WO2007027350A2 - Method of removing surface deposits and passivating interior surfaces of the interior of a chemical vapour deposition (cvd) chamber - Google Patents
Method of removing surface deposits and passivating interior surfaces of the interior of a chemical vapour deposition (cvd) chamber Download PDFInfo
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- WO2007027350A2 WO2007027350A2 PCT/US2006/030032 US2006030032W WO2007027350A2 WO 2007027350 A2 WO2007027350 A2 WO 2007027350A2 US 2006030032 W US2006030032 W US 2006030032W WO 2007027350 A2 WO2007027350 A2 WO 2007027350A2
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- 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
-
- 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
- C23C16/4405—Cleaning of reactor or parts inside the reactor by using reactive gases
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- 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
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/12—Gaseous compositions
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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
- H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
- H01J37/32357—Generation remote from the workpiece, e.g. down-stream
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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
- H01J37/32798—Further details of plasma apparatus not provided for in groups H01J37/3244 - H01J37/32788; special provisions for cleaning or maintenance of the apparatus
- H01J37/32853—Hygiene
- H01J37/32862—In situ cleaning of vessels and/or internal parts
Definitions
- the present invention relates to methods for removing surface deposits by using an activated gas mixture created by activating a gas mixture that includes a nitrogen source, a carbon or sulfur source, and a optionally, an oxygen source, as well as the gas mixtures and activated gases used in these methods.
- the cleaning process may include, for example, the evacuation of reactant gases and their replacement with an activated cleaning gas followed by a flushing step to remove the cleaning gas from the chamber using an inert carrier gas.
- the cleaning gases typically work by etching the contaminant build-ups from the interior surfaces, thus the etching rate of the cleaning gas is an important parameter in the utility and commercial use of the gases. Present cleaning gases are believed to be limited in their effectiveness due to low etch rates.
- the present invention provides effective methods for removing surface deposits from the interior of a CVD reactor using novel cleaning gas mixtures and activated cleaning gas mixtures.
- the methods of the invention include, but are not limited to, the steps of providing a gas mixture, activating the gas mixture in a remote chamber or in a process chamber to form an activated gas mixture, where the gas mixture comprises a source of at least one atom selected from the group consisting of carbon and sulfur, NF 3 , and optionally, an oxygen source, wherein the molar ratio of oxygen : carbon source is at least 0.75:1 ; and contacting the activated gas mixture with surface deposits within the CVD reactor.
- the gas mixtures of the present invention include, but are not limited to, at least one inorganic fluorine source, a carbon source gas or a sulfur source, at least one nitrogen source, and optionally at least one oxygen source.
- the activated gas mixtures produced from the gas mixtures include but are not limited to mixtures of fluorine atoms, nitrogen atoms, at least one atom selected from the group consisting of carbon and sulfur, and optionally oxygen.
- the activated gas mixture comprises (on a moles of atoms basis), from about 60% to about 75% fluorine atoms, from about 10% to about 30% nitrogen atoms, optionally from about 0.4% to about 15% oxygen atoms, and from about 0.3% to about 15% at least one atom selected from the group consisting of carbon and sulfur, optionally including a carrier gas.
- Figure 1 is a schematic diagram of an apparatus useful for carrying out the present process.
- Figure 2 is a schematic diagram of another apparatus useful for carrying out the present process.
- Figure 3 is a plot of silicon nitride etching rate for various compositions at a process chamber pressure of 5 torr and different wafer temperatures
- Figure 4 is a plot of silicon nitride etching for various compositions at a process chamber pressure of 2 torr, as a function of plasma source pressure.
- Figure 5 is a plot of silicon nitride etching for various compositions at a process chamber pressure of 3 torr, as a function of plasma source pressure.
- Figure 6 is a plot of silicon nitride etching for various compositions at a process chamber pressure of 5 torr, as a function of plasma source pressure.
- Figure 7 is a plot of silicon nitride etching at different temperatures at a process chamber pressure of 2 torr, as a function of plasma source pressure.
