WO2013018292A1 - Procédé de formation de film - Google Patents

Procédé de formation de film Download PDF

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Publication number
WO2013018292A1
WO2013018292A1 PCT/JP2012/004522 JP2012004522W WO2013018292A1 WO 2013018292 A1 WO2013018292 A1 WO 2013018292A1 JP 2012004522 W JP2012004522 W JP 2012004522W WO 2013018292 A1 WO2013018292 A1 WO 2013018292A1
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gas
sih
plasma
gas supply
film
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PCT/JP2012/004522
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Japanese (ja)
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雅人 森嶋
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東京エレクトロン株式会社
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
    • H01L31/182—Special manufacturing methods for polycrystalline Si, e.g. Si ribbon, poly Si ingots, thin films of polycrystalline Si
    • H01L31/1824—Special manufacturing methods for microcrystalline Si, uc-Si
    • 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
    • C23C16/24—Deposition of silicon only
    • 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
    • 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
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/511—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using microwave discharges
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02367—Substrates
    • H01L21/0237—Materials
    • H01L21/02422—Non-crystalline insulating materials, e.g. glass, polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02524—Group 14 semiconducting materials
    • H01L21/02532—Silicon, silicon germanium, germanium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/545—Microcrystalline silicon PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a technique for forming a silicon film by converting silane gas into plasma.
  • Thin-film silicon solar cells have been actively studied in recent years because they consume less silicon than bulk type crystalline silicon solar cells, are relatively easy to increase in area, and are low in manufacturing costs.
  • a tandem thin-film silicon solar cell (hereinafter simply referred to as a solar cell) has an amorphous silicon film laminated on the top surface of a microcrystalline silicon film, and each layer absorbs light in different wavelength regions, thereby converting light energy conversion efficiency. It is a thing that raised.
  • a plasma CVD (Chemical Vapor Deposition) method is used.
  • a plasma source in this case, generally capacitively coupled plasma (CCP) using a high frequency power source (RF power source) is used. Coupled Plasma) is used.
  • various active species derived from SiH 4 or H 2 are generated.
  • the dominant active species for growing the ⁇ c-Si film is SiH 3 .
  • active species other than SiH 3 such as Si, SiH, and SiH 2 are taken into the film while having dangling bonds (dangling bonds), thereby increasing the defect density of the ⁇ c-Si film.
  • VHF Ultra high frequency
  • Patent Document 1 H 2 gas is activated to generate the plasma, and SiH 4 gas is supplied to the substrate side from the plasma generation space while suppressing decomposition of SiH 4 due to contact with the plasma.
  • a technique for improving the film quality by forming a film by increasing the proportion of SiH 3 in the active species by reacting with the active species of H 2 is different from the present invention.
  • the present invention has been made under such a background, and an object of the present invention is to provide a film forming method capable of obtaining a silicon film having high crystallinity and low defect density and having a high film forming speed in the plasma CVD method. It is to provide.
  • the film forming method of the present invention comprises: A method of forming a film with plasma on a substrate placed in a processing container, Supplying a silane-based gas and a helium gas as a dilution gas into the processing vessel; Generating inductively coupled plasma or microwave plasma in the processing vessel and activating a silane-based gas; Forming a silicon film on the substrate with a silane-based gas that has been converted to plasma, and Hydrogen gas is not supplied into the processing container.
  • helium (He) gas is used as a dilution gas without supplying a normally used hydrogen gas, and inductively coupled plasma or microwave plasma is used.
  • the gas is turned into plasma. For this reason, the effect is estimated as described later, and a silicon film having a high crystallinity and a low defect density can be quickly formed as supported by experimental examples.
