Abatement of NF.sub.3 with metal oxalates

Abstract

A process for abating NF.sub.3 by contacting it with a metal oxalate or carbonate.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

Not applicable.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

Not applicable.

BACKGROUND OF THE INVENTION

Nitrogen trifluoride (NF.sub.3) is an etchant gas having major utility in the processing of semiconductor materials and particularly in cleaning of furnaces and tools in the manufacture of electronic devices.

NF.sub.3 has been recognized as a global warming gas specie by the industrialized world. This in addition to the fact that it is difficult to abate NF.sub.3 efficiently and very effectively, makes the use of NF.sub.3 by the electronics industry problematic.

Previous attempts to abate NF.sub.3 include burning it at high temperatures, which create undesirable nitrogen oxide effluents, reaction of NF.sub.3 with carbon, which generates CF.sub.4, a much stronger global warming gas and may be explosive, or reaction of NF.sub.3 with metal oxides at elevated temperature, which also creates undesirable nitrogen oxide effluents.

Chlorofluorocarbons have been abated by the use of sodium oxalate. Additionally, oxalates have been used to unsaturate fully fluorinated fluorocarbons. See J. Burdeniiuc and R. H. Crabtree, Mineralization of Chlorofluorocarbons and Aromatization of Saturated Fluorocarbons by a Convenient Thermal Process, Science, vol 271, Jan. 19, 1996, pp340-341.

The drawbacks of the prior art abatements of NF.sub.3 are overcome by the present invention which can abate even dilute quantities of NF.sub.3 safely and efficiently without nitrogen oxide byproducts and without danger or explosion, as will be set forth in greater detail below.

BRIEF SUMMARY OF THE INVENTION

The present invention is a process for abatement of NF.sub.3 in gas streams containing NF.sub.3 comprising contacting the gas stream containing NF.sub.3 with a reagent selected from the group consisting of metal oxalates, metal carbonates and mixtures thereof under reaction conditions sufficient to abate the NF.sub.3.

Preferably, the metal is selected from the group consisting of alkali metals, alkali earth metals and mixtures thereof.

More preferably, the reagent is sodium oxalate.

Alternatively, the reagent is calcium oxalate.

Further alternatively, the reagent is cesium oxalate.

Yet another alternative is that the reagent is sodium carbonate.

Preferably, the temperature of the reaction conditions is in the range of approximately 300 to 450.degree. C.

Preferably, the NF.sub.3 is present in the gas containing NF.sub.3 in an amount of no greater than approximately 1% by volume.

Preferably, the gas containing NF.sub.3 contacts the reagent in a packed bed of the reagent. Alternately, the reagent is in a fluidized bed.

Preferably, the NF.sub.3 is abated to less than 10 ppm by volume.

BRIEF DESCRIPTION OF SEVERAL VIEWS OF THE DRAWINGS

Not Applicable

DETAILED DESCRIPTION OF THE INVENTION

Nitrogen trifluoride (NF.sub.3) has wide applicability for etching and cleaning in the semiconductor industry. It can be used in thermal and plasma cleaning of process tools, furnaces, appliances and components that become fouled with the by-products and materials used during deposition of various films and layers in the fabrication of electronic devices, such as integrated circuits. Typically, layers of silicon dioxide, silicon nitride, as well as various metals, are deposited on silicon substrates in furnaces in electronic fabs. These deposits are performed by chemical vapor deposition, sputtering, and other techniques, but are generally non-specific in that they deposit materials not only on the targeted area, but also on the furnace and tools used for the deposition.

Periodic cleaning of such tools and furnaces is required. NF.sub.3 is widely used to effect the etch and clean of such furnaces and tools. The problem arises when the furnace and tools are evacuated during the cleaning procedure. The evacuated gases and effluents typically contain minor quantities of unreacted NF.sub.3. The industry is concerned about NF.sub.3 effluent due to its determination to be a global warming gas and its toxicity, which requires that it be abated below its Threshold Limit Value (TLV) of 10 parts per million (ppm). Adequate abatement has not been practiced to date, due to the expense, inefficiency or alternative by-products of known abatement techniques. Although NF.sub.3 is a strong oxidizer, at room temperature it is difficult to abate from process streams at low levels of approximately 1% by volume or less.

Abating NF.sub.3 using metal oxalates, such as alkali metal or alkaline earth metal metal oxalates or carbonates overcomes the problem of abatement of NF.sub.3 without forming undesired by-products such as nitrogen oxides. Appropriate oxalates and carbonates include sodium, calcium, potassium, lithium and cesium salts. Elevated temperatures are desirable, such as temperatures in excess of approximately 300.degree. C., preferably approximately 300 to 450.degree. C. The reaction is typified as follows;

2NF.sub.3 +3Na.sub.2 C.sub.2 O.sub.4 .dbd.N.sub.2 +6CO.sub.2 +6NaF

The experimental examples involved placing the metal oxalate into a Monel reactor which is then heated to a temperature in the range of approximately 300 to 450.degree. C. A gas containing approximately 1% by volume NF.sub.3 is introduced into the reactor at an appropriate flowrate. The NF.sub.3 reacts with the metal oxalate to form metal fluorides, nitrogen and carbon dioxide. The nitrogen and carbon dioxide can be vented without any further treatment and the metal fluoride can be disposed of as a solid salt when the bed is nearly fully consumed. The NF.sub.3 reduction from the feed gas content to the effluent gas content is at least 75% by volume, preferably 90% by volume, most preferably approximately 100% by volume. Target reductions would be at or below 10 ppm of NF.sub.3 in the effluent gas, most preferably at or below 1 ppm of NF.sub.3 in the effluent gas.

More specifically, the examples were performed in a 0.5.times.1.0 inch Monel reactor containing 15 cc of metal oxalate at a temperature of 200 to 500.degree. C. with an NF.sub.3 flow of 1-3 sccm in an inert gas flow of 89-267 sccm of helium. The results for a number of experimental runs are reported in Table 1, below.

TABLE 1__________________________________________________________________________ Vol. % He, NF.sub.3, Time,Run Sequence Run No. Temp., C. NF.sub.3 sccm sccm GHSV sec. % NF.sub.3 loss Comments__________________________________________________________________________Reaction of NF.sub.3 with sodium oxalate: NF.sub.3 + Na.sub.2 C.sub.2O.sub.4 .fwdarw. NaF + N.sub.2 + CO.sub.20.5" Monel reactor packed w/15-cc of Na.sub.2 C.sub.2 O.sub.4 (20.5 g)1 15227-5-622 200 1 89 1 360 10 142 15227-5-624 275 1 89 1 360 10 133 15227-5-626 350 1 89 1 360 10 404 15227-6-628 350 1 89 1 360 10 405 15227-6-631 450 1 89 1 360 10 1006 15227-6-634 400 1 89 1 360 10 1007 15227-7-637 400 1 178 2 720 5 338 15227-7-640 450 1 178 2 720 5 789 15227-7-643 450 1 89 1 360 10 100Reaction of NF.sub.3 with sodium carbonate: NF.sub.3 + Na.sub.2 CO.sub.3.fwdarw. NaF + CO.sub.2 + O.sub.2 + N.sub.20.5" Monel reactor packed w/15-cc of Na.sub.2 CO.sub.3 (18.5 g)1 15227-9-657 200 1 89 1 360 10 32 15227-9-660 300 1 89 1 360 10 793 15227-9-662 400 1 89 1 360 10 1004 15227-10-666 400 1 178 2 720 5 695 15227-10-669 500 1 178 2 720 5 95 no N2Reaction of NF.sub.3 with calcium oxalate: NF.sub.3 + CaC.sub.2 O.sub.4.fwdarw. CaF.sub.2 + CO.sub.2 + N.sub.21.0" Monel reactor packed w/15-cc of CaC.sub.2 O.sub.4 on graphite boat(6.86 g)1 15227-11-672 200 1 89 1 360 10 102 15227-11-675 300 1 89 1 360 10 963 15227-12-678 350 1 89 1 360 10 1004 15227-12-681 350 1 178 2 720 5 995 15227-12-684 350 1 267 3 1080 3.33 706 15227-12-687 400 1 267 3 1080 3.33 907 15227-13-690 400 1 178 2 720 5 91Reaction of NF.sub.3 with cesium oxalate: NF.sub.3 + CsC.sub.2 O.sub.4.fwdarw. CsF + CO.sub.2 + N.sub.21.0" Monel reactor packed w/15-cc of CsC.sub.2 O.sub.4 on graphite boat(26.0 g)1 15227-22-798 200 1 89 1 360 10 172 15227-22-801 300 1 89 1 360 10 333 15227-22-804 350 1 89 1 360 10 604 15227-23-807 400 1 89 1 360 10 985 15227-23-810 400 1 178 2 720 5 516 15227-23-813 400 1 89 1 360 10 72__________________________________________________________________________