- Figure 8 is a plot of silicon nitride etching at different temperatures at a process chamber pressure of 3 torr, as a function of plasma source pressure
- Figure 9 is a plot comparing silicon nitride etching rates using C 2 F 6 and
- Figure 10 is a plot comparing silicon nitride etching rates using C 2 F 6 and
- Figure 11 is a plot comparing silicon nitride etching rates using C 2 F 6 , oxygen, and NF 3 at a flow rate of 4800 seem at a process chamber pressure of 5 torr at different wafer temperatures.
- Figure 12 is a plot of silicon nitride etching with different gas compositions using NF 3 and carbon dioxide at a process chamber pressure of 5 torr.
- Figure 13 is a plot comparing silicon nitride etching rates using C 2 F 6 and
- Figure 14 is a plot illustrating nitride etch rates as a function of process chamber pressure comparing different gas compositions.
- Figure 15 is a plot illustrating nitride etch rates as a function of process chamber pressure comparing different gas compositions.
- Surface deposits as referred to herein comprise those materials commonly deposited by chemical vapor deposition (CVD), plasma-enhanced chemical vapor deposition (PECVD) or similar processes. Such materials include nitrogen-containing deposits. Such deposits include, without limitation, silicon nitride, silicon oxynitride, silicon carbonitride (SiCN) 1 silicon boronitride (SiBN), and metal nitrides, such as tungsten nitride, titanium nitride or tantalum nitride. In one embodiment of the invention, the surface deposit is silicon nitride. [0020] In one embodiment of the invention, surface deposits are removed from the interior of a process chamber that is used in fabricating electronic devices.
- Such a process chamber could be a CVD chamber or a PECVD chamber.
- Other embodiments of the invention include, but are not limited to, removing surface deposits from metals, the cleaning of plasma etching chambers and removal of N- containing thin films from a wafer.
- the process of the present invention involves an activating step wherein a cleaning gas mixture is activated, either in the process chamber or in the remote chamber.
- activation means that at least an effective amount of the gas molecules have been substantially decomposed into their atomic species, e.g. a CF 4 gas would be activated to substantially decompose and form an activated gas (also known in the art as a plasma) comprising carbon and fluorine atoms.
- Activation may be accomplished by any energy input means allowing for the achievement of dissociation of a large fraction of the feed gas, such as: radio frequency (RF) energy, direct current (DC) energy, laser illumination, and microwave energy.
- RF radio frequency
- DC direct current
- One embodiment of the invention uses transformer coupled inductively coupled lower frequency RF power sources in which the plasma has a torroidal configuration and acts as the secondary of the transformer.
- the use of lower frequency RF power allows the use of magnetic cores that enhance the inductive coupling with respect to capacitive coupling; thereby allowing the more efficient transfer of energy to the plasma without excessive ion bombardment which limits the lifetime of the remote plasma source chamber interior.
- Typical RF power used has a frequency lower than 1000 kHz.
- the power source is a remote microwave, inductively, or capacitively coupled plasma source.
- the gas is activated using glow discharge. [0022] Activation of the cleaning gas mixture uses sufficient power for a sufficient time to form an activated gas mixture.
- the activated gas mixture has a neutral temperature of at least about 3,000 K.
- the neutral temperature of the resulting plasma depends on the power and the residence time of the gas mixture in the remote chamber. Under certain power input and conditions, neutral temperature will be higher with longer residence times. Under appropriate conditions (considering power, gas composition, gas pressure and gas residence time), neutral temperatures of at least about 6,000 K may be achieved.
- the activated gas may be formed in a separate, remote chamber that is outside of the process chamber, but in close proximity to the process chamber.
- remote chamber refers to the chamber other than the cleaning or process chamber, wherein the plasma may be generated
- the process chamber refers to the chamber wherein the surface deposits are located.
- the remote chamber is connected to the process chamber by any means allowing for transfer of the activated gas from the remote chamber to the process chamber.
- the means for allowing transfer of the activated gas may comprise a short connecting tube and a showerhead of the CVD/PECVD process chamber.
- the means for allowing transfer of the activated gas may further comprise a direct conduit from the remote plasma source chamber to the process chamber.
- the remote chamber and means for connecting the remote chamber with the process chamber are constructed of materials known in this field to be capable of containing activated gas mixtures. For instance, aluminum and anodized aluminum are commonly used for the chamber components. Sometimes AI 2 O 3 is coated on the interior surface to reduce the surface recombination. In other embodiments of the invention, the activated gas mixture may be formed directly in the process chamber.
