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Mark of the Demon (Kara Gillian, Book 1)
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|Publication number
|Publication type
|Application number
|Publication date
|Dec 13, 2005
|Filing date
|Dec 4, 2001
|Priority date
|Jan 29, 2001
|Fee status
|Also published as
|Publication number
|Howard M. Kingston
|Original Assignee
|Metara, Inc.
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (18), Non-Patent Citations (12), Referenced by (13), Classifications (9), Legal Events (7)
|External Links: USPTO, USPTO Assignment, Espacenet
This application claims the benefit of U.S. Provisional Application Ser. No. 60/264,748, filed Jan. 29, 2001.
1. Field of the Invention
This invention relates to a method and apparatus for an in-process, automated analysis using a ratio measurement. More specifically, the disclosed In-process, Atmospheric Pressure Interface, Mass Spectrometer (IP-API-MS) apparatus and related method uses a ratio measurement to characterize the amounts or concentrations of analytes. This characterization may be optimized for quality assurance at and near instrumental detection limits.
2. Description of the Prior Art
Mass spectrometry instrumentation is frequently used as the technique of choice in measuring parts-per-billion (ppb) and sub-ppb levels of elements or compounds in aqueous and other solutions as well as in gases. Mass spectrometers are typically operated and regularly calibrated by experienced technicians. In many cases, however, unattended operation of the mass spectrometer is desired. These cases may include remote operation, around the clock monitoring, or operation either in hostile environments, or where human interaction must be minimized. One such case is that of contamination monitoring and control in the wet process baths, such as, for example, the semiconductor industry which requires a clean room environment where minimal human interaction is desired. Installation of real time, in-situ, sensors into clean room process is a major defect reduction challenge in the industry. International Technology Roadmap for semiconductors 1999 Edition: Defect Reduction, Sematech, Austin Tex., (pg. 270) (1999).
In order to accomplish unattended operation, the method should automatically monitor elemental concentrations at their threshold level, accurately and without the need to compensate for the inevitable systematic errors associated with instrument drift. Quantitation of elemental concentrations may then be obtained without the need for traditional calibration once the threshold level has been exceeded. Traditional calibration techniques use calibration standards to generate a calibration curve which relates instrument response to concentration of standards. The calibration curve is used in order to determine the concentration of unknown sample. A typical calibration curve is illustrated in
Viscosity differences between the sample and standard matrices may also cause unequal instrument responses associated with changing sample introduction rates which are inevitable in real world situations. Matrix effects altering solution viscosity or ionization efficiency can result in calibration changes such as shown in
IDMS is based upon the addition of an enriched isotope standard to a sample to be analyzed. See, generally, U.S. Pat. No. 5,414,259 the disclosure of which is expressly incorporated herein by reference. After equilibration of the sample and standard, the natural isotopic ratio of the sample will have been altered by the enriched standard and the new isotopic ratio is measured by a mass spectrometer. If the concentration of an enriched isotopic standard is known, as well as the enriched isotopic ratio, then the measured ratio of altered natural elemental isotopes provides the elemental concentration of the sample. This method has only a very few well-defined possibilities for error. Each of these possibilities can be calibrated and eliminated, leaving the uncertainty in ratio determination of the two isotopes as the final error for the measurement. This uncertainty is based on the mass spectrometer's ability to make this isotopic ratio measurement. If the enriched isotope standard of known concentration is introduced, in a precisely controlled fashion, to the sample on-line, all normal interferences are eliminated for each element or species being measured. As only the altered isotope ratio is needed to obtain the concentration of the sample, the physical and chemical differences of flow rate and ionization efficiencies are essentially eliminated. Therefore, IDMS is an ultimate correction technique for both long-term and short-term instrument drift, as well as countering non-spectroscopic interference. This procedure, in general, provides accurate detection for the instrument and process necessary for quality control in ultra-trace analysis. In addition, traditional IDMS has been employed primarily with both Inductively Coupled Plasma Mass Spectrometers (ICP-MS) and Thermal Ionization Mass Spectrometers (TIMS). Both ICP-MS and TIMS instrumentation are not deemed suitable for operation in an unattended mode. Fassett, J. D., Paulsen, P. J. Isotope-dilution mass spectrometry for accurate elemental analysis, Anal. Chem. (1989) 61 643A-649A; Rottmann, L., Heumann, K. G., Development of an on-line Isotope Dilution Technique with HPLC/ICP-MS for the accurate determination of elemental species. Fresenius J. Anal. Chem., (1994) 350 221-227; Rottmann, L., Heumann, K. G., Determination of Heavy Metal Interactions with Dissolved Organic Materials in Natural Aquatic Systems by Coupling High-Performance Liquid Chromatography System with an Inductively Coupled Plasma Mass Spectrometer. Anal. Chem., (1994) 66, 3709-3715; Heumann, K. G., Rottmann, L., Vogl, J., Elemental Speciation with Liquid Chromatography-Inductively Coupled Plasma Isotope Dilution Mass Spectrometry. J. Anal. Atom. Spectro. (1994) 9 1351-1355; Horn, M., Heumann, K. G., Comparison of Heavy Metal Analysis in Hydrofluoric Acid used in Microelectronic Industry by ICP-MS and Thermal Ionization Isotope Dilution Mass Spectrometry, Fresenius J. Anal. Chem., (1994) 350 286-292.
A method of using on-line IDMS as an internal standard with an ICP-MS instrument has been suggested with an enriched isotopic standard being continuously introduced into the sample stream and mixed (allowed to equilibrate) prior to introduction into an ICP-MS instrument. Rottmann, L., Heumann, K. G., Development of an on-line Isotope Dilution Technique with HPLC/ICP-MS for the accurate determination of elemental species. Fresenius J. Anal. Chem., (1994) 350 221-227; Rottmann, L., Heumann, K. G., Determination of Heavy Metal Interactions with Dissolved Organic Materials in Natural Aquatic Systems by Coupling High-Performance Liquid Chromatography System with an Inductively Coupled Plasma Mass Spectrometer. Anal. Chem., (1994) 66, 3709-3715; Heumann, K. G., Rottmann, L., Vogl, J., Elemental Speciation with Liquid Chromatography-Inductively Coupled Plasma Isotope Dilution Mass Spectrometry. J. Anal. Atom. Spectro. (1994) 9 1351-1355. An on-line HPLC/ICP-IDMS method for elemental speciation was tested. In the case published, heavy metals in humic complexes found in natural waters were measured using a High Resolution ICP-MS with either an iron, copper, or a molybdenum enriched spike introduced as the IDMS calibration standard. Selection of which element standard was contingent upon the element to be analyzed in the sample. Rottmann, L., Heumann, K. G., Development of an on-line Isotope Dilution Technique with HPLC/ICP-MS for the accurate determination of elemental species. Fresenius J. Anal. Chem., (1994) 350 221-227; Rottmann, L., Heumann, K. G., Determination of Heavy Metal Interactions with Dissolved Organic Materials in Natural Aquatic Systems by Coupling High-Performance Liquid Chromatography System with an Inductively Coupled Plasma Mass Spectrometer. Anal. Chem., (1994) 66, 3709-3715; Heumann, K. G., Rottmann, L., Vogl, J., Elemental Speciation with Liquid Chromatography-Inductively Coupled Plasma Isotope Dilution Mass Spectrometry. J. Anal. Atom. Spectro. (1994) 9 1351-1355. It was stated that "quantitative chromatographic separation of the species to be analyzed" is one of the preconditions for this method and "quantitative separation is essential before the spiking step takes place (for a species-unspecific spike)." It was also stated that "(for a species-unspecific spike), equilibration between the separated species and spike must be guaranteed . . . by high temperature of the argon plasma (in ICP-MS)." Rottmann, L., Heumann, K. G., Development of an on-line Isotope Dilution Technique with HPLC/ICP-MS for the accurate determination of elemental species. Fresenius J. Anal. Chem., (1994) 350 221-227. HPLC separation and ICP-MS measurement are two essential parts of their method.
