Classifications

• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
  • G01N30/02—Column chromatography
  • G01N30/04—Preparation or injection of sample to be analysed
  • G01N30/06—Preparation
  • G01N30/12—Preparation by evaporation
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N1/00—Sampling; Preparing specimens for investigation
  • G01N1/02—Devices for withdrawing samples
  • G01N1/22—Devices for withdrawing samples in the gaseous state
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N1/00—Sampling; Preparing specimens for investigation
  • G01N1/02—Devices for withdrawing samples
  • G01N1/22—Devices for withdrawing samples in the gaseous state
  • G01N1/2202—Devices for withdrawing samples in the gaseous state involving separation of sample components during sampling
  • G01N1/2214—Devices for withdrawing samples in the gaseous state involving separation of sample components during sampling by sorption
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N1/00—Sampling; Preparing specimens for investigation
  • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
  • G01N1/34—Purifying; Cleaning
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N1/00—Sampling; Preparing specimens for investigation
  • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
  • G01N1/44—Sample treatment involving radiation, e.g. heat
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
  • G01N30/02—Column chromatography
  • G01N30/04—Preparation or injection of sample to be analysed
  • G01N30/06—Preparation
  • G01N30/08—Preparation using an enricher
  • G01N2030/085—Preparation using an enricher using absorbing precolumn
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T436/00—Chemistry: analytical and immunological testing
  • Y10T436/25—Chemistry: analytical and immunological testing including sample preparation
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T436/00—Chemistry: analytical and immunological testing
  • Y10T436/25—Chemistry: analytical and immunological testing including sample preparation
  • Y10T436/25375—Liberation or purification of sample or separation of material from a sample [e.g., filtering, centrifuging, etc.]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T436/00—Chemistry: analytical and immunological testing
  • Y10T436/25—Chemistry: analytical and immunological testing including sample preparation
  • Y10T436/25375—Liberation or purification of sample or separation of material from a sample [e.g., filtering, centrifuging, etc.]
  • Y10T436/255—Liberation or purification of sample or separation of material from a sample [e.g., filtering, centrifuging, etc.] including use of a solid sorbent, semipermeable membrane, or liquid extraction