- the gas mixture (that is to be activated to form the activated gas mixture) comprises at least one inorganic fluorine source, at least one source of one or more atoms selected from the group consisting of carbon and sulfur, at least one nitrogen source, and optionally at least one oxygen source.
- Typical inorganic fluorine sources include NF 3 and SF ⁇ . Where SF 6 serves as the inorganic fluorine source, it can also serve as a source of sulfur.
- a carbon source can be a fluorocarbon or a hydrocarbon, carbon dioxide or carbon monoxide.
- a fluorocarbon is herein referred to as a compound containing C and F, and optionally O and H.
- a fluorocarbon is a perfluorocarbon or a mixture of one or more perfluorocarbons.
- a perfluorocarbon compound as referred to in this invention is a compound consisting of C, F and optionally oxygen.
- Such perfluorocarbon compounds include, but are not limited to tetrafluoromethane, hexafluoroethane, octafluoropropane, hexafluororcyclopropane, decafluorobutane, hexafluoropropene, octafluorocyclobutane and octafluorotetrahydrofuran.
- the fluorocarbon of the gas mixture serves as a source of carbon atoms in the activated gas mixture.
- Carbon source gasses also may include hydrofluorocarbons or hydrocarbons.
- the hydrocarbon carbon source is methane. This was unexpected, as it is commonly held in the art that hydrogen atoms in the activated gas mixture are detrimental due to the expected recombination of F atoms with H atoms to form hydrogen fluoride (HF). This would decrease gas phase reactive F atoms concentrations as well as be deleterious to surfaces inside the apparatus.
- Typical nitrogen sources include molecular nitrogen (N 2 ) and NF 3 .
- NF 3 is the inorganic fluorine source, it can also serve as the nitrogen source.
- Typical oxygen sources include molecular oxygen (O 2 ), carbon dioxide, sulfur dioxide and sulfur trioxide.
- carbon dioxide is the oxygen source, it can also serve as a carbon source.
- sulfur dioxide or sulfur trioxide are the oxygen source, they can also serve as a sulfur source.
- the fluorocarbon when the fluorocarbon is a fluoroketone, fluoroaldehyde, fluoroether, carbonyl difluoride (COF 2 ) or otherwise contains an O atom, such as octafluorotetrahydrofuran, the fluorocarbon can also serve as the oxygen source.
- the oxygen:fluorocarbon molar ratio is at least 0.75:1.
- the oxygen ifluorocarbon molar ratio is at least 1 :1.
- the oxygen :fluorocarbon molar ratio may be 2:1.
- the percentage on a molar basis of inorganic fluorine source in the gas stream is from about 50% to about 98%. In another embodiment of the invention the percentage on a molar basis of inorganic fluorine source in the gas stream is from about 60% to about 98%. In yet another embodiment of the invention, the percentage on a molar basis of inorganic fluorine source in the gas stream is from about 70% to about 90%. In yet another embodiment of the invention, when NF 3 is the source for nitrogen and fluorine and carbon dioxide is the carbon and oxygen source, the percentage on a molar basis of carbon dioxide in the gas stream is from about 2% to about 15%.
- the gas mixture may further comprise a carrier gas. Examples of suitable carrier gasses include noble gasses such as argon and helium.
- the activated gas mixture contains from about 66% to about 87% fluorine atoms. In one embodiment, the activated gas mixture contains from about 11% to about 24% nitrogen atoms. In one embodiment, the activated gas mixture contains from about 0.9% to about 11% oxygen atoms. In one embodiment, the activated gas mixture contains about 0.6% to about 11 % carbon atoms, 0.6% to about 11% sulfur atoms, or mixtures thereof.
- the activated gas mixture includes from about 66% to about 74% fluorine atoms, from about 11% to about 24% nitrogen atoms, from about 0.9% to about 11% oxygen atoms, and from about 0.6% to about 11% carbon atoms.
- the temperature in the process chamber during removal of the surface deposits often may be from about 50 °C to about 200 °C. Depending on the location within the apparatus, surface temperatures however may range as high as 400° C.
