US20230100659A1 - Reduction of br2 and cl2 in semiconductor processes - Google Patents
Reduction of br2 and cl2 in semiconductor processes Download PDFInfo
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- US20230100659A1 US20230100659A1 US18/077,087 US202218077087A US2023100659A1 US 20230100659 A1 US20230100659 A1 US 20230100659A1 US 202218077087 A US202218077087 A US 202218077087A US 2023100659 A1 US2023100659 A1 US 2023100659A1
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- 238000000034 method Methods 0.000 title claims abstract description 174
- 239000004065 semiconductor Substances 0.000 title claims abstract description 20
- 239000007789 gas Substances 0.000 claims abstract description 103
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 35
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 12
- 239000005431 greenhouse gas Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 239000006227 byproduct Substances 0.000 claims description 15
- 239000011261 inert gas Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 7
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000004429 atom Chemical group 0.000 claims 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 3
- 229910052760 oxygen Inorganic materials 0.000 claims 3
- 239000001301 oxygen Substances 0.000 claims 3
- 238000005086 pumping Methods 0.000 claims 1
- 231100000331 toxic Toxicity 0.000 abstract description 8
- 230000002588 toxic effect Effects 0.000 abstract description 8
- 125000001246 bromo group Chemical group Br* 0.000 abstract description 3
- 125000001309 chloro group Chemical group Cl* 0.000 abstract description 3
- 210000002381 plasma Anatomy 0.000 description 46
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 32
- 239000000758 substrate Substances 0.000 description 7
- 230000004792 oxidative damage Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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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
- H01J37/32816—Pressure
- H01J37/32834—Exhausting
- H01J37/32844—Treating effluent gases
-
- 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
- H01J37/32082—Radio frequency generated discharge
-
- 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
- H01J37/32082—Radio frequency generated discharge
- H01J37/321—Radio frequency generated discharge the radio frequency energy being inductively coupled to the plasma
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32431—Constructional details of the reactor
- H01J37/3244—Gas supply means
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32431—Constructional details of the reactor
- H01J37/3244—Gas supply means
- H01J37/32449—Gas control, e.g. control of the gas flow
-
- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/3065—Plasma etching; Reactive-ion etching
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/30—Capture or disposal of greenhouse gases of perfluorocarbons [PFC], hydrofluorocarbons [HFC] or sulfur hexafluoride [SF6]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- One or more embodiments described herein generally relate to abatement systems for semiconductor processes, and more particularly, to abatement systems for reducing Br 2 and Cl 2 in semiconductor processes.
- Process gases used by semiconductor processing facilities include many compounds that must be abated or treated before disposal, due to regulatory requirements and environmental concerns.
- etch processes among others, often use fluorinated greenhouse gases (F-GHGs) such as CF 4 , SF 6 , C 4 F 8 , and CHF 3 .
- F-GHGs fluorinated greenhouse gases
- other process gases such as HBr and Cl 2 are often used to improve selectivity and reduce oxidative damage to substrate surfaces during etch processes. Under energetic conditions, HBr is known to equilibrate with H 2 +Br 2 .
- Br 2 and Cl 2 are corrosive and toxic, causing environment concerns. Br 2 is liquid at room temperature and may accumulate in the exhaust duct under certain conditions. Additionally, Br 2 and Cl 2 are not water soluble and may not be completely abated in wet scrubbers. As HBr and Cl 2 flows increase in etch processes due to larger substrates being used in semiconductor processes, increasing Br 2 and Cl 2 emissions are problematic.
- One or more embodiments described herein relate to methods for abating process gases.
- a method for abating process gases includes performing a semiconductor etch process within a process chamber using process gases including fluorinated greenhouse gases (F-GHGs), HBr, and Cl 2 , wherein the process gases are configured to flow out of the process chamber into a plasma reactor; introducing reagent gases from a reagent gas delivery system to the plasma reactor to react with the process gases; and applying RF power to the plasma reactor; wherein a ratio of a reagent gas flow rate to a HBr flow rate is greater than 2:1.
- F-GHGs fluorinated greenhouse gases
- HBr HBr
- Cl 2 fluorinated greenhouse gases
- a method for abating process gases includes performing a semiconductor etch process within a process chamber using process gases including fluorinated greenhouse gases (F-GHGs), HBr, and Cl 2 wherein the process gases are configured to flow out of the process chamber into a plasma reactor; introducing reagent gases from a reagent gas delivery system to the plasma reactor to react with the process gases; and applying RF power to the plasma reactor; wherein a ratio of a regent gas flow rate to a Br 2 byproduct gas is greater than 8:1.
