WO2022108332A1 - Gas supplier and substrate deposition apparatus having same - Google Patents

Gas supplier and substrate deposition apparatus having same Download PDF

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Publication number
WO2022108332A1
WO2022108332A1 PCT/KR2021/016894 KR2021016894W WO2022108332A1 WO 2022108332 A1 WO2022108332 A1 WO 2022108332A1 KR 2021016894 W KR2021016894 W KR 2021016894W WO 2022108332 A1 WO2022108332 A1 WO 2022108332A1
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Prior art keywords
gas
layer
corrosion
resistant layer
deposition apparatus
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PCT/KR2021/016894
Other languages
French (fr)
Inventor
Bum Mo Ahn
Seung Ho Park
Tae Hwan Song
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Point Engineering Co., Ltd.
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Application filed by Point Engineering Co., Ltd. filed Critical Point Engineering Co., Ltd.
Publication of WO2022108332A1 publication Critical patent/WO2022108332A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32431—Constructional details of the reactor
    • H01J37/3244—Gas supply means
    • 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
    • C23C16/40—Oxides
    • C23C16/401—Oxides containing silicon
    • 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
    • C23C16/40—Oxides
    • C23C16/403—Oxides of aluminium, magnesium or beryllium
    • 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
    • C23C16/40—Oxides
    • C23C16/405—Oxides of refractory metals or yttrium
    • 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
    • C23C16/4401—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber
    • C23C16/4404—Coatings or surface treatment on the inside of the reaction chamber or on parts thereof
    • 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]
    • C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
    • 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
    • C23C16/45563—Gas nozzles
    • C23C16/45565—Shower nozzles
    • 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
    • C23C16/505—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 radio frequency discharges
    • C23C16/509—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 radio frequency discharges using internal electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32431—Constructional details of the reactor
    • H01J37/32458—Vessel
    • H01J37/32477—Vessel characterised by the means for protecting vessels or internal parts, e.g. coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32431—Constructional details of the reactor
    • H01J37/32532—Electrodes
    • H01J37/32559—Protection means, e.g. coatings
    • 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
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/67005—Apparatus not specifically provided for elsewhere
    • H01L21/67011—Apparatus for manufacture or treatment
    • H01L21/67017—Apparatus for fluid treatment
    • H01L21/67063—Apparatus for fluid treatment for etching
    • H01L21/67069—Apparatus for fluid treatment for etching for drying etching

Definitions

  • the present disclosure relates to a gas supplier and a substrate deposition apparatus having the same.
  • a substrate deposition apparatus refers to an apparatus that performs process etching or deposition on a substrate using physical or chemical reactions such as plasma development method in a vacuum state.
  • a reaction gas is generally injected through a gas supplier installed in a chamber, and the injected reaction gas forms plasma in the chamber upon application of electric power.
  • Etching or film deposition is performed on the surface of the substrate by a plasma state material such as radicals formed in the chamber, depending on the purpose of the use of the plasma.
  • a gas supplier formed in a shower head shape for supplying gas toward a substrate such as a wafer or glass has been used.
  • a susceptor for supporting the substrate in a processing chamber is installed, and a gas supplier is installed to face the susceptor.
  • the opposed surface of the gas supplier is provided with a plurality of through-holes through which gas passes so that the gas is supplied through these through-holes toward the substrate like water sprayed from a shower head.
  • the substrate deposition apparatus In order for the substrate deposition apparatus to perform high-quality deposition or etching, various conditions such as uniform gas supply, uniform temperature distribution, and a constant distance between the substrate and the plasma electrode are required.
  • the gas supplier is made of aluminum or an aluminum alloy material so that the gas supplier can function as an upper electrode for plasma processing.
  • a metallic body expands due to heat under high-temperature substrate processing conditions.
  • the lower surface of the gas supplier expands more than the upper surface thereof so that the gas supplier may be deformed into a downward convex shape. Since this deformation makes the distance between the substrate and the gas supplier non-uniform, the plasma density becomes non-uniform, resulting in a non-uniform film thickness on the substrate.
  • the above-mentioned problem has not been a big issue but nowadays it is becoming a significant issue as the substrate has become larger and the semiconductor pattern has become finer.
  • Korean Patent No. 10-0492135 discloses the configuration having two outer circumferential grooves around in the periphery of a substrate in order to prevent a gas supply device from being deformed by thermal expansion. These outer circumferential grooves act as mechanical bellows for accommodating horizontal deformation attributable to thermal expansion.
  • the technical means of the related art allows horizontal deformation, the gas hole of the gas supplier is displaced in the horizontal direction. Therefore, the technical means of the related art causes the problem of inhibiting film uniformity in a fine pattern process, depending on the pitch between gas holes of a gas supplier and a process temperature range.
  • Patent Document 1 Korean Patent No. 10-0492135
  • the objective of the present disclosure is to provide a gas supplier and a substrate deposition apparatus, the gas supplier being made of a material different from that of conventional counterparts so as to be minimally deformed in a high-temperature environment, thereby improving the quality of a fine pattern.
  • a gas supplier includes: a quartz body part having a through-hole; and an electrode formed on at least one of an upper surface and a lower surface of the body part.
  • a gas supplier includes a corrosion-resistant layer surrounding the body part and the electrode.
  • the corrosion-resistant layer is also formed on the inner wall of the through-hole.
  • the corrosion-resistant layer includes at least any one of an aluminum oxide layer, an yttrium oxide layer, a hafnium oxide layer, a silicon oxide layer, an erbium oxide layer, a zirconium oxide layer, a fluoride layer, a transition metal layer, a titanium nitride layer, a tantalum nitride layer, and a zirconium nitride layer.
  • the corrosion-resistant layer is formed by alternately supplying a precursor gas, which is at least one of aluminum, silicon, hafnium, zirconium, yttrium, erbium, titanium, and tantalum, and a reactant gas capable of forming the corrosion-resistant layer.
  • a precursor gas which is at least one of aluminum, silicon, hafnium, zirconium, yttrium, erbium, titanium, and tantalum
  • a reactant gas capable of forming the corrosion-resistant layer.
  • a substrate deposition apparatus includes a susceptor for supporting a substrate, and a gas supplier which is disposed to be spaced apart from the susceptor and which includes a body part made of quartz and provided with through-holes through which gas passes.
  • the gas supplier includes an electrode formed on at least one of the upper surfaces and a lower surface of the body part.
  • the gas supplier includes an internal corrosion-resistant layer formed on the inner wall of the through-hole and an external corrosion-resistant layer formed on the exposed surface of the body and the electrode.
  • the inner corrosion-resistant layer and the outer corrosion-resistant layer are integrally formed and are obtained by alternately supplying a precursor gas, which is at least one of aluminum, silicon, hafnium, zirconium, yttrium, erbium, titanium, and tantalum, and a reactant gas capable of forming the corrosion-resistant layer.
  • a precursor gas which is at least one of aluminum, silicon, hafnium, zirconium, yttrium, erbium, titanium, and tantalum
  • a reactant gas capable of forming the corrosion-resistant layer.
  • the present disclosure may provide a gas supplier and a substrate deposition apparatus capable of improving the quality of a fine pattern by minimizing the bending deformation of the gas supplier in a high-temperature environment by changing the material of the conventional gas supplier.
  • FIG. 1 is a view showing a substrate deposition apparatus according to a preferred embodiment of the present disclosure
  • FIG. 2 is a view showing a gas supplier according to a preferred embodiment of the present disclosure
  • FIG. 3 is a view showing a gas supplier according to a preferred embodiment of the present disclosure
  • FIGS. 4 are a view showing a process of forming a corrosion-resistant layer according to a preferred embodiment of the present disclosure.
  • FIG. 5 is a view showing a gas supplier including a functional layer and a corrosion-resistant layer according to a preferred embodiment of the present disclosure.
  • FIG. 1 is a view showing a substrate deposition apparatus according to a preferred embodiment of the present disclosure
  • FIGS. 2 and 3 are views showing a gas supplier according to a preferred embodiment of the present disclosure.
  • FIG. 1 is a view showing a substrate deposition apparatus 2, including a gas supplier 1, according to a preferred embodiment of the present disclosure.
  • a substrate deposition apparatus 2 treats the substrate 3 with a chemical process, which performs one of a series of steps for manufacturing a semiconductor or other electronic device on the substrate.
  • a substrate deposition apparatus 2 includes a deposition apparatus for depositing a thin film on the substrate 3 and an etching apparatus for etching the thin film.
  • the substrate deposition apparatus 2 includes a susceptor 6 and a gas supplier 1.
  • the susceptor 6 is a member for supporting the substrate 3, and the substrate 3 is supported in substrate deposition apparatus 2 by the susceptor 6.
  • Typical examples of the substrate 3 processed in the substrate deposition apparatus 2 include rectangular glass substrates used for flat panel displays or circular semiconductor wafers on which circuits are integrated.
  • the susceptor 6 functions as a bottom electrode and is connected to the bottom of high-frequency power supply P2.
  • the susceptor 6 is provided with a heater therein.
  • the sidewall and the bottom wall of the substrate deposition apparatus 2 are provided as a single wall 15.
  • a hinge-type lid 16 and a gas inlet manifold 18 are provided at an upper part of the substrate deposition apparatus 2.
  • the interior of the substrate deposition apparatus 2 may be accessed by lifting the lid 16.
  • O-ring 19 (some not shown) provides a vacuum seal between the sidewall 15, the lid 16, and the gas inlet manifold 18.
  • the sidewall and bottom wall 15, the lid 16, and the gas inlet manifold 18 are all considered parts of the substrate deposition apparatus 2 wall.
  • one or more gases are supplied into the substrate deposition apparatus 2 through a gas inlet manifold 18.
  • Gas flows into the gas supplier 1 through the gas inlet hole 28 of the gas inlet manifold 18, and the gas flows into the interior of the substrate deposition apparatus 2 through the gas supplier 1.
  • the external gas source supplies the process gas to one or more gas inlet holes 28 in the gas inlet manifold 18, through which the process gas flows into the inner region 26 of the gas inlet manifold 18.
  • the process gas flows from the inner region 26 of the gas inlet manifold 18 to the interior of the substrate deposition apparatus 2 through a plurality (e.g., hundreds or thousands) of through-holes 13 in the gas supplier 1.
  • the gas inlet manifold 18 includes a gas inlet deflector consisting of a circular disk 34 having a diameter slightly larger than the gas inlet orifice 28.
  • the cover 39 may be provided on the upper part of the lid 16.
  • the cover 39 prevents foreign substances from coming into contact with the gas inlet manifold 18 or the gas supplier 1.
  • the sidewall sealing of the gas inlet manifold 18 is achieved by a dielectric liner 24 covering the inner wall of the chamber lid 16.
  • a dielectric liner 35 may be provided between the cover 39 and the gas inlet manifold 18.
  • the dielectric liner 35 may be provided along the periphery of the upper surface of the gas inlet manifold 18. One side of the dielectric liner 35 is in contact with the gas inlet manifold 18, other side is in contact with the cover 29.
  • the components of the substrate deposition apparatus 2 should be made of a material that does not contaminate the semiconductor manufacturing process performed in the chamber and is resistant to corrosion by the process gas.
  • at least some parts other than the gas supplier 1 may be made of aluminum or an aluminum alloy, and in this case, a protective layer for preventing corrosion may be provided on the surface.
  • the gas supplier 1 is spaced apart from the susceptor 6 and mounted on the upper part of the susceptor 6.
  • the body part 10 of the gas supplier 1 is configured to include a through-hole 40 through which the gas passes.
  • the through-hole 40 may be formed through etching or laser processing.
  • the body part 10 of the gas supplier 1 is made of quartz material.
  • the body part 10 of the gas supplier 1 may be formed in a polygonal shape such as a circle or a square.
  • the body part 10, for example, may be formed in the form of a circular plate, the outer surface of the body part 10 may be formed in a stepped shape.
  • the body part 10 is formed to have a diameter of the upper surface larger than the diameter of the lower surface so that the outer surface of the body part 10 has a stepped shape.
  • An electrode 20 is provided on at least one of the upper and lower surfaces of the body 10.
  • Process gas is supplied to the gas supplier 1, and the process gas is supplied to the substrate 3 through the through-hole 40.
  • the substrate deposition apparatus 2 includes an exhaust pipe (not shown).
  • the exhaust pipe (not shown) exhausts the internal gas of the substrate deposition apparatus 2 so that the internal pressure is maintained at a predetermined pressure.
  • a high frequency in a first range e.g., 13 MHz to 60 MHz
  • the plasma is generated to the lower part of the gas supplier 1, and the process gas is activated.
  • the second range of high-frequency (e.g., 0.3Mhz to 13MHz) is applied to the susceptor 6 from the lower high frequency power supply P2, and a bias potential is generated. Ions constituting the plasma reach the substrate 3 to process (deposited or etched) the surface of the substrate 3.
  • the temperature of the gas supplier 1 is increased to a high temperature due to collision heating by plasma and radiative heating by the susceptor 6.
  • the material of the body part 10 is made of a metal material such as aluminum or aluminum alloy so that thermal stress is introduced into the gas supply member 1 due to the temperature gradient generated from the upper and lower sides of the gas supply member 1, and thus the central part of the gas supply member 1 is bent and deformed in a convex shape.
  • the body part 10 is made of quartz material, thermal deformation may be minimized even when thermal stress is introduced into the gas supplier 1, thereby mitigating the conventional bending phenomenon.
  • the gas supplier 1 includes a corrosion-resistant layer 30 formed on the surface of the gas supplier.
  • the corrosion-resistant layer 30 is configured to surround the body part 10 and the electrode 20 and is also formed on the inner wall of the through-hole 40.
  • the corrosion-resistant layer 30 includes an inner corrosion-resistant layer 30A formed on the inner wall of the through-hole 40, and an outer corrosion-resistant layer 30B formed on the exposed surfaces of the body part 10 and the electrode 20. Since the inner wall of the through-hole 40 is exposed to plasma or reactive gas, it is preferable that the internal corrosion-resistant layer 30A is provided.
  • the inner corrosion-resistant layer 30A and the outer corrosion-resistant layer 30B are integrally formed in one manufacturing process.
  • the corrosion-resistant layer 30 may have corrosion resistance to a process gas, including a reaction gas, an etching gas, or a cleaning gas used during a deposition process.
  • the corrosion-resistant layer 30 entirely covers the body part 10 and the electrode 20 of the gas supplier 1 so that the surfaces of the body part 10 and the electrode 20 are not exposed.
  • the corrosion-resistant layer 30 may be formed by alternately supplying the precursor gas (PG) and the reactant gas. In this case, the corrosion-resistant layer 30 may be formed in a different configuration depending on the configuration of the precursor gas (PG) and the reactant gas (RG).
  • the corrosion-resistant layer 30 may be formed by alternately supplying a precursor gas (PG), which is at least one of aluminum, silicon, hafnium, zirconium, yttrium, erbium, titanium, and tantalum, and a reactant gas (RG) capable of forming the corrosion-resistant layer 30.
