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WO2006080782A1 - Method of depositing thin layer using atomic layer deposition - Google Patents

Method of depositing thin layer using atomic layer deposition Download PDF

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Publication number
WO2006080782A1
WO2006080782A1 PCT/KR2006/000169 KR2006000169W WO2006080782A1 WO 2006080782 A1 WO2006080782 A1 WO 2006080782A1 KR 2006000169 W KR2006000169 W KR 2006000169W WO 2006080782 A1 WO2006080782 A1 WO 2006080782A1
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WO
WIPO (PCT)
Prior art keywords
reactant
source
thin layer
chamber
feeding
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2006/000169
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French (fr)
Inventor
Soo-Hyun Kim
Sahng-Kyu Lee
Tae-Wook Seo
Sang-In Lee
Ho-Seung Chang
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IPS Ltd
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IPS Ltd
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Publication of WO2006080782A1 publication Critical patent/WO2006080782A1/en
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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
    • H01L21/02—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]
    • 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
    • C23C16/45536—Use of plasma, radiation or electromagnetic fields
    • C23C16/45538—Plasma being used continuously during the ALD cycle
    • 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
    • C23C16/45531—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 specially adapted for making ternary or higher compositions
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
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    • C23C16/45534—Use of auxiliary reactants other than used for contributing to the composition of the main film, e.g. catalysts, activators or scavengers
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • 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
    • C23C16/45536—Use of plasma, radiation or electromagnetic fields
    • C23C16/45542—Plasma being used non-continuously during the ALD reactions
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C23C16/50—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 using electric discharges
    • C23C16/515—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 using electric discharges using pulsed discharges
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Definitions

  • the present invention relates to a method of depositing a thin layer, and more particularly, to a method of depositing a thin layer using a plasma atomic layer deposition (ALD) process.
  • ALD plasma atomic layer deposition
  • Cu with low resistivity and high electron mobility instead of conventionally used Al for forming interconnection lines.
  • Cu reacts with adjacent materials owing to its high diffusing power, thus deteriorating the performance of the device. Therefore, the use of a diffusion blocking layer made of TaN that can block the diffusion of Cu and has excellent thermal stability and low resistivity is being considered.
  • a chloride and an organic metal are conventionally used for a Ta source.
  • impurities of elemental Cl remain in a thin layer.
  • the organic metal can be deposited at a low temperature, but elemental C remains in the thin layer, and oxygen easily diffuses from the atmosphere into the thin layer owing to the low density of the thin layer, thus increasing the resistivity of the thin layer.
  • FIG. 1 illustrates a conventional process sequence of depositing a thin layer by applying plasma.
  • the conventional method of depositing the thin layer using a plasma ALD process includes repeating a cycle including an operation of first feeding a source into a chamber in which a substrate is loaded, an operation of first purging the source from the chamber, an operation of second feeding a reactant into the chamber, and an operation of second purging an unreacted material or by-products produced in the reaction of the source from the chamber.
  • plasma is applied to the chamber at the same time with the reactant.
  • the plasma facilitates the reaction of the reactant and permits the thin layer to be formed at a low temperature.
  • the applied plasma decomposes the source or reactant into its constituent elements owing to the energy of excited atoms or molecules.
  • the content of residues or unwanted impurities in the thin layer is elevated.
  • the by-products produced in the reaction are excited by the plasma and react with the thin layer during the formation of the thin layer. This phenomenon may be exacerbated by an organic metal reactant rather than an inorganic metal reactant. Disclosure of Invention
  • the present invention provides a method of depositing a thin layer using a plasma atomic layer deposition (ALD) process in which in addition to a source and reactant for forming a thin layer, another reactant and plasma are also supplied to a chamber to deposit a high-quality thin layer.
  • ALD plasma atomic layer deposition
  • the present invention provides a method of depositing a thin layer using a plasma ALD process in which a high-quality thin layer is formed at a low temperature.
  • a method of depositing a thin layer using a plasma ALD process includes feeding one of an organic compound source containing metal atoms and an inorganic compound source containing metal atoms into a chamber in which a wafer is loaded; purging the source from the chamber; feeding a first reactant into the chamber; purging an unreacted portion of the first reactant and by-products produced in the reaction of the source and the first reactant from the chamber; applying plasma while feeding a second reactant into the chamber to improve the quality of a thin layer; and purging an unreacted portion of the second reactant and by-products produced in the reaction of the source and the first reactant from the chamber.
  • a cycle including feeding the source, purging the source, feeding the first reactant, purging the unreacted portion of the first reactant and by-products, applying the plasma while feeding the second reactant, and purging the unreacted portion of the second reactant and by-products is repeated until the thin layer is deposited on the wafer.
  • a method of depositing a thin layer using a plasma ALD process includes repeating n times a sub-cycle including feeding one of an organic compound source containing metal atoms and an inorganic compound source containing metal atoms into a chamber in which a wafer is loaded, purging the source from the chamber, feeding a first reactant into the chamber, and purging an unreacted portion of the first reactant and by-products produced in the reaction of the source from the chamber; applying plasma while feeding a second reactant to the chamber to improve the quality of a thin layer; and purging an unreacted portion of the second reactant and by-products produced in the reaction of the source and the first reactant from the chamber.
  • a cycle including repeating the sub-cycle n times, applying the plasma while feeding the second reactant, and purging the unreacted portion of the second reactant and byproducts is repeated until the thin layer is deposited on the wafer.
  • a method of depositing a thin layer using a plasma ALD process includes repeating n times a sub-cycle including feeding one of an organic compound source containing metal atoms and an inorganic compound source containing metal atoms into a chamber in which a wafer is loaded, purging the source from the chamber, feeding a first reactant into the chamber, purging an unreacted portion of the first reactant and by-products produced in the reaction of the source from the chamber, feeding a second reactant into the chamber to improve the quality of a thin layer, and purging an unreacted portion of the second reactant and by-products produced in the reaction of the source and the first reactant from the chamber; applying plasma while feeding the second reactant to the chamber to improve the quality of the thin layer; and purging the unreacted portion of the second reactant and the by-products produced in the reaction of the source and the first reactant from the chamber.
  • a cycle including repeating the sub-cycle
  • FIG. 1 illustrates a conventional process sequence of depositing a thin layer using a plasma atomic layer deposition (ALD) process
  • FIG. 2 illustrates a schematic construction of a thin layer deposition apparatus using a method of depositing a thin layer using a plasma ALD process according to embodiments of the present invention
  • FIG. 3 illustrates a process sequence of depositing a thin layer using a plasma ALD process according to an embodiment of the present invention in which the application of plasma and the feeding of a second reactant are started and finished at the same time;
  • FIG. 4 illustrates a process sequence of depositing a thin layer using a plasma ALD process according to the embodiment of the present invention, in which the application of plasma is started during the feeding of the second reactant and finished at the same time as the feeding of the second reactant;
  • FIG. 5 illustrates a process sequence of depositing a thin layer using a plasma ALD process according to another embodiment of the present invention
  • FIG. 6 illustrates a process sequence of depositing a thin layer using a plasma ALD process according to yet another embodiment of the present invention.
