WO2013105389A1 - ＴｉＳｉＮ膜の成膜方法および記憶媒体 - Google Patents

ＴｉＳｉＮ膜の成膜方法および記憶媒体 Download PDF

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WO2013105389A1
WO2013105389A1 PCT/JP2012/082367 JP2012082367W WO2013105389A1 WO 2013105389 A1 WO2013105389 A1 WO 2013105389A1 JP 2012082367 W JP2012082367 W JP 2012082367W WO 2013105389 A1 WO2013105389 A1 WO 2013105389A1
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Prior art keywords
film
gas
tisin
supplying
forming
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PCT/JP2012/082367
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English (en)
French (fr)
Japanese (ja)
Inventor
山▲崎▼　英亮
正樹 小泉
麻由子 石川
健史 山本
聡史 川端
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東京エレクトロン株式会社
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Priority claimed from JP2012005310A external-priority patent/JP2013145796A/ja
Priority claimed from JP2012009613A external-priority patent/JP2013147708A/ja
Application filed by 東京エレクトロン株式会社 filed Critical 東京エレクトロン株式会社
Publication of WO2013105389A1 publication Critical patent/WO2013105389A1/ja

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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 potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
    • H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
    • H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
    • H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
    • H01L21/28556—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
    • H01L21/28562—Selective deposition
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45527—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
    • C23C16/45529—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 a layer stack of alternating different compositions or gradient compositions
    • 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
    • H01L28/00—Passive two-terminal components without a potential-jump or surface barrier for integrated circuits; Details thereof; Multistep manufacturing processes therefor
    • H01L28/40—Capacitors
    • H01L28/60—Electrodes

Definitions

  • the present invention relates to a method of forming a TiSiN film and a storage medium.
  • a TiN film is used as a lower electrode of a DRAM capacitor.
  • CVD Chemical Vapor Deposition
  • a TiN film is formed by CVD, TiCl 4 gas as a Ti-containing gas and NH 3 gas as a nitriding gas are used.
  • SFD Sequential Flow Deposition
  • ALD Atomic Layer Deposition
  • Patent Document 3 discloses a method of forming a TiSiN film by ALD. Further, as with the TiN film, the formation of a TiSiN film by SFD is also being studied.
  • an object of the present invention is to provide a TiSiN film forming method capable of obtaining a TiSiN film having a stable specific resistance regardless of the film thickness. Another object is to provide a storage medium storing a program for executing such a method.
  • a substrate to be processed is carried into a processing container, the inside of the processing container is held in a reduced pressure state, and the substrate to be processed is heated while the substrate to be processed is heated.
  • a method of forming a TiSiN film is provided in which the step of supplying the Ti-containing gas and the nitriding gas is performed, or the step of supplying the Ti-containing gas and the step of supplying the nitriding gas are performed.
  • the TiN film is preferably formed in a continuous film state in the first step of film formation. Further, TiCl 4 gas as the Ti-containing gas, NH 3 gas as the nitriding gas, and SiH 2 Cl 2 gas as the Si-containing gas containing Cl can be preferably used.
  • the thickness of the TiSiN film to be formed is preferably 20 nm or less.
  • the steps (1) and (2) are first performed in order with the step of purging the inside of the processing vessel, and then the TiSiN unit film is formed.
  • the operations of performing the steps (1) to (3) in any order with the step of purging the inside of the processing container may be repeated a plurality of times.
  • the operation of forming the TiSiN unit film includes the steps of supplying the Ti-containing gas and nitriding gas, supplying the nitriding gas, supplying the Si-containing gas containing Cl, and supplying the nitriding gas. This step is performed in this order across the step of purging the inside of the processing container, and the operation of forming the TiSiN unit film can be repeated from the initial stage of film formation. In this case, one of the two steps of supplying the nitriding gas can be omitted.
  • the inside of the processing vessel is purged with the step of supplying the Ti-containing gas, the step of supplying the nitriding gas, and the step of supplying the Si-containing gas containing Cl. It is possible to repeat the operation of forming the TiSiN unit film from the initial stage of the film formation in this order across the steps. In this case, after supplying the Si-containing gas containing Cl, a step of supplying another nitriding gas with a purge gas interposed may be performed.