Semiconductor manufacturers rely on the purity of chemicals to create sub-micron devices from silicon wafers. Impure chemicals tend to result in devices that will not work. It is, therefore, important to know whether a wet chemical is, in fact, pure, or adequately pure. Current methods of determining purity tend to be expensive, slow, off-line chemical analyzers. This problem becomes enhanced with continued device shrinkage as in the move to 300-mm wafers and copper interconnects. Captive and contract analytical laboratories tend to produce chemical assays and time frames ranging from 24 to 72 hours. One of the consequences of this lack of timely information is the failure to know when to dispose of these expensive chemicals.
It has been suggested to employ in-line ICP-MS in a method of monitoring concentration of metals in silicon wafer cleaning baths. See Using ICP-MS for in-line monitoring of metallics in silicon wafer cleaning baths.
Isotope dilution Mass Spectrometry for ultra-trace analysis has been previously known. Fassett, J. D. and Kingston, H. M., Determination of Nanogram Quantities of Vanadium in Biological Material by Isotope Dilution Thermal Ionization Mass Spectrometry With Ion Counting Detection, Anal. Chem., (1985) 57 2474-2478. In this publication ultra-trace analysis uses IDMS in the traditional way with isotopically enriched spikes in batch spiked standards. These isotopes are spiked into low concentration samples and blanks and any species information is removed using the batch sample method. Complete transformation of all species is traditionally a prerequisite to most IDMS protocols to prevent multiple species existing in the sample simultaneously. In addition, this transformation prevents the spiked isotopes and the sample isotopes from existing in different species form. As a result, elemental species determinations and evaluations providing both are not possible and are in fact prevented by the traditional IDMS technique.
U.S. Pat. No. 5,012,052 discloses a patent by Hayes describes a method for isotope monitoring for gas that is an on-line continuous combustion from organic components to assist in the determination of the origin of objects based on the C-12 and C-14 ratios. This method requires a combination of gas chromatograph and flame ionization detector (FID), and palladium separator and oxygen charged combustion reactor prior to mass spectrometry. The method requires the use of the combustion chamber, and a palladium separator prior to the mass spectrometer. The goal of this method and instrument is comparison with an isotopic standard to establish isotopic ratios for carbon for origin identification of gases specifically using C-12 and C-14. There is no attempt to perform trace analysis of transition or other metals and quantification is not based on isotope dilution measurements. This method will not work for metals.
U.S. Pat. No. 5,572,024 discloses method and apparatus for quieting the introduction into a mass spectrometer from inductively coupled plasma (ICP) devise by manipulating skimmer cone diameters and pressure. The invention is an improvement of ratio precision measurements over well known ICP-MS and MIP-MS (microwave induced plasma) technology. It describes modifications to a mass spectrometer inlet that enables more precise measurement of isotopes. It requires a plasma device and also reduces the sensitivity of the mass spectrometer.
U.S. Pat. No. 5,872,357 discloses a series of calibrant compositions for organic compounds that enable calibration across a broad mass spectral range for electrospray mass spectrometry, as well a method of using these organic calibrant compositions to calibrate a mass spectrometer. The invention provides a class of new organically based calibrant compositions and limits its application to the usage of these calibrant compositions.
U.S. Pat. No. 6,032,513 discloses a hollow electrode for the improvement of ionization in an atmospheric-pressure ionization source and substitute a more easily ionized carrier gas for the sample gas stream. The disclosure is specific for gas analysis and requires the substitution of the gas stream and the use of a hollow electrode prior to a mass spectrometric measurement. This technology is not applicable in the isotopically based measurements that are the focus of the present invention.
IDMS using Flow Injection Analysis (FIA) introduction to an ICP-MS has been known. Viezian, Miklos; Alexandra Lasztity, Zioaru Wang and Ramon M. Barnes, On-Line Isotope Dilution and Sample Dilution by Flow Injection and Inductively Coupled Plasma Mass Spectrometry, J. Anal. Atom. Spectro., (1990) 5 125-133. This technique uses FIA to mix the isotopically enriched spike and the sample prior to introduction to the ICP-MS. The spike and sample are injected simultaneously to form a zone within a neutral carrier liquid prior to introduction to the ICP-MS. The volume of a fixed sample loop controls the amounts of spike and sample. Physical mixing of the two solutions occurs between the confluence point and the nebulizer. As in traditional IDMS methods species information is unavailable, as the enriched spike is species-unspecific. In addition, the technique suggested on-line dilution using an inert reagent; a technique that is easily accomplished using FIA.
An automated calibrant apparatus was disclosed in U.S. Pat. No. 5,703,360. It introduces a standard reference solution automatically into a mass spectrometer ESI or Atmospheric Pressure Chemical Ionization (APCI) to calibrate or tune the mass spectrometer. In this patent a switching valve is used to introduce the standard as desired to the ESI or APCI. As the standard reference solution and the sample solution are from different sources matrix effects are not eliminated.
U.S. Pat. No. 5,703,360 discloses that one or two traditional standard reference solutions can be used to tune the mass spectrometer with respect to the mass axis, and to assess the functionality of the instrument and to re-calibration the instrument. This technique of introducing two sequential calibration standards will not eliminate the short or long-term drift that can be a problem in unattended operation of a mass spectrometers. See U.S. Pat. No. 5,703,360.
Atmosphere pressure ionization (API) techniques includes electrospray (ES) ionization and atmosphere pressure chemical ionization (APCI). This technique has been widely used to characterize bio-molecules such as peptides, proteins, nucleic acids and carbohydrates. Cole, R. B. Electrospray Ionization Mass Spectrometry: Fundamentals Instrumentation & Applications; John Wiley & Sons, Inc.: New York, 1997. It is also used to qualitatively determine the presence of inorganic, organometallic and complexed metal ions, but quantifying that information has remained a significant challenge. High background due to chemical noise and signal suppression (matrix effects) appear to be the uppermost limiting factors for the quantification of most analytes. Stewart, I. I., Electrospray Mass Spectrometry: a Tool for Elemental Speciation, Spectrochim. Acta. Part-B. (1999) 54B 1649-1695. Collision-induced dissociation (CID) generates energetic collisions and can simplify mass spectra, reduce the background and increase the sensitivity. However, stable operation is limited to a narrow range of solution conductivities and can cause inherent non-linearity signal response during the quantification.
Speciated Isotope Dilution Mass Spectrometry (SIDMS) has been developed to assess the quantification of species and also their transformations. See U.S. Pat. No. 5,414,259. In SIDMS a predetermined species is specifically isotopically labeled and introduced to accomplish these measurements. The species of interest is previously known and specifically evaluated.
