WO2019204382A1 - Dépôt de film de molybdène à basse température utilisant des couches de nucléation de bore - Google Patents

Dépôt de film de molybdène à basse température utilisant des couches de nucléation de bore Download PDF

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Publication number
WO2019204382A1
WO2019204382A1 PCT/US2019/027792 US2019027792W WO2019204382A1 WO 2019204382 A1 WO2019204382 A1 WO 2019204382A1 US 2019027792 W US2019027792 W US 2019027792W WO 2019204382 A1 WO2019204382 A1 WO 2019204382A1
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Prior art keywords
molybdenum
boron
nucleation layer
substrate
layer
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PCT/US2019/027792
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English (en)
Inventor
Shuang Meng
Richard Ulrich Assion
Bryan Clark HENDRIX
Thomas H. Baum
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Entegris, Inc.
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Publication date
Priority claimed from US15/958,568 external-priority patent/US10453744B2/en
Application filed by Entegris, Inc. filed Critical Entegris, Inc.
Priority to CN201980027078.3A priority Critical patent/CN112041980A/zh
Priority to JP2020558011A priority patent/JP7425744B2/ja
Priority to KR1020207033045A priority patent/KR20200135547A/ko
Publication of WO2019204382A1 publication Critical patent/WO2019204382A1/fr

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    • 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
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
    • H01L21/76841—Barrier, adhesion or liner layers
    • H01L21/76871—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers
    • H01L21/76876—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers for deposition from the gas phase, e.g. CVD
    • 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
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
    • 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
    • C23C16/08—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 metal halides
    • C23C16/14—Deposition of only one other metal element
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/405—Oxides of refractory metals or yttrium
    • 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]
    • C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
    • 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
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/28008—Making conductor-insulator-semiconductor electrodes
    • H01L21/28017—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon
    • H01L21/28026—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon characterised by the conductor
    • H01L21/28035—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon characterised by the conductor the final conductor layer next to the insulator being silicon, e.g. polysilicon, with or without impurities
    • H01L21/28044—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon characterised by the conductor the final conductor layer next to the insulator being silicon, e.g. polysilicon, with or without impurities the conductor comprising at least another non-silicon conductive layer
    • H01L21/28061—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon characterised by the conductor the final conductor layer next to the insulator being silicon, e.g. polysilicon, with or without impurities the conductor comprising at least another non-silicon conductive layer the conductor comprising a metal or metal silicide formed by deposition, e.g. sputter deposition, i.e. without a silicidation reaction
    • 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
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
    • H01L21/76841—Barrier, adhesion or liner layers
    • H01L21/76853—Barrier, adhesion or liner layers characterized by particular after-treatment steps

Definitions

  • the present disclosure relates to vapor deposited molybdenum films or layers that can be made at lower process temperatures, but with deposition rates similar to those achieved using traditional high temperature vapor deposition conditions for molybdenum.
  • the resulting molybdenum films or layers formed by the lower temperature deposition also have low resistivity and can be used in a variety of articles like semiconductor devices and display devices.
  • Molybdenum is a low-resistivity refractory metal that can potentially replace tungsten as a material in memory, logic chips, and other devices using poly silicon-metal gate electrode structures.
  • a thin film containing molybdenum can also be used in some organic light emitting diodes, liquid crystal displays, and also in thin film solar cells and photovoltaics.
  • a thin molybdenum film can be used as a barrier film.
  • Precursors include inorganic and organ ometallic reagents and vapor deposition techniques can include chemical vapor deposition (CVD) and atomic layer deposition (ALD) as well as a number of modifications such as UV laser photo-dissociation CVD, plasma assisted CVD, and plasma assisted ALD.
  • CVD and ALD processes are being increasingly used because they can give excellent conformal step coverage on highly non-planar
  • microelectronics device geometries however the costs and complexity of plasma assisted deposition and high temperature deposition systems can increase production costs and tool costs.
  • High temperature processes can also damage previously deposited or underlying structures.
  • the precursors are passed over an optionally heated substrate (e.g., a wafer) in a low pressure or ambient pressure reaction chamber.
  • the precursors react and/or decompose on the substrate surface creating a thin film of deposited material like molybdenum.
  • Volatile by-products are removed by gas flow through tire reaction chamber.
  • Some metal films are formed in a CVD process by supplying two or more gases to a reaction chamber with reaction of the gases leading to the deposition of the rnetal on the substrate.
  • the deposited film thickness and uniformity depends on coordination of many parameters such as temperature, pressure, gas flow rates and mixing uniformity, chemical depletion effects, and time.
  • Refractory metal films have been deposited on substrates in a CVD process comprising heating in an enclosed chamber a substrate like silicon dioxide to a temperature of about 500°C to 800°C, treating the heated surface with a vaporized substance like molybdenum hexafluoride for a brief period of time to increase the adherence of the surface to a molybdenum layer to be subsequently deposited, purging all the unreacted molybdenum hexafluoride from the chamber, and then depositing a molybdenum film by mixing hydrogen with some newly vaporized molybdenum hexafluoride to thereby reduce the molybdenum hexafluoride, generate HF(g), and deposit some of the molybdenum on the heated surface.
  • the high temperatures for this deposition makes the processing equipment complex and consumes thermal budget for temperature sensitive devices. Further, the toxicity of HF(g) and associated abatement and safety equipment for handling HF(g) makes this process expensive and complex.
  • a boron decomposition layer or boron nucleation layer was deposited on the substrate which was subsequently replaced by a high quality ' molybdenum nucleation layer on the substrate at temperatures below 550°C.
  • the molybdenum nucleation layer prepared in this way was found to protect the underlying substrate from the etching effect of for example Mods, to facilitate nucleation of subsequent smooth CVD io Mo growth on top, and to enable CVD Mo deposition at lower temperatures.
  • the molybdenum nucleation layer could also be used to control the grain sizes of the subsequent CVD growth of the bulk molybdenum, and therefore control the electrical resistivity of the final molybdenum film.
  • high amounts of boron, visible by SEM, were found underneath tire molybdenum layer which increased film resistivity. This was especially problematic where
  • reaction forms a molybdenum nucleation layer, can take place in the presence or absence of a reducing gas like hydrogen, and concurrently replaces the boron nucleation layer.
  • the resulting molybdenum nucleation layer lowered the cutoff temperature for a subsequent bulk Mo CVD film forming process, using for example a vapor composition comprising MoOCU or Mods in the presence of a reducing gas like hydrogen, to between from 400°C to 575°C for MoOCU and
  • Molybdenum CVD films formed in this way had low film resistivity, wore smooth, and had better step coverage compared to molybdenum films deposited on substrates by chemical vapor deposited (CVD) molybdenum at high temperatures of about 70Q°C using MoOCU or Mods as the molybdenum precursor and Th as a reducing gas.
  • CVD chemical vapor deposited
  • the disclosure relates to compositions and a method of making a molybdenum nucleation
  • the substrate may itself be a molybdenum nucleation layer.
  • the substrate may be substantially free of molybdenum.
  • the method can include the acts or steps of reaction of a pre-existing solid boron comprising nucleation layer on the substrate with a vapor composition comprising molecules containing molybdenum and chlorine atoms in some versions the vapor composition is
  • the substrate is held at a temperature of between from 450°C to 550°C and the reaction with the vapor consumes at least a portion of the boron nucleation layer while forming a molybdenum nucleation layer atop the substrate.
  • the molybdenum nucleation layer can be formed on a substrate that is held at a temperature of between from 450°C to 480°C.
  • the deposited molybdenum nucleation layer can have a thickness that ranges from about 5 angstroms (5 A) to about 100 angstroms (lOOA).
  • the thickness of the deposited molybdenum nucleation layer may be in the range of from about 5 to about 50 angstroms, optionally in the range of from 5 to about 30 angstroms, for example in the range of from about 5 to about 20 angstroms.
  • the vapor composition comprising molecules of molybdenum and chlorine can be present in the reaction chamber with the heated substrate at a pressure of from between 10 torr to 60 torr, and in some versions at a pressure of from 20 Torr to 40 Torr.
  • An aspect of the inven tion provides a method of making a molybdenum layer, the me thod comprising: reaction of a boron comprising nucleation layer on a substrate with a vapor composition comprising molecules containing molybdenum and chlorine atoms, the substrate being at a temperature of between from 450°C to 550°C; said reaction consuming at least a portion of the boron nucleation layer and fonning a molybdenum nucleation layer atop the substrate.
  • the boron comprising nucleation layer that is substantially consumed can have a thickness that is between from about 5 A to about lOOA.
  • the thickness of the boron comprising nucleation layer may be in the range of from about 5 to about 50 angstroms, optionally in the range of from about 5 to about 30 angstroms, for example in the range of from about 5 to about 20 angstroms.
  • the boron comprising nucleation layer may be substantially consumed by said reaction, such that the molybdenum layer comprises less than 5wt% boron, optionally less than hvt% boron by elemental analysis.
  • the boron nucleation layer may suitably be formed by the decomposition of BiHe on the heated substrate.
  • the substrate is heated to 300°C to 450°C during the boron nucleation layer deposition.
  • Other boron containing precursors and conditions can he used to deposit the boron nucleation layer.
  • the same or substantially the same temperature that is used for the molybdenum deposition between from 450°C to 550°C, could be used for the deposition of the boron nucleation layer.
  • the method comprises depositing the boron comprising nucleation layer atop the substrate, the substrate being at a temperature of between from 300°C to 550°C.
  • the method may optionally comprise depositing a further boron comprising nucleation layer atop said molybdenum nucleation layer atop said substrate, the substrate being at a temperature of between from 300°C to 550°C; optionally 300°C to 450°C, and reaction of the further boron comprising nucleation layer with a vapor composition comprising molecules containing molybdenum and chlorine atoms, the substrate being at a temperature of between from 450°C to 550°C; said reaction consuming at least a portion of the further boron nucleation layer and forming a further molybdenum nucleation layer.