  • the temperature during film formation is a temperature at which Cl is not desorbed from the Si-containing gas containing Cl.
  • the temperature of the susceptor that supports the substrate to be processed in the processing container can be set to 620 ° C. or less, and the film forming process can be performed at 400 to 620 ° C. preferable.
  • a storage medium that operates on a computer and stores a program for controlling a film forming apparatus, and the program performs the film forming method when executed.
  • a storage medium characterized by causing a computer to control the film forming apparatus is provided.
  • TiCl 4 gas which is a diagram illustrating the NH 3 gas, a sequence used for the comparative evaluation for grasping the contribution to the formation of the DCS gas.
  • TiCl 4 gas which is a diagram illustrating the DCS gas and NH 3 X-ray photoelectron spectroscopy of the TiSiN film formed by the sequence using a gas (XPS) analysis.
  • FIG. 2 is a diagram showing the relationship between susceptor temperature and specific resistance for a TiSiN film formed by changing the susceptor temperature between 400 and 680 ° C. and a TiN film changed between 400 and 620 ° C. by the sequence of FIG. It is.
  • the unit of the gas flow rate is mL / min.
  • the value converted into the standard state is used in the present invention.
  • the flow volume converted into the standard state is normally indicated by sccm (Standard Cubic Centimeter per Minutes), sccm is also written together.
  • the standard state here is a state where the temperature is 0 ° C. (273.15 K) and the atmospheric pressure is 1 atm (101325 Pa).
  • FIG. 1 is a schematic cross-sectional view showing an example of a film forming apparatus used for carrying out a method of forming a TiSiN film according to the first embodiment of the present invention.
  • a TiSiN film is formed by thermal CVD will be described as an example.
  • the film forming apparatus 100 has a substantially cylindrical chamber 1. Inside the chamber 1 is a state in which a susceptor 2 made of AlN is supported by a cylindrical support member 3 provided at the center lower portion as a stage for horizontally supporting a wafer W as a substrate to be processed. Is arranged in. A guide ring 4 for guiding the wafer W is provided on the outer edge of the susceptor 2. Further, a heater 5 made of a high melting point metal such as molybdenum is embedded in the susceptor 2, and the heater 5 is heated by a heater power supply 6 to heat the wafer W as a substrate to be processed to a predetermined temperature. To do.
  • a shower head 10 is provided on the top wall 1 a of the chamber 1.
  • the shower head 10 is composed of an upper block body 10a, a middle block body 10b, and a lower block body 10c, and the whole has a substantially disk shape.
  • the upper block body 10a has a horizontal portion 10d that constitutes a shower head main body together with the middle block body 10b and the lower block body 10c, and an annular support portion 10e that is continuous above the outer periphery of the horizontal portion 10d, and is formed in a concave shape. ing.
  • the entire shower head 10 is supported by the annular support portion 10e.
  • Discharge holes 17 and 18 for discharging gas are alternately formed in the lower block body 10c.
  • a first gas inlet 11 and a second gas inlet 12 are formed on the upper surface of the upper block body 10a.
  • a large number of gas passages 13 are branched from the first gas inlet 11.
  • Gas passages 15 are formed in the middle block body 10b, and the gas passages 13 communicate with the gas passages 15 through communication passages 13a extending horizontally. Further, the gas passage 15 communicates with the discharge hole 17 of the lower block body 10c.
  • a large number of gas passages 14 are branched from the second gas introduction port 12.
  • Gas passages 16 are formed in the middle block body 10 b, and the gas passage 14 communicates with these gas passages 16.
  • the gas passage 16 is connected to a communication passage 16a extending horizontally in the middle block body 10b, and the communication passage 16a communicates with a number of discharge holes 18 of the lower block body 10c.
  • the first and second gas inlets 11 and 12 are connected to a gas line of the gas supply mechanism 20.
