The present invention relates to producing ion beams in which one or more gaseous or vaporized feed materials is ionized in an ion source. It also relates to a method and apparatus for operating an ion source to produce an ion beam for ion implantation of semiconductor substrates and substrates for flat panel displays. In particular the invention concerns extension of the productive time (i.e. the “uptime”) of systems that produce ion beams.
Ion beams are produced from ions extracted from an ion source. An ion source typically employs an ionization chamber connected to a high voltage power supply. The ionization chamber is associated with a source of ionizing energy, such as an arc discharge, energetic electrons from an electron-emitting cathode, or a radio frequency or microwave antenna, for example. A source of desired ion species is introduced into the ionization chamber as a feed material in gaseous or vaporized form where it is exposed to the ionizing energy. Extraction of resultant ions from the chamber through an extraction aperture is based on the electric charge of the ions. An extraction electrode is situated outside of the ionization chamber, aligned with the extraction aperture, and at a voltage below that of the ionization chamber. The electrode draws the ions out, typically forming an ion beam. Depending upon desired use, the beam of ions may be mass-analyzed for establishing mass and energy purity, accelerated, focused and subjected to scanning forces. The beam is then transported to its point of use, for example into a processing chamber. As the result of the precise energy qualities of the ion beam, its ions may be implanted with high accuracy at desired depth into semiconductor substrates.
The precise qualities of the ion beam can be severely affected by condensation and deposit of the feed material or of its decomposition products on surfaces of the ion beam-producing system, and in particular surfaces that affect ionization, ion extraction and acceleration.
The Ion Implantation Process
The conventional method of introducing a dopant element into a semiconductor wafer is by introduction of a controlled energy ion beam for ion implantation. This introduces desired impurity species into the material of the semiconductor substrate to form doped (or “impurity”) regions at desired depth. The impurity elements are selected to bond with the semiconductor material to create electrical carriers, thus altering the electrical conductivity of the semiconductor material. The electrical carriers can either be electrons (generated by N-type dopants) or “holes” (i.e., the absence of an electron), generated by P-type dopants. The concentration of dopant impurities so introduced determines the electrical conductivity of the doped region. Many such N- and P-type impurity regions must be created to form transistor structures, isolation structures and other such electronic structures, which collectively function as a semiconductor device.
To produce an ion beam for ion implantation, a gas or vapor feed material is selected to contain the desired dopant element. The gas or vapor is introduced into the evacuated high voltage ionization chamber while energy is introduced to ionize it. This creates ions which contain the dopant element (for example, in silicon the elements As, P, and Sb are donors or N-type dopants, while B and In are acceptors or P-type dopants). An accelerating electric field is provided by the extraction electrode to extract and accelerate the typically positively-charged ions out of the ionization chamber, creating the desired ion beam. When high purity is required, the beam is transported through mass analysis to select the species to be implanted, as is known in the art. The ion beam is ultimately transported to a processing chamber for implantation into the semiconductor wafer.
Similar technology is used in the fabrication of flat-panel displays (FPD's) which incorporate on-substrate driver circuitry to operate the thin-film transistors which populate the displays. The substrate in this case is a transparent panel such as glass to which a semiconductor layer has been applied. Ion sources used in the manufacturing of FPD's are typically physically large, to create large-area ion beams of boron, phosphorus and arsenic-containing materials, for example, which are directed into a chamber containing the substrate to be implanted. Most FPD implanters do not mass-analyze the ion beam prior to its reaching the substrate.
Ion Contamination
In general, ion beams of N-type dopants such as P or As should not contain any significant portion of P-type dopant ions, and ion beams of P-type dopants such as B or In should not contain any significant portion of N-type dopant ions. Such a condition is called “cross-contamination” and is undesirable. Cross-contamination can occur when source feed materials accumulate in the ion source, and the source feed material is then changed, for example, when first running elemental phosphorus feed material to generate an N-type P+ beam, and then switching to BF3 gas to generate a P-type BF2+ beam.
A serious contamination effect occurs when feed materials accumulate within the ion source so that they interfere with the successful operation of the source. Such a condition invariably has called for removal of the ion source and the extraction electrode for cleaning or replacement, resulting in an extended “down” time of the entire ion implantation system, and consequent loss of productivity.
Many ion sources used in ion implanters for device wafer manufacturing are “hot” sources, that is, they operate by sustaining an arc discharge and generating a dense plasma; the ionization chamber of such a “hot” source can reach an operating temperature of 800C or higher, in many cases substantially reducing the accumulation of solid deposits. In addition, the use of BF3 in such sources to generate boron-containing ion beams further reduces deposits, since in the generation of a BF3 plasma, copious amounts of fluorine ions are generated; fluorine can etch the walls of the ion source, and in particular, recover deposited boron through the chemical production of gaseous BF3. With other feed materials, however, detrimental deposits have formed in hot ion sources. Examples include antimony (Sb) metal, and solid indium (In), the ions of which are used for doping silicon substrates.
Cold ion sources, for example the RF bucket-type ion source which uses an immersed RF antenna to excite the source plasma (see, for example, Leung et al., U.S. Pat. No. 6,094,012, herein incorporated by reference), are used in applications where either the design of the ion source includes permanent magnets which must be kept below their Curie temperature, or the ion source is designed to use thermally-sensitive feed materials which break down if exposed to hot surfaces, or where both of these conditions exist. Cold ion sources suffer more from the deposition of feed materials than do hot sources. The use of halogenated feed materials for producing dopants may help reduce deposits to some extent, however, in certain cases, non-halogen feed materials such as hydrides are preferred over halogenated compounds. For non-halogen applications, ion source feed materials such as gaseous B2H6, AsH3, and PH3 are used. In some cases, elemental As and P are used, in vaporized form. The use of these gases and vapors in cold ion sources has resulted in significant materials deposition and has required the ion source to be removed and cleaned, sometimes frequently. Cold ion sources which use B2H6 and PH3 are in common use today in FPD implantation tools. These ion sources suffer from cross-contamination (between N- and P-type dopants) and also from particle formation due to the presence of deposits. When transported to the substrate, particles negatively impact yield. Cross-contamination effects have historically forced FPD manufacturers to use dedicated ion implanters, one for N-type ions, and one for P-type ions, which has severely affected cost of ownership.
Borohydrides
Borohydride materials such as B10H14 (decaborane) and B18H22 (octadecaborane) have attracted interest as ion implantation source materials. Under the right conditions, these materials form the ions B10Hx+, B10Hx−, B18Hx+, and B18Hx−. When implanted, these ions enable very shallow, high dose P-type implants for shallow junction formation in CMOS manufacturing. Since these materials are solid at room temperature, they must be vaporized and the vapor introduced into the ion source for ionization. They are low-temperature materials (e.g., decaborane melts at 100C, and has a vapor pressure of approximately 0.2 Torr at room temperature; also, decaborane dissociates above 350C), and hence must be used in a cold ion source. They are fragile molecules which are easily dissociated, for example, in hot plasma sources.
Contamination Issues of Borohydrides
Boron hydrides such as decaborane and octadecaborane present a severe deposition problem when used to produce ion beams, due to their propensity for readily dissociating within the ion source. Use of these materials in Bernas-style arc discharge ion sources and also in electron-impact (“soft”) ionization sources, have confirmed that boron-containing deposits accumulate within the ion sources at a substantial rate. Indeed, up to half of the borohydride vapor introduced into the source may stay in the ion source as dissociated, condensed material. Eventually, depending on the design of the ion source, the buildup of condensed material interferes with the operation of the source and necessitates removal and cleaning of the ion source.
Contamination of the extraction electrode has also been a problem when using these materials. Both direct ion beam strike and condensed vapor can form layers that degrade operation of the ion beam formation optics, since these boron-containing layers appear to be electrically insulating. Once an electrically insulating layer is deposited, it accumulates electrical charge and creates vacuum discharges, or so-called “glitches”, upon breakdown. Such instabilities affect the precision quality of the ion beam and can contribute to the creation of contaminating particles.
It is an object of this invention to provide a method and apparatus for producing an ion beam which increases service lifetime and reduces equipment down time.
The invention features in-situ cleaning procedures and apparatus for an ion source and associated extraction electrodes and similar components of the ion-beam producing system, which periodically chemically remove deposits, increasing service lifetime and performance, without the need to disassemble the system.
The invention also features an actively heated ion extraction electrode which consists of a material which reduces the frequency and occurrence of electrical discharges, preferably this material being a metal.
Another feature is, in general, heating an extraction electrode above the condensation temperature of feed materials to an ion source, in preferred cases the electrode being comprised of metal, preferably aluminum or molybdenum.
The invention also features steps and construction features that improve the production and utilization of ions. This reduces the required concentration of feed material in the ion source, and in related manner, reduces the rate of accumulation of detrimental deposits on surfaces of the ion-beam producing system.
These and other innovations of the invention may include one or more of the following features:
A supply of a reactive gas is provided and introduced into the ion source, and the ion source is cleaned in situ through exposure to reactive products from that supply such as atomic fluorine, F, or molecular fluorine, F2; the atomic or molecular fluorine is injected into the ion source from a remote plasma source; the ion source is cleaned through exposure to gaseous ClF3 flowing from a remote supply; reactive components of the ionization apparatus are shielded from reactive gas during the cleaning phase of operation; the ion source is fabricated of aluminum; the extraction electrode is fabricated of aluminum; the front face of the extraction electrode is devoid of sharp or rough features; the plates of the extraction electrode are actively temperature controlled; the plates of the extraction electrode are actively heated; heating of the extraction electrode is radiative or is resistive; the plates of the extraction electrode in other situations are actively cooled.
Another feature is the use of the features described with apparatus suitable to form “cluster” or “molecular” ion beams, of feed material that is particularly subject to thermal breakdown and deposit.
While most ion implantation experts would agree that the use of borohydrides to form “cluster” ion beams such as B10Hx+ and B18Hx+ is very attractive for shallow junction formation, means to ionize and transport these large molecules have presented problems. For example, U.S. Pat. Nos. 6,288,403 and 6,452,338 describe ion sources which have successfully produced decaborane ion beams. However, such decaborane ion sources have been found to exhibit particularly short service life as compared to other commercial ion sources used in ion implantation. This short service life has been primarily due to the accumulation of boron-containing deposits within the ion source, and the deposition of insulating coatings on the ion extraction electrode, which has lead to beam instabilities requiring implanter shut down and maintenance.
According to another feature, means are provided to substantially reduce the deposition of such deposits in the borohydride ion source and on the ion extraction electrode, and means are provided to clean deposits on these components without removing them from the ion implanter, i.e., in-situ. This invention enables the commercial use of borohydride cluster beams in semiconductor manufacturing with long service lifetime.
A particular aspect of the invention is a system for generating an ion beam comprising an ion source in combination with an extraction electrode and a reactive gas cleaning system, the ion source comprising an ionization chamber connected to a high voltage power supply and having an inlet for gaseous or vaporized feed materials, an energizeable ionizing system for ionizing the feed material within the ionization chamber and an extraction aperture that communicates with a vacuum housing, the vacuum housing evacuated by a vacuum pumping system, the extraction electrode disposed in the vacuum housing outside of the ionization chamber, aligned with the extraction aperture of the ionization chamber and adapted to be maintained at a voltage below that of the ionization chamber to extract ions through the aperture from within the ionization chamber, and the reactive gas cleaning system operable when the ionization chamber and ionizing system are de-energized to provide a flow of reactive gas through the ionization chamber and through the ion extraction aperture to react with and remove deposits on at least some of the surfaces of the ion generating system.
Preferred embodiments of this aspect have one or more of the following features.
The system is constructed for use in implanting ions in semiconductor wafers, the ionization chamber having a volume less than about 100 ml and an internal surface area of less than about 200 cm2.
The system is constructed to produce a flow of the reactive gas into the ionization chamber at a flow rate of less than about 2 Standard Liters Per Minute.
The extraction electrode is constructed to produce a beam of accelerated ions suitable for transport to a point of utilization.
The extraction electrode is located within a path of reactive gas moving from the extraction aperture to the vacuum pumping system so that the extraction electrode is cleaned by the reactive gas.
The extraction electrode is associated with a heater to maintain the electrode at elevated temperature during extraction by the extraction electrode of ions produced in the ionization chamber, e.g. above the condensation temperature, below the disassociation temperature, of solid-derived, thermally sensitive vapors.
The extraction electrode is associated with a cooling device, e.g. when the electrode is formed of thermally sensitive material and is used with a hot ion source.
The extraction electrode has a smooth, featureless aspect.
The reactive gas cleaning system comprises a plasma chamber, the plasma chamber arranged to receive a feed gas capable of being disassociated by plasma to produce a flow of reactive gas through a chamber outlet, and a conduit for transporting the reactive gas to the ionization chamber.