As can be seen in Table 1, various metal oxalates and carbonates can be effective to abate NF.sub.3 from a gas containing NF.sub.3 to remove up to 100% by volume of the NF.sub.3. The data demonstrates that temperatures should preferably be in the range of 300-450.degree. C. and the flow rate must be set to allow for adequate residence time for the metal oxalate or carbonate to react with the NF.sub.3. Although the experiments were conducted on a 1% by volume NF.sub.3 -containing helium gas, it is expected that the abatement process would be effective on other concentrations of NF.sub.3, because the dilute concentrations of NF.sub.3 have been the most difficult to achieve complete abatement, and therefore, this represents the most difficult test of the efficacy of the process.

Alternatively, the process of the present invention could be used in a fluidized bed in which a portion of the the metal oxalate or carbonate is continually recharged for a continuous process by removal of the metal fluoride and introduction of fresh metal oxalate or carbonate.

Preferably, the reagent is calcium oxalate, which forms calcium fluoride upon reaction with NF.sub.3. The calcium fluoride is more amenable to handling and disposal. The metal oxalates can be pyrolized to the corresponding carbonate at approximately 350.degree. C. for disposal.

The present invention represents a safer, more environmentally desirable process for NF.sub.3 abatement. In the case of calcium oxalate, the process is run at relatively low temperature and results in nonhazardous by-products. Under normal conditions, there is relatively no risk of explosive conditions existing. This process also does not convert NF.sub.3 to HF gas or other gaseous fluoride, which gaseous fluorides must be treated in an aqueous-based scrubber system.

The present invention has been set forth with regard to several preferred embodiments, but the full scope of the present invention should be ascertained from the claims which follow.

Claims

1. A process for abatement of NF.sub.3 in gas streams containing NF.sub.3 comprising contacting said gas stream containing NF.sub.3 with a reagent selected from the group consisting of metal oxalates and mixtures thereof to abate said NF.sub.3.

2. The process of claim 1 wherein said metal is selected from the group consisting of alkali metals, alkali earth metals and mixtures thereof.

3. The process of claim 1 wherein said reagent is sodium oxalate.

4. The process of claim 1 wherein said reagent is calcium oxalate.

5. The process of claim 1 wherein said reagent is cesium oxalate.

6. The process of claim 1 wherein the temperature of said reaction conditions is in the range of 300 to 450.degree. C.

7. The process of claim 1 wherein said NF.sub.3 is present in said gas containing NF.sub.3 in an amount of no greater than 1% by volume.

8. The process of claim 1 wherein said gas containing NF.sub.3 contacts said reagent in a packed bed of said reagent.

9. The process of claim 1 wherein said gas containing NF.sub.3 contacts said reagent in a fluidized bed of said reagent.

10. The process of claim 1 wherein said NF.sub.3 is abated to less than 10 ppm by volume.