In summary, a method and associated apparatus have been developed to accomplish unattended operation of an apparatus that will automatically and accurately monitor elemental concentration threshold levels, identify, and quantify elemental contaminants or compounds and species in fluids.
The present invention employs a ratio measurement analogous to that used in traditional IDMS methods. The ratio measurement allows the characterization of a sample. To obtain the ratio measurement, a spike is added to a sample. After equilibration, the spicked sample is ionized using atmospheric pressure ionization and the resulting ions introduced into a mass spectrometer to form a ratio. A processor may then use the ratio to characterize the sample.
The method and apparatus of this invention employs the relatively-mild ionization provided by an atmospheric pressure ionization process such as, for example, electrospray in contrast to the relatively-harsh ionization encountered within an ICP-MS. Because of this relatively-mild ionization process, species information such as the concentration of a particular ionization state of an element or molecular complex within a sample is preserved thereby eliminating the necessity of a physical separation step after equilibration of the spike and sample. In contrast, such species information may be lost as a species is ionized in an ICP-MS process.
In the present invention, an analyte may be characterized in a sample without requiring the provision of an isotopically-enriched spike in the same speciated form as the analyte. Instead the analyte and spike may be transformed to the same species during equilibration of the spike and sample, through for example, dynamical pre-treatment such as oxidation or simply through a reaction of the spike with the sample's matrix.
In one embodiment, the present invention relates to a method and apparatus that enhances and improves measurement at and near the detection limit of mass spectrometers. In this embodiment, the spike concentration is adjusted based upon pre-determined criteria such as an expected concentration range for the analyte to enhance characterization of an analyte using a ratio measurement.
In one embodiment of the invention, the method and apparatus enables the IP-MS to be operated in an unattended manner that is a substantial departure from attended operation protocol where operator calibration and analysis are typically performed. Direct comparison against a calibration curve is unnecessary through the use of ratio measurements. This is a departure from traditional instrument operation where concentrations of elements are made in comparison and where instrument drift requires frequent re-calibration required for quantitation. In one embodiment, the ratio of the analyte to the spike in a spiked sample is optimized for accuracy and quality assurance at and near the detection limits of the measurement.
In yet another embodiment of the invention, the method and apparatus quantifies elements without speciation information by mixing known enriched isotopes of elements in a semi-continuous process with the in-process sample stream from the chemical solutions being evaluated. The ionization voltage is purposefully set atypically high enough to eliminate species information directly at the source of the mass spectrometer to optimize the elemental quantitation.
In a further aspect of the invention, the method and apparatus mixes non-ligand bound or weakly ligand optimized enriched isotopes allowing for species transformations of the enriched isotopes into the dominant species set by the chemistry of the reagent streams being interrogated. These species are then directly evaluated using very low voltage and softer ionization conditions preserving the species information of the sample solutions using the same apparatus automatically controlled in alternate methods.
In an additional aspect of the invention, the method and apparatus uses additional solution manipulation after introduction of the stable optimized isotopes to alter the chemical species to permit optimum ionization for maximum sensitivity and detection limits. Other solution manipulations may be performed to change the matrix of the fluid to permit optimum ionization for maximum sensitivity and detection limits.
In yet another aspect of the invention, the method and apparatus mixes the optimized stable isotopes with the sample and the resulting solution is separated or pre-concentrated by element and/or species for sequential evaluation, optimization and maximum sensitivity.
In a particular use, wherein contaminant levels may be monitored at the ultra-trace level in baths employed in the semiconductor industry, in the cleaning of wafers an early warning or alarm may be sounded responsive to a contamination level approaching an upper tolerable limit in the case of warning or reaching or exceeding the same in the case of an alarm.
Corresponding apparatus is provided.
These and other objects of the invention will be more fully understood from the following description of the invention with reference to the drawings appended hereto.
The term "specie" as employed herein shall refer to elemental species, ionic species, molecular species, complex species such as organometallic species and any other species which may be adapted for qualitative and quantitative analysis using the present invention.
As used herein, the term "ratio" shall refer to an isotopic ratio of a specie and/or an element.
The term "fluid" as employed herein in respect of a mass stream containing either "specie or element" or "spike" or both in the form of, but not limited to, liquid or gas.
The term "threshold" as employed herein in respect of a level of a "specie or element" above which the "specie or element" can be determined quantitatively using present invention.
The term "quantitative detection limit of an instrument" means the lowest level of concentration of a particular element or specie which an instrument can detect quantitatively.
In this invention the isotopically enriched standard spikes added to the sample are allowed to come to species equilibrium with the isotopes in the sample prior to measurement and quantitative and species information then becomes available in the same solution. Adjustment of the enrichment mix to optimize the ratio for mathematical evaluation at the threshold detection level is not employed in traditional methods as quantitative information rather than threshold detection is the goal.
The method and apparatus are usable in in-process automated ultra-trace element, contaminant, and species analysis. This invention provides for a method and apparatus for a fluid handling in-process/mass spectrometer (IP-MS) analytical apparatus that uses optimized stable isotopic ratios for in-process automated and unattended operation. Both qualitative and quantitative analysis of ultra-trace elements and species information is available through the method and in this apparatus. The method uses a mass spectrometer interface that is an Atmospheric Pressure Ionization (API) system that allows both quantitative elemental measurement and species evaluation. The fluid handling system introduces the separated and optimized isotopes in a highly exchangeable ligand form that is dynamically transformed to the species occurring in the fluids being tested. The stable enriched isotopes are optimized for ratio measurement enabling efficient monitoring at and near the threshold of detection.
The present invention in one embodiment employs dynamic mixing of the standard enriched spike into the sample in order to eliminate undesired matrix effects.
Mass spectrometers are instruments that are not generally operated in an unattended manner for extended time periods, such as several days to a week at a time. Inherent variations in these instruments arise from changes that occur in stability in the calibration and operational conditions that substantially alter the quantitative capability. Changes in reagents and samples also affect mass flow and physical conditions of the instrument and change with time. All of these situations are normally dealt with through the manual and independent calibration and re-calibration of both the mass spectrometer and fluid handling systems. In the present invention, the method and apparatus enable the IP-MS to be operated in an unattended manner that is a substantial departure from attended operation protocol where operator calibration and analysis are typically performed. Direct comparison against a calibation curve is eliminated through the use of ratio measurements. These physical and time dependent alterations are removed through the reliance on isotopic ratios that remove the instrument stability parameters as sources of error in quantitative measurement.
Using the in-process Isotope Dilution methods of the present invention can significantly overcome the problems of signal suppression and non-linear signal response, therefore making quantification of inorganic elements and unattended operation feasible.