  • Gas supply mechanism 20 includes a TiCl 4 gas TiCl 4 gas supply source 21 for supplying as a Ti-containing gas, and a NH 3 gas supply source 23 for supplying the NH 3 gas as nitriding gas.
  • the TiCl 4 gas supply source 21 is connected to the TiCl 4 gas supply line 22, the TiCl 4 gas supply line 22 is connected to the first gas inlet 11.
  • the NH 3 gas supply source 23 is connected to the NH 3 gas supply line 24, the NH 3 gas supply line 24 is connected to the second gas inlet 12.
  • the gas supply line 22 is connected to the N 2 gas supply line 26, as N 2 gas from the N 2 gas supply source 25 into the N 2 gas supply line 26 is supplied as a carrier gas or a purge gas It has become.
  • a DCS gas supply line 28 for supplying dichlorosilane (SiH 2 Cl 2 ; DCS) gas as a Si-containing gas is connected to the NH 3 gas supply line 24, and a DCS gas supply source is connected to the DCS gas supply line 28.
  • the DCS gas is supplied from 27.
  • the NH 3 gas supply line 24 is connected to the N 2 gas supply line 30, N 2 gas is supplied as a carrier gas or a purge gas from the N 2 gas supply source 29 into the N 2 gas supply line 30 It is like that.
  • the gas supply mechanism 20 includes a ClF 3 gas supply source 31 that supplies a ClF 3 gas that is a cleaning gas, and a ClF 3 gas supply line 32 a is connected to the ClF 3 gas supply source 31.
  • the ClF 3 gas supply line 32 a is connected to the TiCl 4 gas supply line 22.
  • a ClF 3 gas supply line 32 b that branches from the ClF 3 gas supply line 32 a and is connected to the NH 3 gas supply line 24 is provided.
  • the TiCl 4 gas supply line 22, the NH 3 gas supply line 24, the DCS gas supply line 28, the N 2 gas supply lines 26 and 30, and the ClF 3 gas supply line 32a include two valves sandwiching the mass flow controller 33 and the mass flow controller 33. 34 is provided. A valve 34 is provided in the ClF 3 gas supply line 32b.
  • the shower head from the first gas inlet port 11 of TiCl 4 N 2 gas from the gas and N 2 gas supply source 25 the shower head 10 through the TiCl 4 gas supply line 22 from the TiCl 4 gas supply source 21 reaches the 10, is discharged from the discharge hole 17 into the chamber 1 through the gas passages 13, 15, NH 3 gas, DCS gas and N 2 gas supply source from DCS gas supply source 27 from the NH 3 gas supply source 23
  • the N 2 gas from 29 reaches the shower head 10 through the NH 3 gas supply line 24 from the second gas inlet 12 of the shower head 10, passes through the gas passages 14 and 16, and is discharged from the discharge hole 18 into the chamber 1. Is discharged.
  • the shower head 10 is configured so that TiCl 4 gas, NH 3 gas, and DCS gas are separately supplied into the chamber 1.
  • the present invention is not limited to this, and a type in which all gases are supplied into the chamber 1 through the same passage in the shower head 10 may be used.
  • NH 3 gas and DCS gas are supplied to the chamber through the same passage from the gas supply line to the shower head, and yet another stage, a separate gas introduction port, a gas passage in the shower head, and a discharge passage.
  • An outlet may be provided so that the NH 3 gas and the DCS gas are not mixed inside the shower head.
  • the DCS gas supply line may be connected to the TiCl 4 gas supply line.
  • Ti-containing gas in addition to TiCl 4 , tetra (isopropoxy) titanium (TTIP), titanium tetrabromide (TiBr 4 ), titanium tetraiodide (TiI 4 ), tetrakisethylmethylaminotitanium (TEMAT), Tetrakisdimethylaminotitanium (TDMAT), tetrakisdiethylaminotitanium (TDEAT), etc. can also be used.
