CN116889785A - Semiconductor manufacturing equipment tail gas treatment system and tail gas treatment method - Google Patents
Semiconductor manufacturing equipment tail gas treatment system and tail gas treatment method Download PDFInfo
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- CN116889785A CN116889785A CN202310869672.5A CN202310869672A CN116889785A CN 116889785 A CN116889785 A CN 116889785A CN 202310869672 A CN202310869672 A CN 202310869672A CN 116889785 A CN116889785 A CN 116889785A
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims description 27
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 68
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 67
- 238000006243 chemical reaction Methods 0.000 claims abstract description 66
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 59
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000011574 phosphorus Substances 0.000 claims abstract description 58
- 230000001590 oxidative effect Effects 0.000 claims abstract description 42
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 266
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 24
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 238000003860 storage Methods 0.000 claims description 12
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 11
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052794 bromium Inorganic materials 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- CTNCAPKYOBYQCX-UHFFFAOYSA-N [P].[As] Chemical compound [P].[As] CTNCAPKYOBYQCX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 abstract description 11
- 238000012423 maintenance Methods 0.000 abstract description 6
- 238000004880 explosion Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000010408 film Substances 0.000 description 6
- 150000004678 hydrides Chemical class 0.000 description 5
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 150000002902 organometallic compounds Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 3
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 230000002269 spontaneous effect Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000407 epitaxy Methods 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000005389 semiconductor device fabrication Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000549527 Fraxinus gooddingii Species 0.000 description 1
- 229910000413 arsenic oxide Inorganic materials 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical class [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/76—Gas phase processes, e.g. by using aerosols
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/10—Oxidants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/10—Oxidants
- B01D2251/102—Oxygen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/10—Oxidants
- B01D2251/104—Ozone
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/10—Oxidants
- B01D2251/108—Halogens or halogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/10—Oxidants
- B01D2251/11—Air
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/55—Compounds of silicon, phosphorus, germanium or arsenic
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
Abstract
The application discloses a semiconductor manufacturing equipment tail gas treatment system, which comprises: a reaction chamber, wherein the tail gas discharged by the reaction chamber contains arsenic and/or phosphorus; a tail gas pipeline for receiving the tail gas exhausted from the reaction chamber; the filter is connected with the reaction chamber through a tail gas pipeline and is used for filtering tail gas discharged by the reaction chamber; the device comprises a gas path system, wherein the gas path system is connected to the tail gas pipeline between the reaction chamber and the filter and is used for conveying oxidizing gas which is subjected to oxidation reaction with active As and/or P into the tail gas pipeline so As to eliminate active arsenic and/or phosphorus in the tail gas. According to the application, the active arsenic and/or phosphorus in the tail gas is eliminated by arranging the active arsenic and phosphorus removing device in the tail gas system, so that the safety of equipment cleaning and maintenance is improved; meanwhile, the oxide after reaction is easier to be filtered by a filter, so that the tail gas filtering efficiency is improved.
Description
Technical Field
The application relates to an exhaust gas treatment system of semiconductor manufacturing equipment, in particular to a device and a method for eliminating active arsenic and phosphorus in the exhaust gas treatment system.
Background
In the field of semiconductors, epitaxial growth of thin film materials is often used for the preparation of photovoltaic devices such as solar cells and LEDs. In the epitaxial process, a thin film is vapor deposited on a substrate (alumina, silicon carbide, gallium arsenide, germanium, etc.) by thermal decomposition reaction in a reaction chamber from a growth raw material such as an organic compound of a group III-V element and a hydride of a group V, VI element. In the process, the reaction chamber continuously stores unreacted complete metal organic compound and hydride and undeposited reaction products, wherein the undeposited reaction products comprise a large amount of H 2 、N 2 And a small amount of AsH 3 、PH 3 Silane, reactive As, P, etc., is discharged to the tail pipe. The effluent is in a gaseous state in a high-temperature low-pressure environment of the reaction chamber, and after being discharged to the tail end, the effluent is continuously cooled to be solid and liquid, and is deposited in the pipe wall of the tail end pipe and the joint gap of the pipe, so that the pipe is easily blocked or the main pump is easily worn for a long time.
In view of the above problems, in the art, a condensation filter is usually selected to be disposed between the reaction chamber and the exhaust outlet, and the effluent of the reaction chamber is filtered, but the condensation filter and the related pipelines thereof need to be cleaned periodically, and during the cleaning operation, the active As and P in the pipelines will undergo severe chemical reaction when encountering air, so that explosion hidden danger exists; if the condensing filter is cleaned by water, a large amount of active As and P float on the water surface and self-ignite immediately, so that serious potential safety hazard exists.