Referring now in greater detail to
Elemental Species are controlled by the chemistry of the solutions and by the processes in the specific chemistry operations that are in process. For example in the semiconductor industry where the cleaning and etching baths that are described in table 1 are present species established in these pure solutions by dominant anion complex formations such as aqueous hydrates, fluoride, chloride, arunonia, and hydroxide. The stability of these ligand complex ions and molecules will be maintained if no other ligand with a higher formation constant Kf is introduced. As a result, the metal ions in the high purity solutions of 1%-10% HF aqueous solution by volume will be dominated by the fluoride ion ligand complex. In solutions of HCl:H2O2:H2O (1:1:6 by volume) the dominant ligand will be the chloride ligand. For example iron(III) has progressively more stable fluoride formation constant of Kf1, Kf2, and a Kf3 of 2�105, 2�109 and 4�1012, respectively, (with a combined Kf of for all three of 4�1026) and chromium(III) Kf1 2�104, Kf2 6�108, and Kf3 of 2�1010 (the combined Cr(III) for a [CrF]complex is 3�1022) is. In the HCl solution Cu(I) has a Kf2 of approximately 3�105 and for iron(III) a Kf1, Kf2, Kf3 and Kf4 of 30, 134, 98 and 1.0, respectively. The other solutions also have differential ligand formation constants for hydroxide, ammonia, water, hydrogen peroxide and sulfate. If the iron is present as a fluoride complex or as a chloride complex or as a hydroxide this will change the fundamental chemistry of the interactions in the baths as the reactions are equilibrium that will be controlled by the solution ligands and the reaction products. By adding the isotopic spikes for iron, for example, in a plus three oxidation state, species in a very weak ligand, such as a nitrate, the ligand of the spike will be dynamically transformed into the species that is dominant in the solution and subsequently will equilibrate dynamically on-line or in-process with the elemental species contaminant in the cleaning bath or chemical process. If a chemical reaction occurs in a process, for example, in wafer cleaning, a reaction with the silica matrix and masking reagents may occur and it may create a different species, Fe(II) or Fe(III) or Fe-organometalic or a stable ligand species it may also be present in solution and a different ligand species will be evident in the speciated mass spectral examination. This is an additional informational adjustment over previous methods that extends the chemical information beyond elemental species contamination and adds the dimension of chemical specificity to the in-process chemistry. In addition, if a contaminant originates in a solution such as the HF bath and then is measured in the sulfate bath or water bath it will very likely retain its ligand of origin permitting the identification of the contamination source. This data is an addition to the complex information that will be obtained employing this method.
In another embodiment a strong chelating or complexing reagent will be added to both the sample and the spike and the quantitative measurement will be made as the complex. This chemical transformation of the species controls the chemistry of the solution and enhances the measurement and enables control of chemistry parameters that may otherwise be detrimental to the detection of the analytes of interest.
As shown in
As the present system is adapted to provide unattended, automated determination of specie identification, qualitatively and quantitatively, or elemental identification, qualitatively and quantitatively, three methods may be employed within the present system.
If it is desired to determine, qualitatively, the presence of a specie, the sample from sample introduction is introduced into the chemical modification step 12, wherein information provided from sample analysis 6 to microprocessor 10 will have entered data collection and analysis 14, which, in turn, distributes the information 16 which is passed onto controller 20, which, in turn, provides an output signal along lead 24 to chemical modification 12 to provide whatever adjustment in the chemistry, such as pH or reagent content, or physical properties, such as temperature, to the sample prior to the next stage of sample processing. The sample, as modified, is then delivered to the solution-handling unit which if the objective is qualitative, evaluation of the sample will deliver the same to atmospheric pressure ionization unit 32 which, in a preferred form, is an electrospray ionizer. This unit serves to ionize the components of the solution including the elements and species and, if desired, de-solvates the sample. The output of this unit is delivered to mass spectrometer 36, which may preferably be a time of flight mass spectrometer, or quadrapole mass spectrometer. The information from the mass spectrometer is delivered to the microprocessor 10 into the data collection and analysis unit 14, which, in turn, delivers it for information distribution to unit 16. Information which is to be employed in controlling operation of the instrument will be fed back to a sample introduction 2, spike introduction 38, chemical modification 12, solution handling 26, atmospheric pressure ionization 32, and mass spectrometer 36 for appropriate action. Further, to the extent to which the information may involve a departure from a desired concentration of contaminants, if an early warning is to be provided or an alert or shutdown ordered, the information is also delivered to the system interface 40 which controls the operation of the physical system which is being monitored by the instrument. This information may also be provided to operational personnel who would be provided with not only the warning and alert information, but also data regarding the then current readings, long-term trends, and other information of interest, including optimization information. Considering another mode of operation of the method, if it is desired to obtain quantitative determinations of an element, the sample introduction 2 delivers a sample to the spike introduction location, wherein enriched separated isotopes are mixed in dilute or a weakly complexing mode where they are mixed with the sample and subjected to equilibration. The equilibrated sample is then passed through chemical modification 12 and solution handling 26 from which it goes to liquid chromatograph 48 and then to atmospheric pressure ionization 32, after which, it is subjected to speciation processing 56 from which it passes to mass spectrometer 36 with the output of the mass spectrometer being processed in microprocessor 10 and, as appropriate, passed on to controller 12 and/or system interface 40. For the elemental mode, the voltage ranges from about 200 to 1,000 volts and preferably about 350-400 volts and for the specie mode from about 2-30 volts. In this approach, an enriched isotope is provided in the spike introduction 38 for each specie or element of contaminant sought to be monitored. If the sample were a gas sample, it would pass from solution handling 26 to gas chromatograph 56 and follow the process.
Where quantitative element determination is to be made, the output of atmospheric pressure ionization 32 is delivered to processing by elemental mode 60 from which the process sample enters the mass spectrometer.
Referring to
Ordinarily, a mass spectrometer will drift and become unstable with time, as demonstrated in the two examples provided here in
Consistent improvement in both precision and accuracy in multiple mass spectrometers with a variety of ionization interfaces demonstrate the general applicability of the invention to enable the mass spectrometer system to function for extended periods of time and to reduce the error caused by instrument drift and conventional calibrations.
It is clear that IDMS analysis is at least an order magnitude more accurate and precise than conventional calibration over a period of 60 minutes.
Table 1 shows typical silicon wafer cleaning solutions and reagents
employed in the semiconductor industry.*
Purpose of
Solution Name
Ultra-Pure Water
H2O Ultra-
Primary Dilution
Organic Removal
"Huang 1"
MetaI Ion
Alkali Ion Removal
"Huang 2"
Metal Hydroxides
Residual Trace
Metal Removal
Alkali Ion Removal
"Huang 2"
Metal Hydroxides
Residual Trace
Metal Removal
Mixture of
Organic Removal
Peroxide, SPM
Diluted HF
Native Oxide
*(as modified in accordance with Kern W., "Handbook of Semiconductor Wafer Cleaning Technology: Science, Technology and Applications", Noyes Publications, 1993).
The method and apparatus goals are to provide close to real-time analytical chemical metrology of contaminant concentrations in these solutions. Generally, the contaminants of primary interest may include at least one element selected from the group consisting of Ca, Co, Cr, Cu, Fe, Mn, Mo, Ni, W, Na, P, B, As, Sb, and Zn, but it is desirable to measure any additional elements present at significant concentrations. The concentration range that must be assessed is mid-ppb to low-ppt and continually will drop as the instrument detection limits are gradually reduced. Thus the character of the measurement will remain the same and will require the optimization of ultra trace measurements progressing but using the same fundamental theoretical considerations. The technology is a critical quality control assessment tool for uses such as in wet process baths in the semiconductor industry as in chip manufacturing activities. As circuitry on wafers continues to shrink, these contaminants will have even greater impact on the viability of the final products.