  • TTIP titanium tetrabromide
  • TiI 4 titanium tetraiodide
  • TEMAT tetrakisethylmethylaminotitanium
  • TDMAT Tetrakisdimethylaminotitanium
  • TDEAT tetrakisdiethylaminotitanium
  • MMH monomethylhydrazine
  • Si-containing gas examples include those containing Cl such as tetrachlorosilane (SiCl 4 ; STC), trichlorosilane (SiHCl 3 ; TCS), and monochlorosilane (SiH 3 Cl; MCS) in addition to DCS. .
  • Cl such as tetrachlorosilane (SiCl 4 ; STC), trichlorosilane (SiHCl 3 ; TCS), and monochlorosilane (SiH 3 Cl; MCS) in addition to DCS.
  • N 2 gas used as the carrier gas and the purge gas
  • other inert gases such as Ar gas can be used.
  • the heater 45 for heating the shower head 10 is provided in the horizontal part 10d of the upper block body 10a of the shower head 10.
  • a heater power source 46 is connected to the heater 45, and the shower head 10 is heated to a desired temperature by supplying power to the heater 45 from the heater power source 46.
  • a heat insulating member 47 is provided in the concave portion of the upper block body 10a.
  • a circular hole 35 is formed in the center of the bottom wall 1b of the chamber 1, and an exhaust chamber 36 is provided on the bottom wall 1b so as to protrude downward so as to cover the hole 35.
  • An exhaust pipe 37 is connected to a side surface of the exhaust chamber 36, and an exhaust device 38 is connected to the exhaust pipe 37. By operating the exhaust device 38, the inside of the chamber 1 can be depressurized to a predetermined degree of vacuum.
  • the susceptor 2 is provided with three (only two are shown) wafer support pins 39 for supporting the wafer W to be moved up and down so as to protrude and retract with respect to the surface of the susceptor 2. It is supported by the plate 40.
  • the wafer support pins 39 are lifted and lowered via the support plate 40 by a drive mechanism 41 such as an air cylinder.
  • a loading / unloading port 42 for loading / unloading the wafer W to / from a wafer transfer chamber (not shown) provided adjacent to the chamber 1, and a gate valve 43 for opening / closing the loading / unloading port 42, Is provided.
  • the heater power supplies 6 and 46, the valve 34, the mass flow controller 33, the drive mechanism 41, and the like, which are constituent parts of the film forming apparatus 100, are connected to and controlled by a control part 50 having a microprocessor (computer). Yes.
  • the control unit 50 includes a user interface 51 including a keyboard for an operator to input commands for managing the film forming apparatus 100, a display for visualizing and displaying the operating status of the film forming apparatus 100, and the like. It is connected. Further, the control unit 50 executes a process for each component of the film forming apparatus 100 according to a program for realizing various processes executed by the film forming apparatus 100 under the control of the control unit 50 and processing conditions.
  • the processing recipe is stored in the storage medium 52 a in the storage unit 52.
  • the storage medium may be a fixed one such as a hard disk or a portable one such as a CDROM or DVD.
  • the processing recipe may be appropriately transmitted from another apparatus, for example, via a dedicated line. Then, if necessary, an arbitrary processing recipe is called from the storage unit 52 according to an instruction from the user interface 51 and is executed by the control unit 50, so that the film forming apparatus 100 performs the control under the control of the control unit 50. Desired processing is performed.
  • TiCl 4 gas and NH 3 gas are introduced into the chamber 1 at a predetermined flow rate through the shower head 10, and the inner wall of the chamber 1, the inner wall of the exhaust chamber 36, and the shower head A TiN film is precoated on the surface of a member in the chamber such as 10.
  • TiCl 4 gas, NH 3 gas and DCS gas may be introduced to pre-coat a TiSiN film on the surface of the chamber inner member, or a laminated film of a TiN film and a TiSiN film may be pre-coated.
  • the gate valve 43 is opened, and the wafer W is loaded into the chamber 1 from the wafer transfer chamber via the transfer port 42 (both not shown) by the transfer device and placed on the susceptor 2. . Then, the wafer W is heated to 300 to 900 ° C. by the heater 5 and N 2 gas is supplied into the chamber 1 to preheat the wafer W. When the temperature of the wafer is substantially stabilized, the TiSiN film is formed.
