WO2011123792A2 - Metal nitride containing film deposition using combination of amino-metal and halogenated metal precursors - Google Patents

Metal nitride containing film deposition using combination of amino-metal and halogenated metal precursors Download PDF

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Publication number
WO2011123792A2
WO2011123792A2 PCT/US2011/030957 US2011030957W WO2011123792A2 WO 2011123792 A2 WO2011123792 A2 WO 2011123792A2 US 2011030957 W US2011030957 W US 2011030957W WO 2011123792 A2 WO2011123792 A2 WO 2011123792A2
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Prior art keywords
metal
precursors
precursor
reactor
film
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PCT/US2011/030957
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French (fr)
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WO2011123792A3 (en
Inventor
Katsuko Higashino
Kazutaka Yanagita
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L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude
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Application filed by L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude filed Critical L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude
Priority to EP11763521.9A priority Critical patent/EP2553141A4/en
Priority to US13/389,242 priority patent/US20130078376A1/en
Priority to CN2011800033921A priority patent/CN102471885A/en
Priority to JP2013502893A priority patent/JP5815669B2/en
Priority to KR1020127005001A priority patent/KR101226876B1/en
Publication of WO2011123792A2 publication Critical patent/WO2011123792A2/en
Publication of WO2011123792A3 publication Critical patent/WO2011123792A3/en

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    • 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
    • C23C16/448—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 generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
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    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
    • 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
    • C23C16/22—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
    • C23C16/345—Silicon nitride
    • 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
    • C23C16/36—Carbonitrides
    • 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
    • H—ELECTRICITY
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    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H01L21/02274—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H01L21/0228—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD

Definitions

  • the metal-nitride-containing film composition may be modified based upon the structure of aminometai precursor.
  • the disclosed processes may be thermal processes or plasma processes at low temperature.
  • Metal-nitride-containing films such as silicon nitride (SiN) films, are widely used in semiconductor devices and ultra-large-scale integrated (ULS! circuits. According to downsizing and the growing sophistication of electronic devices requiring increasingly higher LSI mounting densities, a SiN film is required to improve its film qualities against current leakage. In addition, SiCN film is also used as the etch stopper in a dual-damascene structure for Cu wiring.
  • SiN Silicon nitride
  • the inter-gate dielectric layer may comprise Si0 2 or SiN, for examp!e.
  • carbon doping the SiN layer provides high etch resistance.
  • LSIs large scale integrations
  • ALD atomic layer deposition
  • alkyl group refers to saturated functional groups containing exclusively carbon and hydrogen atoms. Further, the term “alkyl group” refers to linear, branched, or cyclic alkyl groups. Examples of linear alky! groups include, without limitation, methyl groups, ethyl groups, propyl groups, butyl groups, etc. Examples of branched alkyl groups include, without limitation, t-butyl. Examples of cyclic alkyl groups include without limitation, cyciopropyi groups, cyclobuty! groups, cyclopentyi groups, cyclohexyi groups, etc.
  • the abbreviation "Me” refers to a methyl group
  • the abbreviation “Et” refers to an ethyi group
  • the abbreviation “Pr” refers to a propyl group
  • the abbreviation “nPr” refers to a chain propyl group
  • the abbreviation “iPr” refers to an isopropyl group
  • the abbreviation “Bu” refers to a butyl (n-butyl) group
  • the abbreviation “tBu” refers to a tert-buty!
  • the abbreviation “sBu” refers to a sec-butyl group
  • the abbreviation “iBu” refers to an iso-butyl group
  • the abbreviation “TMS” refers to a trimethylsilyl group.
  • a halogenaied metal precursor is introduced into an ALD reactor containing at least one substrate. Excess halogenaied metal precursor is
  • An amino-metal precursor is introduced into the reactor. Excess amino-metal precursor is subsequently from the reactor.
  • a reactant may optionally be introduced into the reactor. Excess optional reactant is subsequently purged from the reactor.
  • the metal of the halogenaied metal precursor and the metal of the amino-metal precursor may be the same or different.
  • a halogenaied metal precursor is introduced into an ALD reactor containing at least one substrate. Excess halogenated metal precursor is
  • An amino-metal precursor is introduced into the reactor. Excess amino-metal precursor is subsequently from the reactor. A reactant is introduced into the reactor. Excess reactant is subsequently purged from the reactor.
  • the metal of the halogenated metal precursor and the metal of the amino-metal precursor may be the same or different.
  • a chlorosilane precursor is introduced into an ALD reactor containing at least one substrate. Excess chlorosiiane precursor is subsequently purged from the reactor.
  • An aminosilane precursor is introduced into the reactor. Excess aminosilane precursor is subsequently from the reactor.
  • a reactant may optionally be introduced into the reactor. Excess optional reactant is subsequently purged from the reactor.
  • a chlorosilane precursor is introduced into an ALD reactor containing at least one substrate. Excess chlorosilane precursor is subsequently purged from the reactor. An aminosilane precursor is introduced into the reactor. Excess aminosilane precursor is subsequently from the reactor. A reactant is introduced into the reactor. Excess reactant is subsequently purged from the reactor.
  • Each of the disclosed methods may further include one or more of the following aspects:
  • the reactant being selected from the group consisting of N 2 , NH 3 , N 2 H 4 , NMeH 2 , NEtH 2 , NMe 2 H, NEt 2 H, NMe 3 , NEt 3 , MeHNNH 2 , Me 2 NNH 2 , phenyl hydrazine, and mixtures thereof;
  • halogenated precursors being chlorometal precursors
  • the metal-nitride-containing film being a metal carbonitride film
  • the metal being selected from transition metal, metal or non-metal elements; • the metal being boron or phosphorus;
  • the metal-nitride-containing film being a silicon-nitride-containing film
  • the halogenated metal precursor being a ch!orosiiane precursor
  • ⁇ the amino-metaS precursor being an aminosilane precursor
  • the silicon-nitride-containing film being carbon-doped SiN film
  • R' and R" are independently selected from H or an alkyl group, and R' and R" may be linked to form a ring structure;
  • aminosilane precursors comprising an aminochlorosilane or an aminoalkyisilane
  • FIG 1 is a graph showing the deposition rate and refractive index of a SiCN film deposited using tris(dimethyiamino)silane (3DMAS) and hexachlorodisilane (HCDS) according to the disclosed method versus the distance of the film from the inlet;
  • 3DMAS tris(dimethyiamino)silane
  • HCDS hexachlorodisilane
  • FIG 2 is a graph showing the deposition rate and refractive index versus distance of a SiCN film deposited using 3DMAS and HCDS according to one alternative of the disclosed method
  • FIG 3 is a graph showing the deposition rate and refractive index versus distance of a SiCN film deposited using 3D AS and HCDS according to a second alternative of the disclosed method
  • FIG 4 is a graph showing the deposition rate and refractive index of a SiCN film deposited using tetrakis(dimethylamino)silane (4DMAS) and hexachlorodisilane (HCDS) according to the disclosed method versus the distance of the film from the inlet;
  • 4DMAS tetrakis(dimethylamino)silane
  • HCDS hexachlorodisilane
  • FIG 5 is a graph showing the deposition rate and refractive index versus distance of a SiCN film deposited using 4DMAS and HCDS according to one alternative of the disclosed method
  • FIG 6 is a graph showing the deposition rate and refractive index versus distance of a SiCN film deposited using 4DMAS and HCDS according to a second alternative of the disclosed method
  • FIG 7 is a graph showing the deposition rate and refractive index of a SiCN film deposited using bis(diethyiamino)silane (BDEAS) and hexachlorodisilane (HCDS) according to the disclosed method versus the distance of the film from the inlet; and
  • FIG 8 is a graph showing the deposition rate and refractive index versus distance of a SiCN film deposited using BDEAS and HCDS according to one alternative of the disclosed method.
  • ALD methods of forming metal-nitride-containing films using the alternate supply of amino-metai precursors and halogenated metal precursors The sequential reaction of the amino-metal precursors with the halogenated metal precursors produces a dense metal-rich film.
  • the metal of the haiogenated metal precursor may be the same as or different from the metai of the amino-metal precursor.
  • ALD methods of forming silicon-nitride-containing films preferably silicon carbonitride films, using the alternate supply of aminosilane precursors and chlorosilane precursors under thermal conditions or low temperature plasma conditions.
  • the sequential reaction of the aminosilane precursors with the chlorosilane precursors produces a dense silicon-rich film at temperatures lower than those of many prior art silicon nitride film deposition processes.
  • the silicon carbonitride films may alternatively be referred to as carbon-doped silicon-nitride films.
  • the level of carbon in the silicon- nitride film determines the appropriate nomenclature, with the amount of carbon in carbon-doped silicon nitride films typically being less than the amount of carbon in silicon carbonitride films.
  • the exact percentage of carbon in the film which determines the appropriate nomenclature is not defined and will vary from person to person.
  • the disclosed methods form metal-nitride-containing films, such as SiN, or a metal carbonitride films, such as SiCN, from amino-metai and haiogenated metal precursors by ALD.