The use of the methods of the present invention at or near the detection limits of the mass spectrometer involves modification of the ratio measurement. When elemental and species components are at concentrations in the fluids well above the detection limits of the mass spectrometer, the use of commercially available isotopes is possible. When these measurements are required at the threshold of detection of the instrument, uncertainties can make the analysis more difficult. In these cases, enhancing the certainty of the detection limit measurement is desirable. The isotopic ratio can be altered in the spiking fluids to optimize the ratio measurement at these levels. An example of how these specially prepared spikes enhance these measurements follows. An optimum ratio at and near the limit of detection is more difficult than measurements at nominally normal or high concentrations. Establishing a ratio that definitively establishes the threshold of detection and enables the uncertainty of the measurement to be known and optimized for the IP/MS is a unique optimization at the detection limit threshold. The optimization of the ratio for detection limit and near detection limit is achieved by using matched quantities of spike optimized for the threshold level and /or mixing both natural and multiple enriched isotopes in separated quantities of the same element. This technique is not present in traditional IDMS methods where this measurement is uncertain over a wide range.
The measurement of elemental contamination at or near the quantitative detection limit of this instrument will progress as the instrument detection limit recedes in future instruments. Because of the needs of many industries, such as the semiconductor industry, for example, the level of elemental contamination will continue to decrease. As the instrumental measurement sensitivity also decreases the need to measure and make accurate measurements at the detection limit of the mass spectrometer will remain in relatively similar relationships. These concepts are durable detection limit threshold measurement optimizations that will progress with detection limit of the instrument and retain their useful attributes as both the need, and capability recede simultaneously.
In order to provide additional insight into the system of the present invention, computer model studies were undertaken with the results being shown in
There is a window of optimum spike concentration from 0.05 ppb to 0.2 ppb (third through sixth column) which enables a preferred quantitative measurement of the 0.05 ppb Ni in the sample with improved precision as compared with the traditional calibration method (first column from the left). The trend demonstrates an optimum spiking ratio range that can be established experimentally and/or theoretically. This optimum range may preferably be used in quantification employing the method.
Two types of information are available using different modes of operation of the IP-MS instrument. Quantification of the element in the fluid and species-specific information about the form of the element are important. The chemistry that is occurring in the process is described by both of these parameters. As both are desirable and must be used to describe the total chemistry of the process, both have been integrated into the method and apparatus.
To obtain quantitative information about the element and for the purpose of determining the isotopic ratio, the species information within the fluid can be eliminated. This is accomplished by changing the instrument operational parameters to collision-induced disassociation (CID) mode. The CID can serve to simplify mass spectra, thereby reducing background and increasing sensitivity. For example, purposefully set the ionization voltage high enough to eliminate species information directly at the source of the mass spectrometer. Voltages of about 200 to 1000 volts on the sampling cone and on various components of the sampling system are used to eliminate the molecular information and to obtain relatively isolated elemental signals.
The molecular species may be evaluated to determine elemental and molecular species occurring in solution. These evaluations are made on unaltered fluid streams and on isotopically labeled fluids. To make these measurements with the IP-MS, the API is operated in a non-species destructive manner, i.e. the instrument is operated under soft ionization conditions such as low cone voltage, slower cone gas flow, and mild de-solvation temperature. Elements that occur in complex ligand or molecularly bound forms are revealed in this operational mode. These complexes that indicate the chemistry occurring in the process are extremely valuable informational components used for qualitative evaluation, and to identify conditional trends and process alternatives.
To quantify these species and evaluate the chemistry, isotopically labeled species are created dynamically. The method and apparatus create the species occurring in the sample from the optimally prepared spike reagent solutions. These spike reagents (enriched isotope solutions) are optimized ratio-separated stable isotopes in a solution of non-complexing or non-ligand forming or weak ligand forming counter ions. Nitrates are good examples of very weak ligand forming counter ions. Nitrate ligand formation constants (Kf) are generally and uniformly several orders of magnitude smaller than fluoride complexes, and several orders weaker than chloride and sulfate ligands. When solutions of enriched isotopic spike are mixed with the sample reagent solutions (for example, listed in Table 1), the spike or isotope ion will conform to the solution species in the reagent solution. The contaminant concentration (in this example, but deliberate concentrations in other fluids) is very small in comparison to these relatively abundant solution components and will cause the formation of these species that are occurring in solution. The creation of spiked species and isotopic labeling is accomplished dynamically for the processing fluids of silicon wafer materials, for example. Mixing of the spike solutions with these fluids establishes the same species that are naturally occurring in these solutions and provides the ability to determine their concentrations in a similar manner using isotopic ratio measurements.
The combination of both the quantitative and qualitative measurements information available from the same instrument operated in different conditions is desirable and necessary for full understanding and evaluation of fluids described in these examples and in other examples. Both are capable from a single instrument as described.
The alteration of the fluid sample is also necessary for the optimization of both quantitative and qualitative measurement of some process fluids. This fluid processing may be accomplished in several ways. For example, the sample may be directly combined with a neutralizing agent for the adjustment of pH. Consider solutions from table 1, NH4OH (a base) and acids HF, HCl and H2SO4 may require neutralization or they may be combined to neutralize each other. Combining these samples with other solutions that have acid-base neutralization capabilities is part of fluid handling. Direct neutralization of an acid with a base, or base with an acid, is also part of the fluid handling system. In this latter case, a reagent, rather than another sample, becomes the neutralizing solution.
Other components of fluid handling are the collection and accumulation of metal ions on chelating, ion-exchange, and normal and reversed phase chromatography columns integrated into the fluid and sampling handling portions of the overall system. These manipulations may be undertaken to optimize the qualitative and quantitative measurement and evaluation of the solution.
Other components of the fluid handling system incorporate automated derivatisation and chemical enhancement of the signal through the addition of modifying agents such as ligands, chelators, surfactants, solvents, and/or other reagents that amplify the ionization and/or the signal in the mass spectrometer.
The fluid handling instrument component incorporates mixing, chemical modification, metering, dilution, pre-concentration, and other aspects of fluid handling used in qualitative and quantitative manipulation of the fluid sample stream.
Appropriate software, which may be developed by those skilled in the art, will be employed in controlling operation of the method and apparatus and processing data obtained therefrom.
While for convenience of illustration emphasis has been placed herein on examples directed toward monitoring of contaminants in wet baths employed in clean rooms in the semiconductor industry, it will be appreciated that the invention is not so limited and, as will be apparent to those skilled in the art, numerous other applications, including in such uses as environmental, pharmaceutical, biotechnology, food processing, chemical manufacture, and production of reagents and standards, both preparation and certification will become apparent to those skilled in the art.
It will be appreciated, therefore, that the present invention provides a method and related apparatus for fully automated comprehensive analytical chemistry tools which can monitor on-line in-process solutions in an accurate and rapid manner for contaminants and thereby enhance the efficiency of manufacture.