- the total pressure in the remote chamber during the activating step may be between about 0.5 torr and about 15 torr using the Astron source.
- the total pressure in the process chamber may be between about 0.5 torr and about 15 torr. With other types of remote plasma sources or in situ plasma sources, the maximum pressure can be reduced.
- Figure 1 shows a schematic diagram of a remote plasma source and apparatus used to measure the etching rates, plasma neutral temperatures, and exhaust emissions.
- the remote plasma source is a commercial toroidal-type MKS ASTRON®ex reactive gas generator unit make by MKS Instruments, Andover, MA, USA.
- FIG. 2 Shown in Figure 2 is another embodiment in which the cleaning gases are mixed using mass flow controller, 102, in this case NF 3 , C 2 F 6 , and O 2 ; however, other mixtures may be used.
- Argon is included to facilitate starting of the Astron®ex source, 101, and can be added during the cleaning process as well.
- An Astron®ex is used in this example, however other remote source may be used.
- the deposition gases are blocked by valve 103.
- the output of the remote plasma source is directed to the chamber through an optional flow restricting device, 104, through the showerhead, 105, which serves as a conduit into the process chamber, 100, and/or directly to the process chamber through a direct conduit, 106.
- the flow restricting device can be an orifice or a valve.
- valves 107 and 108 By use of valves 107 and 108 to vary the direct flow of part or all of the activated gas to the process chamber, the pressure drop and loss of reactant species in the shower head can be reduced allowing greater cleaning rates of the chamber. Combinations of flows through the showerhead, and into the chamber bypassing the showerhead, can be tailored during the cleaning process to optimize the cleaning of the deposits which are peculiar to the particular chamber and process conditions used during the PECVD process. Although the substrate is shown on the mount, it is typically not present during cleaning of the chamber.
- the process chamber can be controlled to control the partial pressure of the reactant during the cleaning process in the process chamber and/or in the exhaust line between the chamber and the pump.
- the reduced loss rate of reactants by surface recombination allows the increase in cleaning gas pressure without excessive loss of the reactants.
- the higher partial pressure of the reactant gases can increase the cleaning rate and efficiency.
- the number, positions, and setting of the throttle valves 109 and 110 can be adjusted before or during the cleaning process to optimize the cleaning of the process chamber and pump exhaust (fore) line. Shown in this example is the use of two throttle valves; however one or more valves may be used.
- valves to optimize the cleaning of the deposits are peculiar to the particular chamber and process conditions used during the PECVD process as well as a function of the temperature of the surfaces and other particulars of the system, but can readily be determined by one of ordinary skill in the art without undue experimentation.
- the feed gases e.g. O 2 , fluorocarbon, NF 3 and carrier gas
- the oxygen is manufactured by Airgas with 99.999% purity.
- the fluorocarbon in the examples is either Zyron® 8020 manufactured by DuPont with a minimum 99.9 vol. % of octafluorocyclobutane or Zyron® 116 N5 manufactured by DuPont with a minimum 99.9 vol. % of hexafluoroethane.
- the NF 3 gas is manufactured by DuPont with 99.999% purity.
- Argon is manufactured by Airgas with a grade of 5.0. Typically, Ar gas is used to ignite the plasmas, after which time flows for the feed gases were initiated, after Ar flow was halted. The activated gas mixture then is passed through an aluminum water-cooled heat exchanger to reduce the thermal loading of the aluminum process chamber. The surface deposits covered wafer was placed on a temperature controlled mounting in the process chamber. The neutral temperature is measured by Optical Emission Spectroscopy (OES), in which rotovibrational transition bands of diatomic species like C- 2 and N 2 are theoretically fitted to yield neutral temperature. See also B. Bai and H Sawin, Journal of Vacuum Science & Technology A 22 (5), 2014 (2004), which is herein incorporated by reference.
- OES Optical Emission Spectroscopy
- the etching rate of surface deposits by the activated gas is measured by interferometry equipment in the process chamber.
- N 2 gas is added at the entrance of the exhaustion pump both to dilute the products to a proper concentration for FTIR measurement and to reduce the hang-up of products in the pump.
- FTIR was used to measure the concentration of species in the pump exhaust.