Disclosure of Invention
In response to the above problems and needs for improvement in the art, the present application provides an exhaust gas treatment system for a semiconductor manufacturing apparatus, comprising:
a reaction chamber, wherein the tail gas discharged by the reaction chamber contains arsenic and/or phosphorus;
a tail gas pipeline for receiving the tail gas exhausted from the reaction chamber;
the filter is connected with the reaction chamber through a tail gas pipeline and is used for filtering tail gas discharged by the reaction chamber;
the device comprises a gas path system, wherein the gas path system is connected to the tail gas pipeline between the reaction chamber and the filter and is used for conveying oxidizing gas which is subjected to oxidation reaction with active As and/or P into the tail gas pipeline so As to eliminate active arsenic and/or phosphorus in the tail gas.
According to some embodiments of the application, the gas circuit system comprises a pneumatic valve and a mass flow control valve, and the semiconductor manufacturing equipment tail gas treatment system further comprises a control unit, wherein the control unit controls the flow of the oxidizing gas by controlling the pneumatic valve and the mass flow control valve.
According to some embodiments of the application, the control unit is adapted to control the pneumatic valve and the mass flow control valve to deliver an oxidizing gas that is subjected to an oxidation reaction with active As and/or P into the exhaust gas conduit during semiconductor device fabrication and/or during standby in the semiconductor manufacturing facility.
According to some embodiments of the application, the gas circuit system comprises:
a first gas storage means for storing an oxidizing gas to be subjected to an oxidation reaction with active As or P;
and the first gas pipeline is used for connecting the first gas storage device and the tail gas pipeline.
According to some embodiments of the application, the gas circuit system further comprises:
a second gas storage device for storing an assist gas that plays an assist role;
and the second gas pipeline is used for connecting the second gas storage device with the tail gas pipeline.
According to some embodiments of the application, a heating belt is wrapped around the exhaust conduit between the reaction chamber and the filter.
According to some embodiments of the application, the oxidizing gas is selected from the group consisting of air, oxygen (O 2 ) Ozone (O) 3 ) Bromine gas (Br) 2 ) Or nitrogen dioxide (NO) 2 ) One or more of the following.
According to some embodiments of the application, the auxiliary gas is an inert gas, such as nitrogen, helium or argon.
In another aspect, the present application provides a method for treating exhaust gas by using the exhaust gas treatment system according to the first aspect, including:
the tail gas contains hydrogen (H) 2 ) In the case of (a), bromine gas (Br) is introduced into the exhaust gas by an active arsenic-phosphorus removal device during the manufacture of semiconductor devices by semiconductor manufacturing equipment and/or during standby 2 ) Or nitrogen dioxide (NO) 2 ) The method is used for removing active arsenic and/or phosphorus in the tail gas; or,
the tail gas contains hydrogen (H) 2 ) In the process of preparing the semiconductor device by the semiconductor manufacturing equipment and/or in the standby process, introducing air, oxygen or ozone into the tail gas by the active arsenic and phosphorus removing device, and controlling the proportion of the hydrogen in the total air flow in the tail gas in the preparation process to be more than 75.6%, preferably more than or equal to 95%; or alternatively
No hydrogen (H) 2 ) In the case of (a), air and oxygen (O) are introduced into the exhaust gas through the active arsenic and phosphorus removal device during the process of preparing semiconductor devices and/or during the standby period of the semiconductor manufacturing equipment 2 ) Or ozone (O) 3 ) Is used for removing active arsenic and/or phosphorus in tail gas.
According to some embodiments of the present application, in the case where hydrogen is contained in the exhaust gas during the manufacture of semiconductor devices in the semiconductor manufacturing apparatus, if air, oxygen or ozone is used as the oxidizing agent, it is necessary to control the proportion of hydrogen in the total gas flow in the exhaust gas during the manufacture to be greater than 75.6%, preferably greater than or equal to 95%.
According to some embodiments of the application, the method further comprises:
detection of an AsH input in a reaction chamber 3 Or pH of 3 The amount of gas used;
based on detected AsH 3 Or pH of 3 The amount of the oxidizing gas is calculated by a control unit, and the flow of the oxidizing gas introduced into the tail gas is controlled according to the flow, so that active arsenic and/or phosphorus in the tail gas are fully removed.
