TOC800 原理說明

TOC Terminology : 

TOC Terminology

TOC Terminology : 

TOC Terminology TOC - Total Organic Carbon TIC (IC) - Inorganic Carbon TC - Total Carbon - sum of TOC and IC TOC = TC - IC

TOC Parameters : 

TOC Parameters TC - Total Carbon IC - Inorganic Carbon TOC - Total Organic Carbon NPOC - Non-Purgeable Organic Carbon POC - Purgeable (volatile) Organic Carbon DOC - Dissolved Organic Carbon

Practical TOC Analytical Flow Chart : 

Practical TOC Analytical Flow Chart Total Carbon (TC) Total Organic Carbon (TOC) Inorganic Carbon (IC) Carbonates CO2 (Dissolved)

Detail TOC Analytical Flow Chart : 

Detail TOC Analytical Flow Chart Total Carbon (TC) Inorganic Carbon (IC) Total Organic Carbon (TOC) Particulate Dissolved Purgeable Organic Carbon (POC) Non-Purgeable Organic Carbon (NPOC) Dissolved (DOC) Particulate TOC = TC - IC (difference)

Organic Carbon (TOC) Sources : 

Organic Carbon (TOC) Sources From Source Water - Municipal, Surface, Wells Organic byproducts of disinfection (THMs) Naturally occurring organics (humic acids) Synthetic organic species Fertilizers, pesticides From Purification and Distribution Systems Plasticizers, byproducts of production materials and resins Heat Exchangers Biofilm Pumps, Welds, etc.

Inorganic Carbon : 

Inorganic Carbon IC = CO2(aq) + HCO3_ + CO32- CO2(aq) is aqueous carbon dioxide HCO3_ is bicarbonate ion CO32- is carbonate ion 2H++CO3= H++HCO3- H2O +CO2 PH>11 PH=7 PH<2

TOC Instrumentation Technologies : 

TOC Instrumentation Technologies

Fundamental Principles of All TOC Analyzers : 

Fundamental Principles of All TOC Analyzers Oxidize organic compounds to CO2 Measure the CO2 produced

Oxidation Techniques : 

Combustion Oxidation Heated Persulfate Oxidation Ultraviolet and Persulfate Oxidation Ultraviolet Oxidation Ultraviolet and Titanium dioxide Oxidation Techniques

Combustion Oxidation High temperature furnace air/O2 + Pt catalyst @ 680-950 oC : 

Advantages High oxidation efficiencies Oxidize particles Disadvantages Background problems Catalyst can be poisoned and must be replaced Requires reagents, gases Combustion Oxidation High temperature furnace air/O2 + Pt catalyst @ 680-950 oC

Heated Persulfate Oxidation S2O8 + heat (90 - 130 oC) _> 2SO4_. SO4_. + H2O _> HSO4_ + OH. : 

Advantages High oxidation efficiencies No catalyst or lamps Heated Persulfate Oxidation S2O8 + heat (90 - 130 oC) _> 2SO4_. SO4_. + H2O _> HSO4_ + OH. Disadvantages May not completely oxidize particles May lose volatile compounds Chemical reagents Carry over in reaction vessel

UV/Persulfate Oxidation H2O + hn (185 nm) _> OH. + H. S2O8 + hn (254 nm) _> 2SO4_. SO4_. + H2O _> HSO4_ + OH. : 

Advantages High oxidation efficiencies at both high and low TOCs Lower maintenance Cleaner system blanks Disadvantages May not completely oxidize particles Chemical reagents Lamps must be replaced UV/Persulfate Oxidation H2O + hn (185 nm) _> OH. + H. S2O8 + hn (254 nm) _> 2SO4_. SO4_. + H2O _> HSO4_ + OH.

Ultraviolet Oxidation H2O + hn (185 nm) _> OH. + H. : 

Advantages No reagents Catalyst not poisoned Lower maintenance for semiconductor Disadvantages Not enough oxygen for higher levels of TOC (>2.5 ppm TOC) May not completely oxidize particles Lamp replacement Ultraviolet Oxidation H2O + hn (185 nm) _> OH. + H.