- This example illustrates the effect of the addition of fluorocarbon on the silicon nitride etch rate in NF 3 systems with oxygen at different gas compositions and different wafer temperatures.
- the feed gas was composed of NF 3 , oxygen and C 2 F 6 .
- Process chamber pressure was 5 torr.
- Total gas flow rate was 1700 seem, with flow rates for the individual gases set proportionally as required for each experiment.
- the oxygen flow rate was 150 seem
- the C 2 F 6 flow rate was 150 seem
- the NF 3 flow rate was 1400 seem.
- the feeding gas was activated by the 400 kHz 5.9-8.7 kW RF power.
- the activated gas then entered the process chamber and etched the silicon nitride surface deposits on the mounting with the temperature controlled at 50 °C.
- the temperature controlled at 50 °C As shown in Figure 3, when 3.5 mole percent oxygen and 2.3 mole percent fluorocarbon were added, the etch rate was over 2500 A/min, and exhibited low sensitivity to variations in the amounts of fluorocarbon and oxygen addition. The same phenomena were observed in all wafer temperatures tested: 5O 0 C, 100 0 C , 15O 0 C and 200 0 C.
- This example illustrated the effect of the addition of fluorocarbon on the silicon nitride etch rate in NF 3 systems with oxygen and the reduced effect of source pressure on etch rate.
- the results are illustrated in Figure 4.
- the feed gas was composed of NF 3 , optionally with O 2 and optionally with C 2 F 6 .
- Process chamber pressure was 2 torr.
- Total gas flow rate was 1700 seem, with flow rates for the individual gases set proportionally as required for each experiment.
- the NF 3 flow rate was 1550 seem and the oxygen flow rate was 150 seem.
- the feeding gas was activated by the 400 kHz 5.0-9.0 kW RF power to a neutral temperature of more than 3000 K.
- the activated gas then entered the process chamber and etched the silicon nitride surface deposits on the mounting with the temperature controlled at 50 0 C.
- Figure 3 when 9 mole percent fluorocarbon and 9 mole percent oxygen were added to NF 3 , high etching rates for silicon nitride were obtained, and the rate exhibited very low sensitivity to variations in source pressure.
- This example illustrates the effect of the addition of C 2 F 6 on the silicon nitride etch rate in mixtures of NF 3 and oxygen with a chamber pressure of 3.0 torr.
- Total gas flow rate was 1700 seem.
- the results are illustrated in Figure 5.
- the feeding gas was activated by the 400 kHz 4.6 Kw RF power to a neutral temperature of more than 3000 K. As the results indicate, when 9 mole percent C 2 F 6 is added to the feed gas, i.e.
- the feed gas mixture was composed of 9 mole percent C 2 F6, 9 mole percent oxygen and 82 mole percent NF 3 , the etching rate of silicon nitride increase to from about 2200 A/min to about 2450 A/min, and exhibited lower variation with variations in source pressure.
- This example illustrates the effect of the addition of C 2 F 6 on the silicon nitride etch rate in mixtures of NF 3 and oxygen and variations in the molar ratio of C 2 Fe to oxygen with a chamber pressure of 5.0 torr.
- Total gas flow rate was 1700 seem.
- the results are illustrated in Figure 6.
- the feeding gas was activated by the 400 kHz RF power to a neutral temperature of more than 3000 K. It was found that the highest etch rate and low variation with variations in source pressure were obtained with an oxygen to C 2 F 6 ratio of 1 :1. That is, with a feed gas mixture of 9 mole percent C 2 F 6 , 9 mole percent oxygen, and 82 mole percent NF 3 .
- Silicon nitride etch rates with this feed gas composition were from about 2050 to about 2300 A/min compared to from about 950 A/min to about 1250 A/min with a oxygen:fluorocarbon ratio of 2:1.
- This example illustrates the effect of process chamber temperature on silicon nitride etch rate using a feed gas mixture of 9 mole percent C 2 F 6 , 9 mole percent oxygen, and 82 mole percent NF 3 and a chamber pressure of 2 torr.
- Total gas flow rate was 1700 seem.
- the results are illustrated in Figure 7.