  • ALD plasma atomic layer deposition
  • FIG. 2 illustrates a schematic construction of a thin layer deposition apparatus using a method of depositing a thin layer using a plasma ALD process according to embodiments of the present invention.
  • the thin layer deposition apparatus includes a reactor 10 in which a wafer 'w' is loaded and a gas box 20 from which a reactant and an inert gas are injected into the reactor 10.
  • Ar is an example of the inert gas for clarity of explanation.
  • Ar will be used as a carrier gas for carrying a source or a reactant or a purge gas for purging the reactor 10.
  • the reactor 10 includes a chamber 11 having a susceptor 12 for mounting the wafer
  • a shower head 13 having a plurality of spray holes positioned toward the wafer 'w', and a plasma generator including a radio-frequency (RF) generator and a matching network.
  • RF radio-frequency
  • the gas box 20 includes at least one canister 21 containing a source, a plurality of mass flow controllers (MFCs) for controlling the flow rate of the carrier gas for carrying the source to the reactor 10 or the purge gas for purging the reactor 10.
  • MFCs mass flow controllers
  • a plurality of valves V are installed in gas lines Ll and L2 among the canister 21, the MFCs, and the reactor 10.
  • the source, a first reactant, a second reactant, and/or Ar gas are carried from the gasbox 20 through the gas lines Ll and L2 to the reactor 10.
  • the gas box 20 can use another canister (not shown) containing a different kind of source, if required.
  • the chamber 11 is a single-wafer-type chamber of which inner wall is maintained at a temperature of 100 to 200 0 C.
  • the susceptor 12 can heat the wafer 'w' to a temperature of 100 to 600 0 C, and the plasma ALD process is carried out while the chamber 11 is being maintained under an internal pressure of 10 mTorr to 10 Torr, preferably, 1 Torr.
  • the source When the source is an organic metal compound, the source may bubble by a carrier gas, such as AR or N, and then injected into the chamber. Alternatively, the source may be injected into the chamber 11 due to a high vapor pressure of the source without the carrier gas. If the vapor pressure of the source is low, the source may be injected into the chamber using a liquid delivery system (LDS) and a vaporizer.
  • LDS liquid delivery system
  • a temperature at which a thin layer is deposited may depend on the kind of the source. In general, the thin layer is deposited in a temperature range at which the source does not decompose but is chemisorbed, and the source is heated to a temperature of 50 to 150 0 C and injected through the shower head 13.
  • Plasma may be generated by the plasma generator in the chamber 11 or externally generated and induced to the chamber 11.
  • the plasma generator uses a power supply with an application power of 100 to 500 W and a frequency of 1 to 1500Hz.
  • a high frequency of 13.56MHz may be applied and a frequency range may be properly selected.
  • FIG. 3 illustrates a process sequence of depositing a thin layer using a plasma ALD process according to an embodiment of the present invention in which the application of plasma and the feeding of a second reactant are started and finished at the same time.
  • FIG. 4 illustrates a process sequence of depositing a thin layer using a plasma ALD process according to the embodiment of the present invention, in which the application of plasma is started during the feeding of the second reactant and finished at the same time as the feeding of the second reactant.
  • the method of depositing the thin layer using the plasma ALD process includes an operation Sl of first feeding an organic or inorganic compound source containing metal atoms into a chamber 11 in which a wafer 'w' is loaded; an operation S2 of first purging the organic or inorganic compound source from the chamber 11; an operation S3 of second feeding a first reactant into the chamber 11 ; an operation S4 of second purging an unreacted portion of the first reactant and by-products produced in the reaction of the source from the chamber 11 ; an operation S 5 of applying plasma while third feeding a second reactant into the chamber 11 to improve the quality of a thin layer; and an operation S6 of purging an unreacted portion of the second reactant and by-products produced in the reaction of the source and the first reactant from the chamber 11, and a cycle including the operation Sl, the operation S2, the operation S3, the operation S4, the operation S5, and the operation S6 is repeated until the thin layer is deposited on the wafer '
  • a binary thin layer is exemplarily described.
  • two different kinds of sources i.e., a first source and a second source, should be co-injected or serially injected into the reactor 10 in the operation Sl.
  • the first source may be TEMATi(Tert-Ethyl-Methyl-Amine-Titatium: Ti(C H -N-CH ) ), and the second
  • 2 5 3 4 source may be TEMASi(Tetrakis(ethylmethylamino)silicon: Si[ N(CH ) CH5] ).
  • the application of plasma and the feeding of the second reactant are started and finished at the same time as shown in FIG. 3.
  • the application of the plasma is started during the feeding of the second reactant and finished at the same time as the feeding of the second reactant.
  • a metal thin layer may be formed on the wafer 'w.'
  • the first reactant may be H
  • the second reactant may be H or a compound containing H atoms.
  • a conductive thin layer may be formed on the wafer 'w.'
  • the first reactant may be N , NH , or a compound containing N atoms and the second reactant may be H or a compound containing H atoms.
  • an insulating thin layer may be formed on the wafer 'w.'
  • the first reactant may be H , O , or a compound containing H or O atoms
  • the second reactant may be O , O , or an oxidizer containing O atoms.
  • the wafer 'w' is loaded onto the susceptor 12, which is heated to a temperature of 250 0 C, and maintained for 10 to 60 seconds until the wafer 'w' reaches a certain temperature.
  • the above-described feeding and purge operations are carried out.
  • a TEMATi source is fed into the chamber 11 through the shower head 13 under a pressure of 1 Torr for 1 to 10 seconds in a bubbling system using an Ar carrier gas that is heated to a temperature of 120 0 C.
  • the time taken for feeding the TEMATi source varies with the dimension of the chamber 11, the kind of the wafer 'w,' and the integration density of a device disposed on the wafer 'w' and can be shortened as much as physically possible.
  • the maximum feeding time is determined considering the productivity of the single-wafer-type chamber. Therefore, when the chamber 11 is a multi-wafer loading system or mini-batch-type chamber in which at least one wafer 'w' is loaded, the time taken for the feeding of the TEMATi source should be extended.
  • the chamber 11 has a volume of 20 litters and the shower head 13 has a typical form.