Whereas particular embodiments have been described herein for purposes of illustration it will be evident to those skilled in the art that numerous variations of the details may be made without departing from the invention as defined in the appended claims.
|Cited Patent
|Filing date
|Publication date
|Dec 27, 1976
|Jan 2, 1979
|Rockwell International Corporation
|Method for evaluating the quality of electroplating baths
|Jun 26, 1980
|Apr 13, 1982
|Cominco Ltd.
|Method and apparatus for controlling the quality of electrolytes
|Jan 21, 1983
|Oct 30, 1984
|International Business Machines Corporation
|Method for determination of concentration of organic additive in plating bath
|Jan 25, 1988
|Apr 17, 1990
|Shipley Company Inc.
|Method for analyzing additive concentration
|Sep 13, 1988
|Dec 4, 1990
|Hoya Corporation
|Process for producing polyurethane lens
|Mar 22, 1988
|Apr 30, 1991
|Indiana University Foundation
|Isotope-ratio-monitoring gas chromatography-mass spectrometry apparatus and method
|Sep 13, 1989
|Jan 26, 1993
|C. Uyemura & Co., Ltd.
|Plating solution automatic control
|May 16, 1991
|Mar 9, 1993
|International Business Machines Corporation
|Cyclic voltammetric method for the measurement of concentrations of subcomponents of plating solution additive mixtures
|Mar 11, 1992
|Oct 4, 1994
|Fisons Plc
|Isotopic-ratio plasma source mass spectrometer
|Jan 5, 1994
|May 9, 1995
|Duquesne University Of The Holy Ghost
|Method of speciated isotope dilution mass spectrometry
|Sep 1, 1995
|Nov 5, 1996
|Fisons Plc
|Apparatus and method for isotopic ratio plasma mass spectrometry
|Mar 20, 1996
|Dec 9, 1997
|Baylor University
|High accuracy determination of chlorine content by isotope dilution flame infrared emission spectrometry (ID-FIRE)
|Aug 30, 1996
|Dec 30, 1997
|Hewlett-Packard Company
|Automated calibrant system for use in a liquid separation/mass spectrometry apparatus
|May 30, 1997
|Feb 16, 1999
|Hewlett-Packard Company
|Mass spectrometry calibration using homogeneously substituted fluorinated triazatriphosphorines
|Jun 30, 1998
|Mar 7, 2000
|Texas Instruments Incorporated
|Apparatus and method for measuring contaminants in semiconductor processing chemicals
|Oct 20, 1999
|Aug 28, 2001
|Advanced Technology Materials, Inc.
|Method and apparatus for determination of additives in metal plating baths
|Oct 29, 1999
|Nov 26, 2002
|Agilent Technologies, Inc.
|Dielectric capillary high pass ion filter
|Jan 28, 1999
|Aug 5, 1999
|Duquesne University Of The Holy Ghost
|Speciated isotope dilution mass spectrometry of reactive species and related methods
|Applications of Isotope Dilution-Mass Spectrometry in Clinical Chemistry, Pharmacokinetics and Toxicology, Mass Spectrometry Reviews, pp 249-307 (1992).
|Cole, Electrospray Ionization Mass Spectrometry: Fundamentals, Instrumentation and Applications, John Wiley & Sons, Inc. (1997), New York.
|Fassett et al., Determination of Nanogram Quantities of Vanadium in Biological Material by Isotope Dilution Thermal Ionization Mass Spectrometry with Ion Counting Detection, Anal. Chem. (Nov. 1985), pp. 2474-2478, V57, No. 13.
|Fassett et al., Isotope Dilution Mass Spectrometry for Accurate Elemental Analysis, Anal. Chem. (May 15, 1989), pp. 643A-649A V61, No. 10.
|Heumann et al., Elemental Speciation with Liquid Chromatography-Inductively Coupled Plasma Isotope Dilution Mass Spectrometry, J. Anal. Atom. Spectro. (Dec. 1994), pp. 1351-1355 V9.
|Horn et al., Comparison of heavy metal analyses in hydrofluoric acid used in microelectronic industry by ICP-MS and thermal ionization isotope dilution mass spectrometry, Fresenius J. Anal. Chem (1994), pp. 286-292, V350.
|International Technology Roadmap for Semiconductors 1999 Edition: Defect Reduction, Sematech, Austin, TX, pp. 269-293.
|Newton et al., Analysis of Copper Planting Baths-Suppressors and Levelers, Electrochemical Society Proceedings, pp. 1-5, V2000-27.
|Rottmann et al., Determination of Heavy Metal Interactions with Dissolved Organic Materials in Natural Aquatic Systems by Coupling a High-Performance Liquid Chromatography System with an Inductively Coupled Mass Spectrometer, Anal. Chem. (Nov. 1, 1994), pp. 3709-3715, V66.
|Rottmann et al., Development of an on-line isotope dilution technique with HPLC/ICP-MS for the accurate determination of elemental species, Fresenius J. Anal Chem. (1994), pp. 221-227, V350.
|Stewart, Electrospray mass spectrometry: a tool for elemental speciation, Spectrochimica, Acta. (1999), pp. 1649-1695, Part-B, vol. 54.
|Viezian et al., On-line Isotope Dilution and Sample Dilution by Flow Injection and Inductively Coupled Plasma Mass Spectrometry, J. Anal. Atom. Spectro. (Apr. 1990), pp. 125-133, V5.
|Citing Patent
|Filing date
|Publication date
|Mar 8, 2011
|Dh Technologies Development Pte. Ltd.
|Methods and apparatus for enhanced ion based sample detection using selective pre-separation and amplification
|Nov 4, 2010
|Nov 26, 2013
|Dh Technologies Development Pte. Ltd.
|Methods and apparatus for enhanced ion based sample detection using selective pre-separation and amplification
|May 19, 2011
|Jun 24, 2014
|Thermo Fisher Scientific Inc.
|Device and method for diluting a sample
|Feb 3, 2010
|Sep 30, 2014
|The Administrators Of The Tulane Educational Fund
|Tuned synthetic dendrimer calibrants for mass spectrometry
|Aug 19, 2015
|May 17, 2016
|Elemental Scientific, Inc.
|Internal standardization with enriched stable isotopes and cool plasma ICPMS
|Dec 17, 2004
|Aug 4, 2005
|Sionex Corporation
|Methods and apparatus for enhanced ion based sample detection using selective pre-separation and amplification
|Dec 9, 2005
|Aug 3, 2006
|Stewart Larry N
|In-process mass spectrometry with sample multiplexing
|Jan 11, 2006
|Mar 1, 2007
|Libo Cao
|Mass spectrometry data analysis engine
|Feb 24, 2011
|Dh Technologies Development Pte. Ltd.
|Methods and apparatus for enhanced ion based sample detection using selective pre-separation and amplificaton
|Feb 3, 2010
|Dec 1, 2011
|The Administrators Of The Tulane Educational Fund
|Tuned synthetic dendrimer calibrants for mass spectrometry
|Jun 13, 2013
|Waters Technologies Corporation
|Techniques for automated installation testing and reporting for analytical instruments
|Dec 17, 2010
|Jun 30, 2011
|Northrop Grumman Systems Corporation
|Solution analysis using atmospheric pressure ionization techniques
|Dec 17, 2010
|Nov 24, 2011
|Northrop Grumman Systems Corporation
|Solution analysis using atmospheric pressure ionization techniques
|U.S. Classification
|250/282, 250/288, 250/281
|International Classification
|Cooperative Classification
|European Classification
|Apr 15, 2002
Owner name: METARA, INC., CALIFORNIA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:KINGSTON, HOWARD M.;REEL/FRAME:012827/0593
Effective date: 20020327
|Apr 29, 2005
Owner name: METARA INC., CALIFORNIA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:HAN, YE;ANDERSON, MARC R.;REEL/FRAME:016184/0731;SIGNINGDATES FROM 20050324 TO 20050414
|Jun 8, 2006
Owner name: BRIDGE BANK N.A., CALIFORNIA
Free format text: SECURITY AGREEMENT;ASSIGNOR:METARA INC.;REEL/FRAME:017730/0947
Effective date: 20060525
|Mar 4, 2008
|Certificate of correction
|Jun 22, 2009
|Maintenance fee reminder mailed
|Dec 13, 2009
|Lapse for failure to pay maintenance fees
|Feb 2, 2010
|Expired due to failure to pay maintenance fee
Effective date: 20091213

subset: commoncrawl


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Cambridgeshire police are investigating "a serious assault" after an 18-year-old man suffered a facial injury in St Ives on May 30.