- F-GHGs fluorinated greenhouse gases
- HBr HBr
- Cl 2 reactive oxygen species
- a process system includes a process chamber; a plasma reactor located downstream of the process chamber; a reagent gas delivery apparatus located between the process chamber and the plasma reactor; a vacuum pump located downstream of the plasma reactor; a wet scrubber located downstream of the vacuum pump; an inert gas delivery apparatus located between the plasma reactor and the vacuum pump; and a controller configured to receive information from the process system, and when executed by a processor performs an operation, including: performing a semiconductor etch process within the process chamber using process gases including fluorinated greenhouse gases (F-GHGs), HBr, and Cl 2 , wherein the process gases are configured to flow out of the process chamber into the plasma reactor; introducing water vapor (H 2 O) from the reagent gas delivery system to the plasma reactor to react with the process gases; and applying RF power to the plasma reactor; wherein a ratio of a H 2 O flow rate to a HBr flow rate is greater than 2:1; and a ratio a H 2 O flow rate to a bromine (Br 2 ) by
- FIG. 1 is a schematic view of a process system according to at least one embodiment described herein;
- FIG. 2 is a flow chart of a method according to at least one embodiment described herein.
- One or more embodiments described herein relate to abatement systems for reducing Br 2 and Cl 2 in semiconductor processes.
- semiconductor etch processes are performed within process chambers.
- F-GHGs such as CF 4 , SF 6 , C 4 F 8 , and CHF 3 are often used.
- other process gases such as HBr and Cl 2 are often used to improve selectivity and reduce oxidative damage to substrate surfaces during etch processes.
- the F-GHGs, HBr, and Cl 2 gases exit the process chamber and enter a plasma reactor.
- reagent gases which include hydrogen and oxygen atoms
- reagent gases are delivered from a reagent gas delivery apparatus to the plasma reactor to mix with the process gases.
- Radio frequency (RF) power is applied to the plasma reactor, which adds energy and “excites” the gases within the plasma reactor.
- the gases within the plasma reactor get excited, the gases dissociate to the atomic level. Thereafter, the atomic elements recombine to form more stable, water soluble compounds which helps greatly reduce or eliminate the F-GHGs which often cause environmental concerns if they exit to the environment.
- HBr is energized within the process chamber and the plasma reactor, it is known to equilibrate with H 2 +Br 2 . As discussed above, Br 2 is corrosive and toxic.
- H 2 O is corrosive and toxic.
- H 2 O the addition of H 2 O in the plasma reactor quenches the Br 2 and Cl 2 emissions, as the H atoms recombine with the Br atoms and the Cl atoms to form HBr and HCl.
- HBr and HCl are readily water-soluble and removed through a wet scrubber, whereas Br 2 and Cl 2 are not effectively abated in a wet scrubber.
- the embodiments described herein provide advantages over conventional abatement systems.
- H atoms do not recombine as effectively to form HBr and HCl, often leaving high amounts of toxic Br 2 and Cl 2 , which are not abated through the wet scrubber.
- Br 2 is liquid at room temperature and may accumulate in the exhaust duct of the process system under certain conditions.
- Br 2 and Cl 2 are converted to water-soluble HBr and HCl, respectively, and the problems above are reduced or eliminated. Additionally, the F-GHGs are greatly reduced and/or eliminated.
- FIG. 1 is a schematic view of a process system 100 according to at least one embodiment described herein.
- the process system 100 includes a process chamber 102 .
- the process chamber 102 is configured to perform semiconductor etch processes to process a substrate.
- the process chamber 102 may be a plasma enhanced chemical vapor deposition (PECVD) chamber configured to perform process material deposition or etching.
- PECVD plasma enhanced chemical vapor deposition
- other chambers can also be used and modified with the embodiments described herein.
- F-GHGs such as CF 4 , SF 6 , C 4 F 8 , and CHF 3 are often used with the process chamber 102 .
- the F-GHGs gases are used to achieve the required anisotropy required in etch processes, especially for deep trench etch processes.
- other process gases such as HBr and Cl 2 are often used to improve selectivity and reduce oxidative damage to substrate surfaces during etch processes.
- the F-GHGs, HBr, and Cl 2 gases are configured to flow out of the process chamber 102 and enter a plasma reactor 106 .
- the plasma reactor 106 is located downstream of the process chamber 102 .
- RF power is applied to the plasma reactor 106 via a remote plasma source 107 .
- the plasma source 107 can be an inductively coupled plasma source and may include a solid state match network.
- the amount of RF power applied may be between about 2000 and about 4000 watts, although other amounts of RF power are also possible.
- the process system 100 also includes a reagent gas delivery apparatus 104 configured to deliver reagent gases, such as water vapor (H 2 O), H 2 , and O 2 , to the plasma reactor 106 to mix with the process gases exiting the process chamber 102 .
- reagent gas delivery apparatus 104 may be a water delivery system configured to introduce water vapor to supply hydrogen and oxygen atoms to the plasma.
- the amount of each of the process gases within the plasma reactor 106 varies, and ratios of each of the different gases within the plasma reactor 106 can vary.
- the ratio of the H 2 O vapor flow rate to the HBr chamber flow rate is greater than 2:1.