According to the tail gas treatment system of the semiconductor manufacturing equipment, the active arsenic and phosphorus removal device is connected to the tail gas pipeline between the reaction chamber and the filter, and the gas path system of the active arsenic and phosphorus removal device is used for conveying the oxidizing gas which has an oxidation reaction with active As and/or P into the tail gas pipeline, so that the active arsenic and/or phosphorus in the tail gas is eliminated, and the safety of equipment cleaning and maintenance is improved; meanwhile, the oxide after reaction is easier to be filtered by a filter, so that the tail gas filtering efficiency is improved.
Drawings
FIG. 1 is a schematic diagram of the overall configuration of a semiconductor manufacturing facility exhaust gas treatment system according to one embodiment of the present application; and
fig. 2 is a schematic diagram of a specific configuration of an exhaust gas treatment system of a semiconductor manufacturing apparatus according to an embodiment of the present application.
Detailed Description
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly described below, and it is noted that the drawings and the description of the specific embodiments are only for better understanding of the present application, and the present application is not limited to the described embodiments.
Technical or scientific terms used herein should be given the ordinary meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The use of the terms "comprising" or "includes" and the like in this specification is intended to be open-ended terms that do not exclude other elements, components, parts, or items than those explicitly listed. The terms "connected" or "connected," and the like, are not limited to physical or mechanical connections, but may include electrical connections, whether direct or indirect. "upper", "lower", "left", "right", etc. are used merely to indicate relative positional relationships, which may also be changed when the absolute position of the object to be described is changed. "first," "second," etc. are used for the purpose of distinguishing between different elements and not necessarily for a specific order.
In general, the present application is directed to an apparatus and method for eliminating active arsenic and/or phosphorus in an exhaust gas treatment system of a semiconductor manufacturing facility that addresses the safety issues in the exhaust gas treatment process of the prior art. The active arsenic and phosphorus refer to AS, P simple substances and unstable compounds which have explosion hidden danger under the natural exposure state.
Fig. 1 is a schematic diagram of the overall configuration of an exhaust gas treatment system of a semiconductor manufacturing apparatus according to an embodiment of the present application. As shown in fig. 1, the semiconductor manufacturing equipment exhaust gas treatment system according to this embodiment includes a reaction chamber 10, an active arsenic phosphorus removal device 20, a filter 30, and an exhaust gas treatment device 40. The reaction chamber 10, the filter 30 and the offgas processor 40 are sequentially connected through the offgas duct 11. The active arsenic and phosphorus removal unit 20 is connected to the off-gas line 11 between the reaction chamber 10 and the filter 30 by a line 21.
In the reaction chamber 10, a thin film material may be epitaxially grown to prepare a semiconductor device such as a solar cell, an LED, or the like. In the epitaxy process, H can be adopted 2 Or N 2 And the like as a carrier gas for transporting the organic compound of the group III-V element and the hydride of the group V, VI element, and the like, and vapor-depositing a thin film on a substrate (alumina, silicon carbide, gallium arsenide, germanium, and the like) in a thermal decomposition reaction manner in the reaction chamber 10. In the above process, the reaction chamber 10 continuously stores unreacted metal organic compound and hydride, and the undeposited reaction product, which contains a large amount of H 2 、N 2 And a small amount of AsH 3 、PH 3 Silane, reactive As, P, etc., is discharged to the tail pipe 11.
In order to avoid the deposition of active arsenic and phosphorus in the filter 30 and the exhaust pipeline 11, which causes explosion of the active arsenic and phosphorus in the subsequent cleaning process, and creates a safety hazard, in the embodiment of the present application, an active arsenic and phosphorus removal device 20 is connected to the exhaust pipeline 11 between the reaction chamber 10 and the filter 30, where the active arsenic and phosphorus removal device 20 includes a gas path system for delivering an oxidizing gas capable of undergoing an oxidation reaction with the active As and/or P into the exhaust pipeline 11, so As to eliminate the active arsenic and/or phosphorus in the exhaust. The oxidizing gas may be, for example, selected from airOxygen (O) 2 ) Ozone (O) 3 ) Bromine gas (Br) 2 ) Or nitrogen dioxide (NO) 2 ) One or more of the following. In practical application, the safety, the cost and the reactant stability can be comprehensively considered to select proper oxidizing gas. The reactive arsenic and phosphorus in the gas exhausted from the reaction chamber 10 are converted into stable arsenic and phosphorus oxides after oxidation reaction with the oxidizing gas. The oxides and other emissions are then filtered together through a filter 30.
