WO2014112572A1 - Procédé de production d'un dispositif à semi-conducteurs, et dispositif de traitement de substrat - Google Patents

Procédé de production d'un dispositif à semi-conducteurs, et dispositif de traitement de substrat Download PDF

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Publication number
WO2014112572A1
WO2014112572A1 PCT/JP2014/050751 JP2014050751W WO2014112572A1 WO 2014112572 A1 WO2014112572 A1 WO 2014112572A1 JP 2014050751 W JP2014050751 W JP 2014050751W WO 2014112572 A1 WO2014112572 A1 WO 2014112572A1
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Prior art keywords
gas
layer
film
carbon
metal element
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PCT/JP2014/050751
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English (en)
Japanese (ja)
Inventor
小川　有人
和宏 原田
加我　友紀直
秀治 板谷
芦原　洋司
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株式会社日立国際電気
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Priority claimed from JP2013009577A external-priority patent/JP6061385B2/ja
Priority claimed from JP2014005809A external-priority patent/JP2014158019A/ja
Application filed by 株式会社日立国際電気 filed Critical 株式会社日立国際電気
Publication of WO2014112572A1 publication Critical patent/WO2014112572A1/fr
Priority to US14/801,984 priority Critical patent/US20150325447A1/en
Priority to US15/961,277 priority patent/US20180247819A1/en
Priority to US16/240,197 priority patent/US10388530B2/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
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
    • H01L21/28088—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 a composite, e.g. TiN
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/36—Carbonitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45527—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof  ; Multistep manufacturing processes therefor
    • H01L29/40—Electrodes ; Multistep manufacturing processes therefor
    • H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
    • H01L29/49—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET
    • H01L29/4966—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET the conductor material next to the insulator being a composite material, e.g. organic material, TiN, MoSi2
    • 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
    • H01L21/28158—Making the insulator
    • H01L21/28167—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation
    • H01L21/28185—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation with a treatment, e.g. annealing, after the formation of the gate insulator and before the formation of the definitive gate conductor
    • 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
    • H01L21/28158—Making the insulator
    • H01L21/28167—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation
    • H01L21/28194—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation by deposition, e.g. evaporation, ALD, CVD, sputtering, laser deposition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof  ; Multistep manufacturing processes therefor
    • H01L29/40—Electrodes ; Multistep manufacturing processes therefor
    • H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
    • H01L29/49—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET
    • H01L29/51—Insulating materials associated therewith
    • H01L29/511—Insulating materials associated therewith with a compositional variation, e.g. multilayer structures
    • H01L29/513—Insulating materials associated therewith with a compositional variation, e.g. multilayer structures the variation being perpendicular to the channel plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof  ; Multistep manufacturing processes therefor
    • H01L29/40—Electrodes ; Multistep manufacturing processes therefor
    • H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
    • H01L29/49—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET
    • H01L29/51—Insulating materials associated therewith
    • H01L29/517—Insulating materials associated therewith the insulating material comprising a metallic compound, e.g. metal oxide, metal silicate

Definitions

  • the present invention relates to a semiconductor device manufacturing method and a substrate processing apparatus.
  • TiN titanium nitride
  • a metal gate electrode having a work function different from TiN is required, if a metal electrode different from TiN is used, a process integration problem (for example, processing problem, thermal stability, diffusion stability, etc.), etc.
  • Vth threshold voltage, threshold voltage
  • MOSFETs Metal-Oxide-Semiconductor Field Effect Transistor
  • various types of metal films are used as electrodes and wirings.
  • metal carbide-based and metal nitride-based metal films are often used from the viewpoints of oxidation resistance, electrical resistivity, work function, etc., for gate electrodes and DRAM (Dynamic Random Access Memory) capacitor electrodes.
  • An object of the present invention is to provide a technique capable of adjusting a work function value to a desired value while ensuring process affinity in integration with a commonly used technique.
  • a method for manufacturing a semiconductor device includes a step of adjusting the work function of the film containing the metal element, carbon, and nitrogen to a desired value by controlling the number of times the step of forming the film is performed.
  • FIG. 2 is a view showing a processing furnace part of the vertical processing furnace shown in FIG.
  • FIG. 2 is a view showing a processing furnace part of the vertical processing furnace shown in FIG.
  • FIG. 1 is a block diagram which shows schematic structure of the controller which the substrate processing apparatus 10 shown in FIG. 1 has.
  • It is a figure which shows the film-forming flow in the sequence of 1st Embodiment of the substrate processing apparatus shown in FIG.
  • It is a figure which shows the gas supply timing in the sequence of 3rd Embodiment.
  • FIG. 9 is a process flowchart showing an example of a gate manufacturing process of the semiconductor device shown in FIG. 8.
  • FIG. 10 is a process flow diagram illustrating an example of a metal film formation process in the gate manufacturing process illustrated in FIG. 9. It is a figure which shows the timing of the gas supply in the film-forming process shown in FIG. It is a figure which shows C / Ti ratio based on the XPS analysis result with respect to the TiCN film
  • FIG. 13A is a diagram showing the C concentration in the TiCN film measured by XPS with respect to the TiCN film obtained in Examples 1 to 3
  • FIG. 13B is the TiCN obtained in Examples 1 to 3. It is a figure which shows N concentration in the TiCN film
  • FIG. 14A is a diagram illustrating a configuration of a capacitor created for an experiment
  • FIG. 14A is a diagram illustrating a capacitor 268a
  • FIG. 14B is a diagram illustrating a capacitor 268b
  • FIG. 18 (a) is a diagram showing the work function with respect to the ratio of C for each of the metal films formed in Examples 4 to 8 of the present invention
  • FIG. 18 (b) is a diagram showing Example 4 of the present invention
  • FIG. 9 is a diagram showing a work function with respect to a ratio of N for each of the metal films formed in ⁇ 8.
  • threshold voltage As an important parameter indicating the characteristics of the MOSFET, there is a threshold voltage (threshold voltage, Vth).
  • This threshold voltage is determined by the work function of the electrode.
  • the work function of the electrode can be tuned (adjusted or modulated) by the metal film constituting the electrode.
  • the required work function value is different between the P-type transistor and the N-type transistor, and the P-type transistor requires 5.0 eV or more, and the N-type transistor requires 4.3 eV or less.
  • other values may be required depending on the application. In such a case, it is desirable that the work function can be adjusted with one film having the same elemental composition.
  • the C (single phase) concentration is controlled, for example, the work function value is increased by increasing the C concentration.
  • the work function can be adjusted according to the application.
  • FIG. 1 and 2 show a substrate processing apparatus 10 preferably used in an embodiment of the present invention.
  • the substrate processing apparatus 10 is configured as an example of a semiconductor manufacturing apparatus used for manufacturing a semiconductor device (device).
  • the processing furnace 202 is provided with a heater 207 which is a heating means (heating mechanism, heating system) for heating the wafer 200 as a substrate.
  • the heater 207 includes a cylindrical heat insulating member whose upper portion is closed and a plurality of heater wires, and has a unit configuration in which the heater wires are provided on the heat insulating member.
  • a reaction tube 203 constituting a reaction vessel (processing vessel) concentrically with the heater 207 is disposed inside the heater 207.
  • the reaction tube 203 is made of a heat-resistant material such as quartz (SiO 2 ) or silicon carbide (SiC), and has a cylindrical shape with the upper end closed and the lower end opened.
  • the lower end of the reaction tube 203 is airtightly closed at the lower end of the reaction tube 203 through, for example, stainless steel via an O-ring 220 that is an airtight member and the lower end opening is sealed through an O-ring 220 by a seal cap 219 that is a lid.
  • a processing chamber 201 is formed by the pipe 203, the manifold 209, and the seal cap 219.
  • a boat 217 which is a substrate support member as a substrate support means (substrate support) is erected on the seal cap 219 via the boat support 218, and the boat support 218 includes a holding body that holds the boat in a state of supporting the boat. It has become.
  • a plurality of wafers 200 to be batch-processed are stacked in a multi-stage in the horizontal direction in the tube axis direction.
  • the boat 217 can be moved up and down (in and out) with respect to the reaction tube 203 by a boat elevator 115 as a transport means (transport mechanism).
  • a boat rotation mechanism 267 that rotates the boat 217 is provided at the lower end of the boat support 218 in order to improve processing uniformity. By driving the boat rotation mechanism 267, the boat 217 supported by the boat support 218 can be rotated.
  • the heater 207 heats the wafer 200 inserted into the processing chamber 201 to a predetermined temperature.
  • a nozzle 410 (first nozzle 410), a nozzle 420 (second nozzle 420), and a nozzle 430 (third nozzle 430) are provided so as to penetrate the lower part of the reaction tube 203.
  • the nozzle 410, the nozzle 420, and the nozzle 430 include a gas supply pipe 310 (first gas supply pipe 310), 320 (second gas supply pipe 320), and 330 (third gas supply pipe 330) as gas supply lines. ) Are connected to each other.
  • the reaction tube 203 is provided with the three nozzles 410, 420, and 430 and the three gas supply tubes 310, 320, and 330.
  • the gas (processing gas) can be supplied.
  • the gas supply pipe 310 is provided with a mass flow controller 312 which is a flow rate control device (flow rate control unit) and a valve 314 which is an on-off valve in order from the upstream side.
  • a nozzle 410 is connected to the tip of the gas supply pipe 310.
  • the nozzle 410 is configured as an L-shaped long nozzle, and its horizontal portion is provided so as to penetrate the side wall of the manifold 209.
  • the vertical portion rises in an arc-shaped space between the inner wall of the reaction tube 203 and the wafer 200 along the upper portion from the lower portion of the inner wall of the reaction tube 203 toward the upper side in the loading direction of the wafer 200 (that is,
  • the wafer arrangement region is provided so as to rise from one end side toward the other end side). That is, the nozzle 410 is provided on the side of the wafer arrangement area where the wafers 200 are arranged, in a region that horizontally surrounds the wafer arrangement area, along the wafer arrangement area.
  • a gas supply hole 410 a for supplying gas is provided on the side surface of the nozzle 410.
  • the gas supply hole 410 a is opened to face the center of the reaction tube 203.
  • a plurality of the gas supply holes 410a are provided from the lower part to the upper part of the reaction tube 203, have the same or inclined opening areas, and are provided at the same opening pitch.
  • a gas supply pipe 310, a mass flow controller 312, a valve 314, and a nozzle 410 constitute a first gas supply system.
  • a carrier gas supply pipe 510 for supplying a carrier gas is connected to the gas supply pipe 310.
  • the carrier gas supply pipe 510 is provided with a mass flow controller 512 and a valve 514.
  • a carrier gas supply pipe 510, a mass flow controller 512, and a valve 514 mainly constitute a first carrier gas supply system.
  • the gas supply pipe 320 is provided with a mass flow controller 322 as a flow rate control device (flow rate control unit) and a valve 324 as an on-off valve in order from the upstream side.
  • a nozzle 420 is connected to the tip of the gas supply pipe 320.
  • the nozzle 420 is configured as an L-shaped long nozzle, and a horizontal portion thereof is provided so as to penetrate the side wall of the manifold 209.
  • the vertical portion rises in an arc-shaped space between the inner wall of the reaction tube 203 and the wafer 200 along the upper portion from the lower portion of the inner wall of the reaction tube 203 toward the upper side in the loading direction of the wafer 200 (that is,
  • the wafer arrangement region is provided so as to rise from one end side toward the other end side). That is, the nozzle 420 is provided on the side of the wafer arrangement area where the wafers 200 are arranged, in a region that horizontally surrounds the wafer arrangement area, along the wafer arrangement area.
  • a gas supply hole 420 a for supplying gas is provided on the side surface of the nozzle 420.
  • the gas supply hole 420 a is opened to face the center of the reaction tube 203.
  • a plurality of the gas supply holes 420a are provided from the lower part to the upper part of the reaction tube 203, have the same or inclined opening areas, and are provided at the same opening pitch.
  • the gas supply pipe 320, the mass flow controller 322, the valve 324, and the nozzle 420 mainly constitute a second gas supply system.
  • a carrier gas supply pipe 520 for supplying a carrier gas is connected to the gas supply pipe 320.