- the ratio of the H 2 O vapor flow rate to the HBr chamber flow rate is greater than 5:1.
- the ratio of the H 2 O vapor flow rate to Br 2 byproduct gas is greater than 8:1.
- the ratio of the H 2 O vapor flow rate to Br 2 byproduct gas is greater than 15:1.
- Water vapor supplied from the reagent gas delivery apparatus 104 mixes with the process gases exiting the process chamber 102 within the plasma reactor 106 .
- the plasma source 107 adds energy, which dissociates the process gases to the atomic level. Thereafter, the atomic elements recombine with the water vapor to form more stable, water soluble compounds which helps greatly reduce or eliminate the F-GHGs which often cause environmental concerns if they exit to the environment.
- HBr is energized within the process chamber and the plasma reactor, it is known to equilibrate with H 2 +Br 2 .
- Br 2 is corrosive and toxic.
- Cl 2 is corrosive and toxic.
- H 2 O in the plasma reactor 107 quenches the Br 2 and Cl 2 emissions, as the H atoms recombine with the Br atoms and the Cl atoms to form HBr and HCl.
- HBr and HCl provide an advantage over conventional abatement systems, in which H atoms do not recombine as effectively to form HBr and HCl, often leaving high amounts of toxic Br 2 and Cl 2 .
- Br 2 is liquid at room temperature and may accumulate in the exhaust duct of the process system 100 under certain conditions.
- the process system 100 includes an inert gas delivery apparatus 108 located downstream of the plasma reactor 106 .
- Inert gases can be delivered to the process system 100 via the inert gas delivery apparatus 108 .
- a vacuum pump 110 is located downstream of the inert gas delivery apparatus 108 . Therefore, the inert gas delivery apparatus 108 is located between the plasma reactor 106 and the vacuum pump 110 .
- the vacuum pump 110 may be used to pump the gases exiting the plasma reactor 106 and the inert gas delivery apparatus 108 to a wet scrubber 112 .
- the wet scrubber 112 is located downstream of the vacuum pump 110 .
- the wet scrubber 112 may be a bubble tower, packed bed tower, or scrubbing tower.
- the wet scrubber 112 acts to abate the remaining gases in the process system 100 before they exit into the environment.
- the wet scrubber 112 does not abate Br 2 and Cl 2 well, as they are not water soluble.
- the wet scrubber 112 does abate HBr and HCl well, as they are water soluble. Therefore, the embodiments described herein provide the advantage of providing a greater amount of HBr and HCl, such that they can be more easily abated by the wet scrubber 112 before exiting into the environment.
- the process system 100 is controlled by a controller 114 .
- the controller 114 is in communication with hardware contained within the entire process system 100 , which acts to control the process parameters within the process system 100 .
- the controller 114 may include a central processing unit (CPU) 114 A, memory 114 B, and support circuits (or I/O) 114 C.
- the CPU 114 A may be one of any form of computer processors that are used in industrial settings for controlling various processes and hardware and monitor the processes.
- the memory 114 B is connected to the CPU 114 A, and may be one or more of a readily available memory, such as random access memory (RAM), read only memory (ROM), floppy disk, hard disk, or any other form of digital storage, local or remote.
- RAM random access memory
- ROM read only memory
- floppy disk hard disk, or any other form of digital storage, local or remote.
- Software instructions, algorithms and data can be coded and stored within the memory 114 B for instructing the CPU 114 A.
- the support circuits 114 C are also connected to the CPU 114 A for supporting the processor in a conventional manner.
- the support circuits 114 C may include conventional cache, power supplies, clock circuits, input/output circuitry, subsystems, and the like.
- a program (or computer instructions) readable by the controller determines which tasks are performable within the process system 100 .
- the program may be software readable by the controller 114 and may include code to monitor and control, the process parameters within the process system 100 .
- FIG. 2 is a flow chart of a method 200 according to at least one embodiment described herein.
- the method 200 is performed with the devices described in FIG. 1 , but is not limited to these devices and can be performed with other similar devices.
- a semiconductor deposition process is performed within the process chamber 102 .
- the semiconductor processes can be etch processes, in which F-GHGs such as CF 4 , SF 6 , C 4 F 8 , and CHF 3 are often used.
- F-GHGs such as CF 4 , SF 6 , C 4 F 8 , and CHF 3
- other process gases such as HBr and Cl 2 are often used to improve selectivity and reduce oxidative damage to substrate surfaces during etch processes.
- reagent gases are introduced to the plasma reactor 106 from a reagent gas delivery apparatus 104 .
- the reagent gases mix with the process gases exiting the process chamber 102 .
- the reagent gas delivery apparatus 104 may be a water delivery system configured to introduce water to supply hydrogen and oxygen atoms to the plasma reactor 106 .
- the amount of each of the process gases within the plasma reactor 106 varies, and ratios of each of the different gases within the plasma reactor 106 can vary.
