US20180155383A1 - Organometallic compounds useful for chemical phase deposition - Google Patents

Organometallic compounds useful for chemical phase deposition Download PDF

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US20180155383A1
US20180155383A1 US15/569,957 US201615569957A US2018155383A1 US 20180155383 A1 US20180155383 A1 US 20180155383A1 US 201615569957 A US201615569957 A US 201615569957A US 2018155383 A1 US2018155383 A1 US 2018155383A1
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compound
metal
group
sico
reagent
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Rajesh Odedra
Cunhai Dong
Shaun CEMBELLA
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Seastar Chemicals ULC
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    • 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
    • C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
    • 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
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/06—Cobalt compounds
    • 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
    • C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
    • 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
    • C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
    • 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
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/02—Iron 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
    • C23C16/06—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
    • C23C16/22—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
    • C23C16/34—Nitrides
    • 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 invention relates to compounds formed from metal carbonyl complexes with trialkyl silyl, germanyl or stannyl ligands, and to methods of preparing thin films of substantially pure metal, alternatively films of metal alloys, metal oxides, nitrides, phosphides, borides or sulphides by chemical vapor deposition (CVD) or atomic layer deposition (ALD) using such compounds.
  • CVD chemical vapor deposition
  • ALD atomic layer deposition
  • Methods of preparing thin films of substantially-pure metal alloys, mixed-metal oxides, mixed-metal nitrides, mixed-metal phosphides, mixed-metal borides or mixed-metal sulphides are also disclosed.
  • Methods of substrate-selective deposition of metal films are also disclosed.
  • organometallic compounds are used to form thin metal films on a variety of substrates, and a variety of deposition techniques have been employed to do so. These include reactive sputtering, ion-assisted deposition, sol-gel deposition, CVD, and ALD, also known as atomic layer epitaxy.
  • CVD and ALD processes are increasingly used as they have the advantages of good compositional control, high film uniformity, good control of doping and, significantly, they give excellent conformal step coverage on highly non-planar microelectronics device geometries.
  • CVD also referred to as metal-organic CVD or MOCVD
  • MOCVD metal-organic CVD
  • MOCVD metal-organic CVD
  • the compounds are passed over a substrate (wafer) within a low pressure or ambient pressure reaction chamber.
  • the compounds react and/or decompose on the substrate surface creating a thin film of deposited material.
  • Volatile by-products are removed by gas flow through the reaction chamber.
  • the deposited film thickness can be difficult to control because it depends on coordination of many parameters such as temperature, pressure, gas flow volumes and uniformity, chemical depletion effects and time.
  • ALD is a common method for the deposition of thin films. It is a self-limiting, sequential, unique film growth technique based on surface reactions that can provide atomic layer-forming control and deposit-conformal thin films of materials provided by compounds onto substrates of varying compositions.
  • the compounds are separated during the reaction. The first compound is passed over the substrate producing a monolayer on the substrate. Any excess unreacted compound is pumped out of the reaction chamber. A second compound is then passed over the substrate and reacts with the first compound, forming a second monolayer of film over the first-formed monolayer of film on the substrate surface. This cycle is repeated to create a film of desired thickness.
  • ALD film growth is self-limited and based on surface reactions, creating uniform depositions that can be controlled at the nanometer-thickness scale.
  • Deposition of good quality metals by CVD and/or ALD is difficult either due to stability issues of the compounds or impurities in the final films.
  • the stability of the compounds can impact the delivery of these materials to the growth chamber and thus the deposition rate or partial decomposition in the lines. If the compounds cannot decompose or react cleanly, then impurities such as C, N, O and H can incorporate into the film which causes the performance of the film to be less than optimum.
  • the incorporation of impurities in the films may also have some impact on film adhesion to the underlying substrate and thus on the device performance.
  • the delivery of the compound and the lifetime of the compound in the bubbler are also important and this can be a challenge when solid compounds are involved, thus there is always a desire to use liquid compounds with good stability.
  • This invention is related to compound engineering to meet some of the challenges highlighted above.