Definitions

• TDTs are normally specific to a certain class of contaminants, usually hydrocarbons, and often suffer from low contaminant capacities, reducing sampling times and requiring frequent replacement. TDTs do not generally meet the efficiency and capacity requirements of purifiers. TDTs are often incompatible with ultra-high purity (UHP) fluid delivery systems. TDTs are not required elements of fluid delivery systems and, thus, increase the cost and complexity of any fluid delivery system. When installed parallel to the process fluid delivery line, TDTs bleed gas from the process, thus increasing gas use and requiring adequate venting. TDTs are easily cross-contaminated during installation and removal from process fluid lines. The trapping efficiencies of many TDTs are not very high, resulting in lower detection limits of 100 ppt.
• UHP ultra-high purity
• Source gases and liquids may contain contaminants.
• System leaks can generate environmental contaminants.
• Off-gassing and permeability of tool materials, mainly plastics but also ceramics and stainless steel can be a source of system contamination.
• Contaminants may arise from the by-products of reactions in the delivery path or UV light induced reactions, e.g., in photolithography.
• Such potential contaminant sources and their effects on the manufacturing process provide impetus for using point-of-use (POU) purifiers.
• POU point-of-use
• POU purifiers include inorganic adsorbents, including zeolites, silica, alumina and transition metal-based adsorbents; palladium cells; organic polymers, which can be imbedded with adsorbent materials; and others known to those skilled in the art.
• Exemplary POU purifiers are those taught in US patents 6,391,090; 6,361,696; 6,241,955; and 6,059,859.
• the POU purifier selected depends on the source of the gas or liquid to be passed through the purifier and the sources of contaminants typically present in the process. Specific contamination issues may vary broadly between gases and liquids, as well as between different classes of gases or liquids. For example, light hydrocarbons (LHC) generally come from impure source gases.
• LHC light hydrocarbons
• Nitrogenous contamination, moisture and organic solvent vapors are generally present in cleanrooms, but may be condensed on surfaces or dissolved in source liquids.
• Heavy hydrocarbons and refractory compounds e.g., siloxanes
• Oxygen (0 ) and carbon dioxide (C0 2 ) typically come from the environment, i.e. leaks in the fluid delivery system.
• Oxygen (0 ) and carbon dioxide (C0 2 ) typically come from the environment, i.e. leaks in the fluid delivery system.
• examining contaminants adsorbed by purifiers indicates sources of contamination in a process. The information generated by such an analysis can be used to improve process control. Identification of contamination sources allows for the isolation of the step to determine the effects on the process.
• the contaminant species cannot be desorbed from the purifier in a chemical state identical to that found in the gas or liquid stream. Furthermore, probably as a result of the solid state diffusion process that occurs in these and many other purifier materials, desorption of the contaminants from the purifier material, even as a chemical relative of the original contaminant species, requires high temperatures, is inaccurate, and involves hazardous conditions.
• the present invention relates to the monitoring of contaminants occurring in manufacturing processes that employ fluid purification devices. More specifically, the present invention provides a sensitive method for analyzing the contaminant concentrations in manufacturing processes that employ gas or liquid purifier materials. In its broadest embodiment the present invention is a method for obtaining information about the contaminants present in a process gas or liquid.
• the method comprises passing the process fluid stream (e.g., the entire volume of the fluid stream) through a purifier material to thereby adsorb contaminants onto the purifier in a manner such that the contaminants retain their integrity and/or do not distort the concentration level of the contaminants; isolating the purifier material from the process fluid stream; desorbing the contaminants from the purifier material; and identifying the contaminants desorbed from the purifier material and determining the concentration thereof using analytical means, wherein the concentration is correlated to the contaminant concentration in the entire volume of the process fluid stream
• the invention provides a method for the analysis of gas or liquid purifiers used in a manufacturing process to determine contaminants removed from the gas or liquid stream by the purifier.
• the purifier is connected to an analytical instrument, e.g. , gas chromatography/fiame ionization detector (GC FID) or gas chromatography/mass spectrometry (GC/MS), and the purifier is subjected to conditions to desorb contaminants, e.g., heating, vacuum or addition of alternative gas, to release products bound to the purifier material.
• Desorption may be effected in a stepwise fashion to release contaminants separately.
• the desorption stream is analyzed to determine the contaminants present and their concentrations. Using data from a particular purifier and process conditions, information about the process may be extrapolated. The information can be used to improve process control.
• an alternative gas can be used to remove the contaminants from the purifier material.
• the alternative gas is chemically inert to the contaminant and/or the purification material.
• the alternative gas is chemically oxidizing to the contaminant compounds and/or the purification material.
• the alternative gas is chemically reducing to the contaminant compounds and/or the purification material.
• the alternative gas is hydrogen.
• the present invention is a method and apparatus for the identification and quantification of contaminants removed from a process gas or liquid by the normal operation of a purifier, wherein the concentration of said contaminant is below the detection limit of analytical equipment commonly used in the manufacturing process or known to those skilled in the art. Detection limits vary by contaminant and analytical equipment varies by manufacturing process, but in this preferred embodiment the extrapolation of contaminant concentrations in the range of about 0.01-1,000 ppt, preferably 0.1-500 ppt, is possible.
• the data obtained after analyzing the desorption gas stream quantitatively reflects the contaminant concentration in the process gas or liquid.
• process specific information includes the flow rate of process gas or liquid, the total time of purifier use, and the duty cycle of the purifier. This information is commonly known by the operators of a particular manufacturing process and would, thus, readily be obtainable by those skilled in the art.
• the method of the present invention requires that contaminants be desorbed from the purifier non-destructively or that they be desorbed from the purifier in a discernible form (e.g., non-destructive).
• oxygen may be chemisorbed by a purifier material to form an oxide layer and released from the purifier material as water after reduction of the oxide layer, in which case the oxygen concentration is discernible by monitoring the water concentration in the desorption stream.