- the ratio of the H 2 O vapor flow rate to the HBr chamber flow rate is greater than 2:1.
- the ratio of the H 2 O vapor flow rate to the HBr chamber flow rate is greater than 5:1.
- the ratio of the H 2 O vapor flow rate to Br 2 byproduct gas is greater than 8:1.
- the ratio of the H 2 O vapor flow rate to Br 2 byproduct gas is greater than 15:1.
- Ratios of HBr and Cl 2 can also be compared with the other gases in the plasma reactor 106 .
- the ratio of the H 2 O vapor flow rate to Cl 2 byproduct gas is greater than 8:1.
- the ratio of the H 2 O vapor flow rate to Cl 2 byproduct gas is greater than 15:1.
- RF power is applied to the plasma reactor 106 .
- the RF power can be applied via a remote plasma source 107 .
- the amount of RF power applied may be about 4000 watts, although other amounts of RF power are also possible.
- inert gases are delivered to the process system 100 via the inert gas delivery apparatus 108 .
- Embodiments described by method 200 provide advantageous results compared to conventional abatement processes.
- the F-GHGs such CF 4 and SF 6
- the F-GHGs are 95% abated.
- Br 2 emissions are reduced from the process chamber 102 by about 30 to 40% compared to conventional processes and Cl 2 emissions are reduced from the process chamber 102 by about 90% compared to conventional processes. Therefore, lesser quantities of the damaging F-GHGs, Br 2 , and Cl 2 gases exit the process system 100 when performing the method 200 . Reducing these potentially harmful emissions becomes even more important as greater amounts of HBr and Cl 2 are used to etch larger substrates within the process chamber 102 during semiconductor processes.
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Abstract
One or more embodiments described herein relate to abatement systems for reducing Br2 and Cl2 in semiconductor processes. In embodiments described herein, semiconductor etch processes are performed within process chambers. Thereafter, fluorinated greenhouse gases (F-GHGs), HBr, and Cl2 gases exit the process chamber and enter a plasma reactor. Reagent gases are delivered from a reagent gas delivery apparatus to the plasma reactor to mix with the process gases. Radio frequency (RF) power is applied to the plasma reactor, which adds energy and “excites” the gases within the process chamber. When HBr is energized, it forms Br2. Br2 and Cl2 are corrosive and toxic. However, the addition of H2O in the plasma reactor quenches the Br2 and Cl2 emissions, as the H atoms recombine with the Br atoms and the Cl atoms to form HBr and HCl. HBr and HCl are readily water-soluble and removed through a wet scrubber.
Description
- This application is a divisional application of U.S. patent application Ser. No. 16/793,983, filed Feb. 18, 2020, which claims priority to U.S. Provisional Patent Application No. 62/840,345, filed Apr. 29, 2019, and U.S. Provisional Patent Application No. 62/808,943, filed Feb. 22, 2019. All of the above applications are herein incorporated by reference in their entireties.
- One or more embodiments described herein generally relate to abatement systems for semiconductor processes, and more particularly, to abatement systems for reducing Br2 and Cl2 in semiconductor processes.
- Process gases used by semiconductor processing facilities include many compounds that must be abated or treated before disposal, due to regulatory requirements and environmental concerns. For example, etch processes, among others, often use fluorinated greenhouse gases (F-GHGs) such as CF4, SF6, C4F8, and CHF3. Along with F-GHGs, other process gases such as HBr and Cl2 are often used to improve selectivity and reduce oxidative damage to substrate surfaces during etch processes. Under energetic conditions, HBr is known to equilibrate with H2+Br2.
- Process chamber plasmas are energetic enough to result in Br2 formation. Conventional abatement systems are also energetic enough to result in Br2 formation. Br2 and Cl2 are corrosive and toxic, causing environment concerns. Br2 is liquid at room temperature and may accumulate in the exhaust duct under certain conditions. Additionally, Br2 and Cl2 are not water soluble and may not be completely abated in wet scrubbers. As HBr and Cl2 flows increase in etch processes due to larger substrates being used in semiconductor processes, increasing Br2 and Cl2 emissions are problematic.
- Accordingly, there is a need for abatement systems that reduce Br2 and Cl2 in semiconductor processes.
- One or more embodiments described herein relate to methods for abating process gases.
- In one embodiment, a method for abating process gases includes performing a semiconductor etch process within a process chamber using process gases including fluorinated greenhouse gases (F-GHGs), HBr, and Cl2, wherein the process gases are configured to flow out of the process chamber into a plasma reactor; introducing reagent gases from a reagent gas delivery system to the plasma reactor to react with the process gases; and applying RF power to the plasma reactor; wherein a ratio of a reagent gas flow rate to a HBr flow rate is greater than 2:1.
- In another embodiment, a method for abating process gases includes performing a semiconductor etch process within a process chamber using process gases including fluorinated greenhouse gases (F-GHGs), HBr, and Cl2 wherein the process gases are configured to flow out of the process chamber into a plasma reactor; introducing reagent gases from a reagent gas delivery system to the plasma reactor to react with the process gases; and applying RF power to the plasma reactor; wherein a ratio of a regent gas flow rate to a Br2 byproduct gas is greater than 8:1.
- One of more embodiments described related to systems for abating process gases.
- In one embodiment, a process system includes a process chamber; a plasma reactor located downstream of the process chamber; a reagent gas delivery apparatus located between the process chamber and the plasma reactor; a vacuum pump located downstream of the plasma reactor; a wet scrubber located downstream of the vacuum pump; an inert gas delivery apparatus located between the plasma reactor and the vacuum pump; and a controller configured to receive information from the process system, and when executed by a processor performs an operation, including: performing a semiconductor etch process within the process chamber using process gases including fluorinated greenhouse gases (F-GHGs), HBr, and Cl2, wherein the process gases are configured to flow out of the process chamber into the plasma reactor; introducing water vapor (H2O) from the reagent gas delivery system to the plasma reactor to react with the process gases; and applying RF power to the plasma reactor; wherein a ratio of a H2O flow rate to a HBr flow rate is greater than 2:1; and a ratio a H2O flow rate to a bromine (Br2) byproduct gas is greater than 15:1.
- 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 typical embodiments of this disclosure and are therefore not to be considered limiting of its scope, for the disclosure may admit to other equally effective embodiments.
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FIG. 1 is a schematic view of a process system according to at least one embodiment described herein; and -
FIG. 2 is a flow chart of a method according to at least one embodiment described herein. - In the following description, numerous specific details are set forth to provide a more thorough understanding of the embodiments of the present disclosure. However, it will be apparent to one of skill in the art that one or more of the embodiments of the present disclosure may be practiced without one or more of these specific details. In other instances, well-known features have not been described in order to avoid obscuring one or more of the embodiments of the present disclosure.
- One or more embodiments described herein relate to abatement systems for reducing Br2 and Cl2 in semiconductor processes. In embodiments described herein, semiconductor etch processes are performed within process chambers. During certain processes, such as etch processes, F-GHGs such as CF4, SF6, C4F8, and CHF3 are often used. Along with the F-GHGs, other process gases such as HBr and Cl2 are often used to improve selectivity and reduce oxidative damage to substrate surfaces during etch processes. Following the etch processes, the F-GHGs, HBr, and Cl2 gases exit the process chamber and enter a plasma reactor.
- In some embodiments, reagent gases, which include hydrogen and oxygen atoms, are delivered from a reagent gas delivery apparatus to the plasma reactor to mix with the process gases. Radio frequency (RF) power is applied to the plasma reactor, which adds energy and “excites” the gases within the plasma reactor. When the gases within the plasma reactor get excited, the gases dissociate to the atomic level. Thereafter, the atomic elements recombine to form more stable, water soluble compounds which helps greatly reduce or eliminate the F-GHGs which often cause environmental concerns if they exit to the environment. When HBr is energized within the process chamber and the plasma reactor, it is known to equilibrate with H2+Br2. As discussed above, Br2 is corrosive and toxic. Additionally, Cl2 is corrosive and toxic. However, the addition of H2O in the plasma reactor quenches the Br2 and Cl2 emissions, as the H atoms recombine with the Br atoms and the Cl atoms to form HBr and HCl. HBr and HCl are readily water-soluble and removed through a wet scrubber, whereas Br2 and Cl2 are not effectively abated in a wet scrubber.
- As such, the embodiments described herein provide advantages over conventional abatement systems. In conventional abatement systems, H atoms do not recombine as effectively to form HBr and HCl, often leaving high amounts of toxic Br2 and Cl2, which are not abated through the wet scrubber. Additionally, in conventional abatement systems, Br2 is liquid at room temperature and may accumulate in the exhaust duct of the process system under certain conditions. In the embodiments described herein, Br2 and Cl2 are converted to water-soluble HBr and HCl, respectively, and the problems above are reduced or eliminated. Additionally, the F-GHGs are greatly reduced and/or eliminated.