  • PG precursor gas
  • RG reactant gas
  • the corrosion-resistant layer 30 formed by alternately supplying the precursor gas (PG) and the reactant gas (RG) may include at least one of an aluminum oxide layer, an yttrium oxide layer, a hafnium oxide layer, a silicon oxide layer, an erbium oxide layer, a zirconium oxide layer, a fluoride layer, a transition metal layer, a titanium nitride layer, and a zirconium nitride layer depending on the configuration of the precursor gas (PG) and the reactant gas (RG).
  • the precursor gas (PG) may include at least one of aluminum alkoxide (Al(T-OC 4 H 9 ) 3 ), aluminum chloride (AlCl 3 ), trimethylaluminum (TMA: Al(CH 3 ) 3 ), diethylaluminum ethoxide, tris(ethylmethylamido)aluminum, aluminum sec-butoxide, aluminum tribromide, aluminum trichloride, triethylaluminum, triisobutylaluminum, trimethylaluminum, and tris(diethylamide)aluminum.
  • Al(T-OC 4 H 9 ) 3 aluminum chloride
  • TMA trimethylaluminum
  • TMA Al(CH 3 ) 3
  • diethylaluminum ethoxide tris(ethylmethylamido)aluminum
  • aluminum sec-butoxide aluminum tribromide
  • aluminum trichloride triethylaluminum, triisobut
  • Al(T-OC 4 H 9 ) 3 aluminum alkoxide (Al(T-OC 4 H 9 ) 3 ), diethylaluminum ethoxide, tris(ethylmethylamido)aluminum, aluminum sec-butoxide, aluminum tribromide, aluminum trichloride, triethylaluminum, triisobutylaluminum, trimethylaluminum, and tris(diethylamido)aluminum is used as the precursor gas (PG), H 2 O may be used as the reactant gas (RG).
  • Al(T-OC 4 H 9 ) 3 aluminum alkoxide (Al(T-OC 4 H 9 ) 3 )
  • AlCl 3 aluminum chloride
  • RG reactant gas
  • TMA trimethyl aluminum
  • PG precursor gas
  • RG reactant gas
  • the precursor gas (PG) may include at least one of yttrium chloride (YCl 3 ), Y(C 5 H 5 ) 3 , tris(N,N-bis(trimethylsilyl)amide)yttrium(III), Yttrium(III)butoxide, tris(cyclopentadienyl)yttrium(III), tris(butylcyclopentadienyl)yttrium(III),tris(2,2,6,6-tetramethyl-3,5-heptane)dionato)yttrium(III), tris(cyclopentadienyl)yttrium (Cp 3 Y), tris(methylcyclopentadienyl)yttrium((CpMe) 3 Y), tris(butylcyclopentadienyl)yttrium, and tris(ethylcyclopentadienyl)y
  • O 3 may be used as the reactant gas (RG).
  • the precursor gas (PG) may include at least one of hafnium chloride (HfCl 4 ), Hf(N(CH 3 )(C 2 H 5 )) 4 , Hf(N(C 2 H 5 ) 2 ) 4 , tetra(ethylmethylamido)hafnium, and pentakis(dimethylamido)tantalum.
  • hafnium chloride HfCl 4
  • Hf(N(CH 3 )(C 2 H 5 )) 4 Hf(N(C 2 H 5 ) 2 ) 4
  • tetra(ethylmethylamido)hafnium tetra(ethylmethylamido)hafnium
  • pentakis(dimethylamido)tantalum pentakis(dimethylamido)tantalum.
  • HfCl 4 hafnium chloride
  • Hf(N(CH 3 )(C 2 H 5 )) 4 and Hf(N(C 2 H 5 ) 2 ) 4 is used as the precursor gas (PG)
  • O 3 may be used as the reactant gas (RG).
  • At least one of tetra(ethylmethylamido)hafnium and pentakis(dimethylamido)tantalum is used as the precursor gas (PG)
  • at least one of H 2 O, O 2 , and O 3 may be used as the reactant gas (RG).
  • the precursor gas (PG) may include Si(OC 2 H 5 ) 4 .
  • O 3 may be used as the reactant gas (RG).
  • the precursor gas (PG) may include at least one of tris-methylcyclopentadienyl erbium(III)(Er(MeCp) 3 ), erbium boranamide (Er(BA) 3 ), Er(TMHD) 3 , erbium(III)tris(2,2,6,6-tetramethyl-3,5-heptanedionate), tris(butylcyclopentadienyl)erbium(III), tris(2,2,6,6-tetramethyl-3,5-heptandionato)erbium (Er(thd) 3 ), Er(PrCp) 3 , Er(CpMe) 2 , Er(BuCp) 3 , and Er(thd) 3 .
  • an O-radical may be used as the reactant gas (RG).
  • the precursor gas (PG) may include at least one of zirconium tetrachloride (ZrCl 4 ), Zr(T-OC 4 H 9 ) 4 , zirconium (IV) bromide, tetrakis(diethylamido)zirconium (IV), tetrakis(dimethylamido)zirconium(IV), tetrakis(ethylmethylamido)zirconium(IV), tetrakis(N,N'-dimethyl-formamidinate)zirconium, tetra(ethylmethylamido)hafnium, pentakis(dimethylamido)tantalum, tris(dimethylamino)(cyclopentadienyl)zirconium, and tris(2,2,6,6-tetramethyl-heptane-3,5-dionate)erbium.
  • zirconium tetrachloride ZrCl
  • At least one of these configurations is used as the precursor gas (PG)
  • at least one of H 2 O, O 2 , O 3 , and an O-radical may be used as the reactant gas (RG).
  • the precursor gas (PG) may include tris(2,2,6,6-tetramethyl-3,5-heptanedionato)yttrium(III).
  • the reactant gas (RG) may be used as the reactant gas (RG).
  • the precursor gas (PG) may include at least one of tantalum chloride (TaCl 5 ) and titanium tetrachloride (TiCl 4 ).
  • an H-radical may be used as the reactant gas (RG).
  • the transition metal layer may be composed of a tantalum layer.
  • the transition metal layer may be composed of a titanium layer.
  • the precursor gas (PG) may include one of bis(diethylamido)bis(dimethylamido)titanium(IV), tetrakis(diethylamido)titanium(IV), tetrakis(dimethylamido)titanium(IV), tetrakis(ethylmethylamido)titanium(IV), titanium(IV) bromide, titanium(IV) chloride, and titanium(IV) tert-butoxide.
  • at least one of H 2 O, O 2 , O 3 , and an O-radical may be used as the reactant gas (RG).
  • the precursor gas (PG) may include pentakis(dimethylamido) tantalum (V), tantalum(V) chloride, tantalum(V) ethoxide, and tris (diethylamino)(tert-butylimido) tantalum(V).
  • the reactant gas (RG) may be used as the reactant gas (RG).
  • the precursor gas (PG) may include zirconium(IV) bromide, zirconium(IV) chloride, zirconium(IV) tert-butoxide, tetrakis(diethylamido)zirconium(IV), tetrakis(dimethylamido)zirconium(IV), and tetrakis(ethylmethylamido)zirconium(IV).
  • the precursor gas (RG) may include zirconium(IV) bromide, zirconium(IV) chloride, zirconium(IV) tert-butoxide, tetrakis(diethylamido)zirconium(IV), tetrakis(dimethylamido)zirconium(IV), and tetrakis(ethylmethylamido)zirconium(IV).