  • lower alkyl group refers to linear, branched, or cyclic alkyl groups having from 1 to 8 carbon atoms.
  • linear alkyl groups include, without limitation, methyl groups, ethyl groups, propyl groups, and butyl groups.
  • branched alkyl groups include, without limitation, isopropyl groups and t-butyl groups.
  • cyclic alkyl groups include, without limitation, cyclopropyl groups, cycopentyl groups, and cyclohexyl groups.
  • lower alcohol refers to a primary, secondary or tertiary alcohol having from 1 to 4 carbon atoms.
  • examples of such alcohols include, without limitation, methanol, ethanol, isopropanol and tertiary butanol.
  • lower alkyl amine refers to a primary or secondary amine having lower alkyl group(s) each having from 1 to 4 carbon atoms.
  • examples of such amines include, without limitation, methylamine, ethylamine, di-isopropylamine and tertiarybutylamine.
  • substituted hydrazine refers to hydrazines having from 1 to 4 substituents which are independently-selected lower alkyl groups, each having from 1 to 4 carbon atoms, or a phenyl group.
  • substituents include, without limitation, N,N-dimethyl hydrazine, tertiary-butyl hydrazine, methyl hydrazine and phenyl hydrazine.
  • lower alkyl phosphine refers to a primary or secondary phosphine having lower alkyl group(s) each having from 1 to 4 carbon atoms.
  • examples of such amines include, without limitation, methylphosphine, dimethylphosphine, ethylphosphine, and tertiary butylphosphine.
  • lower alkyl thiol refers to a primary, secondary or tertiary thiol having from 1 to 4 carbon atoms.
  • examples of such alcohols include, without limitation, methane thiol, ethane thiol, and tertiary-butyl thiol.
  • lower alkyl borane refers to a primary, secondary or tertiary borane, or a precursor thereof, having from 1 to 4 carbon atoms.
  • boranes include, without limitation, methyl borane, ethyl borane, and trimethyl borane.
  • cobalt group metals refers to the elements Co, Rh, and Ir.
  • manganese group metals refers to the elements Mn and Re.
  • chromium group metals refers to the elements Cr, Mo, and W.
  • iron group metals refers to the elements Fe, Ru, and Os.
  • the term “compound” refers to an organometallic molecule, complex and/or compound which is deposited or delivered to or passed over a substrate to form a thin film by a vapor deposition process such as CVD or ALD.
  • metal-containing film refers to a film of substantially pure metal, metal oxide, metal nitride, metal sulphide, metal boride or metal phosphide.
  • vapor deposition process refers to any type of vapor deposition technique such as CVD or ALD.
  • CVD may take the form of conventional (pulsed) CVD, liquid injection CVD or photo-assisted CVD.
  • ALD may take the form of conventional (pulsed) ALD, liquid injection ALD, photo-assisted ALD, plasma-assisted ALD, or plasma-enhanced ALD. Such techniques are well-known in the art.
  • the present invention provides an organometallic compound.
  • the compound corresponds in structure to Formula 1:
  • R 1 , R 2 and R 3 are independently selected from the group consisting of H, a lower alkyl group and a phenyl group optionally substituted with at least one independently selected lower alkyl group, with the proviso that at least one of R 1 , R 2 and R 3 must be other than H;
  • M is selected from the group consisting of the cobalt group metals, the iron group metals, the manganese group metals, and the chromium group metals;
  • A is selected from the group consisting of Si, Ge, and Sn; and wherein:
  • M is selected from the group consisting of a cobalt group metal
  • M is selected from the group consisting of a manganese group metal
  • M is selected from the group consisting of a chromium group metal
  • the compounds are useful in chemical phase deposition processes such as atomic layer deposition (ALD) and chemical vapor deposition (CVD)
  • Methods of deposition of metal-containing films involve the reaction of the compound with at least one co-reagent to generate metal carbonyl hydrides which decompose cleanly and thermally to form substantially-pure metal films.
  • substantially-pure metal oxide, nitride, phosphide, boride or sulphide films may be prepared by selection of appropriate co-reagents, as described herein.