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A planning proposal to turn a warehouse unit in St Ives into a church has been submitted to Huntingdonshire District Council.
A business consortium has purchased premises in Huntingdon's High Street that was formerly home to a gift shop.
The library in St Ives has been selected to trial new technology which could help safeguard its opening hours.
A St Neots mum who is raising money to fund surgery for her son who has cerebral palsy was chosen for the Good Morning Britain Toughmums Challenge.
A rare Roman silver coin believed to date back more than 1,600-years-old has been discovered in St Neots.
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Ben Hicks has won a seat on St Neots Town Council, representing the Eaton Socon ward, after a by-election in the town on May 19.
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Organisers of the first ever Mobility Scooter Grand Prix in St Ives have hailed the event a great success.
Hinchingbrooke Hospital's board will press ahead with plans to merge with Peterborough it was confirmed at a packed meeting today (Monday).
Adam Fahey hit a fabulous first century in English cricket to fire Warboys to the top of the Tucker Gardner League Division Two table.
St Ives Corn Exchange played host to the fifth annual Book Jam event on May 14, with some 500 children taking part in activities and workshops held by published authors and illustrators.
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text:
Race Baiting Liberal Changes His Story as He Sees Video, and hears 911 Call
When police showed Saldana the surveillance video from the convenience store, he realized his actions looked less innocuous than he had remembered. (He knew he couldn't sell the story he had told...)
By: Superezforme | Comments: 115 | Views: 4964 | Votes: 10 | Shared: 15
Location: Wichita, Kansas, United States | Leaked: Mar-19-2016 in Other News, WTF
Dumbest People In America! Fucking Scum!
Some dumb fucking pile of shit family thinks that because their son needed money for clothes, and food (drugs and chains), that he should just be able to break into someone's house and take their stuf
By: tful3398 | Comments: 229 | Views: 7897 | Votes: 18 | Shared: 1
Location: Miami, Florida, United States | Leaked: Mar-17-2016 in WTF
Aljazeera Network Caught Airing Fake News & Their Famous Host Is A Former Thief
Aljazeera network caught airing fake news on 6 & 7 October 2013, about Muslim Brotherhood protests and what is going on in Egypt. They are working hard on spreading lies about Egyptians are d
By: blootoof | Comments: 7 | Views: 1236 | Votes: 0 | Shared: 0
Leaked: Mar-17-2016 in Other Middle East
Criminal Is Killed By Home Owner In Her Own Home!
A local family of loser obama phone recipients is upset one of their own died in the act of a crime before he could reach his potential : ^ ( 17-year-old Treyvon Johnson (Yes, his name really
By: Anon51 | Comments: 191 | Views: 5647 | Votes: 23 | Shared: 7
Location: United States | Leaked: Mar-16-2016 in Other News
Bernie Sanders drop out, and will he endorse Donald Trump By March 14 2016 36 Bernie Sanders only holds a lead in one of next week's eleven Super Tuesday states, and the news gets even wo
By: Downunder75 | Comments: 76 | Views: 2191 | Votes: 3 | Shared: 3
Location: Washington, District of Columbia, United States | Leaked: Mar-14-2016 in Politics
Technology SITREP: How Russian engineering made the current operation in Syria possible
The pace and effectiveness of the Russian Air Force (well, technically they are now called AirSpace Forces or ASF so I will refer to them as RASF from now on) has the western military experts in shock
By: Lepanto | Comments: 48 | Views: 5776 | Votes: 32 | Shared: 18
Location: Syria | Leaked: Mar-11-2016 in Other News, Syria
Twisted montreal berger blanc torturing animals........
Dont know how to add subs sorry https://www.youtube.com/watch?v=K5NmSTakew4 1 00:00:08,760 --> 00:00:12,760 They're discreet in the day but at night the alleys belong to them. 2 00:0
By: BOSS-STATUS | Comments: 4 | Views: 22063 | Votes: 0 | Shared: 0
Location: Montreal, Quebec, Canada | Leaked: Mar-10-2016 in World News, Other News, WTF
European Central Bank cuts main interest rate to zero to try to lift eurozone economy
The European Central Bank has cut its main interest rate to try to get the eurozone economy growing and to stave off ultra-low inflation – or deflation. The benchmark rate goes to zero from 0.05
By: Euronews | Comments: 15 | Views: 851 | Votes: 0 | Shared: 4
Leaked: Mar-10-2016 in Other News
Blood libel
Let's talk about Jewish Ritual Murders, or like the Jews like to call it Blood libel? Do you believe in it? Here is some historical record I come across. 169 B.C. – "King Antiochus
By: Cheeki Breeki | Comments: 5 | Views: 5707 | Votes: 3 | Shared: 0
Location: United States | Leaked: Mar-9-2016 in Religion
Bernie Sanders Shocks The Political World By Winning The Michigan Primary
By Jason Easley on Tue, Mar 8th, 2016 at 11:34 pm A win that nobody saw coming came true, as Bernie Sanders finally had a close election go his way with a big upset of Hillary Clin
By: Grover3 | Comments: 26 | Views: 1040 | Votes: 2 | Shared: 0
Leaked: Mar-9-2016 in Politics
What Is Really Going On With Clinton's Email System – The Truth About Clinton's Email Dilemma.
Even though Clinton supporters like Texas Democratic Rep. Joaquin Castro, who said Sunday that the Justice Department "cleared" Clinton in its ongoing investigation, this is completely false and
By: rgbapps | Comments: 119 | Views: 1467 | Votes: 11 | Shared: 14
Location: United States | Leaked: Mar-8-2016 in Politics
Lazy,ouzo-swilling,olive-pit spitting Greeks or how Goldman sacked Greece
Sunday, November 6, 2015 by Greg Palast for In These Times Here's what we're told: Greece's economy blew apart because a bunch of olive-spitting, ouzo-guzzling, lazy-ass Greeks refuse to put
By: CBS CBS | Comments: 31 | Views: 1270 | Votes: 1 | Shared: 0
Location: New York, New York, United States | Leaked: Mar-8-2016 in Other News
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Page 15
They say that laughter is the best medicine.
What do you call a doctor who is always on the telephone?
An ON-CALLogist
What do you call bugs with cancer?
MalignANT and BEEnign
Why don't needles need to go to school?
Because they're already so sharp.
What would you get if you crossed an x-ray technician and a seamstress?
Hospital gowns.
How can nurses stand to work at busy hospitals?
They have lots of patients.
Why do doctor's send out bills?
So the ducks can eat.
My Favorite Three-Time Cancer Survivorby Carolyn Vachani, MSN, RN, AOCN
May 23, 2014
Criticize Your Doctors at Your Own Risk: HIPAA Violations and Online Reviewsby Rodney Warner, JD
May 31, 2016


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|By Marketwired .