  • the thickness of the further boron comprising nucleation layer may suitably be between from 5A to 1 OOA.
  • the thickness of the further boron comprising nucleation layer may be in the range of from about 5 to about 50 angstroms, optionally in the range of from about 5 to about 30 angstroms, for example in the range of from about 5 to about 20 angstroms.
  • the deposited thickness of the further boron comprising nucleation layer may be less than the deposited thickness of the boron comprising nucleation layer atop the substrate.
  • the method may comprise vapor depositing the boron comprising nucleation layer atop the substrate for a first period of time and vapor depositing the further boron compri sing nucleation layer for a second period of time, the second period of time being shorter than the first period of time.
  • the further boron comprising nucleation layer may be substantially consumed by said reaction, such that the further molybdenum layer comprises less than 5wt% boron, optionally less than lwt% boron by elemental analysis.
  • the steps of depositing and reaction may be repeated thereby forming a plurality of further molybdenum nucleation layers.
  • the molybdenum nucleation layer(s) can be formed on a substrate that is held at a temperature of between from 450°C to 480°C.
  • the vapor composition may ⁇ be at a pressure of from between 10 torr to 60 torr.
  • the vapor composition may be substantially free of a reducing gas.
  • the method may comprise making a top molybdenum nucleation layer.
  • the molybdenum nucleation layer atop said substrate, or a further molybdenum nucleation layer, may constitute the top molybdenum nucleation layer.
  • another version of the me thod, for making a top molybdenum nucleation layer comprises depositing a boron comprising nucleation layer atop a substrate or atop a molybdenum nucleation layer atop the substrate where the substrate or molybdenum nucleation layer atop the substrate is at a temperature of between from 300°C to 550°C, optionally 300°C to 450°C, and subsequently reaction of the boron comprising nucleation layer with a vapor composition comprising molecules containing molybdenum and chlorine atoms, the substrate being at a temperature of between from 450°C to 550°C.
  • the thickness of the boron comprising nucleation layer can be between from 5 A to lOOA
  • the thickness of the boron comprising nucleation layer may be in the range of from about 5 to about 50 angstroms, optionally in the range of from about 5 to about 30 angstroms, for example in the range of from about 5 to about 20 angstroms.
  • the consuming at least a portion of the boron nucleation layer substantially or completely consumes the boron nucleation layer.
  • the consuming at least a portion of the boron nucleation layer may generate volatile boron compounds.
  • a boron comprising nucleation layer also referred to as a boron
  • the decomposition layer and reacting it with a vapor composition comprising molecules containing molybdenum and chlorine can be repeated one or more times.
  • the one or more molybdenum nucleation layers can be substantially free of boron as determined from SEM analysis, elemental analysis, or an electrical resistivity measurement.
  • the method of making a molybdenum nucleation layer may comprise vapor depositing a bulk molybdenum layer atop a top molybdenum nucleation layer at a temperature between from 450°C to 550°C.
  • a molybdenum complex can be used to vapor deposit the bulk molybdenum layer.
  • the molybdenum complex contains molybdenum and chlorine.
  • the molybdenum complex can comprise MoCls or it can comprise MoOCU.
  • the thickness of the film can be 200 angstroms or more and the resistivity of the molybdenum film can be ⁇ 20% of the resistivity ' measured at room temperature (RT, 20°C ⁇
  • the moly bdenum film atop the substrate includes the top most bulk molybdenum layer and one or more underlying
  • the molybdenum film can have an electrical resistivity that is less than 25 mW-cm for a molybdenum film layer thickness of 200 angstroms or more, in some versions the molybdenum film has electrical resistivity that is less than 20 mW-cm for the molybdenum layer thickness of 200 angstroms or more. Lower resistivity' molybdenum films consume less power and generate less heat than devices having higher resistivity molybdenum films.
  • the molybdenum fi lm atop the substrate includes the top most bulk molybdenum layer and one or more underlying molybdenum nucleation layers.
  • the molybdenum film atop the substrate can have an electrical resistivity measured at room temperature (RT, 20°C-23°C) that is between from 10 mW-cm to 25 mWchi, m some versions the electrical resistivity can be between from 12 mW-cm to 25 m ⁇ -cm, and in some other versions the electrical resistivity can be between from 10 mW-cm to 20 mW-crn, for a molybdenum film having a thickness of from between 800 angstroms to 200 angstroms. In some versions the molybdenum film has a thickness of 200 A to 1000 A.
  • the resistivity of the molybdenum film can be within ⁇ 20% of the resistivity measured at room temperature (RT, 20°C-23°C) of a vapor deposited molybdenum film of similar thickness ⁇ 10% deposited at 700°C on a similar substrate.
  • One version of a method of making a molybdenum film on a substrate can include the acts or steps of exposing the substrate to BTT, gas in the temperature range from 250°C to 550°C and pressure range from 10 Torr to 60 Torr; forming a solid boron nucleation layer on the substrate surface; exposing the boron nucleation layer to a vapor comprising molybdenum and chlorine atoms at temperature above 450°C and converting the boron layer into an molybdenum nucleation layer and generating boron compounds like BCb (g) or BOC1 (g); optionally repeating the first four steps one or more times to form additional molybdenum nucleation layers; and CVD depositing molybdenum at a temperature of 550 °C or less atop the top molybdenum nucleation layer by Hr reduction of a molybdenum complex comprising molybdenum and chlorine atoms.
  • Another version of making a molybdenum film on a substrate includes the acts or steps of first exposing the substrate to BiHe gas in the temperature range from 300°C to 550°C and pressure range from 10 Torr to 60 Torr.
  • a boron decomposition or boron nucleation layer is formed on the substrate surface and the thickness of this layer can be controlled by BIHG flow and dose time.
  • the boron layer is subsequently exposed to Mods at temperature above 450°C.
  • the reaction converts the boron layer into a molybdenum nucleation layer with volatile gas comprising BCb(g) or BOCl(g) as a by-product.
  • the thickness of the resu lting molybdenum nucleation layer depends on the starting thickness of the boron decomposition layer.
  • the process of making a boron nucleation layer and converting it to a molybdenum nucleation layer can be repeated for a number of times until a desired top molybdenum nucleation layer is achieved.
  • Subsequently conventional CVD molybdenum deposition can proceed on the top molybdenum nucleation layer.
  • the molybdenum nucleation layer can help to lower the CVD molybdenum deposition temperature cut-off from 550°C to 450°C.
  • the CVD molybdenum film deposited on the top nucleation layer has low roughness and good step coverage on deep via structures.
  • the version s of the method of making a molybdenum film can be carried out in a manufacturing process that forms a semiconductor device on a substrate.
  • the molybdenum films of the disclosure can also be deposited during the manufacture of a variety of electronic, display, or photovoltaic devices. Examples of electronic devices include dynamic random access devices (DRAM) for digital memory 7 storage and 3-D NAND logic gates used in flash memory devices.
  • DRAM dynamic random access devices
  • 3-D NAND logic gates used in flash memory devices.
  • the disclosure relates to methods of making molybdenum fdms on substrates utilizing boron and molybdenum nucleation layers.
  • the resulting molybdenum films may have low electrical resistivity, may be substantially free of boron, and can be made at reduced
  • the molybdenum nucleation layer formed by this process can protect the substrate from the etching effect of chlorine containing precursors like Mods or MoOCU, can facilitate nucleation of subsequent CVD Mo growth atop of the molybdenum nucleation layer, and enables molybdenum CVD deposition at lower temperatures.
  • the molybdenum nucleation layer can also be used to control the grain sizes of the subsequent CVD molybdenum growth, and therefore control the electrical resistivity of the final molybdenum film.
  • the boron nucleation layer can be formed by first exposing the substrate (which may include a thin overlying film), to B jHe gas in the temperature range from 300°C to 550°C and pressure range of from 10 Torr to 60 Torr.
  • a solid nucleation or decomposition layer comprising boron is formed on the substrate surface (or overlying thin fi lm) and the thickness of this boron comprising nucleation layer or boron comprising decomposition layer can be controlled by BiHe flow and dose time.
  • the thickness of this boron comprising nucleation layer can be between from SA to IOOA.
  • the thickness of the boron comprising nucleation layer may be in the range of from about 5 to about 50 angstroms, optionally in the range of from 5 to about 30 angstroms, for example in the range of from about 5 to about 20 angstroms.
  • the molybdenum nucleation layer can be formed by exposure and reaction of the boron nucleation layer to a vapor composition that includes molybdenum, chlorine, and optionally oxygen at elevated temperatures. This reaction with the vapor composition consumes the boron nucleation layer and replaces it with a molybdenum nucleation layer
  • vapor composition can include MoClj, MoOCU or other materials.
  • the substrate with the boron nucleation layer can held at a temperature of between 450°C and 550° C on a stage in the reactor and can be exposed to a composition that comprises or consists only of Mods, or exposed to a composition that can he a mixture including MoCl and an inert gas like argon (Ar), or exposed to a composition that can be a mixture including Mods and a reducing gas like hydrogen (Eh).
  • a composition that comprises or consists only of Mods or exposed to a composition that can he a mixture including MoCl and an inert gas like argon (Ar), or exposed to a composition that can be a mixture including Mods and a reducing gas like hydrogen (Eh).
  • the substrate on a heated stage with the boron nucleation layer can be held at a temperature of between 450°C and 550° C and exposed to a composition that comprises or consists of MoOC or exposed to a composition that can be a mixture including MoOCU and an inert gas like argon (Ar), or exposed to a composition that can be a mixture including MoOCU and a reducing gas like hydrogen (Eh). Exposure of the boron nucleation layer at a temperature of between 450°C and 550° C to one or more of these compositions converts the boron nucleation layer into a molybdenum comprising nucleation layer.
  • BCU or other boron containing volatile materials can be generated as a byproduct of the conversion of the boron nucleation layer to the molybdenum nucleation layer.
  • This reaction has temperature cutoff of approximately 450 °C.
  • the reaction by-products may include HC1, BCb and OCb (in the case of vapor composition comprising MoOGU).
  • the reaction can occur with or without Hi co- reactant on the boron nucleation layer.
  • the thickness of the resulting molybdenum nucleation layer depends on the starting thickness of the boron nucleation layer.
  • a vapor composition that includes molybdenum, chlorine, and optionally oxygen, but that does not include a reducing gas, can be used to convert the boron nucleation layer into the molybdenum nucleation layer.
  • the thickness of the resulting molybdenum nucleation layer is proportional to the thickness of boron nucleation layer.
  • the steps of depositing a boron nucl eation layer and reaction of the boron nucleation layer to form a molybdenum nucleation layer may be repeated to form one or more further boron nucleation layers.
  • boron nucleation layers may be made in substantially identical fashion. Alternatively, differing conditions may be employed for different layers, e.g. as described anywhere herein.
  • the method may comprise making a top molybdenum nucleation layer.
  • the molybdenum nucleation layer atop said substrate, or a further molybdenum nucleation layer, may constitute the top molybdenum nucleation layer.
  • Versions of the molybdenum film forming process can further include the act or step of vapor depositing a molybdenum complex on a top molybdenum nucleation layer on the substrate to form a bulk molybdenum layer.
  • the bulk molybdenum layer and one or more underlying molybdenum nucleation layers make up the molybdenum film and the molybdenum film can have a thicknesses that range from 5qA to 3000A; in some versions the thickness of the molybdenum film can be from 200 A to lOOOA
  • the substrate can he at temperatures between from 450°C to 550°C during this bulk vapor deposition act or step.
  • the molybdenum complex can be a vapor composition comprising molybdenum and chlorine atoms, and in other cases the molybdenum complex can be a vapor composition comprising molybdenum, chlorine, and oxygen atoms.
  • molybdenum complexes that can be used in versions of the method include MoCls and MoOCk
  • a composition comprising molecules containing molybdenum and chlorine atoms or a molybdenum complex containing molybdenum and chlorine atoms can be vaporized to make vapor compositions containing molybdenum and chlorine atoms for use the molybdenum film forming method.
  • the composition or complex can separately comprise MoCls (in some versions at a molecular purity of 99% or higher) or MoQCU (in some versions at a molecular purity of 99% or higher).
  • the molybdenum complex can be an organometa!lic molybdenum compounds containing cyclopen tadienyl and other ligands.
  • the molybdenum complex can be purified by sublimation to a molecular purity of greater than 99.99%.
  • Mods can be purified by sublimation to remove trace amounts of higher vapor pressure MoOCk
  • Versions of the disclosure can include an ampoule adapted for used in a vapor deposition process, the ampoule contains MoCls at a molecular purity of greater than 99.99%.
  • Another version of the discl osure can include an ampoule adapted for used in a vapor deposition process, the ampoule contains MoOC at a molecular purity of greater than 99.99%.
  • Sublimation can be used to purify the Mods or MoOCU and remove unwanted rnetal halides and metal oxyhahdes.
  • Reference to the boron nucleation layer being substantially consumed in versions of the method of making a molybdenum film may refer to no boron being visible by SEM analysis of a cross section of a sample that had one or more boron nucleation layers replaced with one or more molybdenum nucleation layers. Substantially consumed may additionally or alternatively refer to less than 5wt%, and in some cases less than 1 wt% boron being present in a molybdenum film and in any underlying molybdenum nucleation layers.
  • the boron content can be determined by acid dissolution of the film from a substrate and measured by elemental analysis.
  • Substantially consumed can also refer to a molybdenum film that has a resistivity measured at room temperature (RT, 20°C-23°C) that is within ⁇ 20% or less of a molybdenum layer of similar thickness ( ⁇ 10%) vapor deposited on a similar substrate at 700°C from MoCls.
  • RT room temperature
  • ⁇ 10% vapor deposited on a similar substrate at 700°C from MoCls.
  • Thermal budget refers to the cumulative thermal energy imparted to a semiconductor microelectronic transistor, logic gate, or photovoltaic by ail thermal processing steps during manufacturing. Controlling the thermal budget of a process can help prevent dopant
  • the molybdenum nucleation layers and bulk molybdenum layers can be deposited at temperatures below 500°C and with similar deposition times compared to the 700°C molybdenum process without the Mo nucleation layers.
  • the lower deposition temperature for the new method disclosed herein can be used to decrease the demand on the thermal budget for processes where molybdenum films are used in semiconductor device manufacturing. Additionally, the lower process temperatures achieved by the current process can reduce costs by allowing the utilization of less expensive process equipment and designs.
  • the decomposition layer or nucleation layer comprising boron is substantially free of borides.
  • the molybdenum nucleation layer and molybdenum film are substantially free of borides.
  • Borides are materials that are formed between boron and a more electronegative element like silicon. Boride layers have been suggested as barrier layers in the manufacture of integrated circuits to inhibit the diffusion of metals and other impurities into regions underlying barrier layers. Borides are typically formed using chemical vapor deposition (CVD) techniques. For example, a metal tetrachloride may be reacted with diborane to form a metal diboride using CVD.
  • boride layers formed using CVD chlorine -based chemistries typically have a high chlorine content (e.g., chlorine content greater than about 3%).
  • a high chlorine content is undesirable because the chlorine may migrate from the boride barrier layer into adjacent interconnection layers, which can increase the contact resistance of such interconnection layers and potentially change the characteristics of integrated circuits made therefrom.
  • Molybdenum films prepared by the methods disclosed herein have been found to protect the substrate from the etching effect of Mods, MoOCU.
  • Vapor deposition includes any of chemical vapor deposition (CVD), atomic layer deposition (ALD), high and low pressure versions of these, and versions including assisted versions of these such as but not limited to plasma enhanced CVD, laser assisted, and microwav e assisted .
  • CVD chemical vapor deposition
  • ALD atomic layer deposition
  • assisted versions of these such as but not limited to plasma enhanced CVD, laser assisted, and microwav e assisted .
  • This layer can be for example, but is not limited to, titanium nitride, molybdenum, or other material that would underlie a bulk molybdenum layer in a semiconductor device.
  • a thin conductive diffusion barrier can be disposed between the polysilicon and the elemental metal to prevent silicidation of the elemental metal during high-temperature processing.
  • the diffusion barrier is typically comprised of conductive metal nitrides such as tungsten nitride (WN), titanium nitride (TiN), tantalum nitride (TaN) and/or respective silicon- containing ternar compounds such as WSiN, TiSiN, and TaSiN.
  • conductive metal nitrides such as tungsten nitride (WN), titanium nitride (TiN), tantalum nitride (TaN) and/or respective silicon- containing ternar compounds such as WSiN, TiSiN, and TaSiN.
  • the substrate comprises a molybdenum nucleation layer, for example a molybdenum nucleation layer previously formed in accordance with the invention.
  • Substrates that can be used in versions of the method include silicon, silicon oxide, gallium arsenide, alumina, and other ceramics and metals with suitable chemical and temperature properties.
  • a boron nucleation layer or boron decomposition layer can have a thickness that ranges from about 5 angstroms (5 A) to about 100 angstroms (100 A).
  • a molybdenum nucleation layer can have a thickness that ranges from about 5 angstroms (5 A) to about 100 angstroms (100 A).
  • the boron nucleation layer can be deposited on the substrate or a layer on top of the substrate that is heated to a temperature that is between 250° C up to and including 550° C In some versions the boron nucleation layer can be deposited on the substrate or a layer on top of tire substrate that is heated to a temperature that is between 300° C up to and including 450° C.
  • Boron nucleation layers made between 300° C up to and including 450° C provide bulk molybdenum layers that are smooth and that have low resistivity.
  • the one or more B2H6 nucleation layers can be deposited by exposing the substrate to BiHe gas in tire temperature range from 300 °C to 550 °C and pressure range from 10 Torr to 60 Torr.
  • the molybdenum pentachloride MoCl complex can be delivered to the reaction chamber by sublimation from a vessel or ampoule with a flow of Ni or Ar carrier gas.
  • An ampoule vessel containing the molybdenum pentachloride as the complex can for example be heated to a temperature of between 70 °C and 100 °C. The temperature for the vaporization will vary depending on the molybdenum complex used. Lower ampoule temperatures are beneficial for all vapor generation because it can decrease the decomposition of the molybdenum complex and thereby provide more consistent molybdenum deposition rates.
  • This example illustrates deposition of molybdenum on top of a 50 A thick titanium nitride layer on a substrate.
  • the thickness of the titanium nitride layer after deposition of the molybdenum nucleation layer and bulk molybdenum was within ⁇ 20% of the thickness of the initially measured TiN layer thickness illustrating that the molybdenum nucleation layer provided etch resistance to the underlying TiN from chlorine-containing precursor and byproducts.
  • the molybdenum film atop the substrate was deposited by a multi-step process at varying temperatures and pressures as detailed in Table 1 below'.
  • the first step included sub-steps of: depositing a solid boron nucleation layer on a titanium nitride layer on top of a SiC substrate: and exposure of the solid boron nucleation layer (or boron decomposition layer) to a composition that included Mods and hydrogen resulting in substantial replacement of the boron nucleation layer with a molybdenum nucleation layer.
  • the next step was the deposition of a new boron nucleation layer atop the molybdenum nucleation layer in a shorter soak than the first boron layer nucleation, and then a bulk molybdenum deposition that began by substantially consuming the new boron nucleation to form molybdenum followed seamlessly by bulk deposition of molybdenum to form the molybdenum film on the substrate by reaction of MoCl with Th.
  • the electrical resistivity of the film was measured at room temperature (RT, 2G°C to
  • the deposition temperature of m olybdenum nucleation layer was conducted at temperatures of from 480°C to 450°C and specifically at temperatures of 480°C, 460°C, or 450°C.