  • reference numeral 1 denotes a processing container (vacuum chamber) that is configured in a cylindrical shape as a whole, for example, and a substrate S that is a glass substrate for a flat panel display, for example, is placed in the approximate center of the processing container 1.
  • a mounting table 2 for this purpose is provided via an insulating material 21.
  • the mounting table 2 is made of, for example, aluminum nitride (AlN) or Al 2 O 3 , and a cooling jacket 22 through which a cooling medium flows is provided.
  • a heater 23 is provided as a heating unit that constitutes a temperature control mechanism together with the cooling jacket 22.
  • the mounting surface of the mounting table 2 is provided with an electrostatic chuck (not shown) so that the substrate S can be held.
  • a first gas supply unit 3 for supplying helium gas into the processing container 1 is provided on the upper side wall of the processing container 1.
  • the first gas supply unit 3 is provided over the entire circumference in the side wall of the processing container 1 and a plurality of gas supply holes 31 that are bored substantially evenly in the side wall of the processing container 1 over the entire circumference.
  • the buffer chamber 32 is connected to the gas supply hole 31.
  • the buffer chamber 32 is connected by a gas flow path 33 to a first gas supply source 36 for supplying helium gas via a valve 34 and a flow rate adjustment unit (MFC) 35.
  • MFC flow rate adjustment unit
  • a second planar shape is formed in a substantially circular shape, for example, below the upper space and between the mounting table 2 and the height level of the first gas supply unit 3.
  • a gas supply unit 4 is provided.
  • the second gas supply unit 4 is made of a dielectric material.
  • a gas channel network 41 is formed in a lattice shape inside the second gas supply unit 4, and a large number of gas supply holes 42 are formed from the gas channel network 41. 2 is drilled toward the upper surface of the gas supply unit 4 (surface opposite to the mounting table 2).
  • the gas supply passage 43 to the gas flow passage network 41, via a valve 44 and a flow rate adjuster (MFC) 45, silane gas, such as monosilane (SiH 4) of the second gas supply source for supplying a gas 46 is connected.
  • the second gas supply unit 4 is formed with a large number of openings 47 penetrating vertically through the second gas supply unit 4 so as to sew the gaps of the reaction gas channel network 41.
  • the opening 47 is for allowing gas to pass from the upper region to the lower region of the second gas supply unit 4.
  • the ceiling of the processing vessel 1 is open, and a plasma generation mechanism 5 serving as an activating means is provided at this portion via a seal member (not shown) such as an O-ring.
  • the plasma generation mechanism 5 includes a cover plate 51 made of a dielectric provided so as to face the second gas supply unit 4, and above the cover plate 51 (outside the processing container 1).
  • An antenna 52 that is a conductor, for example, a spiral coil, and a high-frequency (for example, RF) power supply 53 are provided.
  • the high frequency power supply 53 is connected between both ends of the antenna 52, and includes a high frequency (for example, RF) power supply 53 that generates a high frequency of 13.56 Hz, for example.
  • the plasma generation mechanism 5 generates a high-frequency magnetic field by flowing a high-frequency current through the antenna 52 from a high-frequency power source 53, and causes high-frequency discharge in the space above the processing container 1 by an induction electric field generated by electromagnetic induction by the high-frequency magnetic field. To generate plasma.
  • An exhaust port 11 is provided at the bottom of the processing container 1, and an exhaust pipe 12 is connected to the exhaust port 11.
  • the exhaust pipe 12 is connected to a vacuum pump 14 via a pressure adjusting unit 13 so that the inside of the processing container 1 can be evacuated to a predetermined pressure.
  • the plasma film forming apparatus in this embodiment is provided with a control unit 6, which starts and stops the high-frequency power supply 53, opens and closes the valves 34 and 44, and adjusts the gas flow rate by the flow rate adjustment units 35 and 45.
  • the pressure adjustment in the processing container 1 by the adjustment and pressure adjustment unit 13 is controlled.
  • the operation of the present embodiment will be described with an example in which a microcrystalline silicon thin film ( ⁇ c-Si film) is formed on the substrate S.