  • a chemisorbed molecular layer (and sometimes both of the chemisorbed molecular layer and a portion of the physisorbed layer) may remain on the wafer 'w.'
  • a deposition rate and layer quality can be adjusted by controlling the extent of a purge/pumping process. For example, when the purge/ pumping process is carried out for a long time of 10 seconds or more to leave only the chemisorbed layer, only one atomic layer can be desirably deposited for 1 cycle.
  • NH which is heated to a temperature of 120 0 C, is fed as the first reactant into the chamber 11 for 1 to 10 seconds to induce a primary reaction.
  • NH is injected at a flow rate of 100 to 500 seem while the chamber 11 is maintained under an internal pressure of 1 Torr.
  • H is fed as the second reactant into the chamber 11 at a flow rate of 100 to 500 seem to induce a secondary reaction, and simultaneously, power is supplied to the plasma generator to generate plasma in the chamber 11.
  • H is excited by the plasma and functions as a reducing agent to remove impurities from the thin layer, thus improving the quality of the thin layer.
  • a power of 100 to 300 Watt is supplied for 1 to 10 seconds.
  • the formation of the TiN layer is exemplarily described, but a ternary thin layer, such as a TiAlN layer or a TiSiN layer, may be deposited.
  • a ternary thin layer such as a TiAlN layer or a TiSiN layer
  • TEMATi and TEMASi may be co-injected into the shower head 13 using an additional supply system and mixed in the shower head 13 or serially injected into the shower head 13.
  • a ternary thin layer i.e., a TiSiN thin layer
  • TEMATi when TEMATi is fed, the chamber 11 is purged, a first reactant is fed, the chamber 11 is purged, TEMASi is fed, the chamber 11 is purged, a first reactant is fed, the chamber 11 is purged, a second reactant is fed and plasma is applied, and the chamber 11 is purged, so that a ternary thin layer (i.e., a TiSiN thin layer) is deposited.
  • a ternary thin layer i.e., a TiSiN thin layer
  • FIG. 5 illustrates a process sequence of depositing a thin layer using a plasma ALD process according to another embodiment of the present invention.
  • the method of depositing the thin layer using the plasma ALD process includes a sub-cycle operation SlOO of repeating n times an operation Sl of first feeding an organic or inorganic compound source containing metal atoms into a chamber 11 in which a wafer 'w' is loaded, an operation S2 of first purging the organic or inorganic compound source from the chamber 11, an operation S3 of second feeding a first reactant into the chamber 11, and an operation S4 of second purging an unreacted portion of the first reactant and by-products produced in the reaction of the source from the chamber 11; an operation Sl 10 of applying plasma while third feeding a second reactant to the chamber 11 to improve the quality of a thin layer; and an operation S 120 of third purging an unreacted portion of the first reactant and byproducts produced in the reaction of the source and the first reactant from the chamber 11, and a cycle including the sub-cycle operation SlOO, the operation Sl 10, and the operation S 120 is repeated until the thin layer is deposited on the wa
  • a metal thin layer may be formed on the wafer 'w.'
  • the first reactant may be H
  • the second reactant may be H or a compound containing H atoms.
  • a conductive thin layer may be formed on the wafer 'w.
  • the first reactant may be N , NH , or a compound containing N atoms and the second reactant may be H or a compound containing H atoms.
  • an insulating thin layer may be formed on the wafer 'w.
  • the first reactant may be H , O , or a compound containing H or O atoms
  • the second reactant may be O , O , or an oxidizer containing O atoms.
  • an oxidizer containing O atoms may be used as the first reactant, and O , O , or an oxidizer containing O atoms may be activated and used as the second reactant.
  • H is fed as the second reactant into the chamber 11 at a flow rate of 100 to 500 seem to induce a secondary reaction, and simultaneously, power is supplied to the plasma generator to generate plasma in the chamber 11.
  • H is excited by the plasma and functions as a reducing agent to remove impurities from the thin layer, thus improving the quality of the thin layer.
  • a power of 100 to 300 Watt is supplied for 1 to 10 seconds.
  • the deposited thin layer of the present embodiment has inferior characteristics
  • a deposition rate greatly improves owing to the sub-cycle, and a device is less degraded because the number of times plasma is applied is reduced.
  • FIG. 6 illustrates a process sequence of depositing a thin layer using a plasma ALD process according to yet another embodiment of the present invention.
  • the method of depositing the thin layer using the plasma ALD process includes a sub-cycle operation S200 of repeating n times a sub-cycle including an operation S 1 of first feeding an organic or inorganic compound source containing metal atoms into a chamber 11 in which a wafer 'w' is loaded, an operation S2 of first purging the organic or inorganic compound source from the chamber 11, an operation S3 of second feeding a first reactant into the chamber 11, an operation S4 of second purging an unreacted portion of the first reactant and by-products produced in the reaction of the source and the first reactant from the chamber 11, an operation S5 of third feeding a second reactant into the chamber 11 to improve the quality of a thin layer, and an operation S6 of third purging an unreacted portion of the second reactant or by-products produced in the reaction of the source and the first reactant from the chamber 11; an operation S210 of fourth applying plasma while feeding the second reactant to the chamber 11 to improve the quality of the thin layer; and an operation S210 of fourth applying plasma while feeding
  • the present embodiment is different from the previous embodiment in that the sub-cycle of the previous embodiment includes the operation Sl, the operation S2, the operation S3, and the operation S4, while the sub-cycle of the present embodiment includes the operation Sl, the operation S2, the operation S3, the operation S4, the operation S5, and the operation S6.
  • the sub-cycle operation S200 further includes the operations S 5 and S 6 of third feeding and third purging the second reactant.
  • the deposited thin layer of the present embodiment has superior film quality than the previous embodiment, but a deposition rate is slightly degraded.
  • a metal thin layer may be formed on the wafer 'w.'
  • the first reactant may be H
  • the second reactant may be H or a compound containing H atoms.
  • a conductive thin layer may be formed on the wafer 'w.
  • the first reactant may be N , NH , or a compound containing N atoms and the second reactant may be H or a compound containing H atoms.
  • an insulating thin layer may be formed on the wafer 'w.
  • the first reactant may be H , O , or a compound containing H or O atoms
  • the second reactant may be O , O , or an oxidizer containing O atoms.
  • an oxidizer containing O atoms may be used as the first reactant, and O , O , or an oxidizer containing O atoms may be activated and used as the second reactant.
  • the thin layer obtained through the above-described methods may be a nitride layer formed of TiN, TaN, HfN, TiAlN, TiSiN, or TaSiN, a metal layer formed of Al, Cu, Ti, Ta, Hf, Ru, Si, Pt, or Ir, a carbide layer formed of TiC, TaC, or HfC, or a compound layer formed of TiCN, TaCN, or HfCN.