  • the pressure for the nucleation or bulk molybdenum deposition step was changed between 10 Torr and 40 Torr.
  • the MoCL ⁇ ampoule temperature (Amp temp °C) was 90 degrees Cel sms.
  • results of this example show that molybdenum films were made comprising die bulk molybdenum layer and one or more molybdenum nucleation layers which had a four point electrical resistivity ' measured at room temperature (RT, 20°C-23°C) that was between from 12 mW-cm to 20 mW-cm for the molybdenum films having a thickness of from between 700 angstroms to 300 angstroms respectively. All films showed low' resistivity of below 20 mW-cm w'hen measured at room temperature (RT, 20°C-23°C).
  • This comparati ve example illustrates the deposition of molybdenum on a substrate without a molybdenum nucleation layer. Deposition was tested at stage temperatures of from 550°C to 700°C and deposition times were varied from 30 seconds to 600 seconds. Deposits of MoClri to form Mo were made on a IOqA TiN layer on top of a SiCh substrate. The Mods ampoule was heated to 70°C, the chamber pressure was 60 Torr, Hr flow' rate was 2000 seem, and argon carrier gas flow was 50 seem.
  • the results of this example show that at approximately the same deposition time of 180 seconds, the thickness of the deposi ted molybdenum film decreased from 341 A at 700°C (deposition rate of 1.89 A/sec), to 150 A at 600°C (deposition rate of 0.83 A/sec), and was as low' as 37 A at 550°C (deposition rate of 0.2 A/sec).
  • the molybdenum film resistivity measured at room temperature (RT, 20°C-23°C) increased with decreasing deposition temperature.
  • the 241 A thick Mo film deposited at 550°C had a resistivity of 60 mW-cm; the 248 A thick Mo film that was deposited at 600°C had a resistivity of 30.3 mW-em, while the 231 A thick film that was deposited at 700°C had resistivity of 21.8 mW-cm.
  • This example illustrates making a molybdenum film comprising one or more molybdenum nucleation layers and a bulk molybdenum layer deposited by vapor deposition from Mods.
  • the substrates used had a 50 A titanium nitride layer atop SiC .
  • Formation of the solid boron nucleation layer on the TiN layer was performed at a stage temperature of 300°C chamber pressure of 40 Torr, a B2H6 flow of 35 seem and an argon flow of 250 seem; times were varied between 60 and 30 seconds depending on whether a boron nucleation layer was being formed on the TiN or on the initial molybdenum nucleation layer.
  • the estimated thickness of the boron nucleation layer was 5 to 30 angstroms.
  • MoCls ampoule temperature was 90°C
  • chamber pressure was 20 Torr
  • argon carrier flow was 100 seem
  • Th was 2000 seem and stage temperature varied from 480°C to 500°C.
  • Reaction times were varied between 30 seconds and 600 seconds depending on whether a molybdenum nucleation layer w3 ⁇ 4s being formed by consuming the initial boron nucleation layer or whether the second molybdenum nucleation layer was being formed followed by bulk Mo CVD.
  • molybdenum films had electrical resistivities measured at room temperature that ranged between from 12 mW-cm to 25 mW-em for the molybdenum layer having a thickness of from between 800 angstroms to 200 angstroms respectively.
  • the results of this example further show that low resistivity molybdenum films can be made at substrate temperatures of between from 480°C and 500°C by consuming a boron nucleation layer via the reaction of the boron comprising nucleation layer on the substrate with a vapor composition comprising molecules containing molybdenum and chlorine atoms.
  • the resistivity of the bulk molybdenum film in this example was ⁇ 20% of the resistivity as measured at room temperature of a bulk molybdenum layer of substantially similar thickness ( ⁇ 10%) deposited from the same molybdenum complex on a similar substrate at 700°C that was absent the molybdenum nucleation layer.
  • the deposition of molybdenum on a similar substrate using the molybdenum complex of sample 322-237-12 in Example 2 gave a film with a resistivity of about 16.1 mW-cm for a 340 A thick film.
  • This example illustrates the detrimental effect of excessive residual boron on resistivity of molybdenum films deposited with boron nucleation layers and the cutoff temperature for the deposition of molybdenum using boron nucleation layers.
  • the molybdenum thickness following deposition at substrate temperatures 450°C, 500°C, and 550°C were measured after 1, 2, 3, 4, 5 cycles. After 5 nucleation cycles, the molybdenum film thickness at the 450° C deposition temperature was less than 25 A. After 5 nucleation cycles, the molybdenum film thickness at the 500° C deposition temperature was about 275 A. After 5 nucleation cycles, the molybdenum film thickness at the 550° C deposition temperature was about 410 A. Based on these results the cutoff temperature for the reaction between MoCls and boron was determined to be between 450°C and 500°C.
  • the molybdenum film resistivities measured at room temperature following deposition at substrate temperatures 500°C, and 550°C were measured after 1 , 2, 3, 4, 5 cycles.