  • a TiSiN film is formed by SFD or ALD using a Ti-containing gas, a nitriding gas, and a Si-containing gas.
  • a Si-containing gas a gas containing Cl typified by DCS is used.
  • the TiSiN unit film is formed by performing the steps (3) to (3) in an appropriate order with the purge gas supplied, and the TiSiN unit film is formed a plurality of times to form a TiSiN unit film having a predetermined thickness. Film.
  • the steps (1) to (3) are not limited to once.
  • the nitriding step (2) is preferably performed both after the step (1) and after the step (3) because nitriding is further promoted.
  • TiCl 4 gas is used as the Ti-containing gas
  • NH 3 gas is used as the nitriding gas
  • DCS gas is used as the Si-containing gas
  • N 2 gas is used as the purge gas.
  • step S2 the supply of TiCl 4 gas and NH 3 gas is stopped, and the inside of the chamber 1 is purged with N 2 gas flowing from the N 2 gas supply sources 25 and 29 (step S2).
  • step S3 NH 3 gas is supplied together with N 2 gas as a carrier gas, and a first nitriding treatment is performed (step S3).
  • step S4 the supply of the NH 3 gas is stopped, and the inside of the chamber 1 is purged with the N 2 gas flowing from the N 2 gas supply sources 25 and 29 (step S4).
  • DCS gas is supplied from the DCS gas supply source 27 together with N 2 gas as a carrier gas, and a thin TiN film on the wafer W is doped with Si (Si film formation) to form a thin TiSiN film (step S5).
  • the supply of DCS gas is stopped, and the inside of the chamber 1 is purged with the N 2 gas flowing from the N 2 gas supply sources 25 and 29 (step S6).
  • NH 3 gas is supplied together with N 2 gas as a carrier gas, and a second nitriding process is performed (step S7).
  • the supply of the NH 3 gas is stopped, and the inside of the chamber 1 is purged with the N 2 gas flowing from the N 2 gas supply sources 25 and 29 (step S8).
  • a TiSiN unit film is formed by the operations in steps S1 to S8 described above, and this operation is repeated a predetermined number of times to form a TiSiN film having a predetermined thickness.
  • the number of cycles at this time is appropriately set according to the film thickness. For example, about 2 to 60 times.
  • the gas switching at this time is performed by switching the valve according to a command from the control unit 50.
  • the basic conditions are set as follows by the above sequence, and the first step S1 is performed in 2 sec, the same as the second and subsequent times (no additional time), and only the first step S1 is increased by 6.7 sec.
  • the sample additional time 6.7 sec
  • the number of repetitions was changed, TiSiN films having various thicknesses were formed, and the specific resistance of the films was measured.
  • Step S1 TiN film formation
  • Chamber pressure 260Pa TiCl 4 gas flow rate: 60 mL / min (sccm) NH 3 gas flow rate: 60 mL / min (sccm) N 2 gas flow rate (2 systems): 170 mL / min (sccm) each Time: 2 sec
  • Step S3 first nitriding
  • Chamber pressure 260Pa NH 3 gas flow rate: 4500 mL / min (sccm) N 2 gas flow rate (2 systems): 200 mL / min (sccm) each Time: 5 sec
  • Step S5 Si film formation
  • Chamber pressure 667Pa DCS gas flow rate: 25 mL / min (sccm) N 2 gas flow rate (2 systems): 500 mL / min (sccm) each Time: 8 sec
  • Chamber pressure 260Pa NH 3 gas flow rate: 4500 mL / min (sccm) N 2
  • FIG. 3 is a diagram showing an image of a film state when a TiSiN film is formed under the above conditions.
  • FIG. 3A shows a case where the first step S1 is set to 2 sec after the second time (no additional time).
  • (B) shows a case where only the first step S1 is increased by 6.7 sec (addition time 6.7 sec).
  • the base insulating film such as a SiO 2 film or a SiN film is formed. Only the island-like TiN film is formed, and the base insulating film is partially exposed.
  • the additional time of (b) is 6.7 sec, a firm TiN film is formed in the first steps S1 and S2.