  • the metal-nitride-containing film may be a metal carbonitride film containing one or two metals.
  • the metal carbonitride film may be a SiHfCN film.
  • the SiN film may be carbon-doped.
  • metal-nitride- containing films having specified stoichiometry may be produced by varying the order of the disclosed method steps. Furthermore, the duration of the disclosed method steps may also be varied in order to "tune" the resulting film.
  • the haiogenated metal precursors are introduced into an ALD reactor containing one or more substrates.
  • the haiogenated metal precursors may be introduced into the ALD reactor before or after the amino-metal precursor.
  • the conditions within the reactor permit at ieast part of the haiogenated metal precursors to self adsorb on the substrates.
  • substrate properties will define whether the halogenated metal precursor undergoes
  • halogenated metal precursors are introduced into the reactor after the amino-metal precursors, at Ieast part of the halogenated metal precursors will react/chemisorp with the portion of the amino-metal precursors deposited in the prior step. Any non-adsorbed or "excess" halogenated metal precursor is purged out of the reactor.
  • the halogenated metal precursors are reactive with NH 3 /amino-metal precursors at low
  • the halogenated metal precursors may be chlorometal precursors.
  • the meta! of the halogenated metal or chlorometal precursors may be any transition metal, metal, or non-metal elements as commonly defined on the periodic table of elements.
  • Preferred transition metals include but are not limited to Hf.
  • Preferred metals include but are not limited to Zn.
  • Preferred non-metals include but are not limited to B, Si, and P.
  • the halogenated metal precursor may be applied as a mixture of two or more halogenated metal precursors.
  • the halogenated metal precursors are chiorosilane precursors.
  • Exemplary chlorosilane precursors include hexachlorodisilane (HCDS), SiCI 4 , SiHCI 3 , 5 ⁇ 2 ⁇ 5 ⁇ , etc., and mixtures thereof, such as HCDS and SiCI 4 or HCDS and SiHCI 3 .
  • HCDS hexachlorodisilane
  • SiCI 4 SiCI 4
  • SiHCI 3 5 ⁇ 2 ⁇ 5 ⁇ , etc.
  • mixtures thereof such as HCDS and SiCI 4 or HCDS and SiHCI 3 .
  • the halogenated metai precursor comprises HfC! 4 or HCDS, and more preferably HCDS.
  • the amino-metal precursors are introduced into the reactor.
  • the conditions within the reactor permit at Ieast part of the amino-metal precursors to self adsorb on the substrates.
  • the amino-metal precursors may be introduced into the ALD reactor before or after the halogenated metal precursors.
  • the substrate properties will define whether the amino-metal precursor undergoes physiadsorption or chemisorption in this step. For example, if the amino-metal precursors are introduced into the reactor after the ha!ogenated metal precursors, at least part of the amino-metal precursors will react/chemisorp with the portion of the haiogenated metal precursors deposited in the prior step.
  • any non-adsorbed or "excess" amino-metai precursor is then purged out of the reactor.
  • the amino-metal precursors may act as both a C-source and N-source, as opposed to the prior art NH 3 precursors which only act as a N-source.
  • the alky!amino groups of the aminometal precursors serve as good leaving groups and lead to good adsorption. Varying the ligands of the aminometal precursors provides the ability to modify the carbon content of the metal-nitride-containing fi!m.
  • the metal of the amino-metal precursors may be any transition metal, metal, or non-metal elements as commonly defined on the periodic table of elements.
  • Preferred transition metals include but are not limited to Hf.
  • Preferred metals include but are not limited to Zn.
  • Preferred non- metals include but are not limited to B, Si, and P.
  • the amino-metal precursor may be applied as a mixture of two or more amino-metal precursors.
  • the amino-metal precursor may be aminosilane precursors.
  • the aminosilane precursor may be an aminochlorosilane precursor or an aminoalkylsilane precursor.
  • the amino-metal precursor is bis ⁇ diethylamino)silane (BDEAS), tris(dimethylamino)siSane (3DMAS), tetrakis(dimethy!amino) silane (4DMAS), or tetrakis(ethylmethylamino)hafnium, and more
  • halogenated metal precursors and aminometal precursors are each individually introduced into the reactor in vapor form.
  • “individually” and “each” refers to the specified class of precursors, for example “the halogenated metal precursors”, which may consist of one or more halogenated precursors. In the following paragraphs, individually is not intended to mean that the vapors of only one halogenated metal precursor are introduced into the reactor.
  • the precursors may be individually fed in liquid state to a vaporizer where they are each individually vaporized before introduction into the reactor. Prior to vaporization, each of the precursors may optionally be mixed with one or more solvents.
  • the solvents may be selected from the group consisting of toluene, ethyl benzene, xylene, mesitylene, decane, dodecane, octane, hexane, pentane, or others.
  • the resulting concentration may range from approximately 0.05 M to approximately 2 M.
  • the precursors may be individually vaporized by passing a carrier gas into a container containing each of the precursors or by bubbling the carrier gas into each of the precursors.
  • Each of the precursors may optionally be mixed in the container with one or more solvents.
  • the carrier gas and individual precursors are then introduced into the reactor as a vapor.
  • the carrier gas may include, but is not limited to, Ar, He, N 2 ,and mixtures thereof. Bubbling with a carrier gas may also remove any dissolved oxygen present in the precursors' solution.
  • the container may be heated to a temperature that permits the precursors to be in liquid phase and to have a sufficient vapor pressure.
  • the container may be maintained at temperatures in the range of, for example, 0°C to 1 50°C.
  • the temperature of the container may be adjusted in a known manner to control the amount of precursor vaporized.
  • the vapor of each precursor may be introduced into the reactor for a time period ranging from approximate!y 0.01 seconds to approximately 60 seconds, alternatively from approximately 5 seconds to approximately 25 seconds, alternatively from approximately 10 seconds to approximately 20 seconds.
  • a reactant may be introduced into the reactor, where it reacts with the seif adsorbed layers on the substrates. Any non- reacted or "excess" reactant is then purged out of the reactor.
  • the reactant may be N 2 , NH 3 , N 2 H 4 , NMeH 2 , NEtH 2 , NMe 2 H, NEt 2 H, NMe 3 , NEt 3 , MeHNNH 2 , Me 2 NNH 2 , phenyl hydrazine, and mixtures thereof.
  • the reactant is NH 3 .
  • inclusion of the optional reactant steps " will depend upon the desired stoichiometric ratio of elements in the resulting metal- nitride-containing film.
  • the reactant may be treated by plasma in order to decompose the reactant into its radical form.
  • the plasma may be generated or present within the reactor itself. Alternatively, the plasma may generally be at a location removed from the reactor, for instance, in a remotely located plasma system.
  • One of skill in the art will recognize methods and apparatus suitable for such plasma treatment.
  • the reactant may be introduced into a direct plasma reactor, which generates a plasma in the reactor, to produce the plasma- treated reactant in the reactor.
  • exemplary direct plasma reactors include the TitanTM PECVD System produced by Trion Technologies.
  • the reactant may be introduced and held in the reactor prior to plasma processing.
  • In-situ plasma is typically a 3.56 MHz RF capacitively coupled plasma that is generated between the showerhead and the substrate holder.
  • the substrate or the showerhead may be the powered electrode depending on whether positive ion impact occurs.
  • Typical applied powers in in-situ plasma generators are from approximately 100 W to approximately 1000 W.
  • the disassociation of the reactant using in-situ plasma is typically less than achieved using a remote plasma source for the same power input and is therefore not as efficient in reactant disassociation as a remote plasma system, which may be beneficial for the deposition of metai-nitride-containing films on substrates easily damaged by plasma.
  • the plasma-treated reactant may be produced outside of the reactor.
  • the MKS Instruments' ASTRON ® i reactive gas generator may be used to treat the reactant prior to passage into the reactor.
  • the reactant NF 3 may be decomposed into three F " radicals with more than 96% decomposing efficiency.
  • the remote piasma may be generated with a power ranging from about 1 kW to about 10 kW, more preferably from about 2.5 kW to about 7.5 kW.
  • the ALD reactor may be a heated vesse! which has at least one or more substrates disposed within it.
  • the reactor has an outlet which may be connected to a vacuum pump to allow by-products to be removed from the reactor, or to allow the pressure within the reactor to be modified or regulated.
  • suitable ALD reactors include, without limitation, a parallel-plate type reactor, a cold-wall type reactor, a hot-wall type reactor, a single-wafer reactor, a multi-wafer reactor, a direct plasma reactor, or other types of deposition systems under conditions suitable to cause the precursors to react and form the layers.
  • the reactor contains one or more substrates onto which the metal-nitride-containing films will be deposited.
  • the reactor may contain from 1 to 200 silicon wafers having from 25.4 mm to 450 mm diameters.
  • the substrates may be any suitable substrate used in semiconductor, photovoltaic, flat panel, or LCD-TFT device manufacturing.
  • the substrates may contain one or more additional layers of materials, which may be present from a previous manufacturing step. Dielectric and conductive layers are examples of these.
