CIC Photonics
Transcription
CIC Photonics
CIC Photonics IRGAS Training Schedule - Day 1 FTIR analysis – – – – IR spectrum Michelson c e so interferometer te e o ete Fast Fourier transform and corrections Interferogram, single beam spectrum, absorption spectrum and transmission spectrum – Beer’s B ’ llaw – Instrument resolution – Quantification analysis analysis--Classical Least Squares introduction H d Hardware d description i ti – Bomem WorkIR – Instrument purge – Manual manifold SPGAS software – IRGAS 100 – IRGAS configuration manager – Data retrieval Schedule - Day 2 SPGAS software cont. – Qmax – quantification manager – IRGAS spectra reprocessing software Hardware installation – System power – Pipe installation – Instrument purge Software installation – IRGAS software – Bomem Ethernet drivers – System y verification System maintenance Schedule - Day 3 IRGAS worksheet IRGAS options IRGAS p product array y Marketing and selling strategies and techniques Competitors and competing products S i and Service d maintenance i t FTIR Analysis Tab 1 Light Spectrum Infrared is invisible light ranging from 1mm to 750nm in wavelength Infrared light can be divided into three parts: – Far infrared -1mm to 10µm – Mid iinfrared f d - 10µm 10 tto 2 2.5µm 5 – Near infrared - 2.5µm to 750 nm Infrared (IR) Spectrum IRGAS System mid infrared range – 2.5µm – 25µm in wavelength – 4000 cm-1 – 400 cm-1 in wavenumbers Wavelength (λ (λ) – Wavelength g = (1/wavenumber))*10,000 , Wavenumber (cm-1) – Wavenumber = (1/λ)*10 ) 10,000 000 IR Molecules Not every molecule absorbs infrared light – Monoatomic M t i He, Ar, Ne, etc… – Homoatomic diatomic N2, O2, H2, etc… – N N M l Molecules l that th t do d absorb b b iinfrared f d lilight ht – Water is a good example O H H Michelson Interferometer 2 1 3 4 Step p 1: Beam leaves IR source and hits beamsplitter p where it is sent straight through and at a 90° 90° angle Step 2: The 90° 90° angle beam hits a fixed mirror and is sent back to the beamsplitter Step p 3: The beam that went straight g through g hits a movable mirror and is sent back to beamsplitter Step 4: The two beams recombine, go through the gas cell and travel to the detector Michelson Interferometer When AB=AC the phase of the frequencies look the same When AB=AC+1/4λ AB=AC+1/4λ, then the phase of the frequencies are opposite in regards to maximums and minimums AB AC Michelson Interferometer When AB=AC and the two recombine you gett stronger t maximums i and d minimums i i When AB=AC+1/4λ AB=AC+1/4λ and the two recombine they cancel one another out and result in a flat line ABB Bomem Michelson Interferometer It has two sets of mirrors that move by a pivoting motion This design is called a wishbone configuration – This Thi configuration fi ti iis more robust b t It can be placed in any orientation This configuration only has to be smooth at one point vs. the traditional interferogram that has to be smooth along a rail ABB Bomem Michelson Interferometer ABB Bomem Michelson Interferometer IR Source Laser Fast Fourier Transform The highest peak intensity is attained when AB=AC The maximum of the highest intensity peak is called the zero path difference (ZPD) point After the interferogram has been created by the instrument, the Fourier transform is applied to it, which then results in a single beam spectrum Inte r fer ogr a m ZPD 1 0 V o l t s -1 -2 -3 3 20 0 3 00 0 2 80 0 2 60 0 2 40 0 Data Points 2 20 0 2 00 0 1 80 0 Single Beam Spectrum 28 26 24 22 Arbitrary units 20 18 16 14 12 10 8 6 4 4000 3000 2000 Wavenumbers (cm-1) 1000 Single Beam Spectrum 28 26 24 22 20 %T 18 16 14 12 10 8 6 4 4000 3000 2000 Wavenumbers (cm-1) 1000 Single Beam Spectrum 28 26 24 22 20 %T 18 16 14 12 10 8 6 4 4000 3000 2000 Wavenumbers (cm-1) 1000 Single Beam Spectrum 28 27 26 25 24 23 22 21 %T 20 19 18 17 16 15 14 13 12 11 10 9 2000 1500 Wavenumbers (cm-1) Transmission The ratio between the sample and the background spectrum ⎛S⎞ T Transmissi i ion = ⎜ ⎟ *100 ⎝ B⎠ Transmittance Spectrum 110 100 90 80 Absorbance 70 60 50 40 30 20 10 0 4000 3000 2000 Wavenumbers (cm-1) 1000 Chemometrics Based on the transmission spectrum chemometrics h t i can b be applied li d – Chemometrics: The application of statistical and d mathematical th ti l methods th d ffor th the d design i or optimization of chemical experiments and for the efficient extraction of information from chemical data Two types of chemometrics: – Qualitative (identification) – Quantitative Q tit ti (quantity) ( tit ) Absorbance 0.50 0.45 0 40 0.40 Absorban nce 0.35 0.30 0.25 0.20 0.15 0.10 0.05 4000 3000 2000 Wavenumbers (cm-1) 100 ⎛ ⎞ Absorbance = log⎜ ⎟ ⎝ transmission ⎠ 1000 Beer’s Law Says that concentration is directly proportional ti l tto absorbance b b (li (linearity) it ) Beer’s law equation is A= abC – Where A = absorbance a = absorptivityy of the molecule b = pathlength that the light travels C = concentration Instrument Resolution The more points per peak the higher the resolution l ti The higher the resolution the more noise, but the better peak separation Common resolution used for an ABB Bomem instrument is 2 cm-1 Ranges between 1 cm-1 to 128 cm-1 Why Do We Need a Gas Cell Intensity of a peak is directly related to the # off moles l iin a sample l In the same area: – Solid will be very packed – Liquid will be less packed – Gas will be even less packed Long Path Gas Cell Obj ti mirrors Objective i ¼” VCR fi fittings i Field mirror Window retainers 4Runner 6 Meter Gas Cell Gas Cell Mirrors Objecti ve Mirrors Field Mirror Tra ns fer Mirrors Source Top view of field mirror IR Beam Path Classical Least Squares (CLS) The base equation is As = Ac*K + e – Where Wh As A = sample l absorption b ti Ac = calibrated absorption K = concentration e = noise Using the above equation find K that minimizes e To minimize e we use the CLS method In this situation there are more equations then variables Classical Least Squares (CLS) To simplify matters we assume that e = 0 – The Th equation ti then th b becomes: A As = A Ac*K *K Matrix form: A = Ac As A *K ⎡ As1 ⎤ ⎡ Ac1 ⎤ ⎢ As ⎥ ⎢ Ac ⎥ A A ⎢ 2⎥ ⎢ 2⎥ ⎢ . ⎥ ