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WO2020190449A1 - Method of growing thick oxide films at low temperature of thermal oxide quality - Google Patents

Method of growing thick oxide films at low temperature of thermal oxide quality Download PDF

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Publication number
WO2020190449A1
WO2020190449A1 PCT/US2020/019394 US2020019394W WO2020190449A1 WO 2020190449 A1 WO2020190449 A1 WO 2020190449A1 US 2020019394 W US2020019394 W US 2020019394W WO 2020190449 A1 WO2020190449 A1 WO 2020190449A1
Authority
WO
WIPO (PCT)
Prior art keywords
silicon
silicon oxide
oxide film
containing film
degrees celsius
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2020/019394
Other languages
French (fr)
Inventor
Kurtis Leschkies
Johanes F. Swenberg
Benjamin Colombeau
Steven Verhaverbeke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Applied Materials Inc
Original Assignee
Applied Materials Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Applied Materials Inc filed Critical Applied Materials Inc
Priority to JP2021555610A priority Critical patent/JP7580386B2/en
Priority to KR1020217033596A priority patent/KR102783961B1/en
Priority to CN202080020204.5A priority patent/CN113557589B/en
Priority to EP20773316.3A priority patent/EP3942596A4/en
Publication of WO2020190449A1 publication Critical patent/WO2020190449A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
    • H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
    • H01L21/02321—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment introduction of substances into an already existing insulating layer
    • H01L21/02323—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment introduction of substances into an already existing insulating layer introduction of oxygen
    • H01L21/02326—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment introduction of substances into an already existing insulating layer introduction of oxygen into a nitride layer, e.g. changing SiN to SiON
    • H—ELECTRICITY
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    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/02227—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process
    • H01L21/0223—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate
    • 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
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • C23C16/345—Silicon nitride
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    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/10—Oxidising
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    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
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    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/24—Nitriding
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/34—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases more than one element being applied in more than one step
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    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02164—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon oxide, e.g. SiO2
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    • H01L21/02107—Forming insulating materials on a substrate
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    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/0217—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz
    • H—ELECTRICITY
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    • H01L21/0223—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate
    • H01L21/02233—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate of the semiconductor substrate or a semiconductor layer
    • H01L21/02236—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate of the semiconductor substrate or a semiconductor layer group IV semiconductor
    • H01L21/02238—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate of the semiconductor substrate or a semiconductor layer group IV semiconductor silicon in uncombined form, i.e. pure silicon
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    • H01L21/02337—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to a gas or vapour
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Definitions

  • Embodiments described herein generally relate to methods for forming a low-k dielectric material on a semiconductor substrate. More specifically, embodiments described herein relate to methods of forming a silicon oxide film at high pressure and low temperatures using an oxidative medium comprising an additive.
  • Formation of semiconductor devices involves deposition of low-k dielectric films over semiconductor substrates.
  • the low-k dielectric film is used to make the circuitry for manufacturing the device.
  • Current dry or wet silicon oxidation techniques are often performed at temperatures greater than 800 degrees Celsius. However, materials deposited on the semiconductor substrate may not survive temperatures greater than 800 degrees Celsius. As a result, the low-k dielectric film may not be deposited at a temperature greater than a thermal budget of 800 degrees Celsius, and films deposited within the thermal budget often suffer from poor quality. Additionally, current dry or wet silicon oxidation techniques are unable to deposit quality low-k dielectric films having a thickness greater than 100 angstroms.
  • Embodiments described herein generally relate to methods for forming a low-k dielectric material on a semiconductor substrate. More specifically, embodiments described herein relate to methods of forming a silicon oxide film at high pressure and low temperatures.
  • a method of forming a silicon oxide film comprises loading a substrate having a silicon-containing film formed thereon into a processing region of a high-pressure vessel. The method further comprises forming a silicon oxide film on the silicon-containing film. Forming the silicon oxide film on the silicon-containing film comprises exposing the silicon-containing film to an oxidative medium comprising an amine additive at a pressure greater than about 1 bar and maintaining the high-pressure vessel at a temperature between about 100 degrees Celsius and about 550 degrees Celsius.
  • a method of forming a silicon oxide film comprises loading a substrate having a silicon-containing film deposited thereon into a processing region of a high- pressure vessel and forming a silicon oxide film on the silicon-containing film.
  • Forming the silicon oxide film on the silicon-containing film comprises exposing the silicon-containing film to an oxidative medium comprising an amine additive at a pressure greater than about 1 bar and maintaining the high-pressure vessel at a temperature between about 100 degrees Celsius and about 550 degrees Celsius
  • a method of forming a conformal silicon oxide film comprises depositing a silicon-containing film on a substrate comprising a plurality of vias.
  • the silicon- containing film is deposited on each exposed surface of the substrate and the plurality of vias.
  • the method further comprises the substrate having the silicon- containing film deposited thereon into a processing region of a high-pressure vessel and forming a conformal silicon oxide film on the silicon-containing film.
  • Forming the conformal silicon oxide film on the silicon-containing film comprises exposing the silicon-containing film to an oxidative medium comprising an amine additive, wherein the oxidative medium comprises about 1 ,000 ppm to about 20,000 ppm of the amine additive, and maintaining the high-pressure vessel at a temperature between about 100 degrees Celsius and about 550 degrees Celsius and at a pressure between about 1 bar to about 65 bar.
  • a method of forming a silicon oxide film comprises loading a substrate having a silicon-containing film deposited thereon into a processing region of a high- pressure vessel and forming a silicon oxide film on the silicon-containing film.
  • Forming the silicon oxide film on the silicon-containing film comprises exposing the silicon-containing film to an oxidative medium comprising ammonia, wherein the oxidative medium is selected from a group of steam, oxygen, and peroxide, and maintaining the high-pressure vessel at a temperature between about 400 degrees Celsius and about 505 degrees Celsius and at a pressure greater than about 10 bar.
  • the silicon oxide film has a uniform thickness between about 100 angstroms to about 400 angstroms.
  • Figure 1 depicts a simplified front cross-sectional view of one example of a high-pressure vessel that may be used to practice one or more implementations described herein.
  • Figure 2A illustrates a semiconductor device having a silicon-containing film deposited thereon, according to embodiments disclosed herein.
  • Figures 2B-2D illustrates various views of the semiconductor device having a conformal and uniform silicon oxide film formed thereon, according to embodiments disclosed herein.
  • Figure 3 is a flowchart illustrating a method of forming a conformal silicon oxide film according to one embodiment.
  • Embodiments described herein generally relate to methods for forming a low-k dielectric material on a semiconductor substrate. More specifically, embodiments described herein relate to methods of forming a silicon oxide film at high pressure and low temperatures.
  • a method of forming a silicon oxide film comprises loading a substrate having a silicon-containing film formed thereon into a processing region of a high-pressure vessel. The method further comprises forming a silicon oxide film on the silicon-containing film. Forming the silicon oxide film on the silicon-containing film comprises exposing the silicon-containing film to an oxidative medium comprising an amine additive at a pressure greater than about 1 bar and maintaining the high-pressure vessel at a temperature between about 100 degrees Celsius and about 550 degrees Celsius.
  • FIG. 1 is simplified front cross-sectional view of a high-pressure vessel 100 for the high-pressure annealing process.
  • the high-pressure vessel 100 has a body 1 10 with an outer surface 1 12 and an inner surface 1 13 that encloses a processing region 1 15.
  • the body 1 10 has an annular cross section, though in other implementations, the cross-section of the body 1 10 may be rectangular or any closed shape.
  • the outer surface 1 12 of the body 1 10 may be made from a corrosion resistant steel (CRS), such as but not limited to stainless steel.
  • the inner surface 1 13 of the body 110 is made from nickel-based steel alloys that exhibit high resistance to corrosion, such as but not limited to Hastelloy ® .
  • the high-pressure vessel 100 has a door 120 configured to sealably enclose the processing region 1 15 within the body 1 10 such that the processing region 1 15 can be accessed when the door 120 is open.
  • a high-pressure seal 122 is utilized to seal the door 120 to the body 1 10 in order to seal the processing region 1 15 for processing.
  • the high-pressure seal 122 may be made from a polymer, such as but not limited to a perfluoroelastomer.
  • a cooling channel 124 is disposed on the door 120 adjacent to the high-pressure seal 122 in order to maintain the high- pressure seal 122 below the maximum safe-operating temperature of the high- pressure seal 122 during processing.
  • a cooling agent such as but not limited to an inert, dielectric, and/or high-performance heat transfer fluid, may be circulated within the cooling channel 124 to maintain the high-pressure seal 122 at a temperature between about 150 degrees Celsius and 250 degrees Celsius.