The plasma chamber is constructed and arranged to receive and disassociate a compound capable of being disassociated to atomic fluorine, for instance NF3, C3F8 or CF4.
The reactive gas cleaning system is constructed and arranged to share a service facility associated with the ion source.
The system is constructed to direct an ion beam through a mass analyzer, in which the reactive gas cleaning system is constructed and arranged to share a service facility with the mass analyzer.
The reactive gas cleaning system comprises a conduit from a container of pressurized reactive gas, for instance ClF3.
The system is in combination with an end-point detection system adapted to at least assist in detecting substantial completion of reaction of the reactive gas with contamination on a surface of the system for generating an ion beam.
The end point detection system comprises an analysis system for the chemical makeup of gas that has been exposed to the surface during operation of the reactive gas cleaning system.
A temperature detector is arranged to detect substantial termination of an exothermic reaction of the reactive gas with contamination on a surface of the system.
The energizeable ionizing system includes a component within or in communication with the ionization chamber that is susceptible to harm by the reactive gas and means are provided to shield the component from reactive gas flowing through the system.
The means to shield the component comprises an arrangement for producing a flow of inert gas, such as argon, past the component.
The means for shielding a component comprises a shield member that is impermeable to the reactive gas.
The system is constructed to operate with reactive halogen gas as the reactive gas and the extraction electrode and associated parts comprise aluminum (Al) or alumina (Al2O3).
The ion source is constructed to produce ions within the ionization chamber via an arc-discharge, an RF field, a microwave field or an electron beam.
The system is associated with a vaporizer of condensable solid feed material for producing feed vapor to the ionization chamber.
The ion source is constructed to vaporize feed material capable of producing cluster or molecular ions, and the ionization system is constructed to ionize the material to form cluster or molecular ions for implantation.
The vacuum housing of the system is associated with a pumping system comprising a high vacuum pump capable of producing high vacuum and a backing pump capable of producing vacuum, the high vacuum pump operable during operation of the ion source, and being capable of being isolated from the vacuum housing during operation of the reactive cleaning system, the backing pump operable during operation of the reactive gas cleaning system.
The system is associated with an ion implantation apparatus, the apparatus constructed to transport ions following the extraction electrode implantation station within a vacuum chamber. In preferred embodiments an isolation valve is included for isolating the implantation station from the ionization chamber and the extraction electrode during operation of the reactive gas cleaning system.
The ion source is constructed and adapted to generate dopant ions for semiconductor processing, and the reactive gas cleaning system is adapted to deliver fluorine, F, or chlorine, Cl, ions to the ionization chamber or the extraction electrode for cleaning deposits from a surface.
The ion source is adapted to be temperature-controlled to a given temperature.
The ion source is adapted to generate a boron-containing ion beam; in preferred embodiments the boron-containing ion beam is generated by feeding vaporized borohydride material into the ion source, especially either decaborane, B10H14 or octadecaborane, B18H22.
The ion source is adapted to generate arsenic-containing ion beams.
The ion source is adapted to generate phosphorus-containing ion beams.
The ionization chamber of the ion source comprises aluminum.
The ionization chamber of the ion source or the extraction electrode comprises a material resistant to attack by halogen gases such as fluorine, F.
Another particular aspect of the invention is a method of in-situ cleaning using the system of any of the foregoing description, or of an ion source associated with an ion implanter, in which reactive halogen gas is flowed into an ion source while the ion source is de-energized and under vacuum.
Embodiments of this aspect have one or more of the following features.
The reactive halogen gas is fluorine, F.
The reactive halogen gas is chlorine, Cl.
The fluorine gas is introduced into the ion source from a remote plasma source.
The fluorine gas is produced in the remote plasma source by an NF3 plasma.
The fluorine gas is produced in the remote plasma source by a C3F8 or CF4 plasma.
The reactive halogen gas is ClF3.
The cleaning procedure is conducted to remove deposits after the ion source has ionized decaborane, B10H14.
The cleaning procedure is conducted to remove deposits after the ion source has ionized octadecaborane, B18H22.
The cleaning procedure is conducted to remove deposits after the ion source has ionized arsenic-containing compounds, such as arsine, AsH3, or elemental arsenic, As.
The cleaning procedure is conducted to remove deposits after the ion source has ionized phosphorus-containing compounds, such as elemental phosphorus, P, or phosphine, PH3.
The cleaning procedure is conducted to remove deposits after the ion source has ionized antimony-containing compounds, such as trimethylantimony, Sb(CH4)3, or antimony pentaflouride, SbF5.
The cleaning procedure is conducted for an ion source in situ in an ion implanter between changing ion source feed materials in order to implant a different ion species.
Another particular aspect of the invention is an ion implantation system having an ion source and an extraction electrode for extracting ions from the ion source, in which the extraction electrode includes a heater constructed to maintain the electrode at an elevated temperature sufficient to substantially reduce condensation on the electrode of gases or vapors being ionized and products produced therefrom.
Embodiments of this aspect have one or more of the following features.
The electrode comprises aluminum.
The electrode comprises of molybdenum.
The electrode is heated by radiative heaters.
The electrode is heated by resistive heaters).
The temperature of the electrode is controlled to a desired temperature; in embodiments the temperature is between 150C and 250C.
The electrode is periodically cleaned in situ by exposure to reactive halogen-containing gas.
Another aspect of the invention is a method of in-situ cleaning of an ion extraction electrode of any of the systems described or an ion extraction electrode which is associated with an ion implanter, in which reactive halogen gas is flowed over the ion extraction electrode while the electrode is in situ and under vacuum.
Embodiments of this aspect have one ore more of the following features.
The reactive halogen gas is fluorine, F or chlorine, Cl.
Fluorine gas is introduced from a remote plasma source into a vacuum housing in which the extraction electrode resides.
Fluorine gas is produced in the remote plasma source by a NF3 plasma.
Fluorine gas is produced in the remote plasma source by a C3F8 or CF4 plasma.
The reactive gas is ClF3.
The cleaning procedure is conducted to remove deposits after the ion source has ionized decaborane, B10H14. The cleaning procedure is conducted to remove deposits after the ion source has ionized octadecaborane, B18H22.
The cleaning procedure is conducted to remove deposits after the ion source has ionized arsenic-containing compounds, such as arsine, AsH3, or elemental arsenic, As.
