1. Field of the Invention
The present invention relates to improved systems and methods for the abatement of industrial effluent fluids, such as effluent gases produced in semiconductor manufacturing processes, while reducing the deposition of reaction products in the treatment systems.
2. Description of the Related Art
The gaseous effluents from the manufacturing of semiconductor materials, devices, products and memory articles involve a wide variety of chemical compounds used and produced in the process facility. These compounds include inorganic and organic compounds, breakdown products of photo-resist and other reagents, and a wide variety of other gases that must be removed from the waste gas before being vented from the process facility into the atmosphere.
Semiconductor manufacturing processes utilize a variety of chemicals, many of which have extremely low human tolerance levels. Such materials include gaseous hydrides of antimony, arsenic, boron, germanium, nitrogen, phosphorous, silicon, selenium, silane, silane mixtures with phosphine, argon, hydrogen, organosilanes, halosilanes, halogens, organometallics and other organic compounds.
Halogens, e.g., fluorine (F2) and other fluorinated compounds, are particularly problematic among the various components requiring abatement. The electronics industry uses perfluorinated compounds (PFCs) in wafer processing tools to remove residue from deposition steps and to etch thin films. PFCs are recognized to be strong contributors to global warming and the electronics industry is working to reduce the emissions of these gases. The most commonly used PFCs include, but are not limited to, CF4, C2F6, SF6, C3F8, C4H8, C4H8O and NF3. In practice, these PFCs are dissociated in a plasma to generate highly reactive fluoride ions and fluorine radicals, which do the actual cleaning and/or etching. The effluent from these processing operations include mostly fluorine, silicon tetrafluoride (SiF4), hydrogen fluoride (HF), carbonyl fluoride (COF2), CF4 and C2F6.
A significant problem of the semiconductor industry has been the removal of these materials from the effluent gas streams. While virtually all U.S. semiconductor manufacturing facilities utilize scrubbers or similar means for treatment of their effluent gases, the technology employed in these facilities is not capable of removing all toxic or otherwise unacceptable impurities.
One solution to this problem is to incinerate the process gas to oxidize the toxic materials, converting them to less toxic forms. Such systems are almost always over-designed in terms of treatment capacity, and typically do not have the ability to safely deal with a large number of mixed chemistry streams without posing complex reactive chemical risks. Further, conventional incinerators typically achieve less than complete combustion thereby allowing the release of pollutants, such as carbon monoxide (CO) and hydrocarbons (HC), to the atmosphere. Furthermore, one of the problems of great concern in effluent treatment is the formation of acid mist, acid vapors, acid gases and NOx (NO, NO2) prior to discharge. A further limitation of conventional incinerators is their inability to mix sufficient combustible fuel with a nonflammable process stream in order to render the resultant mixture flammable and completely combustible.
Oxygen or oxygen-enriched air may be added directly into the combustion chamber for mixing with the waste gas to increase combustion temperatures, however, oxides, particularly silicon oxides may be formed and these oxides tend to deposit on the walls of the combustion chamber. The mass of silicon oxides formed can be relatively large and the gradual deposition within the combustion chamber can induce poor combustion or cause clogging of the combustion chamber, thereby necessitating increased maintenance of the equipment. Depending on the circumstances, the cleaning operation of the abatement apparatus may need to be performed once or twice a week.
It is well known in the arts that the destruction of a halogen gas requires high temperature conditions. To handle the high temperatures, some prior art combustion chambers have included a circumferentially continuous combustion chamber made of ceramic materials to oxidize the effluent within the chamber (see, e.g., U.S. Pat. No. 6,494,711 in the name of Takemura et al., issued Dec. 17, 2002). However, under the extreme temperatures needed to abate halogen gases, these circumferentially continuous ceramic combustion chambers crack due to thermal shock and thus, the thermal insulating function of the combustion chamber fails. An alternative includes the controlled decomposition/oxidation (CDO) systems of the prior art, wherein the effluent gases undergo combustion in the metal inlet tubes, however, the metal inlet tubes of the CDO's are physically and corrosively compromised at the high temperatures, e.g., ≈1260° C.-1600° C., needed to efficiently decompose halogen compounds such as CF4.
