WO2012096293A1 - MÉTHODE DE FORMATION D'UN FILM DE TiSiN ET SUPPORT DE STOCKAGE - Google Patents

MÉTHODE DE FORMATION D'UN FILM DE TiSiN ET SUPPORT DE STOCKAGE Download PDF

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WO2012096293A1
WO2012096293A1 PCT/JP2012/050350 JP2012050350W WO2012096293A1 WO 2012096293 A1 WO2012096293 A1 WO 2012096293A1 JP 2012050350 W JP2012050350 W JP 2012050350W WO 2012096293 A1 WO2012096293 A1 WO 2012096293A1
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gas
nitriding
film
tisin
supplying
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PCT/JP2012/050350
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English (en)
Japanese (ja)
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山▲崎▼　英亮
秀樹 湯浅
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東京エレクトロン株式会社
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Publication of WO2012096293A1 publication Critical patent/WO2012096293A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
    • H01L21/76841—Barrier, adhesion or liner layers
    • 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
    • C23C16/45531—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

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 A method of forming a TiSiN film applicable as a lower electrode of a DRAM capacitor by CVD is disclosed in Patent Document 3.
  • a substrate to be processed is carried into a processing container, and a Ti-containing gas and a nitriding gas are supplied into the processing container in a state where the inside of the processing container is maintained in a reduced pressure state.
  • An operation of forming the TiSiN unit film includes a TiSiN film forming method including a nitriding step of supplying a nitriding gas into the processing vessel at least once.
  • the nitriding step includes supplying the Ti-containing gas and the nitriding gas into the processing container and supplying the Si-containing gas into the processing container in the operation of forming the TiSiN unit film. And can be done after that. Further, in the operation of forming the TiSiN unit film, the nitriding step includes a step of supplying the Ti-containing gas and a nitriding gas into the processing container and a step of supplying the Si-containing gas into the processing container. You may go in between.
  • the nitriding step includes a step of supplying the Ti-containing gas and a nitriding gas into the processing container and a step of supplying the Si-containing gas into the processing container. And between the step of supplying the Ti-containing gas and the nitriding gas into the processing container and the step of supplying the Si-containing gas into the processing container.
  • the operation of forming the TiSiN unit film includes a step of supplying the Ti-containing gas and the nitriding gas into the processing container, and a first nitriding step of supplying the nitriding gas into the processing container.
  • a step of supplying the Si-containing gas into the processing container and a second nitriding step of supplying the nitriding gas into the processing container are sequentially performed with a purge in the processing container interposed therebetween.
  • the second nitriding step preferably has a pressure (Pa) ⁇ time (sec) value of 1800 or more and 48000 or less. Furthermore, it is more preferable that the second nitriding step has a pressure (Pa) ⁇ time (sec) value of 3330 or more and 15600 or less.
  • TiCl 4 gas can be used as the Ti-containing gas
  • NH 3 gas can be used as the nitriding gas
  • dichlorosilane can be used as the Si-containing gas.
  • the present invention is also a storage medium that operates on a computer and stores a program for controlling the film forming apparatus, and the program is stored in the computer so that the film forming method is performed at the time of execution.
  • a storage medium for controlling a film forming apparatus is provided.
  • 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 an embodiment of the present invention.
  • a TiSiN film is formed by thermal CVD will be described as an example.
  • 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).
  • 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 continues 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 branch 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 into 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.
  • 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
  • the Si-containing gas includes tetrachlorosilane (SiCl 4 ; STC), trichlorosilane (SiHCl 3 ; TCS), monochlorosilane (SiH 3 Cl; MCS), silane (SiH 4 ), and disilane (Si 2 H). 6 ) and the like.
  • tetrachlorosilane SiCl 4 ; STC
  • trichlorosilane SiHCl 3 ; TCS
  • monochlorosilane SiH 3 Cl
  • MCS monochlorosilane
  • SiH 4 silane
  • disilane Si 2 H
  • 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 CD-ROM 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 A TiN film is pre-coated on the surface of a member in the chamber such as the head 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 nitriding step is periodically inserted into the TiSiN film forming sequence by SFD.
  • a TiSiN unit film including a step of supplying a Ti-containing gas (for example, TiCl 4 gas) and a nitriding gas (for example, NH 3 gas) and a step of supplying a Si-containing gas (for example, DCS gas) is formed.
  • a Ti-containing gas for example, TiCl 4 gas
  • a nitriding gas for example, NH 3 gas
  • a Si-containing gas for example, DCS gas
  • the nitriding step is performed by stopping the Ti-containing gas and the Si-containing gas and supplying the nitriding gas.
  • the thickness of the TiSiN unit film including the step of supplying the Ti-containing gas and the nitriding gas and the step of supplying the Si-containing gas is 0.1 to 3 nm.
  • a TiSiN film is formed by repeating the operation of forming a TiSiN unit film by simply supplying TiCl 4 gas, which is Ti-containing gas, and NH 3 gas, which is nitriding gas, and supplying DCS gas, which is Si-containing gas.
  • TiCl 4 gas which is Ti-containing gas
  • NH 3 gas which is nitriding gas
  • DCS gas which is Si-containing gas.
  • At least one nitriding step is inserted into the operation of forming one TiSiN unit film, thereby promoting the nitridation of Si and Ti and the Ti—Si bond having low chemical resistance. And Si—Si bonds are reduced. Thereby, a TiSiN film having high chemical resistance can be formed.
  • the TiSiN film formed without inserting the nitriding step is also excellent, and the TiSiN film of this embodiment naturally has high oxidation resistance.
  • the nitriding step is preferably performed after performing the step of supplying the Ti-containing gas and the nitriding gas and the step of supplying the Si-containing gas in the operation of forming the TiSiN unit film.
  • the bond between Si and N and the bond between Ti and N are increased, and a nitride film having a stronger bond can be formed, and a TiSiN film having a stable structure can be obtained.
  • nitriding can be further promoted by inserting a nitriding step between the step of supplying the Ti-containing gas and the nitriding gas and the step of supplying the Si-containing gas.
  • the nitriding step may be performed only between the step of supplying the Ti-containing gas and the nitriding gas and the step of supplying the Si-containing gas.
  • the step of supplying the Ti-containing gas and the nitriding gas or the step of supplying the Si-containing gas may be performed first.
  • the step of supplying the Ti-containing gas and the nitriding gas and the step of supplying the Si-containing gas are not limited to one time. Further, the number of nitriding steps is not particularly limited. For example, after performing a step of supplying a Ti-containing gas and a nitriding gas and a step of supplying a Si-containing gas, the nitriding step and the step of supplying the Si-containing gas are performed once or a plurality of times to form a TiSiN unit film.
  • the TiSiN unit film may be formed by performing the step of supplying the Ti-containing gas and the nitriding gas and the nitriding step once or a plurality of times and then the step of supplying the Si-containing gas. .
  • 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 of steps S1 to S8 described above, and this operation is repeated as a single cycle for a plurality of cycles, preferably about 2 to 30 times, more preferably about 5 to 20 times to form a TiSiN film having a predetermined thickness. Form a film.
  • the gas switching at this time is performed by switching the valve according to a command from the control unit 50.
  • the preferable conditions for this film formation are as follows. (1) In-chamber pressure at step S1: 66.6 to 1333 Pa, more preferably 133 to 800 Pa (2) TiCl 4 gas flow rate at step S1: 10 to 200 mL / min (sccm), more preferably 40 to 100 mL / min (sccm) (3) NH 3 gas flow rate at step S1: 10 to 200 mL / min (sccm), more preferably 40 to 100 mL / min (sccm) (4) In-chamber pressure at step S3: 66.6 to 1333 Pa, more preferably 133 to 800 Pa (5) NH 3 gas flow rate at step S3: 100 to 10000 mL / min (sccm), more preferably 1000 to 5000 mL / min (sccm) (6) In-chamber pressure at step S5: 66.6 to 1333 Pa, more preferably 133 to 800 Pa (7) DCS gas flow rate at step S5: 1 to 1000 mL / min (s
  • Step S1 time T1 0.1 to 30 sec, more preferably 0.5 to 10 sec (13) Purge time T2, T4, T6, T8: 1 to 60 sec, more preferably 3 to 20 sec (14) Time T3 of step S3: 1 to 180 sec, more preferably 3 to 60 sec (15) Time T5 of step S5: 0.1 to 60 sec, more preferably 1 to 20 sec (16) Time T7 of step S7: 1 to 180 sec, more preferably 3 to 60 sec
  • the time and pressure of the second nitriding in step S7 are particularly important. That is, the nitriding power is determined by the total amount of nitriding gas to be supplied, and the larger the value of pressure (partial pressure of nitriding gas) ⁇ time, the better. Therefore, nitriding of the film can be strengthened if the time is long even if the pressure is low, and conversely, if the pressure is high even if the time is short, the nitriding of the film can be similarly strengthened.
  • the value of pressure (Pa) ⁇ time (sec) is preferably 1800 or more and 48000 or less, and more preferably 3330 or more and 15600 or less.
  • nitriding is sufficiently strengthened by setting the time to 7 sec or more, and even if the time is 5 sec or less, by setting the pressure to 360 Pa or more. be able to. More preferably, when the pressure is 260 Pa or less, nitriding can be further strengthened by setting the time to 13 sec or more, and when the pressure is 5 sec or less, the pressure is set to 600 Pa or more. Further, the pressure in the chamber at the time of Si doping in step S5 is also important for increasing the bond between Si and N, and the pressure at that time is preferably 66.6 Pa or more and particularly preferably 133 Pa or more.
  • the second nitriding treatment (step S7) after the formation of the thin TiSiN film in step S5 can increase the bond between Ti and N and the bond between Si and N.
  • the nitriding process (step S7) is more important, and the first nitriding process may be omitted as shown in the sequence of FIG.
  • step S3 since the TiN film is nitrided in a state where the TiN film is exposed on the surface, Ti that is not sufficiently bonded to nitrogen is nitrided, and further, the nitrogen under the TiN film and However, the effect of nitriding is lower than that of the second nitriding treatment (step S7), but the effect of increasing the bond between Ti and N and the bond between Si and N is increased. Therefore, as shown in the sequence of FIG. 4, only the first nitriding process (step S3) may be performed. Further, as shown in FIG. 5, DCS gas may be supplied first (step S5) to adsorb Si.
  • the first nitriding process (step S3) nitrides the surface where Si is exposed. Even when the DCS gas is supplied first (step S5), either the first nitriding process (step S3) or the second nitriding process (step S7) may be omitted.
  • the etching is almost 100%, whereas in the film subjected to the first and second nitridation, the ratio of the etched region
  • the value of pressure (Pa) ⁇ time (sec) is 7800, which is a preferable value of 1800 or more and 48000 or less. Therefore, it was not etched at all in the DHF immersion test.
  • FIG. 8 shows the results of measuring the Si spectrum by X-ray photoelectron spectroscopy (XPS).
  • XPS X-ray photoelectron spectroscopy
  • the thickness of the film was measured by XPS while sputtering the film.
  • the profile of each element in the vertical direction was grasped.
  • FIGS. 10A and 10B As shown in these figures, it was confirmed that there was no significant difference between the compositions in the film thickness direction.
  • the time for etching all the films obtained under the respective conditions that is, the sputtering time until the component of the SiO 2 film as the base film is detected is obtained by setting the second nitriding step to 260.0 Pa, 30 sec. It was confirmed that the film was longer and the structure of the film was strengthened.
  • the TiSiN unit film is formed in the TiSiN film formation sequence by SFD that includes the steps of supplying the Ti-containing gas and the nitriding gas and the step of supplying the Si-containing gas. Since the operation for forming the film includes at least one nitriding step, nitriding of the film is promoted, and a TiSiN film having high chemical resistance can be obtained.
  • 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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  • Chemical Vapour Deposition (AREA)