Because the active arsenic and phosphorus removing device 20 is arranged, the active arsenic and phosphorus are basically eliminated before the tail gas reaches the filter 30, so that the serious chemical reaction of the active As and the active P when encountering air during the subsequent cleaning of the filter and related pipelines is avoided, the potential safety hazard of explosion is generated, and the safety of equipment cleaning and maintenance is improved; meanwhile, the oxide after reaction is easier to be filtered by a filter, so that the tail gas filtering efficiency is improved. Meanwhile, the active arsenic and phosphorus removing device can be used for conveying oxidizing gas which is subjected to oxidation reaction with active As and/or P into the tail gas pipeline in the process of preparing semiconductor devices by semiconductor manufacturing equipment, so that active arsenic and/or phosphorus in the tail gas can be removed online in the production process, the downtime is reduced, and the production efficiency of the equipment is greatly improved.
In order to prevent the condensation and deposition of harmful substances such as arsenic, phosphorus, etc. in the gaseous effluent in the exhaust gas pipe 11, and to reduce the efficiency of the oxidation reaction, it is preferable in some embodiments to wrap a heating belt on the exhaust gas pipe 11. By wrapping the heating belt, the proportion of arsenic and phosphorus deposited in the pipeline due to pipeline cooling can be reduced, and the arsenic and phosphorus removal efficiency is further improved.
In some embodiments, bromine gas (Br) may be optionally introduced during semiconductor device fabrication 2 ) Nitrogen dioxide (NO) 2 ) The iso-oxidizing gas is used for removing active arsenic and phosphorus in the tail gas pipeline. Bromine gas (Br) 2 ) Or nitrogen dioxide (NO) 2 ) Active arsenic and phosphorus are removed, and the oxygen and hydrogen (H) existing in the preparation process of the semiconductor device can be avoided when oxidizing gases such as air or oxygen are adopted 2 ) The reaction occurs, resulting in an explosion. Of course, lower cost can also be usedWhen air, oxygen or ozone is used as the oxidizing gas, the proportion of H2 in the total gas flow in the tail gas during the preparation process must be controlled to be greater than 75.6%, for example greater than or equal to 95%, so as to avoid the risk of explosion.
When the equipment is standby, H is not present 2 In the environment, air, oxygen (O) 2 ) Ozone (O) 3 ) And the like as oxidizing gas for removing active arsenic and phosphorus in the tail gas pipeline. Also, when at H 2 In the preparation of the film in the environment, when air and oxygen are used as oxidizing agents, H in the preparation process must be controlled 2 The proportion of the total air flow is much greater than 75.6%.
In some embodiments, the gas path system of the active arsenic and phosphorus removing device 20 may further include an auxiliary gas, preferably an inert gas such as nitrogen, helium, argon, etc., as a diluent gas to adjust the gas flow ratio or as a carrier gas to transport the oxidizing gas.
In some embodiments, in order to precisely control the flow rate of the oxidizing gas, a pneumatic valve and a mass flow control valve may be provided in the gas path system of the active arsenic and phosphorus removal unit, and a control unit may be provided in the semiconductor manufacturing equipment exhaust gas treatment system to control the flow rate of the oxidizing gas by controlling the pneumatic valve and the mass flow control valve.
For example, in some embodiments, a gas detector may be provided to detect AsH that is introduced into the reaction chamber 3 Or pH of 3 The dosage is based on the detected AsH 3 Or pH of 3 The amount of the oxidizing gas is calculated by a control unit, and the flow of the oxidizing gas introduced into the tail gas is controlled according to the flow, so that active arsenic and/or phosphorus in the tail gas are fully removed.
The specific process of eliminating active arsenic and phosphorus in the tail gas filtering system by using the device is as follows:
during the preparation of the film, a gas detector mounted in the gas conduit detects the introduction of gas into the reaction chamber (e.g. AsH 3 、PH 3 ) When the control unit detects the AsH used in the film growth according to the detection result of the gas detector 3 、PH 3 The amount of the oxidizing gas is controlled by controlling the pneumatic valve and the mass flow controller according to the combination reaction proportion, so that the tail gas is fully oxidized in the filter and the pipeline.