-
FIG. 1 is a schematic view of aprocess system 100 according to at least one embodiment described herein. Theprocess system 100 includes aprocess chamber 102. Theprocess chamber 102 is configured to perform semiconductor etch processes to process a substrate. In some embodiments, theprocess chamber 102 may be a plasma enhanced chemical vapor deposition (PECVD) chamber configured to perform process material deposition or etching. However, other chambers can also be used and modified with the embodiments described herein. During the deposition processes, such as etch processes, potentially damaging F-GHGs such as CF4, SF6, C4F8, and CHF3 are often used with theprocess chamber 102. The F-GHGs gases are used to achieve the required anisotropy required in etch processes, especially for deep trench etch processes. Along with the F-GHGs, other process gases such as HBr and Cl2 are often used to improve selectivity and reduce oxidative damage to substrate surfaces during etch processes. - Following the etch processes, the F-GHGs, HBr, and Cl2 gases are configured to flow out of the
process chamber 102 and enter aplasma reactor 106. Theplasma reactor 106 is located downstream of theprocess chamber 102. RF power is applied to theplasma reactor 106 via aremote plasma source 107. Theplasma source 107 can be an inductively coupled plasma source and may include a solid state match network. In some embodiments, the amount of RF power applied may be between about 2000 and about 4000 watts, although other amounts of RF power are also possible. Theprocess system 100 also includes a reagentgas delivery apparatus 104 configured to deliver reagent gases, such as water vapor (H2O), H2, and O2, to theplasma reactor 106 to mix with the process gases exiting theprocess chamber 102. In some embodiments, the reagentgas delivery apparatus 104 may be a water delivery system configured to introduce water vapor to supply hydrogen and oxygen atoms to the plasma. - The amount of each of the process gases within the
plasma reactor 106 varies, and ratios of each of the different gases within theplasma reactor 106 can vary. In some embodiments, the ratio of the H2O vapor flow rate to the HBr chamber flow rate is greater than 2:1. In other embodiments, the ratio of the H2O vapor flow rate to the HBr chamber flow rate is greater than 5:1. In some embodiments, the ratio of the H2O vapor flow rate to Br2 byproduct gas is greater than 8:1. In other embodiments, the ratio of the H2O vapor flow rate to Br2 byproduct gas is greater than 15:1. In some embodiments, there can be higher amounts of H2O than F-GHGs gases, and vice versa. In other embodiments, there can be higher amounts of H2 and/or O2 than F-GHGs gases, and vice versa. In other embodiments, there can be substantially similar amounts of some or all of the gases within theplasma reactor 106. - Water vapor supplied from the reagent
gas delivery apparatus 104 mixes with the process gases exiting theprocess chamber 102 within theplasma reactor 106. Theplasma source 107 adds energy, which dissociates the process gases to the atomic level. Thereafter, the atomic elements recombine with the water vapor to form more stable, water soluble compounds which helps greatly reduce or eliminate the F-GHGs which often cause environmental concerns if they exit to the environment. When HBr is energized within the process chamber and the plasma reactor, it is known to equilibrate with H2+Br2. As discussed above, Br2 is corrosive and toxic. Additionally, Cl2 is corrosive and toxic. However, the addition of H2O in theplasma reactor 107 quenches the Br2 and Cl2 emissions, as the H atoms recombine with the Br atoms and the Cl atoms to form HBr and HCl. HBr and HCl provide an advantage over conventional abatement systems, in which H atoms do not recombine as effectively to form HBr and HCl, often leaving high amounts of toxic Br2 and Cl2. Additionally, in conventional abatement systems, Br2 is liquid at room temperature and may accumulate in the exhaust duct of theprocess system 100 under certain conditions. - In some embodiments, the
process system 100 includes an inertgas delivery apparatus 108 located downstream of theplasma reactor 106. Inert gases can be delivered to theprocess system 100 via the inertgas delivery apparatus 108. Furthermore, avacuum pump 110 is located downstream of the inertgas delivery apparatus 108. Therefore, the inertgas delivery apparatus 108 is located between theplasma reactor 106 and thevacuum pump 110. Thevacuum pump 110 may be used to pump the gases exiting theplasma reactor 106 and the inertgas delivery apparatus 108 to awet scrubber 112. Thewet scrubber 112 is located downstream of thevacuum pump 110. In some embodiments, thewet scrubber 112 may be a bubble tower, packed bed tower, or scrubbing tower. Any suitable wet scrubber may be used. Thewet scrubber 112 acts to abate the remaining gases in theprocess system 100 before they exit into the environment. Thewet scrubber 112 does not abate Br2 and Cl2 well, as they are not water soluble. However, thewet scrubber 112 does abate HBr and HCl well, as they are water soluble. Therefore, the embodiments described herein provide the advantage of providing a greater amount of HBr and HCl, such that they can be more easily abated by thewet scrubber 112 before exiting into the environment. - In some embodiments, the