  • at least one of H 2 O, O 2 , O 3 , and an O-radical may be used as the reactant gas
  • the corrosion-resistant layer 30 may be formed in a type of configuration according to the configuration of the precursor gas (PG) and the reactant gas (RG) used.
  • the corrosion-resistant layer 30 is provided with the electrode 20 on the surface of the body part 10 made of quartz material.
  • the corrosion-resistant layer 30 may be formed by repeatedly performing a cycle (hereinafter, referred to as "monoatomic layer generation cycle") of adsorbing the precursor gas (PG) and supplying the reactant gas (RG) to generate the monoatomic layer M through chemical substitution of the precursor gas (PG) and the reactant gas (RG).
  • the corrosion-resistant layer 30 may have a predetermined thickness while the monoatomic layer M is stacked in multiple layers according to the number of times the monoatomic layer generation cycle is performed.
  • the monoatomic layer generation cycle includes: a precursor gas adsorption step (FIG. 4A) of adsorbing a precursor gas to the surface of the gas supplier 1 having the electrode 20 on the surface of the body 10; the step of exhausting the excess precursor gas by supplying and exhausting the inert gas (FIG. 4B); the reactant gas adsorption step (FIG. 4C); and the step of exhausting the excess reactant gas by supplying and exhausting the inert gas (FIG. 4D).
  • a precursor gas adsorption step FIG. 4A of adsorbing a precursor gas to the surface of the gas supplier 1 having the electrode 20 on the surface of the body 10
  • the step of exhausting the excess precursor gas by supplying and exhausting the inert gas FIG. 4B
  • the reactant gas adsorption step FIG. 4C
  • the step of exhausting the excess reactant gas by supplying and exhausting the inert gas FIG. 4D
  • a process of forming a precursor adsorption layer may be performed by supplying and adsorbing the precursor gas (PG) to the surface of the gas supply member 1 in which the electrode 20 is provided on the surface of the body part 10.
  • the precursor adsorption layer is formed with only one layer by a self-limiting reaction (FIG. 4A).
  • a process of removing an absorbed excess precursor that has not been adsorbed by supplying and exhausting an inert gas is performed.
  • the inert gas may remove excess precursor remaining in the precursor adsorption layer in which only one layer is formed by the self-limiting reaction (FIG. 4B).
  • a reactant gas adsorption step may be performed.
  • a process of supplying a reactant gas (RG) to the surface of the precursor adsorption layer to adsorb the reactant gas (RG) to the surface of the precursor adsorption layer may be performed.
  • a process of removing excess reactant gas (RG) that is not adsorbed by supplying and exhausting an inert gas is performed (FIG. 4D).
  • the monoatomic layer generation cycle is repeatedly performed to generate a plurality of monoatomic layers M.
  • the corrosion-resistant layer 30 of a predetermined thickness severeal nm to several hundred nm
  • the corrosion resistance layer (30) may be formed by laminating one material of an aluminum oxide layer, an yttrium oxide layer, a hafnium oxide layer, a silicon oxide layer, an erbium oxide layer, a zirconium oxide layer, a fluoride layer, a transition metal layer, a titanium nitride layer, a tantalum nitride layer, and a zirconium nitride layer by a plurality of monoatomic layer generation cycles.
  • the corrosion-resistant layer 30 may be formed of a plurality of layers depending on the configuration of the precursor gas (PG) and the reactant gas (RG).
  • the corrosion-resistant layer 30 may be formed of a plurality of layers while including at least two of an aluminum oxide layer, an yttrium oxide layer, a hafnium oxide layer, a silicon oxide layer, an erbium oxide layer, a zirconium oxide layer, a fluoride layer, a transition metal layer, a titanium nitride layer, a tantalum nitride layer, and a zirconium nitride layer.
  • a chemical vapor deposition (CVD) may be considered as a method of forming the corrosion-resistant layer 30.
  • the CVD method requires heating to a high temperature of 400°C to 500°C or higher so that the electrode 20 may be dissolved, limiting the usable electrode materials.
  • the corrosion-resistant layer 30 is formed using a monoatomic layer generation cycle, the corrosion-resistant layer 30 is formed at a temperature of about room temperature to 200°C, thus is formed at a lowest temperature than the CVD method. For this reason, not only does the electrode 20 prevent dissolution, but also the electrode 20 of material usable in a low-temperature process may be used.
  • the electrode 20 includes aluminum or an aluminum alloy material.
  • the electrode 20 of the gas supplier 1 is formed on the surface of the body part 10 through a deposition process.
  • the body part 10 of the gas supplier 1 is made of quartz material
  • the electrode 20 of the gas supplier 1 is made of a metal material and is composed of a different material.
  • minute gaps may exist at the interface of both parts in a high-temperature atmosphere in the semiconductor manufacturing process, and foreign substances may adhere to the minute gaps and act as a semiconductor contamination source, causing semiconductor defects.
  • the corrosion-resistant layer 30 fills the minute gaps while enclosing the body 10 and the electrode 20 as a whole by the monoatomic layer generation cycle, the above-described problems may be prevented.
  • the functional layer 50 may be deposited by a monoatomic layer generation cycle.
  • the functional layer 50 is configured to surround the body part 10 and the electrode 20 and is also formed on the inner wall of the through-hole 40.
  • the functional layer 50 includes an internal functional layer formed on the inner wall of the through-hole 40 and an external functional layer formed on the exposed surfaces of the body part 10 and the electrode 20.
  • the inner and the outer functional layers are corrosion-resistant layers integrally formed by a monoatomic layer generation cycle, and entirely cover the body part 10 and the electrode 20 of the gas supplier 1 so that the surfaces of the body part 10 and the electrode 20 are not exposed.
  • the functional layer 50 includes aluminum oxide (e.g., Al 2 O 3 ), silicon oxide (e.g., SiO 2 ), aluminum nitride, or combinations thereof.
  • the functional layer 50 may be provided under the corrosion-resistant layer 30 when the substrate deposition apparatus 2 is used in a semiconductor manufacturing process to mitigate cracks in the corrosion-resistant layer 30. Accordingly, the functional layer 50 may prevent cracking and peeling of the corrosion-resistant layer 30 and improve the adhesion of the corrosion-resistant layer 30.
  • the functional layer 50 is non-porous and may have a thickness of 100 nm or more and 10 ⁇ m or less, or 200 nm or more and 1 ⁇ m.
  • Substrate 10 Body part
  • Electrode 30 Corrosion-resistant layer

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Abstract

Proposed are a gas supplier and a substrate deposition apparatus. The gas supplier is made of a material different from that of conventional gas suppliers so as to exhibit minimized bending deformation in a high-temperature environment, thereby enabling improvement in the quality of a fine pattern.

Description

GAS SUPPLIER AND SUBSTRATE DEPOSITION APPARATUS HAVING SAME
The present disclosure relates to a gas supplier and a substrate deposition apparatus having the same.
In the manufacturing process of semiconductor devices or liquid crystal devices, processes such as deposition and etching are performed on substrates such as semiconductor wafers or glass, and a substrate deposition apparatus is used for the processes. A substrate deposition apparatus refers to an apparatus that performs process etching or deposition on a substrate using physical or chemical reactions such as plasma development method in a vacuum state. In a substrate deposition apparatus, a reaction gas is generally injected through a gas supplier installed in a chamber, and the injected reaction gas forms plasma in the chamber upon application of electric power. Etching or film deposition is performed on the surface of the substrate by a plasma state material such as radicals formed in the chamber, depending on the purpose of the use of the plasma.