  • the carrier gas supply pipe 520 is provided with a mass flow controller 522 and a valve 524.
  • the carrier gas supply pipe 520, the mass flow controller 522, and the valve 524 mainly constitute a second carrier gas supply system.
  • the gas supply pipe 330 is provided with a mass flow controller 332 that is a flow rate control device (flow rate control unit) and a valve 334 that is an on-off valve in order from the upstream side.
  • a nozzle 430 is connected to the tip of the gas supply pipe 330.
  • the nozzle 430 is configured as an L-shaped long nozzle, and a horizontal portion thereof is provided so as to penetrate the side wall of the manifold 209.
  • the vertical portion rises in an arc-shaped space between the inner wall of the reaction tube 203 and the wafer 200 along the upper portion from the lower portion of the inner wall of the reaction tube 203 toward the upper side in the loading direction of the wafer 200 (that is,
  • the wafer arrangement region is provided so as to rise from one end side toward the other end side). That is, the nozzle 430 is provided along the wafer arrangement region in a region that horizontally surrounds the wafer arrangement region on the side of the wafer arrangement region where the wafers 200 are arranged.
  • a gas supply hole 430a for supplying gas is provided on the side surface of the nozzle 430.
  • the gas supply hole 430 a is opened to face the center of the reaction tube 203.
  • a plurality of the gas supply holes 430a are provided from the lower part to the upper part of the reaction tube 203, have the same or inclined opening areas, and are provided at the same opening pitch.
  • the gas supply pipe 330, the mass flow controller 332, the valve 334, and the nozzle 430 mainly constitute a third gas supply system.
  • a carrier gas supply pipe 530 for supplying a carrier gas is connected to the gas supply pipe 330.
  • the carrier gas supply pipe 530 is provided with a mass flow controller 532 and a valve 534.
  • a third carrier gas supply system is mainly configured by the carrier gas supply pipe 530, the mass flow controller 532, and the valve 534.
  • the gas supply method includes a nozzle 410 arranged in an arc-like vertically long space defined by the inner wall of the reaction tube 203 and the ends of a plurality of stacked wafers 200,
  • the gas is conveyed through 420 and 430, and the gas is jetted into the reaction tube 203 for the first time in the vicinity of the wafer 200 from the gas supply holes 410a, 420b and 430c opened in the nozzles 410, 420 and 430, respectively.
  • the main flow of gas in the reaction tube 203 is set in a direction parallel to the surface of the wafer 200, that is, in a horizontal direction.
  • the residual gas after the reaction flows toward the exhaust port, that is, the direction of the exhaust pipe 231 described later.
  • the direction of the residual gas flow is appropriately specified by the position of the exhaust port and is limited to the vertical direction. It is not a thing.
  • a metal-containing gas (metal compound) that is a raw material gas and a titanium (Ti) element is used as the first processing gas containing the first predetermined element.
  • metal compound metal compound
  • Ti titanium
  • TiCl 4 Titanium tetrachloride
  • the liquid material is vaporized by a vaporization system such as a vaporizer or bubbler and supplied as TiCl 4 gas that is a Ti-containing gas. It becomes.
  • the second processing gas containing the second predetermined element for example, Hf [C 5], which is a C-containing gas (carbon raw material) containing at least a carbon (C) element as the first reaction gas.
  • H 4 (CH 3 )] 2 (CH 3 ) 2 is supplied into the processing chamber 201.
  • Hf [C 5 H 4 ( CH 3)] 2 (CH 3) as a 2
  • the material ECH (ethylcyclohexane ) Or THF (tetrahydrofuran) or the like to form a liquid state
  • the liquid state material is vaporized by a vaporization system such as a vaporizer or bubbler and supplied as a gas.
  • the third processing gas containing the third predetermined element for example, an N-containing gas containing at least nitrogen (N) as the second reaction gas, and a nitriding raw material, ie, a nitriding gas, ammonia. (NH 3 ) is supplied into the processing chamber 201.
  • N nitrogen
  • a nitriding raw material ie, a nitriding gas, ammonia.
  • nitrogen (N 2 ) gas is supplied from the mass flow controllers 512, 522 and 532, valves 514, 524 and 534, gas supply pipes 510, 520 and 530, and nozzles 410 and 420, respectively. And 430 to the inside of the processing chamber 201.
  • the source gas supply system is configured by the first gas supply system.
  • the source gas supply system is also referred to as a metal-containing gas supply system.
  • the second gas supply system constitutes a C-containing gas supply system (carbon raw material supply system).
  • the third gas supply system constitutes an N-containing gas supply system (nitriding material supply system).
  • the C-containing gas supply system constitutes a first reaction gas supply system
  • the N-containing gas supply system constitutes a second reaction gas supply system.
  • the source gas supply system, the C-containing gas supply system, and the N-containing gas supply system are also simply referred to as a metal source supply system, a carbon source supply system, and a nitriding source supply system, respectively.
  • the reaction tube 203 is provided with an exhaust pipe 231 for exhausting the atmosphere in the processing chamber 201.
  • the exhaust pipe 231 has a side on which the gas supply hole 410 a of the nozzle 410 of the reaction pipe 203, the gas supply hole 420 a of the nozzle 420, and the gas supply hole 430 a of the nozzle 430 are provided. It is provided on the opposite side, that is, on the opposite side to the gas supply holes 410a, 420a, and 430a with the wafer 200 in between.
  • the exhaust pipe 231 is provided below the portion where the gas supply holes 410a, 420a, and 430a are provided in a longitudinal sectional view.
  • the gas supplied from the gas supply holes 410a, 420a, and 430a to the vicinity of the wafer 200 in the processing chamber 201 flows in the horizontal direction, that is, in the direction parallel to the surface of the wafer 200, and then downward. Then, the air flows through the exhaust pipe 231. As described above, the main flow of gas in the processing chamber 201 is a flow in the horizontal direction.
  • a pressure sensor 245 as a pressure detector (pressure detection unit) that detects the pressure in the processing chamber 201 in order from the upstream side, and an exhaust valve configured as a pressure regulator (pressure adjustment unit).
  • An APC (Auto Pressure Controller) valve 243 and a vacuum pump 246 as a vacuum exhaust device are connected.
  • the exhaust pipe 231 has a trap device that captures reaction by-products and unreacted source gas in the exhaust gas, and a detoxification device that removes corrosive components and toxic components contained in the exhaust gas. May be connected.
  • An exhaust system that is, an exhaust line, is mainly configured by the exhaust pipe 231, the APC valve 243, and the pressure sensor 245.
  • the vacuum pump 246 may be included in the exhaust system.
  • a trap device or a detoxifying device may be included in the exhaust system.
  • the APC valve 243 can open and close the vacuum pump 246 while the vacuum pump 246 is operated, thereby performing vacuum evacuation and stop of the vacuum exhaust in the processing chamber 201. Further, the APC valve 243 is in a state where the vacuum pump 246 is operated. The valve is configured so that the pressure in the processing chamber 201 can be adjusted by adjusting the valve opening degree.
  • a temperature sensor 263 as a temperature detector is installed in the reaction tube 203, and the temperature in the processing chamber 201 is adjusted by adjusting the power supply to the heater 207 based on the temperature information detected by the temperature sensor 263. It is configured to have a desired temperature distribution.
  • the temperature sensor 263 is configured in an L shape similarly to the nozzles 410, 420, and 430, and is provided along the inner wall of the reaction tube 203.
  • FIG. 3 shows the controller 121.
  • the controller 121 includes a CPU (Central Processing Unit) 121a, a RAM (Random). (Access Memory) 121b, a storage device 121c, and an I / O port 121d.
  • the RAM 121b, the storage device 121c, and the I / O port 121d are configured to exchange data with the CPU 121a via the internal bus 121e.
  • an input / output device 122 configured as a touch panel or the like is connected to the controller 121.
  • the storage device 121c includes, for example, a flash memory, an HDD (Hard Disk Drive), and the like.
  • a control program that controls the operation of the substrate processing apparatus, a process recipe that describes the procedure and conditions of the substrate processing described later, and the like are stored in a readable manner.
  • the process recipe is a combination of functions so that a predetermined result can be obtained by causing the controller 121 to execute each procedure in a substrate processing step to be described later, and functions as a program.
  • the process recipe, the control program, and the like are collectively referred to as simply a program.
  • the RAM 121b is configured as a memory area (work area) in which programs, data, and the like read by the CPU 121a are temporarily stored.
  • the I / O port 121d includes the mass flow controllers 312, 322, 332, 512, 522, 532, the valves 314, 324, 334, 514, 524, 534, 614, the pressure sensor 245, the APC valve 243, the vacuum pump 246, The heater 207, temperature sensor 263, rotation mechanism 267, boat elevator 115, and the like are connected.
  • the CPU 121a is configured to read and execute a control program from the storage device 121c, and to read a process recipe from the storage device 121c in response to an operation command input from the input / output device 122 or the like. Then, the CPU 121a adjusts the flow rates of various gases by the mass flow controllers 312, 322, 332, 512, 522, 532, valves 314, 324, 334, 514, 524, 534, in accordance with the contents of the read process recipe.
  • APC valve 243 opening and closing operation, pressure adjustment operation based on pressure sensor 245 by APC valve 243, temperature adjustment operation of heater 207 based on temperature sensor 263, starting and stopping of vacuum pump 246, boat by rotation mechanism 267 It is configured to control the rotation and rotation speed adjustment operation of 217, the raising / lowering operation of the boat 217 by the boat elevator 115, and the like.
  • the controller 121 is not limited to being configured as a dedicated computer, and may be configured as a general-purpose computer.
  • an external storage device storing the above-described program for example, magnetic tape, magnetic disk such as a flexible disk or hard disk, optical disk such as CD or DVD, magneto-optical disk such as MO, semiconductor memory such as USB memory or memory card
  • the controller 121 according to the present embodiment can be configured by installing a program in a general-purpose computer using the external storage device 123.
  • the means for supplying the program to the computer is not limited to supplying the program via the external storage device 123.
  • the program may be supplied without using the external storage device 123 by using communication means such as the Internet or a dedicated line.
  • the storage device 121c and the external storage device 123 are configured as computer-readable recording media. Hereinafter, these are collectively referred to simply as a recording medium. Note that when the term “recording medium” is used in this specification, it may include only the storage device 121c alone, may include only the external storage device 123 alone, or may include both.
  • FIG. 4 is a diagram showing a film forming flow in a preferred sequence of the present embodiment.
  • FIG. 5 is a diagram showing gas supply timings in a preferred sequence of the present embodiment.
  • the preferred sequence of this embodiment is By supplying a titanium (Ti) -containing gas and a carbon (C) -containing gas to the wafer 200, a metal carbide layer (TiC layer) as a first layer containing titanium and carbon is formed on the wafer 200. And a process of By supplying a nitrogen (N) -containing gas to the wafer 200, the metal carbonization (TiC) layer is nitrided to form a metal carbonitride layer (TiCN layer) as a second layer containing titanium, carbon, and nitrogen.
  • a metal carbonized layer corresponding to the number of executions of the step of forming a metal carbonitride film (TiCN film) having a predetermined thickness on the wafer 200 and forming a metal carbonitride layer (TiCN layer) is performed.
  • the work function of the metal carbonitride film (TiCN film) is adjusted (tuned and modulated) to a desired value by controlling the number of times the step of forming the (TiC layer) is performed.
  • wafer when the term “wafer” is used, it means “wafer itself” or “a laminate (aggregate) of a wafer and a predetermined layer or film formed on the surface thereof”. "(That is, a wafer including a predetermined layer or film formed on the surface).
  • wafer surface when the term “wafer surface” is used in this specification, it means “the surface of the wafer itself (exposed surface)” or “the surface of a predetermined layer or film formed on the wafer”. That is, it may mean “the outermost surface of the wafer as a laminated body”.
  • the phrase “supplying a predetermined gas to the wafer” means “supplying a predetermined gas directly to the surface (exposed surface) of the wafer itself”. , It may mean that “a predetermined gas is supplied to a layer, a film, or the like formed on the wafer, that is, to the outermost surface of the wafer as a laminated body”. Further, in this specification, when “describe a predetermined layer (or film) on the wafer” is described, “determine a predetermined layer (or film) directly on the surface (exposed surface) of the wafer itself”. This means that a predetermined layer (or film) is formed on a layer or film formed on the wafer, that is, on the outermost surface of the wafer as a laminate. There is a case.