  • substrates include without limitation, metal substrates, metal nitride substrates, silicon substrates, silica substrates, silicon nitride substrates, siiicon oxynitride substrates, tungsten substrates, and combinations thereof. Additionally, substrates comprising tungsten or nobie metals (e.g. platinum, palladium, rhodium, or gold) may be used.
  • the substrate is a metal film or metal nitride film.
  • the temperature of the reactor may be controlled by either controlling the temperature of the substrate holder or controlling the temperature of the reactor wail. Devices used to heat the substrate are known in the art.
  • the reactor is heated to a sufficient temperature to obtain the desired metal-nitride-containing film at a sufficient growth rate and with desired physical state and composition.
  • a non-limiting exemplary temperature range to which the reactor may be heated includes from approximately 200°C to approximately 700°C.
  • the deposition temperature may range from approximately 200°C to approximately 550°C.
  • the deposition temperature may range from approximately 400°C to approximately 600°C.
  • the pressure in the ALD reactor is approximately 0.1 Torr (13 Pa) to approximately 10 Torr (1300 Pa).
  • the disclosed methods utilize ch!orosilane precursors, preferably HfCI 4 or HCDS, and aminosi!ane precursors, preferably 3DMAS, 4DMAS, or tetrakis(ethylmethySamino) hafnium, to form SiN-containing or SiCN-containing films.
  • the films formed have very Sow (from approximately 0 to approximately 5 atomic %) chlorine or oxygen content.
  • the disclosed methods solve the problem about the film quality of SiN-containing films by atomic layer deposition at low temperature, and C insertion in SiN-containing films.
  • a dense SiCN film was deposited using an ALD method and trichlorosilane (3CS) and tris(dimethylamino)silane (3DMAS) precursors.
  • the reaction chamber was controlled at 5 Torr, 550°C, and 100 seem of Ar was continuously flowing.
  • the deposition process consisted of the following steps of: 1 ) supplying a pulse of approx.1 seem of 3CS to the reaction chamber for 10 seconds, 2) purging the 3CS precursor with 00 seem of Ar for 30 seconds, 3) supplying a pulse of approx.1 seem of 3DMAS to the reaction chamber for 0 seconds, 4) purging the 3DMAS precursors with 100 seem of Ar for 30 seconds. Sequences 1 ) through 4) were repeated until the deposited layer achieves suitable layer thickness.
  • the deposited film shows that the deposition rate is around
  • a dense SiCN film was deposited using an ALD method with hexach!orodisilane (HCDS) and tris(dimethylamino)silane (3DMAS) precursors and an ammonia (NH 3 ) reactant.
  • the reaction chamber was controlled at 5 Torr, 550°C, and 55 seem of Ar was continuously flowing.
  • the deposition process comprised the following steps of: 1 ) introducing a pulse of approx.1 seem of 3DMAS into the reaction chamber for 10 seconds, 2) purging the 3DMAS precursor with 55 seem of Ar for 30 seconds, 3) introducing a pulse of approx.1 seem of HCDS into the reaction chamber for 10 seconds, 4) purging the HCDS precursor with 55 seem of Ar for 30 seconds, 5) introducing amodule of approx. 50 seem of NH 3 into the reaction chamber for 0 seconds, and 6) purging the NH 3 reactant with 55 seem of Ar for 10 seconds. Sequences 1 ) through 6) were repeated until the deposited layer achieved suitable layer thickness.
  • the deposition rate and the refractive index of the deposited film are shown in FIG 1 .
  • the atomic composition percentage of silicon and nitrogen in the resulting film was greater than 40% but less than 45% for each, with an atomic composition percentage of approximately 10% for the carbon.
  • the atomic composition percentage of chlorine and oxygen in the resulting fi!m was 0% or greater but less than 5% for each.
  • the wet etch rate of the resulting film by a HF solution was 4.24 A/min.
  • a dense SiCN film was deposited using an ALD method with HCDS 3DMAS precursors and an ammonia (NH 3 ) reactant.
  • the reaction chamber was controlled at 5 Torr, 550°C, and 55 seem of Ar was continuously flowing.
  • the deposition process comprised the following steps of: 1 ) introducing a pulse of approx.1 seem of HCDS into the reaction chamber for 10 seconds, 2) purging the HCDS precursor with 55 seem of Ar for 30 seconds, 3) introducing a pulse of approx.1 seem of 3DMAS into the reaction chamber for 10 seconds, 4) purging the 3D AS precursor with 55 seem of Ar for 30 seconds, 5) introducing a pu!se of approx. 50 seem of NH 3 into the reaction chamber for 10 seconds, and 6) purging the NH 3 reactant with 55 seem of Ar for 10 seconds. Sequences 1 ) through 6) were repeated until the deposited layer achieved suitable layer thickness.
  • the deposition rate and the refractive index of the deposited film are shown in FIG 2.
  • the atomic composition percentage of silicon in the resulting film was greater than 45% but less than 50%
  • the atomic composition percentage of nitrogen in the resulting film was greater than 30% but less than 35%
  • the atomic composition percentage of carbon was greater than 15% but iess than 20%.
  • the atomic composition percentage of chlorine and oxygen in the resulting film was 0% or greater but less than 5% for each.
  • the wet etch rate of the resulting film by a HF solution was 0.54 A/min.
  • a dense SiCN film was deposited using an ALD method with HCDS and 3DMAS precursors.
  • the reaction chamber was controlled at 5 Torr, 550°C, and 55 seem of Ar was continuously flowing.
  • the deposition process comprised the following steps of: 1 ) introducing a pulse of approx.1 seem of 3DMAS into the reaction chamber for 10 seconds, 2) purging the
  • 3DMAS precursor with 55 seem of Ar for 30 seconds 3) introducing a pulse of approx.1 seem of HCDS into the reaction chamber for 10 seconds, and 4) purging the HCDS precursor with 55 seem of Ar for 30 seconds.
  • Sequences 1 ) through 4) were repeated until the deposited layer achieved suitable layer thickness.
  • the deposition rate and the refractive index of the deposited film are shown in FIG 3.
  • the atomic composition percentage of silicon in the resulting film was greater than 50% but less than 55%
  • the atomic composition percentage of carbon in the resulting film was greater than 30% but less than 35%
  • the atomic composition percentage of nitrogen was approximately 0%.
  • the atomic composition percentage of chlorine and oxygen in the resulting film was 1 % or greater but less than 5% for each.
  • the wet etch rate of the resulting film by a HF solution was 0.04 A/min.
  • a dense SiCN film was deposited using an ALD method with hexachlorodisilane (HCDS) and tetrakis(dimethylamino)silane (4D AS) precursors and an ammonia (NH 3 ) reactant.
  • the reaction chamber was controlled at 5 Torr, 550°C, and 55 seem of Ar was continuously flowing.
  • the deposition process comprised the following steps of: 1 ) introducing a pulse of approx.1 seem of 4DMAS into the reaction chamber for 10 seconds, 2) purging the 4DMAS precursor with 55 seem of Ar for 30 seconds, 3) introducing a pulse of approx.1 seem of HCDS into the reaction chamber for 10 seconds, 4) purging the HCDS precursor with 55 seem of A for 30 seconds, 5) introducing a pulse of approx. 50 seem of NH 3 into the reaction chamber for 10 seconds, and 6) purging the NH 3 reactant with 55 seem of Ar for 10 seconds. Sequences 1 ) through 6) were repeated until the deposited layer achieved suitable layer thickness.
  • the deposition rate and the refractive index of the deposited film are shown in FIG 4.
  • the atomic composition percentage of nitrogen in the resulting film was approximately 45%
  • the atomic composition percentage of silicon in the resulting film was greater than 40% but less than 45%
  • the atomic composition percentage of carbon was greater than 5% but less than 10%.
  • the atomic composition percentage of chlorine and oxygen in the resulting film was 0% or greater but less than 5% for each.
  • the wet etch rate of the resulting film by a HF solution was 5.76 A/min.
  • a dense SiCN film was deposited using an ALD method with HCDS and 4DMAS precursors and an ammonia (NH 3 ) reactant.
  • the reaction chamber was controlled at 5 Torr, 550°C, and 55 seem of Ar was continuously flowing.
  • the deposition process comprised the following steps of: 1 ) introducing amite of approx.1 seem of HCDS into the reaction chamber for 10 seconds, 2) purging the HCDS precursor with 55 seem of Ar for 30 seconds, 3) introducing a pulse of approx.1 seem of 4DMAS into the reaction chamber for 0 seconds, 4) purging the 4D AS precursor with 55 seem of Ar for 30 seconds, 5) introducing a pulse of approx. 50 seem of NH 3 into the reaction chamber for 10 seconds, and 6) purging the NH 3 reactant with 55 seem of Ar for 10 seconds. Sequences 1 ) through 6) were repeated untii the deposited iayer achieved suitable layer thickness.
  • the deposition rate and the refractive index of the deposited film are shown in FIG 5.