  • the plasma is applied while feeding the additional reactant into the chamber, the decomposition of the source or the reactant into its constituent elements is inhibited.
  • the content of residues or unwanted impurities in the thin layer is not elevated.
  • a reaction of excited by-products with the thin layer is prevented during the formation of the thin layer.
  • the thin layer can further improve in film quality.

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Abstract

Provided is a method of depositing a thin layer using a plasma atomic layer deposition (ALD) process. The method includes feeding one of an organic compound source containing metal atoms and an inorganic compound source containing metal atoms into a chamber in which a wafer is loaded; purging the source from the chamber; feeding a first reactant into the chamber; purging an unreacted portion of the first reactant and by-products produced in the reaction of the source from the chamber; applying plasma while feeding a second reactant into the chamber to improve the quality of the thin layer; and purging an unreacted portion of the second reactant and by-products produced in the reaction of the source and the first reactant from the chamber. A cycle including feeding the source, purging the source, feeding the first reactant, purging the unreacted portion of the first reactant and by-products, applying the plasma while feeding the second reactant, and purging the unreacted portion of the second reactant and by-products is repeated until the thin layer is deposited on the wafer.

Description

Description METHOD OF DEPOSITING THIN LAYER USING ATOMIC
LAYER DEPOSITION
Technical Field
[1] The present invention relates to a method of depositing a thin layer, and more particularly, to a method of depositing a thin layer using a plasma atomic layer deposition (ALD) process.
Background Art
[2] The downscaling of the line width of the circuits of a device has lead to the use of
Cu with low resistivity and high electron mobility instead of conventionally used Al for forming interconnection lines. However, Cu reacts with adjacent materials owing to its high diffusing power, thus deteriorating the performance of the device. Therefore, the use of a diffusion blocking layer made of TaN that can block the diffusion of Cu and has excellent thermal stability and low resistivity is being considered.
[3] To form a TaN diffusion blocking layer, a chloride and an organic metal are conventionally used for a Ta source. However, impurities of elemental Cl remain in a thin layer. Also, the organic metal can be deposited at a low temperature, but elemental C remains in the thin layer, and oxygen easily diffuses from the atmosphere into the thin layer owing to the low density of the thin layer, thus increasing the resistivity of the thin layer.
[4] To overcome the forgoing drawbacks, there have been a lot of attempts at facilitating the reaction of a source and at attaining low resistivity by increasing the density of a thin layer using a plasma process.
[5] FIG. 1 illustrates a conventional process sequence of depositing a thin layer by applying plasma.
[6] Referring to FIG. 1, the conventional method of depositing the thin layer using a plasma ALD process includes repeating a cycle including an operation of first feeding a source into a chamber in which a substrate is loaded, an operation of first purging the source from the chamber, an operation of second feeding a reactant into the chamber, and an operation of second purging an unreacted material or by-products produced in the reaction of the source from the chamber. In this case, plasma is applied to the chamber at the same time with the reactant. Thus, the plasma facilitates the reaction of the reactant and permits the thin layer to be formed at a low temperature.
[7] However, the applied plasma decomposes the source or reactant into its constituent elements owing to the energy of excited atoms or molecules. Thus, the content of residues or unwanted impurities in the thin layer is elevated. [8] Also, the by-products produced in the reaction are excited by the plasma and react with the thin layer during the formation of the thin layer. This phenomenon may be exacerbated by an organic metal reactant rather than an inorganic metal reactant. Disclosure of Invention
Technical Problem
[9]
Technical Solution
[10] The present invention provides a method of depositing a thin layer using a plasma atomic layer deposition (ALD) process in which in addition to a source and reactant for forming a thin layer, another reactant and plasma are also supplied to a chamber to deposit a high-quality thin layer.
[11] Also, the present invention provides a method of depositing a thin layer using a plasma ALD process in which a high-quality thin layer is formed at a low temperature.
[12] According to an aspect of the present invention, there is provided a method of depositing a thin layer using a plasma ALD process. The method includes feeding one of an organic compound source containing metal atoms and an inorganic compound source containing metal atoms into a chamber in which a wafer is loaded; purging the source from the chamber; feeding a first reactant into the chamber; purging an unreacted portion of the first reactant and by-products produced in the reaction of the source and the first reactant from the chamber; applying plasma while feeding a second reactant into the chamber to improve the quality of a thin layer; and purging an unreacted portion of the second reactant and by-products produced in the reaction of the source and the first reactant from the chamber. Herein, a cycle including feeding the source, purging the source, feeding the first reactant, purging the unreacted portion of the first reactant and by-products, applying the plasma while feeding the second reactant, and purging the unreacted portion of the second reactant and by-products is repeated until the thin layer is deposited on the wafer.
[13] According to another aspect of the present invention, there is provided a method of depositing a thin layer using a plasma ALD process. The method includes repeating n times a sub-cycle including feeding one of an organic compound source containing metal atoms and an inorganic compound source containing metal atoms into a chamber in which a wafer is loaded, purging the source from the chamber, feeding a first reactant into the chamber, and purging an unreacted portion of the first reactant and by-products produced in the reaction of the source from the chamber; applying plasma while feeding a second reactant to the chamber to improve the quality of a thin layer; and purging an unreacted portion of the second reactant and by-products produced in the reaction of the source and the first reactant from the chamber. Herein, a cycle including repeating the sub-cycle n times, applying the plasma while feeding the second reactant, and purging the unreacted portion of the second reactant and byproducts is repeated until the thin layer is deposited on the wafer.
[14] According to yet another aspect of the present invention, there is provided a method of depositing a thin layer using a plasma ALD process. The method includes repeating n times a sub-cycle including feeding one of an organic compound source containing metal atoms and an inorganic compound source containing metal atoms into a chamber in which a wafer is loaded, purging the source from the chamber, feeding a first reactant into the chamber, purging an unreacted portion of the first reactant and by-products produced in the reaction of the source from the chamber, feeding a second reactant into the chamber to improve the quality of a thin layer, and purging an unreacted portion of the second reactant and by-products produced in the reaction of the source and the first reactant from the chamber; applying plasma while feeding the second reactant to the chamber to improve the quality of the thin layer; and purging the unreacted portion of the second reactant and the by-products produced in the reaction of the source and the first reactant from the chamber. Herein, a cycle including repeating the sub-cycle n times, applying the plasma while feeding the second reactant, and purging the unreacted portion of the second reactant and by-products is repeated until the thin layer is deposited on the wafer.