  • FIG. 4 shows the relationship between the film thickness of the TiSiN film formed by these sequences and the specific resistance by a scanning microscope (SEM).
  • SEM scanning microscope
  • the change in specific resistance in this film thickness region means that the resistance value of the lower electrode material varies due to the film thickness variation during actual device production. This is a problem because it leads to variations in speed.
  • the first step S1 in (b) has an additional time of 6.7 sec, the specific resistance hardly changes depending on the film thickness.
  • Such a difference is that when the first step S1 in (a) has no additional time, the DCS gas is supplied with the underlying insulating film such as the SiO 2 film exposed.
  • the first step S1 of (b) is for an additional time of 6.7 sec, it is formed on the underlying insulating film at the initial stage of film formation. Since the TiCl 4 gas and the NH 3 gas are allowed to flow for a sufficient time to form the TiN film, the DCS gas for adding Si is started to flow while the TiN film is formed on the SiO 2 film of the base insulating film. This is because the DCS gas is supplied to the TiN film without touching elements such as Si and O.
  • FIG. 5 shows the result of comparing the Si concentration in the film according to the film thickness (SEM film thickness) of the TiSiN film formed by the above two sequences. As shown in this figure, it can be seen that the Si concentration in the film is not changed in both cases, and the way of incorporation of Si into the TiSiN film is not changed.
  • the dissociation energy obtained from quantum chemistry calculations when Cl atoms are detached from the surface is 0.08 to 0.29 eV in the case of Ti—Cl bonds, whereas 0.54 in the case of Si—Cl bonds. It can be seen that the energy at which the Si—Cl bond is broken is about 2 to 7 times higher than the energy at which the Ti—Cl bond is broken.
  • the surface state of the base when the DCS gas, which is a Si-containing gas containing Cl, is flowed at the initial stage of film formation is important.
  • the base insulating film is exposed, SiO 2 , SiN, etc. are formed. It is considered that a Si—Cl bond is formed when Cl contained in DCS or Cl element separated from DCS reaches Si element on the surface.
  • the energy of dissociation of the Si—Cl bond is large. Therefore, it is difficult to break this Si—Cl bond in the normal film formation process.
  • a sequence is used in which the TiN film is first formed and then the operation of forming the TiSiN unit film for supplying DCS gas, which is a Si-containing gas containing Cl, is repeated a plurality of times.
  • DCS gas which is a Si-containing gas containing Cl
  • a TiSiN film whose specific resistance does not depend on the film thickness can be formed.
  • the TiN film formed first is preferably a continuous film. Thereby, such an effect can be obtained with certainty.
  • a step of supplying a Ti-containing gas and a nitriding gas is performed for at least a time corresponding to an incubation time for forming the TiN film, or a Ti-containing gas is supplied. If the TiN film is formed immediately after the step of performing and the step of supplying the nitriding gas, in the subsequent operation of forming the TiSiN unit film, (1) the step of supplying the Ti-containing gas Alternatively, the step of supplying the Ti-containing gas and the nitriding gas, (2) the step of supplying the nitriding gas, and (3) the step of supplying the Si-containing gas containing Cl may be performed in any order with the purge step interposed therebetween. it can. In this case as well, a TiSiN film whose specific resistance does not depend on the film thickness can be formed.
  • the nitriding process is performed twice in the formation of the TiSiN unit film to strengthen the nitriding.
  • the first nitriding process in step S3 may be omitted
  • the second nitriding process in step S7 may be omitted as shown in the sequence of FIG.
  • step S1 both TiCl 4 gas and NH 3 gas are supplied to form a TiN skeleton.
  • NH 3 gas is supplied instead of step S1.
  • step S1 ′ for supplying only TiCl 4 gas and adsorbing Ti may be performed to form an ALD film.
  • the pressure, the TiCl 4 flow rate, and the N 2 flow rate can be the same as in step S1, and the time T1 ′ can be the same as the time T1 in step S1.