Accordingly, it would be advantageous to provide an improved thermal reactor for the decomposition of highly thermally resistant contaminants in a waste gas that provides high temperatures, through the introduction of highly flammable gases, to ensure substantially complete decomposition of said waste stream while simultaneously reducing deposition of unwanted reaction products within the thermal reaction unit. Further, it would be advantageous to provide an improved thermal reaction chamber that does not succumb to the extreme temperatures and corrosive conditions needed to effectively abate the waste gas.
The present invention relates to methods and systems for providing controlled decomposition of gaseous liquid crystal display (LCD) and semiconductor wastes in a thermal reactor while reducing accumulation of the particulate products of said decomposition within the system. The present invention further relates to an improved thermal reactor design to reduce reactor chamber cracking during the decomposition of the gaseous waste gases.
In one aspect, the present invention relates to a thermal reactor for removing pollutant from waste gas, the thermal reactor comprising:
a) a thermal reaction unit comprising:
b) a water quench.
In yet another aspect, the present invention relates to a thermal reactor for removing pollutant from waste gas, the thermal reactor comprising:
a) a thermal reaction unit comprising:
b) a water quench.
In a further aspect, the present invention relates to a method for controlled decomposition of gaseous pollutant in a waste gas in a thermal reactor, the method comprising:
Other aspects and advantages of the invention will be more fully apparent from the ensuing disclosure and appended claims
The present invention relates to methods and systems for providing controlled decomposition of effluent gases in a thermal reactor while reducing accumulation of deposition products within the system. The present invention further relates to an improved thermal reactor design to reduce thermal reaction unit cracking during the high temperature decomposition of effluent gases.
Waste gas to be abated may include species generated by a semiconductor process and/or species that were delivered to and egressed from the semiconductor process without chemical alteration. As used herein, the term “semiconductor process” is intended to be broadly construed to include any and all processing and unit operations in the manufacture of semiconductor products and/or LCD products, as well as all operations involving treatment or processing of materials used in or produced by a semiconductor and/or LCD manufacturing facility, as well as all operations carried out in connection with the semiconductor and/or LCD manufacturing facility not involving active manufacturing (examples include conditioning of process equipment, purging of chemical delivery lines in preparation of operation, etch cleaning of process tool chambers, abatement of toxic or hazardous gases from effluents produced by the semiconductor and/or LCD manufacturing facility, etc.).
The improved thermal reaction system disclosed herein has a thermal reaction unit 30 and a lower quenching chamber 150 as shown in
In one embodiment of the invention, the interior walls of the waste gas inlet 14 may be altered to reduce the affinity of particles for the interior walls of the inlet. For example, a surface may be electropolished to reduce the mechanical roughness (Ra) to a value less than 30, more preferably less than 17, most preferably less than 4. Reducing the mechanical roughness reduces the amount of particulate matter that adheres to the surface as well as improving the corrosion resistance of the surface. In the alternative, the interior wall of the inlet may be coated with a fluoropolymer coating, for example Teflon® or Halar®, which will also act to reduce the amount of particulate matter adhered at the interior wall as well as allow for easy cleaning. Pure Teflon® or pure Halar® layers are preferred, however, these materials are easily scratched or abraded. As such, in practice, the fluoropolymer coating is applied as follows. First the surface to be coated is cleaned with a solvent to remove oils, etc. Then, the surface is bead-blasted to provide texture thereto. Following texturization, a pure layer of fluoropolymer, e.g., Teflon®, a layer of ceramic filled fluoropolymer, and another pure layer of fluoropolymer are deposited on the surface in that order. The resultant fluoropolymer-containing layer is essentially scratch-resistant.