Advantageous Effects
[15]
Description of Drawings
[16] FIG. 1 illustrates a conventional process sequence of depositing a thin layer using a plasma atomic layer deposition (ALD) process;
[17] FIG. 2 illustrates a schematic construction of a thin layer deposition apparatus using a method of depositing a thin layer using a plasma ALD process according to embodiments of the present invention;
[18] FIG. 3 illustrates a process sequence of depositing a thin layer using a plasma ALD process according to an embodiment of the present invention in which the application of plasma and the feeding of a second reactant are started and finished at the same time;
[19] FIG. 4 illustrates a process sequence of depositing a thin layer using a plasma ALD process according to the embodiment of the present invention, in which the application of plasma is started during the feeding of the second reactant and finished at the same time as the feeding of the second reactant;
[20] FIG. 5 illustrates a process sequence of depositing a thin layer using a plasma ALD process according to another embodiment of the present invention; and [21] FIG. 6 illustrates a process sequence of depositing a thin layer using a plasma ALD process according to yet another embodiment of the present invention.
Best Mode
[22] A method of depositing a thin layer using a plasma atomic layer deposition (ALD) process according to the present invention will now be described more fully hereinafter with reference to the accompanying drawings, in which embodiments of the invention are shown.
[23] FIG. 2 illustrates a schematic construction of a thin layer deposition apparatus using a method of depositing a thin layer using a plasma ALD process according to embodiments of the present invention.
[24] Referring to FIG. 2, the thin layer deposition apparatus includes a reactor 10 in which a wafer 'w' is loaded and a gas box 20 from which a reactant and an inert gas are injected into the reactor 10. In the present embodiment, Ar is an example of the inert gas for clarity of explanation. Thus, Ar will be used as a carrier gas for carrying a source or a reactant or a purge gas for purging the reactor 10.
[25] The reactor 10 includes a chamber 11 having a susceptor 12 for mounting the wafer
'w', a shower head 13 having a plurality of spray holes positioned toward the wafer 'w', and a plasma generator including a radio-frequency (RF) generator and a matching network. In this case, the susceptor 12 heats the wafer 'w' to a certain temperature.
[26] The gas box 20 includes at least one canister 21 containing a source, a plurality of mass flow controllers (MFCs) for controlling the flow rate of the carrier gas for carrying the source to the reactor 10 or the purge gas for purging the reactor 10. A plurality of valves V are installed in gas lines Ll and L2 among the canister 21, the MFCs, and the reactor 10. The source, a first reactant, a second reactant, and/or Ar gas are carried from the gasbox 20 through the gas lines Ll and L2 to the reactor 10. In this case, although only one canister 21 containing a kind of source is exemplarily illustrated in FIG. 2, it is obvious that the gas box 20 can use another canister (not shown) containing a different kind of source, if required.
[27] In the present embodiment, the chamber 11 is a single-wafer-type chamber of which inner wall is maintained at a temperature of 100 to 200 0C. Also, the susceptor 12 can heat the wafer 'w' to a temperature of 100 to 600 0C, and the plasma ALD process is carried out while the chamber 11 is being maintained under an internal pressure of 10 mTorr to 10 Torr, preferably, 1 Torr.
[28] When the source is an organic metal compound, the source may bubble by a carrier gas, such as AR or N, and then injected into the chamber. Alternatively, the source may be injected into the chamber 11 due to a high vapor pressure of the source without the carrier gas. If the vapor pressure of the source is low, the source may be injected into the chamber using a liquid delivery system (LDS) and a vaporizer. [29] A temperature at which a thin layer is deposited may depend on the kind of the source. In general, the thin layer is deposited in a temperature range at which the source does not decompose but is chemisorbed, and the source is heated to a temperature of 50 to 150 0C and injected through the shower head 13.
[30] Plasma may be generated by the plasma generator in the chamber 11 or externally generated and induced to the chamber 11. In the present embodiment, it is exemplarily described that plasma is generated in the chamber 11. In this case, the plasma generator uses a power supply with an application power of 100 to 500 W and a frequency of 1 to 1500Hz. However, a high frequency of 13.56MHz may be applied and a frequency range may be properly selected.
[31] A method of depositing a thin layer using a plasma ALD process used in the above described thin layer deposition apparatus according to an embodiment of the present invention will now be described.
[32] FIG. 3 illustrates a process sequence of depositing a thin layer using a plasma ALD process according to an embodiment of the present invention in which the application of plasma and the feeding of a second reactant are started and finished at the same time. FIG. 4 illustrates a process sequence of depositing a thin layer using a plasma ALD process according to the embodiment of the present invention, in which the application of plasma is started during the feeding of the second reactant and finished at the same time as the feeding of the second reactant.
[33] Referring to FIGS. 3 and 4, the method of depositing the thin layer using the plasma ALD process includes an operation Sl of first feeding an organic or inorganic compound source containing metal atoms into a chamber 11 in which a wafer 'w' is loaded; an operation S2 of first purging the organic or inorganic compound source from the chamber 11; an operation S3 of second feeding a first reactant into the chamber 11 ; an operation S4 of second purging an unreacted portion of the first reactant and by-products produced in the reaction of the source from the chamber 11 ; an operation S 5 of applying plasma while third feeding a second reactant into the chamber 11 to improve the quality of a thin layer; and an operation S6 of purging an unreacted portion of the second reactant and by-products produced in the reaction of the source and the first reactant from the chamber 11, and a cycle including the operation Sl, the operation S2, the operation S3, the operation S4, the operation S5, and the operation S6 is repeated until the thin layer is deposited on the wafer 'w.' When the cycle including the operations Sl through S6 is performed once, a first atomic layer or a first molecular layer is formed on the wafer 'w.' In this case, the source may be one selected from the group consisting of TEMATi, TEMASi, ECTDMAT, PEMAT, TBTEMAT, and DER[2,4-(Dimethylpentadienyl)(Ethylcyclopentadienyl)Ruthenium] .
[34] In the present embodiment, a binary thin layer is exemplarily described. However, when a ternary thin layer is formed, two different kinds of sources, i.e., a first source and a second source, should be co-injected or serially injected into the reactor 10 in the operation Sl. For example, the first source may be TEMATi(Tert-Ethyl-Methyl-Amine-Titatium: Ti(C H -N-CH ) ), and the second
2 5 3 4 source may be TEMASi(Tetrakis(ethylmethylamino)silicon: Si[ N(CH ) CH5] ). [35] In the operation S5, the application of plasma and the feeding of the second reactant are started and finished at the same time as shown in FIG. 3. [36] Alternatively, in the operation S5, the application of the plasma is started during the feeding of the second reactant and finished at the same time as the feeding of the second reactant. [37] In the above-described process, a metal thin layer may be formed on the wafer 'w.'