  • the flow of the cooling agent within the cooling channel 124 is controlled by a controller 180 through feedback received from a temperature sensor 1 16 or a flow sensor (not shown).
  • the high-pressure vessel 100 has a port 1 17 through the body 1 10.
  • the port 1 17 has a pipe 1 18 therethrough, which is coupled to a heater 1 19.
  • One end of the pipe 1 18 is connected to the processing region 1 15.
  • the other end of the pipe 118 bifurcates into an inlet conduit 157 and an outlet conduit 161.
  • the inlet conduit 157 is fluidly connected to a gas panel 150 via an isolation valve 155.
  • the inlet conduit 157 is coupled to a heater 158.
  • the outlet conduit 161 is fluidly connected to a condenser 160 via an isolation valve 165.
  • the outlet conduit 161 is coupled to a heater 162.
  • the heaters 1 19, 158, and 162 are configured to maintain a processing gas, such as an oxidative medium, flowing through the pipe 1 18, inlet conduit 157, and the outlet conduit 161 respectively at a temperature between the condensation point of the processing gas and about 250 degrees Celsius.
  • the heaters 1 19, 158 and 162 are powered by a power source 145.
  • the gas panel 150 is configured to provide a processing gas, such as an oxidative medium, under pressure into the inlet conduit 157 for transmission into the processing region 1 15 through the pipe 1 18.
  • the oxidative medium comprises an amine additive.
  • the pressure of the processing gas introduced into the processing region 1 15 is monitored by a pressure sensor 1 14 coupled to the body 1 10.
  • the condenser 160 is fluidly coupled to a cooling fluid and configured to condense a gaseous product flowing through the outlet conduit 161 after removal from the processing region 1 15 through the pipe 1 18.
  • the condenser 160 converts the gaseous products from the gas phase into liquid phase.
  • a pump 170 is fluidly connected to the condenser 160 and pumps out the liquefied products from the condenser 160. The operation of the gas panel 150, the condenser 160, and the pump 170 are controlled by the controller 180.
  • the isolation valves 155 and 165 are configured to allow only one fluid to flow through the pipe 1 18 into the processing region 1 15 at a time.
  • the isolation valve 165 is closed such that a processing gas flowing through inlet conduit 157 enters into the processing region 1 15, preventing the flow of the processing gas into the condenser 160.
  • the isolation valve 165 is open, the isolation valve 155 is closed such that a gaseous product is removed from the processing region 1 15 and flows through the outlet conduit 161 , preventing the flow of the gaseous product into the gas panel 150.
  • One or more heaters 140a, 140b are disposed on the body 1 10 and configured to heat the processing region 1 15 within the high-pressure vessel 100.
  • the heaters 140 are disposed on an outer surface 1 12 of the body 1 10 as shown in Figure 1 , though in other implementations, the heaters 140 may be disposed on an inner surface 1 13 of the body 1 10.
  • Each of the heaters 140 may be a resistive coil, a lamp, a ceramic heater, a graphite-based carbon fiber composite (CFC) heater, a stainless steel heater or an aluminum heater.
  • the heaters 140 are powered by the power source 145. Power to the heaters 140 is controlled by the controller 180 through feedback received from the temperature sensor 1 16.
  • the temperature sensor 1 16 is coupled to the body 1 10 and monitors the temperature of the processing region 1 15.
  • a cassette 130 coupled to an actuator (not shown) is moved in and out of the processing region 1 15.
  • the cassette 130 has a top surface 132, a bottom surface 134, and a wall 136.
  • the wall 136 of the cassette 130 has a plurality of substrate storage slots 138.
  • Each substrate storage slot 138 is evenly spaced along the wall 136 of the cassette 130.
  • Each substrate storage slot 138 is configured to hold a substrate 135 therein.
  • the cassette 130 may have as many as fifty substrate storage slots 138 for holding the substrates 135.
  • the cassette 130 provides an effective vehicle both for transferring a plurality of substrates 135 into and out of the high-pressure vessel 100 and for processing the plurality of substrates 135 in the processing region 1 15.
  • the controller 180 controls the operation of the high-pressure vessel 100.
  • the controller 180 controls the operation of the gas panel 150, the condenser 160, the pump 170, the isolation valve 155, and the isolation valve 165, as well as the power source 145.
  • the controller 180 is also communicatively connected to the temperature sensor 1 16, the pressure sensor 1 14, and the cooling channel 124.
  • the controller 180 includes a central processing unit (CPU) 182, a memory 184, and a support circuit 186.
  • the CPU 182 may be any form of a general-purpose computer processor that may be used in an industrial setting.
  • the memory 184 may be a random access memory, a read-only memory, a floppy, or a hard disk drive, or other form of digital storage.
  • the support circuit 186 is conventionally coupled to the CPU 182 and may include cache, clock circuits, input/output systems, power supplies, and the like.
  • the high-pressure vessel 100 provides a convenient chamber to perform the method of forming a silicon oxide film on the plurality of substrates 135 at a temperature of 550 degrees Celsius or less.
  • the heaters 140 are powered on to pre-heat the high-pressure vessel 100 and maintain the processing region 1 15 at a temperature of about 550 degrees Celsius or less.
  • the heaters 119, 158, and 162 are powered on to pre-heat the pipe 1 18, the inlet conduit 157, and the outlet conduit 161 respectively.
  • the plurality of substrates 135 are loaded on the cassette 130.
  • the door 120 of the high-pressure vessel 100 is opened to move the cassette 130 into the processing region 115.
  • the door 120 is then sealably closed to turn the high- pressure vessel 100 into a high-pressure vessel.
  • the high-pressure seal 122 ensures that there is no leakage of pressure from the processing region 1 15 once the door 120 is closed.
  • the processing gas (i.e., the oxidative medium comprising the amine additive) is provided by the gas panel 150 into the processing region 1 15 inside the high-pressure vessel 100.
  • the isolation valve 155 is turned on by the controller 180 to allow the processing gas to flow through the inlet conduit 157 and the pipe 1 18 into the processing region 1 15.
  • the processing gas is introduced at a flow rate of between, for example, about 500 seem and about 2000 seem.
  • the isolation valve 165 remains off at this time.
  • the pressure in the high- pressure vessel 100 is increased incrementally. The high pressure is effective in driving oxygen into the silicon-containing film into a more complete oxidation state, particularly in the deeper portions of the trenches.
  • the processing gas is steam comprising the amine additive under a pressure between about 1 bar and about 65 bar (e.g., between about 35 bar and about 65 bar; or between about 40 bar and 60 bar).
  • oxidative mediums such as but not limited to ozone, oxygen, a peroxide, or a hydroxide-containing compound may be used with the steam or instead of the steam.
  • the amine additive added to the oxidative medium may be ammonium or ammonia.
  • the isolation valve 155 is turned off by the controller 180 when sufficient steam has been released by the gas panel 150.
  • the processing region 1 15 as well as the inlet conduit 157, the outlet conduit 161 , and the pipe 1 18 are maintained at a temperature and pressure such that the processing gas stays in gaseous phase.
  • the temperatures of the processing region 1 15 as well as the inlet conduit 157, the outlet conduit 161 , and the pipe 1 18 are maintained at a temperature greater than the condensation point of the processing gas (e.g., 100 degrees Celsius) at the applied pressure but at 550 degrees Celsius or less.
  • the processing region 1 15 as well as the inlet conduit 157, the outlet conduit 161 , and the pipe 1 18 are maintained at a pressure less than the condensation pressure of the processing gas at the applied temperature.
  • the processing gas is selected accordingly.
  • steam under a pressure of between about 1 bar and about 65 bar is an effective processing gas, when the high-pressure vessel is maintained at a temperature between about 100 degrees Celsius and about 550 degrees Celsius. This ensures that the steam does not condense into water, which is harmful for the silicon film deposited on the substrate 135.
  • the processing is complete when the film is observed to have the targeted density, as verified by testing the wet etch rate of the film and electrical leakage and breakdown characteristics.
  • the isolation valve 165 is then opened to flow the processing gas from the processing region 1 15 through the pipe 1 18 and outlet conduit 161 into the condenser 160.
  • the processing gas is condensed into liquid phase in the condenser 160.
  • the liquefied processing gas then removed by the pump 170. When the liquefied processing gas is completely removed, the isolation valve 165 closes.
  • the heaters 140, 1 19, 158, and 162 are then powered off.
  • the door 120 of the high-pressure vessel 100 is then opened to remove the cassette 130 from the processing region 1 15.
  • FIG. 2A illustrates a semiconductor device 200 comprising a substrate 202 and a silicon-containing film 208 deposited on the substrate 202 in accordance with one or more implementations described herein.
  • the substrate 202 may be used in place of each of the substrates 135 when loaded on the cassette 130, as shown in Figure 1 .
  • One or more openings or vias 204 may be formed in the substrate 202. While only one via 204 is shown in the semiconductor device 200, a plurality of vias 204 may be included. In such an embodiment, each via 204 of the plurality of vias may have the same dimensions, such as having a depth of about 10 pm. Additionally, the sides 214 and the bottom 216 of the vias 204 may be patterned and may not be planar as shown.
  • the silicon-containing film 208 may be deposited on each exposed surface (i.e. , a top surface 212, the sides 214, and the bottom 216) of the substrate 202 and vias 204.
  • the silicon-containing film 208 may be deposited using atomic layer deposition (ALD).
  • the silicon-containing film 208 may be comprised of silicon or silicon nitride.
  • the substrate 202 may contain one or more materials used in forming semiconductor devices such as metal contacts, trench isolations, gates, bitlines, or any other interconnect features.
  • the substrate 202 may comprise one or more metal layers, one or more dielectric materials, semiconductor material, and combinations thereof utilized to fabricate semiconductor devices.
  • the substrate 202 may include an oxide material, a nitride material, a polysilicon material, or the like, depending upon application.
  • the substrate 202 may include the silicon substrate material, an oxide material, and a nitride material, with or without polysilicon sandwiched in between.
  • the substrate 202 may include a plurality of alternating oxide and nitride materials (i.e., oxide-nitride-oxide (ONO)) (not shown) deposited on the surface of the substrate.
  • the substrate 202 may include a plurality of alternating oxide and nitride materials, one or more oxide or nitride materials, polysilicon or amorphous silicon materials, oxides alternating with amorphous silicon, oxides alternating with polysilicon, undoped silicon alternating with doped silicon, undoped polysilicon alternating with doped polysilicon, or undoped amorphous silicon alternating with doped amorphous silicon.
  • the substrate 202 may be any substrate or material surface upon which film processing is performed.
  • the substrate 202 may be a material such as crystalline silicon, silicon oxide, silicon oxynitride, silicon nitride, strained silicon, silicon germanium, tungsten, titanium nitride, doped or undoped polysilicon, doped or undoped silicon wafers and patterned or non-patterned wafers, silicon on insulator (SOI), carbon doped silicon oxides, silicon nitrides, doped silicon, germanium, gallium arsenide, glass, sapphire, low k dielectrics, and combinations thereof.
  • SOI silicon on insulator
  • Figure 2B illustrates the semiconductor device 200 having a conformal silicon oxide film 206 formed in the vias 204, in accordance with one or more implementations described herein.
  • the silicon oxide film 206 is formed on the substrate 202 and the silicon-comprising film 208 at a temperature of 550 degrees Celsius or less, such as at a temperature of about 350 degrees Celsius to about 505 degrees Celsius.
  • the silicon oxide film 206 is formed using a high pressure anneal at a pressure of 1 bar or greater, such as about 35 bar to about 65 bar, in an oxidative medium comprising an amine additive.
  • the oxidative medium may comprise steam, oxygen, peroxide, etc.
  • the amine additive may comprise ammonium (NFU) or ammonia (NH 3 ).
  • the oxidative medium may comprise about 1 ,000 ppm to about 20,000 ppm of the amine additive, such as about 7,000 ppm.
  • steam is used as the oxidative medium with about 7,000 ppm of NH 3 as the amine additive.
  • a hydrogen-based additive may be added to the oxidative medium.
  • the hydrogen-based additive may be added in addition or as an alternative to the amine additive when reacting silicon nitride comprising films.
  • the hydrogen-based additive may comprise pure hydrogen (H 2 ) or trace amounts of hydrogen as a constituent of inert gas.
  • the amine and/or hydrogen-based additives added to the oxidative medium may enhance the oxidation rate by about 2 to 3 times, as compared to high temperature rapid thermal oxidation films.
  • the annealing process used to form the silicon oxide film 206 is done at a pressure of about 40 bar to about 60 bar for about one hour.
  • the silicon-containing film 208 is disposed between the substrate 202 and the silicon oxide film 206; however, the silicon-containing film 208 may have a smaller thickness following the formation of the silicon oxide film 206.
  • the silicon-containing film 208 is completely oxidized such that the silicon-containing film 208 is no longer disposed between the silicon oxide film 206 and the substrate 202 (i.e. , the silicon oxide film 206 may be in contact with the substrate 202). While not shown, the silicon oxide film 206 and/or the silicon- containing film 208 may be disposed on the surface 212 of the substrate 202.
  • Figure 2C illustrates a zoomed-in cross-sectional view through the top portion of the semiconductor device 200 at the 2C-2C line.
  • the 2C-2C line may be about 500 nm below the surface 212 of the semiconductor device 200.
  • Figure 2D illustrates a zoomed-in cross-sectional view through the bottom portion of the semiconductor device 200 at the 2D-2D line.
  • the 2D-2D line may be about 500 nm above the bottom 216 of the semiconductor device 200.
  • the silicon oxide film 206 of the top portion of Figure 2C has a thickness of 210A and the silicon oxide film 206 of the bottom portion of Figure 2D has a thickness of 210B (collectively 210).
  • the thickness 210A of the top portion of the silicon oxide film 206 is about the same as the thickness 210B of the bottom portion of the silicon oxide film 206.
  • the silicon oxide film 206 has about a uniform thickness 210 at both the top and bottom portions of the via 204, indicating about 100% conformality (i.e., a ratio of the thickness 210A of the top portion to the thickness 210B of the bottom portion) of the silicon oxide layer 206.
  • the silicon oxide film 206 formed using oxidative medium comprising the amine additive at a temperature of less than about 550 degrees Celsius and a pressure greater than 1 bar may have a near uniform conformality on the sides 214 and bottom 216 of the via 204 of greater than about 90%.
  • the silicon oxide film 206 has a uniform thickness 210 of about 20 angstroms to about 400 angstroms, such as about 150 angstroms to about 400 angstroms.
  • Figure 3 depicts a process flow diagram of a method 300 for forming a silicon oxide film on a substrate in accordance with one or more implementations described herein.
  • the substrate may be substrate 135 as depicted in Figure 1 or the substrate 202 as depicted in Figures 2A-2D.
  • method 300 will be described with reference to elements of the semiconductor device 200 of Figures 2A-2D.
  • the method 300 begins at operation 310 by loading a substrate 202 having a silicon-containing film 208 deposited thereon (like shown in Figure 2A) into a high-pressure vessel.
  • the high-pressure vessel may be the high-pressure vessel 100 depicted in Figure 1.
  • the substrate 202 may be positioned in a cassette such as cassette 130 as shown in Figure 1 .
  • the silicon-containing film 208 Prior to loading the substrate 202 in the high- pressure vessel, the silicon-containing film 208 is deposited on each exposed side or surface 212, 214, 216 of the substrate 202 and vias 204.
  • the silicon-containing film 208 may be deposited using ALD.
  • the silicon-containing film 208 may be comprised of silicon or silicon nitride.
  • the substrate 202 may be comprised of any of the materials discussed above in Figures 2A-2D.
  • a surface 212 of the substrate 202 comprises patterned structures, for example, a surface having trenches, holes, or vias 204 formed therein, like shown in Figures 2A-2D.
  • the silicon- containing film 208 is disposed on the sides 214 and bottom 216 of the vias 204.
  • the surface 212 of the substrate 202 may be substantially planar.
  • the substrate 202 may also have a substantially planar surface 212 having a structure formed thereon or therein at a targeted elevation. While the surface 212 of the substrate 202 may comprise trenches, holes, vias, or elevations, the patterns of the surface 212 will be referred to as vias throughout, and the term“via” is not intended to be limiting.
  • the substrate 202 is exposed to an oxidative medium comprising an amine additive at a target temperature between a condensation point of the oxidative medium (e.g., about 100 degrees Celsius) and about 550 degrees Celsius and a pressure greater than 1 bar.
  • the target temperature is between about 100 degrees Celsius and about 550 degrees Celsius (e.g., between about 350 degrees Celsius and about 520 degrees Celsius; or between about 400 degrees Celsius and about 505 degrees Celsius).
  • the temperature may be ramped to the target temperature using the heaters 140a, 140b.
  • the pressure may be ramped to a target pressure.
  • the pressure is between about 1 bar and about 65 bar (e.g., between about 30 bar and about 65 bar; or between about 40 bar to about 60 bar).
  • the oxidative medium is selected from a group consisting of steam, ozone, oxygen, water vapor, heavy water, a peroxide, a hydroxide-containing compound, oxygen isotopes (14, 15, 15, 17, 18, etc.), and hydrogen isotopes (1 , 2, 3), and combinations thereof.