  • the substrate S is carried into the processing container 1 by a transport mechanism (not shown), placed on the mounting table 2 by a cooperative action of a lifting pin (not shown) and the transport mechanism, and held by an electrostatic chuck (not shown) of the mounting table 2. Is done.
  • the temperature of the mounting table 2 is adjusted by the cooling jacket 22 and the heater 23 so that the substrate S is heated to 200 ° C., for example.
  • the processing container 1 is decompressed by the vacuum pump 14 and the pressure is adjusted to, for example, 0.6 Pa to 20 Pa by the pressure adjusting unit 13.
  • helium gas is supplied from the first gas supply unit 3 to the upper space in the processing container 1 at a flow rate of 200 sccm, for example, and monosilane gas is adjusted from the second gas supply unit 4 at a flow rate of 20 sccm, for example.
  • high frequency power 13.56 MHz and 2000 W is applied to the antenna 52 by the high frequency power source 53.
  • the gas supplied into the processing container 1 is turned into plasma and a silicon film is formed on the substrate S. The situation is shown schematically.
  • the helium gas supplied to the upper space of the processing container 1 is turned into plasma by the high-frequency electric field induced in the upper space of the processing container 1 based on the high-frequency power applied to the antenna 52 to generate active helium species. Is done. Since the atmosphere in the processing container 1 is evacuated at the lower part of the processing container 1, the activated helium gas flows downward. On the other hand, the monosilane gas discharged upward from the second gas supply unit 4 is partially activated by the high-frequency electric field, but most is activated (plasmaized) in contact with the activated species of helium gas. It is thought. In this case, it can be said that the monosilane gas is activated by the inductively coupled plasma as a result.
  • the monosilane gas is mixed with plasma helium gas and supplied to the substrate S through the opening 47 of the second gas supply unit 4 while being activated.
  • the estimation mechanism of the activation of the monosilane gas is described in the following a to c.
  • the generated active species of hydrogen react with SiH 4 to produce SiH 3 as an active species as follows, and further, the active species of hydrogen generated during this reaction react with SiH 3. Te SiH 2 is generated, the chain reactions as described below takes place and so on.
  • the concentration of active species SiH 3 is increased, and the concentration of active species (for example, SiH 2 , SiH, Si, etc.) further decomposed from SiH 3 is increased. It is known that it is necessary to suppress this.
  • the active species obtained by further decomposing SiH 3 is taken into the film while having dangling bonds (dangling bonds), thereby increasing the defect density of the microcrystalline silicon film.
  • helium gas is used as a dilution gas without using hydrogen gas.
  • the monosilane gas is converted into plasma mainly by helium gas converted into plasma, so that helium gas can also be referred to as plasma generation gas.
  • hydrogen gas is supplied to the substrate at a flow rate of, for example, several tens of times that of monosilane gas in order to improve crystallinity.
  • Such a method is a film forming method with high production efficiency because it can promote hydrogenation of silicon dangling bonds while maintaining high crystallinity in a plasma CVD process using capacitively coupled plasma, for example.
  • FIG. 5 shows an image in which SiH 3 is deposited on the substrate S, and the active species indicated by oblique lines in the figure are those generated by further decomposition of SiH 3 . Then, after a preset time has elapsed, the application of high-frequency power is stopped, and then the gas supply is stopped.
  • silane-based gas monosilane gas is used as the silane-based gas, but other silane-based gases such as disilane (Si 2 H 6 ) gas and trichlorosilane (SiHCl 3 ) gas may be used.
  • inductively coupled plasma is generated.
  • an antenna in which a cross-shaped opening is formed in a spiral shape on a circular conductor plate may be used.
  • a waveguide is joined to the central portion of the antenna, microwaves are radiated from the waveguide through the antenna, and gas is turned into plasma by the microwaves.
  • the present invention requires that no hydrogen gas is used, and the adverse effect of promoting the decomposition of the monosilane gas by adding the hydrogen gas appears.