  • substrate in this specification is the same as the term “wafer”, and in that case, the “wafer” may be replaced with “substrate” in the above description. .
  • supplying the metal-containing gas and the carbon (C) -containing gas means that when the supply of the metal-containing gas and the supply of the carbon-containing gas are set as one set, when this set is performed once, This includes both cases where this set is performed multiple times. In other words, this means that this set is performed once or more (a predetermined number of times).
  • this set is preferably performed a plurality of times. The C concentration of the TiCN film can be increased by increasing the number of times of performing the setting. Further, in order to obtain a TiCN film having a relatively low C concentration, it is preferable to reduce the number of executions of this set (for example, once).
  • the step of forming the TiC layer and the step of forming the TiCN layer are alternately performed a predetermined number of times” means that “a Ti-containing gas and a C-containing gas are supplied to the wafer 200 in the processing chamber 201.
  • the “step of forming the TiCN layer” is defined as one cycle, this includes both the case where this cycle is performed once and the case where this cycle is performed a plurality of times. In other words, this means that this cycle is performed once or more (a predetermined number of times). As will be described later, this cycle is preferably performed a plurality of times rather than once.
  • metal film means a film made of a conductive substance containing a metal atom, and includes a conductive single metal film made of a single metal.
  • Conductive metal nitride film, conductive metal oxide film, conductive metal oxynitride film, conductive metal composite film, conductive metal alloy film, conductive metal silicide film, conductive metal carbide film (Metal carbide film), conductive metal carbonitride film (metal carbonitride film) and the like are also included.
  • the TiCN film titanium carbonitride film is a conductive metal carbonitride film.
  • the processing chamber 201 is evacuated by a vacuum pump 246 so that a desired pressure (degree of vacuum) is obtained. At this time, the pressure in the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 243 is feedback-controlled based on the measured pressure information (pressure adjustment). Note that the vacuum pump 246 keeps being operated at least until the processing on the wafer 200 is completed. Further, the processing chamber 201 is heated by the heater 207 so as to have a desired temperature. At this time, the power supply to the heater 207 is feedback-controlled based on the temperature information detected by the temperature sensor 263 so that the inside of the processing chamber 201 has a desired temperature distribution (temperature adjustment).
  • the heating of the processing chamber 201 by the heater 207 is continuously performed at least until the processing on the wafer 200 is completed.
  • the rotation mechanism 267 starts the rotation of the boat 217 and the wafer 200. Note that the rotation of the boat 217 and the wafer 200 by the rotation mechanism 267 is continuously performed at least until the processing on the wafer 200 is completed. Thereafter, the following six steps are sequentially executed.
  • Step 11> TiCl 4 gas supply
  • the valve 314 of the gas supply pipe 310 is opened, and TiCl 4 gas is allowed to flow into the gas supply pipe 310.
  • the flow rate of the TiCl 4 gas that has flowed through the gas supply pipe 310 is adjusted by the mass flow controller 312.
  • the flow-adjusted TiCl 4 gas is supplied from the gas supply hole 410 a of the nozzle 410 into the processing chamber 201 and is exhausted from the exhaust pipe 231. At this time, TiCl 4 gas is supplied to the wafer 200. That is, the surface of the wafer 200 is exposed to TiCl 4 gas.
  • the valve 514 is opened, and an inert gas such as N 2 gas is allowed to flow into the carrier gas supply pipe 510.
  • the flow rate of the N 2 gas flowing through the carrier gas supply pipe 510 is adjusted by the mass flow controller 512.
  • the N 2 gas whose flow rate has been adjusted is supplied into the processing chamber 201 together with the TiCl 4 gas, and is exhausted from the exhaust pipe 231.
  • the valves 524 and 534 are opened, and N 2 gas is allowed to flow into the carrier gas supply pipe 520 and the carrier gas supply pipe 530.
  • N 2 gas is supplied into the processing chamber 201 through the gas supply pipe 320, the gas supply pipe 330, the nozzle 420, and the nozzle 430, and is exhausted from the exhaust pipe 231.
  • the APC valve 243 is appropriately adjusted so that the pressure in the processing chamber 201 is, for example, in the range of 10 to 2000 Pa.
  • the supply flow rate of TiCl 4 gas controlled by the mass flow controller 512 is, for example, a flow rate in the range of 10 to 2000 sccm.
  • the supply flow rate of the N 2 gas controlled by the mass flow controllers 512, 522, and 532 is set to a flow rate in the range of, for example, 100 to 10,000 sccm.
  • the time for supplying the TiCl 4 gas to the wafer 200, that is, the gas supply time (irradiation time) is, for example, a time within the range of 0.1 to 120 seconds.
  • the temperature of the heater 207 is set to such a temperature that the temperature of the wafer 200 becomes a temperature within the range of 200 to 400 ° C., for example.
  • the wafer temperature is less than 200 ° C.
  • the temperature of the wafer 200 is preferably set to a temperature within the range of 200 to 400 ° C.
  • Ti titanium
  • Ti a titanium (Ti) -containing layer containing chlorine (Cl), that is, a layer containing Ti and Cl is formed on the wafer 200.
  • the Ti-containing layer containing Cl may be a chemisorption layer by an intermediate of TiCl 4 formed by decomposition of TiCl 4 and TiCl 4 , or a titanium layer containing Cl formed by thermal decomposition of TiCl 4 (Ti layer), that is, a Ti deposited layer, or both of them may be included.
  • Step 12> (Residual gas removal) After the Ti-containing layer containing Cl is formed, the valve 314 of the gas supply pipe 310 is closed, and the supply of TiCl 4 gas is stopped. At this time, after the APC valve 243 of the exhaust pipe 231 is kept open, the inside of the processing chamber 201 is evacuated by the vacuum pump 246 to contribute to the formation of a Ti-containing layer containing unreacted or Cl remaining in the processing chamber 201. The TiCl 4 gas is removed from the processing chamber 201. At this time, the valves 514, 524, and 534 are kept open, and the supply of N 2 gas into the processing chamber 201 is maintained. The N 2 gas acts as a purge gas, thereby enhancing the effect of removing the TiCl 4 gas remaining in the processing chamber 201 or contributing to the formation of the Ti-containing layer containing Cl from the processing chamber 201. it can.
  • the gas remaining in the processing chamber 201 may not be completely removed, and the processing chamber 201 may not be completely purged. If the amount of gas remaining in the processing chamber 201 is very small, there will be no adverse effect in the subsequent step 13. At this time, the flow rate of the N 2 gas supplied into the processing chamber 201 does not need to be a large flow rate. Purging to such an extent that no occurrence occurs can be performed. Thus, by not completely purging the inside of the processing chamber 201, the purge time can be shortened and the throughput can be improved. In addition, consumption of N 2 gas can be minimized.
  • Step 13 (Hf [C 5 H 4 (CH 3 )] 2 (CH 3 ) 2 gas supply)
  • step 12 is completed and residual gas in the processing chamber 201 is removed, the valve 324 of the gas supply pipe 320 is opened, and Hf [C 5 H 4 (CH 3 )] 2 (CH 3 ) 2 is placed in the gas supply pipe 320.
  • Flow gas The flow rate of Hf [C 5 H 4 (CH 3 )] 2 (CH 3 ) 2 gas flowing through the gas supply pipe 320 is adjusted by the mass flow controller 322.
  • Hf [C 5 H 4 (CH 3 )] 2 (CH 3 ) 2 gas is supplied from the gas supply hole 420 a of the nozzle 420 into the processing chamber 201 and exhausted from the exhaust pipe 231.
  • Hf [C 5 H 4 (CH 3 )] 2 (CH 3 ) 2 gas is supplied to the wafer 200. That is, the surface of the wafer 200 is exposed to Hf [C 5 H 4 (CH 3 )] 2 (CH 3 ) 2 gas.
  • the valve 524 is opened, and N 2 gas is caused to flow into the carrier gas supply pipe 520.
  • the N 2 gas that has flowed through the carrier gas supply pipe 520 is adjusted in flow rate by the mass flow controller 522.
  • the N 2 gas whose flow rate is adjusted is supplied into the processing chamber 201 together with the Hf [C 5 H 4 (CH 3 )] 2 (CH 3 ) 2 gas, and is exhausted from the exhaust pipe 231.
  • the valves 510 and 530 are opened, and the carrier gas supply pipe is opened.
  • N 2 gas is allowed to flow into the carrier gas supply pipe 530.
  • the N 2 gas is supplied into the processing chamber 201 through the gas supply pipe 310, the gas supply pipe 330, the nozzle 410, and the nozzle 430 and is exhausted from the exhaust pipe 231.
  • the APC valve 243 is appropriately adjusted, and the pressure in the processing chamber 201 is set to a pressure in the range of 10 to 2000 Pa, for example, as in Step 11.
  • the supply flow rate of Hf [C 5 H 4 (CH 3 )] 2 (CH 3 ) 2 gas controlled by the mass flow controller 322 is, for example, a flow rate in the range of 10 to 2000 sccm.
  • the supply flow rate of N 2 gas controlled by the mass flow controller 522 is, for example, a flow rate in the range of 100 to 10,000 sccm.
  • the time for supplying Hf [C 5 H 4 (CH 3 )] 2 (CH 3 ) 2 gas to the wafer 200 is, for example, within a range of 0.1 to 120 seconds.
  • the temperature of the heater 207 at this time is set to such a temperature that the temperature of the wafer 200 becomes a temperature in the range of 250 to 400 ° C., for example, as in step 11.
  • the Ti-containing layer containing Cl formed on the wafer 200 in Step 11 reacts with the Hf [C5H4 (CH3)] 2 (CH3) 2 gas. To do. At this time, mainly the Cl of the Ti-containing layer containing Cl formed on the wafer 200 in Step 11 reacts with Hf [C5H4 (CH3)] 2 of Hf [C5H4 (CH3)] 2 (CH3) 2. Thus, a gaseous substance is generated and discharged as a gas.
  • Cl in the Ti-containing layer containing Cl may react with the methyl group (CH3) or cyclopenta group (C5H4) of Hf [C5H4 (CH3)] 2 (CH3) 2.
  • Hf [C5H4 (CH3)] 2 (CH3) 2 decomposes so that hafnium (Hf), hydrogen (H), etc. constituting Hf [C5H4 (CH3)] 2 (CH3) 2
  • a gaseous substance is generated by reacting with Cl in the Ti-containing layer and is discharged as a gas.
  • Cl contained in TiCl4 and Hf contained in Hf [C5H4 (CH3)] 2 (CH3) 2 are converted into gaseous substances and discharged.
  • Step 14> (Residual gas removal) Thereafter, the valve 324 of the gas supply pipe 320 is closed, and the supply of Hf [C 5 H 4 (CH 3 )] 2 (CH 3 ) 2 gas is stopped. At this time, the APC valve 243 of the exhaust pipe 231 is kept open, the process chamber 201 is evacuated by the vacuum pump 246, and Hf [C after contributing to unreacted or TiC layer formation remaining in the process chamber 201 5 H 4 (CH 3 )] 2 (CH 3 ) 2 gas and reaction by-products are excluded from the processing chamber 201. At this time, the valves 510, 520, and 530 remain open, and the supply of N 2 gas into the processing chamber 201 is maintained.
  • the N 2 gas acts as a purge gas, whereby Hf [C 5 H 4 (CH 3 )] 2 (CH 3 ) 2 gas and reaction after remaining in the processing chamber 201 or contributing to TiC layer formation.
  • the effect of removing the by-product from the processing chamber 201 can be enhanced.
  • the gas remaining in the processing chamber 201 may not be completely removed, and the processing chamber 201 may not be completely purged. If the amount of gas remaining in the processing chamber 201 is very small, no adverse effects will occur in the subsequent step 11 or step 15. At this time, the flow rate of the N 2 gas supplied into the processing chamber 201 does not need to be a large flow rate. For example, by supplying an amount similar to the volume of the reaction tube 203 (processing chamber 201), step 11 or step 15 can be purged to the extent that no adverse effects occur. Thus, by not completely purging the inside of the processing chamber 201, the purge time can be shortened and the throughput can be improved. In addition, consumption of N 2 gas can be minimized.
