of which is the ability to simply heat the precursor in a container, and then, bubble a carrier gas through it to achieve a steady and constant stream of precursor vapor into the reactor.
  • thermal stability Another advantage of thermal stability is that the precursor will only metallize the heated substrate surface and not decompose in other parts of the reactor. Once the precursor reacts with the reducing agent, it deposits a copper film and releases volatile by-products, which are pumped away as vapors.
  • copper precursors of the Cu(hfac)(tmvs) type metallize a substrate by a thermal disproportionation reaction, which releases Cu +2 (hfac) 2 as one of its volatile by- products.
  • This reaction is shown below in Formula 1.
  • the Cu +2 (hfac) 2 compound is a solid at room temperature, which accumulates in cool regions of the reactor, so special provisions must be made to manage this solid material.
  • the disproportionation dictates that 50% of the original copper precursor is lost as this by-product.
  • the thermally stable fluorinated copper precursors of the present invention do not disproportionate, so both the effective 50% loss of precursor and accumulation of copper *2 by-product are avoided.
  • the copper *1 complexes of the present invention are sufficiently chemically reactive that they can grow a copper film by reaction with a reducing agent below 200 0 C, despite their outstanding thermal stability.
  • This low processing temperature regime is especially attractive, since it permits an overall low 'thermal budget' for growing copper films onto silicon based electronic devices, such as central processing units, CPUs, which helps avoid their overheating during processing.
  • Another advantage of the volatile low mellting fluorinated thermally stable copper precursors of the present invention is that they can be readily purified by vacuum distillation or sublimation.
  • Other liquid fluorinated copper precursors of the type Cu(hfac)(tmvs) do not readily lend themselves to vacuum distillation since they tend to thermally degrade during the process.
  • the precursors described in the present invention are the fluorinated analogues of the non-fluorinated copper precursors described in US 2006/0145142.
  • the precursors comprise the class of metal complexes of the structure:
  • R 1 , R 2 and R 3 are independently H, alkyl or fluoroalkyl groups, but at least one of R 1 ,
  • R 2 and R 3 is fluoroalkyl and M is a monovalent metal and L is a ligand, capable of coordinating to the metal M, R 4 is an aliphatic hydrocarbon chain.
  • R 4 aliphatic hydrocarbon chain is normal or branched C M0 .
  • R 4 aliphatic hydrocarbon chain includes functional groups selected from the group consisting of oxygen, nitrogen, silicon and mixtures thereof.
  • the metal is copper.
  • the fluoroalkyl is C M0 . More preferably, the fluoroalkyl is perfluorinated.
  • the ligand L is selected from the group consisting of alkene, alkyne, nitrile, isonitrile, cyanate, isocyanate, imine and phosphine. More preferably, the ligand L is normal or branched C M O alkenyl. Most preferably, the ligand L is C 2 alkenyl.
  • the metal complex is in admixture with other liquid molecules that enhance the ALD or CVD process, and the resulting mixtures evaporation for delivery to the deposition chamber by DLL
  • the metal complex wherein M is copper is in admixture with a metal complex wherein M is selected from the group consisting of titanium, tantalum, hafnium, silver, gold, tungsten and nickel, capable of the deposition of copper alloys.
  • these molecules are low melting solids at room temperature, are exceptionally thermally stable, are highly volatile and are highly reactive towards reducing agents, such as hydrogen, formic acid, silane, borane or mixtures thereof at low temperatures.
  • reducing agents such as hydrogen, formic acid, silane, borane or mixtures thereof at low temperatures.
  • the unexpected combined properties of high thermal stability and high volatility of these new compounds is readily demonstrated by comparing the TGA/DSC scans of these compounds compared to their unfluorinated counterparts. In these experiments a small quantity of a precursor is placed in a microbalance pan, which is then steadily heated at a fixed temperature ramp rate under a steady fixed flow of nitrogen. [0024] As the precursor heats up it begins to vaporize, as manifest by a steady weight loss. This process continues until either complete evaporation occurs or an involatile residue remains.
  • the former case indicates no thermal degradation to have occurred during evaporation, whereas the latter indicates some decomposition to have taken place. A greater amount of residue indicates a greater degree of decomposition.
  • any exothermic events (often decomposition) or endothermic events (often phase changes such as melting or heat loss by evaporative cooling) are detected by the Differential Scanning Calorimeter (DSC).
  • DSC Differential Scanning Calorimeter
  • a precursor which remains perfectly thermally stable during evaporation, shows a smooth curve for 100% weight loss down to almost 0% residue (the experimental error of TGS is + or - 0.5%).