The cleaning procedure is conducted to remove deposits after the ion source has ionized phosphorus-containing compounds, such as elemental phosphorus, P, or phosphine, PH3.
The cleaning procedure is conducted between changing ion source feed materials in order to implant a different ion species.
Ion Source Provided with In-situ Etch Cleaning
According to a preferred embodiment, the in situ chemical cleaning process utilizes atomic F gas, to effectively clean deposits from the ion source and from the ion extraction electrode, while the ion source and extraction electrode remain installed in the ion beam-producing system. In a preferred embodiment an electron impact ion source with cooled chamber walls is employed. Preferably, the ionization chamber and source block are fabricated of aluminum or of an aluminum containing complex, enabling aluminum fluoride to be created on the aluminum surfaces to act as a passivating layer, that prevents further chemical attack by F.
One embodiment of this feature uses the outlet of a remote reactive gas source directly coupled to an inlet to the ion source.
In a preferred embodiment the reactive gas source is a plasma source which introduces an etch feed gas, such as NF3 or C3F8, into a supplemental ionization chamber. By sustaining a plasma in the supplemental chamber, reactive gases such as F and F2 are produced, and these reactive gases, introduced to the main ion source, chemically attack the deposited materials. By-products released in the gas phase are drawn through the extraction aperture of the ionization chamber and are pumped away by the vacuum system of the installation, cleaning the chamber.
Deposition Model
It is a generally observed principle of physics that when two objects interact, there can be more than one outcome. Furthermore, one can assign probabilities or likelihoods to each outcome such that, when all possible outcomes are considered, the sum of their individual probabilities is 100%. In atomic and molecular physics such possible outcomes are sometimes called “channels” and the probability associated with each interaction channel is called a “cross section”. More precisely, the likelihood of two particles (say, an electron and a gas molecule) interacting with each other at all is the “total cross section”, while the likelihoods of certain types of interactions (such as the interaction represented by the electron attaching itself to the gas molecule thus forming a negative ion, or by removing an electron from the gas molecule thus forming a positive ion, or by dissociating the molecule into fragments, or by elastically scattering from the molecule with no chemical change of the molecule) are the “partial cross sections”.
This state of affairs can be represented by a mathematical relation which expresses the total cross section σT as the sum of its i partial cross sections:
σT=σ1+σ2+σ3+ . . . σi, or (1)
σT=Σσi. (2)
The ion sources used in ion implanters typically display modest ionization fractions. That is, only a small fraction (from a few percent to a few tens of percent) of the gas or vapor fed into the ion source is ionized. The rest of the gas or vapor typically leaves the source in the gas phase, either in its original state or in some other neutral state. That is, the ionization cross section is much smaller than the total cross section. Of course, some of the gas components can stay in the ion source as deposited materials, although this tends to be a small percentage of the total for the commonly used implantation feed materials. While feed materials vaporized by heating such as elemental As or P more readily produce deposits than do normally gaseous feed materials, the heated vapor tends to stay in the gas phase if the walls of the ion source are at a higher temperature than the vaporizer, and do not pose a severe deposition risk. However, significant detrimental deposits may still be produced when producing boron beams from gaseous BF3 feed gas, for example, as well as beam from In and Sb.
Also, in general, over time, deposits of condensable materials do occur on certain other components of ion producing systems, affecting their operational life before disassembly and cleaning.
Furthermore, in the case of the borohydrides, the total cross section representing all interactions with the ionizing medium (i.e., electrons in the ion source) appears large, the ionization cross section is small, and by far the largest cross section represents the channel for dissociation of the borohydride molecules into non-volatile fragments, which then remain on surfaces in the ion source. The problem of deposition of these fragments is adversely influenced by cooling of the ionization chamber walls in an effort to reduce thermal decomposition of the feed material. In sum, it appears that deposition from borohydrides of boron-containing fragments in the source is a fundamental phenomenon which would be observed in any type of ion source acting on this material, and solution to the problem is of broad, critical interest to the semiconductor manufacturing industry.
Electron Impact Ion Source Suitable for Borohydrides
An ion source particularly suitable for borohydrides is an electron-impact ion source which is fully temperature-controlled (see U.S. Pat. Nos. 6,452,338 and 6,686,595; also International Application no. PCT/U.S.03/20197, each herein incorporated by reference); also see
Extension of Ion Source Lifetime with Decaborane Between Cleanings
The impact of vapor flow rate on source lifetime (maintenance interval) was studied in a quantitative manner. The electron impact ion source was run continuously with decaborane feed material under controlled conditions at a given vapor flow, until it was determined that the buildup of material was causing a significant decrease in decaborane beam current. Five different flow rates were tested, ranging from about 0.40 sccm to 1.2 sccm. This resulted in mass-analyzed decaborane beam currents (B10Hx+) ranging from about 150 μA to 700 μA. It is noted that typical feed gas flows in ion sources used in ion implantation range from 1 to about 3 sccm, so this test range is considered a “low” flow regime.
The results of these lifetime tests are summarized in
(flow rate)×(flow duration)=constant. (3)
Equation (3) simply states that lifetime (i.e., flow duration) is inversely proportional to flow rate; the constant is the amount of deposited material. If equation (3) is accurate, then the fraction of deposited material is independent of the rate of flow of material, which is consistent with our model describing a fixed cross section for dissociation and subsequent deposition. These data show that, using the electron impact ion source with about 0.5 sccm decaborane vapor flow, dedicated decaborane operation can be sustained for more than 100 hours. While this is acceptable in many cases, in commercial semiconductor fabrication facilities, source lifetimes of well over 200 hours are desired. When the ion source is used in conjunction with the novel in-situ cleaning procedure of the present invention, greatly extended source lifetimes are achieved.
Advantages of Certain Features of In-situ Ion Source Chemical Cleaning
There are several very important advantages to using a supplemental ion source to produce the reactive gas for in situ cleaning of the ion source. Such plasma sources have been developed for effluent removal applications from process exhaust systems (such as the Litmus 1501 offered by Advanced Energy, Inc.), and for cleaning large CVD process chambers (such as the MKS Astron reactive gas generator), but to the inventors' knowledge it has not been previously recognized that a remote reactive gas generator could be usefully applied to cleaning the ionization chamber of an ion source and the extraction electrode used to generate an ion beam. Remote reactive gas generators such as the MKS Astron have been used to clean process chambers (i.e., relatively large vacuum chambers wherein semiconductor wafers are processed), an application which uses high flows of feed gas (several Standard Liters per Minute (SLM)), and high RF power applied to the plasma source (about 6 kW). The system of the present invention can employ a much more modest feed gas rate, e.g. less than about 0.5 SLM of NF3, and much less RF power (less than about 2.5 kW), for the very small volume of the ionization chamber of the ion source being cleaned (the volume of the ionization chamber for an implanter of semiconductor wafers is typically less than about 100 ml, e.g. only about 75 ml, with a surface area of less than about 200 cm2, e.g. about 100 cm2). The reactive gas flow into the ionization chamber is less than about 2 Standard Liters Per Minute.
One might think it strange to use an external ion source to generate plasma by-products to introduce into the main ion source of the system; why not just introduce the (e.g., NF3) gas directly into the main ion source to create the plasma by-products within that source directly? The reasons seem not obvious. In order to achieve etch rates which far exceed deposition rates from the feed gas during a small fraction of the uptime (productive period) of the ion implantation system, it is found that the reactive gas must be produced and introduced at relatively very high flows into the small ionization chamber, e.g., flows on the order of 102 to 103 sccm, compared to typical feed flow rates for the main ion source for ion implantation in the range of 1-3 sccm; such high flows would raise the pressure within the ionization chamber of the main ion source far beyond that for which it is designed to operate for ion implantation. Furthermore, sustaining a high-density NF3 plasma within the main ion source would etch away sensitive components, such as hot tungsten filaments. This is because halogen gases etch refractory metals at a high rate which increases exponentially with temperature. (For example, Rosner et al. propose a model for F etching of a tungsten substrate:
Rate(microns/min)=2.92×10−14T1/2NFe−3900/T, (4)
Where NF is the concentration of fluorine in atoms per cm3, and T is the substrate temperature in degrees Kelvin.)
Since virtually all ion sources for ion implantation incorporate hot filaments, and since in many cases the ion source chambers are also made of refractory metals such as Mo and W, or graphite (which is aggressively attacked by F), these ion sources would quickly fail under high temperature operating conditions, making the etch cleaning process unusable.
In the presently preferred embodiment, atomic fluorine is caused to enter the cold ionization chamber of the de-energized main ion source at a flow rate of 100 sccm or more, and the total gas flow into the ionization chamber is 500 sccm or more. Under these conditions, the gas pressure within the ionization chamber is about 0.5 Torr, while the pressure within the vacuum source housing of the implanter is a few tens of milliTorr or more. In a preferred mode of operation, preceding the cleaning phase, an isolation valve is closed between the vacuum housing of the ion source and the implanter vacuum system, and the turbo-molecular pump of the ion source is isolated. The housing of the ion source is then pumped with high-capacity roughing pumps of the vacuum system (i.e., the pumps which normally back the turbomolecular pumps and evacuate the vacuum system down to a “rough” vacuum).
A different embodiment of a related etch clean process, shown in
Advantages of the in-situ chemical cleaning of the ion source for an ion implanter include: a) extending source life to hundreds, or possibly thousands, of hours before service is required; b) reducing or eliminating cross-contamination brought about by a species change, for example, when switching from octadecaborane ion implantation to arsenic or phosphorus ion implantation, and from arsenic or phosphorus ion implantation to octadecaborane ion implantation; and c) sustaining peak ion source performance during the service life of the ion source. For example, performing a 10 minute chemical cleaning protocol every eight hours (i.e., once every shift change of operating personnel) and between each species change would have a minimal impact on the uptime of the implanter, and would be acceptable to a modern semiconductor fabrication facility.
Endpoint Detection
It is realized to be beneficial to provide endpoint detection during the cleaning process, so that quantitative information on the efficacy and required duration of the cleaning process may be generated, and the reproducibility of the chemical cleaning process may be assured.
Novel Ion Extraction Electrode
Borohydrides such as decaborane and octadecaborane are thermally sensitive materials. They vaporize and condense at temperatures between 20C and 100C. It is therefore important to maintain all surfaces with which these materials come into contact at a temperature higher than the vaporizer temperature (but below the temperature at which they dissociate), to prevent condensation. We have found that contamination of the extraction electrode is a problem when using such a borohydride. Both direct ion beam strike and condensed feed vapor or products of its molecular disassociation can degrade operation of the ion beam formation optics, since these boron-containing layers appear to be electrically insulating. Once electrically insulating layers are deposited, they acquire an electrical charge (“charge up”) and create vacuum discharges, or “glitches”, upon electrical breakdown. Such a discharge creates instabilities in the ion beam current and can contribute to the creation of particles that may reach a process chamber to which the ion beam is directed. An ion implanter which has an ion beam-producing system that experiences many glitches per hour is not considered production-worthy in modern semiconductor fabrication facilities. Furthermore, even in absence of such discharges, as insulating coatings become thicker, the electric charge on electrode surfaces create unwanted stray electric fields which can result in beam steering effects, creating beam loss and may adversely affect ion beam quality.
Discovery of new information has led to a robust solution to this problem. Most implanter ion extraction electrodes are made of graphite. Graphite has been seen to have many advantages in this application, including low materials cost, ease of machining, high electrical conductivity, low coefficient of thermal expansion, and good mechanical stability at high temperatures. However, using a graphite extraction electrode, instabilities were observed after producing an ion beam of borohydrides. It was suspected that the surfaces of the electrode had become insulating. Samples of the electrode deposits were collected and a chemical analysis performed by x-ray fluorescence spectroscopy. The study revealed a chemical stoichiometry consistent with a boron-carbon compound of the form B2C, which was found to be insulating. In addition, it appeared that metal surfaces in the vicinity of the ion source, including the front plate (i.e., the ion extraction aperture plate) of the ion source also had deposited insulating coatings after long use. It was conceived to fabricate the electrode of aluminum, and provide radiant heaters to keep the electrode plates, i.e., the suppression and ground electrodes, at a well-controlled, elevated temperature (see
The extraction electrode, thus produced, demonstrated excellent performance, and operated reliably for more than 100 hours (at least ten times as long as the graphite electrode) with very low glitch frequency. This great improvement is attributed to: i) Al construction (i.e., metal versus graphite), ii) Active heating and temperature control of the electrode plates, and iii) smooth electrode surfaces. It was found that operating the electrode plates at 200C gave good results when running decaborane, significantly reducing the amount of deposited material. In general, the temperature of the extraction electrode should be kept below the dissociation temperature of the feed material. In the case of decaborane the temperature should be kept below 350C, preferably in the range 150C to 250C For octadecaborane operation, the temperature should not exceed 160C, since chemical changes occur in octadecaborane above this temperature; when running octadecaborane, an extraction electrode temperature between 120C and 150C yields good results.
The radiative design shown in
For constructing a heated extraction electrode, other metals would also work, for example molybdenum. Molybdenum has the advantage of being refractory, so it can withstand very high temperatures. It also has good thermal conductivity. Aluminum, on the other hand, is a column III element like In and B of the periodic table, and therefore offers the advantage of being only a mild contaminant in silicon (it is a P-type dopant in silicon), while transition metals such as molybdenum are very detrimental to carrier lifetimes in integrated circuits. Aluminum is also not readily attacked by halogens, whereas transition metals such as molybdenum are susceptible to attack, particularly at elevated temperatures. The primary disadvantage of aluminum, however, is that it is not a high temperature material, and should be used below about 400 C.
For these reasons, depending upon the particular use, the heated electrode is constructed of a selected heat-resistant material, aluminum or an aluminum containing complex often being preferred when used in association with in situ etch cleaning.
a: B18Hx+ beam profiles.
Novel Ion Beam-Generating System
In order to extract ions of a well-defined energy, the ion source 400 is held at a high positive voltage (in the more common case where a positively-charged ion beam is generated), with respect to the extraction electrode 405 and vacuum housing 410, by high voltage power supply 460. The extraction electrode 405 is disposed close to and aligned with the extraction aperture 504 of the ionization chamber. It consists of at least two aperture-containing electrode plates, a so-called suppression electrode 406 closest to ionization chamber 500, and a “ground” electrode 407. The suppression electrode 406 is biased negative with respect to ground electrode 407 to reject or suppress unwanted electrons which are attracted to the positively-biased ion source 400 when generating positively-charged ion beams. The ground electrode 407, vacuum housing 410, and terminal enclosure (not shown) are all at the so-called terminal potential, which is at earth ground unless it is desirable to float the entire terminal above ground, as is the case for certain implantation systems, for example for medium-current ion implanters. The extraction electrode 405 may be of the novel temperature-controlled metallic design, described below.
(If a negatively charged ion beam is generated the ion source is held at an elevated negative voltage with other suitable changes, the terminal enclosure typically remaining at ground.)
For ion sources suitable for use with ion implantation systems, e.g. for doping semiconductor wafers, the ionization chamber is small, having a volume less than about 100 ml, has an internal surface area of less than about 200 cm2, and is constructed to receive a flow of the reactive gas, e.g. atomic fluorine or a reactive fluorine-containing compound at a flow rate of less than about 200 Standard Liters Per Minute.
It is seen that the system of
Chemical Cleaning System
The embodiment of
To initiate a cleaning cycle, the ion source is shut down and vacuum housing isolation valve 425 is closed; the high vacuum pump 421 of the vacuum pumping system 420 is isolated and the vacuum housing 410 is put into a rough vacuum state of <1 Torr by the introduction of dry N2 gas while the housing is actively pumped by backing pump 422. Once under rough vacuum, argon gas (from Ar gas source 466) is introduced into the plasma source 455 and the plasma source is energized by on-board circuitry which couples radio-frequency (RF) power into the plasma source 455. Once a plasma discharge is initiated, Ar flow is reduced and the F-containing cleaning gas feed 465, e.g. NF3, is introduced into plasma source 455. Reactive F gas, in neutral form, and other by-products of disassociated cleaning gas feed 465, are introduced through reactive gas inlet 430 into the de-energized ionization chamber 500 of ion source 400. The flow rates of Ar and NF3 (for example) are high, between 0.1 SLM (Standard Liters per Minute) and a few SLM. Thus, up to about 1 SLM of reactive F as a dissociation product can be introduced into the ion source 400 in this way. Because of the small volume and surface area of ionization chamber 500, this results in very high etch rates for deposited materials. The ionization chamber 500 has a front plate facing the extraction electrode, containing the extraction aperture 504 of cross sectional area between about 0.2 cm2 and 2 cm2, through which, during energized operation, ions are extracted by extraction electrode 405. During cleaning, the reactive gas load is drawn from ionization chamber 500 through the aperture 504 by vacuum of housing 410; from housing 410 the gas load is pumped by roughing pump 422. Since the extraction electrode 405 is near and faces aperture 504 of ionization chamber 500, the electrode surfaces intercept a considerable volume of the reactive gas flow. This results in an electrode cleaning action, removing deposits from the electrode surfaces, especially from the front surface of suppression electrode 406, which is in position to have received the largest deposits. Thus, it is beneficial to fabricate extraction electrode and its mounting of F-resistant materials, such as Al and Al2O3.
The embodiment of
An advantage of the embodiment of
The embodiment of
Preferred Ion Source and Vaporizer
Vapor Flow Control Into the Ion Generating System
The flow of vapor to ionization chamber of
To establish a stable flow over time, separate closed loop control of the vaporizer temperature and vapor pressure is implemented using dual PID controllers, such as the Omron E5CK control loop digital controller. The control (feedback) variables are thermocouple output for temperature, and gauge output for pressure. The diagram of
In
A second, slow level of control is implemented by digital feed controller 220, accommodating the rate at which solid feed material vaporizes being a function of its open surface area, particularly the available surface area at the solid-vacuum interface. As feed material within the vaporizer is consumed over time, this available surface area steadily decreases until the evolution rate of vapors cannot support the desired vapor flow rate, resulting in a decrease in the vapor pressure upstream of the throttle valve 100. This is known as “evolution rate limited” operation. So, with a fresh charge of feed material in the vaporizer, a vaporizer temperature of, say, 25C might support the required vapor flow at a nominal throttle valve position at the low end of its dynamic range (i.e., the throttling valve only partially open). Over time (for example, after 20% of the feed material is consumed), the valve position would open further and further to maintain the desired flow. When the throttle valve is near the high conductance limit of its dynamic range (i.e., mostly open), this valve position is sensed by the controller 220, which sends a new, higher heater set point temperature to the vaporizer heater control 215. The increment is selected to restore, once the vaporizer temperature settles to its new value, the nominal throttle valve operating point near the low end of its dynamic range. Thus, the ability of the digital controller 220 to accommodate both short-timescale changes in set point vapor pressure and long-timescale changes in vaporizer temperature makes the control of vapor flow over the lifetime of the feed material charge very robust. Such control prevents over-feeding of vapor to the ionization chamber. This has the effect of limiting the amount of unwanted deposits on surfaces of the ion generating system, thus extending the ion source life between cleanings.