  • the above steps 11 to 14 are set as one set, and this set is performed a predetermined number of times to form a TiC layer having a predetermined thickness.
  • FIG. 5 shows how this set is performed m times.
  • the number of executions (m) of the setting is, for example, 1 to 200 times, preferably 1 to 100 times, and more preferably 1 to 20 times.
  • the set may be performed several times (m), for example, about 2 to 6 times.
  • By controlling (adjusting) the number of executions (m) of setting it is possible to control the C concentration of the TiCN film finally formed. By changing the C concentration, the work function of the TiCN film can be adjusted (tuned) to a desired value according to the application.
  • this set is preferably performed a plurality of times rather than once.
  • the C concentration of the TiCN film can be increased by increasing the number of times of performing the setting.
  • Step 15> (NH 3 gas supply process) After a TiC layer having a predetermined thickness is formed and residual gas in the processing chamber 201 is removed, the valve 334 of the gas supply pipe 330 is opened, and NH 3 gas is allowed to flow into the gas supply pipe 330. The flow rate of the NH 3 gas flowing through the gas supply pipe 330 is adjusted by the mass flow controller 324. The NH 3 gas whose flow rate has been adjusted is supplied into the processing chamber 201 from the gas supply hole 430 a of the nozzle 430. The NH 3 gas supplied into the processing chamber 201 is activated by heat and exhausted from the exhaust pipe 231. At this time, NH 3 gas activated by heat is supplied to the wafer 200.
  • the surface of the wafer 200 is exposed to heat activated NH 3 gas.
  • the valve 534 is opened, and N 2 gas is caused to flow into the carrier gas supply pipe 530.
  • the flow rate of the N 2 gas flowing through the carrier gas supply pipe 530 is adjusted by the mass flow controller 532.
  • the N 2 gas is supplied into the processing chamber 201 together with the NH 3 gas, and is exhausted from the exhaust pipe 231.
  • the valves 514 and 524 are opened, and the N 2 gas is allowed to flow into the carrier gas supply pipes 510 and 520.
  • the N 2 gas is supplied into the processing chamber 201 through the gas supply pipes 310 and 320, the nozzle 410 and the nozzle 420, and is exhausted from the exhaust pipe 231.
  • the APC valve 243 is appropriately adjusted so that the pressure in the processing chamber 201 is, for example, in the range of 10 to 2000 Pa.
  • the NH 3 gas can be thermally activated by non-plasma.
  • a soft reaction can be caused by supplying the NH 3 gas activated by heat, and nitridation described later can be performed softly.
  • the supply flow rate of NH 3 gas controlled by the mass flow controller 332 is, for example, a flow rate in the range of 10 to 10,000 sccm.
  • the supply flow rate of the N 2 gas controlled by the mass flow controllers 512, 522, and 532 is set to a flow rate in the range of, for example, 100 to 10,000 sccm.
  • the time for supplying the NH 3 gas activated by heat to the wafer 200, that is, the gas supply time (irradiation time) is, for example, a time within the range of 0.1 to 120 seconds.
  • the temperature of the heater 207 is set to such a temperature that the temperature of the wafer 200 becomes a temperature in the range of 200 to 400 ° C., for example, as in Steps 11 and 13.
  • a NH 3 gas is thermally activated by increasing the pressure in the processing chamber 201, TiCl 4 gas into the processing chamber 201 Hf [C 5 H 4 (CH 3 )] 2 (CH 3 ) 2 gas is not flowing. Therefore, the NH 3 gas does not cause a gas phase reaction, and the activated NH 3 gas reacts with at least a part of the TiC layer containing Ti and C formed on the wafer 200 in Step 13. Thereby, the TiC layer is nitrided and modified into a titanium carbonitride layer (TiCN layer).
  • TiCN layer may be referred to as a C-doped TiN layer (C-added TiN layer).
  • the TiC layer when the TiC layer is thermally nitrided with NH 3 gas activated by heat and modified (changed) into the TiCN layer, the TiC layer is modified into the TiCN layer while adding an N component to the TiC layer. Will be allowed to.
  • Ti—N bonds in the TiC layer increase due to the action of thermal nitridation by NH 3 gas. That is, the TiC layer can be modified into a TiCN layer while changing the composition ratio in the direction of increasing the nitrogen concentration.
  • the processing conditions such as the pressure in the processing chamber 201 and the gas supply time, the ratio of the N component in the TiCN layer, that is, the nitrogen concentration can be finely adjusted, and the composition ratio of the TiCN layer can be adjusted. It can be controlled more precisely.
  • Step 16> (Residual gas removal) Thereafter, the valve 334 of the gas supply pipe 330 is closed, and the supply of NH 3 gas is stopped. At this time, the APC valve 243 of the exhaust pipe 231 is kept open, the inside of the processing chamber 201 is evacuated by the vacuum pump 246, and the NH 3 gas remaining in the processing chamber 201 and contributing to the formation of the TiCN layer is left. And reaction by-products are removed from the processing chamber 201. At this time, the valves 514, 524, and 534 are kept open, and the supply of N 2 gas into the processing chamber 201 is maintained. The N 2 gas acts as a purge gas, thereby enhancing the effect of eliminating NH 3 gas and reaction by-products remaining in the processing chamber 201 and contributing to the formation of the TiCN layer from the processing chamber 201. Can do.
  • the gas remaining in the processing chamber 201 may not be completely removed, and the processing chamber 201 may not be completely purged. If the amount of gas remaining in the processing chamber 201 is very small, no adverse effect will occur in the subsequent step 1. At this time, the flow rate of the N 2 gas supplied into the processing chamber 201 does not need to be a large flow rate. For example, by supplying an amount similar to the volume of the reaction tube 203 (processing chamber 201), there is an adverse effect in step 1. Purge to such an extent that no occurrence occurs. Thus, by not completely purging the inside of the processing chamber 201, the purge time can be shortened and the throughput can be improved. In addition, consumption of N 2 gas can be minimized.
  • the step of sequentially performing steps 11 to 14 a predetermined number of times and the step of performing steps 15 and 16 are defined as one cycle.
  • a TiCN film having a predetermined composition and a predetermined film thickness is formed on wafer 200. Is deposited.
  • the TiCN film may be referred to as a C-doped TiN film (C-added TiN film).
  • FIG. 5 shows how this cycle is performed n times. By controlling (adjusting) the number of executions (n) of the cycle, the thickness of the TiCN film finally formed can be adjusted.
  • the number of cycles (n) is set within a range of 1 to 5 times. And This cycle is preferably performed a plurality of times rather than once. That is, it is preferable that the thickness of the TiCN layer formed per cycle is made smaller than the desired film thickness, and the above cycle is repeated a plurality of times until the desired film thickness is obtained.
  • the action of nitriding performed in step 15 can be delivered to the entire TiC layer. Then, the TiCN film is nitrided more uniformly, and the N concentration of the TiCN film can be made more uniform in the thickness direction.
  • Hf [C 5 H 4 (CH 3 )] 2 (CH 3 ) 2 gas is used as the carbon raw material.
  • the embodiment is not limited thereto, and Zr [C 5 H 4 (CH 3 )] 2 (CH 3 ) 2 gas, ethylene (C 2 H 4 ), propylene (C 3 H 6 ), butene (C 4 H 8 ), pentene (C 5 H 10 ), hexene (C 6 H 12), heptene (C 7 H 14), octene (C 8 H 16), ethane (C 2 H 6), propane (C 3 H 8), butane (C 4 H 10), pentane (C 5 H 12 ), hexane (C 6 H 14 ), heptane (C 7 H 16 ), octane (C 8 H 18 ) and the like may be used.
  • FIG. 6 shows gas supply timings in a good sequence for forming a TiAlC film by supplying three types of gases to the wafer 200.
  • TiCl 4 titanium tetrachloride
  • C carbon
  • a TiAlC film having a predetermined thickness can be formed by the following sequence.
  • a titanium tetrachloride (TiCl 4 ) gas which is a titanium (Ti) -containing gas, and a carbon (C) -containing gas are alternately supplied a predetermined number of times to the wafer 200 in the processing chamber 201, so that the wafer 200 is placed on the wafer 200.
  • TMA, (CH 3 ) 3 Al trimethylaluminum
  • Al-containing gas that is a metal source gas containing aluminum (Al)
  • Ti titanium
  • carbon A second step of forming a titanium aluminum carbide layer (TiAlC layer) containing (C) and aluminum (Al);
  • the first step of forming the titanium carbide layer (TiC layer) and the second step of forming the titanium aluminum carbide layer (TiAlC layer) are alternately performed a predetermined number of times, whereby a predetermined film thickness is formed on the wafer 200.
  • the titanium aluminum carbide film (TiAlC film) is formed, and the work function of the obtained TiAlC film is adjusted (tuned) by controlling the number of times the first step is performed.
  • FIG. 7 shows gas supply timings in a good sequence in which a TiAlC film is formed by supplying two types of gases to the wafer 200.
  • a TiAlC film having a predetermined thickness can be formed by the following sequence.
  • the wafer 200 in the processing chamber 201 is alternately supplied a predetermined number of times by a process of supplying a TiCl 4 gas as a Ti-containing gas and a process of supplying a TMA gas as a raw material containing C and Al.
  • a TiAlC layer containing Ti, Al, and C is formed thereon.
  • the work function of the TiAlC film obtained is controlled to a desired value by controlling the ratio of the number of times of performing each step between the step of supplying the TiCl 4 gas and the step of supplying the TMA gas to a predetermined value. Adjust (tune) so that
  • the C concentration in the obtained TiAlC film can be increased.
  • the value of the work function becomes smaller.
  • the C concentration in the obtained TiAlC film can be lowered by setting the number of steps of supplying the TMA gas to a small number (for example, once). As the C concentration decreases, the work function value becomes larger.
  • a TMA gas as the metal source gas is a Al-containing gas is not limited thereto, it may be used AlCl 3 or the like.
  • a TiCN film or a TiAlC film is formed.
  • the present invention is not limited to this, and tantalum (Ta), cobalt (Co), tungsten (W), and molybdenum (Mo).
  • Ta tantalum
  • Co cobalt
  • W tungsten
  • Mo molybdenum
  • Forming a metal carbide film containing one or more metal elements such as ruthenium (Ru), yttrium (Y), lanthanum (La), zirconium (Zr), hafnium (Hf), or a silicide film obtained by adding silicon (Si) to these metal elements In this case, it can be suitably applied.
  • tantalum chloride (TaCl 4 ) or the like can be used as the Ta-containing raw material, and Co amd [(tBu) NC (CH 3 ) N (tBu) 2 Co] or the like can be used as the Co-containing raw material.
  • Tungsten fluoride (WF 6 ) or the like can be used as the W-containing raw material
  • molybdenum chloride (MoCl 3 or MoCl 5 ) or the like can be used as the Mo-containing raw material
  • a fourth embodiment will be described.
  • a TiCN film having a predetermined thickness is formed on the wafer 200.
  • a titanium aluminum carbonitride film (TiAlCN film) having a predetermined thickness is formed on the wafer 200.
  • TiAlCN film can be formed by supplying three kinds of gases.
  • TMA trimethyl containing at least a carbon (C) element and an aluminum (Al) element as a source gas containing carbon and a second metal element
  • Aluminum (CH 3 ) 3 Al) is supplied into the processing chamber 201 through the mass flow controller 322, the valve 324, and the nozzle 420.
  • a liquid raw material will be vaporized by vaporization systems, such as a vaporizer and a bubbler, and will be supplied as C and Al containing gas.
  • a carbon-containing raw material supply system (or carbon and metal-containing raw material supply system) is configured by the second gas supply system.
  • a MOSFET is taken as an example of the semiconductor device.
  • FIG. 8 is an explanatory diagram showing an example of the gate configuration of the MOSFET.
  • the gate of the MOSFET includes a silicon-based insulating film made of silicon oxide (SiO 2 ) formed on a silicon (Si) substrate, and hafnium oxide (HfO 2 ) formed on this SiO 2.