  • Methods of selective deposition are also provided, such that metal or metal nitride films are deposited selectively on certain substrates and not on other substrate materials.
  • One such method involves the use of substrate materials having a surface with a strong affinity for the silyl (or germanyl or tin) ligand component of the compound, such that after reaction of the compound with the co-reagent(s) the silyl ligand attaches to the surface having an affinity for Si, inhibiting the deposition of metal on that surface.
  • substrate materials having an affinity include SiO 2 , SiN, TiN, TaN.
  • An alternative method of selective deposition involves the use of substrate materials having an affinity for CO, such that after reaction of the compound with the co-reagent(s) the metal carbonyl is bound to the surface having such affinity.
  • the metal carbonyl is subsequently dissociated thermally, leaving the metal coating the surface while the CO is removed as gas.
  • substrate materials having an affinity for CO include the nickel group metals Ni, Pd, Pt, cobalt group metals Co, Rh, Ir, and iron group metals Fe, Ru, and Os.
  • FIG. 1 shows the vapour pressures of compounds of the invention compared to a compound of the art.
  • FIG. 2 shows the thermal stability of t BuMe 2 SiCo(CO) 4 .
  • FIG. 3 shows the thermal stability of a compound of the art CCTBA (3,3-Dimethyl-1-butyne)dicobalthexacarbonyl).
  • FIG. 4 shows a schematic of a CVD system used for exemplary thin film deposition.
  • FIG. 5 shows the binding energies of t BuMe 2 SiCo(CO) 4 on different surfaces.
  • FIG. 6 shows the TGA of EtMe 2 SiCo(CO) 4 .
  • FIG. 7 shows the vapor pressure of EtMe 2 SiCo(CO) 4 .
  • FIG. 8 shows the NMR spectrum of Et 3 SiCo(CO) 4 .
  • FIG. 9 shows the NMR spectrum of BuMe 2 SiCo(CO) 4 .
  • FIG. 10 shows the TGA of t BuMe 2 SiCo(CO) 4 .
  • FIG. 11 shows the vapour pressure of t BuMe 2 SiCo(CO) 4 .
  • FIG. 12 shows the thermal growth rate as a function of temperature for deposition using t BuMe 2 SiCo(CO) 4 .
  • FIG. 13 shows the NMR of PhMe 2 SiCo(CO) 4 .
  • FIG. 14 shows the resistivity of a cobalt film deposited using t BuMe 2 SiCo(CO) 4 .
  • FIG. 15 shows the growth rate as a function of pressure and the hydrogen to ammonia ratio for deposition using tBuMe 2 SiCo(CO) 4 .
  • FIG. 16 shows a demonstration of the process of selective deposition using a compound of the invention.
  • An organometallic compound is provided.
  • the compound corresponds in structure to Formula 1:
  • R 1 , R 2 and R 3 are independently selected from the group consisting of H, a lower alkyl group and a phenyl group optionally substituted with at least one independently selected lower alkyl group, with the proviso that at least one of R 1 , R 2 and R 3 must be other than H;
  • M is selected from the group consisting of the cobalt group metals, the won group metals, the manganese group metals, and the chromium group metals;
  • A is selected from the group consisting of Si, Ge, and Sn; and wherein:
  • M is selected from the group consisting of a cobalt group metal
  • M is selected from the group consisting of a manganese group metal
  • M is selected from the group consisting of a chromium group metal
  • metal carbonyl compounds with trialkyl silyl, germanyl or stannyl ligands methods of making such compounds and methods of using such compounds, in the presence of appropriate co-reagents, to form substantially-pure metal-containing films, such as, but not limited to, metal, metal phosphide, metal sulphide, metal oxide, metal boride and metal nitride films, are provided.
  • the compound corresponds to Formula 1 wherein M is a cobalt group metal and A is Si.
  • exemplary compounds include EtMe 2 SiCo(CO) 4 , Et 3 SiCo(CO) 4 , Me 2 SiCo(CO) 4 and PhMe 2 SiCo(CO) 4 .
  • Exemplary compounds include (Et 3 Si) 2 Fe(CO) 4 .
  • the compound corresponds to Formula 1 wherein M is a manganese group metal and A is Si.
  • Exemplary compounds include Et 3 SiMn(CO) 5 .
  • the compound corresponds to Formula 1 wherein M is a chromium group metals and A is Si.
  • Exemplary compounds include (PhMe 2 Si) 2 W(CO) 4 .
  • Embodiments of the invention include those in which R 1 , R 2 and R 3 are independently selected from the group consisting of a lower alkyl group and a phenyl group optionally substituted with at least one independently selected lower alkyl group.
  • Exemplary compounds include those in which R 1 , R 2 and R 3 are independently selected from the group consisting of a lower alkyl group having from 1 to 5 carbon atoms. Other exemplary compounds include those in which at least one of R 1 , R 2 and R 3 is a methyl group.
  • exemplary compounds include those in which R 1 , R 2 and R 3 are independently selected from the group consisting of a lower alkyl group having from 1 to 4 carbon atoms.
  • Other exemplary compounds include those in which at least one of R 1 , R 2 and R 3 is a methyl group
  • R 1 , R 2 and R 3 are independently selected from the group consisting of a lower alkyl group having from 1 to 4 carbon atoms, two of which are methyl group, the third of which is a lower alkyl group having from 3 to 4 carbon atoms.
  • the compounds of Formula 1 are useful in chemical phase deposition processes such as atomic layer deposition (ALD) and chemical vapor deposition (CVD).
  • ALD atomic layer deposition
  • CVD chemical vapor deposition
  • methods of forming metal-containing films by vapor deposition processes comprise using at least one compound of Formula 1 together with one or more co-reagents, as disclosed herein.
  • FIG. 4 shows a schematic of a CVD system used for exemplary thin film deposition.
  • An inert carrier gas ( 1 ) such as Ar, is passed through a mass flow controller ( 2 ) at a controlled flow rate to bubbler ( 6 ), which contains a compound of Formula 1 ( 7 ) and carries the vaporized compound of Formula 1 to the reaction chamber ( 15 ).
  • a liquid co-reagent ( 14 ) is delivered to the reaction chamber in a similar fashion, whereas a gaseous co-reagent is delivered directly to the reaction chamber at a controlled flow rate without going through the bubbler.
  • the bubbler may be heated or cooled to obtain a suitable vapor pressure in the desired range.
  • the temperature of the delivery line is higher than that of the bubbler by about 20 C.°, so that the vapor does not condense before reaching reaction chamber.
  • the compound of Formula 1 and the co-reagent are delivered simultaneously.
  • substrate(s) ( 16 ) rest on a pre-heated graphite holder ( 17 ) at a set temperature controlled by a heater ( 18 ) and a thermocouple ( 19 ).
  • the pressure in the reaction chamber is controlled by a pressure regulating valve ( 20 ), which is connected to a vacuum pump.
  • the delivered compound of Formula 1 and co-reagent react in the reaction chamber, deposit on substrate(s), and so form a thin film.
  • the by-products of the reaction are pumped off under reduced pressure.
  • reaction of a compound of Formula 1 with co-reagents generates metal carbonyl hydrides, which can decompose cleanly and thermally to form substantially pure metal films, while the volatile carbonyl and hydrolyzed trialkyl silyl ligands evaporate and are removed.
  • co-reagents include, but are not limited to, H2, ammonia, a lower alkyl amine, a lower alcohol, hydrazine and a substituted hydrazine.
  • reaction of a compound of Formula 1 with co-reagents generates metal carbonyl oxides, which can decompose cleanly and thermally to form metal oxide films, while the volatile carbonyl and trialkyl silyl ligands evaporate and are removed.
  • co-reagents include, but are not limited to, H 2 O, O 2 , O 3 , and a lower alcohol.
  • reaction of a compound of Formula 1 with co-reagents generates metal carbonyl amides, which can decompose cleanly and thermally to form metal nitride films, while the volatile carbonyl and trialkyl silyl ligands evaporate and are removed.