For this, the first reactant may be H , and the second reactant may be H or a compound containing H atoms. [38] In another case, a conductive thin layer may be formed on the wafer 'w.' For this, the first reactant may be N , NH , or a compound containing N atoms and the second reactant may be H or a compound containing H atoms. [39] In yet another case, an insulating thin layer may be formed on the wafer 'w.' For this, the first reactant may be H , O , or a compound containing H or O atoms, and the second reactant may be O , O , or an oxidizer containing O atoms. [40] Alternatively, to form the insulating thin layer on the wafer 'w,' O , O , or an oxidizer containing O atoms may be used as the first reactant, and O , O , or an oxidizer containing O atoms may be activated and used as the second reactant. [41] Alternatively, to form the insulating thin layer on the wafer 'w,' H may be used as the first reactant, and O , O , or an oxidizer containing O atoms may be activated and used as the second reactant. [42] Hereinafter, a method of depositing a TiN thin layer according to the present embodiment will be exemplarily described. [43] Initially, the wafer 'w' is loaded onto the susceptor 12, which is heated to a temperature of 250 0C, and maintained for 10 to 60 seconds until the wafer 'w' reaches a certain temperature. Next, the above-described feeding and purge operations are carried out. [44] In the operation Sl, a TEMATi source is fed into the chamber 11 through the shower head 13 under a pressure of 1 Torr for 1 to 10 seconds in a bubbling system using an Ar carrier gas that is heated to a temperature of 120 0C. In this case, the time taken for feeding the TEMATi source varies with the dimension of the chamber 11, the kind of the wafer 'w,' and the integration density of a device disposed on the wafer 'w' and can be shortened as much as physically possible. [45] Also, the maximum feeding time is determined considering the productivity of the single-wafer-type chamber. Therefore, when the chamber 11 is a multi-wafer loading system or mini-batch-type chamber in which at least one wafer 'w' is loaded, the time taken for the feeding of the TEMATi source should be extended. In the present embodiment, the chamber 11 has a volume of 20 litters and the shower head 13 has a typical form.
[46] In the operation S2, while Ar gas, which is heated to a temperature of 120 0C, is being fed as a purge gas into the chamber 11, not only TEMATi remaining in the gas lines Ll and L2, the shower head 13, and the chamber 11 but also partial or whole TEMATi that is physisorbed on the wafer 'w' are purged and pumped out of the chamber 11 for 1 to 30 seconds.
[47] After the operation S2, a chemisorbed molecular layer (and sometimes both of the chemisorbed molecular layer and a portion of the physisorbed layer) may remain on the wafer 'w.' In this case, a deposition rate and layer quality can be adjusted by controlling the extent of a purge/pumping process. For example, when the purge/ pumping process is carried out for a long time of 10 seconds or more to leave only the chemisorbed layer, only one atomic layer can be desirably deposited for 1 cycle. However, when the operation S2 is carried out for a short time of less than 10 seconds (e.g., 1 to 5 seconds), not only the chemisorbed molecular layer but also a portion of the physisorbed layer remain on the wafer 'w,' thus several atomic layers are deposited during 1 cycle.
[48] In the operation S3, NH , which is heated to a temperature of 120 0C, is fed as the first reactant into the chamber 11 for 1 to 10 seconds to induce a primary reaction. In this case, NH is injected at a flow rate of 100 to 500 seem while the chamber 11 is maintained under an internal pressure of 1 Torr.
[49] In the operation S4, a purge process is carried out in the same manner as in the case of the operation S2 in order to eliminate unreacted residue of NH and by-products produced in the primary reaction.
[50] In the operation S5, H is fed as the second reactant into the chamber 11 at a flow rate of 100 to 500 seem to induce a secondary reaction, and simultaneously, power is supplied to the plasma generator to generate plasma in the chamber 11. As a result, H is excited by the plasma and functions as a reducing agent to remove impurities from the thin layer, thus improving the quality of the thin layer. In this case, a power of 100 to 300 Watt is supplied for 1 to 10 seconds.
[51] In the operation S6, a purge/pumping process is carried out using Ar gas that is heated to a temperature of 120 0C.
[52] The above-described operations Sl through S6 forms one cycle of forming a thin layer of an atomic layer, and the atomic layer is deposited by repeating the cycle. When one cycle including the operations Sl through S6 is completed, a 1-5- A thick TiN layer is obtained.
[53] In the present embodiment, the formation of the TiN layer is exemplarily described, but a ternary thin layer, such as a TiAlN layer or a TiSiN layer, may be deposited. For instance, when the TiSiN thin layer is deposited, TEMATi and TEMASi may be co-injected into the shower head 13 using an additional supply system and mixed in the shower head 13 or serially injected into the shower head 13.
[54] When the constituents of a thin layer are changed using the co-injection method, the flow rates of TEMATi and TEMASi and partial pressure can be controlled. When the constituents of the thin layer are changed using the serial injection method, the flow rates of TEMATi and TEMASi and injection time can be controlled.
[55] Specifically, when TEMATi and TEMASi are fed, the chamber 11 is purged, a first reactant is fed, the chamber 11 is purged, a second reactant is fed and plasma is applied, and the chamber 11 is purged, so that a ternary thin layer (i.e., a TiSiN thin layer) is deposited. Alternatively, when TEMATi is fed, the chamber 11 is purged, a first reactant is fed, the chamber 11 is purged, TEMASi is fed, the chamber 11 is purged, a first reactant is fed, the chamber 11 is purged, a second reactant is fed and plasma is applied, and the chamber 11 is purged, so that a ternary thin layer (i.e., a TiSiN thin layer) is deposited.
[56] Hereinafter, a method of depositing a thin layer using a plasma ALD process in the above-described thin layer deposition apparatus according to another embodiment of the present invention will be described with reference to FIG. 5.
[57] FIG. 5 illustrates a process sequence of depositing a thin layer using a plasma ALD process according to another embodiment of the present invention.
[58] Referring to FIG. 5, the method of depositing the thin layer using the plasma ALD process includes a sub-cycle operation SlOO of repeating n times an operation Sl of first feeding an organic or inorganic compound source containing metal atoms into a chamber 11 in which a wafer 'w' is loaded, an operation S2 of first purging the organic or inorganic compound source from the chamber 11, an operation S3 of second feeding a first reactant into the chamber 11, and an operation S4 of second purging an unreacted portion of the first reactant and by-products produced in the reaction of the source from the chamber 11; an operation Sl 10 of applying plasma while third feeding a second reactant to the chamber 11 to improve the quality of a thin layer; and an operation S 120 of third purging an unreacted portion of the first reactant and byproducts produced in the reaction of the source and the first reactant from the chamber 11, and a cycle including the sub-cycle operation SlOO, the operation Sl 10, and the operation S 120 is repeated until the thin layer is deposited on the wafer 'w.' In this case, the source may be one selected from the group consisting of TEMATi, TEMASi, ECTDMAT, PEMAT, TBTEMAT, and DER. [59] In the sub-cycle operation SlOO, a pure thermal reaction is caused without applying plasma, and the sub-cycle including the operation Sl, the operation S2, the operation S3, and the operation S4 is repeated n times.