When the machine stand is in standby, the flow rate of the introduced gas can be freely selected, and the pneumatic valve and the mass flow controller are controlled by the control unit to control the flow rate of the introduced oxidizing gas, so that the tail gas is subjected to full oxidation reaction in the filter and the pipeline.
In nitrogen growth environment or nitrogen standby, air, oxygen (O) 2 ) The gas is used as oxidizing gas to treat active arsenic and phosphorus before an exhaust gas processor in an exhaust gas treatment system.
Since hydrogen is generally used as the ambient gas during the film production process, in which case the hydrogen is discharged into the tail gas pipeline, bromine gas (Br) which is harmless to the reaction of hydrogen can be selected during the film production process, i.e. during the operation of the reaction chamber 2 ) Nitrogen dioxide (NO) 2 ) As oxidizing gas, active arsenic and phosphorus are removed, so that the real-time treatment effect is achieved, and the use efficiency of the machine is improved.
Fig. 2 is a schematic diagram of a specific configuration of an exhaust gas treatment system of a semiconductor manufacturing apparatus according to an embodiment of the present application. As shown in fig. 2, the semiconductor manufacturing equipment exhaust gas treatment system according to this embodiment includes a reaction chamber 10 that discharges exhaust gas containing arsenic and/or phosphorus; a tail gas pipeline 1 for receiving tail gas discharged from the reaction chamber 10; a condensation filter 30 connected with the reaction chamber 10 through a tail gas pipe 1 for filtering tail gas discharged from the reaction chamber 10; wherein an active arsenic-phosphorus removal device is connected to the off-gas line 1 between the reaction chamber 10 and the filter 30. The active arsenic and phosphorus removal device comprises a gas path system which is connected to the tail gas pipeline 1 between the reaction chamber 10 and the filter 30, preferably to the pipeline 1 near one side of the filter 30, so that an interface of the active arsenic and phosphorus removal device is connected to the tail end of the tail gas pipeline 1 between the reaction chamber 10 and the filter 30 and is used for conveying oxidizing gas which has oxidation reaction with active As and/or P into the tail gas pipeline so As to eliminate active arsenic and/or phosphorus in the tail gas.
Specifically, the gas path system includes a first gas storage device 22 for storing an oxidizing gas 1 to be subjected to an oxidation reaction with active As or P; and a first gas pipe for connecting the first gas storage device with the exhaust pipe 1. The gas circuit system also comprises a second gas storage device 23 for storing auxiliary gas 2 with auxiliary effect; and a second gas pipe for connecting the second gas storage device with the exhaust pipe 1. Specifically, the first gas conduit is composed of conduit 5, conduit 4, conduit 3 and conduit 2, and the second gas conduit is composed of conduit 6, conduit 4, conduit 3 and conduit 2.
Specifically, referring to fig. 2, the reaction chamber 10 is connected to the condensing filter 30 through a pipe 1, and a three-way pipe 2 is provided in the pipe 1 for connecting the pipe 1 and the pipe 3. In this embodiment, only two gas lines are illustrated, including the gases 1, 2, and various gas lines are known in the art as required. The gas outlet of the gas 1 is connected with a gas 1 Mass Flow Controller (MFC) 24, the other end of the gas 1 Mass Flow Controller (MFC) 24 is connected with a pneumatic valve 2, and the pneumatic valve 2 is connected with a pipeline 5; the gas outlet of the gas 2 is connected with a gas 2 Mass Flow Controller (MFC) 25, the other end of the gas 2 Mass Flow Controller (MFC) 25 is connected with a pneumatic valve 3, and the pneumatic valve 3 is connected with a pipeline 6.
The pipeline 4 is a three-way pipeline, the pipeline 5 and the pipeline 6 are connected to the pipeline 3 through the pipeline 4, the pipeline 3 is connected with the pipeline 1 through the pipeline 2, and the pneumatic valve 1 is connected between the pipeline 2 and the pipeline 3. The pipeline 1 and the pipeline 2 are both wrapped with heating belts. The pneumatic valves 1, 2, 3 are each connected to a control unit 50 in an exhaust gas treatment system of a semiconductor manufacturing apparatus (e.g., MOCVD apparatus) by a signal line or in a wireless manner, and the control unit 50 outputs an electrical signal to control the opening and closing of the pneumatic valve. The gas 1MFC 24 and the gas 2MFC 25 are connected to the MOCVD equipment control unit 50 through signal lines or in a wireless manner, and the control unit 50 outputs an electric signal to control the flow rate of the gas through the MFC.