  • co-reagents include, but are not limited to, ammonia, a lower alkyl amine, a lower alcohol, hydrazine and a substituted hydrazine.
  • reaction of a compound of Formula 1 with co-reagents generates metal carbonyl phosphide, which can decompose cleanly and thermally to form metal phosphide films, while the volatile carbonyl and trialkyl silyl ligands evaporate and are removed.
  • co-reagents include, but are not limited to, PH 3 and a lower alkyl phosphine.
  • reaction of a compound of Formula 1 with co-reagents generates metal carbonyl sulphide, which can decompose cleanly and thermally to form metal sulphide films, while the volatile carbonyl and trialkyl silyl ligands evaporate and are removed.
  • co-reagents include, but are not limited to, H 2 S and a lower alkyl thiol.
  • reaction of a compound of Formula 1 with co-reagents generates metal carbonyl borides, which can decompose cleanly and thermally to form metal boride films, while the volatile carbonyl and trialkyl silyl ligands evaporate and are removed.
  • co-reagents include, but are not limited to, borane and a lower alkyl borane.
  • the use of more than one compound of Formula 1, each having a different value of M, in the deposition processes disclosed herein results in the formation of films of substantially-pure metal alloys, mixed-metal oxides, mixed-metal nitrides, mixed-metal phosphides, mixed-metal borides or mixed-metal sulphides, the nature of the film formed being dependent upon the nature of the co-reagent used, as described herein.
  • methods of selective deposition are provided such that metal or metal nitride films are deposited selectively on certain substrates and not on other substrate materials.
  • a thirteenth embodiment of the invention involves the use of substrate materials having a surface with a strong affinity for the silyl (or germanyl or tin, as appropriate) ligand component of the compound of Formula 1 such that, after reaction of the compound of Formula 1 with the co-reagent, the silyl (or germanyl or tin, as appropriate) ligand attaches to the surface having such affinity, inhibiting the deposition of metal on that surface.
  • Such substrate materials having an affinity include, but are not limited to, SiO 2 , SiN, TiN, and TaN.
  • a fourteenth embodiment of the invention involves the use of substrate materials having an affinity for CO such that, after reaction of the compound of Formula 1 with the co-reagent, the metal carbonyl is bound to the surface having such affinity.
  • the metal carbonyl is subsequently dissociated thermally, leaving the metal coating the surface whilst the CO is removed as gas.
  • Such substrate materials having an affinity for CO include, but are not limited to, the nickel group metals Ni, Pd, Pt, cobalt group metals Co, Rh, Ir, and iron group metals Fe, Ru, and Os.
  • FIG. 5 shows the binding energies of t BuMe 2 SiCo(CO) 4 to different surfaces. The more negative the energy, the better binding, meaning that the molecule will bind preferentially to Co or Cu. and thus the deposition will preferentially take place on that surface compared to silicon oxide where the binding is weak.
  • FIG. 12 shows that t BuMe 2 SiCo(CO) 4 has good thermal stability up to about 150° C., making it suitable for use in deposition.
  • EtMe 2 SiCo(CO) 4 compound in a bubbler was heated at 60° C., while the NH 3 gas was at room temperature.
  • the temperature of the substrate holder was 200° C.
  • the carrier gas for Co reagent was Ar containing 5% H 2 .
  • the flow rate of both was ca. 200 sccm.
  • the pressure in the reaction chamber was 500 mbar.
  • Substrates used were glass slide, Cu slide and TiN slide. Deposition was carried out for 6 minutes. All substrates were coated with shining Co thin film.
  • Et 3 SiCo(CO) 4 compound in a bubbler was heated at 60° C., while methanol was cooled to 0° C.
  • the temperature of the substrate holder was 200° C.
  • the carrier gas for Co reagent was Ar containing 5% H 2 .
  • the flow rate of both was ca. 200 sccm.
  • the pressure in the reaction chamber was 500 mbar.