Novel Heated Electrode
During the decaborane lifetime tests shown in
This patent application is a continuation of U.S. patent application Ser. No. 10/582,392, filed on Jun. 23, 2006, which is a U.S. national phase application under 35 U.S.C. §371 of International Patent Application PCT/US2004/041525, filed Dec. 9, 2004, which claims priority to and the benefit of U.S. Provisional Patent Application No. 60/529,343, filed Dec. 12, 2003.
Number | Name | Date | Kind |
---|---|---|---|
4105916 | Siegel | Aug 1978 | A |
4254340 | Camplan et al. | Mar 1981 | A |
4409486 | Bates | Oct 1983 | A |
4412900 | Tanaka et al. | Nov 1983 | A |
4512812 | Liebert et al. | Apr 1985 | A |
4529474 | Fujiyama et al. | Jul 1985 | A |
4619844 | Pierce et al. | Oct 1986 | A |
4640221 | Barbee et al. | Feb 1987 | A |
4657616 | Benzing et al. | Apr 1987 | A |
4665315 | Bacchetti et al. | May 1987 | A |
4703183 | Guerra | Oct 1987 | A |
4723967 | Tom | Feb 1988 | A |
4738693 | Tom | Apr 1988 | A |
4786352 | Benzing | Nov 1988 | A |
4851668 | Ohno et al. | Jul 1989 | A |
4958078 | Becchetti | Sep 1990 | A |
4960488 | Law et al. | Oct 1990 | A |
4983850 | Tsukakoshi et al. | Jan 1991 | A |
5028791 | Koshiishi et al. | Jul 1991 | A |
5049784 | Matsudo | Sep 1991 | A |
5083061 | Koshiishi et al. | Jan 1992 | A |
5089747 | Koshiishi et al. | Feb 1992 | A |
5097179 | Takayama | Mar 1992 | A |
5101110 | Matsudo et al. | Mar 1992 | A |
5129958 | Nagashima et al. | Jul 1992 | A |
5132545 | Shono et al. | Jul 1992 | A |
5144147 | Shiozaki et al. | Sep 1992 | A |
5158644 | Cheung et al. | Oct 1992 | A |
5186120 | Ohnishi et al. | Feb 1993 | A |
5206516 | Keller et al. | Apr 1993 | A |
5216330 | Ahonen | Jun 1993 | A |
5262652 | Bright et al. | Nov 1993 | A |
5279129 | Ito | Jan 1994 | A |
5281302 | Gabric et al. | Jan 1994 | A |
5296713 | Tanaka | Mar 1994 | A |
5306921 | Tanaka et al. | Apr 1994 | A |
5312519 | Sakai et al. | May 1994 | A |
5350926 | White et al. | Sep 1994 | A |
5354698 | Cathey, Jr. | Oct 1994 | A |
5362328 | Gardiner et al. | Nov 1994 | A |
5369279 | Martin | Nov 1994 | A |
5429070 | Campbell et al. | Jul 1995 | A |
5451258 | Hillman et al. | Sep 1995 | A |
5466942 | Sakai et al. | Nov 1995 | A |
5486235 | Ye et al. | Jan 1996 | A |
5489550 | Moslehi | Feb 1996 | A |
5497006 | Sferlazzo | Mar 1996 | A |
5536330 | Chen et al. | Jul 1996 | A |
5554854 | Blake | Sep 1996 | A |
5576538 | Sakai et al. | Nov 1996 | A |
5616208 | Lee | Apr 1997 | A |
5633506 | Blake | May 1997 | A |
5661308 | Benveniste et al. | Aug 1997 | A |
5676759 | Ye et al. | Oct 1997 | A |
5685916 | Ye et al. | Nov 1997 | A |
5700327 | Babacz et al. | Dec 1997 | A |
5714738 | Hauschulz et al. | Feb 1998 | A |
5747936 | Harrison et al. | May 1998 | A |
5751002 | Ogata et al. | May 1998 | A |
5779849 | Blalock | Jul 1998 | A |
5780863 | Benveniste et al. | Jul 1998 | A |
5785796 | Lee | Jul 1998 | A |
5788778 | Shang et al. | Aug 1998 | A |
5824375 | Gupta | Oct 1998 | A |
5832177 | Shinagawa et al. | Nov 1998 | A |
5843239 | Shrotriya | Dec 1998 | A |
5882416 | Van Buskirk et al. | Mar 1999 | A |
5883364 | Frei et al. | Mar 1999 | A |
5883391 | Adibi et al. | Mar 1999 | A |
5886355 | Bright et al. | Mar 1999 | A |
5932882 | England et al. | Aug 1999 | A |
5940724 | Warren | Aug 1999 | A |
5993766 | Tom et al. | Nov 1999 | A |
6013332 | Goto et al. | Jan 2000 | A |
6060034 | Tsukamoto | May 2000 | A |
6068729 | Shrotriya | May 2000 | A |
6093625 | Wagner et al. | Jul 2000 | A |
6094012 | Leung et al. | Jul 2000 | A |
6107634 | Horsky | Aug 2000 | A |
6130436 | Renau et al. | Oct 2000 | A |
6143084 | Li et al. | Nov 2000 | A |
6150628 | Smith et al. | Nov 2000 | A |
6160262 | Aoki et al. | Dec 2000 | A |
6178952 | Lammerts et al. | Jan 2001 | B1 |
6184532 | Dudnikov et al. | Feb 2001 | B1 |
6221169 | Bernstein et al. | Apr 2001 | B1 |
6242750 | Takahashi et al. | Jun 2001 | B1 |
6253783 | Carlsen et al. | Jul 2001 | B1 |
6259105 | Eddy et al. | Jul 2001 | B1 |
6271529 | Farley et al. | Aug 2001 | B1 |
6288403 | Horsky et al. | Sep 2001 | B1 |
6313475 | Renau et al. | Nov 2001 | B1 |
6335534 | Suguro et al. | Jan 2002 | B1 |
6338312 | Hayes et al. | Jan 2002 | B2 |
6355933 | Tripsas et al. | Mar 2002 | B1 |
6423976 | Glavish et al. | Jul 2002 | B1 |
6441382 | Huang | Aug 2002 | B1 |