- the feeding gas was activated by the 400 kHz 6.0 ⁇ 6.6 kW RF power to a neutral temperature of more than 3000 K. It was found that etch rate increases somewhat as the chamber temperature is increased from 50 0 C to 100 °C. No significant difference in this trend was observed with changes is source pressure.
- This example illustrates the effect of process chamber temperature on silicon nitride etch rate using a feed gas mixture of 9 mole percent C 2 F 6 , 9 mole percent oxygen, and 82 mole percent NF 3 and a chamber pressure of 3 torr.
- Total gas flow rate was 1700 seem.
- the results are illustrated in Figure 8.
- the feeding gas was activated by the 400 kHz 6.7-7.2 kW RF power to a neutral temperature of more than 3000 K. It was found that etch rate increases somewhat as the chamber temperature is increased from 50°C to 100 °C. At 100 °C there is little variation in etch rate with changes in source pressure.
- Example 7 compares nitride etching using octafluorocyclobutane as the fluorocarbon.
- the feed gas mixtures were either 9 mole percent C 2 F 6l 9 mole percent oxygen, and 82 mole percent NF 3 , or 4.5 mole percent C 4 F 8 , 9 mole percent oxygen, and 86.5 mole percent NF 3 .
- Total gas flow rate was 1700 seem.
- the chamber pressure was 2 torr.
- the feeding gas was activated by the 400 kHz 6.5 Kw RF power to a neutral temperature of more than 3000 K.
- the results are illustrated in Figure 9.
- Octafluorocyclobutane exhibited similar etching performance compared to hexafluoroethane with respect to etch rate, and variation with variations in source pressure.
- This example compares nitride etching using octafluorocyclobutane as the fluorocarbon.
- the feed gas mixtures were either 9 mole percent C 2 F6, 9 mole percent oxygen, and 82 mole percent NF 3 , or 4.5 mole percent C 4 Fs, 9 mole percent oxygen, and 86.5 mole percent NF 3 .
- the chamber pressure was 3 torr. Total gas flow rate was 1700 seem.
- the feeding gas was activated by the 400 kHz 6.9 Kw RF power to a neutral temperature of more than 3000 K. The results are illustrated in Figure 10.
- Octafluorocyclobutane exhibited similar etching performance compared to hexafluoroethane with respect to etch rate, and variation with variations in source pressure.
- This example illustrates the effect of the addition of fluorocarbon on the silicon nitride etch rate in NF 3 systems with oxygen at different gas compositions and different wafer temperatures.
- the feed gas was composed of NF 3 , with oxygen and C 2 F 6 .
- Process chamber pressure was 5 torr.
- Total gas flow rate was 4800 seem, with flow rates for the individual gases set proportionally as required for each experiment.
- the oxygen flow rate was 85 seem
- the C 2 F 6 flow rate was 50 seem
- the NF 3 flow rate was 4665 seem.
- the feeding gas was activated by the 400 kHz 5-8 kW RF power.
- the activated gas then entered the process chamber and etched the silicon nitride surface deposits on the mounting with the temperature controlled at 50 °C.
- the etch rate was over 7500 A/min, and exhibited low sensitivity to variations in the amounts of fluorocarbon and oxygen addition.
- the same phenomena were observed in all wafer temperatures tested: 5O 0 C, 100 0 C and 15O 0 C. Even at 1.2 mole % O 2 and 0.8 mole % C 2 F 6 , high etch rates were observed.
- This example illustrates the use of carbon dioxide as a carbon source and oxygen source etching silicon nitride with NF 3 .
- Process chamber pressure was 5 torr.
- Total gas flow rate was 1700 seem, with flow rates for the individual gases set proportionally as required for each experiment.
- the feeding gas was activated by the 400 kHz 5-8 kW RF power.
- the activated gas then entered the process chamber and etched the silicon nitride surface deposits on the mounting with the temperature controlled at 50 0 C.
- the etch rate was 8000 A/min. Etch rates higher than NF 3 alone were observed for up to 13.5% CO 2 .
- This example compares CH 4 and C 2 F 6 as carbon sources in nitride etching experiments in NF 3 systems with oxygen at different gas compositions.
- the feed gas was composed of NF 3 , with oxygen and carbon source.
- Process chamber pressure was 5 torr.