  • the atomic composition percentage of silicon in the resulting film was greater than 40% but less than 45%, the atomic composition percentage of nitrogen in the resulting film was approximately 40%, and the atomic composition percentage of carbon was greater than 10% but less than 15%.
  • the atomic composition percentage of chlorine and oxygen in the resulting film was 0% or greater but less than 5% for each.
  • the wet etch rate of the resulting film by a HF solution was 4.31 A/min.
  • a dense SiCN film was deposited using an ALD method with HCDS and 4DMAS precursors.
  • the reaction chamber was controlled at 5 Torr, 550°C, and 55 seem of Ar was continuously flowing.
  • the deposition process comprised the following steps of: 1 ) introducing a pulse of approx.1 seem of 4D AS into the reaction chamber for 10 seconds, 2) purging the 4DMAS precursor with 55 seem of Ar for 30 seconds, 3) introducing a pulse of approx.1 seem of HCDS into the reaction chamber for 0 seconds, and 4) purging the HCDS precursor with 55 seem of Ar for 30 seconds.
  • Sequences 1 ) through 4) were repeated until the deposited Iayer achieved suitable Iayer thickness.
  • the deposition rate and the refractive index of the deposited film are shown in FIG 6.
  • the atomic composition percentage of silicon in the resuiting film was greater than 50% but less than 55%
  • the atomic composition percentage of carbon in the resuiting film was greater than 30% but less than 35%
  • the atomic composition percentage of nitrogen was approximately 10%.
  • the atomic composition percentage of chlorine and oxygen in the resuiting film was 1 % or greater but less than 5% for each.
  • the wet etch rate of the resuiting film by a HF solution was 0.15 A/min.
  • a dense SiCN film was deposited using an ALD method with hexachlorodisilane (HCDS) and bis(diethylamino)silane (BDEAS) precursors and an ammonia (NH 3 ) reactant.
  • the reaction chamber was controlled at 5 Torr, 550°C, and 55 seem of A was continuously flowing.
  • the deposition process comprised the following steps of: 1 ) introducing a pulse of approx.1 seem of BDEAS into the reaction chamber for 10 seconds, 2 ⁇ purging the BDEAS precursor with 55 seem of Ar for 30 seconds, 3) introducing amite of approx.1 seem of HCDS into the reaction chamber for 10 seconds, 4) purging the HCDS precursor with 55 seem of Ar for 30 seconds, 5) introducing a pulse of approx. 50 seem of NH 3 into the reaction chamber for 10 seconds, and 6) purging the NH 3 reactant with 55 seem of Ar for 10 seconds. Sequences 1 ) through 6) were repeated until the deposited layer achieved suitable layer thickness.
  • the deposition rate and the refractive index of the deposited film are shown in FIG 7.
  • the atomic composition percentage of silicon in the resuiting film was slightly greater than approximately 40%
  • the atomic composition percentage of nitrogen in the resuiting film was slightly !ess than 40%
  • the atomic composition percentage of carbon was slightly greater than 1 5%.
  • the atomic composition percentage of chlorine and oxygen in the resulting film was0% or greater but !ess than 5% for each.
  • the wet etch rate of the resulting film by a HF solution was 1 .65 A/min.
  • a dense SiCN film was deposited using an ALD method with HCDS and BDEAS precursors and an ammonia (NH 3 ) reactant.
  • the reaction chamber was controlled at 5 Torr, 550°C, and 55 seem of Ar was
  • the deposition process comprised the following steps of: 1 ) introducing a pulse of approx.1 seem of HCDS into the reaction chamber for 10 seconds, 2) purging the HCDS precursor with 55 seem of Ar for 30 seconds, 3) introducing a pulse of approx.1 seem of BDEAS into the reaction chamber for 10 seconds, 4) purging the BDEAS precursor with 55 seem of Ar for 30 seconds, 5 ⁇ introducing a pulse of approx. 50 seem of NH 3 into the reaction chamber for 10 seconds, and 6) purging the NH 3 reactant with 55 seem of Ar for 10 seconds. Sequences 1 ) through 6) were repeated until the deposited layer achieved suitable layer thickness.
  • the deposition rate and the refractive index of the deposited film are shown in FIG 8.
  • the atomic composition percentage of silicon in the resulting film was approximately 45%
  • the atomic composition percentage of nitrogen in the resulting film was approximately 30%
  • the atomic composition percentage of carbon was approximately 20%.
  • the atomic composition percentage of chlorine and oxygen in the resulting film was 0% or greater but less than 5% for each.
  • the wet etch rate of the resulting film by a HF solution was 0.54 A/min.
  • a dense SiCN film was deposited using an ALD method with HCDS and BDEAS precursors.
  • the reaction chamber was controlled at 5 Torr, 550°C, and 55 seem of Ar was continuously flowing.
  • the deposition process comprised the following steps of: 1 ) introducing a pulse of approx.1 seem of BDEAS into the reaction chamber for 10 seconds, 2) purging the BDEAS precursor with 55 seem of Ar for 30 seconds, 3) introducing a pulse of approx.1 seem of HCDS into the reaction chamber for 10 seconds, and 4) purging the HCDS precursor with 55 seem of Ar for 30 seconds.
  • Sequences 1 ) through 4) were repeated until the deposited iayer achieved suitable layer thickness.
  • the carbon content of the resulting film was too high to allow for the measurement of deposition rate and refractive index by eilipsometry.
  • the atomic composition percentage of silicon in the resulting film was greater than 55% but less than 60%, the atomic composition percentage of carbon in the resulting film was greater than 30% but less than 35%, and the atomic composition percentage of nitrogen was slightly greater than 5%.
  • the atomic composition percentage of chlorine and oxygen in the resulting film was 0% or greater but less than 5% for each.
  • the wet etch rate of the resulting film by a HF solution was 0.15 A/min.

Abstract

Disclosed are methods of forming metal-nitride-containing films from the combination of amino-metal precursors and halogenated metal precursors, preferably forming SiN-containing films from the combination of aminosilane precursors and chlorosilane precursors. Varying the sequential reaction of the amino-metal precursors and halogenated metal precursors provide for the formation of metal-nitride-containing films having varying stoichiometry. In addition, the metal-nitride-containing film composition may be modified based upon the structure of aminometal precursor. The disclosed processes may be thermal processes or plasma processes at low temperatures.

Description

METAL NITRIDE CONTAINING FILM DEPOSITION
USING COMBINATION OF AMINO-METAL AND HALOGENATED METAL PRECURSORS
Cross-Reference to Related Applications
This app!ication claims the benefit of U.S. Provisional Application No. 61/320,236, filed April 1 , 2010, the entire contents of which are incorporated herein by reference.
Technical Field
Disclosed are methods of forming metai-nitride-containing films from the combination of amino-metal precursors and halogenated metal precursors, preferably forming SiN-containing films from the combination of aminosilane precursors and chlorosilane precursors. Varying the sequential reaction of the amino-metal precursors and halogenated metai precursors provide for the formation of metal-nitride-containing films having varying stoichiometry. In addition, the metal-nitride-containing film composition may be modified based upon the structure of aminometai precursor. The disclosed processes may be thermal processes or plasma processes at low temperature.
Background
Metal-nitride-containing films, such as silicon nitride (SiN) films, are widely used in semiconductor devices and ultra-large-scale integrated (ULS!) circuits. According to downsizing and the growing sophistication of electronic devices requiring increasingly higher LSI mounting densities, a SiN film is required to improve its film qualities against current leakage. In addition, SiCN film is also used as the etch stopper in a dual-damascene structure for Cu wiring.
Silicon nitride (SiN) films have been investigated to apply as etch stop/liner layer within a damascene at the back end of the line (BEOL) process. Within floating gate transistors, the inter-gate dielectric layer may comprise Si02 or SiN, for examp!e. In addition, carbon doping the SiN layer provides high etch resistance.
As the size of large scale integrations (LSIs) is scaled down, film depth should be thinner requiring a more precisely controlled process, for example atomic layer deposition (ALD). In addition, a decrease in deposition temperature is required. ALD is widely used for many
processes, for example Si02, SiN and metal films. See, e.g., US Pat. No. 7648927. However, the deposition rate tends to be Sower than chemical vapor deposition (CVD). When the deposition temperature is lower, the deposition rate and the film quality of SiN have been worse.
Many articles have reported deposition of high quality SiN and SiCN films by using chlorosilane and activated NH3 by PECVD, PEALD and introducing amine, CH4 or C2H4 as a carbon source (see e.g.,
WO2009/149167 and US2008/0213479).
A need remains for more precisely controlled processes to deposit metal-nitride-containing films.
Notation and Nomenclature
Certain abbreviations, symbols, and terms are used throughout the following description and claims and include: the abbreviation "A" refers to Angstroms and 1 Angstrom = 100 picometers; the abbreviation "PECVD" refers to plasma enhanced chemical vapor deposition; the abbreviation "CVD" refers to chemical vapor deposition; the abbreviation "RF" refers to radiofrequency, the abbreviation "DR" refers to deposition rate, and the abbreviation "Rl" refers to refractive index.
The term "alkyl group" refers to saturated functional groups containing exclusively carbon and hydrogen atoms. Further, the term "alkyl group" refers to linear, branched, or cyclic alkyl groups. Examples of linear alky! groups include, without limitation, methyl groups, ethyl groups, propyl groups, butyl groups, etc. Examples of branched alkyl groups include, without limitation, t-butyl. Examples of cyclic alkyl groups include without limitation, cyciopropyi groups, cyclobuty! groups, cyclopentyi groups, cyclohexyi groups, etc.
As used herein, the abbreviation "Me" refers to a methyl group; the abbreviation "Et" refers to an ethyi group; the abbreviation "Pr" refers to a propyl group; the abbreviation "nPr" refers to a chain propyl group; the abbreviation "iPr" refers to an isopropyl group; the abbreviation "Bu" refers to a butyl (n-butyl) group; the abbreviation "tBu" refers to a tert-buty! group; the abbreviation "sBu" refers to a sec-butyl group; the abbreviation "iBu" refers to an iso-butyl group; and the abbreviation "TMS" refers to a trimethylsilyl group.
The standard abbreviations of the elements from the periodic table of elements are used herein. It should be understood that elements may be referred to by these abbreviations (e.g., Si refers to silicon, C refers to carbon, etc.).
Summary
Disclosed are methods of forming metal-nitride-containing films. A halogenaied metal precursor is introduced into an ALD reactor containing at least one substrate. Excess halogenaied metal precursor is
subsequently purged from the reactor. An amino-metal precursor is introduced into the reactor. Excess amino-metal precursor is subsequently from the reactor. A reactant may optionally be introduced into the reactor. Excess optional reactant is subsequently purged from the reactor. The metal of the halogenaied metal precursor and the metal of the amino-metal precursor may be the same or different.
Also disclosed are methods of forming metal-nit de-containing films. A halogenaied metal precursor is introduced into an ALD reactor containing at least one substrate. Excess halogenated metal precursor is
subsequently purged from the reactor. An amino-metal precursor is introduced into the reactor. Excess amino-metal precursor is subsequently from the reactor. A reactant is introduced into the reactor. Excess reactant is subsequently purged from the reactor. The metal of the halogenated metal precursor and the metal of the amino-metal precursor may be the same or different.
Also disclosed are methods of forming silicon-nitride-containing films. A chlorosilane precursor is introduced into an ALD reactor containing at least one substrate. Excess chlorosiiane precursor is subsequently purged from the reactor. An aminosilane precursor is introduced into the reactor. Excess aminosilane precursor is subsequently from the reactor. A reactant may optionally be introduced into the reactor. Excess optional reactant is subsequently purged from the reactor.
Also disclosed are methods of forming silicon-nitride-containing films. A chlorosilane precursor is introduced into an ALD reactor containing at least one substrate. Excess chlorosilane precursor is subsequently purged from the reactor. An aminosilane precursor is introduced into the reactor. Excess aminosilane precursor is subsequently from the reactor. A reactant is introduced into the reactor. Excess reactant is subsequently purged from the reactor.
Each of the disclosed methods may further include one or more of the following aspects:
• the reactant being selected from the group consisting of N2, NH3, N2H4, NMeH2, NEtH2, NMe2H, NEt2H, NMe3, NEt3, MeHNNH2, Me2NNH2, phenyl hydrazine, and mixtures thereof;
• the reactant being NH3;
· producing metal-nitride-containing films having specified
stoichiometry by varying the order of the method steps;
• the halogenated precursors being chlorometal precursors;
• the metal-nitride-containing film being a metal carbonitride film
containing one or two metals;
· the metal being selected from transition metal, metal or non-metal elements; • the metal being boron or phosphorus;
• the metal-nitride-containing film being a silicon-nitride-containing film;
• the halogenated metal precursor being a ch!orosiiane precursor; · the amino-metaS precursor being an aminosilane precursor;
• the silicon-nitride-containing film being carbon-doped SiN film;
• the chlorosilane precursor having the formula SiaHbClc, wherein b+c = 2a+2;
• the chlorosilane precursors being introduced as a mixture;
· the aminosilane precursors having the formula H_i_xSi{NR'R")x,
wherein x = 1 , 2, 3, or 4, R' and R" are independently selected from H or an alkyl group, and R' and R" may be linked to form a ring structure;
• the aminosilane precursors comprising an aminochlorosilane or an aminoalkyisilane;
• the aminochlorosilane precursors having the formula CI4.xSi(NR'R")x, wherein x = 2 or 3, R' and R" are independently selected from H or an alkyl group, and R' and R" may be linked to form a ring structure; and
* the aminoalkyisilane precursors having a formula R"VxSi(NR'R")x, wherein x = 1 , 2, or 3, R' and R" are independently selected from H or an alkyl group, R' and R" may be linked to form a ring structure, and R'" group is an alkyl group having less than 3 carbons. Brief Description of the Drawings
For a further understanding of the nature and objects of the present invention, reference should be made to the following detailed description, taken in conjunction with the accompanying drawings, wherein:
FIG 1 is a graph showing the deposition rate and refractive index of a SiCN film deposited using tris(dimethyiamino)silane (3DMAS) and hexachlorodisilane (HCDS) according to the disclosed method versus the distance of the film from the inlet;
FIG 2 is a graph showing the deposition rate and refractive index versus distance of a SiCN film deposited using 3DMAS and HCDS according to one alternative of the disclosed method;
FIG 3 is a graph showing the deposition rate and refractive index versus distance of a SiCN film deposited using 3D AS and HCDS according to a second alternative of the disclosed method;
FIG 4 is a graph showing the deposition rate and refractive index of a SiCN film deposited using tetrakis(dimethylamino)silane (4DMAS) and hexachlorodisilane (HCDS) according to the disclosed method versus the distance of the film from the inlet;
FIG 5 is a graph showing the deposition rate and refractive index versus distance of a SiCN film deposited using 4DMAS and HCDS according to one alternative of the disclosed method;
FIG 6 is a graph showing the deposition rate and refractive index versus distance of a SiCN film deposited using 4DMAS and HCDS according to a second alternative of the disclosed method;
FIG 7 is a graph showing the deposition rate and refractive index of a SiCN film deposited using bis(diethyiamino)silane (BDEAS) and hexachlorodisilane (HCDS) according to the disclosed method versus the distance of the film from the inlet; and
FIG 8 is a graph showing the deposition rate and refractive index versus distance of a SiCN film deposited using BDEAS and HCDS according to one alternative of the disclosed method.
Detailed Description of Preferred Embodiments
Disclosed are ALD methods of forming metal-nitride-containing films using the alternate supply of amino-metai precursors and halogenated metal precursors. The sequential reaction of the amino-metal precursors with the halogenated metal precursors produces a dense metal-rich film. The metal of the haiogenated metal precursor may be the same as or different from the metai of the amino-metal precursor.
Also disclosed are ALD methods of forming silicon-nitride-containing films, preferably silicon carbonitride films, using the alternate supply of aminosilane precursors and chlorosilane precursors under thermal conditions or low temperature plasma conditions. The sequential reaction of the aminosilane precursors with the chlorosilane precursors produces a dense silicon-rich film at temperatures lower than those of many prior art silicon nitride film deposition processes. The silicon carbonitride films may alternatively be referred to as carbon-doped silicon-nitride films. One of ordinary skill in the art will recognize that the level of carbon in the silicon- nitride film determines the appropriate nomenclature, with the amount of carbon in carbon-doped silicon nitride films typically being less than the amount of carbon in silicon carbonitride films. However, one of ordinary skill in the art will further recognize that the exact percentage of carbon in the film which determines the appropriate nomenclature is not defined and will vary from person to person.
The disclosed methods form metal-nitride-containing films, such as SiN, or a metal carbonitride films, such as SiCN, from amino-metai and haiogenated metal precursors by ALD. The metal-nitride-containing film may be a metal carbonitride film containing one or two metals. For example, the metal carbonitride film may be a SiHfCN film. Alternatively, the SiN film may be carbon-doped.
As will be described in further detail in Examples 2-4, metal-nitride- containing films having specified stoichiometry may be produced by varying the order of the disclosed method steps. Furthermore, the duration of the disclosed method steps may also be varied in order to "tune" the resulting film.
The haiogenated metal precursors are introduced into an ALD reactor containing one or more substrates. The haiogenated metal precursors may be introduced into the ALD reactor before or after the amino-metal precursor. The conditions within the reactor permit at ieast part of the haiogenated metal precursors to self adsorb on the substrates. One of ordinary skill in the art will recognize that the substrate properties will define whether the halogenated metal precursor undergoes
physiadsorption or chemisorption in this step. For example, if the haiogenated metal precursors are introduced into the reactor after the amino-metal precursors, at Ieast part of the halogenated metal precursors will react/chemisorp with the portion of the amino-metal precursors deposited in the prior step. Any non-adsorbed or "excess" halogenated metal precursor is purged out of the reactor. The halogenated metal precursors are reactive with NH3/amino-metal precursors at low
temperature.