In another embodiment of the invention, the waste gas inlet 14 tube is subjected to thermophoresis, wherein the interior wall of the inlet is heated thereby reducing particle adhesion thereto. Thermophoresis may be effected by actually heating the surface of the interior wall with an on-line heater or alternatively, a hot nitrogen gas injection may be used, whereby 50-100 L per minute of hot nitrogen gas flows through the inlet. The additional advantage of the latter is the nitrogen gas flow minimizes the amount of time waste gases reside in the inlet thereby minimizing the possibility of nucleation therein.
Prior art inlet adaptors have included limited porosity ceramic plates as the interior plate of the inlet adaptor. A disadvantage of these limited porosity interior plates includes the accumulation of particles on said surface, eventually leading to inlet port clogging and flame detection error. The present invention overcomes these disadvantages by using a reticulated ceramic foam as the interior plate 12.
Although not wishing to be bound by theory, the reticulated ceramic foam interior plate helps prevent particle buildup on the interior plate in part because the exposed planar surface area is reduced thereby reducing the amount of surface available for build-up, because the reticulation of the interior plate provides smaller attachment points for growing particulate matter which will depart the interior plate upon attainment of a critical mass and because the air passing through the pores of the interior plate forms a “boundary layer,” keeping particles from migrating to the surface for deposition thereon.
Ceramic foam bodies have an open cell structure characterized by a plurality of interconnected voids surrounded by a web of ceramic structure. They exhibit excellent physical properties such as high strength, low thermal mass, high thermal shock resistance, and high resistance to corrosion at elevated temperatures. Preferably, the voids are uniformly distributed throughout the material and the voids are of a size that permits fluids to easily diffuse through the material. The ceramic foam bodies should not react appreciably with PFC's in the effluent to form highly volatile halogen species. The ceramic foam bodies may include alumina materials, magnesium oxide, refractory metal oxides such as ZrO2, silicon carbide and silicon nitride, preferably higher purity alumina materials, e.g., spinel, and yttria-doped alumina materials. Most preferably, the ceramic foam bodies are ceramic bodies formed from yttria-doped alumina materials and yttria-stabilized zirconia-alumina (YZA). The preparation of ceramic foam bodies is well within the knowledge of those skilled in the art.
To further reduce particle build-up on the interior plate 12, a fluid inlet passageway may be incorporated into the center jet 16 of the inlet adaptor 10 (see for example
In yet another embodiment, the thermal reaction unit includes a porous ceramic cylinder design defining the thermal reaction chamber 32. High velocity air may be directed through the pores of the thermal reaction unit 30 to at least partially reduce particle buildup on the interior walls of the thermal reaction unit. The ceramic cylinder of the present invention includes at least two ceramic rings stacked upon one another, for example as illustrated in
Each ceramic ring may be a circumferentially continuous ceramic ring or alternatively, may be at least two sections that may be joined together to make up the ceramic ring.
The advantage of having a thermal reaction chamber defined by individual stacked ceramic rings includes the reduction of cracking of the ceramic rings of the chamber due to thermal shock and concomitantly a reduction of equipment costs. For example, if one ceramic ring cracks, the damaged ring may be readily replaced for a fraction of the cost and the thermal reactor placed back online immediately.
The ceramic rings of the invention must be held to another to form the thermal reaction unit 30 whereby high velocity air may be directed through the pores of the ceramic rings of the thermal reaction unit to at least partially reduce particle buildup at the interior walls of the thermal reaction unit. Towards that end, a perforated metal shell may be used to encase the stacked ceramic rings of the thermal reaction unit as well as control the flow of axially directed air through the porous interior walls of the thermal reaction unit.