CO2 Measuring Techniques : 

CO2 Measuring Techniques Non dispersive infrared (NDIR) Direct conductivity Membrane conductivity

Sensor configurations : 

Sensor configurations sample in waste electrode electrode UV lamp Membrane Conductivity Direct Conductivity Purge in NDIR IR Lamp Membrane waste deionized water Purge out

NDIR Detection : 

Advantages Measures both DI and non-DI water Established technology High Selectivity Disadvantages Frequent Calibration Large size Takes long time to warm up Limited dynamic range Water interference (must dry gas) Must remove CO2 from solution (purge gas) NDIR Detection

Direct Conductivity : 

Advantages Simple system, no purge gas, drier High sensitivity, stable calibration Disadvantages Only works in deionized water Limited selectivity - measures all ions Interferences from halogenated compounds and all sulfur-, nitrogen- and phosphorus- containing compounds Direct Conductivity

Membrane Conductivity : 

Advantages Measures DI and non-DI water High sensitivity, selectivity and precision Stable calibration, electrodes not fouled No purge gas, drier Disadvantages Reagents required for non-deionized water 50 ppm upper limit Membrane Conductivity

Typical Linearity Data : 

Typical Linearity Data

Slide 22: 

Interferences - Organic Heteroatoms

Slide 23: 

High Selectivity 100X Less Sensitive than Conductometric Methods Detector drifts Short linearity range Water Interferes Purge in IR Lamp Purge out IR detector NDIR Detection

Sievers TOC 800 Instrumentation : 

Sievers TOC 800 Instrumentation

Slide 25: 

Model 800 Specification Highlights Display Back-lit LCD Screen TOC Range 0.05ppb to 50,000 ppb Repeatability TOC = +/- 3 % TC Value Analysis Time 6 Minutes Sampling Method Continuous(On-Line and Grab Mode) Calibration Frequency 1 Year Stability - Field Calibration USP Standards USP Traceable Standards Available IQ/OQ Guidelines Included Sample Temperature O-100 Co Ambient Temperature 10-40 Co Sample Pressure Up to 100 psi Weight 30 pounds

Slide 26: 

membrane module membrane module sampling pump U.V. oxidation reactor acid reservoir sample inlet peroxydisulfate reservoir syringe pump delay coil syringe pump conductivity & temperature conductivity & temperature waste DI water, resin bed & pump DI valves Sievers Patented Method- Model 800

Slide 27: 

Conductometric/Membrane Detector conductivity & temperature DI water, resin bed & pump DI valve CO2 (aq) + H2O HCO3- + H+ DI Side HCO3- + H+ CO2 (aq) + H2O CO3-2 + H+ Sample Side CO2(aq) = CT pH = 2

TOC Testing Points : 

TOC Testing Points raw water storage activated carbon heat exchanger city water RO UV DI DI Storage Sievers Model 800 Applied to the Front End To the Loop

Effective Monitoring of Organic Contaminants in Water Recycling Systems : 

Effective Monitoring of Organic Contaminants in Water Recycling Systems

Today’s Presentation : 

Today’s Presentation Importance of water recycling Practical concerns Fast, continuous, accurate TOC analyzer Monitoring organic contaminants

Slide 31: 

Importance of Water Recycling Water recycling Economic benefits (site specific) Increased water demand for larger wafers Improved control of feed water Re-use and Reclaim

Slide 32: 

Limited water resources Taiwan -- 70 % of spent water is required to be recycled Japan -- zero discharge interest Europe -- immediate interest USA -- Texas, California

Slide 33: 

Recycling water reduces the costs of: City water Water purification Waste discharge

Sievers TOC Instrumentation in Micro-Electronics Water Reclaim : 

Sievers TOC Instrumentation in Micro-Electronics Water Reclaim

Risks for Water Re-use : 

Risks for Water Re-use Wafer fabrication wastes will contaminate wafer rinse water. Lack of experience causes fear of unknown risks and challenges. Unsuccessful past projects- poor designs Lack of fast process analytical analysis equipment.