The halogenated metal precursors may be chlorometal precursors. The meta! of the halogenated metal or chlorometal precursors may be any transition metal, metal, or non-metal elements as commonly defined on the periodic table of elements. Preferred transition metals include but are not limited to Hf. Preferred metals include but are not limited to Zn. Preferred non-metals include but are not limited to B, Si, and P. The halogenated metal precursor may be applied as a mixture of two or more halogenated metal precursors. Preferably, the halogenated metal precursors are chiorosilane precursors. Exemplary chlorosilane precursors have the formula SiaHbCIc, wherein b+c = 2a+2. Exemplary chlorosilane precursors include hexachlorodisilane (HCDS), SiCI4, SiHCI3, 5ί2Η5ΟΙ, etc., and mixtures thereof, such as HCDS and SiCI4 or HCDS and SiHCI3.
Preferably, the halogenated metai precursor comprises HfC!4 or HCDS, and more preferably HCDS.
The amino-metal precursors are introduced into the reactor. The conditions within the reactor permit at Ieast part of the amino-metal precursors to self adsorb on the substrates. The amino-metal precursors may be introduced into the ALD reactor before or after the halogenated metal precursors. Once again, one of ordinary skill in the art will recognize that the substrate properties will define whether the amino-metal precursor undergoes physiadsorption or chemisorption in this step. For example, if the amino-metal precursors are introduced into the reactor after the ha!ogenated metal precursors, at least part of the amino-metal precursors will react/chemisorp with the portion of the haiogenated metal precursors deposited in the prior step. Any non-adsorbed or "excess" amino-metai precursor is then purged out of the reactor. The amino-metal precursors may act as both a C-source and N-source, as opposed to the prior art NH3 precursors which only act as a N-source. The alky!amino groups of the aminometal precursors serve as good leaving groups and lead to good adsorption. Varying the ligands of the aminometal precursors provides the ability to modify the carbon content of the metal-nitride-containing fi!m.
The metal of the amino-metal precursors may be any transition metal, metal, or non-metal elements as commonly defined on the periodic table of elements. Preferred transition metals include but are not limited to Hf. Preferred metals include but are not limited to Zn. Preferred non- metals include but are not limited to B, Si, and P. The amino-metal precursor may be applied as a mixture of two or more amino-metal precursors. The amino-metal precursor may be aminosilane precursors. Exemplary aminosilane precursors have the formula H4,xSi(NR'R")x, wherein x = 1 , 2, 3, or 4, R' and R" are independently selected from H or an alkyl group, and R' and R" may be linked to form a ring structure.
Alternatively, the aminosilane precursor may be an aminochlorosilane precursor or an aminoalkylsilane precursor. Exemplary aminochlorosilane precursors have the formula CI4->iSi(NR'R")x, wherein x = 2 or 3, and R' and R" are as previously defined. Exemplary aminoalkylsilane precursors have the formula R'"4.xSi{NR'R")x wherein x = , 2, or 3, R' and R" are as previously defined, and R"' group is an alkyl group having less than 3 carbons. Preferably, the amino-metal precursor is bis{diethylamino)silane (BDEAS), tris(dimethylamino)siSane (3DMAS), tetrakis(dimethy!amino) silane (4DMAS), or tetrakis(ethylmethylamino)hafnium, and more
preferably 3DMAS and/or 4DMAS.
The halogenated metal precursors and aminometal precursors (collectively, the "precursors") are each individually introduced into the reactor in vapor form. In this context, "individually" and "each" refers to the specified class of precursors, for example "the halogenated metal precursors", which may consist of one or more halogenated precursors. In the following paragraphs, individually is not intended to mean that the vapors of only one halogenated metal precursor are introduced into the reactor.
The precursors may be individually fed in liquid state to a vaporizer where they are each individually vaporized before introduction into the reactor. Prior to vaporization, each of the precursors may optionally be mixed with one or more solvents. The solvents may be selected from the group consisting of toluene, ethyl benzene, xylene, mesitylene, decane, dodecane, octane, hexane, pentane, or others. The resulting concentration may range from approximately 0.05 M to approximately 2 M.
Alternatively, the precursors may be individually vaporized by passing a carrier gas into a container containing each of the precursors or by bubbling the carrier gas into each of the precursors. Each of the precursors may optionally be mixed in the container with one or more solvents. The carrier gas and individual precursors are then introduced into the reactor as a vapor. The carrier gas may include, but is not limited to, Ar, He, N2,and mixtures thereof. Bubbling with a carrier gas may also remove any dissolved oxygen present in the precursors' solution.
If necessary, the container may be heated to a temperature that permits the precursors to be in liquid phase and to have a sufficient vapor pressure. The container may be maintained at temperatures in the range of, for example, 0°C to 1 50°C. Those skilled in the art recognize that the temperature of the container may be adjusted in a known manner to control the amount of precursor vaporized. The vapor of each precursor may be introduced into the reactor for a time period ranging from approximate!y 0.01 seconds to approximately 60 seconds, alternatively from approximately 5 seconds to approximately 25 seconds, alternatively from approximately 10 seconds to approximately 20 seconds.
In one embodiment, a reactant may be introduced into the reactor, where it reacts with the seif adsorbed layers on the substrates. Any non- reacted or "excess" reactant is then purged out of the reactor. The reactant may be N2, NH3, N2H4, NMeH2, NEtH2, NMe2H, NEt2H, NMe3, NEt3, MeHNNH2, Me2NNH2, phenyl hydrazine, and mixtures thereof. Preferably, the reactant is NH3. However, as will be described in further detail in the Examples that follow, inclusion of the optional reactant steps" will depend upon the desired stoichiometric ratio of elements in the resulting metal- nitride-containing film.
The reactant may be treated by plasma in order to decompose the reactant into its radical form. The plasma may be generated or present within the reactor itself. Alternatively, the plasma may generally be at a location removed from the reactor, for instance, in a remotely located plasma system. One of skill in the art will recognize methods and apparatus suitable for such plasma treatment.
For example, the reactant may be introduced into a direct plasma reactor, which generates a plasma in the reactor, to produce the plasma- treated reactant in the reactor. Exemplary direct plasma reactors include the Titan™ PECVD System produced by Trion Technologies. The reactant may be introduced and held in the reactor prior to plasma processing.
Alternatively, the plasma processing may occur simultaneously with the introduction of reactant. In-situ plasma is typically a 3.56 MHz RF capacitively coupled plasma that is generated between the showerhead and the substrate holder. The substrate or the showerhead may be the powered electrode depending on whether positive ion impact occurs.
Typical applied powers in in-situ plasma generators are from approximately 100 W to approximately 1000 W. The disassociation of the reactant using in-situ plasma is typically less than achieved using a remote plasma source for the same power input and is therefore not as efficient in reactant disassociation as a remote plasma system, which may be beneficial for the deposition of metai-nitride-containing films on substrates easily damaged by plasma.
Alternatively, the plasma-treated reactant may be produced outside of the reactor. The MKS Instruments' ASTRON®i reactive gas generator may be used to treat the reactant prior to passage into the reactor.
Operated at 2.45 GHz, 7kW plasma power, and a pressure ranging from approximately 3 Torr to approximately 10 Torr, the reactant NF3 may be decomposed into three F" radicals with more than 96% decomposing efficiency. Preferably, the remote piasma may be generated with a power ranging from about 1 kW to about 10 kW, more preferably from about 2.5 kW to about 7.5 kW.
The ALD reactor may be a heated vesse! which has at least one or more substrates disposed within it. The reactor has an outlet which may be connected to a vacuum pump to allow by-products to be removed from the reactor, or to allow the pressure within the reactor to be modified or regulated. Examples of suitable ALD reactors include, without limitation, a parallel-plate type reactor, a cold-wall type reactor, a hot-wall type reactor, a single-wafer reactor, a multi-wafer reactor, a direct plasma reactor, or other types of deposition systems under conditions suitable to cause the precursors to react and form the layers.
Generally, the reactor contains one or more substrates onto which the metal-nitride-containing films will be deposited. For example, the reactor may contain from 1 to 200 silicon wafers having from 25.4 mm to 450 mm diameters. The substrates may be any suitable substrate used in semiconductor, photovoltaic, flat panel, or LCD-TFT device manufacturing. The substrates may contain one or more additional layers of materials, which may be present from a previous manufacturing step. Dielectric and conductive layers are examples of these. Within the scope of this
application, all of the substrate and any layers deposited on the substrate are collectively included within the term substrate. Examples of suitable substrates include without limitation, metal substrates, metal nitride substrates, silicon substrates, silica substrates, silicon nitride substrates, siiicon oxynitride substrates, tungsten substrates, and combinations thereof. Additionally, substrates comprising tungsten or nobie metals (e.g. platinum, palladium, rhodium, or gold) may be used. Preferably, the substrate is a metal film or metal nitride film.