Gas 1 and gas 2 can be oxygen-selected respectivelyChemical gases and diluent gases. Preferably, the oxidizing gas is typically air, oxygen (O 2 ) Ozone (O) 3 ) Bromine gas (Br) 2 ) Nitrogen dioxide (NO) 2 ) Etc. When using air and oxygen, care should be taken to control the flow of the incoming air and oxygen to ensure that the hydrogen is much greater than 75.6% of the total gas flow (taking into account the explosion limits of the hydrogen). Preferably, nitrogen, helium, or the like is used as the diluent gas.
The exhaust treatment system of the above-described embodiment of the present application can be used to eliminate active arsenic and phosphorus in the exhaust filter 30 of the MOCVD (metal organic chemical vapor deposition) growth equipment. The PH is used in large quantities for growing LEDs 3 The process of eliminating active arsenic and/or phosphorus provided by the embodiments of the present application is further described by way of example.
In the epitaxial growth of GaInP, the total gas flow from the reaction chamber 10 is about 40L/Min, where PH 3 Flow rate is about 1L/Min, PH 3 Can be decomposed into P simple substance and H under the high-temperature environment of the reaction chamber 10 2 (above 500 ℃ C.) the temperature in the reaction chamber 10 is typically above 600 ℃ C. At pH 3 After being completely decomposed, a small amount of P reacts with an MO (metal organic compound) source and is deposited on a substrate, and a large amount of P simple substance which is not completely reacted is taken away by tail gas and enters a tail end pipeline. Due to the excess pH generally introduced during growth 3 ，PH 3 Utilization of about 1%, unreacted complete PH 3 The flow rate was about 1L/Min.
The exhaust gas flows through the epitaxial reaction chamber 10 to the tail pipe, and sequentially passes through the filter 30, the main pump 60, and the exhaust gas processor 40. The tail gas pipelines 1 and 2 are wrapped by heating belts, and the temperature of the heating belts can be 120 ℃. The device is connected between the reaction chamber 10 and the condensing filter 30 in the tail gas pipeline through a three-way pipeline 2 and is close to the condensing filter 30, and the gas 1 can select nitrogen dioxide (NO 2 ) The mixed gas (such as mixed gas of nitrogen dioxide and nitrogen), the gas 2 can be nitrogen, the gas 1MFC 24 and the pneumatic valve 2 can respectively control the opening and closing of the gas 1 pipeline and the flow rate of the mixed gas introduced into the pipeline 3, under the condition that the mixed gas mainly comprises NO 2 And N 2 。
At the beginning of epitaxial growth, the apparatus control unit 50 sequentially opens the air-operated valve 1, the air-operated valve 3, and the air-operated valve 2 while controlling the opening of the hydride valve, and controls the flow rates of the gas 1 and the gas 2 through the gas 1mfc 24 and the gas 2mfc 25. Under the above conditions, the gas 1MFC 24 can be controlled so that the nitrogen dioxide (NO 2 ) The airflow rate is slowly increased from 0L/Min to 2.5L/Min; the gas 2MFC 25 can be controlled to enable the flow rate of the introduced nitrogen gas to be slowly increased from 0L/Min to 0.5L/Min, the gas 2 flow change time is 120s, the total flow rate of the introduced gas is 3L/Min, the influence of the gas flow change on the pipeline pressure is reduced, and the introduced NO is ensured 2 Can completely react with P, for example, according to the reaction equation 8P+10NO 2 ＝4P 2 O 5 +5N 2 。
Small amounts of metal organics (e.g., trimethylgallium, trimethylaluminum, etc.) and NO 2 Will react to form metal oxides, and elemental P will react with NO2 to form oxides of P (e.g., P 4 O 10 ) The metal oxide formed by the reaction and the oxide of P are filtered while passing through the condensing filter 30. After the epitaxial growth is finished, firstly, the pneumatic valve 2 is closed to enable the gas which is introduced into the tail gas pipeline by the device to be N 2 At the end of the epitaxy process, the pneumatic valve 3 and the pneumatic valve 1 are closed. P (P) 4 O 10 The oxides are stable in air, and the risk of fire and explosion can be reduced when the filter is cleaned.
Further, H is introduced into the reaction chamber 10 as a carrier gas 2 Or N 2 Can range from 20000sccm to 50000sccm.
Further, the mass flow controller control flow range of the dilution gas may be: 100sccm to 5000sccm.