  • a high-dielectric film (High-k film) made of and a metal film as a gate electrode made of titanium aluminum carbonitride (TiAlCN) formed on this HfO 2 are stacked.
  • the feature of this embodiment is the formation of a metal film that constitutes the gate electrode.
  • FIG. 9 is a process flow showing an example of a MOSFET gate manufacturing process.
  • the silicon substrate is treated with, for example, a 1% HF aqueous solution to remove the sacrificial oxide film on the Si substrate (“HF treatment” step).
  • silicon oxide (SiO 2 ) is deposited on the surface of the Si substrate by thermal oxidation (“SiO 2 formation” step). SiO 2 is formed as an interface layer at the interface between the Si substrate and HfO 2 to be formed later.
  • hafnium oxide HfO 2
  • a gate insulating film is composed of SiO 2 and HfO 2 .
  • PDA Post Deposition Annealing
  • This PDA uses, for example, a heat treatment furnace (for example, an RTP (Rapid Thermal Process) apparatus), stores a Si substrate on which HfO 2 is formed in a processing chamber of the RTP apparatus, and supplies N 2 gas into the processing chamber. Annealing is performed. PDA is performed impurity removal during HfO 2, the densification or crystallization of HfO 2 purposes.
  • TiAlCN is formed as a metal film on HfO 2 (“TiAlCN deposition” step).
  • TiAlCN deposition a process of forming a titanium nitride (TiN) layer (first layer) (“TiN formation”) X times (first predetermined number of times), aluminum (
  • AlCTiN formation AlCTiN formation
  • PVD Physical
  • Titanium nitride (TiN) is deposited by vapor deposition (physical vapor deposition) (“Cap TiN deposition” step).
  • Cap TiN deposition physical vapor deposition
  • FGA Forming
  • FGA hydrogen gas annealing gas annealing
  • the metal film forming step is performed as one step of the semiconductor device (MOSFET) manufacturing process using the processing furnace 202 of the substrate processing apparatus 10 described above.
  • the preferred sequence of this embodiment is Performing a process for forming a first layer (eg, TiN) containing a metal element (eg, Ti) and nitrogen (N) on the wafer 200 for a first predetermined number of times; Performing a process for forming a second layer (eg, AlCTiN) containing the metal element (eg, Ti), nitrogen (N), and carbon (C) on the wafer 200 a second predetermined number of times; Are alternately performed for a third predetermined number of times to form a metal film (for example, TiAlCN) containing nitrogen (C) and carbon (C) at a predetermined ratio on the wafer 200.
  • a first layer eg, TiN
  • a metal element eg, Ti
  • N nitrogen
  • C carbon
  • the suitable sequence of this embodiment is A step of alternately supplying a first raw material (eg, TiCl 4 ) containing a metal element (eg, Ti) and a second raw material (eg, NH 3 ) containing nitrogen (N) to the wafer 200 a first predetermined number of times.
  • a first raw material eg, TiCl 4
  • a second raw material eg, NH 3
  • a third raw material for example, TMA
  • a fourth raw material for example, TiCl 4
  • the metal element eg, Ti
  • a fifth raw material containing nitrogen (N) For example, supplying NH 3 ) alternately for a second predetermined number of times; Are alternately performed for a third predetermined number of times to form a metal film (for example, TiAlCN) containing nitrogen (N) and carbon (C) at a predetermined ratio on the wafer 200.
  • a metal film for example, TiAlCN
  • the first predetermined number of times, the second predetermined number of times, and the third predetermined number of times are the ratio of nitrogen (N) or carbon (C) included in the metal film (for example, TiAlCN), in other words, For example, it is determined according to the work function of the target gate electrode.
  • TiAlCN titanium aluminum carbonitride
  • TiAlCN titanium aluminum carbonitride
  • FIG. 10 is a process flow diagram showing an example of a metal film (TiAlCN) film forming process in the process flow shown in FIG.
  • FIG. 11 is a diagram showing gas supply timings in the film forming process shown in FIG.
  • the operation of each unit constituting the substrate processing apparatus 10 is controlled by the controller 121.
  • the processing chamber 201 is evacuated by a vacuum pump 246 so that a desired pressure (degree of vacuum) is obtained. At this time, the pressure in the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 243 is feedback-controlled based on the measured pressure information (pressure adjustment). Note that the vacuum pump 246 keeps being operated at least until the processing on the wafer 200 is completed. Further, the processing chamber 201 is heated by the heater 207 so as to have a desired temperature. At this time, the energization amount to the heater 207 is feedback-controlled based on the temperature information detected by the temperature sensor 263 so that the processing chamber 201 has a desired temperature distribution (temperature adjustment).
  • the heating of the processing chamber 201 by the heater 207 is continuously performed at least until the processing on the wafer 200 is completed.
  • the rotation mechanism 267 starts the rotation of the boat 217 and the wafer 200. Note that the rotation of the boat 217 and the wafer 200 by the rotation mechanism 267 is continuously performed at least until the processing on the wafer 200 is completed.
  • Step 21 to Step 24 a process of forming a TiN layer.
  • Step 21> TiCl 4 gas supply
  • the valve 314 of the gas supply pipe 310 is opened, and TiCl 4 gas as the first raw material is caused to flow into the gas supply pipe 310.
  • the flow rate of the TiCl 4 gas that has flowed through the gas supply pipe 310 is adjusted by the mass flow controller 312.
  • the flow-adjusted TiCl 4 gas is supplied from the gas supply hole 410 a of the nozzle 410 into the processing chamber 201 and is exhausted from the exhaust pipe 231. At this time, TiCl 4 gas is supplied to the wafer 200. That is, the surface of the wafer 200 is exposed to TiCl 4 gas.
  • the valve 514 is opened, and an inert gas such as N 2 gas is allowed to flow into the carrier gas supply pipe 510.
  • the flow rate of the N 2 gas flowing through the carrier gas supply pipe 510 is adjusted by the mass flow controller 512.
  • the N 2 gas whose flow rate has been adjusted is supplied into the processing chamber 201 together with the TiCl 4 gas, and is exhausted from the exhaust pipe 231.
  • the valves 524 and 534 are opened, and N 2 gas is allowed to flow into the carrier gas supply pipe 520 and the carrier gas supply pipe 530.
  • N 2 gas is supplied into the processing chamber 201 through the gas supply pipe 320, the gas supply pipe 330, the nozzle 420, and the nozzle 430, and is exhausted from the exhaust pipe 231.
  • the APC valve 243 is appropriately adjusted so that the pressure in the processing chamber 201 is, for example, in the range of 1 to 10,000 Pa.
  • the supply flow rate of the TiCl 4 gas controlled by the mass flow controller 312 is, for example, a flow rate in the range of 10 to 10,000 sccm.
  • the supply flow rate of N 2 gas controlled by the mass flow controllers 512, 522, and 532 is set to a flow rate in the range of 10 to 10,000 sccm, for example.
  • the time for supplying the TiCl 4 gas to the wafer 200, that is, the gas supply time (irradiation time) is, for example, a time within the range of 0.1 to 120 seconds.
  • the temperature of the heater 207 is set to such a temperature that the temperature of the wafer 200 becomes a temperature within a range of 200 to 500 ° C., for example.
  • a Ti-containing layer having a thickness of, for example, less than one atomic layer to several atomic layers is formed on the wafer 200.
  • Step 22> (Residual gas removal) After the Ti-containing layer is formed, the valve 314 of the gas supply pipe 310 is closed and the supply of TiCl 4 gas is stopped. At this time, the APC valve 243 of the exhaust pipe 231 is kept open, the inside of the processing chamber 201 is evacuated by the vacuum pump 246, and TiCl 4 after remaining in the processing chamber 201 or contributing to the formation of the Ti-containing layer. The gas is removed from the processing chamber 201. At this time, the valves 514, 524, and 534 are kept open, and the supply of N 2 gas into the processing chamber 201 is maintained. The N 2 gas acts as a purge gas, which can enhance the effect of removing the unreacted or residual TiCl 4 gas that has contributed to the formation of the Ti-containing layer from the processing chamber 201.
  • the gas remaining in the processing chamber 201 may not be completely removed, and the processing chamber 201 may not be completely purged. If the amount of gas remaining in the processing chamber 201 is very small, no adverse effect will occur in the subsequent steps. At this time, the flow rate of the N 2 gas supplied into the processing chamber 201 does not need to be a large flow rate. Purge can be performed to the extent that no adverse effect occurs. Thus, by not completely purging the inside of the processing chamber 201, the purge time can be shortened and the throughput can be improved. In addition, consumption of N 2 gas can be minimized.
  • Step 23> (NH 3 gas supply) After removing the residual gas in the processing chamber 201, the valve 334 of the gas supply pipe 330 is opened, and NH 3 gas is allowed to flow into the gas supply pipe 330. The flow rate of the NH 3 gas that has flowed through the gas supply pipe 330 is adjusted by the mass flow controller 332. The NH 3 gas whose flow rate has been adjusted is supplied into the processing chamber 201 from the gas supply hole 430 a of the nozzle 430. The NH 3 gas supplied into the processing chamber 201 is activated by heat and then exhausted from the exhaust pipe 231. At this time, NH 3 gas activated by heat is supplied to the wafer 200. That is, the surface of the wafer 200 is exposed to heat activated NH 3 gas.
  • the valve 534 is opened, and N 2 gas is caused to flow into the carrier gas supply pipe 530.
  • the flow rate of the N 2 gas flowing through the carrier gas supply pipe 530 is adjusted by the mass flow controller 532.
  • the N 2 gas is supplied into the processing chamber 201 together with the NH 3 gas, and is exhausted from the exhaust pipe 231.
  • the valves 514 and 524 are opened, and the N 2 gas is allowed to flow into the carrier gas supply pipes 510 and 520.
  • the N 2 gas is supplied into the processing chamber 201 through the gas supply pipes 310 and 320, the nozzle 410 and the nozzle 420, and is exhausted from the exhaust pipe 231.
  • the APC valve 243 is appropriately adjusted so that the pressure in the processing chamber 201 is, for example, in the range of 1 to 10,000 Pa.
  • the supply flow rate of NH 3 gas controlled by the mass flow controller 332 is set, for example, within a range of 10 to 50000 sccm.
  • the supply flow rate of N 2 gas controlled by the mass flow controllers 512, 522, and 532 is set to a flow rate in the range of 10 to 10,000 sccm, for example.
  • the time for supplying the NH 3 gas activated by heat to the wafer 200, that is, the gas supply time (irradiation time) is, for example, a time within the range of 0.1 to 120 seconds.
  • the temperature of the heater 207 at this time is set to such a temperature that the temperature of the wafer 200 becomes a temperature within the range of 200 to 500 ° C., for example, as in step 21.
  • the gas flowing in the processing chamber 201 is NH 3 gas that is thermally activated by increasing the pressure in the processing chamber 201, and this activated NH 3 gas is converted into the wafer in step 21. Reacts with at least a portion of the Ti-containing layer formed on 200. As a result, the Ti-containing layer is nitrided and modified into a titanium nitride layer (TiN layer).
  • Step 24> (Residual gas removal)
  • the valve 334 of the gas supply pipe 330 is closed to stop the supply of NH 3 gas.
  • the APC valve 243 of the exhaust pipe 231 is kept open, the inside of the processing chamber 201 is evacuated by the vacuum pump 246, and the NH 3 gas remaining in the processing chamber 201 and contributing to the formation of the TiN layer remains.
  • reaction by-products are removed from the processing chamber 201.
  • the valves 514, 524, and 534 are kept open, and the supply of N 2 gas into the processing chamber 201 is maintained.
  • the N 2 gas acts as a purge gas, thereby enhancing the effect of removing NH 3 gas and reaction by-products remaining in the processing chamber 201 and contributing to formation of the TiN layer from the processing chamber 201. Can do.
  • the gas remaining in the processing chamber 201 may not be completely removed, and the processing chamber 201 may not be completely purged. If the amount of gas remaining in the processing chamber 201 is very small, no adverse effect will occur in the subsequent steps. At this time, the flow rate of the N 2 gas supplied into the processing chamber 201 does not need to be a large flow rate. Purge can be performed to the extent that no adverse effect occurs. Thus, by not completely purging the inside of the processing chamber 201, the purge time can be shortened and the throughput can be improved. In addition, consumption of N 2 gas can be minimized.