  • the DSC curve is also smooth, as it registers only the endotherm of evaporative cooling of the sample. This is the case for the fluorinated copper precursor Cu-1 of the present invention, whose TGA/DSC and chemical structure are shown in Figure 1 and Formula 2, below, respectively.
  • Figure 2 and Formula 3, below, respectively, show the TGA/DSC and chemical structure of the homologous unfluorinated precursor Cu-2.
  • Formula 2 shows the only difference between Cu-1 and Cu-2.
  • Cu-1 has fluorinated CF 3 groups on the ketoimine anion portion of the complex in place of the corresponding unfluorinated methyl groups of Cu-2.
  • the TGA/DSC performance of the copper precursor Cu-1 is far superior to that of Cu-2 as seen by comparing the Figures 1 and 2.
  • the involatile residue for Cu-1 is only 2.3%, with the final evaporation temperature being ⁇ 225°C
  • Figure 2 shows an involatile residue for Cu-2 of ⁇ 30%, with a final evaporation temperature of ⁇ 240°C.
  • Figure 2 also shows an endotherm of melting at -73 0 C
  • Figure 1 shows an endotherm of melting at 41 0 C, which is an additional advantage, since lower melting points are desirable for CVD and ALD precursors, because then only a relatively low temperature is needed to maintain the molecule in the liquid state.
  • a further exceptional property of the copper precursor Cu-1 when compared to the copper precursor Cu-2, is the greater volatility of the former, which is quantified in Figure 3, below, which plots vapor pressure versus temperature for these two precursors. This shows that for a given temperature, Cu-1 is about eight times more volatile than Cu-2. In practical terms, this represents a great advantage, because higher volatility means it is easier to flow a greater vapor pressure of precursor through an ALD or CVD reactor, which can yield faster cycle times, greater copper growth rates and overall lower temperatures for the evaporation of precursor and heated vapor delivery lines to the reactor. This performance is only possible by the unexpected combination of thermal stability and volatility of Cu-1.
  • the partially fluorinated metal complexes are used for metal deposition, such as copper deposition comprising a thin film deposition process using the metal complexes in a process selected from the group consisting of CVD, pulsed CVD, PECVD or ALD, where vapors of the metal complexes are contacted with a suitable reagent selected from the group consisting of hydrogen, formic acid, silane, borane, and mixtures thereof, on a heated substrate surface.
  • the growth of copper films uses super critical carbon dioxide and a reducing agent selected from the group consisting of hydrogen, formic acid, borane, silane and mixtures thereof.
  • the process is used to grow a copper film onto a diffusion barrier material whereby the metal complex selectively deposits copper onto the diffusion barrier material rather than onto copper by selection of appropriate process conditions, wherein the copper deposition process becomes self limiting upon achieving a certain copper film thickness and is essentially 'self healing' in that if barrier metal becomes exposed through the copper film, fresh copper will deposit there to restore the continuous copper film.
  • the diffusion barrier material is ruthenium.
  • PrOdUCt CF 3 C(O)CH 2 C(NCH 2 CH 2 NHMe)CF 3
  • Example 8 Examples of copper ALD deposition
  • Cu- 1 was used at a source temperature of 75 0 C using nitrogen as carrier gas. Its vapors were pulsed through an ALD reactor, alternating with hydrogen reagent gas, over ruthenium coated silicon wafer samples at between 20 and 500 mTorr pressure. Three experiments were run at 200 0 C, 225°C and 250 0 C for 1800, 600 and 700 cycles respectively resulting in the deposition of copper films, as confirmed by Auger spectroscopy.
  • a 25g sampleof Cu-1 in a stainless steel bubbler was fitted to an experimental hotwall CVD reactor, and CVD copper films were grown onto ruthenium substrates using formic acid vapor as a reducing gas added by vapor draw from a quartz bubbler.
  • the CVD chamber pressure was maintained at 2.0 Torr, and 25 seem of helium carrier gas was flowed through the bubbler.
  • Each run was of 30 minutes duration at wafer temperatures of 150, 200 and 250 0 C, and for each of these wafer temperatures, the Cu-1 bubbler held at 57, 64 or 75°C.
  • the formic acid vapor was metered through a needle valve and determined to be an average of 160 seem for each run, as determined by weight loss of formic acid from its container for each run.
  • Table 1 shows all the runs with their respective average CVD copper film thickness grown, shown in units of Angstroms. Copper film thickness was determined by etching a hole in the copper film down to the underlying ruthenium (not etched) using 50% nitric acid, washing with water, drying, then measuring the resulting copper step by stylus profilometry. These results are also shown in the Figure 6 Arrhenius graph, below, which indicates a linear relationship between the logarithum of copper growth rate in Angstoms per minute versus the reciprocal of absolute temperature, along with a higher overall growth rate of copper with increasing source temperature, as typically seen for CVD metallization processes. The copper metal deposited was confirmed by electron dispersive X-ray (EDX) analysis. Table 1