process system 100 is controlled by acontroller 114. Thecontroller 114 is in communication with hardware contained within theentire process system 100, which acts to control the process parameters within theprocess system 100. Thecontroller 114 may include a central processing unit (CPU) 114A,memory 114B, and support circuits (or I/O) 114C. TheCPU 114A may be one of any form of computer processors that are used in industrial settings for controlling various processes and hardware and monitor the processes. Thememory 114B is connected to theCPU 114A, and may be one or more of a readily available memory, such as random access memory (RAM), read only memory (ROM), floppy disk, hard disk, or any other form of digital storage, local or remote. Software instructions, algorithms and data can be coded and stored within thememory 114B for instructing theCPU 114A. Thesupport circuits 114C are also connected to theCPU 114A for supporting the processor in a conventional manner. Thesupport circuits 114C may include conventional cache, power supplies, clock circuits, input/output circuitry, subsystems, and the like. A program (or computer instructions) readable by the controller determines which tasks are performable within theprocess system 100. The program may be software readable by thecontroller 114 and may include code to monitor and control, the process parameters within theprocess system 100. -
FIG. 2 is a flow chart of amethod 200 according to at least one embodiment described herein. In these embodiments, themethod 200 is performed with the devices described inFIG. 1 , but is not limited to these devices and can be performed with other similar devices. Inblock 202, a semiconductor deposition process is performed within theprocess chamber 102. The semiconductor processes can be etch processes, in which F-GHGs such as CF4, SF6, C4F8, and CHF3 are often used. Along with the F-GHGs, other process gases such as HBr and Cl2 are often used to improve selectivity and reduce oxidative damage to substrate surfaces during etch processes. - In
block 204, reagent gases are introduced to theplasma reactor 106 from a reagentgas delivery apparatus 104. The reagent gases mix with the process gases exiting theprocess chamber 102. In some embodiments, the reagentgas delivery apparatus 104 may be a water delivery system configured to introduce water to supply hydrogen and oxygen atoms to theplasma reactor 106. - As discussed above, the amount of each of the process gases within the
plasma reactor 106 varies, and ratios of each of the different gases within theplasma reactor 106 can vary. In some embodiments, the ratio of the H2O vapor flow rate to the HBr chamber flow rate is greater than 2:1. In other embodiments, the ratio of the H2O vapor flow rate to the HBr chamber flow rate is greater than 5:1. In some embodiments, the ratio of the H2O vapor flow rate to Br2 byproduct gas is greater than 8:1. In other embodiments, the ratio of the H2O vapor flow rate to Br2 byproduct gas is greater than 15:1. In some embodiments, there can be higher amounts of H2O than F-GHGs gases, and vice versa. In other embodiments, there can be higher amounts of H2 and/or O2 than F-GHGs gases, and vice versa. Ratios of HBr and Cl2 can also be compared with the other gases in theplasma reactor 106. For example, in some embodiments, the ratio of the H2O vapor flow rate to Cl2 byproduct gas is greater than 8:1. In other embodiments, the ratio of the H2O vapor flow rate to Cl2 byproduct gas is greater than 15:1. In other embodiments, there can be substantially similar amounts of some of all of the gases within theplasma reactor 106. - In
block 206, RF power is applied to theplasma reactor 106. The RF power can be applied via aremote plasma source 107. In some embodiments, the amount of RF power applied may be about 4000 watts, although other amounts of RF power are also possible. Inoptional block 208, inert gases are delivered to theprocess system 100 via the inertgas delivery apparatus 108. - Embodiments described by
method 200 provide advantageous results compared to conventional abatement processes. For example, after performing themethod 200, the F-GHGs, such CF4 and SF6, are 95% abated. Additionally, Br2 emissions are reduced from theprocess chamber 102 by about 30 to 40% compared to conventional processes and Cl2 emissions are reduced from theprocess chamber 102 by about 90% compared to conventional processes. Therefore, lesser quantities of the damaging F-GHGs, Br2, and Cl2 gases exit theprocess system 100 when performing themethod 200. Reducing these potentially harmful emissions becomes even more important as greater amounts of HBr and Cl2 are used to etch larger substrates within theprocess chamber 102 during semiconductor processes. - While the foregoing is directed to implementations of the present invention, other and further implementations of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (20)
1. A process system, comprising
a process chamber;
a plasma reactor located downstream of the process chamber;
a reagent gas delivery apparatus located between the process chamber and the plasma reactor;
a vacuum pump located downstream of the plasma reactor;
a wet scrubber located downstream of the vacuum pump;
an inert gas delivery apparatus located between the plasma reactor and the vacuum pump; and
a controller configured to control an operation performed in the process system, the operation comprising:
performing a semiconductor etch process within the process chamber using process gases including fluorinated greenhouse gases (F-GHGs), HBr, and Cl2, wherein the process gases are configured to flow out of the process chamber into the plasma reactor;
introducing water vapor (H2O) from the reagent gas delivery system to the plasma reactor to react with the process gases; and
applying RF power to the plasma reactor; wherein
a ratio of a H2O flow rate to a HBr flow rate is greater than 2:1; and
a ratio a H2O flow rate to a Br2 byproduct gas is greater than 15:1.
2. The process system of claim 1 , wherein the F-GHGs include CF4, SF6, C4F8, and CHF3.
3. The process system of claim 1 , wherein the reagent gas delivery system is configured to supply hydrogen (H) and oxygen (O) atoms to the plasma reactor.