• the total oxygen contaminant concentration and total water contaminant concentration may be analyzed separately by, for example, first desorbing the water under non-reducing conditions followed by reductive treatment to release chemisorbed oxygen.
• the invention is an apparatus for the analysis of contaminants desorbed from a purifier.
• Such an apparatus comprises a connector with a valve or other controller to attach the purifier to the device while limiting exchange between the purifier and the apparatus; a heater and thermostat for regulating the temperature of the purifier material; a gas source and a connector with a controller to attach the gas source to the apparatus while limiting exchange between the gas source and the apparatus; and an analytical instrument to detect the desorbed contaminants.
• the apparatus preferably contains a quantitative analytical instrument to determine the quantity of the contaminants released. Further, the apparatus may contain mass flow controllers and valves, desorption tubes and/or cold traps for collecting contaminants and a computer or other logical tool that can be used for data analysis.
• FIG. 1 is a schematic diagram of the apparatus of the present invention, representing a preferred embodiment thereof.
• FIG. 2 is a gas chromatograph of a six-component hydrocarbon mixture in air detected by flame ionization detection. The analytes were sampled with a liquid nitrogen cooled cold trap.
• FIG. 3 is a gas chromatograph of a six-component hydrocarbon mixture in air thermally desorbed from a point-of-use purifier and detected by flame ionization detection.
• FIG. 4 is a plot of FID response, i.e., detected concentration, versus inlet concentration, calculated from the dilution levels, for varying six-component hydrocarbon mixture concentrations in air. The plot compares the calibration standard thermally desorbed from a test purifier to the same standard when the purifier is bypassed.
• the invention is a method for the sub-0.1 ppm analysis of contaminant concentrations in high purity gases or liquids.
• the method comprises a purifier that removes the contaminants from a process fluid stream while on line and detection of the contaminants desorbed from the purifier while off line.
• An advantage of the invention is that the method can be used to monitor a process fluid streams that contains levels of contaminants that are normally undetectable.
• the invention allows one to ascertain the concentration of contaminants in a process fluid stream using integrative sampling of the contaminants (i.e., all of the fluid stream passes through the purifier material) so that over time the concentration of adsorbed contaminants in the purifier reaches detectable levels; in contrast to periodic sampling where the contaminant levels are otherwise undetectable.
• the integrative sampling period can be over the useful life of the purifier material or over the entire life time of the process. This provides a significant advantage over the traditional use of thermal desorption tubes, where only a portion of the process fluid stream is directed through the TDT rather than the entire process fluid stream.
• the invention further provides end user access to high sensitivity analysis of contaminants adsorbed by the purifier without having to purchase expensive analysis equipment.
• the invention may further include analysis of the manufacturing process based on the contaminants desorbed from the purifier allowing optimization of the manufacturing process.
• a purifier is installed in a fluid delivery line servicing a manufacturing process. Since purifiers are commonly installed in fluid delivery lines, especially point-of-use purifiers in lines servicing microelectronics process tools, no additional equipment or functional input is required by the end-user to practice the present invention.
• the purifier is disconnected from the manufacturing process. This may be accomplished by physical deinstallation of the purifier from the fluid delivery line or by closure of the fluid's flow through the purifier material, as in the case of assemblies of valves, mass flow controllers, and other mechanical devices.
• a desorption gas is then made to flow through the purifier and the effluents, which contain the desorbed contaminants, are monitored by a suitable analytical device. Analysis and quantification of the contaminants over the process period can be made prior to regenerating the purifier material.
• the invention requires the use of specific purifier materials that remove contaminants in a discernible manner.
• contaminants are removed by the purifier non-destructively, but certain other adsorption mechanisms particular to specific purifier materials would also be considered discernible according to the method of the present invention.
• Purifier materials that are especially suited to the method of the present invention are Gate KeeperTM point-of-use purifiers available from Mykrolis Corporation, Billerica, MA. The exact adsorption/desorption mechanisms of various contaminants in combination with various types of these purifiers are unknown and speculative, but the requirement of an analytical relationship between process contaminant concentration and contaminants detected by the method of the present invention is met by these purifier materials.
• an end user of a purifier at regular intervals or upon development of a problem, disconnects the purifier from the apparatus to which it is attached and ships it to the manufacturer or other qualified analyst to determine the contaminants in the process gas or liquid.
• the purifier may be effectively detached from the apparatus to which it is attached by means of a bypass line. Regardless of the location of the purifier and the analysis equipment, the process for analyzing contaminant concentrations is the same.
• Contaminants removed from the fluid stream include, but are not limited to, organic compounds (e.g., C ⁇ -C 20 hydrocarbons), carbon dioxide, carbon monoxide, nitrogen-containing compounds (e.g., NO, N0 2 , N 2 0, NH 3 , organic amines, or NX 3 ; wherein X is a halogen atom), sulfur-containing compounds (e.g., S0 2 , SO 3 , H 2 S, organic thiols or thioethers), hydride compounds (e.g., BH 3 , AIH 3 , S1H 4 , GeH 4 , NH3, PH 3 , or AsH 3 ), hydrogen, halide compounds (e.g., HF, HC1, HBr, fluorocarbons, chlorocarbons, SiF 4 , SiC , NF3, SFe, or organic halides), halogens (e.g.,
• Contaminants may be identified by methods including, but not limited to, GC retention time, MS fragmentation pattern, and infrared (IR) spectroscopy.
• the contaminants may be further concentrated in the effluent stream using a desorption tube, cold trap, or other method well known to those skilled in the art. Concentration improves the detection limits of the method and provides a method for separating dissimilar contaminants.
• information about the process may be extrapolated.
• mathematical algorithms may be used to relate the desorption time and temperature of a particular contaminant as a function of its known adsorption properties, thereby extrapolating information about the manner of its adsorption, e.g., time or purifier coverage. This information can be used to improve process control.