  • the influence of hydrogen gas becomes a problem when supplying many times the amount of monosilane gas, and hardly affects when supplying the same amount of hydrogen gas as monosilane gas.
  • the addition of such a small amount of hydrogen gas has no technical meaning in the first place, and this approach is an unreasonable practice that seeks to dive into the limitations of the expression of the claims while carrying out the present invention. Therefore, the term “do not use hydrogen gas” in the claims does not exclude the addition of a small amount of hydrogen gas which has no technical meaning.
  • the process pressure is set to 0.4 Pa to 1.0 Pa so that substantially the same film forming conditions are obtained in each embodiment.
  • the SiH 4 gas supply amount is fixed in the range of 5 sccm to 6 sccm, and a microcrystalline silicon ( ⁇ c-Si) film is formed by ICP-CVD while adding various dilution gases about 10 times the monosilane (SiH 4 ) gas. Was deposited.
  • the microcrystalline silicon film was measured by Raman spectroscopy and the deposition rate.
  • the dilution gas described below is a gas added to the reaction gas during the film forming process.
  • Example 1 High frequency power: 2000W Reaction gas species and reaction gas supply amount: SiH 4 , 5 sccm Dilution gas type and dilution gas supply amount: Helium (He), 49 sccm Process pressure: 0.6Pa (Reference Example 1) High frequency power: 2000W Reaction gas species and reaction gas supply amount: SiH 4 , 5 sccm Dilution gas type and dilution gas supply amount: Ar, 50 sccm Process pressure: 0.9Pa (Comparative Example 1-1) High frequency power: 2000W Reaction gas species and reaction gas supply amount: SiH 4 , 6 sccm Dilution gas type and dilution gas supply: No dilution gas is supplied.
  • Process pressure 1.0 Pa (Comparative Example 1-2) High frequency power: 2000W Reaction gas species and reaction gas supply amount: SiH 4 , 5 sccm Dilution gas type and dilution gas supply amount: H 2 , 50 sccm Process pressure: 0.4 Pa
  • the Raman spectroscopic measurement result in this experiment is shown in FIG. 6, and the calculated value of the intensity ratio Xc and the film formation rate calculated from the Raman spectroscopic measurement result are shown in Table 1.
  • the intensity patterns a, b, c, and d in FIG. 6 correspond to Example 1, Reference Example 1, Comparative Example 1-1, and Comparative Example 1-2, respectively.
  • the intensity Ia at a wave number of 480 cm ⁇ 1 in Raman spectroscopy corresponds to the amount of material of amorphous silicon (a-Si), and the intensity Ic at 520 cm ⁇ 1 corresponds to the amount of material of microcrystalline silicon ( ⁇ c-Si). .
  • Example 1 the wave number at the peak position of the intensity pattern is quite close to 520 cm ⁇ 1 (ideal wave number) corresponding to ⁇ c-Si, but in Reference Example 1, the wave number at the peak position. Is about 515 cm ⁇ 1, which is slightly shifted from the ideal wave number.
  • the wave number at the peak position in Comparative Example 1-1 is further shifted from the ideal wave number, and in Comparative Example 1-2, the wave number at the peak position is below 510 cm ⁇ 1 .
  • Example 1 is slower than Comparative Example 1-1 and Comparative Example 1-2, but as can be seen from the results of the following Experiment 2, film formation is performed by increasing the flow rates of monosilane gas and helium gas. Speed can be improved.
  • the strength ratio Xc is 80% or more, and it can be seen that the crystallinity is good.
  • Example 2 High frequency power: 2000W Reaction gas species and reaction gas supply amount: SiH 4 , 5, 10, 15, 20 sccm Dilution gas type and dilution gas supply amount: He, 10 times the reaction gas supply amount Process pressure: 0.6 Pa to 1.9 Pa (Comparative Example 2) High frequency power: 2000W Reactive gas species and reactive gas supply amount: SiH 4 , 6, 8, 12 sccm Dilution gas type and dilution gas supply: No dilution gas is supplied. Process pressure: 1.0 Pa
  • FIG. 7 shows the experimental results when no He gas is added.
  • SiH 4 gas supply amount was 6 sccm
  • Xc 60% or more
  • the SiH 4 gas supply amount was 8 sccm or more
  • the deposition rate increased in proportion to the SiH 4 gas supply amount.
  • Xc was significantly reduced.
  • H 2 gas was added.
  • He gas is added, as shown in FIG. 8, as the SiH 4 gas supply amount is increased, the deposition rate increases almost in proportion to this, and when Xc is not added with He gas (comparison).
  • the high value of about 80% was maintained without decreasing as in Example 2).