Popular Reclaim Water System Design : 

Popular Reclaim Water System Design One Tank Design Tank 1 Tank2 Tank 3 TOC Tank Reclaim In To TOC Three Tanks Design Reclaim In To TOC Analyser

Slide 38: 

Organic Constituents Used in the Wafer Processing : Acetone IPA MEK (Methyl ethyl ketone NMP (N-methyl pyrrolidine) Butyl acetate Cyclohexanone PGMEA (Propylene glycol methyl ether acetate) Trimethyl amine Xylene Ethylene glycol TMAH (Tetramethyl ammonium hydroxide) Chloroform Acetic acid FC 93 Perfluoroalkyl sulfonate OHS Alkyl phenoxy polyethylene

Fast, Continuous, Accurate TOC Analyzer:Turbo TOC : 

Fast, Continuous, Accurate TOC Analyzer:Turbo TOC Powerful UV persulfate oxidation Selective membrane based conductance detector No false positives Improved operational performance over NDIR’s 3.5 second measurement periods 3.5 minutes total instrument delay

Slide 40: 

membrane module membrane module sampling pump U.V. oxidation reactor acid reservoir sample inlet peroxydisulfate reservoir syringe pump delay coil syringe pump conductivity & temperature conductivity & temperature waste DI water, resin bed & pump Model 800 Turbo Schematic

Slide 41: 

Conductometric/Membrane Detector conductivity & temperature DI water, resin bed & pump DI valve CO2 (aq) + H2O HCO3- + H+ DI Side HCO3- + H+ CO2 (aq) + H2O CO3-2 + H+ Sample Side CO2(aq) = CT pH = 2

Slide 43: 

Xertex Analysis Method- Tocon and T&C Oxidation Reactor TC Conductivity Sensor Conductivity Sensor Inlet Flow Meter Manual Valve Waste

Slide 44: 

Sievers Patented Method- Turbo TOC Based on complete oxidation to CO2, using UV persulfate, up to 5 PPM. CO2 selective membrane for both IC and TC. Conductivity Detector and Temp used to calculate CO2. Sensitive (LOD~5 PPB) continuous measurement. Oxidation and acid reagents Answers change with changes in : TOC level

Sievers Turbo compared to the Xertex type analyzers : 

Sievers Turbo compared to the Xertex type analyzers Fast responding, not as accurate as Turbo. Differential conductivity measurement around a less powerful UV oxidation reactor. Responds to variations in O2, H2, CO2, Salts, pH, Organic Compounds and TOC. Turbo responds to variations in TOC only.

Slide 47: 

Turbo Response to TOC Spikes 2 min. 1 min. 3 min.

Slide 48: 

Test Conditions Analyzer Setup Oxidizer flow rate: 0.5 mL/min Acid flow rate: 2.0 mL/min Grab sampling from flasks Solution Preparation Gravimetric method for pure chemicals Volumetric method for dilutions and water 2.0 ± 0.02 ppm as Carbon

Slide 49: 

TOC Recoveries for the Sievers Turbo

Summary : 

Summary Introduced and evaluated a fast, continuous TOC analyzer. Successfully applied membrane based conductometric Turbo TOC technology to achieve full recovery of organics used in wafer processing. Turbo TOC technology provides operators safety and confidence to re-use wafer rinse water.