[60] In the sub-cycle operation SlOO, since the source and the first reactant are repetitively fed and purged without applying plasma, a complete thin layer is not formed. Accordingly, the second reactant and the plasma are additionally injected in the subsequent operation Sl 10, so that the thin layer is completed.
[61] In the above-described process, a metal thin layer may be formed on the wafer 'w.'
For this, the first reactant may be H , and the second reactant may be H or a compound containing H atoms.
[62] In another case, a conductive thin layer may be formed on the wafer 'w.' For this, the first reactant may be N , NH , or a compound containing N atoms and the second reactant may be H or a compound containing H atoms.
[63] In yet another case, an insulating thin layer may be formed on the wafer 'w.' For this, the first reactant may be H , O , or a compound containing H or O atoms, and the second reactant may be O , O , or an oxidizer containing O atoms.
[64] Alternatively, to form the insulating thin layer on the wafer 'w,' O , O , or an oxidizer containing O atoms may be used as the first reactant, and O , O , or an oxidizer containing O atoms may be activated and used as the second reactant.
[65] Alternatively, to form the insulating thin layer on the wafer 'w,' H may be used as the first reactant, and O , O , or an oxidizer containing O atoms may be activated and used as the second reactant.
[66] For example, in the third operation Sl 10, H is fed as the second reactant into the chamber 11 at a flow rate of 100 to 500 seem to induce a secondary reaction, and simultaneously, power is supplied to the plasma generator to generate plasma in the chamber 11. As a result, H is excited by the plasma and functions as a reducing agent to remove impurities from the thin layer, thus improving the quality of the thin layer. In this case, a power of 100 to 300 Watt is supplied for 1 to 10 seconds.
[67] In the operation S 120, a purge/pumping process is carried out using Ar gas that is heated to a temperature of 120 0C.
[68] The sub-cycle operation SlOO, the operation Sl 10, and the operation S 120 is repeated until the thin layer is formed to a desired thickness.
[69] The deposited thin layer of the present embodiment has inferior characteristics
(e.g., density) than that of the previous embodiment. However, a deposition rate greatly improves owing to the sub-cycle, and a device is less degraded because the number of times plasma is applied is reduced.
[70] Hereinafter, a method of depositing a thin layer using a plasma ALD process in the above-described thin layer deposition apparatus according to yet another embodiment of the present invention will be described with reference to FIG. 6.
[71] FIG. 6 illustrates a process sequence of depositing a thin layer using a plasma ALD process according to yet another embodiment of the present invention.
[72] Referring to FIG. 6, the method of depositing the thin layer using the plasma ALD process includes a sub-cycle operation S200 of repeating n times a sub-cycle including an operation S 1 of first feeding an organic or inorganic compound source containing metal atoms into a chamber 11 in which a wafer 'w' is loaded, an operation S2 of first purging the organic or inorganic compound source from the chamber 11, an operation S3 of second feeding a first reactant into the chamber 11, an operation S4 of second purging an unreacted portion of the first reactant and by-products produced in the reaction of the source and the first reactant from the chamber 11, an operation S5 of third feeding a second reactant into the chamber 11 to improve the quality of a thin layer, and an operation S6 of third purging an unreacted portion of the second reactant or by-products produced in the reaction of the source and the first reactant from the chamber 11; an operation S210 of fourth applying plasma while feeding the second reactant to the chamber 11 to improve the quality of the thin layer; and an operation S220 of fourth purging the unreacted portion of the second reactant or the by-products produced in the reaction of the source and the first reactant from the chamber 11, and a cycle including the sub-cycle operation S200, the operation S210, and the operation S220 is repeated until the thin layer is deposited on the wafer 'w.' In this case, the source may be one selected from the group consisting of TEMATi, TEMASi, ECTDMAT, PEMAT, TBTEMAT, and DER.
[73] The present embodiment is different from the previous embodiment in that the sub- cycle of the previous embodiment includes the operation Sl, the operation S2, the operation S3, and the operation S4, while the sub-cycle of the present embodiment includes the operation Sl, the operation S2, the operation S3, the operation S4, the operation S5, and the operation S6.
[74] In the present embodiment, the sub-cycle operation S200 further includes the operations S 5 and S 6 of third feeding and third purging the second reactant. As a result, the deposited thin layer of the present embodiment has superior film quality than the previous embodiment, but a deposition rate is slightly degraded.
[75] In the above-described process, a metal thin layer may be formed on the wafer 'w.'
For this, the first reactant may be H , and the second reactant may be H or a compound containing H atoms.
[76] In another case, a conductive thin layer may be formed on the wafer 'w.' For this, the first reactant may be N , NH , or a compound containing N atoms and the second reactant may be H or a compound containing H atoms.
[77] In yet another case, an insulating thin layer may be formed on the wafer 'w.' For this, the first reactant may be H , O , or a compound containing H or O atoms, and the second reactant may be O , O , or an oxidizer containing O atoms.
[78] Alternatively, to form the insulating thin layer on the wafer 'w,' O , O , or an oxidizer containing O atoms may be used as the first reactant, and O , O , or an oxidizer containing O atoms may be activated and used as the second reactant.
[79] Alternatively, to form the insulating thin layer on the wafer 'w,' H may be used as the first reactant, and O , O , or an oxidizer containing O atoms may be activated and used as the second reactant.
[80] The thin layer obtained through the above-described methods may be a nitride layer formed of TiN, TaN, HfN, TiAlN, TiSiN, or TaSiN, a metal layer formed of Al, Cu, Ti, Ta, Hf, Ru, Si, Pt, or Ir, a carbide layer formed of TiC, TaC, or HfC, or a compound layer formed of TiCN, TaCN, or HfCN.
[81] According to the present invention as described above, in addition to a source and reactant for forming a thin layer, another reactant and plasma are additionally supplied to a chamber, so that a high-quality thin layer can be deposited at a relatively low temperature.
[82] Also, since the plasma is applied while feeding the additional reactant into the chamber, the decomposition of the source or the reactant into its constituent elements is inhibited. Thus, the content of residues or unwanted impurities in the thin layer is not elevated. Further, a reaction of excited by-products with the thin layer is prevented during the formation of the thin layer. As a consequence, the thin layer can further improve in film quality.
[83] While the present invention has been particularly shown and described with reference to embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims.