4. The process system of claim 3 , wherein the amount of H and O atoms are greater than the amount of F-GHGs.
5. The process system of claim 3 , wherein the amount of F-GHGs is greater the amount of H and O atoms.
6. The process system of claim 5 , wherein the amount of RF power is between about 2000 Watts and about 4000 Watts.
7. The process system of claim 1 , wherein the F-GHGs include at least one of CF4, SF6, C4F8, or CHF3.
8. A process system, comprising:
a process chamber;
a plasma reactor located downstream of the process chamber;
a reagent gas delivery apparatus located between the process chamber and the plasma reactor;
a vacuum pump located downstream of the plasma reactor;
a wet scrubber located downstream of the vacuum pump;
an inert gas delivery apparatus located between the plasma reactor and the vacuum pump; and
a controller configured to control an operation performed in the process system, the operation comprising:
performing a semiconductor etch process within the process chamber using process gases including fluorinated greenhouse gases (F-GHGs), HBr, and Cl2, wherein the process gases are configured to flow out of the process chamber into the plasma reactor;
introducing a reagent vapor from the reagent gas delivery system to the plasma reactor to react with the process gases;
applying RF power to the plasma reactor converting the process gases at least partially to a Br2 byproduct gas within the plasma reactor and reacting the Br2 byproduct gas with the reagent vapor to form HBr, wherein a ratio of a reagent vapor flow rate to a HBr flow rate of the HBr gas to the process chamber is greater than 2:1; and
introducing an inert gas between the plasma reactor and a pump configured to pump gases exiting the plasma reactor.
9. The process system of claim 8 , wherein a ratio a H2O flow rate to a Br2 byproduct gas is greater than 15:1.
10. The process system of claim 8 , wherein the reagent vapor includes H2O.
11. The process system of claim 8 , wherein the reagent vapor includes hydrogen (H) and oxygen (O) atoms.
12. The process system of claim 10 , wherein the amount of F-GHGs are greater the amount of H and O atoms.
13. The process system of claim 8 , the amount of RF power is between about 2000 Watts and about 4000 Watts.
14. A process system, comprising:
a process chamber;
a plasma reactor located downstream of the process chamber;
a reagent gas delivery apparatus located between the process chamber and the plasma reactor;
a vacuum pump located downstream of the plasma reactor;
a wet scrubber located downstream of the vacuum pump;
an inert gas delivery apparatus located between the plasma reactor and the vacuum pump; and
a controller configured to control an operation performed in the process system, the operation comprising:
performing a semiconductor etch process within the process chamber using process gases including fluorinated greenhouse gases (F-GHGs), HBr, and Cl2, wherein the process gases are configured to flow out of the process chamber into the plasma reactor;
introducing a reagent vapor from the reagent gas delivery system to the plasma reactor to react with the process gases;
applying RF power to the plasma reactor converting the process gases at least partially to a HCL byproduct gas within the plasma reactor and reacting the Cl2 byproduct gas with the reagent vapor to form HCl; and
introducing an inert gas between the plasma reactor and a pump configured to pump gases exiting the plasma reactor.
15. The process system of claim 14 , wherein the reagent vapor includes H2O.
16. The process system of claim 14 , wherein the reagent vapor includes hydrogen (H) and oxygen (O) atoms.
17. The process system of claim 14 , wherein the F-GHGs include at least one of CF4, SF6, C4F8, or CHF3.
18. The process system of claim 16 , wherein the amount of F-GHGs are greater the amount of H and O atoms.
19. The process system of claim 14 , wherein a ratio a H2O flow rate to a Br2 byproduct gas is greater than 15:1.
20. The process system of claim 14 , wherein the operations further comprise pumping gases exiting the plasma reactor and the inert gas into the wet scrubber.
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US6888040B1 (en) * | 1996-06-28 | 2005-05-03 | Lam Research Corporation | Method and apparatus for abatement of reaction products from a vacuum processing chamber |
US6361706B1 (en) * | 1999-08-13 | 2002-03-26 | Philips Electronics North America Corp. | Method for reducing the amount of perfluorocompound gas contained in exhaust emissions from plasma processing |
US20080102011A1 (en) | 2006-10-27 | 2008-05-01 | Applied Materials, Inc. | Treatment of effluent containing chlorine-containing gas |
US20100258510A1 (en) | 2009-04-10 | 2010-10-14 | Applied Materials, Inc. | Methods and apparatus for treating effluent |
US20110023908A1 (en) | 2009-07-30 | 2011-02-03 | Applied Materials, Inc. | Methods and apparatus for process abatement with recovery and reuse of abatement effluent |
US8747762B2 (en) | 2009-12-03 | 2014-06-10 | Applied Materials, Inc. | Methods and apparatus for treating exhaust gas in a processing system |
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US9847225B2 (en) * | 2011-11-15 | 2017-12-19 | Taiwan Semiconductor Manufacturing Company, Ltd. | Semiconductor device and method of manufacturing the same |
US9240308B2 (en) | 2014-03-06 | 2016-01-19 | Applied Materials, Inc. | Hall effect enhanced capacitively coupled plasma source, an abatement system, and vacuum processing system |
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