The temperature of the reactor may be controlled by either controlling the temperature of the substrate holder or controlling the temperature of the reactor wail. Devices used to heat the substrate are known in the art. The reactor is heated to a sufficient temperature to obtain the desired metal-nitride-containing film at a sufficient growth rate and with desired physical state and composition. A non-limiting exemplary temperature range to which the reactor may be heated includes from approximately 200°C to approximately 700°C. When a plasma deposition process is utilized, the deposition temperature may range from approximately 200°C to approximately 550°C. Alternatively, when a thermal process is performed, the deposition temperature may range from approximately 400°C to approximately 600°C.
The pressure in the ALD reactor is approximately 0.1 Torr (13 Pa) to approximately 10 Torr (1300 Pa).
In one preferred embodiment, the disclosed methods utilize ch!orosilane precursors, preferably HfCI4 or HCDS, and aminosi!ane precursors, preferably 3DMAS, 4DMAS, or tetrakis(ethylmethySamino) hafnium, to form SiN-containing or SiCN-containing films. The films formed have very Sow (from approximately 0 to approximately 5 atomic %) chlorine or oxygen content. The disclosed methods solve the problem about the film quality of SiN-containing films by atomic layer deposition at low temperature, and C insertion in SiN-containing films.
The disclosed methods provide the following advantages over the existing methods:
- Carbon insertion into SiN film with tunable combination of
aminosi!ane and chlorosilane
The reasons are:
- A ratio change in the combination makes different composition films.
Examples
The following non-limiting examples are provided to further illustrate embodiments of the invention. However, the examples are not intended to be all inclusive and are not intended to limit the scope of the inventions described herein.
Example 1
A dense SiCN film was deposited using an ALD method and trichlorosilane (3CS) and tris(dimethylamino)silane (3DMAS) precursors. The reaction chamber was controlled at 5 Torr, 550°C, and 100 seem of Ar was continuously flowing. The deposition process consisted of the following steps of: 1 ) supplying a pulse of approx.1 seem of 3CS to the reaction chamber for 10 seconds, 2) purging the 3CS precursor with 00 seem of Ar for 30 seconds, 3) supplying a pulse of approx.1 seem of 3DMAS to the reaction chamber for 0 seconds, 4) purging the 3DMAS precursors with 100 seem of Ar for 30 seconds. Sequences 1 ) through 4) were repeated until the deposited layer achieves suitable layer thickness.
The deposited film shows that the deposition rate is around
0.6A/cycle. The refractive index is above 2.1 . Example 2a
A dense SiCN film was deposited using an ALD method with hexach!orodisilane (HCDS) and tris(dimethylamino)silane (3DMAS) precursors and an ammonia (NH3) reactant. The reaction chamber was controlled at 5 Torr, 550°C, and 55 seem of Ar was continuously flowing. The deposition process comprised the following steps of: 1 ) introducing a pulse of approx.1 seem of 3DMAS into the reaction chamber for 10 seconds, 2) purging the 3DMAS precursor with 55 seem of Ar for 30 seconds, 3) introducing a pulse of approx.1 seem of HCDS into the reaction chamber for 10 seconds, 4) purging the HCDS precursor with 55 seem of Ar for 30 seconds, 5) introducing a puise of approx. 50 seem of NH3 into the reaction chamber for 0 seconds, and 6) purging the NH3 reactant with 55 seem of Ar for 10 seconds. Sequences 1 ) through 6) were repeated until the deposited layer achieved suitable layer thickness.
The deposition rate and the refractive index of the deposited film are shown in FIG 1 . The atomic composition percentage of silicon and nitrogen in the resulting film was greater than 40% but less than 45% for each, with an atomic composition percentage of approximately 10% for the carbon. The atomic composition percentage of chlorine and oxygen in the resulting fi!m was 0% or greater but less than 5% for each. The wet etch rate of the resulting film by a HF solution was 4.24 A/min.
Example 2b
A dense SiCN film was deposited using an ALD method with HCDS 3DMAS precursors and an ammonia (NH3) reactant. The reaction chamber was controlled at 5 Torr, 550°C, and 55 seem of Ar was continuously flowing. The deposition process comprised the following steps of: 1 ) introducing a pulse of approx.1 seem of HCDS into the reaction chamber for 10 seconds, 2) purging the HCDS precursor with 55 seem of Ar for 30 seconds, 3) introducing a pulse of approx.1 seem of 3DMAS into the reaction chamber for 10 seconds, 4) purging the 3D AS precursor with 55 seem of Ar for 30 seconds, 5) introducing a pu!se of approx. 50 seem of NH3 into the reaction chamber for 10 seconds, and 6) purging the NH3 reactant with 55 seem of Ar for 10 seconds. Sequences 1 ) through 6) were repeated until the deposited layer achieved suitable layer thickness.
The deposition rate and the refractive index of the deposited film are shown in FIG 2. The atomic composition percentage of silicon in the resulting film was greater than 45% but less than 50%, the atomic composition percentage of nitrogen in the resulting film was greater than 30% but less than 35%, and the atomic composition percentage of carbon was greater than 15% but iess than 20%. The atomic composition percentage of chlorine and oxygen in the resulting film was 0% or greater but less than 5% for each. The wet etch rate of the resulting film by a HF solution was 0.54 A/min. Example 2c
A dense SiCN film was deposited using an ALD method with HCDS and 3DMAS precursors. The reaction chamber was controlled at 5 Torr, 550°C, and 55 seem of Ar was continuously flowing. The deposition process comprised the following steps of: 1 ) introducing a pulse of approx.1 seem of 3DMAS into the reaction chamber for 10 seconds, 2) purging the
3DMAS precursor with 55 seem of Ar for 30 seconds, 3) introducing a pulse of approx.1 seem of HCDS into the reaction chamber for 10 seconds, and 4) purging the HCDS precursor with 55 seem of Ar for 30 seconds.
Sequences 1 ) through 4) were repeated until the deposited layer achieved suitable layer thickness.
The deposition rate and the refractive index of the deposited film are shown in FIG 3. The atomic composition percentage of silicon in the resulting film was greater than 50% but less than 55%, the atomic composition percentage of carbon in the resulting film was greater than 30% but less than 35%, and the atomic composition percentage of nitrogen was approximately 0%. The atomic composition percentage of chlorine and oxygen in the resulting film was 1 % or greater but less than 5% for each. The wet etch rate of the resulting film by a HF solution was 0.04 A/min.
Example 3a
A dense SiCN film was deposited using an ALD method with hexachlorodisilane (HCDS) and tetrakis(dimethylamino)silane (4D AS) precursors and an ammonia (NH3) reactant. The reaction chamber was controlled at 5 Torr, 550°C, and 55 seem of Ar was continuously flowing. The deposition process comprised the following steps of: 1 ) introducing a pulse of approx.1 seem of 4DMAS into the reaction chamber for 10 seconds, 2) purging the 4DMAS precursor with 55 seem of Ar for 30 seconds, 3) introducing a pulse of approx.1 seem of HCDS into the reaction chamber for 10 seconds, 4) purging the HCDS precursor with 55 seem of A for 30 seconds, 5) introducing a pulse of approx. 50 seem of NH3 into the reaction chamber for 10 seconds, and 6) purging the NH3 reactant with 55 seem of Ar for 10 seconds. Sequences 1 ) through 6) were repeated until the deposited layer achieved suitable layer thickness.
The deposition rate and the refractive index of the deposited film are shown in FIG 4. The atomic composition percentage of nitrogen in the resulting film was approximately 45%, the atomic composition percentage of silicon in the resulting film was greater than 40% but less than 45%, and the atomic composition percentage of carbon was greater than 5% but less than 10%. The atomic composition percentage of chlorine and oxygen in the resulting film was 0% or greater but less than 5% for each. The wet etch rate of the resulting film by a HF solution was 5.76 A/min.
Example 3b
A dense SiCN film was deposited using an ALD method with HCDS and 4DMAS precursors and an ammonia (NH3) reactant. The reaction chamber was controlled at 5 Torr, 550°C, and 55 seem of Ar was continuously flowing. The deposition process comprised the following steps of: 1 ) introducing a puise of approx.1 seem of HCDS into the reaction chamber for 10 seconds, 2) purging the HCDS precursor with 55 seem of Ar for 30 seconds, 3) introducing a pulse of approx.1 seem of 4DMAS into the reaction chamber for 0 seconds, 4) purging the 4D AS precursor with 55 seem of Ar for 30 seconds, 5) introducing a pulse of approx. 50 seem of NH3 into the reaction chamber for 10 seconds, and 6) purging the NH3 reactant with 55 seem of Ar for 10 seconds. Sequences 1 ) through 6) were repeated untii the deposited iayer achieved suitable layer thickness.
