[0001] 1. Field of the Invention
[0002] The present invention relates to a method and apparatus for the production of highly pure ruthenium and ruthenium dioxide and is a divisional of application Ser. No. 09/655,307, filed Sep. 5, 2000, now allowed.
[0003] 2. Description of the Related Art and General Background
[0004] A member of the platinum group, ruthenium occurs naturally with other members of the platinum group in ores found in Russia's Ural mountains, North and South America, and particularly, South Africa. It is also found along with other platinum metals in small but commercial quantities in both the pentlandite of the Sudbury, Ontario, nickel-mining region, and in the pyroxinite deposits of South Africa. Commercially, ruthenium may be isolated from the other platinum metals through several complex chemical processes, the final stage of which generally includes the hydrogen reduction of ammonium ruthenium chloride or nitrosylruthenium chloride, to produce ruthenium metal powder.
[0005] Ruthenium, a hard, white metal, is one of the most effective hardeners for platinum and palladium and is typically alloyed with these metals to produce electrical contacts for severe wear resistance. There have also been reports that a ruthenium alloy, specifically a ruthenium-molybdenum alloy, exhibits superconductivity at 10.6° K. It has also been reported that the corrosion resistance of titanium can be improved over 100 times by adding as little as 0.1% ruthenium. Ruthenium is also a versatile catalyst and is frequently used in petrochemical and other industrial processes to remove H
[0006] One method for extracting ruthenium is disclosed in U.S. Pat. No. 3,997,337 (“the '337 patent”). The '337 patent included a discussion of both earlier methods for the separation and purification of precious metals, including ruthenium, from a concentrate of by-metals and the improved method taught by the patent. The improvement disclosed in the '337 patent for the separation and purification of precious metals, including ruthenium, from a concentrate of by-metals comprised heating the concentrate to a temperature between 1100° C. and 1500° C., preferably at about 1300° C., in a gaseous stream which comprises oxygen. This heating step is continued for a period sufficient to ensure quantitative removal of one or more of lead, arsenic, silver, bismuth and/or tellurium and the oxidation of ruthenium, rhodium and iridium. The referenced by-metal concentrate is obtained as a by-product of the separation of platinum, palladium, and gold from an ore or other mixed source.
[0007] In the previous process, the by-metal concentrate was fused with potassium bisulphate (KHSO
[0008] The improvement outlined in the '337 patent was intended to provide a process for the treatment of a by-metal concentrate for 1) to remove troublesome impurities such as Te, As, Bi, Ag, and Pb; 2) the removal of osmium; and 3) to reduce the bulk of the by-metals being refined thereby providing saving in both reagents and equipment. This was accomplished by treating a concentrate of by-metals by heating to between about 1100° C. and 1500° C. in an oxygen-containing gaseous stream for a period of time (examples include times of 20 hours) sufficient to ensure both quantitative removal of one or more of lead, arsenic, silver, bismuth and/or tellurium and the oxidation of ruthenium, rhodium and iridium to their oxides. According to the patent, the oxygen-containing gaseous stream could be air and the exhaust gas could be scrubbed with a liquid to recover osmium. The '337 patent also provided for the separation of ruthenium from the other platinum group metals by fusing the ignited by-metal concentrate with potassium hydroxide and leaching the melt with water to dissolve ruthenium complexes formed during the fusion process. As described in the '337 patent, a by-metal concentrate was heated to about 1300° C. for 20 hours in a stream of air, a process by which osmium, together with lead, arsenic, silver, bismuth and tellurium, were quantitatively removed from the concentrate while less than 10% of the ruthenium and only traces of the other platinum group metals were volatilized. The vapors were scrubbed with a 10% NaOH solution to precipitate all the metals, with the exception of ruthenium and osmium, as hydrous oxides (which settle to the bottom of the receiving vessel). The ruthenium and osmium oxides which are converted to soluble sodium salts according to the following reactions:
[0009] The ruthenium was then precipitated from the alkali solution by the addition of ethanol to reduce the oxo-anion RuO
[0010] U.S. Pat. No. 4,105,442 (“the '442 patent”) teaches an alternative process for the separation and purification of ruthenium involving the conversion of the ruthenium present in solution to a nitrosylruthenium complex with the ruthenium in the Ru+2 oxidation state. The nitrosylruthenium complex is then converted to a nitrosylruthenium chlorocomplex, which is then removed from solution using a suitable liquid or resin anion exchanger.
[0011] The '442 patent notes the existence of conventional techniques for the recovery and purification of ruthenium and osmium based on the formation of low boiling temperature oxides in solution, with the oxides being subsequently removed from the solution by heating. For osmium, oxidation of the metal to the VIII oxidation state is relatively easy, and a number of oxidizing agents can be used. Furthermore, osmium can be efficiently removed as the tetraoxide forms even under fairly strongly acid conditions. In the case of ruthenium however, the oxidation is more difficult and control of the solution pH at a relatively high value is essential. Under these circumstances, removal of ruthenium from solution is incomplete, typically leaving several hundred parts per million of ruthenium in the solution. This not only represents a loss in ruthenium recovery, but the remaining ruthenium constitutes an impurity element during the refining and recovery of the other platinum group metals. Further disadvantages of this process include contamination of the ruthenium distillate with an acid and the explosion danger associated with the highly unstable nature of ruthenium tetraoxide.