6449521 | Gupta | Sep 2002 | B1 |
6452198 | Mani et al. | Sep 2002 | B1 |
6452338 | Horsky | Sep 2002 | B1 |
6464891 | Druz et al. | Oct 2002 | B1 |
6479828 | Perel | Nov 2002 | B2 |
6486431 | Smith et al. | Nov 2002 | B1 |
6489622 | Chen et al. | Dec 2002 | B1 |
6498348 | Aitken | Dec 2002 | B2 |
6528804 | Sullivan et al. | Mar 2003 | B1 |
6545419 | Vella | Apr 2003 | B2 |
6559462 | Carpenter et al. | May 2003 | B1 |
6583544 | Horsky et al. | Jun 2003 | B1 |
6614033 | Suguro et al. | Sep 2003 | B2 |
6617593 | Lien | Sep 2003 | B2 |
6620256 | Arno et al. | Sep 2003 | B1 |
6639227 | Glavish et al. | Oct 2003 | B1 |
6653643 | Saadatmand et al. | Nov 2003 | B2 |
6664547 | Benveniste | Dec 2003 | B2 |
6670623 | Vella | Dec 2003 | B2 |
6670624 | Adams et al. | Dec 2003 | B1 |
6686595 | Horsky | Feb 2004 | B2 |
6686601 | Murrell et al. | Feb 2004 | B2 |
6703628 | Ye et al. | Mar 2004 | B2 |
6710358 | Chen et al. | Mar 2004 | B1 |
6712084 | Shajii et al. | Mar 2004 | B2 |
6740586 | Wang et al. | May 2004 | B1 |
6768121 | Horsky et al. | Jul 2004 | B2 |
6770888 | Benveniste et al. | Aug 2004 | B1 |
6772776 | Klebanoff et al. | Aug 2004 | B2 |
6777696 | Rathmell et al. | Aug 2004 | B1 |
6818909 | Murrell et al. | Nov 2004 | B2 |
6830631 | Nenyei et al. | Dec 2004 | B2 |
6835930 | Benveniste et al. | Dec 2004 | B2 |
6841141 | Arno et al. | Jan 2005 | B2 |
6852242 | Sun et al. | Feb 2005 | B2 |
6885014 | Benveniste | Apr 2005 | B2 |
6885812 | Groom | Apr 2005 | B2 |
6909102 | Buccos | Jun 2005 | B1 |
6909839 | Wang et al. | Jun 2005 | B2 |
6921062 | Gregg et al. | Jul 2005 | B2 |
6946667 | Chen et al. | Sep 2005 | B2 |
6956225 | Benveniste | Oct 2005 | B1 |
6958481 | Horsky et al. | Oct 2005 | B2 |
6974957 | Glukhoy | Dec 2005 | B2 |
6992311 | Ring et al. | Jan 2006 | B1 |
7022999 | Horsky et al. | Apr 2006 | B2 |
7107929 | Horsky et al. | Sep 2006 | B2 |
7112804 | Horsky et al. | Sep 2006 | B2 |
7185602 | Horsky et al. | Mar 2007 | B2 |
7531819 | DiVergilio et al. | May 2009 | B2 |
20030030010 | Perel et al. | Feb 2003 | A1 |
20030111014 | Donatucci et al. | Jun 2003 | A1 |
20030230986 | Horsky et al. | Dec 2003 | A1 |
20040000647 | Horsky | Jan 2004 | A1 |
20040002202 | Horsky | Jan 2004 | A1 |
20040104682 | Horsky et al. | Jun 2004 | A1 |
20040175160 | Groom | Sep 2004 | A1 |
20040188631 | Horsky et al. | Sep 2004 | A1 |
20050051096 | Horsky et al. | Mar 2005 | A1 |
20050169828 | Spielvogel et al. | Aug 2005 | A1 |
20050178975 | Glukhoy | Aug 2005 | A1 |
20050202657 | Borland et al. | Sep 2005 | A1 |
20050258380 | White et al. | Nov 2005 | A1 |
20050269520 | Horsky et al. | Dec 2005 | A1 |
20050277246 | Kirkpatrick et al. | Dec 2005 | A1 |
20060017010 | Vanderberg et al. | Jan 2006 | A1 |
20060097193 | Horsky et al. | May 2006 | A1 |
20060097645 | Horsky | May 2006 | A1 |
20060237663 | Balogh | Oct 2006 | A1 |
20060272775 | Horsky et al. | Dec 2006 | A1 |
20060272776 | Horsky et al. | Dec 2006 | A1 |
20070107841 | Horsky et al. | May 2007 | A1 |
20070108394 | Horsky | May 2007 | A1 |
20070108395 | Horsky et al. | May 2007 | A1 |
20070170372 | Horsky | Jul 2007 | A1 |
20070210260 | Horsky et al. | Sep 2007 | A1 |
20070241689 | Horsky et al. | Oct 2007 | A1 |
20070262262 | Horsky et al. | Nov 2007 | A1 |
20070278417 | Horsky et al. | Dec 2007 | A1 |
20080042580 | Horsky | Feb 2008 | A1 |
20080047607 | Horsky et al. | Feb 2008 | A1 |
20080087219 | Horsky | Apr 2008 | A1 |
20080121811 | Horsky et al. | May 2008 | A1 |
20080223409 | Horsky et al. | Sep 2008 | A1 |
Number | Date | Country |
---|---|---|
0140975 | May 1985 | EP |
0474108 | Mar 1992 | EP |
0555546 | Aug 1993 | EP |
0648861 | Apr 1995 | EP |
0697467 | Feb 1996 | EP |
0762469 | Mar 1997 | EP |
0954008 | Nov 1999 | EP |
1061550 | Dec 2000 | EP |
55-145338 | Nov 1980 | JP |
56-026539 | Mar 1981 | JP |
56-166935 | Dec 1981 | JP |
61-135037 | Jun 1986 | JP |
02-155147 | Jun 1990 | JP |
06-084837 | Mar 1994 | JP |
2000323051 | Nov 2000 | JP |
WO 9615545 | May 1996 | WO |
WO 2004003973 | Jan 2004 | WO |
WO 2005059942 | Jun 2005 | WO |
Number | Date | Country | |
---|---|---|---|
20080121811 A1 | May 2008 | US |
Number | Date | Country | |
---|---|---|---|
60529343 | Dec 2003 | US |
Number | Date | Country | |
---|---|---|---|
Parent | 10582392 | US | |
Child | 11647714 | US |