  • the deposition rate of the silicon film is 0.55 nm / sec or more and the peak intensity ratio (crystallinity) Xc is 70% or more, it is a preferable manufacturing method in terms of productivity and crystallinity of the silicon film. Can do.
  • Example 3 As described in the above-described embodiment, the present inventor has activated SiH 4 under a condition in which the radical density is suppressed by the He radical having a high electron temperature. Therefore, the active species SiH 3 is further decomposed. It is considered that film formation can be performed in a state where the above is suppressed. Therefore, in this experiment, the degree of decomposition from SiH 3 to SiH 2 was investigated for each of the case using helium gas (Example 3) and the case using hydrogen gas (Comparative Example 3). Specifically, the concentration of SiH, which is a further active product of decomposition of SiH 2 , and the concentration of Si in the processing atmosphere were identified by emission spectroscopy (OES).
  • OES emission spectroscopy
  • SiH 4 gas flow rate ratio is the ratio of the SiH 4 gas supply amount to the total gas supply amount of the SiH 4 gas and the dilution gas.
  • the SiH 4 gas flow rate ratio of 100% indicates a case where only SiH 4 gas is supplied without adding a dilution gas.
  • the diluent gas is hydrogen gas
  • the emission intensity ratio SiH / Si tends to decrease. That is, as the ratio of the supply amount of hydrogen gas in the mixed gas is increased, the degree to which SiH 3 is decomposed into SiH 2 tends to increase.
  • the dilution gas is helium gas
  • the emission intensity ratio SiH / Si increases as the SiH 4 gas flow rate ratio is increased from 5% (the flow rate ratio of helium gas is decreased from 95%).
  • the emission intensity ratio SiH / Si is presumed to decrease, but hydrogen gas is used by adjusting the supply amount of helium gas. It can be seen that a considerably high value is obtained for the emission intensity ratio SiH / Si as compared to the case.
  • Plasma source ICP, high frequency power 2000W Reaction gas species and reaction gas supply amount: SiH 4 , 5 sccm Dilution gas type and dilution gas supply ratio: He, 10/1 Process pressure: 0.6Pa (Comparative Example 4-1) Plasma source: ICP, high frequency power 2000W Reaction gas species and reaction gas supply amount: SiH 4 , 6 sccm Dilution gas type and dilution gas supply ratio: No dilution gas is supplied.
  • Example 4 Comparative Example 4-1, and Comparative Example 4-2, which are examples of ICP-CVD, are performed in order of increasing peak intensity ratio I (220) / I (111).
  • the results were 4, Comparative Example 4-1, and Comparative Example 4-2. That is, the crystal orientation was good in the order of He dilution, SiH 4 supply, and H 2 dilution.
  • Example 4 when Example 4 is compared with Reference Example 4-1 and Reference Example 4-2, which are CCP-CVD examples, Example 4 does not reach Reference Example 4-1 in terms of crystal orientation. However, it was better than Reference Example 4-2.
  • Plasma source ICP, high frequency power 2000W Reaction gas species and reaction gas supply amount: SiH 4 , 15 sccm Dilution gas type and dilution gas supply ratio: He, 6/1 Process pressure: 1.0 Pa (Comparative Example 5-1) Plasma source: ICP, high frequency power 2000W Reaction gas species and reaction gas supply amount: SiH 4 , 6 sccm Dilution gas type and dilution gas supply ratio: No dilution gas is supplied.
  • Process pressure 1.0 Pa (Comparative Example 5-2)
  • Plasma source ICP, high frequency power 1600W Reaction gas species and reaction gas supply amount: SiH 4 , 2 sccm Dilution gas type and dilution gas supply ratio: H 2 , 7/1
  • Process pressure 1.0 Pa (Reference Example 5)
  • Plasma source CCP, high frequency power 100-700W Reaction gas species and reaction gas supply amount: SiH 4 , 5 to 40 sccm Dilution gas type and dilution gas supply ratio: H 2 , 50/1 to 100/1
  • Process pressure 800-1200Pa
  • Example 5 shows the measurement results in this experiment. As shown in Table 2, the detection value of ESR analysis in Example 5 is smaller than that in Comparative Example 5-1 and Comparative Example 5-2, so that dangling bonds are reduced by adding He gas. It is presumed that defects in the formed silicon film are reduced. As for the degree of crystallinity Xc and the film formation rate, Example 5 was better than Comparative Example 5-1 and Comparative Example 5-2. Example 5 resulted in more dangling bonds compared to Reference Example 5, which is a silicon film formed by CCP-CVD.