[0012] Other methods for the separation and purification of ruthenium using solvent extraction and ion exchange methods have met with limited success and usually involve solvent extraction from a nitric acid solution. In such solutions ruthenium occurs as a series of nitrosylruthenium nitrate complexes that can be separated from the solution by solvent extraction with, typically, long chain tertiary amines. It is well known that ruthenium forms a very large number of nitrosylruthenium complexes and that the stability of such complexes is greater for ruthenium than for any other element. Thus, for example, in hydrochloric acid solution the nitrosylruthenium complex RuNOCl
[0013] The '442 patent goes on to address these issues to provide a process for the extraction of ruthenium as a nitrosylruthenium complex with both high yield and selectivity with respect to the other platinum group metals.
[0014] Yet another alternative process for the purification of ruthenium metal involved zone-refining. According to this process, a sample of impure ruthenium metal is subjected to one or more heat treatments to form a zone of molten ruthenium, surrounded by solid ruthenium, and move this molten zone along the ruthenium sample and thereby segregate impurities from the ruthenium. Although this technique can produce very pure ruthenium, ruthenium's relatively high melting point (approximately 2280° C.) makes this process very energy intensive and requires more specialized equipment to implement than the applicants' invention.
[0015] The present invention comprises a new and improved method capable of purifying ruthenium sources to obtain high purity ruthenium without the need for high temperature processing, expensive reagents, complex series of wet processes, or expensive equipment required to practice prior art processes. According to the present invention, a gas stream including ozone (O
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[0023] The present invention comprises a new and improved method capable of purifying ruthenium sources to obtain high purity ruthenium without the need for high temperature processing, expensive reagents, complex series of wet processes, or expensive equipment required to practice prior art processes. According to the present invention, a gas stream including ozone (O
[0024] In its crystal form, ruthenium (VIII) oxide (RuO
[0025] The ruthenium tetraoxide, along with unreacted ozone and other gases is then fed from one or more reaction vessels into a heated collection vessel, the conditions in the collection vessel being sufficient to convert a major portion of the gaseous ruthenium tetraoxide into ruthenium dioxide (RuO
[0026] The ruthenium dioxide deposits on the walls of the collection vessel and/or collection surfaces or substrates disposed within the collection vessel. The collected ruthenium dioxide is then reduced to produce the purified ruthenium. When using hydrogen gas as the reducing agent, the reduction proceeds according to the reaction (3) below:
[0027] The morphology of both the ruthenium dioxide and the resulting ruthenium was related to the temperature of the collection vessel. The collection vessel employed by the applicants was surrounded by a single zone furnace that resulted in a non-uniform temperature profile along the length of the collection vessel. The furnace temperature set point was achieved near the midpoint of the collection vessel, with the temperature decreasing towards both ends of the collection vessel. The predominant morphology of the purified ruthenium deposited in the collection vessel was crystalline needles, but a finer grained mirror-like region was also observed toward the inlet side of the collection vessel. If desired, a collection vessel with a more uniform profile could be utilized to produce deposits comprising essentially a single morphology, either crystalline needles or a mirror-like layer. This crystallographic selectivity could also be employed to coat selected substrates, e.g. wafers or metallic substrates, with either the crystalline needles or a mirror-like layer of ruthenium dioxide or, after reduction, ruthenium.
[0028] Similarly, a collection vessel could be provided with a series of heated collection surfaces (
[0029] Using the apparatus generally depicted in
[0030] ruthenium in the first reaction vessel and 11.0 g of ruthenium in the second reaction vessel. The ozone reacted with the ruthenium metal sponge at room temperature and pressure to form ruthenium tetraoxide which was visible in the reaction vessels (TABLE 1 Starting After Purification Trace Metal (ppm) (ppm) Ni 2 0.3 Cu 2 0.1 Fe 88 2.0 Al <10 0.3 Ca 15 0.2 Si 76 10 Mg 8 0.1 Cr 4.1 0.6
[0031] Among the advantages provided by the present invention is the high purity achieved by an essentially “dry” process that does not require temperatures above 500° C. and eliminates the need for expensive reagents or resins and does not require highly specialized equipment. Another advantage is that the concentration of ruthenium tetraoxide is relatively low and its residence time in the apparatus is relatively short (as it flows from the reactor into the collection vessel) so the risk of explosion is minimized. The applicants also believe that the relatively limited residence time also reduces the formation of undesireable byproducts within the apparatus and/or on the ruthenium source.
[0032] The reaction rates obtained with experimental apparatus utilized by the applicants (
[0033] One configuration that would achieve this improvement would involve flowing the ozone/oxygen mixture through a large chamber (
[0034] In addition to the purification of ruthenium and ruthenium compounds, the basic chemistry embodied in the present invention has practical application as an etch process for semiconductor, circuit board, or other instances in which a thin ruthenium film is to be etched. Compared to other metal etching processes, the low temperature and relatively high pressures (near ambient pressure and temperature) at which ozone could be used to etch ruthenium layers eliminate the need for expensive process gases, vacuum chambers and their associated load locks and vacuum pumps, and reduce the overall power consumption associated with the etch process. Any ozone necessary for the process could be produced on site, thereby, avoiding the risks associated with the transportation, storage, and use of high pressure gas cylinders. Similarly, any unreacted ozone could be removed from the exhaust stream by known catalytic or temperature treatments, thereby reducing any environmental impact of the present process when compared with some of the prior art etch chemistries. The advantages provided by the on-site production of the ozone are, of course, equally applicable to the disclosed process for the purification of ruthenium. As envisioned by the applicants, a typical etch process would start with a semiconductor wafer having as its surface layer ruthenium metal. The wafer would be patterned with some barrier material, such as photoresist, and then contacted with an ozone-containing gas stream to oxidize the exposed ruthenium metal to produce the volatile ruthenium tetraoxide RuO