- Total gas flow rate was 1700 seem, with flow rates for the individual gases set proportionally as required for each experiment.
- the feeding gas was activated by the 400 kHz 5-8 kW RF power.
- This example compares a blend of NF 3 / C 2 F 6 / O 2 (82/9/9) with NF 3 alone and NF 3 plus C 2 F 6 with a wafer temperature of 200 0 C.
- Chamber pressures were varied from 0.7 torr to 10 torr.
- the pressure at the remote source was about 15 torr.
- Total gas flow rate was 4800 seem, with flow rates for the individual gasses set proportionally as required for each experiment.
- the valve (104) as illustrated in Figure 2 was replaced with an orifice that was operated in choked flow so that the source pressure remained essentially constant while the chamber pressure was varied.
- This example compares a blend of NF 3 / C 2 F 6 / O 2 (82/9/9) with NF 3 with a wafer temperature of 100 0 C and chamber pressures from 0.7 torr to 5 torr.
- the pressure at the remote source was about 15 torr.
- Total gas flow rate was 4800 seem, with flow rates for the individual gasses set proportionally as required for each experiment.
- the valve (104) as illustrated in Figure 2 was replaced with an orifice that was operated in choked flow so that the source pressure remained essentially constant while the chamber pressure was varied.
- the nitride etch rate using a blend of NF 3 / C 2 F 6 / O 2 is roughly 3 to 4 times that observed with NF 3 alone, and increases with increasing chamber pressure.
Abstract
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JP2008525139A JP2009503905A (en) | 2005-08-02 | 2006-08-02 | Method for removing surface deposits and passivating internal surfaces inside chemical vapor deposition (CVD) chambers |
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US60/704,840 | 2005-08-02 | ||
US77947006P | 2006-03-06 | 2006-03-06 | |
US60/779,470 | 2006-03-06 |
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WO2007027350A2 true WO2007027350A2 (en) | 2007-03-08 |
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PCT/US2006/030032 WO2007027350A2 (en) | 2005-08-02 | 2006-08-02 | Method of removing surface deposits and passivating interior surfaces of the interior of a chemical vapour deposition (cvd) chamber |
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Country | Link |
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JP (1) | JP2009503905A (en) |
KR (1) | KR20080050403A (en) |
RU (1) | RU2008108013A (en) |
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WO (1) | WO2007027350A2 (en) |
Cited By (14)
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WO2007059140A1 (en) * | 2005-11-14 | 2007-05-24 | Massachusetts Institute Of Technology | Method of removing surface deposits from reaction chambers using nf3 |
WO2008039465A2 (en) * | 2006-09-25 | 2008-04-03 | E. I. Du Pont De Nemours And Company | Method for removing surface deposits in the interior of a chemical vapor deposition reactor |
EP1991373A2 (en) * | 2006-02-21 | 2008-11-19 | Applied Materials, Inc. | Enhancement of remote plasma source clean for dielectric films |
WO2010003266A1 (en) * | 2008-07-09 | 2010-01-14 | Oerlikon Solar Ip Ag, Trübbach | Remote plasma cleaning method and apparatus for applying said method |
US20130061870A1 (en) * | 2011-09-13 | 2013-03-14 | Akio Ui | Method of cleaning film forming apparatus |
CN109075066A (en) * | 2016-03-31 | 2018-12-21 | 东京毅力科创株式会社 | Dry etch process feature is controlled using non-wafer dry clean emission spectrum |
US10760158B2 (en) | 2017-12-15 | 2020-09-01 | Lam Research Corporation | Ex situ coating of chamber components for semiconductor processing |
WO2021081289A1 (en) * | 2019-10-25 | 2021-04-29 | Applied Materials, Inc. | Extreme ultraviolet mask blank defect reduction methods |
CN113594017A (en) * | 2016-12-19 | 2021-11-02 | 朗姆研究公司 | Chamber conditioning for remote plasma processing |