Introducing the Next Generation in Water System Monitoring : 

Confidential Business Information 51 Introducing the Next Generation in Water System Monitoring Sievers Instruments, Inc.Boulder, Colorado USA

Sievers Ultrapure PPT TOC : 

Sievers Ultrapure PPT TOC a whole new way to look at your water

The Sievers Ultrapure PPT TOC Analyzer : 

The Sievers Ultrapure PPT TOC Analyzer Absolute Accuracy Verifiable on Site Unparalleled Sensitivity and Stability Measures TOC in Low Dissolved Oxygen Environments Measures Organo-Halides (TOX) Separately

Agenda : 

Agenda Principles of TOC Technologies Accuracy of TOC Measurements New Ultrapure PPT TOC Technology

Slide 55: 

Principles of TOC Measurements CO2 Detection Oxidation

Ultraviolet Oxidation : 

Ultraviolet Oxidation Organics + hn (185 nm) ® CO2 + H2O H2O + hn (185 nm) ® OH· + H· OH· + Organics ® CO2 + H2O

CO2 Detection Techniques : 

CO2 Detection Techniques Non Dispersive Infrared (NDIR) Direct Conductivity Membrane Conductivity Organics CO2 + H2O H2CO3 H+ + HCO3- UV

Direct Conductometric Method : 

Direct Conductometric Method Simple Sensitive Limited Selectivity Interferences from Compounds: R-X, R-S, R-N, and R-P Sample in Sample out Electrodes

Slide 59: 

Compound Methylene chloride Chloroform Dichlorobromomethane Chlorodibromomethane Bromoform 1,1,1-Trichloroethane 1,2,3-Trichloropropane 4-Chlorotoluene 1-Chloronapthalene Actual ppb C Analyzed ppb C Yield% 18 15 11 10 12 119 235 489 746 209 513 271 250 332 4090 6700 779 838 1160 3410 2450 2490 2490 3440 2850 174 112 False Positive Phenomena By Direct Conductometric Method

Slide 60: 

Principle of False Positive Organic Compounds That Interfere with Non-Selective TOC Methods

Slide 61: 

Fear Fab Shutdowns Fab Alerts THM’s In Water Supply Not REALLY Meeting Water Quality Specs Uncertainty Accuracy Issue False Positives ( Negatives) Selective Vs. Non-selective TOC Methods Doubt Performance Verification/Calibration Challenges

Slide 62: 

New Ultrapure PPT Technology

Slide 63: 

Cl - NO3- SO42- CO2 Non-Selective Conductivity Method Selective Conductivity Method Accuracy

Slide 64: 

PPT Schematic

Slide 65: 

CC1 = Incoming R25 CC2 - CC1 = Non-Selective TOC CC3 = Selective or True TOC Non-Selective TOC - Selective TOC Þ TOX TOC, TOX and Conductivity

AccuracyCalibration : 

AccuracyCalibration Calibration = Comparison of instrument response to known, characterized gravimetric standard. Instrument-to-instrument agreement is not a reflection of accurate measurement

Slide 67: 

Accuracy and Linearity TOC Measurements Using Standard Addition Technique

Slide 68: 

Accuracy and Linearity Conductivity Measurements Using Standard Addition Technique

Slide 69: 

Calibration Verification Preliminary Data from Various Semiconductor Beta Facilities

Slide 70: 

Calibration Verification Standard Addition of 1 ppb Sucrose as Carbon

Slide 71: 

Selectivity Interference Comparison with Selective vs. Non-Selective Detection Technology

Conclusions : 

Conclusions PPT represents the only selective TOC method that eliminates false positives and is capable of accurate process measurement of trace organic contamination in UPW. PPT also measures a new variable, TOX , which is expected to provide new insights into water quality and water system management.

Conclusions : 

Conclusions PPT is the only process TOC instrument that can be calibrated and verified on-line at the TOC operating ranges typical in ultrapure water. On-Site, In-Situ Calibration ( TOC & Resistivity ) avoids all pluming work and is time effective and cost effective.

TOC Manufacturers - On Line : 

TOC Manufacturers - On Line

Maintenance Compared - On Line : 

Maintenance Compared - On Line

Calibration Compared : 

Sievers 800 & PPT ` Anatel A-1000 NDIR Detectors Stable for 1 year Stable for 6 months Requires weekly or daily calibration Easily calibrated by user in-place Cannot be easily calibrated by user Calibration Compared