Further, the mass flow controller flow rate of the oxidizing gas used may range from 100sccm to 5000sccm.
Further, the Ash to be treated 3 、PH 3 The dosage range of (2) can be as follows: 10sccm to 1000sccm.
The GaAs film is prepared in a similar way to the above case, and Br can be selected 2 As an oxidizing gas, a large amount of the oxidizing gas is not completely reactedThe corresponding elementary substances As entering the tail end pipeline will be equal to Br 2 Reaction to produce AsBr 3 ，AsBr 3 Is more stable in air and can be filtered when passing through the condensing filter, thereby reducing the risk of fire and explosion during maintenance such as filter cleaning.
The application will be further described by taking the exhaust pipeline treatment during standby as an example:
the device is usually used for N with lower flow rate when standby 2 And (3) performing environmental purging, and introducing oxidizing gas to perform oxidation reaction on the active arsenic and phosphorus in the tail gas pipeline. Due to N 2 In the environment, air or oxygen with lower cost can be used as the oxidizing gas.
In this example, the device control unit 50 is first used to control the flow of the valve switch and the mass flow controller, the flow is controlled to be 80% of the upper limit of the measuring range, the treatment time of the introduced gas can be adjusted according to the actual situation, and in this example, 60 minutes of air is introduced. The valve was then closed and N was vented for 60 minutes 2 Purging is carried out, and the cavity environment and the pipeline environment are guaranteed to be restored to the state before treatment.
In order to improve the treatment efficiency, the step of introducing high-temperature reducing gas may be performed before the above steps: the reaction chamber 10 is first warmed to 600 c while the mass flow controller is controlled to pass approximately 20L of H 2 60 minutes, and then about 20L of N is introduced 2 H is added for 30 minutes 2 After the displacement, a step of removing active arsenic and phosphorus by introducing an oxidizing gas is then performed. H at high temperature flowing to the tail end in the process 2 The solid arsenic and phosphorus adhered to the pipeline are reduced as reducing gas, and simultaneously the solid arsenic and phosphorus are changed into gas from solid state, so that the treatment efficiency of the subsequent steps is improved.
According to the embodiment of the application, the active arsenic and the phosphorus in the tail gas treatment system are subjected to oxidation treatment, so that inflammable and explosive substances which are not easy to burn or explode when meeting air can be formed after chemical reaction, the condition that the residual substances in the tail gas treatment system burn or explode can be avoided when the tail gas treatment system is disassembled for cleaning, and the cleaning safety of the tail gas treatment system is further ensured. The design obviously improves the spontaneous combustion risk of As and P simple substances existing in the maintenance of the tail end pipeline and the spontaneous combustion problem of a large amount of As and P simple substances in the cleaning of the tail gas filter, can improve the efficiency of tail gas filtration and the safety in the maintenance, and reduces the spontaneous combustion probability in the cleaning of the tail gas filter.
The foregoing embodiments are merely illustrative of the principles and configurations of the present application, and are not intended to be limiting, it will be appreciated by those skilled in the art that any changes and modifications may be made without departing from the general inventive concept. The protection scope of the present application should be defined as the scope of the claims of the present application.
Claims (10)
1. A semiconductor manufacturing facility exhaust gas treatment system, comprising:
a reaction chamber, wherein the tail gas discharged by the reaction chamber contains arsenic and/or phosphorus;
a tail gas pipeline for receiving the tail gas exhausted from the reaction chamber;
the filter is connected with the reaction chamber through a tail gas pipeline and is used for filtering tail gas discharged by the reaction chamber;
the device comprises a gas path system, wherein the gas path system is connected to the tail gas pipeline between the reaction chamber and the filter and is used for conveying oxidizing gas which is subjected to oxidation reaction with active As and/or P into the tail gas pipeline so As to eliminate active arsenic and/or phosphorus in the tail gas.
2. The semiconductor manufacturing equipment exhaust gas treatment system of claim 1, wherein the gas circuit system comprises a pneumatic valve and a mass flow control valve therein, the semiconductor manufacturing equipment exhaust gas treatment system further comprising a control unit that controls the flow rate of the oxidizing gas by controlling the pneumatic valve and the mass flow control valve.
3. The semiconductor manufacturing equipment exhaust gas treatment system of claim 2, wherein the control unit is adapted to control the pneumatic valve and the mass flow control valve to deliver an oxidizing gas that is oxidized with active As and/or P into the exhaust gas conduit during semiconductor manufacturing equipment manufacturing and/or during standby.