Claims

Claims
[1] A method of depositing a thin layer using a plasma ALD (atomic layer deposition) process, the method comprising: feeding one of an organic compound source containing metal atoms and an inorganic compound source containing metal atoms into a chamber in which a wafer is loaded; purging the source from the chamber; feeding a first reactant into the chamber; purging an unreacted portion of the first reactant and by-products produced in the reaction of the source from the chamber; applying plasma while feeding a second reactant into the chamber to improve the quality of a thin layer; and purging an unreacted portion of the second reactant and by-products produced in the reaction of the source and the first reactant from the chamber, wherein a cycle including feeding the source, purging the source, feeding the first reactant, purging the unreacted portion of the first reactant and by-products, applying the plasma while feeding the second reactant, and purging the unreacted portion of the second reactant and by-products is repeated until the thin layer is deposited on the wafer.
[2] The method of claim 1, wherein the applying of the plasma and the feeding of the second reactant are started and finished at the same time.
[3] The method of claim 1, wherein the applying of the plasma is started during the feeding of the second reactant and finished at the same as the feeding of the second reactant.
[4] The method of any one of claims 2 and 3, wherein to form a metal thin layer, the source is one selected from the group consisting of TEMATi, TEMASi, ECTDMAT, PEMAT, TBTEMAT, and DER, the first reactant is H , and the second reactant is one of H and a compound containing H atoms.
[5] The method of any one of claims 2 and 3, wherein to form a conductive thin layer, the source is one selected from the group consisting of TEMATi, TEMASi, ECTDMAT, PEMAT, TBTEMAT, and DER, the first reactant is one selected from the group consisting of N , NH , and a compound containing N atoms, and the second reactant is one of H and a compound containing H atoms.
[6] The method of any one of claims 2 and 3, wherein to form an insulating thin layer, the source is one selected from the group consisting of TEMATi, TEMASi, ECTDMAT, PEMAT, TBTEMAT, and DER, the first reactant is one selected from the group consisting of O , O , and an oxidizer containing O atoms, and the second reactant is one selected from the group consisting of O , O , and an oxidizer containing O atoms and activated.
[7] The method of any one of claims 2 and 3, wherein to form an insulating thin layer, the source is one selected from the group consisting of TEMATi, TEMASi, ECTDMAT, PEMAT, TBTEMAT, and DER, the first reactant is H , and the second reactant is one selected from the group consisting of O , O , and an oxidizer containing O atoms and activated.
[8] A method of depositing a thin layer using a plasma ALD process, the method comprising: repeating n times a sub-cycle including feeding one of an organic compound source containing metal atoms and an inorganic compound source containing metal atoms into a chamber in which a wafer is loaded, purging the source from the chamber, feeding a first reactant into the chamber, and purging an unreacted portion of the first reactant and by-products produced in the reaction of the source from the chamber; applying plasma while feeding a second reactant to the chamber to improve the quality of a thin layer; and purging an unreacted portion of the second reactant and by-products produced in the reaction of the source and the first reactant from the chamber, wherein a cycle including repeating the sub-cycle n times, applying the plasma while feeding the second reactant, and purging the unreacted portion of the second reactant and by-products is repeated until the thin layer is deposited on the wafer.
[9] The method of claim 8, wherein to form a metal thin layer, the source is one selected from the group consisting of TEMATi, TEMASi, ECTDMAT, PEMAT, TBTEMAT, and DER, the first reactant is H , and the second reactant is one of H and a compound containing H atoms.
[10] The method of claim 8, wherein to form a conductive thin layer, the source is one selected from the group consisting of TEMATi, TEMASi, ECTDMAT, PEMAT, TBTEMAT, and DER, the first reactant is one selected from the group consisting of N , NH , and a compound containing N atoms, and the second reactant is one of H and a compound containing H atoms.
[11] The method of claim 8, wherein to form an insulating thin layer, the source is one selected from the group consisting of TEMATi, TEMASi, ECTDMAT, PEMAT, TBTEMAT, and DER, the first reactant is one selected from the group consisting of O , O , and an oxidizer containing O atoms, and the second reactant is one selected from the group consisting of O , O , and an oxidizer containing O atoms and activated.
[12] The method of claim 8, wherein to form an insulating thin layer, the source is one selected from the group consisting of TEMATi, TEMASi, ECTDMAT, PEMAT, TBTEMAT, and DER, the first reactant is H , and the second reactant is one selected from the group consisting of O , O , and an oxidizer containing O atoms and activated.
[13] A method of depositing a thin layer using a plasma ALD process, the method comprising: repeating n times a sub-cycle including feeding one of an organic compound source containing metal atoms and an inorganic compound source containing metal atoms into a chamber in which a wafer is loaded, purging the source from the chamber, feeding a first reactant into the chamber, purging an unreacted portion of the first reactant and by-products produced in the reaction of the source from the chamber, feeding a second reactant into the chamber to improve the quality of the thin layer, and purging an unreacted portion of the second reactant and by-products produced in the reaction of the source and the first reactant from the chamber; applying plasma while feeding the second reactant to the chamber to improve the quality of the thin layer; and purging the unreacted portion of the second reactant and the by-products produced in the reaction of the source and the first reactant from the chamber, wherein a cycle including repeating the sub-cycle n times, applying the plasma while feeding the second reactant, and purging the unreacted portion of the second reactant and by-products is repeated until the thin layer is deposited on the wafer.
[14] The method of claim 13, wherein to form a metal thin layer, the source is one selected from the group consisting of TEMATi, TEMASi, ECTDMAT, PEMAT, TBTEMAT, and DER, the first reactant is H , and the second reactant is one of H and a compound containing H atoms.
[15] The method of claim 13, wherein to form a conductive thin layer, the source is one selected from the group consisting of TEMATi, TEMASi, ECTDMAT, PEMAT, TBTEMAT, and DER, the first reactant is one selected from the group consisting of N , NH , and a compound containing N atoms, and the second reactant is one of H and a compound containing H atoms.
[16] The method of claim 13, wherein to form an insulating thin layer, the source is one selected from the group consisting of TEMATi, TEMASi, ECTDMAT, PEMAT, TBTEMAT, and DER, the first reactant is one selected from the group consisting of O , O , and an oxidizer containing O atoms, and the second reactant is one selected from the group consisting of O , O , and an oxidizer containing O atoms and activated.
[17] The method of claim 13, wherein to form an insulating thin layer, the source is one selected from the group consisting of TEMATi, TEMASi, ECTDMAT, PEMAT, TBTEMAT, and DER, the first reactant is H , and the second reactant is one selected from the group consisting of O , O , and an oxidizer containing O atoms and activated.
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