Conventionally, in a substrate deposition apparatus, a gas supplier formed in a shower head shape for supplying gas toward a substrate such as a wafer or glass has been used. For example, in a plasma deposition apparatus that performs a plasma etching process on a substrate, such as a semiconductor wafer, a susceptor for supporting the substrate in a processing chamber is installed, and a gas supplier is installed to face the susceptor. The opposed surface of the gas supplier is provided with a plurality of through-holes through which gas passes so that the gas is supplied through these through-holes toward the substrate like water sprayed from a shower head.
In order for the substrate deposition apparatus to perform high-quality deposition or etching, various conditions such as uniform gas supply, uniform temperature distribution, and a constant distance between the substrate and the plasma electrode are required.
The gas supplier is made of aluminum or an aluminum alloy material so that the gas supplier can function as an upper electrode for plasma processing. However, such a metallic body expands due to heat under high-temperature substrate processing conditions. Thus, there is a temperature difference between the upper side and the lower side of the gas supplier, and as a result, the lower surface of the gas supplier expands more than the upper surface thereof so that the gas supplier may be deformed into a downward convex shape. Since this deformation makes the distance between the substrate and the gas supplier non-uniform, the plasma density becomes non-uniform, resulting in a non-uniform film thickness on the substrate. The above-mentioned problem has not been a big issue but nowadays it is becoming a significant issue as the substrate has become larger and the semiconductor pattern has become finer.
As an invention for solving this problem, Korean Patent No. 10-0492135 (hereinafter referred to as "related art") discloses the configuration having two outer circumferential grooves around in the periphery of a substrate in order to prevent a gas supply device from being deformed by thermal expansion. These outer circumferential grooves act as mechanical bellows for accommodating horizontal deformation attributable to thermal expansion. However, since the technical means of the related art allows horizontal deformation, the gas hole of the gas supplier is displaced in the horizontal direction. Therefore, the technical means of the related art causes the problem of inhibiting film uniformity in a fine pattern process, depending on the pitch between gas holes of a gas supplier and a process temperature range.
<Documents of Related Art>
(Patent Document 1) Korean Patent No. 10-0492135
Accordingly, the objective of the present disclosure is to provide a gas supplier and a substrate deposition apparatus, the gas supplier being made of a material different from that of conventional counterparts so as to be minimally deformed in a high-temperature environment, thereby improving the quality of a fine pattern.
In order to achieve the objective of the present disclosure, a gas supplier, according to the present disclosure, includes: a quartz body part having a through-hole; and an electrode formed on at least one of an upper surface and a lower surface of the body part.
In addition, a gas supplier includes a corrosion-resistant layer surrounding the body part and the electrode.
In addition, the corrosion-resistant layer is also formed on the inner wall of the through-hole.
In addition, the corrosion-resistant layer includes at least any one of an aluminum oxide layer, an yttrium oxide layer, a hafnium oxide layer, a silicon oxide layer, an erbium oxide layer, a zirconium oxide layer, a fluoride layer, a transition metal layer, a titanium nitride layer, a tantalum nitride layer, and a zirconium nitride layer.
In addition, the corrosion-resistant layer is formed by alternately supplying a precursor gas, which is at least one of aluminum, silicon, hafnium, zirconium, yttrium, erbium, titanium, and tantalum, and a reactant gas capable of forming the corrosion-resistant layer.
On the other hand, in order to achieve the objective of the present disclosure, a substrate deposition apparatus according to the present disclosure includes a susceptor for supporting a substrate, and a gas supplier which is disposed to be spaced apart from the susceptor and which includes a body part made of quartz and provided with through-holes through which gas passes.
In addition, the gas supplier includes an electrode formed on at least one of the upper surfaces and a lower surface of the body part.
In addition, the gas supplier includes an internal corrosion-resistant layer formed on the inner wall of the through-hole and an external corrosion-resistant layer formed on the exposed surface of the body and the electrode.
In addition, the inner corrosion-resistant layer and the outer corrosion-resistant layer are integrally formed and are obtained by alternately supplying a precursor gas, which is at least one of aluminum, silicon, hafnium, zirconium, yttrium, erbium, titanium, and tantalum, and a reactant gas capable of forming the corrosion-resistant layer.
The present disclosure may provide a gas supplier and a substrate deposition apparatus capable of improving the quality of a fine pattern by minimizing the bending deformation of the gas supplier in a high-temperature environment by changing the material of the conventional gas supplier.
FIG. 1 is a view showing a substrate deposition apparatus according to a preferred embodiment of the present disclosure;
FIG. 2 is a view showing a gas supplier according to a preferred embodiment of the present disclosure;
FIG. 3 is a view showing a gas supplier according to a preferred embodiment of the present disclosure;
FIGS. 4 are a view showing a process of forming a corrosion-resistant layer according to a preferred embodiment of the present disclosure; and
FIG. 5 is a view showing a gas supplier including a functional layer and a corrosion-resistant layer according to a preferred embodiment of the present disclosure.
The following is merely illustrative of the principles of the disclosure. Therefore, those skilled in the art can devise various devices that, although not explicitly described or shown herein, embody the principles of the invention and are included in the spirit and scope of the invention. In addition, it should be understood that all conditional terms and examples listed herein are, in principle, expressly intended only for the purpose of ensuring that the concept of the invention is understood and are not limited to such specific listed embodiments and states.
The above-described objectives, features, and advantages will become more apparent through the following detailed description in relation to the accompanying drawings, and accordingly, those of ordinary skill in the art to which the invention pertains will be able to practice the technical idea of the invention easily.
FIG. 1 is a view showing a substrate deposition apparatus according to a preferred embodiment of the present disclosure, and FIGS. 2 and 3 are views showing a gas supplier according to a preferred embodiment of the present disclosure.
FIG. 1 is a view showing a substrate deposition apparatus 2, including a gas supplier 1, according to a preferred embodiment of the present disclosure.
A substrate deposition apparatus 2 treats the substrate 3 with a chemical process, which performs one of a series of steps for manufacturing a semiconductor or other electronic device on the substrate. A substrate deposition apparatus 2 includes a deposition apparatus for depositing a thin film on the substrate 3 and an etching apparatus for etching the thin film.
The substrate deposition apparatus 2 includes a susceptor 6 and a gas supplier 1. The susceptor 6 is a member for supporting the substrate 3, and the substrate 3 is supported in substrate deposition apparatus 2 by the susceptor 6. Typical examples of the substrate 3 processed in the substrate deposition apparatus 2 include rectangular glass substrates used for flat panel displays or circular semiconductor wafers on which circuits are integrated. The susceptor 6 functions as a bottom electrode and is connected to the bottom of high-frequency power supply P2. The susceptor 6 is provided with a heater therein.
The sidewall and the bottom wall of the substrate deposition apparatus 2 are provided as a single wall 15. A hinge-type lid 16 and a gas inlet manifold 18 are provided at an upper part of the substrate deposition apparatus 2. The interior of the substrate deposition apparatus 2 may be accessed by lifting the lid 16. O-ring 19 (some not shown) provides a vacuum seal between the sidewall 15, the lid 16, and the gas inlet manifold 18. The sidewall and bottom wall 15, the lid 16, and the gas inlet manifold 18 are all considered parts of the substrate deposition apparatus 2 wall.
While performing a process for manufacturing a semiconductor or other electronic device on the substrate 3, one or more gases are supplied into the substrate deposition apparatus 2 through a gas inlet manifold 18. Gas flows into the gas supplier 1 through the gas inlet hole 28 of the gas inlet manifold 18, and the gas flows into the interior of the substrate deposition apparatus 2 through the gas supplier 1. The external gas source supplies the process gas to one or more gas inlet holes 28 in the gas inlet manifold 18, through which the process gas flows into the inner region 26 of the gas inlet manifold 18. The process gas flows from the inner region 26 of the gas inlet manifold 18 to the interior of the substrate deposition apparatus 2 through a plurality (e.g., hundreds or thousands) of through-holes 13 in the gas supplier 1.