4. The semiconductor manufacturing facility exhaust gas treatment system of claim 1, wherein the gas circuit system comprises:
a first gas storage means for storing an oxidizing gas to be subjected to an oxidation reaction with active As or P; and
and the first gas pipeline is used for connecting the first gas storage device and the tail gas pipeline.
5. The semiconductor manufacturing facility exhaust treatment system of claim 4, wherein the gas circuit system further comprises:
a second gas storage device for storing an assist gas that plays an assist role; and
and the second gas pipeline is used for connecting the second gas storage device with the tail gas pipeline.
6. The semiconductor manufacturing equipment exhaust gas treatment system of claim 1, wherein a heating belt is wrapped on the exhaust gas conduit between the reaction chamber and the filter.
7. The semiconductor manufacturing facility exhaust gas treatment system of claim 1, wherein the oxidizing gas is selected from the group consisting of air, oxygen (O 2 ) Ozone (O) 3 ) Bromine gas (Br) 2 ) Or nitrogen dioxide (NO) 2 ) One or more of the following.
8. The semiconductor manufacturing facility exhaust gas treatment system of claim 5, wherein the assist gas is an inert gas such as nitrogen, helium or argon.
9. A method of treating exhaust gas with the exhaust gas treatment system of any of claims 1-8, comprising:
the tail gas contains hydrogen (H) 2 ) In the case of (a), bromine gas (Br) is introduced into the exhaust gas by an active arsenic-phosphorus removal device during the manufacture of semiconductor devices by semiconductor manufacturing equipment and/or during standby 2 ) Or nitrogen dioxide (NO) 2 ) The method is used for removing active arsenic and/or phosphorus in the tail gas; or,
the tail gas contains hydrogen (H) 2 ) In the process of preparing the semiconductor device by the semiconductor manufacturing equipment and/or in the standby process, introducing air, oxygen or ozone into the tail gas by the active arsenic and phosphorus removing device, and controlling the proportion of the hydrogen in the total air flow in the tail gas in the preparation process to be more than 75.6%, preferably more than or equal to 95%; or alternatively
No hydrogen (H) 2 ) In the case of (a), air and oxygen (O) are introduced into the exhaust gas through the active arsenic and phosphorus removal device during the process of preparing semiconductor devices and/or during the standby period of the semiconductor manufacturing equipment 2 ) Or ozone (O) 3 ) Is used for removing active arsenic and/or phosphorus in tail gas.
10. The method of claim 9, further comprising:
AsH for detecting input of reaction chamber 3 Or pH of 3 The gas consumption; and
based on detected AsH 3 Or pH of 3 The amount of the oxidizing gas is calculated by a control unit, and the flow of the oxidizing gas introduced into the tail gas is controlled according to the flow, so that active arsenic and/or phosphorus in the tail gas are fully removed.
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| JPH0271512A (en) * | 1988-09-06 | 1990-03-12 | Fuji Electric Co Ltd | Vapor growth of compound semiconductor containing phosphorus |
| KR20150081698A (en) * | 2014-01-06 | 2015-07-15 | 주식회사 엘지실트론 | Apparatus for treating exhaust gases of ingot grower and method for growing ingot using the same |
| CN111151524A (en) * | 2018-11-07 | 2020-05-15 | 长鑫存储技术有限公司 | Pipeline cleaning method and device |
| CN111744349A (en) * | 2019-03-27 | 2020-10-09 | 东泰高科装备科技有限公司 | Cleaning method of tail gas treatment system |
| CN115948723A (en) * | 2022-12-29 | 2023-04-11 | 楚赟精工科技(上海)有限公司 | MOCVD (Metal organic chemical vapor deposition) exhaust system and cleaning method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0271512A (en) * | 1988-09-06 | 1990-03-12 | Fuji Electric Co Ltd | Vapor growth of compound semiconductor containing phosphorus |
| KR20150081698A (en) * | 2014-01-06 | 2015-07-15 | 주식회사 엘지실트론 | Apparatus for treating exhaust gases of ingot grower and method for growing ingot using the same |
| CN111151524A (en) * | 2018-11-07 | 2020-05-15 | 长鑫存储技术有限公司 | Pipeline cleaning method and device |
| CN111744349A (en) * | 2019-03-27 | 2020-10-09 | 东泰高科装备科技有限公司 | Cleaning method of tail gas treatment system |
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