  • the first step S1 ′ and the first nitriding step S3 are conditions for forming a TiN film as a continuous film. If sufficient nitriding can be performed in the first nitriding step S3, the second nitriding step S7 can be omitted.
  • Si film formation and Ti film formation in the timing charts of FIG. 2 and FIGS. 6 to 8 merely indicate the act of operation, and whether or not the film is actually formed is a problem. is not.
  • a TiSiN film deposition sequence in which the operation of forming the TiSiN unit film on the Si-containing portion of the substrate to be processed is repeated a plurality of times including the steps (1) to (3) of supplying the Si-containing gas.
  • the step of supplying the Ti-containing gas and the nitriding gas is performed at the beginning of the step, or the step of supplying the Ti-containing gas and the step of supplying the nitriding gas are performed, and then the Si-containing gas containing Cl is supplied. Si-Cl bond is not formed at the interface between the portion containing the SiSiN film and the TiSiN film, and a TiSiN film having a stable specific resistance is obtained even when the film thickness is thin Door can be.
  • the film forming apparatus shown in FIG. 1 is used as an example of the film forming apparatus.
  • the inner wall of the chamber 1, the inner wall of the exhaust chamber 36, and the shower After pre-coating the surface of the chamber member such as the head 10, the wafer W is pre-heated, and when the temperature of the wafer is almost stabilized, the TiSiN film is formed.
  • a TiSiN film is formed by SFD or ALD using Ti-containing gas, nitriding gas, and Si-containing gas, as in the first embodiment.
  • Si-containing gas a gas containing Cl typified by DCS is used.
  • the TiSiN unit film is formed by performing the steps (3) to (3) in an arbitrary order with the supply of the purge gas, and the TiSiN unit film is formed a plurality of times to form a TiSiN film having a predetermined thickness. Film.
  • the steps (1) to (3) are not limited to once.
  • the nitriding step (2) is preferably performed both after the step (1) and after the step (3) because nitriding is further promoted.
  • Step S1 TiN film formation
  • Chamber pressure 133Pa TiCl 4 gas flow rate: 60 mL / min (sccm)
  • NH 3 gas flow rate 60 mL / min (sccm)
  • Steps S3 and S7 nitriding
  • Chamber pressure 260Pa NH 3 gas flow rate: 4500 mL / min (sccm) N 2 gas flow rate (2 systems): 200 mL / min (sccm) each Time: 5 sec
  • Step S5 Si film formation
  • Chamber pressure 667Pa DCS gas flow rate: 100 mL / min (sccm) N 2 gas flow rate (2 systems): 500 mL / min (sccm) each
  • FIG. 9 is a diagram showing the relationship between the temperature and the thickness of the SiN film when the TiSiN film is formed under the above conditions.
  • the film thickness of the SiN film is calculated by measuring the film thickness of the TiSiN film with a transmission electron microscope (TEM), and subtracting the film thickness of the TiN film calculated from the Ti count of fluorescent X-ray analysis (XRF) from that value. did.
  • TEM transmission electron microscope
  • XRF fluorescent X-ray analysis
  • FIG. 10 is a diagram in which the results are arranged with an Arrhenius plot. As shown in this figure, since the slope of the straight line changes around 620 ° C., it can be seen that the activation energy during film formation changes at that temperature.
  • the activation energy estimated from the Arrhenius plot of FIG. 10 was 0.57 eV in the temperature region of 620 ° C. or higher and 0.018 eV in the temperature region of 600 ° C. or lower.
  • the dissociation energy when H atoms are desorbed from DCS on the surface and the dissociation energy when Cl atoms are desorbed are 0.02 to 0.04 eV and 0.54 to 0, respectively, obtained from quantum chemical calculations. .59eV, the activation energy in the temperature region above 620 ° C. coincides with the energy from which Cl is desorbed from DCS, and the activation energy in the temperature region below 620 ° C. coincides with the energy from which H is desorbed from DCS. To do. That is, at a temperature of 620 ° C. or higher, Cl is desorbed from the DCS that has reached the wafer surface and Si film formation proceeds, whereas at a temperature of 620 ° C.