The gas inlet manifold 18 includes a gas inlet deflector consisting of a circular disk 34 having a diameter slightly larger than the gas inlet orifice 28.
The cover 39 may be provided on the upper part of the lid 16. The cover 39 prevents foreign substances from coming into contact with the gas inlet manifold 18 or the gas supplier 1.
The sidewall sealing of the gas inlet manifold 18 is achieved by a dielectric liner 24 covering the inner wall of the chamber lid 16. A dielectric liner 35 may be provided between the cover 39 and the gas inlet manifold 18. The dielectric liner 35 may be provided along the periphery of the upper surface of the gas inlet manifold 18. One side of the dielectric liner 35 is in contact with the gas inlet manifold 18, other side is in contact with the cover 29.
The components of the substrate deposition apparatus 2 should be made of a material that does not contaminate the semiconductor manufacturing process performed in the chamber and is resistant to corrosion by the process gas. Preferably, at least some parts other than the gas supplier 1 may be made of aluminum or an aluminum alloy, and in this case, a protective layer for preventing corrosion may be provided on the surface.
The gas supplier 1 is spaced apart from the susceptor 6 and mounted on the upper part of the susceptor 6. The body part 10 of the gas supplier 1 is configured to include a through-hole 40 through which the gas passes. The through-hole 40 may be formed through etching or laser processing.
The body part 10 of the gas supplier 1 is made of quartz material. The body part 10 of the gas supplier 1 may be formed in a polygonal shape such as a circle or a square. The body part 10, for example, may be formed in the form of a circular plate, the outer surface of the body part 10 may be formed in a stepped shape. The body part 10 is formed to have a diameter of the upper surface larger than the diameter of the lower surface so that the outer surface of the body part 10 has a stepped shape.
An electrode 20 is provided on at least one of the upper and lower surfaces of the body 10. Process gas is supplied to the gas supplier 1, and the process gas is supplied to the substrate 3 through the through-hole 40. The substrate deposition apparatus 2 includes an exhaust pipe (not shown). The exhaust pipe (not shown) exhausts the internal gas of the substrate deposition apparatus 2 so that the internal pressure is maintained at a predetermined pressure. When the high-frequency power sources P1 and P2 are operated in a state in which the process gas is supplied, a high frequency in a first range (e.g., 13 MHz to 60 MHz) is applied to the electrode 20 from the upper high-frequency power source P1, and the plasma is generated to the lower part of the gas supplier 1, and the process gas is activated. At the same time, the second range of high-frequency (e.g., 0.3Mhz to 13MHz) is applied to the susceptor 6 from the lower high frequency power supply P2, and a bias potential is generated. Ions constituting the plasma reach the substrate 3 to process (deposited or etched) the surface of the substrate 3.
The temperature of the gas supplier 1 is increased to a high temperature due to collision heating by plasma and radiative heating by the susceptor 6. In the conventional gas supplier 1, since the material of the body part 10 is made of a metal material such as aluminum or aluminum alloy so that thermal stress is introduced into the gas supply member 1 due to the temperature gradient generated from the upper and lower sides of the gas supply member 1, and thus the central part of the gas supply member 1 is bent and deformed in a convex shape. On the other hand, in the gas supplier 1, according to the preferred embodiment of the present disclosure, since the body part 10 is made of quartz material, thermal deformation may be minimized even when thermal stress is introduced into the gas supplier 1, thereby mitigating the conventional bending phenomenon.
The gas supplier 1 includes a corrosion-resistant layer 30 formed on the surface of the gas supplier. The corrosion-resistant layer 30 is configured to surround the body part 10 and the electrode 20 and is also formed on the inner wall of the through-hole 40. The corrosion-resistant layer 30 includes an inner corrosion-resistant layer 30A formed on the inner wall of the through-hole 40, and an outer corrosion-resistant layer 30B formed on the exposed surfaces of the body part 10 and the electrode 20. Since the inner wall of the through-hole 40 is exposed to plasma or reactive gas, it is preferable that the internal corrosion-resistant layer 30A is provided.
The inner corrosion-resistant layer 30A and the outer corrosion-resistant layer 30B are integrally formed in one manufacturing process. The corrosion-resistant layer 30 may have corrosion resistance to a process gas, including a reaction gas, an etching gas, or a cleaning gas used during a deposition process. The corrosion-resistant layer 30 entirely covers the body part 10 and the electrode 20 of the gas supplier 1 so that the surfaces of the body part 10 and the electrode 20 are not exposed.
The corrosion-resistant layer 30 may be formed by alternately supplying the precursor gas (PG) and the reactant gas. In this case, the corrosion-resistant layer 30 may be formed in a different configuration depending on the configuration of the precursor gas (PG) and the reactant gas (RG).
As an example, the corrosion-resistant layer 30 may be formed by alternately supplying a precursor gas (PG), which is at least one of aluminum, silicon, hafnium, zirconium, yttrium, erbium, titanium, and tantalum, and a reactant gas (RG) capable of forming the corrosion-resistant layer 30.
The corrosion-resistant layer 30 formed by alternately supplying the precursor gas (PG) and the reactant gas (RG) may include at least one of an aluminum oxide layer, an yttrium oxide layer, a hafnium oxide layer, a silicon oxide layer, an erbium oxide layer, a zirconium oxide layer, a fluoride layer, a transition metal layer, a titanium nitride layer, and a zirconium nitride layer depending on the configuration of the precursor gas (PG) and the reactant gas (RG).
Specifically, when the corrosion-resistant layer 30 is formed of an aluminum oxide layer, the precursor gas (PG) may include at least one of aluminum alkoxide (Al(T-OC4H9)3), aluminum chloride (AlCl3), trimethylaluminum (TMA: Al(CH3)3), diethylaluminum ethoxide, tris(ethylmethylamido)aluminum, aluminum sec-butoxide, aluminum tribromide, aluminum trichloride, triethylaluminum, triisobutylaluminum, trimethylaluminum, and tris(diethylamide)aluminum.
At this time, when at least one of aluminum alkoxide (Al(T-OC4H9)3), diethylaluminum ethoxide, tris(ethylmethylamido)aluminum, aluminum sec-butoxide, aluminum tribromide, aluminum trichloride, triethylaluminum, triisobutylaluminum, trimethylaluminum, and tris(diethylamido)aluminum is used as the precursor gas (PG), H2O may be used as the reactant gas (RG).
When aluminum chloride (AlCl3) is used as the precursor gas (PG), O3 may be used as the reactant gas (RG).
When trimethyl aluminum (TMA: Al(CH3)3) is used as the precursor gas (PG), O3 or H2O may be used as the reactant gas (RG).
When the corrosion-resistant layer 30 is composed of an yttrium oxide layer, the precursor gas (PG) may include at least one of yttrium chloride (YCl3), Y(C5H5)3, tris(N,N-bis(trimethylsilyl)amide)yttrium(III), Yttrium(III)butoxide, tris(cyclopentadienyl)yttrium(III), tris(butylcyclopentadienyl)yttrium(III),tris(2,2,6,6-tetramethyl-3,5-heptane)dionato)yttrium(III), tris(cyclopentadienyl)yttrium (Cp3Y), tris(methylcyclopentadienyl)yttrium((CpMe)3Y), tris(butylcyclopentadienyl)yttrium, and tris(ethylcyclopentadienyl)yttrium.
In this case, when at least one of yttrium chloride (YCl3) and Y(C5H5)3 is used as the precursor gas (PG), O3 may be used as the reactant gas (RG).
When at least one of tris(N,N-bis(trimethylsilyl)amide)yttrium(III), yttrium(III)butoxide, tris(cyclopentadienyl)yttrium(III), tris(butylcyclopentadie nyl) yttrium (III), tris (2,2,6,6-tetramethyl-3,5-heptanedionato) yttrium (III), tris (cyclopentadienyl) yttrium (Cp3Y), tris (methylcyclopentadienyl)yttrium ((CpMe)3Y), tris(butylcyclopentadienyl)yttrium, and tris(ethylcyclopentadienyl)yttrium is used as the precursor gas (PG), at least one of H2O, O2, and O3 may be used as the reactant gas (RG).
When the corrosion-resistant layer 30 is formed of a hafnium oxide layer, the precursor gas (PG) may include at least one of hafnium chloride (HfCl4), Hf(N(CH3)(C2H5))4, Hf(N(C2H5)2)4, tetra(ethylmethylamido)hafnium, and pentakis(dimethylamido)tantalum.
In this case, when at least one of hafnium chloride (HfCl4), Hf(N(CH3)(C2H5))4 and Hf(N(C2H5)2)4 is used as the precursor gas (PG), O3 may be used as the reactant gas (RG).
When at least one of tetra(ethylmethylamido)hafnium and pentakis(dimethylamido)tantalum is used as the precursor gas (PG), at least one of H2O, O2, and O3 may be used as the reactant gas (RG).
When the corrosion-resistant layer 30 is formed of a silicon oxide layer, the precursor gas (PG) may include Si(OC2H5)4. In this case, O3 may be used as the reactant gas (RG).
When the corrosion-resistant layer 30 is formed of an erbium oxide layer, the precursor gas (PG) may include at least one of tris-methylcyclopentadienyl erbium(III)(Er(MeCp)3), erbium boranamide (Er(BA)3), Er(TMHD)3, erbium(III)tris(2,2,6,6-tetramethyl-3,5-heptanedionate), tris(butylcyclopentadienyl)erbium(III), tris(2,2,6,6-tetramethyl-3,5-heptandionato)erbium (Er(thd)3), Er(PrCp)3, Er(CpMe)2, Er(BuCp)3, and Er(thd)3.
In this case, when at least one of tris-methylcyclopentadienyl erbium(III)(Er(MeCp)3), erbium boranamide (Er(BA)3), Er(TMHD)3, erbium(III)tris(2,2,6,6-tetramethyl-3,5-heptanedionate), and tris(butylcyclopentadienyl)erbium(III) is used as the precursor gas (PG), at least one of H2O, O2, and O3 may be used as the reactant gas (RG).
When at least one of tris(2,2,6,6-tetramethyl-3,5-heptanedionato)erbium(Er(thd)3), Er(PrCp)3, Er(CpMe)2, and Er (BuCp)3 is used as the precursor gas (PG), O3 may be used as the reactant gas (RG).
When Er(thd)3 is used as the precursor gas (PG), an O-radical may be used as the reactant gas (RG).
When the corrosion-resistant layer 30 is formed of zirconium oxide, the precursor gas (PG) may include at least one of zirconium tetrachloride (ZrCl4), Zr(T-OC4H9)4, zirconium (IV) bromide, tetrakis(diethylamido)zirconium (IV), tetrakis(dimethylamido)zirconium(IV), tetrakis(ethylmethylamido)zirconium(IV), tetrakis(N,N'-dimethyl-formamidinate)zirconium, tetra(ethylmethylamido)hafnium, pentakis(dimethylamido)tantalum, tris(dimethylamino)(cyclopentadienyl)zirconium, and tris(2,2,6,6-tetramethyl-heptane-3,5-dionate)erbium.
When at least one of these configurations is used as the precursor gas (PG), at least one of H2O, O2, O3, and an O-radical may be used as the reactant gas (RG).
When the corrosion-resistant layer 30 is formed of a fluoride layer, the precursor gas (PG) may include tris(2,2,6,6-tetramethyl-3,5-heptanedionato)yttrium(III). In this case, at least one of H2O, O2, and O3 may be used as the reactant gas (RG).
When the corrosion-resistant layer 30 is formed of a transition metal layer, the precursor gas (PG) may include at least one of tantalum chloride (TaCl5) and titanium tetrachloride (TiCl4). In this case, an H-radical may be used as the reactant gas (RG).
Specifically, when tantalum chloride (TaCl5) is used as the precursor gas (PG), and H-radical is used as the reactant gas (RG), the transition metal layer may be composed of a tantalum layer.
Alternatively, when titanium tetrachloride (TiCl4) is used as the precursor gas (PG), and H-radical is used as the reactant gas (RG), the transition metal layer may be composed of a titanium layer.
When the corrosion-resistant layer 30 is formed of a titanium nitride layer, the precursor gas (PG) may include one of bis(diethylamido)bis(dimethylamido)titanium(IV), tetrakis(diethylamido)titanium(IV), tetrakis(dimethylamido)titanium(IV), tetrakis(ethylmethylamido)titanium(IV), titanium(IV) bromide, titanium(IV) chloride, and titanium(IV) tert-butoxide. In this case, at least one of H2O, O2, O3, and an O-radical may be used as the reactant gas (RG).
When the corrosion-resistant layer 30 is formed of a tantalum nitride layer, the precursor gas (PG) may include pentakis(dimethylamido) tantalum (V), tantalum(V) chloride, tantalum(V) ethoxide, and tris (diethylamino)(tert-butylimido) tantalum(V). In this case, at least one of H2O, O2, O3, and an O-radical may be used as the reactant gas (RG).
When the corrosion-resistant layer 30 is formed of a zirconium nitride layer, the precursor gas (PG) may include zirconium(IV) bromide, zirconium(IV) chloride, zirconium(IV) tert-butoxide, tetrakis(diethylamido)zirconium(IV), tetrakis(dimethylamido)zirconium(IV), and tetrakis(ethylmethylamido)zirconium(IV). In this case, at least one of H2O, O2, O3, and an O-radical may be used as the reactant gas (RG).
As such, the corrosion-resistant layer 30 may be formed in a type of configuration according to the configuration of the precursor gas (PG) and the reactant gas (RG) used.
As shown in FIGS. 4, the corrosion-resistant layer 30 is provided with the electrode 20 on the surface of the body part 10 made of quartz material. The corrosion-resistant layer 30 may be formed by repeatedly performing a cycle (hereinafter, referred to as "monoatomic layer generation cycle") of adsorbing the precursor gas (PG) and supplying the reactant gas (RG) to generate the monoatomic layer M through chemical substitution of the precursor gas (PG) and the reactant gas (RG). The corrosion-resistant layer 30 may have a predetermined thickness while the monoatomic layer M is stacked in multiple layers according to the number of times the monoatomic layer generation cycle is performed.
The monoatomic layer generation cycle includes: a precursor gas adsorption step (FIG. 4A) of adsorbing a precursor gas to the surface of the gas supplier 1 having the electrode 20 on the surface of the body 10; the step of exhausting the excess precursor gas by supplying and exhausting the inert gas (FIG. 4B); the reactant gas adsorption step (FIG. 4C); and the step of exhausting the excess reactant gas by supplying and exhausting the inert gas (FIG. 4D). By repeatedly performing such a monoatomic layer generation cycle, a plurality of monoatomic layers M is generated to form a corrosion-resistant layer 110 with a predetermined thickness (FIG. 4E).
More specifically, in the precursor gas adsorption step, a process of forming a precursor adsorption layer may be performed by supplying and adsorbing the precursor gas (PG) to the surface of the gas supply member 1 in which the electrode 20 is provided on the surface of the body part 10. The precursor adsorption layer is formed with only one layer by a self-limiting reaction (FIG. 4A). Then, a process of removing an absorbed excess precursor that has not been adsorbed by supplying and exhausting an inert gas is performed. The inert gas may remove excess precursor remaining in the precursor adsorption layer in which only one layer is formed by the self-limiting reaction (FIG. 4B). Then, a reactant gas adsorption step may be performed. In the reactant adsorption step, a process of supplying a reactant gas (RG) to the surface of the precursor adsorption layer to adsorb the reactant gas (RG) to the surface of the precursor adsorption layer may be performed. Then, a process of removing excess reactant gas (RG) that is not adsorbed by supplying and exhausting an inert gas is performed (FIG. 4D). The monoatomic layer generation cycle is repeatedly performed to generate a plurality of monoatomic layers M. Through this performing, the corrosion-resistant layer 30 of a predetermined thickness (several nm to several hundred nm) may be formed (FIG. 4E).
The corrosion resistance layer (30) may be formed by laminating one material of an aluminum oxide layer, an yttrium oxide layer, a hafnium oxide layer, a silicon oxide layer, an erbium oxide layer, a zirconium oxide layer, a fluoride layer, a transition metal layer, a titanium nitride layer, a tantalum nitride layer, and a zirconium nitride layer by a plurality of monoatomic layer generation cycles.
Alternatively, the corrosion-resistant layer 30 may be formed of a plurality of layers depending on the configuration of the precursor gas (PG) and the reactant gas (RG). The corrosion-resistant layer 30 may be formed of a plurality of layers while including at least two of an aluminum oxide layer, an yttrium oxide layer, a hafnium oxide layer, a silicon oxide layer, an erbium oxide layer, a zirconium oxide layer, a fluoride layer, a transition metal layer, a titanium nitride layer, a tantalum nitride layer, and a zirconium nitride layer.
A chemical vapor deposition (CVD) may be considered as a method of forming the corrosion-resistant layer 30. However, the CVD method requires heating to a high temperature of 400°C to 500°C or higher so that the electrode 20 may be dissolved, limiting the usable electrode materials. On the other hand, when the corrosion-resistant layer 30 is formed using a monoatomic layer generation cycle, the corrosion-resistant layer 30 is formed at a temperature of about room temperature to 200°C, thus is formed at a lowest temperature than the CVD method. For this reason, not only does the electrode 20 prevent dissolution, but also the electrode 20 of material usable in a low-temperature process may be used. The electrode 20 includes aluminum or an aluminum alloy material.
The electrode 20 of the gas supplier 1 is formed on the surface of the body part 10 through a deposition process. However, the body part 10 of the gas supplier 1 is made of quartz material, and the electrode 20 of the gas supplier 1 is made of a metal material and is composed of a different material. As a result, minute gaps may exist at the interface of both parts in a high-temperature atmosphere in the semiconductor manufacturing process, and foreign substances may adhere to the minute gaps and act as a semiconductor contamination source, causing semiconductor defects. However, according to a preferred embodiment of the present disclosure, since the corrosion-resistant layer 30 fills the minute gaps while enclosing the body 10 and the electrode 20 as a whole by the monoatomic layer generation cycle, the above-described problems may be prevented.
Meanwhile, referring to FIG. 5, before deposition of the corrosion-resistant layer 30, the functional layer 50 may be deposited by a monoatomic layer generation cycle. The functional layer 50 is configured to surround the body part 10 and the electrode 20 and is also formed on the inner wall of the through-hole 40. The functional layer 50 includes an internal functional layer formed on the inner wall of the through-hole 40 and an external functional layer formed on the exposed surfaces of the body part 10 and the electrode 20. The inner and the outer functional layers are corrosion-resistant layers integrally formed by a monoatomic layer generation cycle, and entirely cover the body part 10 and the electrode 20 of the gas supplier 1 so that the surfaces of the body part 10 and the electrode 20 are not exposed.
The functional layer 50 includes aluminum oxide (e.g., Al2O3), silicon oxide (e.g., SiO2), aluminum nitride, or combinations thereof. The functional layer 50 may be provided under the corrosion-resistant layer 30 when the substrate deposition apparatus 2 is used in a semiconductor manufacturing process to mitigate cracks in the corrosion-resistant layer 30. Accordingly, the functional layer 50 may prevent cracking and peeling of the corrosion-resistant layer 30 and improve the adhesion of the corrosion-resistant layer 30. As an embodiment, the functional layer 50 is non-porous and may have a thickness of 100 nm or more and 10 μm or less, or 200 nm or more and 1 μm.
[0079] As described above, although the preferred embodiment of the present invention has been described, those skilled in the art may variously modify or modify the present invention within the scope not departing from the spirit and scope of the present invention described in the following claims.
<Description of the Reference Numerals in the Drawings>
1: Gas supplier 2: Substrate deposition apparatus
3: Substrate 10: Body part
20: Electrode 30: Corrosion-resistant layer
40: Through-hole 50: Functional layer

Claims (9)

  1. A gas supplier comprising:
    a quartz body part with a through-hole; and
    an electrode formed on at least one of upper and lower surfaces of the body part.
  2. The gas supplier of claim 1, further comprising a corrosion-resistant layer surrounding the body part and the electrode.
  3. The gas supplier of claim 2, wherein the corrosion-resistant layer is formed on the inner wall of the through-hole.
  4. The gas supplier of claim 2, wherein the corrosion-resistant layer comprises at least one of an aluminum oxide layer, an yttrium oxide layer, a hafnium oxide layer, a silicon oxide layer, an erbium oxide layer, a zirconium oxide layer, a fluoride layer, a transition metal layer, a titanium nitride layer, a tantalum nitride layer, and a zirconium nitride layer.
  5. The gas supplier of claim 2, wherein the corrosion-resistant layer is formed by alternately supplying a precursor gas, which is at least one of aluminum, silicon, hafnium, zirconium, yttrium, erbium, titanium, and tantalum, and a reactant gas capable of forming the corrosion-resistant layer.
  6. A substrate deposition apparatus comprising:
    a susceptor configured to support the substrate; and
    a gas supplier disposed to be spaced apart from the susceptor and including a quartz body part having a through-hole through which gas passes.
  7. The substrate deposition apparatus of claim 6, wherein the gas supplier comprises an electrode formed on at least one of upper and lower surfaces of the body part.
  8. The substrate deposition apparatus of claim 7, further comprising:
    an internal corrosion-resistant layer formed on the inner wall of the through-hole; and
    an external corrosion-resistant layer formed on the exposed surface of the body and the electrode.
  9. The substrate deposition apparatus of claim 8, wherein the inner corrosion resistance layer and the outer corrosion resistance layer are formed integrally and are obtained by alternately supplying a precursor gas that is at least one selected from aluminum, silicon, hafnium, zirconium, yttrium, erbium, titanium, and tantalum, and a reactant gas capable of forming the corrosion-resistant layer.
PCT/KR2021/016894 2020-11-18 2021-11-17 Gas supplier and substrate deposition apparatus having same WO2022108332A1 (en)

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US20140116338A1 (en) * 2012-10-29 2014-05-01 Advanced Micro-Fabrication Equipment Inc, Shanghai Coating for performance enhancement of semiconductor apparatus
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