  • the peroxide may be hydrogen peroxide in a gaseous phase.
  • the oxidative medium comprises a hydroxide ion, such as, but not limited to water vapor or heavy water in vapor form.
  • the amine additive may be comprised of ammonium or ammonia.
  • the oxidative medium may comprise about 1 ,000 ppm to about 20,000 ppm of the amine additive, such as about 7,000 ppm. In one embodiment, steam is used as the oxidative medium with about 7,000 ppm of Nhh as the amine additive.
  • a hydrogen-based additive may be added to the oxidative medium.
  • the hydrogen-based additive may be added in addition or as an alternative to the amine additive when reacting silicon nitride comprising films.
  • the hydrogen-based additive may comprise pure hydrogen (H2) or trace amounts of hydrogen as a constituent of inert gas.
  • the amine and/or hydrogen-based additives added to the oxidative medium may enhance the oxidation rate by about 2 to 3 times, as compared to high temperature rapid thermal oxidation films.
  • the substrate 202 or the plurality of substrates are exposed to steam comprising the amine additive at a pressure between about 5 bar to about 60 bar, where the pressure may be incrementally increased from 5 bar to about 60 bar.
  • steam comprising the amine additive is introduced into the high-pressure vessel at a flow rate of between, for example, between about 500 seem and about 5,000 seem (e.g., between about 500 seem and about 5,000 seem; or between about 500 seem and about 2,000 seem.
  • water vapor comprising the amine additive is injected into the high- pressure vessel and the water vapor forms steam comprising the amine additive upon being heated in the high-pressure vessel.
  • a silicon oxide film 206 is formed on the substrate 202.
  • the silicon oxide film 206 is formed as a conformal or uniform layer.
  • the silicon oxide film 206 is uniformly formed on the sides 214 and bottom 216 of the vias 204 and on the surface 212 of the substrate 202.
  • the silicon oxide film 206 may be deposited to have a conformality on the sides 214 and bottom 216 of the via 204 of greater than about 90%, as shown in Figures 2A-2D.
  • the silicon oxide film 206 may have a thickness 210 of about 20 angstroms to about 400 angstroms, such as about 150 angstroms to about 400 angstroms.
  • the high-pressure vessel is maintained at a temperature between a condensation point of the oxidative medium and about 550 degrees Celsius as the substrate 202 with the silicon-containing film 208 is exposed to the oxidative medium comprising the amine additive to form the silicon oxide film 206.
  • the temperature of the high-pressure vessel is maintained between about 400 degrees Celsius and about 505 degrees Celsius.
  • forming the silicon oxide film 206 on the substrate 202 of operation 330 is performed for a time-period between about 5 minutes to about 150 minutes, such as about 30 minutes to about 120 minutes.
  • utilizing the oxidative medium comprising the amine additive at a temperature between about 400 degrees Celsius to about 505 degrees Celsius and a pressure of about 60 bar for about 120 minutes completely oxidizes the silicon-containing film 208 such that the silicon-containing film 208 is no longer disposed between the substrate 202 and the silicon oxide layer 206.
  • an oxidative medium comprising an amine additive, such as steam comprising ammonia
  • an oxidative medium comprising an amine additive, such as steam comprising ammonia
  • an amine additive such as steam comprising ammonia
  • the high pressure inside the high-pressure vessel drives the diffusion of the oxidizing species into deeper vias.
  • the presence of the amine additive in the steam allows the target pressure to be achieved at a much faster rate and increases the oxidation rate by 2-3 times, as compared to high temperature rapid thermal oxidation films.
  • the quality of the silicon oxide film 206 can be verified by comparing a wet etch rate of the silicon oxide film 206 formed using the oxidative medium comprising the amine additive at a temperature of less than 550 degrees Celsius and a pressure greater than 1 bar to the wet etch rate of a silicon oxide film formed at temperatures exceeding 800 degrees Celsius at low pressures without utilizing an amine additive (i.e. , high temperature rapid thermal oxidation films).
  • an amine additive i.e. , high temperature rapid thermal oxidation films.
  • the wet etch rate is about the same for both films.
  • both the silicon oxide film 206 and the high temperature rapid thermal oxidation film had a wet etch rate of about 26 angstroms/min to about 32 angstroms/min.
  • the quality of the silicon oxide film 206 can be further verified by comparing the leakage and capacitive equivalent thickness of the silicon oxide film 206 formed using the oxidative medium comprising the amine additive at a temperature of less than 550 degrees Celsius and a pressure greater than 1 bar to a high temperature rapid thermal oxidation film.
  • the leakage of the silicon oxide film 206 having a thickness greater than about 20 angstroms to the leakage of a high temperature rapid thermal oxidation film having the same thickness both silicon oxide films were disposed along a thermal trend line or an extrapolated thermal trend line of a voltage leakage verses thickness graph.
  • the leakage and capacitive equivalent thickness of the silicon oxide film 206 is about the same or comparable to a high temperature rapid thermal oxidation film.
  • both the silicon oxide film 206 and the high temperature rapid thermal oxidation film had a leakage versus capacitive equivalent thickness of about 0.22 V/angstroms to about 0.25 V/angstroms.
  • the achievement in film quality improvement is substantially similar to a process performed at 800 degrees Celsius or greater at a lower pressure.
  • the process performed at a relatively low temperature of 550 degrees Celsius or less utilizing an oxidative medium comprising an amine additive enables the silicon oxide layer to be uniformly deposited, including depositions on substrates having a challenging or uneven structure.
  • forming silicon oxide films using the oxidative medium comprising the amine and/or hydrogen-based additives at a temperature of less than 550 degrees Celsius and a pressure greater than 1 bar enables the silicon oxide film to achieve a thickness greater than the capabilities of a high temperature rapid thermal oxidation process while maintaining a high quality.
  • utilizing the oxidative medium comprising the amine additive at a temperature of less than 550 degrees Celsius and a pressure greater than 1 bar to deposit a silicon oxide film results in a conformal or uniform silicon oxide film having an increased oxidation rate and the same quality as a high temperature rapid thermal oxidation film.
  • utilizing the oxidative medium comprising the amine additive at a temperature of less than about 550 degrees Celsius to deposit a silicon oxide film expands the process window for forming silicon oxide films, as the process window is no longer confined to temperatures of about 800 degrees Celsius or greater. Expanding the process window increases the capabilities of the current tools used to form silicon oxide films, reducing less overall resources.

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Abstract

Implementations described herein generally relate to methods for forming a low-k dielectric material on a semiconductor substrate. More specifically, implementations described herein relate to methods of forming a silicon oxide film at high pressure and low temperatures. A method of forming a silicon oxide film comprises loading a substrate having a silicon-containing film formed thereon into a processing region of a high-pressure vessel. The method further comprises forming a silicon oxide film on the silicon-containing film. Forming the silicon oxide film on the silicon-containing film comprises exposing the silicon-containing film to an oxidative medium comprising an amine additive at a pressure greater than about 1 bar and maintaining the high-pressure vessel at a temperature between about 100 degrees Celsius and about 550 degrees Celsius.

Description

METHOD OF GROWING THICK OXIDE FILMS AT LOW TEMPERATURE OF
THERMAL OXIDE QUALITY
BACKGROUND
Field
[0001] Embodiments described herein generally relate to methods for forming a low-k dielectric material on a semiconductor substrate. More specifically, embodiments described herein relate to methods of forming a silicon oxide film at high pressure and low temperatures using an oxidative medium comprising an additive.
Description of the Related Art
[0002] Formation of semiconductor devices, such as memory devices, logic devices, microprocessors, etc. involves deposition of low-k dielectric films over semiconductor substrates. The low-k dielectric film is used to make the circuitry for manufacturing the device. Current dry or wet silicon oxidation techniques are often performed at temperatures greater than 800 degrees Celsius. However, materials deposited on the semiconductor substrate may not survive temperatures greater than 800 degrees Celsius. As a result, the low-k dielectric film may not be deposited at a temperature greater than a thermal budget of 800 degrees Celsius, and films deposited within the thermal budget often suffer from poor quality. Additionally, current dry or wet silicon oxidation techniques are unable to deposit quality low-k dielectric films having a thickness greater than 100 angstroms.
[0003] Thus, there is a need for a method of depositing high quality low-k dielectric films at temperatures that meet thermal budget targets.
SUMMARY
[0004] Embodiments described herein generally relate to methods for forming a low-k dielectric material on a semiconductor substrate. More specifically, embodiments described herein relate to methods of forming a silicon oxide film at high pressure and low temperatures. A method of forming a silicon oxide film comprises loading a substrate having a silicon-containing film formed thereon into a processing region of a high-pressure vessel. The method further comprises forming a silicon oxide film on the silicon-containing film. Forming the silicon oxide film on the silicon-containing film comprises exposing the silicon-containing film to an oxidative medium comprising an amine additive at a pressure greater than about 1 bar and maintaining the high-pressure vessel at a temperature between about 100 degrees Celsius and about 550 degrees Celsius.
[0005] A method of forming a silicon oxide film comprises loading a substrate having a silicon-containing film deposited thereon into a processing region of a high- pressure vessel and forming a silicon oxide film on the silicon-containing film. Forming the silicon oxide film on the silicon-containing film comprises exposing the silicon-containing film to an oxidative medium comprising an amine additive at a pressure greater than about 1 bar and maintaining the high-pressure vessel at a temperature between about 100 degrees Celsius and about 550 degrees Celsius
[0006] A method of forming a conformal silicon oxide film comprises depositing a silicon-containing film on a substrate comprising a plurality of vias. The silicon- containing film is deposited on each exposed surface of the substrate and the plurality of vias. The method further comprises the substrate having the silicon- containing film deposited thereon into a processing region of a high-pressure vessel and forming a conformal silicon oxide film on the silicon-containing film. Forming the conformal silicon oxide film on the silicon-containing film comprises exposing the silicon-containing film to an oxidative medium comprising an amine additive, wherein the oxidative medium comprises about 1 ,000 ppm to about 20,000 ppm of the amine additive, and maintaining the high-pressure vessel at a temperature between about 100 degrees Celsius and about 550 degrees Celsius and at a pressure between about 1 bar to about 65 bar.
[0007] A method of forming a silicon oxide film comprises loading a substrate having a silicon-containing film deposited thereon into a processing region of a high- pressure vessel and forming a silicon oxide film on the silicon-containing film. Forming the silicon oxide film on the silicon-containing film comprises exposing the silicon-containing film to an oxidative medium comprising ammonia, wherein the oxidative medium is selected from a group of steam, oxygen, and peroxide, and maintaining the high-pressure vessel at a temperature between about 400 degrees Celsius and about 505 degrees Celsius and at a pressure greater than about 10 bar. The silicon oxide film has a uniform thickness between about 100 angstroms to about 400 angstroms.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] So that the manner in which the above recited features of the present disclosure can be understood in detail, a more particular description of the disclosure, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only exemplary embodiments and are therefore not to be considered limiting of its scope, and may admit to other equally effective embodiments.
[0009] Figure 1 depicts a simplified front cross-sectional view of one example of a high-pressure vessel that may be used to practice one or more implementations described herein.
[0010] Figure 2A illustrates a semiconductor device having a silicon-containing film deposited thereon, according to embodiments disclosed herein.
[0011] Figures 2B-2D illustrates various views of the semiconductor device having a conformal and uniform silicon oxide film formed thereon, according to embodiments disclosed herein.
[0012] Figure 3 is a flowchart illustrating a method of forming a conformal silicon oxide film according to one embodiment.
[0013] To facilitate understanding, identical reference numerals have been used, where possible, to designate identical elements that are common to the figures. It is contemplated that elements and features of one embodiment may be beneficially incorporated in other embodiments without further recitation.
DETAILED DESCRIPTION
[0014] Embodiments described herein generally relate to methods for forming a low-k dielectric material on a semiconductor substrate. More specifically, embodiments described herein relate to methods of forming a silicon oxide film at high pressure and low temperatures. A method of forming a silicon oxide film comprises loading a substrate having a silicon-containing film formed thereon into a processing region of a high-pressure vessel. The method further comprises forming a silicon oxide film on the silicon-containing film. Forming the silicon oxide film on the silicon-containing film comprises exposing the silicon-containing film to an oxidative medium comprising an amine additive at a pressure greater than about 1 bar and maintaining the high-pressure vessel at a temperature between about 100 degrees Celsius and about 550 degrees Celsius.
[0015] Implementations described herein will be described below in reference to a high-pressure oxidation process that can be carried out using a high-pressure oxidation system. The apparatus description described herein, in Figure 1 is illustrative, and should not be construed or interpreted as limiting the scope of the embodiments described herein.
[0016] Figure 1 is simplified front cross-sectional view of a high-pressure vessel 100 for the high-pressure annealing process. The high-pressure vessel 100 has a body 1 10 with an outer surface 1 12 and an inner surface 1 13 that encloses a processing region 1 15. In some implementations such as in Figure 1 , the body 1 10 has an annular cross section, though in other implementations, the cross-section of the body 1 10 may be rectangular or any closed shape. The outer surface 1 12 of the body 1 10 may be made from a corrosion resistant steel (CRS), such as but not limited to stainless steel. In one implementation, the inner surface 1 13 of the body 110 is made from nickel-based steel alloys that exhibit high resistance to corrosion, such as but not limited to Hastelloy®.
[0017] The high-pressure vessel 100 has a door 120 configured to sealably enclose the processing region 1 15 within the body 1 10 such that the processing region 1 15 can be accessed when the door 120 is open. A high-pressure seal 122 is utilized to seal the door 120 to the body 1 10 in order to seal the processing region 1 15 for processing. The high-pressure seal 122 may be made from a polymer, such as but not limited to a perfluoroelastomer. A cooling channel 124 is disposed on the door 120 adjacent to the high-pressure seal 122 in order to maintain the high- pressure seal 122 below the maximum safe-operating temperature of the high- pressure seal 122 during processing. A cooling agent, such as but not limited to an inert, dielectric, and/or high-performance heat transfer fluid, may be circulated within the cooling channel 124 to maintain the high-pressure seal 122 at a temperature between about 150 degrees Celsius and 250 degrees Celsius. The flow of the cooling agent within the cooling channel 124 is controlled by a controller 180 through feedback received from a temperature sensor 1 16 or a flow sensor (not shown).
[0018] The high-pressure vessel 100 has a port 1 17 through the body 1 10. The port 1 17 has a pipe 1 18 therethrough, which is coupled to a heater 1 19. One end of the pipe 1 18 is connected to the processing region 1 15. The other end of the pipe 118 bifurcates into an inlet conduit 157 and an outlet conduit 161. The inlet conduit 157 is fluidly connected to a gas panel 150 via an isolation valve 155. The inlet conduit 157 is coupled to a heater 158. The outlet conduit 161 is fluidly connected to a condenser 160 via an isolation valve 165. The outlet conduit 161 is coupled to a heater 162. The heaters 1 19, 158, and 162 are configured to maintain a processing gas, such as an oxidative medium, flowing through the pipe 1 18, inlet conduit 157, and the outlet conduit 161 respectively at a temperature between the condensation point of the processing gas and about 250 degrees Celsius. The heaters 1 19, 158 and 162 are powered by a power source 145.
[0019] The gas panel 150 is configured to provide a processing gas, such as an oxidative medium, under pressure into the inlet conduit 157 for transmission into the processing region 1 15 through the pipe 1 18. The oxidative medium comprises an amine additive. The pressure of the processing gas introduced into the processing region 1 15 is monitored by a pressure sensor 1 14 coupled to the body 1 10. The condenser 160 is fluidly coupled to a cooling fluid and configured to condense a gaseous product flowing through the outlet conduit 161 after removal from the processing region 1 15 through the pipe 1 18. The condenser 160 converts the gaseous products from the gas phase into liquid phase. A pump 170 is fluidly connected to the condenser 160 and pumps out the liquefied products from the condenser 160. The operation of the gas panel 150, the condenser 160, and the pump 170 are controlled by the controller 180.
[0020] The isolation valves 155 and 165 are configured to allow only one fluid to flow through the pipe 1 18 into the processing region 1 15 at a time. When the isolation valve 155 is open, the isolation valve 165 is closed such that a processing gas flowing through inlet conduit 157 enters into the processing region 1 15, preventing the flow of the processing gas into the condenser 160. On the other hand, when the isolation valve 165 is open, the isolation valve 155 is closed such that a gaseous product is removed from the processing region 1 15 and flows through the outlet conduit 161 , preventing the flow of the gaseous product into the gas panel 150.
[0021] One or more heaters 140a, 140b (collectively 140) are disposed on the body 1 10 and configured to heat the processing region 1 15 within the high-pressure vessel 100. In some implementations, the heaters 140 are disposed on an outer surface 1 12 of the body 1 10 as shown in Figure 1 , though in other implementations, the heaters 140 may be disposed on an inner surface 1 13 of the body 1 10. Each of the heaters 140 may be a resistive coil, a lamp, a ceramic heater, a graphite-based carbon fiber composite (CFC) heater, a stainless steel heater or an aluminum heater. The heaters 140 are powered by the power source 145. Power to the heaters 140 is controlled by the controller 180 through feedback received from the temperature sensor 1 16. The temperature sensor 1 16 is coupled to the body 1 10 and monitors the temperature of the processing region 1 15.
[0022] A cassette 130 coupled to an actuator (not shown) is moved in and out of the processing region 1 15. The cassette 130 has a top surface 132, a bottom surface 134, and a wall 136. The wall 136 of the cassette 130 has a plurality of substrate storage slots 138. Each substrate storage slot 138 is evenly spaced along the wall 136 of the cassette 130. Each substrate storage slot 138 is configured to hold a substrate 135 therein. The cassette 130 may have as many as fifty substrate storage slots 138 for holding the substrates 135. The cassette 130 provides an effective vehicle both for transferring a plurality of substrates 135 into and out of the high-pressure vessel 100 and for processing the plurality of substrates 135 in the processing region 1 15.
[0023] The controller 180 controls the operation of the high-pressure vessel 100. The controller 180 controls the operation of the gas panel 150, the condenser 160, the pump 170, the isolation valve 155, and the isolation valve 165, as well as the power source 145. The controller 180 is also communicatively connected to the temperature sensor 1 16, the pressure sensor 1 14, and the cooling channel 124. The controller 180 includes a central processing unit (CPU) 182, a memory 184, and a support circuit 186. The CPU 182 may be any form of a general-purpose computer processor that may be used in an industrial setting. The memory 184 may be a random access memory, a read-only memory, a floppy, or a hard disk drive, or other form of digital storage. The support circuit 186 is conventionally coupled to the CPU 182 and may include cache, clock circuits, input/output systems, power supplies, and the like.
[0024] The high-pressure vessel 100 provides a convenient chamber to perform the method of forming a silicon oxide film on the plurality of substrates 135 at a temperature of 550 degrees Celsius or less. The heaters 140 are powered on to pre-heat the high-pressure vessel 100 and maintain the processing region 1 15 at a temperature of about 550 degrees Celsius or less. At the same time, the heaters 119, 158, and 162 are powered on to pre-heat the pipe 1 18, the inlet conduit 157, and the outlet conduit 161 respectively.
[0025] The plurality of substrates 135 are loaded on the cassette 130. The door 120 of the high-pressure vessel 100 is opened to move the cassette 130 into the processing region 115. The door 120 is then sealably closed to turn the high- pressure vessel 100 into a high-pressure vessel. The high-pressure seal 122 ensures that there is no leakage of pressure from the processing region 1 15 once the door 120 is closed.
[0026] The processing gas (i.e., the oxidative medium comprising the amine additive) is provided by the gas panel 150 into the processing region 1 15 inside the high-pressure vessel 100. The isolation valve 155 is turned on by the controller 180 to allow the processing gas to flow through the inlet conduit 157 and the pipe 1 18 into the processing region 1 15. The processing gas is introduced at a flow rate of between, for example, about 500 seem and about 2000 seem. The isolation valve 165 remains off at this time. In some implementations, the pressure in the high- pressure vessel 100 is increased incrementally. The high pressure is effective in driving oxygen into the silicon-containing film into a more complete oxidation state, particularly in the deeper portions of the trenches.
[0027] In some implementations described herein, the processing gas is steam comprising the amine additive under a pressure between about 1 bar and about 65 bar (e.g., between about 35 bar and about 65 bar; or between about 40 bar and 60 bar). However, in other implementations, other oxidative mediums, such as but not limited to ozone, oxygen, a peroxide, or a hydroxide-containing compound may be used with the steam or instead of the steam. The amine additive added to the oxidative medium may be ammonium or ammonia. The isolation valve 155 is turned off by the controller 180 when sufficient steam has been released by the gas panel 150.
[0028] During processing of the substrates 135, the processing region 1 15 as well as the inlet conduit 157, the outlet conduit 161 , and the pipe 1 18 are maintained at a temperature and pressure such that the processing gas stays in gaseous phase. The temperatures of the processing region 1 15 as well as the inlet conduit 157, the outlet conduit 161 , and the pipe 1 18 are maintained at a temperature greater than the condensation point of the processing gas (e.g., 100 degrees Celsius) at the applied pressure but at 550 degrees Celsius or less. The processing region 1 15 as well as the inlet conduit 157, the outlet conduit 161 , and the pipe 1 18 are maintained at a pressure less than the condensation pressure of the processing gas at the applied temperature. The processing gas is selected accordingly. In the implementation described herein, steam under a pressure of between about 1 bar and about 65 bar is an effective processing gas, when the high-pressure vessel is maintained at a temperature between about 100 degrees Celsius and about 550 degrees Celsius. This ensures that the steam does not condense into water, which is harmful for the silicon film deposited on the substrate 135.
[0029] The processing is complete when the film is observed to have the targeted density, as verified by testing the wet etch rate of the film and electrical leakage and breakdown characteristics. The isolation valve 165 is then opened to flow the processing gas from the processing region 1 15 through the pipe 1 18 and outlet conduit 161 into the condenser 160. The processing gas is condensed into liquid phase in the condenser 160. The liquefied processing gas then removed by the pump 170. When the liquefied processing gas is completely removed, the isolation valve 165 closes. The heaters 140, 1 19, 158, and 162 are then powered off. The door 120 of the high-pressure vessel 100 is then opened to remove the cassette 130 from the processing region 1 15. [0030] Figure 2A illustrates a semiconductor device 200 comprising a substrate 202 and a silicon-containing film 208 deposited on the substrate 202 in accordance with one or more implementations described herein. The substrate 202 may be used in place of each of the substrates 135 when loaded on the cassette 130, as shown in Figure 1 . One or more openings or vias 204 may be formed in the substrate 202. While only one via 204 is shown in the semiconductor device 200, a plurality of vias 204 may be included. In such an embodiment, each via 204 of the plurality of vias may have the same dimensions, such as having a depth of about 10 pm. Additionally, the sides 214 and the bottom 216 of the vias 204 may be patterned and may not be planar as shown. The silicon-containing film 208 may be deposited on each exposed surface (i.e. , a top surface 212, the sides 214, and the bottom 216) of the substrate 202 and vias 204. The silicon-containing film 208 may be deposited using atomic layer deposition (ALD). The silicon-containing film 208 may be comprised of silicon or silicon nitride.
[0031] The substrate 202 may contain one or more materials used in forming semiconductor devices such as metal contacts, trench isolations, gates, bitlines, or any other interconnect features. The substrate 202 may comprise one or more metal layers, one or more dielectric materials, semiconductor material, and combinations thereof utilized to fabricate semiconductor devices. For example, the substrate 202 may include an oxide material, a nitride material, a polysilicon material, or the like, depending upon application. In one implementation where a memory application is targeted, the substrate 202 may include the silicon substrate material, an oxide material, and a nitride material, with or without polysilicon sandwiched in between.
[0032] In another implementation, the substrate 202 may include a plurality of alternating oxide and nitride materials (i.e., oxide-nitride-oxide (ONO)) (not shown) deposited on the surface of the substrate. In various implementations, the substrate 202 may include a plurality of alternating oxide and nitride materials, one or more oxide or nitride materials, polysilicon or amorphous silicon materials, oxides alternating with amorphous silicon, oxides alternating with polysilicon, undoped silicon alternating with doped silicon, undoped polysilicon alternating with doped polysilicon, or undoped amorphous silicon alternating with doped amorphous silicon. The substrate 202 may be any substrate or material surface upon which film processing is performed. For example, the substrate 202 may be a material such as crystalline silicon, silicon oxide, silicon oxynitride, silicon nitride, strained silicon, silicon germanium, tungsten, titanium nitride, doped or undoped polysilicon, doped or undoped silicon wafers and patterned or non-patterned wafers, silicon on insulator (SOI), carbon doped silicon oxides, silicon nitrides, doped silicon, germanium, gallium arsenide, glass, sapphire, low k dielectrics, and combinations thereof.
[0033] Figure 2B illustrates the semiconductor device 200 having a conformal silicon oxide film 206 formed in the vias 204, in accordance with one or more implementations described herein. The silicon oxide film 206 is formed on the substrate 202 and the silicon-comprising film 208 at a temperature of 550 degrees Celsius or less, such as at a temperature of about 350 degrees Celsius to about 505 degrees Celsius. The silicon oxide film 206 is formed using a high pressure anneal at a pressure of 1 bar or greater, such as about 35 bar to about 65 bar, in an oxidative medium comprising an amine additive.
[0034] The oxidative medium may comprise steam, oxygen, peroxide, etc., and the amine additive may comprise ammonium (NFU) or ammonia (NH3). The oxidative medium may comprise about 1 ,000 ppm to about 20,000 ppm of the amine additive, such as about 7,000 ppm. In one embodiment, steam is used as the oxidative medium with about 7,000 ppm of NH3 as the amine additive. When reacting films comprising silicon nitride, a hydrogen-based additive may be added to the oxidative medium. The hydrogen-based additive may be added in addition or as an alternative to the amine additive when reacting silicon nitride comprising films. The hydrogen-based additive may comprise pure hydrogen (H2) or trace amounts of hydrogen as a constituent of inert gas. The amine and/or hydrogen-based additives added to the oxidative medium may enhance the oxidation rate by about 2 to 3 times, as compared to high temperature rapid thermal oxidation films. In one embodiment, the annealing process used to form the silicon oxide film 206 is done at a pressure of about 40 bar to about 60 bar for about one hour.
[0035] The silicon-containing film 208 is disposed between the substrate 202 and the silicon oxide film 206; however, the silicon-containing film 208 may have a smaller thickness following the formation of the silicon oxide film 206. In one embodiment, the silicon-containing film 208 is completely oxidized such that the silicon-containing film 208 is no longer disposed between the silicon oxide film 206 and the substrate 202 (i.e. , the silicon oxide film 206 may be in contact with the substrate 202). While not shown, the silicon oxide film 206 and/or the silicon- containing film 208 may be disposed on the surface 212 of the substrate 202.
[0036] Figure 2C illustrates a zoomed-in cross-sectional view through the top portion of the semiconductor device 200 at the 2C-2C line. The 2C-2C line may be about 500 nm below the surface 212 of the semiconductor device 200. Figure 2D illustrates a zoomed-in cross-sectional view through the bottom portion of the semiconductor device 200 at the 2D-2D line. The 2D-2D line may be about 500 nm above the bottom 216 of the semiconductor device 200. The silicon oxide film 206 of the top portion of Figure 2C has a thickness of 210A and the silicon oxide film 206 of the bottom portion of Figure 2D has a thickness of 210B (collectively 210).
[0037] As shown in Figures 2C and 2D, the thickness 210A of the top portion of the silicon oxide film 206 is about the same as the thickness 210B of the bottom portion of the silicon oxide film 206. The silicon oxide film 206 has about a uniform thickness 210 at both the top and bottom portions of the via 204, indicating about 100% conformality (i.e., a ratio of the thickness 210A of the top portion to the thickness 210B of the bottom portion) of the silicon oxide layer 206. The silicon oxide film 206 formed using oxidative medium comprising the amine additive at a temperature of less than about 550 degrees Celsius and a pressure greater than 1 bar may have a near uniform conformality on the sides 214 and bottom 216 of the via 204 of greater than about 90%. The silicon oxide film 206 has a uniform thickness 210 of about 20 angstroms to about 400 angstroms, such as about 150 angstroms to about 400 angstroms.
[0038] Figure 3 depicts a process flow diagram of a method 300 for forming a silicon oxide film on a substrate in accordance with one or more implementations described herein. The substrate may be substrate 135 as depicted in Figure 1 or the substrate 202 as depicted in Figures 2A-2D. For clarity, method 300 will be described with reference to elements of the semiconductor device 200 of Figures 2A-2D. [0039] The method 300 begins at operation 310 by loading a substrate 202 having a silicon-containing film 208 deposited thereon (like shown in Figure 2A) into a high-pressure vessel. The high-pressure vessel may be the high-pressure vessel 100 depicted in Figure 1. The substrate 202 may be positioned in a cassette such as cassette 130 as shown in Figure 1 . Prior to loading the substrate 202 in the high- pressure vessel, the silicon-containing film 208 is deposited on each exposed side or surface 212, 214, 216 of the substrate 202 and vias 204. The silicon-containing film 208 may be deposited using ALD. The silicon-containing film 208 may be comprised of silicon or silicon nitride. The substrate 202 may be comprised of any of the materials discussed above in Figures 2A-2D.
[0040] In one implementation, a surface 212 of the substrate 202 comprises patterned structures, for example, a surface having trenches, holes, or vias 204 formed therein, like shown in Figures 2A-2D. In such an embodiment, the silicon- containing film 208 is disposed on the sides 214 and bottom 216 of the vias 204. Alternatively, the surface 212 of the substrate 202 may be substantially planar. The substrate 202 may also have a substantially planar surface 212 having a structure formed thereon or therein at a targeted elevation. While the surface 212 of the substrate 202 may comprise trenches, holes, vias, or elevations, the patterns of the surface 212 will be referred to as vias throughout, and the term“via” is not intended to be limiting.
[0041] At operation 320, the substrate 202 is exposed to an oxidative medium comprising an amine additive at a target temperature between a condensation point of the oxidative medium (e.g., about 100 degrees Celsius) and about 550 degrees Celsius and a pressure greater than 1 bar. In one implementation, the target temperature is between about 100 degrees Celsius and about 550 degrees Celsius (e.g., between about 350 degrees Celsius and about 520 degrees Celsius; or between about 400 degrees Celsius and about 505 degrees Celsius). The temperature may be ramped to the target temperature using the heaters 140a, 140b. In addition to ramping the temperature, the pressure may be ramped to a target pressure. In one implementation, the pressure is between about 1 bar and about 65 bar (e.g., between about 30 bar and about 65 bar; or between about 40 bar to about 60 bar). [0042] In one implementation, the oxidative medium is selected from a group consisting of steam, ozone, oxygen, water vapor, heavy water, a peroxide, a hydroxide-containing compound, oxygen isotopes (14, 15, 15, 17, 18, etc.), and hydrogen isotopes (1 , 2, 3), and combinations thereof. The peroxide may be hydrogen peroxide in a gaseous phase. In some implementations, the oxidative medium comprises a hydroxide ion, such as, but not limited to water vapor or heavy water in vapor form. The amine additive may be comprised of ammonium or ammonia. The oxidative medium may comprise about 1 ,000 ppm to about 20,000 ppm of the amine additive, such as about 7,000 ppm. In one embodiment, steam is used as the oxidative medium with about 7,000 ppm of Nhh as the amine additive. When reacting films comprising silicon nitride, a hydrogen-based additive may be added to the oxidative medium. The hydrogen-based additive may be added in addition or as an alternative to the amine additive when reacting silicon nitride comprising films. The hydrogen-based additive may comprise pure hydrogen (H2) or trace amounts of hydrogen as a constituent of inert gas. The amine and/or hydrogen-based additives added to the oxidative medium may enhance the oxidation rate by about 2 to 3 times, as compared to high temperature rapid thermal oxidation films.
[0043] In some implementations, the substrate 202 or the plurality of substrates are exposed to steam comprising the amine additive at a pressure between about 5 bar to about 60 bar, where the pressure may be incrementally increased from 5 bar to about 60 bar. In some implementations, steam comprising the amine additive is introduced into the high-pressure vessel at a flow rate of between, for example, between about 500 seem and about 5,000 seem (e.g., between about 500 seem and about 5,000 seem; or between about 500 seem and about 2,000 seem. In one implementation, water vapor comprising the amine additive is injected into the high- pressure vessel and the water vapor forms steam comprising the amine additive upon being heated in the high-pressure vessel. In another implementation, water or water vapor comprising the amine additive is present in the high-pressure vessel prior to heating to the target temperature. The water or water vapor present in the high-pressure vessel forms steam comprising the amine additive as the high- pressure vessel is heated to the target temperature. [0044] At operation 330, a silicon oxide film 206 is formed on the substrate 202. The silicon oxide film 206 is formed as a conformal or uniform layer. The silicon oxide film 206 is uniformly formed on the sides 214 and bottom 216 of the vias 204 and on the surface 212 of the substrate 202. The silicon oxide film 206 may be deposited to have a conformality on the sides 214 and bottom 216 of the via 204 of greater than about 90%, as shown in Figures 2A-2D. The silicon oxide film 206 may have a thickness 210 of about 20 angstroms to about 400 angstroms, such as about 150 angstroms to about 400 angstroms.
[0045] At operation 330, the high-pressure vessel is maintained at a temperature between a condensation point of the oxidative medium and about 550 degrees Celsius as the substrate 202 with the silicon-containing film 208 is exposed to the oxidative medium comprising the amine additive to form the silicon oxide film 206. In one implementation where steam comprising the amine additive at a pressure between about 40 bar to about 60 bar is used, the temperature of the high-pressure vessel is maintained between about 400 degrees Celsius and about 505 degrees Celsius. In some implementations, forming the silicon oxide film 206 on the substrate 202 of operation 330 is performed for a time-period between about 5 minutes to about 150 minutes, such as about 30 minutes to about 120 minutes. In at least one implementation, utilizing the oxidative medium comprising the amine additive at a temperature between about 400 degrees Celsius to about 505 degrees Celsius and a pressure of about 60 bar for about 120 minutes completely oxidizes the silicon-containing film 208 such that the silicon-containing film 208 is no longer disposed between the substrate 202 and the silicon oxide layer 206.
[0046] Application of an oxidative medium comprising an amine additive, such as steam comprising ammonia, under high pressure allows a high concentration of the oxidizing species from the oxidative medium to infiltrate deeply into the silicon- containing film such that the oxidizing species can produce more of the silicon oxide film material through oxidation. Not to be bound by theory, but it is believed that the high pressure inside the high-pressure vessel drives the diffusion of the oxidizing species into deeper vias. In addition, it is believed that the presence of the amine additive in the steam allows the target pressure to be achieved at a much faster rate and increases the oxidation rate by 2-3 times, as compared to high temperature rapid thermal oxidation films.
[0047] The quality of the silicon oxide film 206 can be verified by comparing a wet etch rate of the silicon oxide film 206 formed using the oxidative medium comprising the amine additive at a temperature of less than 550 degrees Celsius and a pressure greater than 1 bar to the wet etch rate of a silicon oxide film formed at temperatures exceeding 800 degrees Celsius at low pressures without utilizing an amine additive (i.e. , high temperature rapid thermal oxidation films). When performing a wet etch on both the silicon oxide film 206 having a thickness greater than about 20 angstroms and a high temperature rapid thermal oxidation film having the same thickness, the wet etch rate is about the same for both films. In one embodiment, both the silicon oxide film 206 and the high temperature rapid thermal oxidation film had a wet etch rate of about 26 angstroms/min to about 32 angstroms/min.
[0048] Additionally, the quality of the silicon oxide film 206 can be further verified by comparing the leakage and capacitive equivalent thickness of the silicon oxide film 206 formed using the oxidative medium comprising the amine additive at a temperature of less than 550 degrees Celsius and a pressure greater than 1 bar to a high temperature rapid thermal oxidation film. When comparing of the leakage of the silicon oxide film 206 having a thickness greater than about 20 angstroms to the leakage of a high temperature rapid thermal oxidation film having the same thickness, both silicon oxide films were disposed along a thermal trend line or an extrapolated thermal trend line of a voltage leakage verses thickness graph. As such, the leakage and capacitive equivalent thickness of the silicon oxide film 206 is about the same or comparable to a high temperature rapid thermal oxidation film. In one embodiment, both the silicon oxide film 206 and the high temperature rapid thermal oxidation film had a leakage versus capacitive equivalent thickness of about 0.22 V/angstroms to about 0.25 V/angstroms.
[0049] Therefore, for a process performed at a relatively low temperature of 550 degrees Celsius or less, the achievement in film quality improvement is substantially similar to a process performed at 800 degrees Celsius or greater at a lower pressure. The process performed at a relatively low temperature of 550 degrees Celsius or less utilizing an oxidative medium comprising an amine additive enables the silicon oxide layer to be uniformly deposited, including depositions on substrates having a challenging or uneven structure.
[0050] Moreover, forming silicon oxide films using the oxidative medium comprising the amine and/or hydrogen-based additives at a temperature of less than 550 degrees Celsius and a pressure greater than 1 bar enables the silicon oxide film to achieve a thickness greater than the capabilities of a high temperature rapid thermal oxidation process while maintaining a high quality. As such, utilizing the oxidative medium comprising the amine additive at a temperature of less than 550 degrees Celsius and a pressure greater than 1 bar to deposit a silicon oxide film results in a conformal or uniform silicon oxide film having an increased oxidation rate and the same quality as a high temperature rapid thermal oxidation film.
[0051] Furthermore, utilizing the oxidative medium comprising the amine additive at a temperature of less than about 550 degrees Celsius to deposit a silicon oxide film expands the process window for forming silicon oxide films, as the process window is no longer confined to temperatures of about 800 degrees Celsius or greater. Expanding the process window increases the capabilities of the current tools used to form silicon oxide films, reducing less overall resources.
[0052] While the foregoing is directed to embodiments of the present disclosure, other and further embodiments of the disclosure may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.

Claims

What is claimed is:
1. A method of forming a silicon oxide film, comprising:
loading a substrate having a silicon-containing film deposited thereon into a processing region of a high-pressure vessel; and
forming a silicon oxide film on the silicon-containing film, comprising:
exposing the silicon-containing film to an oxidative medium comprising an amine additive at a pressure greater than about 1 bar; and
maintaining the high-pressure vessel at a temperature between about 100 degrees Celsius and about 550 degrees Celsius.
2. The method of claim 1 , wherein the amine additive comprises ammonium or ammonia, and wherein the oxidative medium comprises about 1 ,000 ppm to about 20,000 ppm of the amine additive.
3. The method of claim 1 , wherein the oxidative medium is selected from a group consisting of steam, peroxide, oxygen, ozone, water vapor, heavy water, a hydroxide-containing compound, oxygen isotopes, hydrogen isotopes, and combinations thereof.
4. The method of claim 1 , wherein the silicon-containing film is a silicon nitride film, and wherein the oxidative medium further comprises a hydrogen-based additive.
5. The method of claim 1 , wherein the silicon oxide film has a uniform thickness between about 20 angstroms to about 400 angstroms, and wherein the temperature is between about 400 degrees Celsius and about 505 degrees Celsius.
6. The method of claim 1 , wherein forming the silicon oxide film on the silicon- containing film is performed for a time-period between about 5 minutes to about 150 minutes.
7. A method of forming a conformal silicon oxide film, comprising: depositing a silicon-containing film on a substrate comprising a plurality of vias, the silicon-containing film being deposited on each exposed surface of the substrate and the plurality of vias;
loading the substrate having the silicon-containing film deposited thereon into a processing region of a high-pressure vessel; and
forming a conformal silicon oxide film on the silicon-containing film, comprising:
exposing the silicon-containing film to an oxidative medium comprising an amine additive, wherein the oxidative medium comprises about 1 ,000 ppm to about 20,000 ppm of the amine additive; and
maintaining the high-pressure vessel at a temperature between about 100 degrees Celsius and about 550 degrees Celsius and at a pressure between about 1 bar to about 65 bar.
8. The method of claim 7, wherein the amine additive comprises ammonium or ammonia, and wherein the oxidative medium comprises about 7,000 ppm of the amine additive.
9. The method of claim 7, wherein the oxidative medium is selected from a group consisting of steam, peroxide, oxygen, ozone, water vapor, heavy water, a hydroxide-containing compound, oxygen isotopes, hydrogen isotopes, and combinations thereof, and wherein the silicon-containing film comprises silicon or silicon nitride.
10. The method of claim 7, wherein the oxidative medium is steam and the amine additive is ammonia, wherein the silicon-containing film is a silicon nitride film, and wherein the oxidative medium further comprises a hydrogen-based additive.
1 1. The method of claim 7, wherein forming the silicon oxide film on the silicon- containing film is performed for a time-period between about 5 minutes to about 150 minutes at a temperature between about 400 degrees Celsius to about 505 degrees Celsius, and wherein the conformal silicon oxide film has a uniform thickness between about 20 angstroms to about 400 angstroms.
12. A method of forming a silicon oxide film, comprising:
loading a substrate having a silicon-containing film deposited thereon into a processing region of a high-pressure vessel; and
forming a silicon oxide film on the silicon-containing film, comprising:
exposing the silicon-containing film to an oxidative medium comprising ammonia, wherein the oxidative medium is selected from a group of steam, oxygen, and peroxide; and
maintaining the high-pressure vessel at a temperature between about 400 degrees Celsius and about 505 degrees Celsius and at a pressure greater than about 10 bar, wherein the silicon oxide film has a uniform thickness between about 100 angstroms to about 400 angstroms.
13. The method of claim 12, wherein the oxidative medium comprises about 1 ,000 ppm to about 20,000 ppm of the ammonia.
14. The method of claim 12, wherein the silicon-containing film comprises silicon or silicon nitride, and wherein the pressure is between about 10 bar to about 60 bar.
15. The method of claim 12, wherein forming the silicon oxide film on the silicon- containing film is performed for a time-period of about 5 minutes to about 120 minutes.
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CN113557589B (en) 2025-05-13
JP2022525460A (en) 2022-05-16
EP3942596A4 (en) 2022-12-07
TW202104662A (en) 2021-02-01
CN113557589A (en) 2021-10-26
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