US11417503B2 (en) * | 2016-07-12 | 2022-08-16 | Abm Co., Ltd. | Metal component and manufacturing method thereof and process chamber having the metal component |
TWI794238B (en) * | 2017-07-13 | 2023-03-01 | 荷蘭商Asm智慧財產控股公司 | Apparatus and method for removal of oxide and carbon from semiconductor films in a single processing chamber |
US11732355B2 (en) | 2018-12-20 | 2023-08-22 | Applied Materials, Inc. | Method and apparatus for supplying improved gas flow to a processing volume of a processing chamber |
US11761079B2 (en) | 2017-12-07 | 2023-09-19 | Lam Research Corporation | Oxidation resistant protective layer in chamber conditioning |
US11920239B2 (en) | 2015-03-26 | 2024-03-05 | Lam Research Corporation | Minimizing radical recombination using ALD silicon oxide surface coating with intermittent restoration plasma |
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KR101630234B1 (en) * | 2009-11-17 | 2016-06-15 | 주성엔지니어링(주) | Method of Cleaning Process Chamber |
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WO2007059140A1 (en) * | 2005-11-14 | 2007-05-24 | Massachusetts Institute Of Technology | Method of removing surface deposits from reaction chambers using nf3 |
EP1991373A2 (en) * | 2006-02-21 | 2008-11-19 | Applied Materials, Inc. | Enhancement of remote plasma source clean for dielectric films |
EP1991373A4 (en) * | 2006-02-21 | 2009-07-01 | Applied Materials Inc | Enhancement of remote plasma source clean for dielectric films |
WO2008039465A2 (en) * | 2006-09-25 | 2008-04-03 | E. I. Du Pont De Nemours And Company | Method for removing surface deposits in the interior of a chemical vapor deposition reactor |
WO2008039465A3 (en) * | 2006-09-25 | 2008-12-18 | Du Pont | Method for removing surface deposits in the interior of a chemical vapor deposition reactor |
WO2010003266A1 (en) * | 2008-07-09 | 2010-01-14 | Oerlikon Solar Ip Ag, Trübbach | Remote plasma cleaning method and apparatus for applying said method |
US20130061870A1 (en) * | 2011-09-13 | 2013-03-14 | Akio Ui | Method of cleaning film forming apparatus |
US11920239B2 (en) | 2015-03-26 | 2024-03-05 | Lam Research Corporation | Minimizing radical recombination using ALD silicon oxide surface coating with intermittent restoration plasma |
CN109075066A (en) * | 2016-03-31 | 2018-12-21 | 东京毅力科创株式会社 | Dry etch process feature is controlled using non-wafer dry clean emission spectrum |
CN109075066B (en) * | 2016-03-31 | 2023-08-04 | 东京毅力科创株式会社 | Method for controlling dry etching process using waferless dry cleaning emission spectrum |
US11417503B2 (en) * | 2016-07-12 | 2022-08-16 | Abm Co., Ltd. | Metal component and manufacturing method thereof and process chamber having the metal component |
CN113594017A (en) * | 2016-12-19 | 2021-11-02 | 朗姆研究公司 | Chamber conditioning for remote plasma processing |
TWI794238B (en) * | 2017-07-13 | 2023-03-01 | 荷蘭商Asm智慧財產控股公司 | Apparatus and method for removal of oxide and carbon from semiconductor films in a single processing chamber |
US11761079B2 (en) | 2017-12-07 | 2023-09-19 | Lam Research Corporation | Oxidation resistant protective layer in chamber conditioning |
US11365479B2 (en) | 2017-12-15 | 2022-06-21 | Lam Research Corporation | Ex situ coating of chamber components for semiconductor processing |
US10760158B2 (en) | 2017-12-15 | 2020-09-01 | Lam Research Corporation | Ex situ coating of chamber components for semiconductor processing |
US11732355B2 (en) | 2018-12-20 | 2023-08-22 | Applied Materials, Inc. | Method and apparatus for supplying improved gas flow to a processing volume of a processing chamber |
WO2021081289A1 (en) * | 2019-10-25 | 2021-04-29 | Applied Materials, Inc. | Extreme ultraviolet mask blank defect reduction methods |
Also Published As
Publication number | Publication date |
---|---|
KR20080050403A (en) | 2008-06-05 |
TW200711757A (en) | 2007-04-01 |
WO2007027350A3 (en) | 2007-05-03 |
RU2008108013A (en) | 2009-09-10 |
JP2009503905A (en) | 2009-01-29 |
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