Abstract

Un film de TiSiN d'une épaisseur prédéterminée est formé en répétant plusieurs fois une opération de formation d'un film unitaire de TiSiN sur un substrat à traiter, ladite opération comprenant : une étape dans laquelle le substrat à traiter est introduit dans une chambre de traitement et un gaz contenant du Ti ainsi qu'un gaz nitrurant sont introduits dans la chambre de traitement tout en maintenant l'intérieur de la chambre de traitement sous pression réduite; et une étape dans laquelle un gaz contenant du Si est introduit dans la chambre de traitement. Dans cette connexion, l'opération de formation d'un film unitaire de TiSiN comprend une étape de nitruration dans laquelle un gaz nitrurant est introduit dans la chambre de traitement, au moins une fois.
PCT/JP2012/050350 2011-01-14 2012-01-11 MÉTHODE DE FORMATION D'UN FILM DE TiSiN ET SUPPORT DE STOCKAGE WO2012096293A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013105389A1 (fr) * 2012-01-13 2013-07-18 東京エレクトロン株式会社 PROCÉDÉ PERMETTANT DE FORMER UN FILM DE TiSiN ET SUPPORT D'ENREGISTREMENT

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003077864A (ja) * 2001-09-03 2003-03-14 Tokyo Electron Ltd 成膜方法
JP2003531291A (ja) * 2000-04-13 2003-10-21 ゲレスト インコーポレイテッド チタニウム−シリコン−窒素フィルムの化学的蒸着方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003531291A (ja) * 2000-04-13 2003-10-21 ゲレスト インコーポレイテッド チタニウム−シリコン−窒素フィルムの化学的蒸着方法
JP2003077864A (ja) * 2001-09-03 2003-03-14 Tokyo Electron Ltd 成膜方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013105389A1 (fr) * 2012-01-13 2013-07-18 東京エレクトロン株式会社 PROCÉDÉ PERMETTANT DE FORMER UN FILM DE TiSiN ET SUPPORT D'ENREGISTREMENT

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