  • step 21 to step 24 is executed X times (first predetermined number of times) set in advance. That is, the process from step 21 to step 24 is set as one set, and these processes are executed for X sets. In this way, TiN 4 gas supply and NH 3 gas supply are alternately performed X times to form a TiN layer (first layer) having a predetermined thickness (for example, 0.03 to 20 nm).
  • step 25 to step 30 After performing the above-described processing from step 21 to step 24 X times (X set), the following process of forming an AlCTiN layer (step 25 to step 30) is executed.
  • TMA gas supply The valve 324 of the gas supply pipe 320 is opened, and TMA (trimethylaluminum. (CH 3 ) 3 Al) gas is allowed to flow through the gas supply pipe 320.
  • the flow rate of the TMA gas flowing through the gas supply pipe 320 is adjusted by the mass flow controller 322.
  • the flow-adjusted TMA gas is supplied from the gas supply hole 420 a of the nozzle 420 into the processing chamber 201 and is exhausted from the exhaust pipe 231.
  • TMA gas is supplied to the wafer 200. That is, the surface of the wafer 200 is exposed to TMA gas.
  • the valve 524 is opened, and N 2 gas is caused to flow into the carrier gas supply pipe 520.
  • the N 2 gas that has flowed through the carrier gas supply pipe 520 is adjusted in flow rate by the mass flow controller 522.
  • the N 2 gas whose flow rate has been adjusted is supplied into the processing chamber 201 together with the TMA gas, and is exhausted from the exhaust pipe 231.
  • the valves 514 and 534 are opened, and N 2 gas is allowed to flow into the carrier gas supply pipe 510 and the carrier gas supply pipe 530.
  • the N 2 gas is supplied into the processing chamber 201 through the gas supply pipe 310, the gas supply pipe 330, the nozzle 410, and the nozzle 430 and is exhausted from the exhaust pipe 231.
  • the APC valve 243 is appropriately adjusted so that the pressure in the processing chamber 201 is, for example, in the range of 1 to 10000 Pa, as in step 21.
  • the supply flow rate of TMA gas controlled by the mass flow controller 322 is, for example, a flow rate in the range of 10 to 10000 sccm.
  • the supply flow rate of N 2 gas controlled by the mass flow controllers 512, 522, and 532 is set to a flow rate in the range of 10 to 10,000 sccm, for example.
  • the time for supplying the TMA gas to the wafer 200, that is, the gas supply time (irradiation time) is, for example, a time within the range of 0.1 to 120 seconds.
  • the temperature of the heater 207 at this time is set to such a temperature that the temperature of the wafer 200 becomes a temperature within the range of 200 to 500 ° C., for example, as in step 21.
  • a layer containing carbon (C) and aluminum (Al) is formed on the TiN layer.
  • the layer containing C and Al is formed to a thickness of, for example, less than one atomic layer to several atomic layers.
  • Step 26> (Residual gas removal) Thereafter, the valve 324 of the gas supply pipe 320 is closed to stop the supply of TMA gas. At this time, the APC valve 243 of the exhaust pipe 231 is kept open, and the inside of the processing chamber 201 is evacuated by the vacuum pump 246 to form an unreacted or residual layer containing C and Al remaining in the processing chamber 201. The TMA gas after the contribution is removed from the processing chamber 201. At this time, the valves 510, 520, and 530 remain open, and the supply of N 2 gas into the processing chamber 201 is maintained. The N 2 gas acts as a purge gas, thereby increasing the effect of removing the TMA gas remaining in the processing chamber 201 or contributing to the formation of the layer containing C and Al from the processing chamber 201. be able to.
  • the gas remaining in the processing chamber 201 may not be completely removed, and the processing chamber 201 may not be completely purged. If the amount of gas remaining in the processing chamber 201 is very small, no adverse effect will occur in the subsequent steps. At this time, the flow rate of the N 2 gas supplied into the processing chamber 201 does not need to be a large flow rate. Purge can be performed to the extent that no adverse effect occurs. Thus, by not completely purging the inside of the processing chamber 201, the purge time can be shortened and the throughput can be improved. In addition, consumption of N 2 gas can be minimized.
  • TiCl 4 gas is supplied into the processing chamber 201 by the same processing as in step 21.
  • the APC valve 243 is appropriately adjusted so that the pressure in the processing chamber 201 is, for example, in the range of 1 to 10,000 Pa.
  • the supply flow rate of the TiCl 4 gas controlled by the mass flow controller 312 is, for example, a flow rate in the range of 10 to 10,000 sccm.
  • the supply flow rate of N 2 gas controlled by the mass flow controllers 512, 522, and 532 is set to a flow rate in the range of 10 to 10,000 sccm, for example.
  • the time for supplying the TiCl 4 gas to the wafer 200 is, for example, a time within the range of 0.1 to 120 seconds.
  • the temperature of the heater 207 is set to such a temperature that the temperature of the wafer 200 becomes a temperature within a range of 200 to 500 ° C., for example.
  • TiCl 4 gas supplied into the processing chamber 201 reacts with at least a part of the layer containing C and Al. Thereby, the layer containing C and Al is modified into a layer containing carbon (C), aluminum (Al), and titanium (Ti).
  • Step 28> (Residual gas removal) Subsequently, TiCl 4 gas and by-products that have remained in the processing chamber 201 or contributed to the formation of the above-described layer containing C, Al, and Ti by the same processing as in step 22 and the like are processed in the processing chamber 201. Eliminate from within.
  • NH 3 gas is supplied into the processing chamber 201 by the same processing as in step 23.
  • the APC valve 243 is appropriately adjusted so that the pressure in the processing chamber 201 is, for example, in the range of 1 to 10,000 Pa.
  • the supply flow rate of NH 3 gas controlled by the mass flow controller 332 is set, for example, within a range of 10 to 50000 sccm.
  • the supply flow rate of N 2 gas controlled by the mass flow controllers 512, 522, and 532 is set to a flow rate in the range of 10 to 10,000 sccm, for example.
  • the time for supplying the NH 3 gas activated by heat to the wafer 200 is, for example, 0.1-12.
  • the time is in the range of 0 seconds.
  • the temperature of the heater 207 at this time is set to such a temperature that the temperature of the wafer 200 becomes a temperature within the range of 200 to 500 ° C., for example, as in step 21.
  • the NH 3 gas supplied into the processing chamber 201 reacts with at least a part of the layer containing C, Al, and Ti. Thereby, the layer containing C, Al, and Ti is modified into the AlCTiN-containing layer described above.
  • Step 30> (Residual gas removal) Subsequently, the TiCl 4 gas and the by-product remaining in the processing chamber 201 and contributing to the formation of the AlCTiN-containing layer are removed from the processing chamber 201 by the same processing as in step 24 and the like.
  • step 25 to step 30 described above is executed Y times (second predetermined number) set in advance. That is, the process from step 25 to step 30 is set as one set, and these processes are executed for Y sets. In this way, by alternately performing TMA gas supply, TiCl 4 gas supply, and NH 3 gas supply Y times, an AlCTiN layer (second layer) having a predetermined thickness (for example, 0.1 to 20 nm) Form.
  • the TiAlCN film as the gate electrode is composed of a laminate of the TiN layer and the AlCTiN layer described above. By repeating the step of forming the TiN layer and the step of forming the AlCTiN layer alternately Z times (a third predetermined number of times), a predetermined thickness (for example, 1.0 to 20 nm) is obtained. A TiAlCN film is formed.
  • the TiAlCN film can also be referred to as an AlC-doped TiN film (AlC-added TiN film) obtained by doping Al and C into a TiN film.
  • the number of times of performing the processing from step 21 to step 24 for forming the TiN layer (the above-mentioned X or the multiplication value of X and Z) and the number of times of performing the processing from step 25 to step 30 for forming the AlCTiN layer.
  • the ratio of each element contained in the TiAlCN film can be adjusted by (the above-mentioned Y or a multiplication value of Y and Z).
  • the work function of the gate electrode formed of the TiAlCN film can be tuned (adjusted or modulated) by adjusting the number of times of each process.
  • the values of X, Y, and Z are determined according to the ratio of nitrogen or carbon (or the ratio of nitrogen, carbon, titanium, and aluminum) included in the TiAlCN film.
  • X and Y are integers of 0 or more, and Z is an integer of 1 or more.
  • X and / or Y is preferably an integer of 1 or more.
  • the work functions of the two metal elements are both about 4.3 eV.
  • the inventors of the present application have obtained the knowledge that the work function can be increased or decreased based on about 4.3 eV which is the work function of Ti and Al by adjusting the ratio of C and N in the TiAlCN film. Yes. Specifically, when the proportion of C is increased, a work function lower than 4.3 eV can be obtained, and when the proportion of N is increased, a work function higher than 4.3 eV can be obtained. Therefore, a metal film having a desired work function can be formed by determining each value of X, Y, and Z according to the ratio of N or C included in the TiAlCN film.
  • a TiN layer that is, a metal nitride film is formed as the first layer constituting the TiAlCN film.
  • a metal nitride film is used instead of the metal nitride film.
  • a carbonized film is formed.
  • a TiAlCN film having a metal carbide film as the first layer can be formed by the following sequence. Performing a process for forming a first layer (eg, TiC) containing a metal element (eg, Ti) and carbon (C) on the wafer 200 for a first predetermined number of times; Performing a process for forming a second layer (eg, AlCTiN) containing the metal element (eg, Ti), nitrogen (N), and carbon (C) on the wafer 200 a second predetermined number of times; Are alternately performed for a third predetermined number of times to form a metal film (for example, TiAlCN) containing nitrogen (C) and carbon (C) at a predetermined ratio on the wafer 200.
  • a first layer eg, TiC
  • a metal element eg, Ti
  • C metal element
  • C carbon
  • the suitable sequence of this embodiment is A first raw material (for example, TiCl 4 ) containing a metal element (for example, Ti) and a second raw material (for example, Hf [C 5 H 4 (CH 3 )] 2 (CH 3 ) containing carbon (C) with respect to the wafer 200.
  • a first raw material for example, TiCl 4
  • a metal element for example, Ti
  • a second raw material for example, Hf [C 5 H 4 (CH 3 )] 2 (CH 3 ) containing carbon (C) with respect to the wafer 200.
  • a third raw material for example, TMA
  • a fourth raw material for example, TiCl 4
  • the metal element eg, Ti
  • a fifth raw material containing nitrogen (N) for example, supplying NH 3 ) alternately for a second predetermined number of times;
  • a metal film for example, TiAlCN
  • a gas supply system for supplying Hf [C 5 H 4 (CH 3 )] 2 (CH 3 ) 2 to the processing chamber 201 is added to the substrate processing apparatus 10.
  • a TiAlCN film is formed as a metal film constituting a gate electrode.
  • the metal film is not limited to this, and tantalum (Ta), Metal carbide film containing one or more metal elements such as cobalt (Co), tungsten (W), molybdenum (Mo), ruthenium (Ru), yttrium (Y), lanthanum (La), zirconium (Zr), hafnium (Hf)
  • a metal nitride film, a metal carbonitride film, or a silicide film obtained by adding silicon (Si) to these may be formed.
  • tantalum chloride (TaCl 4 ) or the like can be used as the Ta-containing raw material, and Co amd [(tBu) NC (CH 3 ) N (tBu) 2 Co] or the like can be used as the Co-containing raw material.
  • Tungsten fluoride (WF 6 ) or the like can be used as the W-containing raw material
  • molybdenum chloride (MoCl 3 or MoCl 5 ) or the like can be used as the Mo-containing raw material
  • the first layer includes two or more metal elements (for example, Ti and Al). May be included.
  • the same metal element is included in the first layer and the second layer, but this is not always necessary.
  • Ti may be included in the first layer and Ti may not be included in the second layer.
  • a TiAlN film or a TiN film can be formed instead of the TiAlCN film.
  • a TiAlC film or a TiC film can be formed instead of the TiAlCN film.
  • the TiN layer and the AlCTiN layer are formed in this order, but the AlCTiN layer and the TiN layer are formed in this order. Also good.