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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)
  • Chemical Vapour Deposition (AREA)
  • Electrodes Of Semiconductors (AREA)

Abstract

La présente invention concerne des composés de cuivre +1 pour le dépôt de film de cuivre, qui conservent les avantages de traitement à basse température typiques des composés de cuivre +1 mais qui présentent la stabilité thermique normalement associée aux composés de cuivre +2. De tels composés conviennent pour une utilisation en tant que précurseurs de cuivre pour le développement de films fins de cuivre pour diverses applications par déposition en phase vapeur par procédé chimique (CVD) ou déposition par couches atomiques (ALD).
PCT/US2007/026215 2006-12-28 2007-12-21 Précurseurs de cuivre liquide volatile pour des applications de film fin WO2008085426A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2060577A1 (fr) * 2007-11-05 2009-05-20 Air Products and Chemicals, Inc. Précurseurs en cuivre pour dépôt de film mince
US8163341B2 (en) 2008-11-19 2012-04-24 Micron Technology, Inc. Methods of forming metal-containing structures, and methods of forming germanium-containing structures
US8263795B2 (en) 2007-11-05 2012-09-11 Air Products And Chemicals, Inc. Copper precursors for thin film deposition
US9453036B2 (en) 2011-05-13 2016-09-27 Greencentre Canada Group 11 mono-metallic precursor compounds and use thereof in metal deposition

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5144049A (en) * 1991-02-04 1992-09-01 Air Products And Chemicals, Inc. Volatile liquid precursors for the chemical vapor deposition of copper
USRE35614E (en) * 1993-05-18 1997-09-23 Air Products And Chemicals, Inc. Process for improved quality of CVD copper films
US6090963A (en) * 1998-11-10 2000-07-18 Sharp Laboratories Of America, Inc. Alkene ligand precursor and synthesis method
US6818783B2 (en) * 2000-04-03 2004-11-16 Air Products And Chemicals, Inc. Volatile precursors for deposition of metals and metal-containing films
US6838573B1 (en) * 2004-01-30 2005-01-04 Air Products And Chemicals, Inc. Copper CVD precursors with enhanced adhesion properties

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5144049A (en) * 1991-02-04 1992-09-01 Air Products And Chemicals, Inc. Volatile liquid precursors for the chemical vapor deposition of copper
USRE35614E (en) * 1993-05-18 1997-09-23 Air Products And Chemicals, Inc. Process for improved quality of CVD copper films
US6090963A (en) * 1998-11-10 2000-07-18 Sharp Laboratories Of America, Inc. Alkene ligand precursor and synthesis method
US6818783B2 (en) * 2000-04-03 2004-11-16 Air Products And Chemicals, Inc. Volatile precursors for deposition of metals and metal-containing films
US6838573B1 (en) * 2004-01-30 2005-01-04 Air Products And Chemicals, Inc. Copper CVD precursors with enhanced adhesion properties

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2060577A1 (fr) * 2007-11-05 2009-05-20 Air Products and Chemicals, Inc. Précurseurs en cuivre pour dépôt de film mince
US8263795B2 (en) 2007-11-05 2012-09-11 Air Products And Chemicals, Inc. Copper precursors for thin film deposition
US8163341B2 (en) 2008-11-19 2012-04-24 Micron Technology, Inc. Methods of forming metal-containing structures, and methods of forming germanium-containing structures
US8323736B2 (en) 2008-11-19 2012-12-04 Micron Technology, Inc. Methods of forming metal-containing structures, and methods of forming germanium-containing structures
US9453036B2 (en) 2011-05-13 2016-09-27 Greencentre Canada Group 11 mono-metallic precursor compounds and use thereof in metal deposition

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