  • the susceptor temperature is 620 ° C. or less, and controllability is ideal. Approximately one atomic layer of Si can be introduced into the film. Further, from the viewpoint of forming a TiSiN film having a stable structure, the susceptor temperature is preferably 400 ° C. or higher. When the susceptor temperature is lower than 400 ° C., it is difficult to desorb Cl at the time of film formation, so the Cl concentration in the film becomes high and the film structure becomes unstable.
  • preferable conditions are the same as those in the first embodiment.
  • the TiSiN film forming sequence in which the operation of forming the TiSiN unit film on the substrate to be processed is repeated a plurality of times including the steps (1) to (3) of supplying the Si-containing gas containing Is set to a temperature at which Cl does not desorb from the Si-containing gas containing Cl, so that the Si-containing gas containing Cl that has reached the surface of the substrate to be processed does not progress in decomposition, and Si can be introduced with good controllability.
  • a TiSiN film having good controllability of Si concentration and high stability can be obtained.
  • Si is introduced with good controllability without considering the point of forming the TiN film at the beginning of the film formation, with the film formation temperature being the temperature at which Cl is not desorbed from the Si-containing gas containing Cl.
  • the step (3) of supplying the Si-containing gas containing Cl in the operation of forming the TiSiN unit film once may be performed first.
  • a specific example of the sequence at that time is shown in FIG. Also in this case, either the first nitriding process (step S3) or the second nitriding process (step S7) may be omitted.
  • the film may be formed in an ALD manner by using step S1 ′ in which NH 3 is not introduced instead of step S1.
  • the film forming conditions at this time are as follows.
  • TiCl 4 supply step TiCl 4 gas flow rate: 90 mL / min (sccm) N 2 gas flow rate: Total 2000 mL / min (sccm)
  • the TiSiN film is considered to be separated into a TiN component and a SiN component, as shown in Table 1, from the TiN film thickness calculated from the TEM film thickness and the Ti count of XRF, TiCl 4 gas, DCS gas and It can be seen that when three types of NH 3 gas are supplied, a SiN film having a film thickness almost equal to that of the TiN film is formed. From this, it can be seen that the formation of SiN components in the TiSiN film can be promoted when three kinds of gases are supplied.
  • the bonding between the Si element and other elements was examined based on the X-ray photoelectron spectroscopy (XPS) analysis result of the TiSiN film formed in the above (a).
  • XPS X-ray photoelectron spectroscopy
  • the specific resistance of the TiSiN film formed by changing the susceptor temperature between 400 and 680 ° C. and the TiN film changed between 400 and 620 ° C. were measured by the sequence shown in FIG. Conditions other than the temperature at the time of forming the TiSiN film were the same as in the experiment for obtaining the relationship shown in FIG. The result is shown in FIG.
  • the film thickness used when obtaining the specific resistance the TiN film uses the film thickness converted from the Ti count of XRF, and the TiSiN film uses the TEM film thickness.
  • the TiSiN film has a material inherent resistance higher than that of the TiN film.
  • the TiSiN film has a specific resistance higher than that of the TiN film in a wide temperature range of 400 to 620 ° C.
  • the height is higher than cm, and it is higher by one digit at 400 ° C. This is because the catalytic effect of the TiN film or Ti element is exhibited even in the film formation using the sequence of TiN film formation ⁇ nitridation ⁇ DCS gas supply ⁇ nitridation shown in FIG.
  • TiSiN film Means that a high-resistance TiSiN film is formed, and Si in the film in a wide temperature range by a sequence of three kinds of gases, TiCl 4 gas, NH 3 gas, and DCS gas. It was confirmed that a TiSiN film can be formed by adding.
  • the present invention is not limited to the above embodiment and can be variously modified.
  • the film forming apparatus of FIG. 1 used in the above embodiment is merely an example, and is not limited to the apparatus of FIG.
  • the semiconductor wafer is exemplified as the substrate to be processed.
  • the present invention is not limited to this in the principle of the present invention.
  • another substrate such as an FPD substrate represented by a substrate for a liquid crystal display device may be used. Needless to say, it is good.

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