  • the AlCTiN layer and the TiC layer may be formed in this order.
  • the present invention is not limited to this, and the present invention is not limited to this.
  • the present invention can also be suitably applied when a film is formed using a single-wafer type substrate processing apparatus that processes one or several substrates.
  • an example of forming a film using a substrate processing apparatus having a hot wall type processing furnace has been described.
  • the present invention is not limited to this, and the substrate processing having a cold wall type processing furnace is performed.
  • the present invention can also be suitably applied when forming a film using an apparatus.
  • TiCl 4 gas is used as the metal source gas that is a Ti-containing source.
  • the present invention is not limited to this, and tetrakisdimethylaminotitanium (TDMAT, Ti [N (CH 3 ) 2 ] 4 ), tetrakisdiethylaminotitanium (TDEAT, Ti [N (CH 2 CH 3 ) 2 ] 4 ) or other organic compounds other than halogen compounds or titanium (Ti) containing gas that is an amino compound may be used. Good.
  • NH 3 gas is used as a nitriding raw material.
  • the present invention is not limited to this, but diazene (N 2 H 2 ) gas, hydrazine (N 2 H 4 ) gas, N 3 H 8 gas, nitrogen (N 2 ), nitrous oxide (N 2 O), monomethylhydrazine (CH 6 N 2 ), dimethylhydrazine (C 2 H 8 N 2 ), or the like may be used.
  • a rare gas such as Ar gas, He gas, Ne gas, Xe gas, etc. may be used in addition to N 2 gas.
  • the present invention can be realized by changing a process recipe of an existing substrate processing apparatus, for example.
  • the process recipe according to the present invention is installed in an existing substrate processing apparatus via a telecommunication line or a recording medium recording the process recipe, or input / output of the existing substrate processing apparatus It is also possible to operate the apparatus and change the process recipe itself to the process recipe according to the present invention.
  • TiCl 4 gas that is Ti-containing gas is used as the first processing gas
  • Hf [C 5 H 4 (CH 3 )] 2 (CH 3 ) that is C-containing gas is used as the second processing gas.
  • a TiCN film was formed by using NH 3 gas, which is N-containing gas, as the third processing gas, using the two gases and the film formation flow of FIG. 4 and the gas supply timing of FIG.
  • the wafer is loaded into the processing chamber (wafer loading), the wafer is heated under N 2 atmosphere (preheating), TiCl 4 gas and Hf [C 5 H 4 (CH 3 )] 2 (CH 3 ) 2 gas TiC film formation (metal carbide layer formation) by alternately and repeatedly supplying NH 3 irradiation (nitriding treatment) to the formed TiC layer alternately, forming a TiCN film, and then processing Residual substances in the chamber were evacuated (gas exhaust), the film-formed wafer was unloaded from the processing chamber (wafer unload), and XPS (X-ray Photoelectron Spectroscopy) analysis was performed.
  • the processing conditions in each step at that time were set as follows.
  • Step 11 Processing room temperature: 400 ° C Processing chamber pressure: 50 Pa (0.38 Torr) TiCl 4 gas supply flow rate: 10-50 sccm TiCl 4 gas irradiation time: 2 seconds
  • Step 13 Processing room temperature: 400 ° C Processing chamber pressure: 50 Pa (0.38 Torr) Hf [C 5 H 4 (CH 3 )] 2 (CH 3 ) 2 gas supply flow rate: 10 to 50 sccm Hf [C 5 H 4 (CH 3 )] 2 (CH 3 ) 2 gas irradiation time: 50 seconds
  • step 15 Processing room temperature: 400 ° C Processing chamber pressure: 50 Pa (0.38 Torr) NH 3 supply flow rate: 1000 sccm NH 3 irradiation time: 20 seconds
  • the thickness of the TiCN film to be formed was 5 nm, and a 5 nm TiN film was formed in situ as a cap layer on the obtained TiCN film.
  • Other processing conditions were the same as in Example 1.
  • Other processing conditions were the same as in Example 1.
  • Table 1 summarizes the processing conditions in Examples 1 to 3 and the C concentration of the obtained TiCN film.
  • the C concentration of the obtained TiCN film was 17 to 18% in Example 1, 25 to 30% in Example 2, and 25 to 30% in Example 3, respectively.
  • FIG. 12 shows a graph summarizing Ti strength and C strength measured by XPS for the TiCN film obtained in each example as a C / Ti ratio.
  • the horizontal axis represents the number m of sets of steps 11 to 14, and the vertical axis represents the C / Ti ratio by XPS analysis.
  • FIG. 13A shows the C concentration in the TiCN film measured by XPS with respect to the TiCN film obtained in each example
  • FIG. 13B shows the C concentration in the TiCN film obtained in each example.
  • the N concentration in the TiCN film measured by XPS is shown.
  • the horizontal axis indicates the etching time
  • the vertical axis indicates the C atom concentration (C atomic%) and the N atom concentration (N atomic%), respectively.
  • 13A and 13B a layer to be etched in the corresponding etching time along the horizontal axis is shown.
  • FIG. 13A shows that the C atom concentration at the etching time indicating the analysis result for the TiCN film increased by about 11% in the case of Examples 2 and 3 with respect to Example 1.
  • FIG. 13B shows that the N atom concentration in the etching time indicating the analysis result for the TiCN film was reduced by about 3.6% in the case of Examples 2 and 3 with respect to Example 1.
  • the capacitors 268a to 268c form an SiO 2 film (silicon oxide film) 270 as an insulating film on the surface of the silicon (Si) wafer 200
  • HfO 2 films (hafnium oxide films) 272a to 272c, which are insulating films, are formed so as to be stacked on the SiO 2 film 270
  • a TiCN film 276 is formed so as to be stacked on the HfO 2 films 272a to 272c, respectively.
  • the TiN film (titanium nitride film) 278 is formed so as to be laminated on the H.276.
  • the TiCN film 276 is formed by the sequence described in the above embodiment. That is, the TiCN film 276 uses TiCl 4 gas as the Ti-containing gas, Hf [C 5 H 4 (CH 3 )] 2 (CH 3 ) 2 gas as the C-containing gas, and NH 3 gas as the N-containing gas. The film is formed by the film formation flow 4 and the gas supply timing shown in FIG.
  • the insulating films 272a, 272b, and 272c are formed by changing the thicknesses, respectively.
  • FIG. 15 shows the work function calculated by plotting eWF (Effective Work Function) for each EOT (Equivalent Oxide Thickness) of these capacitors on a graph.
  • FIG. 15 is a graph plotting the EOT and eWF values of the TiCN film in the capacitors 268a, 268b, and 268c.
  • a High-k film such as an HfO 2 film
  • oxygen in the High-k film diffuses and escapes from the High-k film due to heat treatment in the process, so that an interface dipole is formed between the High-k film and the interface layer.
  • the effective work function becomes high.
  • the work function of the TiN film is about 5.0 eV including the dipole, whereas the work function of the TiCN film 276 calculated from the graph shown in FIG. 68 eV. It should be noted that the effect of the dipole e ⁇ dipole was taking into account the (0.31eV, Y.
  • a TiAlCN film was formed on the wafer 200 (specifically, on the HfO film which is a high dielectric film) by the sequence shown in FIGS. 10 and 11 described above.
  • Example 4 a process of forming TiN layers by alternately supplying TiCl 4 gas and NH 3 gas six times, and TMA gas, TiCl 4 gas, and NH 3 gas once each.
  • the TiAlCN film was formed by alternately repeating the step of supplying and forming the AlCTiN layer 36 times.
  • the processing conditions in each step at that time were set as follows.
  • Step 21 Processing room temperature: 350 ° C Processing chamber pressure: 45Pa TiCl 4 gas supply rate: 1.16 g / min TiCl 4 gas irradiation time: 5 seconds
  • step 23 Processing room temperature: 350 ° C Processing chamber pressure: 65 Pa NH 3 gas supply flow rate: 7500sccm NH 3 gas irradiation time: 15 seconds
  • Step 25 Processing room temperature: 350 ° C Processing chamber pressure: 65 Pa TMA gas supply amount: 0.6 g / min TMA gas irradiation time: 6 seconds
  • Step 27 Processing room temperature: 350 ° C Processing chamber pressure: 45Pa TiCl 4 gas supply rate: 1.16 g / min TiCl 4 gas irradiation time: 5 seconds
  • step 29 Processing room temperature: 350 ° C Processing chamber pressure: 65 Pa NH 3 gas supply flow rate: 7500sccm NH 3 gas irradiation time: 15 seconds
  • the thickness of the TiAlCN film formed by the above treatment was 10 nm, and a 30 nm TiN film was formed as a cap layer on the TiAlCN film.
  • Example 5 a process of forming TiN layers by alternately supplying TiCl 4 gas and NH 3 gas three times, and TMA gas, TiCl 4 gas, and NH 3 gas once each.
  • the step of supplying and forming the AlCTiN layer was repeated 52 times alternately to form a TiAlCN film.
  • the processing conditions in each step at that time are the same as in the fourth embodiment.
  • the thickness of the TiAlCN film formed in Example 5 is 10 nm.
  • Example 6 a process of forming a TiN layer by supplying TiCl 4 gas and NH 3 gas once, and supplying TMA gas, TiCl 4 gas, and NH 3 gas once each. Then, the step of forming the AlCTiN layer was alternately repeated 78 times to form a TiAlCN film.
  • the processing conditions in each step at that time are the same as in the fourth embodiment.
  • the thickness of the TiAlCN film formed in Example 6 is 10 nm.
  • Example 4 the TiAlCN film was formed by repeating the process of supplying the TMA gas, TiCl 4 gas, and NH 3 gas once to form the AlCTiN layer 100 times.
  • the processing conditions in each step at that time are the same as in the fourth embodiment.
  • the thickness of the TiAlCN film formed in Example 4 is 10 nm.
  • Example 5 the TiN film was formed by repeating the process of supplying the TiCl 4 gas and the NH 3 gas once to form the TiN layer 340 times.
  • the processing conditions in each step at that time are the same as in the fourth embodiment.
  • the thickness of the TiN film formed in Example 5 is 10 nm.
  • FIG. 16 shows the relationship between EOT (equivalent oxide thickness) and Vfb (flat band voltage) for each of the metal films (TiAlCN film or TiN film) formed in Examples 4 to 8. As shown in the figure, it can be seen that the Vfb shifts in the negative direction as the C ratio (concentration) is higher (N ratio (concentration) is lower). When Vfb shifts in the negative direction, the work function decreases.
  • FIG. 17 shows the relationship between the ratio of C and N and the effective work function eWF for each of the metal films (TiAlCN film or TiN film) formed in Examples 4 to 8.
  • 18A shows the work function with respect to the ratio of C for each of the metal films formed in Examples 4 to 8
  • FIG. 18B shows the metal film formed in Examples 4 to 8.
  • the work function for the percentage of N is shown.
  • the work function of the metal film itself is tuned by adjusting each value of X, Y, and Z.
  • the film was formed in each embodiment.
  • the effective work function eWF of the gate electrode containing a metal film is shown.
  • This effective work function eWF is a value calculated from the above-mentioned Vfb, and is a value including a dipole at the HfO 2 / SiO 2 interface.
  • the effective work function eWF decreases as the ratio of C contained in the TiAlCN film (or TiN film) increases, and the effective work function eWF increases as the ratio of N increases.
  • the dipole is determined according to the type of the high dielectric film, and is constant in each embodiment. Therefore, it can be said that the work function of the TiAlCN film decreases as the proportion of C contained in the TiAlCN film increases, and the work function of the TiAlCN film increases as the proportion of N increases.
  • the work function of the TiN film that is the metal film according to the fifth embodiment is about 5.0 eV including the dipole, whereas the work function of the TiAlCN film that is the metal film according to the fourth to fourth embodiments.
  • the work function is 4.52 to 4.68 eV. In consideration of the influence of dipole e ⁇ dipole (0.31 eV. Quoted from Y.
  • the work function of the TiAlCN film is 4.21-4. It was confirmed that the work function can be tuned based on the above-described work function of Ti and Al (about 4.3 eV) by controlling the ratio of C and / or N contained therein. .