  • Substrates used were glass slide, Cu slide and TiN slide. Deposition was carried out for 10 minutes. All substrates were coated with shining Co thin film.
  • (Et 3 Si) 2 Fe(CO) 4 compound in a bubbler was heated at 80° C., while the NH 3 gas was at room temperature.
  • the temperature of the substrate holder was 250° C.
  • the carrier gas for Co reagent was Ar containing 5% H 2 .
  • the flow rate of both was ca. 200 sccm.
  • the pressure in the reaction chamber was 500 mbar.
  • Substrates used were glass slide, Cu slide and TiN slide. Deposition was carried out for 10 minutes. Fe deposition was confirmed by EDX.
  • EtMe 2 SiCo(CO) 4 compound in bubbler was heated at 60° C. while the methanol was at room temperature.
  • the temperature of the substrate holder was 200° C.
  • the carrier gas for Co reagent was N 2 .
  • the flow rate of both was ca. 200 sccm.
  • the pressure in the reaction chamber was 500 mbar.
  • Substrates used were glass slide, and TiN slide. Deposition was carried out for 6 minutes. All substrates were coated with CoO thin film. During the deposition air was present in the reactor system, resulting in higher oxygen content in the Co film that was deposited. This shows that CoO can be grown with O 2 as co-reagent.
  • t BuMe 2 SiCo(CO) 4 compound in a bubbler was heated at 40° C., while the NH 3 /H 2 gas mixture containing 25% H 2 was kept at room temperature.
  • the temperature of the reactor was 200° C.
  • the carrier gas for Co reagent was N 2 .
  • the flow rate of both was 200 sccm.
  • the pressure in the reaction chamber was 100 Torr. Deposition was carried out for 30 minutes. A resistivity of 6.09 ⁇ 10 ⁇ 5 ⁇ cm was achieved.
  • FIG. 14 shows the conductivity of the cobalt films obtained as a function of hydrogen/ammonia mixture, demonstrating that good quality films with high conductivities can be prepared using a hydrogen/ammonia mixture with greater than about 25% hydrogen.
  • FIG. 15 shows that the growth rate flattens out when about 25-80% hydrogen is used with ammonia, confirming the conductivity data from FIG. 14 . Film growth stability is observed.
  • EtMe 2 SiCo(CO) 4 compound in bubbler was heated at 40° C. while the NH 3 gas was at room temperature.
  • the temperature of the substrate holder was 200° C.
  • the carrier gas for Co reagent was N 2 .
  • the flow rate of both was ca. 200 sccm.
  • the pressure in the reaction chamber was 90 torr.
  • Initially low pressure CVD was carried out to deposit seed layers of Co metal on Cu Substrate. This was then followed with selective ALD growth of cobalt on the seed cobalt layers.
  • there was induction period on the SiO 2 surface compared to Cu which allows for selective deposition of cobalt on copper as compared to silicon oxide, as shown in FIG. 16 .
  • FIG. 4 1 Inert carrier gas input; 2 Mass flow controller; 3 Valve controlling direct input of inert carrier gas to reaction chamber; 4 Valve controlling input of inert carrier gas to bubbler; 5 Valve controlling input of inert carrier gas containing vaporized precursor to reaction chamber 6 Bubbler containing compound; 7 Compound; 8 Input of gaseous co-reagent or inert carrier gas for liquid co-reagent; 9 Mass flow controller; 10 Valve controlling direct input of gaseous co-reagent or inert carrier gas; 11 Valve controlling input of inert carrier gas to bubbler; 12 Valve controlling input of inert carrier gas containing vaporized co-reagent to reaction chamber; 13 Bubbler containing co-reagent; 14 Liquid co-reagent; 15 Quartz tube wall of reaction chamber; 16 Substrate; 17 Graphite substrate holder with heater and thermocouple; 18 Heater; 19 Thermocouple; 20 Pressure regulating valve to vacuum pump controlling gas pressure in reaction chamber; and 21 Metal

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US11205573B2 (en) 2017-08-09 2021-12-21 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Ge-containing Co-film forming material, Ge-containing Co film and film forming method thereof
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