  • the resistivity after 1 nucleation cycle at 500°C was too high to measure, while the resistivity of molybdenum film after 1 nucleation cycle at 550°C was about 310 mW-cm.
  • the resistivity after 2 nucleation cycles for the molybdenum film formed at 500°C was about 250 mW-cm, while the resistivity of molybdenum film after 2 nucleation cycle at 550°C was about 275 mW-crn.
  • the resistivity after 5 nucleation cycles for the molybdenum film formed at 500°C was about 250 mW-cm, while the resistivity of molybdenum film after 5 nucleation cycle at 550°C was about 340 mW-cm.
  • the resistivities after 2 nucleation cycles in this example are much higher than similar films made after 2 nucleation cycles Example 1 for example, and without wishing to be bound by theory, is believe to be due to the presence of the boron in the films.
  • This example illustrates the deposition of molybdenum on a substrate without a boron nucleation layer that had a TiN layer.
  • the substrate was heated to 700°C on a stage in the reactor and treated with a composition comprising MoCls vapor and differing amounts of hydrogen gas.
  • Process conditions included an inert argon gas flow of 50 seem, a chamber pressure of 60 Torr, and a low hydrogen flow rates of 2000 seem and a high hydrogen flow rate of 4000 seem .
  • results of this example show' that the 4 point measured electrical resistivity of the molybdenum film deposited on the substrate without a nucleation layer ranged from about 15pO cm to 23 mW-cm for a 2G0A thick molybdenum film deposited without a boron nucleation layer to about 10 mW-cm to 16 mW-cm for a 600-800A thick molybdenum film deposited without a boron nucleation layer.
  • compositions and methods are described in terms of “comprising” various components or steps (interpreted as meaning “including, but not limited to”), the compositions and methods can also “consist essentially of or “consist of the various components and steps, such terminology should be interpreted as defining essentially closed or closed member groups.

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Abstract

L'invention concerne un procédé de fabrication de films de molybdène utilisant des couches de nucléation de bore et de molybdène. Les films de molybdène ainsi obtenus présentent une faible résistivité électrique, sont sensiblement dépourvus de bore et peuvent être fabriqués à des températures réduites par comparaison avec des procédés de dépôt chimique en phase vapeur classiques qui n'utilisent pas les couches de nucléation de bore ou de molybdène. La couche de nucléation de molybdène formée par ce procédé peut protéger le substrat vis-à-vis de l'effet de gravure de MoCl5 ou de MoOCl4, facilite la nucléation d'une croissance de Mo par CVD ultérieure sur la partie supérieure de couche de nucléation de molybdène et permet un dépôt CVD de Mo à des températures inférieures. La couche de nucléation peut également être utilisée pour contrôler les tailles de grain de la croissance de Mo par CVD ultérieure, et, par conséquent, régule la résistivité électrique du film de Mo.
PCT/US2019/027792 2018-04-20 2019-04-17 Dépôt de film de molybdène à basse température utilisant des couches de nucléation de bore WO2019204382A1 (fr)

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JP2020558011A JP7425744B2 (ja) 2018-04-20 2019-04-17 ホウ素核形成層を利用した低温モリブデン膜堆積
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Citations (5)

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US20050118804A1 (en) * 2000-06-27 2005-06-02 Applied Materials, Inc. Formation of boride barrier layers using chemisorption techniques
US20050181598A1 (en) * 2003-01-15 2005-08-18 Kailasam Sridhar K. Methods of providing an adhesion layer for adhesion of barrier and/or seed layers to dielectric films
US20150262828A1 (en) * 2014-03-14 2015-09-17 Applied Materials, Inc. MULTI-THRESHOLD VOLTAGE (Vt) WORKFUNCTION METAL BY SELECTIVE ATOMIC LAYER DEPOSITION (ALD)
US20170207087A1 (en) * 2016-01-16 2017-07-20 Applied Materials, Inc. PECVD Tungsten Containing Hardmask Films And Methods Of Making
US20180019165A1 (en) * 2016-07-14 2018-01-18 Entegris, Inc. CVD Mo DEPOSITION BY USING MoOCl4

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050118804A1 (en) * 2000-06-27 2005-06-02 Applied Materials, Inc. Formation of boride barrier layers using chemisorption techniques
US20050181598A1 (en) * 2003-01-15 2005-08-18 Kailasam Sridhar K. Methods of providing an adhesion layer for adhesion of barrier and/or seed layers to dielectric films
US20150262828A1 (en) * 2014-03-14 2015-09-17 Applied Materials, Inc. MULTI-THRESHOLD VOLTAGE (Vt) WORKFUNCTION METAL BY SELECTIVE ATOMIC LAYER DEPOSITION (ALD)
US20170207087A1 (en) * 2016-01-16 2017-07-20 Applied Materials, Inc. PECVD Tungsten Containing Hardmask Films And Methods Of Making
US20180019165A1 (en) * 2016-07-14 2018-01-18 Entegris, Inc. CVD Mo DEPOSITION BY USING MoOCl4

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