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Abstract

L'objet de la présente invention est de fournir un procédé de formation de film présentant une vitesse de formation de film élevée permettant d'obtenir un film en silicium à cristallinité élevée et densité à faible défaut, au moyen d'une technique de dépôt chimique en phase vapeur assistée par plasma. A cet effet, une antenne en forme de bobine (52) est disposée au niveau de la surface supérieure d'un contenant de traitement (1) et un courant alternatif à haute fréquence est appliqué sur l'antenne (52), de sorte qu'un espace de production de plasma soit formé au niveau d'une section supérieure dans le contenant de traitement (1). Une espèce active d'hélium est créée par amenée de gaz hélium d'une première unité d'amenée de gaz à l'espace de production de plasma. Au niveau d'une section plus basse que la première unité d'amenée de gaz, le gaz monosilane est évacué vers le haut à partir d'une seconde unité d'amenée de gaz (4). L'espèce active d'hélium est mélangée au gaz monosilane et le monosilane est transformé en plasma. Le gaz mélangé contenant le monosilane ayant été transformé en plasma est amené à un substrat (S) en vue du traitement de formation de film. Le gaz hydrogène n'est pas utilisé dans le traitement de formation de film.
PCT/JP2012/004522 2011-08-01 2012-07-12 Procédé de formation de film WO2013018292A1 (fr)

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JP2011-168766 2011-08-01
JP2011168766A JP2013033828A (ja) 2011-08-01 2011-08-01 成膜方法

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WO2013018292A1 true WO2013018292A1 (fr) 2013-02-07

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CN107408497A (zh) * 2015-03-13 2017-11-28 新南创新私人有限公司 用于处理硅材料的方法

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Publication number Priority date Publication date Assignee Title
JP6861479B2 (ja) * 2016-06-24 2021-04-21 東京エレクトロン株式会社 プラズマ成膜方法およびプラズマ成膜装置
JP6914149B2 (ja) * 2017-09-07 2021-08-04 東京エレクトロン株式会社 プラズマ処理装置

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JPH02202018A (ja) * 1989-01-31 1990-08-10 Tonen Corp 多結晶シリコン薄膜の製造方法
JPH05275354A (ja) * 1992-03-27 1993-10-22 Tokuyama Soda Co Ltd シリコン薄膜の製造法
JP2007165717A (ja) * 2005-12-15 2007-06-28 Tokyo Electron Ltd 成膜方法及び成膜装置

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JPH02202018A (ja) * 1989-01-31 1990-08-10 Tonen Corp 多結晶シリコン薄膜の製造方法
JPH05275354A (ja) * 1992-03-27 1993-10-22 Tokuyama Soda Co Ltd シリコン薄膜の製造法
JP2007165717A (ja) * 2005-12-15 2007-06-28 Tokyo Electron Ltd 成膜方法及び成膜装置

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107408497A (zh) * 2015-03-13 2017-11-28 新南创新私人有限公司 用于处理硅材料的方法

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