Article Rating:
|December 27, 2012 06:00 AM EST
FORT LAUDERDALE, FL -- (Marketwire) -- 12/27/12 -- Out with the old, in with the new! Companies ready to shift to a more effective online PR strategy will want to attend the South Florida Interactive Marketing Association's first event of the new year, "Using Search and Social Media to Maximize Online PR." On January 10, a panel discussion featuring noted speaker, writer and consultant Lisa Buyer will cover the key ingredients needed for great PR results online.
Buyer will be joined by Toby Srebnik who oversees digital media efforts for well-known local brands such as Aventura Mall and Anthony's Coal-Fired Pizza, and has launched successful campaigns for Dunkin' Donuts and Truly Nolen of America. The panel will also feature South Florida-based attorney and foreclosure defense expert Roy Oppenheim, a partner at Oppenheim Law who gained local, regional and national media coverage using Buyer's social media PR strategies. The discussion will be moderated by Joe Laratro, past SFIMA president and founder of SEO consulting firm Tandem Interactive.
Interactive marketers, PR pros and SEO geeks alike will discover how to mix up search engine marketing, social media and public relations to ensure their stories make it to journalist newsfeeds, search engines, social networks, and directly to the eyeballs of customers. Attendees will leave with actionable items they can implement immediately to create a new online PR routine for 2013.
Lisa Buyer is the CEO of The Buyer Group, an interactive public relations and branding agency based in Florida. The Buyer Group's Social PR/SEO clients consist of public and private companies in the technology, real estate and health/beauty industries. The firm also offers consulting services to agencies transitioning to today's best search engine strategies. Buyer writes a monthly column on Search Engine Watch and publishes SocialPR Chat. She is also a Certified Google Adword Professional (just for the fun of it), past member of SEMPO, SFIMA and Agency Management Roundtable.
Toby Srebnik is director of social media for O'Connell & Goldberg Public Relations in Hollywood, Fla., where he manages social media initiatives for clients while also deepening the firm's social media branding strategy. Prior to joining O'Connell & Goldberg, Srebnik served as Manager of Social Media for Tilson Communications in Boca Raton. He has presented at numerous universities and businesses about the influence of social media, and is a Social Media Club South Florida board member and the 2013 President for the Public Relations Society of America's Greater Fort Lauderdale chapter.
Roy Oppenheim is the co-founder and senior partner at Oppenheim Law, a firm he founded in 1989 with his wife, Ellen Pilelsky. He is a successful serial entrepreneur and attorney focusing on Florida foreclosure defense, Internet ventures and direct sales companies. Oppenheim is a motivational speaker and shares his inspirations and Florida foreclosure expertise through his social media channels, including an award-winning South Florida foreclosure law blog www.southfloridalawblog.com, Twitter @oplaw, foreclosure defense YouTube Channel, and interactive communications with his peers, clients and colleagues.
The SFIMA discussion takes place Thursday, January 10, at the IGFA Fishing Hall of Fame and Museum in Dania Beach, Fla. Networking runs from 6:30 p.m. to 7:15 p.m. The discussion runs from 7:30 p.m. to 8:30 p.m. The event is free for SFIMA members. Non-members pay $39 in advance, $49 at the door. To register, visit http://tinyurl.com/bwndlhe.
SFIMA news releases are distributed by wire distribution partner, Marketwire, www.marketwire.com.
The South Florida Interactive Marketing Association is a forum dedicated to professionals specializing in interactive marketing. www.sfima.com, @SFIMA
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Jennifer R. Hudson
PR Chair
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The essence of data analysis involves setting up data pipelines that consist of several operations that are chained together – starting from data collection, data quality checks, data integration, data analysis and data visualization (including the setting up of interaction paths in that visualization). In our opinion, the challenges stem from the technology diversity at each stage of the data pipeline as well as the lack of process around the analysis.
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WebRTC is bringing significant change to the communications landscape that will bridge the worlds of web and telephony, making the Internet the new standard for communications. Cloud9 took the road less traveled and used WebRTC to create a downloadable enterprise-grade communications platform that is changing the communication dynamic in the financial sector. In his session at @ThingsExpo, Leo Papadopoulos, CTO of Cloud9, will discuss the importance of WebRTC and how it enables companies to fo...
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Designing IoT applications is complex, but deploying them in a scalable fashion is even more complex. A scalable, API first IaaS cloud is a good start, but in order to understand the various components specific to deploying IoT applications, one needs to understand the architecture of these applications and figure out how to scale these components independently. In his session at @ThingsExpo, Nara Rajagopalan is CEO of Accelerite, will discuss the fundamental architecture of IoT applications, ...
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Korean Broadcasting System (KBS) will feature the upcoming 18th Cloud Expo | @ThingsExpo in a New York news documentary about the "New IT for the Future." The documentary will cover how big companies are transmitting or adopting the new IT for the future and will be filmed on the expo floor between June 7-June 9, 2016, at the Javits Center in New York City, New York. KBS has long been a leader in the development of the broadcasting culture of Korea. As the key public service broadcaster of Korea...
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As cloud and storage projections continue to rise, the number of organizations moving to the cloud is escalating and it is clear cloud storage is here to stay. However, is it secure? Data is the lifeblood for government entities, countries, cloud service providers and enterprises alike and losing or exposing that data can have disastrous results. There are new concepts for data storage on the horizon that will deliver secure solutions for storing and moving sensitive data around the world. ...
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In his session at 18th Cloud Expo, Bruce Swann, Senior Product Marketing Manager at Adobe, will discuss how the Adobe Marketing Cloud can help marketers embrace opportunities for personalized, relevant and real-time customer engagement across offline (direct mail, point of sale, call center) and digital (email, website, SMS, mobile apps, social networks, connected objects). Bruce Swann has more than 15 years of experience working with digital marketing disciplines like web analytics, social med...
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What a difference a year makes. Organizations aren't just talking about IoT possibilities, it is now baked into their core business strategy. With IoT, billions of devices generating data from different companies on different networks around the globe need to interact. From efficiency to better customer insights to completely new business models, IoT will turn traditional business models upside down. In the new customer-centric age, the key to success is delivering critical services and apps wit...
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With major technology companies and startups seriously embracing IoT strategies, now is the perfect time to attend @ThingsExpo 2016 in New York and Silicon Valley. Learn what is going on, contribute to the discussions, and ensure that your enterprise is as "IoT-Ready" as it can be! Internet of @ThingsExpo, taking place Nov 3-5, 2015, at the Santa Clara Convention Center in Santa Clara, CA, is co-located with 17th Cloud Expo and will feature technical sessions from a rock star conference faculty ...
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There are several IoTs: the Industrial Internet, Consumer Wearables, Wearables and Healthcare, Supply Chains, and the movement toward Smart Grids, Cities, Regions, and Nations. There are competing communications standards every step of the way, a bewildering array of sensors and devices, and an entire world of competing data analytics platforms. To some this appears to be chaos. In this power panel at @ThingsExpo, moderated by Conference Chair Roger Strukhoff, panelists will discuss the vast to...
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SYS-CON Events announced today that Enzu, a leading provider of cloud hosting solutions, will exhibit at SYS-CON's 18th International Cloud Expo®, which will take place on June 7-9, 2016, at the Javits Center in New York City, NY. Enzu's mission is to be the leading provider of enterprise cloud solutions worldwide. Enzu enables online businesses to use its IT infrastructure to their competitive advantage. By offering a suite of proven hosting and management services, Enzu wants companies to foc...
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