The deposition rate and the refractive index of the deposited film are shown in FIG 5. The atomic composition percentage of silicon in the resulting film was greater than 40% but less than 45%, the atomic composition percentage of nitrogen in the resulting film was approximately 40%, and the atomic composition percentage of carbon was greater than 10% but less than 15%. The atomic composition percentage of chlorine and oxygen in the resulting film was 0% or greater but less than 5% for each. The wet etch rate of the resulting film by a HF solution was 4.31 A/min. Example 3c
A dense SiCN film was deposited using an ALD method with HCDS and 4DMAS precursors. The reaction chamber was controlled at 5 Torr, 550°C, and 55 seem of Ar was continuously flowing. The deposition process comprised the following steps of: 1 ) introducing a pulse of approx.1 seem of 4D AS into the reaction chamber for 10 seconds, 2) purging the 4DMAS precursor with 55 seem of Ar for 30 seconds, 3) introducing a pulse of approx.1 seem of HCDS into the reaction chamber for 0 seconds, and 4) purging the HCDS precursor with 55 seem of Ar for 30 seconds.
Sequences 1 ) through 4) were repeated until the deposited Iayer achieved suitable Iayer thickness. The deposition rate and the refractive index of the deposited film are shown in FIG 6. The atomic composition percentage of silicon in the resuiting film was greater than 50% but less than 55%, the atomic composition percentage of carbon in the resuiting film was greater than 30% but less than 35%, and the atomic composition percentage of nitrogen was approximately 10%. The atomic composition percentage of chlorine and oxygen in the resuiting film was 1 % or greater but less than 5% for each. The wet etch rate of the resuiting film by a HF solution was 0.15 A/min.
Example 4a
A dense SiCN film was deposited using an ALD method with hexachlorodisilane (HCDS) and bis(diethylamino)silane (BDEAS) precursors and an ammonia (NH3) reactant. The reaction chamber was controlled at 5 Torr, 550°C, and 55 seem of A was continuously flowing. The deposition process comprised the following steps of: 1 ) introducing a pulse of approx.1 seem of BDEAS into the reaction chamber for 10 seconds, 2} purging the BDEAS precursor with 55 seem of Ar for 30 seconds, 3) introducing a puise of approx.1 seem of HCDS into the reaction chamber for 10 seconds, 4) purging the HCDS precursor with 55 seem of Ar for 30 seconds, 5) introducing a pulse of approx. 50 seem of NH3 into the reaction chamber for 10 seconds, and 6) purging the NH3 reactant with 55 seem of Ar for 10 seconds. Sequences 1 ) through 6) were repeated until the deposited layer achieved suitable layer thickness.
The deposition rate and the refractive index of the deposited film are shown in FIG 7. The atomic composition percentage of silicon in the resuiting film was slightly greater than approximately 40%, the atomic composition percentage of nitrogen in the resuiting film was slightly !ess than 40%, and the atomic composition percentage of carbon was slightly greater than 1 5%. The atomic composition percentage of chlorine and oxygen in the resulting film was0% or greater but !ess than 5% for each. The wet etch rate of the resulting film by a HF solution was 1 .65 A/min.
Example 4b
A dense SiCN film was deposited using an ALD method with HCDS and BDEAS precursors and an ammonia (NH3) reactant. The reaction chamber was controlled at 5 Torr, 550°C, and 55 seem of Ar was
continuously flowing. The deposition process comprised the following steps of: 1 ) introducing a pulse of approx.1 seem of HCDS into the reaction chamber for 10 seconds, 2) purging the HCDS precursor with 55 seem of Ar for 30 seconds, 3) introducing a pulse of approx.1 seem of BDEAS into the reaction chamber for 10 seconds, 4) purging the BDEAS precursor with 55 seem of Ar for 30 seconds, 5} introducing a pulse of approx. 50 seem of NH3 into the reaction chamber for 10 seconds, and 6) purging the NH3 reactant with 55 seem of Ar for 10 seconds. Sequences 1 ) through 6) were repeated until the deposited layer achieved suitable layer thickness.
The deposition rate and the refractive index of the deposited film are shown in FIG 8. The atomic composition percentage of silicon in the resulting film was approximately 45%, the atomic composition percentage of nitrogen in the resulting film was approximately 30%, and the atomic composition percentage of carbon was approximately 20%. The atomic composition percentage of chlorine and oxygen in the resulting film was 0% or greater but less than 5% for each. The wet etch rate of the resulting film by a HF solution was 0.54 A/min.
Example 4c
A dense SiCN film was deposited using an ALD method with HCDS and BDEAS precursors. The reaction chamber was controlled at 5 Torr, 550°C, and 55 seem of Ar was continuously flowing. The deposition process comprised the following steps of: 1 ) introducing a pulse of approx.1 seem of BDEAS into the reaction chamber for 10 seconds, 2) purging the BDEAS precursor with 55 seem of Ar for 30 seconds, 3) introducing a pulse of approx.1 seem of HCDS into the reaction chamber for 10 seconds, and 4) purging the HCDS precursor with 55 seem of Ar for 30 seconds.
Sequences 1 ) through 4) were repeated until the deposited iayer achieved suitable layer thickness.
The carbon content of the resulting film was too high to allow for the measurement of deposition rate and refractive index by eilipsometry. The atomic composition percentage of silicon in the resulting film was greater than 55% but less than 60%, the atomic composition percentage of carbon in the resulting film was greater than 30% but less than 35%, and the atomic composition percentage of nitrogen was slightly greater than 5%. The atomic composition percentage of chlorine and oxygen in the resulting film was 0% or greater but less than 5% for each. The wet etch rate of the resulting film by a HF solution was 0.15 A/min.
Example 5
Applicants believe that dense HfSiCN films will be deposited using the disclosed ALD methods with HfCl4 and 3DMAS precursors. Applicants believe that the disclosed methods may be used to alter the stoichiometric ratios in the resulting film.
Example 6
Applicants be!ieve that dense HfSiCN films will be deposited using the disclosed ALD methods with tetrakis(ethylmethylamino)hafnium and HCDS precursors. Applicants believe that the disclosed methods may be used to alter the stoichiometric ratios in the resulting film.
It will be understood that many additional changes in the details, materials, steps, and arrangement of parts, which have been herein described and illustrated in order to explain the nature of the invention, may be made by those skilled in the art within the principle and scope of the invention as expressed in the appended claims. Thus, the present invention is not intended to be !imited to the specific embodiments in examples given above and/or the attached drawings.

Claims

What is claimed is: . A method of forming a meta!-nitride-containing film, said method comprising the steps of:
a) introducing a halogenated metal precursor into an ALD
reactor containing at !east one substrate;
b) purging excess halogenated metal precursor from the reactor; c) introducing an amino-metal precursor into the reactor; and d) purging excess amino-metal precursor from the reactor, e) optionally introducing a reactant into the reactor,
f) optionally purging excess reactant from the reactor, wherein a metal of the halogenated metal precursor and amino-metal precursor is the same or different.
2. The method of claim 1 , wherein the reactant is selected from the group consisting of N2, NH3, N2H4, NMeH2, NEtH2, NMe2H, NEt2H, NMe3, NEt3, MeHNNH2, Me2NNH2, phenyl hydrazine, and mixtures thereof, and preferably is NH3.
3. The method of claim 1 or 2, wherein metal-nitride-containing films having specified stoichiometry may be produced by varying an order of the method steps.
4. The method of any one of claims 1 to 3, wherein the halogenated precursors are chlorometal precursors.
5. The method of any one of claims 1 to 4, wherein the metal-nitride- containing fi!m is a metal carbonitride film containing one or two metals.
6. The method of any one of c!aims 1 to 5, wherein the metal is selected from transition metal, metal, or non-metal elements.
7. The method of any one of claims 1 to 6, wherein the metal is boron or phosphorus.
8. The method of any one of claims 1 to 7, wherein the metal-nitride- containing film is a si!icon-nitride-containing film, the halogenated metal precursor is a chlorosilane precursor, and the amino-meta! precursor is an aminosilane precursor.
9. The method of claim 8, wherein the silicon-nitride-containing film is carbon-doped SiN film.
10. The method of claim 8 or 9, wherein the chlorosilane precursors have the formula SiaHbCICl wherein b+c = 2a+2,
1 1. The method of any one of claims 8 to 10, wherein the chlorosilane precursors are introduced as a mixture.
12. The method of any one of claims 8 to 11 , wherein the aminosilane precursors have formula H4.xSi(NR'Rf')x, wherein x = 1 , 2, 3, or 4, R' and R" are independently selected from H or an alky! group, and R' and R" may be linked to form a ring structure.
13. The method of claim 12, wherein the aminosilane precursors comprise an aminochlorosilane or an aminoalkylsilane.
14. The method of claim 13, wherein the aminochlorosilane precursors have a formula Cl4-xSi(NR'R")x, wherein x - 2 or 3 and R' and R" are as previously defined.
15. The method of claim 13, wherein the aminoalkylsilane precursors have a formula R'YxSi(NR'R")x wherein x = , 2, or 3, R' and R" are as previously defined, and R'" group is an alkyi group having iess than 3 carbons.
PCT/US2011/030957 2010-04-01 2011-04-01 Metal nitride containing film deposition using combination of amino-metal and halogenated metal precursors WO2011123792A2 (en)

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TWI498447B (en) 2015-09-01
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JP5815669B2 (en) 2015-11-17
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