The metal shell 110 has a perforated pattern whereby preferably more air is directed towards the top of the thermal reaction unit, e.g., the portion closer to the inlet adaptor 10, than the bottom of the thermal reaction unit, e.g., the lower chamber (see
Referring to
In practice, fluid flow is axially and controllably introduced through the perforations of the metal shell, the fibrous blanket 140 and the reticulated ceramic rings of the cylinder. The fluid experiences a pressure drop from the exterior of the thermal reaction unit to the interior of the thermal reaction unit in a range from about 0.05 psi to about 0.30 psi, preferably about 0.1 psi to 0.2 psi. The fluid may be introduced in a continuous or a pulsating mode, preferably a continuous mode to reduce the recirculation of the fluid within the thermal reaction chamber. It should be appreciated that an increased residence time within the thermal reaction chamber, wherein the gases are recirculated, results in the formation of larger particulate material and an increased probability of deposition within the reactor. The fluid may include any gas sufficient to reduce deposition on the interior walls of the ceramic rings while not detrimentally affecting the abatement treatment in the thermal reaction chamber. Gases contemplated include air, CDA, oxygen-enriched air, oxygen, ozone and inert gases, e.g., Ar, N2, etc.
To introduce fluid to the walls of the thermal reaction unit for passage through to the thermal reaction chamber 32, the entire thermal reaction unit 30 is encased within an outer stainless steel reactor shell 60 (see, e.g.,
Referring to
Downstream of the thermal reaction chamber is a water quenching means positioned in the lower quenching chamber 150 to capture the particulate matter that egresses from the thermal reaction chamber. The water quenching means may include a water curtain as disclosed in co-pending U.S. patent application Ser. No. 10/249,703 in the name of Glenn Tom et al., entitled “Gas Processing System Comprising a Water Curtain for Preventing Solids Deposition on Interior Walls Thereof,” which is hereby incorporated by reference in the entirety. Referring to
To ensure that the bottom-most ceramic ring does not get wet, a shield 202 (see, e.g.,
In practice, effluent gases enter the thermal reaction chamber 32 from at least one inlet provided in the inlet adaptor 10, and the fuel/oxidant mixture enter the thermal reaction chamber 32 from at least one burner jet 15. The pilot flame of the center jet 16 is used to ignite the burner jets 15 of the inlet adaptor, creating thermal reaction unit temperatures in a range from about 500° C. to about 2000° C. The high temperatures facilitate decomposition of the effluent gases that are present within the thermal reaction chamber. It is also possible that some effluent gases undergo combustion/oxidation in the presence of the fuel/oxidant mixture. The pressure within the thermal reaction chamber is in a range from about 0.5 atm to about 5 atm, preferably slightly subatmospheric, e.g., about 0.98 atm to about 0.99 atm.
Following decomposition/combustion, the effluent gases pass to the lower chamber 150 wherein a water curtain 156 may be used to cool the walls of the lower chamber and inhibit deposition of particulate matter on the walls. It is contemplated that some particulate matter and water soluble gases may be removed from the gas stream using the water curtain 156. Further downstream of the water curtain, a water spraying means 154 may be positioned within the lower quenching chamber 150 to cool the gas stream, and remove the particulate matter and water soluble gases. Cooling the gas stream allows for the use of lower temperature materials downstream of the water spraying means thereby reducing material costs. Gases passing through the lower quenching chamber may be released to the atmosphere or alternatively may be directed to additional treatment units including, but not limited to, liquid/liquid scrubbing, physical and/or chemical adsorption, coal traps, electrostatic precipitators, and cyclones. Following passage through the thermal reaction unit and the lower quenching chamber, the concentration of the effluent gases is preferably below detection limits, e.g., less than 1 ppm. Specifically, the apparatus and method described herein removes greater than 90% of the toxic effluent components that enter the abatement apparatus, preferably greater than 98%, most preferably greater than 99.9%.
In an alternative embodiment, an “air knife” is positioned within the thermal reaction unit. Referring to
To demonstrate the abatement effectiveness of the improved thermal reactor described herein, a series of experiments were performed to quantify the efficiency of abatement using said thermal reactor. It can be seen that greater than 99% of the test gases were abated using the improved thermal reactor, as shown in Table 1.
Although the invention has been variously described herein with reference to illustrative embodiments and features, it will be appreciated that the embodiments and features described hereinabove are not intended to limit the invention, and that other variations, modifications and other embodiments will readily suggest themselves to those of ordinary skill in the art, based on the disclosure herein. The invention therefore is to be broadly construed, consistent with the claims hereafter set forth.
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