  • the work function of TiAlN film containing Ti as a metal element and not containing C and TiN film is about 4.6 to 4.7 eV, and the work function of TiAlC film containing Ti as a metal element and not containing N is about 4
  • the inventors have confirmed that the voltage is 1 V. That is, the TiAlCN film containing Ti as a metal element and further containing C and N controls the work function of the TiAlC film and the work function of the TiAlN film (or TiN film) by controlling the ratio of C and N. It can be tuned to the desired value between functions.
  • a metal capable of adjusting Vth that is, a TiAlCN film as a metal film whose work function can be tuned is provided. It was confirmed by experiments. Therefore, according to the present invention, it is possible to adjust the work function with one metal film having the same elemental composition even when different work function values are required depending on the application.
  • the effective work function can be tuned by a ⁇ dipole or ⁇ FLP (Fermi-Level Pinning). However, it is desirable to tune the work function of the metal film itself constituting the gate electrode for the following reason.
  • the value of the ⁇ dipole is controlled by the film type of the high dielectric film or by diffusing Al, La, or the like from the gate electrode into the high dielectric film.
  • the dipole value is shifted in the same direction in both NMOS and PMOS (a dipole that shifts in the negative direction in NMOS and in the positive direction in PMOS is required). Therefore, it is necessary to make a high dielectric film separately for NMOS and PMOS, which complicates the process.
  • heat treatment at about 1000 ° C. is necessary.
  • a high dielectric film when used, it is generally a gate last process, and the heat treatment at about 1000 ° C. is performed before the formation of the gate stack (electrode / high dielectric film / SiO 2 / Si substrate).
  • This heat treatment is a process for activating the source / drain. Therefore, in the gate last process, it is desirable that a heat treatment at about 1000 ° C. is unnecessary after the gate stack.
  • [Appendix 1] Forming a first layer containing the first metal element and carbon on the substrate by supplying a metal-containing gas containing a metal element and a carbon-containing gas to the substrate; By supplying a nitrogen-containing gas to the substrate on which the first layer has been formed, the first layer is nitrided to form a second layer containing the first metal element, carbon and nitrogen And a process of Are alternately performed a predetermined number of times to form a film containing the first metal element, carbon and nitrogen with a predetermined film thickness on the substrate, and the second layer is formed with respect to the number of executions of the step of forming the second layer.
  • a method for manufacturing a semiconductor device comprising: adjusting a work function of a film containing the first metal element, carbon, and nitrogen to have a desired value by controlling the number of times of performing the step of forming one layer. Provided.
  • the first metal element is tantalum (Ta), cobalt (Co), tungsten (W), molybdenum (Mo), ruthenium (Ru), yttrium (Y), lanthanum (La), zirconium (Zr), It contains at least one element selected from the group consisting of hafnium (Hf).
  • the metal-containing gas includes TiCl 4 and TaCl 4 .
  • the carbon-containing gas contains Hf [C 5 H 4 (CH 3 )] 2 (CH 3 ) 2 .
  • the carbon-containing gas includes a second metal element different from the first metal element.
  • the second metal element includes hafnium.
  • the film containing the first metal element, carbon, and nitrogen is increased by increasing the number of times of performing the step of forming the first layer as compared with the number of times of performing the step of forming the second layer. Adjust the work function to be higher.
  • carbon contained in the film containing the first metal element, carbon and nitrogen is controlled by controlling the number of times of the step of forming the first layer with respect to the number of times of the step of forming the second layer.
  • the work function of the film containing the first metal element, carbon, and nitrogen is adjusted to a desired value.
  • [Appendix 9] According to another aspect of the invention, Supplying a metal-containing gas containing a metal element to the substrate; Supplying a carbon-containing gas to the substrate; Supplying a nitrogen-containing gas to the substrate; A step of supplying the metal-containing gas and / or supplying the nitrogen-containing gas by forming a film containing the metal element, carbon and nitrogen having a predetermined thickness on the substrate.
  • a method of manufacturing a semiconductor device comprising: adjusting a work function of a film containing the metal element, carbon, and nitrogen to a desired value by controlling the number of times of supplying the carbon-containing gas with respect to the number of times Is provided.
  • Forming a first layer containing the first metal element on the substrate by supplying a first metal-containing gas containing the first metal element to the substrate; By supplying a second metal-containing gas containing a second metal element and carbon to the substrate on which the first layer is formed, the first metal element and the second metal element on the substrate are supplied.
  • Forming a second layer containing a metal element and carbon Performing the step of forming the first layer by forming a film containing the first metal element, the second metal element, and carbon having a predetermined thickness on the substrate
  • the work function of the film containing the first metal element, the second metal element, and carbon is adjusted to a desired value by controlling the number of times of performing the step of forming the second layer with respect to the number of times.
  • the first metal element includes titanium or tantalum
  • the second metal element includes aluminum
  • the first metal-containing gas includes TiCl 4 and TaCl 4
  • the second metal-containing gas includes TMA
  • Forming the first layer with respect to the number of executions of the step of forming the second layer by forming a film containing the metal element, carbon and nitrogen with a predetermined thickness on the substrate.
  • the metal-containing gas supply system, the carbon-containing gas supply system, and the nitrogen-containing gas are adjusted so that the work function of the film containing the metal element, carbon, and nitrogen is adjusted to a desired value.
  • I will control the gas supply system When configured control unit, A substrate processing apparatus is provided.
  • a processing chamber for accommodating the substrate;
  • a first metal-containing gas supply system for supplying a first metal-containing gas containing a first metal element to the substrate in the processing chamber;
  • a second metal-containing gas supply system for supplying a second metal-containing gas containing a second metal element and carbon to the substrate in the processing chamber;
  • a second layer containing the first metal element, the second metal element, and carbon is formed on the substrate by supplying the second metal-containing gas to the formed substrate.
  • a film containing the first metal element, the second metal element, and carbon having a predetermined film thickness is formed on the substrate, and the first layer is formed.
  • the work function of the film containing the first metal element, the second metal element and carbon becomes a desired value. Adjusting the first metal-containing gas supply system and the front When configured controller to control the second metal-containing gas supply system, A substrate processing apparatus is provided.
  • [Appendix 15] Forming a first layer containing the metal element on the substrate by supplying a metal-containing gas containing a metal element and a carbon-containing gas to a substrate in a processing chamber of the substrate processing apparatus; A step of nitriding the first layer by supplying a nitrogen-containing gas to the substrate on which the first layer is formed to form the second layer containing the metal element, carbon and nitrogen; , Is performed a predetermined number of times to form a film containing the metal element, carbon and nitrogen with a predetermined film thickness on the substrate, and the first layer with respect to the number of executions of the procedure of forming the second layer
  • a program for causing a computer to execute a procedure for adjusting the work function of the film containing the metal element, carbon and nitrogen to a desired value.
  • a computer-readable recording medium storing a program for causing a computer to execute a procedure for adjusting the work function of the film containing the metal element, carbon, and nitrogen to a desired value by controlling the number of times the procedure is performed Provided.
  • Appendix 21 Performing a process for forming a first layer containing a metal element and nitrogen or carbon for a first predetermined number of times; Performing a second predetermined number of times to form a second layer containing the metal element, nitrogen and carbon; By alternately performing the third predetermined number of times, a method of manufacturing a semiconductor device including a step of forming a metal film containing nitrogen and carbon at a predetermined ratio on a substrate is provided.
  • the first predetermined number of times, the second predetermined number of times, and the third predetermined number of times are determined according to a ratio of nitrogen or carbon included in the metal film.
  • the second layer includes a second metal element different from the metal element.
  • the third raw material includes a second metal element different from the metal element.
  • the metal film is formed on a high dielectric film formed on the substrate.
  • the metal element includes at least one element selected from the group consisting of titanium, tantalum, hafnium, zirconium, molybdenum, and tungsten.
  • the second metal element includes aluminum.
  • the first raw material and the fourth raw material include TiCl 4 .
  • the third raw material includes TMA (trimethylaluminum).
  • the metal element is titanium
  • the work function of the metal film is a value between the work function of TiN or TiAlN and the work function of TiAlC.
  • the metal element is titanium
  • the second metal element is aluminum
  • the work function of the metal film is a value between the work function of TiN or TiAlN and the work function of TiAlC.
  • Appendix 33 Performing a process for forming a first layer containing a metal element and nitrogen or carbon for a first predetermined number of times; Performing a second predetermined treatment for forming a second layer containing the metal element, nitrogen and carbon; By alternately performing the third predetermined number of times, a substrate processing method including a step of forming a metal film containing nitrogen and carbon at a predetermined ratio on the substrate is provided.
  • the first predetermined number of times, the second predetermined number of times, and the third predetermined number of times are determined according to a ratio of nitrogen or carbon included in the metal film.
  • a processing chamber for accommodating the substrate;
  • a metal-containing raw material supply system for supplying a metal-containing raw material containing a metal element to the substrate connected to the processing chamber and housed in the processing chamber;
  • a nitrogen-containing material supply system for supplying a nitrogen-containing material containing nitrogen to the substrate connected to the processing chamber and housed in the processing chamber;
  • a carbon-containing raw material supply system for supplying a carbon-containing raw material containing carbon to the substrate connected to the processing chamber and housed in the processing chamber;
  • the metal-containing raw material supply system, the nitrogen-containing raw material supply system and the carbon-containing raw material supply system are connected to the substrate housed in the processing chamber and the metal-containing raw material and the nitrogen-containing raw material or the A process of alternately supplying a carbon-containing raw material for a first predetermined number of times and a process of alternately supplying the metal-containing raw material, the nitrogen-containing raw material, and the carbon-containing raw material for a second predetermined number of times are thirdly performed.
  • a control unit configured to control and execute the system;
  • a substrate processing apparatus is provided.
  • the first predetermined number of times, the second predetermined number of times, and the third predetermined number of times are determined according to a ratio of the nitrogen or the carbon included in the metal film.
  • the first predetermined number of times, the second predetermined number of times, and the third predetermined number of times are determined according to a ratio of nitrogen or carbon included in the metal film.
  • the first predetermined number of times, the second predetermined number of times, and the third predetermined number of times are determined according to a ratio of nitrogen or carbon included in the metal film.
  • the present invention can be used for, for example, a method for manufacturing a semiconductor device, a substrate processing apparatus for processing a substrate such as a semiconductor wafer or a glass substrate, and the like.

Abstract

Le problème à résoudre dans le cadre de la présente invention consiste à fournir un procédé de production d'un dispositif à semi-conducteurs et à un dispositif de traitement de substrat pour lesquels une valeur de travail de sortie peut être ajustée. La solution proposée consiste en un procédé qui comprend les étapes consistant à : former une première couche sur le substrat dans une chambre de traitement en fournissant à cette dernière un gaz contenant un métal qui contient un élément métallique, ainsi qu'un gaz contenant du carbone, la première couche contenant l'élément métallique et le carbone ; et former une seconde couche en fournissant au substrat un gaz contenant de l'azote, la première couche étant formée sur cette dernière, de sorte à nitrifier la première couche. L'étape consistant à former la première couche et l'étape consistant à former la seconde couche sont effectuées alternativement de telle sorte que les étapes soient chacune effectuées à des moments prédéterminés de sorte à former sur le substrat un film qui présente une épaisseur de film prédéterminée et qui contient l'élément métallique, le carbone et l'azote. Le nombre de fois où est effectuée l'étape consistant à former la première couche, est déterminé par rapport au nombre de fois où est effectuée l'étape consistant à former la seconde couche de telle sorte qu'un travail de sortie du film qui contient l'élément métallique, le carbone et l'azote soit ajusté de sorte à avoir une valeur souhaitée.
PCT/JP2014/050751 2013-01-18 2014-01-17 Procédé de production d'un dispositif à semi-conducteurs, et dispositif de traitement de substrat WO2014112572A1 (fr)

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US16/240,197 US10388530B2 (en) 2013-01-18 2019-01-04 Method of manufacturing semiconductor device and substrate processing apparatus

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TWI840694B (zh) 2020-09-23 2024-05-01 日商國際電氣股份有限公司 基板處理方法、半導體裝置的製造方法、基板處理裝置及程式

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