• Contaminants and their concentrations can be plotted as a function of their desorption temperature and time. This provides information about the process of contamination.
• the first contaminants desorbed are either the last adsorbed or those least tightly bound by the adsorbent.
• This information can be useful for process control as it may be related to a specific time in the process, e.g., changing of the source gas or liquid; a tool malfunction or service, e.g., temporal material replacement or service; a process step, e.g., substrate change in a molecular beam epitaxy (MBE) or photolithography tool; or a conflicting process step in the facility.
• MBE molecular beam epitaxy
• the data obtained can be used to identify the source of the contaminant, be it input gas quality, system integrity, material out-gassing, or process-product breakdown. This information can be used to optimize the manufacturing process.
• the present invention is particularly suited to process analysis after a system upset has occurred, e.g., such noticeable defects in semiconductor wafers as film hazing or unwanted doping.
• the apparatus for the analysis of contaminants desorbed from a purifier may comprise any of a number of analyzers depending on the detection levels required and the suspected contaminants based on the purifier to be analyzed and the process in which it is used.
• Such an apparatus comprises a connector with a valve or other controller to attach the purifier to the device while limiting exchange between the purifier and the apparatus; a heater and thermostat for regulating the temperature of the purifier material; a gas source and a connector with a controller to attach the gas source to the apparatus while limiting exchange between the gas source and the apparatus; and an analytical instrument to detect the desorbed contaminants.
• the apparatus preferably contains a quantitative analytical instrument to determine the quantity of the contaminants released.
• a quantitative analytical instrument to determine the quantity of the contaminants released.
• An example of a preferred instrument is a GC/APIMS (atmospheric pressure ionization mass spectrometer) which can separate contaminants according to their boiling points, identify them according to their masses and fragmentation patterns and quantify them by their peak intensities.
• GC/APIMS atmospheric pressure ionization mass spectrometer
• TOC total organic content
• TSC total sulfur content
• moisture detectors moisture detectors
• infrared spectrometers infrared spectrometer
• the apparatus may contain mass flow controllers and valves, desorption tubes and/or cold traps for collecting contaminants, and a computer or other logical tool that can be used for data analysis.
• Software including algorithms for extrapolating process information from the desorption data may be used to analyze the results of the desorption.
• a number of these components are used in the analysis of a purifier.
• the desorption gas, air enters the apparatus through pressure regulator 2 and is purified to ⁇ 1 ppt hydrocarbon contaminants by purifier 4. While this purification step is optional, it is desirable to use a desorption gas of the highest possible purity, because background contamination can interfere with the analysis and limit detection.
• a known gas standard enters the apparatus through pressure regulator 6.
• the two gas streams are combined in double dilution manifold 12, comprising MFC2 8, MFCl 14, valve 16, pressure gauge 18, back pressure regulator 20, MFC3 22, valve 24, and MFC4 26.
• the double dilution manifold is optional, but often is required by limitations in available gas standards and mass flow controller operating parameters.
• valve 30 The gas is then sent through valve 30, while bypass loop 32 containing test purifier 34 is isolated by closing valves 28 and 36.
• the gas enters collection device 38 through valve 46, which is preferably a cold trap but may also be a TDT or similar device, and is vented through rotameter 50.
• Pressure gauge 52 and back pressure regulator 54 allow for venting of excess gas not going through the cold trap during sample collection.
• gas is released from collection device 38 and flows through valves 40 and 42 to quantitative analytical device 44, which is preferably a gas chromatograph fitted with a suitable detector, e.g., FID for hydrocarbons, PFPD for inorganics, or MS for atmospheric or any contaminants.
• valves 28 and 36 are opened, valve 30 is closed, and test purifier 34 is exposed to the desorption gas.
• desorption may be accomplished in a number of ways.
• This preferred embodiment favors isothermal desorption, wherein 34 is heated by heating element 48 to a desired temperature at which all effluents are collected.
• Another embodiment using the apparatus of FIG. 1 employs ramped thermal desorption, wherein the temperature of 34 is increased by 48, e.g., linearly, exponentially, or step-wise, over time and different effluents fractions are collected at different times in the desorption process.
• FIG. 1 involves the use of an alternative gas to assist in the desorption of contaminants.
• One slight modification comprised by this embodiment is the substitution of hydrogen for air as the desorption gas.
• the effluent of 34 flows through 36 and 46 and enters 38, which is preferably a cold trap but may also be a TDT or similar device. After a certain collection period, gas is released from 38 and flows through 40 and 42 to 44, which is preferably a gas chromatograph fitted with a suitable detector, e.g., FID for hydrocarbons, PFPD for inorganics, or MS for atmospheric or any contaminants.
• FIGs. 2-4 show data obtained using the apparatus of FIG. 1.
• FIG. 2 is a gas chromatograph of a 10 ppm six-component (benzene, toluene, ethyl benzene, ortho-, meta-, and /r ⁇ ra-xylene) diluted to 1 ppt and analyzed by the cold trap/GC/FID method.
• FIG. 3 plots 1 ppb six-component hydrocarbon gas standard desorbed from the test purifier after a 25 minute purification cycle, during which all hydrocarbons were removed to ⁇ 1 ppt outlet purity, and a 5 minute desorption cycle with air at 300 °C.
• Trace 60 is the 100 ppt hydrocarbon mixture directly sampled by the cold trap/GC/FID method when the test purifier is bypassed.
• Trace 62 is the same mixture desorbed from the test purifier and analyzed by the cold trap/GC/FID method.
• the test purifier non-destructively desorbs all of the contaminants originally removed from the test process gas stream. If longer desorption time or higher temperature were used, quantitative desorption could be effected.
• FIG. 4 is a plot of total inlet exposure of the test purifier to the same six-component hydrocarbon mixture and the total desorbed contaminants after a 5 minute exposure to desorbing gas at 300 °C. It can be seen from the combination of FIGs. 2-4 that hydrocarbon analysis according to the method of the present invention is easily accomplished with very low detection limits and, by extrapolation, extremely low contaminant detection in a process gas or liquid stream, either chronic or impulsive. The differentiation between chronic and impulsive contamination requires knowledge of the particular process and, sometimes, a history of the particular fluid delivery system. However, even without this information the method provides contaminant information that would otherwise be inaccessible using prior art methods.

Landscapes

• Life Sciences & Earth Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical & Material Sciences (AREA)
• Pathology (AREA)
• General Physics & Mathematics (AREA)
• Physics & Mathematics (AREA)
• Immunology (AREA)
• Analytical Chemistry (AREA)
• Biochemistry (AREA)
• General Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Molecular Biology (AREA)
• Biomedical Technology (AREA)
• Food Science & Technology (AREA)
• Medicinal Chemistry (AREA)
• Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
• Sampling And Sample Adjustment (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Publications (2)

Family

ID=32927506

Family Applications (1)

Country Status (8)

Cited By (6)

Families Citing this family (13)

Family Cites Families (24)

• 2004
  • 2004-02-20 EP EP04713293A patent/EP1595132B1/en not_active Expired - Lifetime
  • 2004-02-20 DE DE602004004369T patent/DE602004004369T2/de not_active Expired - Fee Related
  • 2004-02-20 JP JP2006503693A patent/JP2006518468A/ja active Pending
  • 2004-02-20 TW TW093104226A patent/TW200506334A/zh unknown
  • 2004-02-20 KR KR1020057015353A patent/KR20050103946A/ko not_active Withdrawn
  • 2004-02-20 CN CNA200480004583XA patent/CN1756945A/zh active Pending
  • 2004-02-20 WO PCT/US2004/004845 patent/WO2004077015A2/en not_active Ceased
  • 2004-02-20 US US10/544,309 patent/US8664004B2/en active Active

Also Published As

Similar Documents

Legal Events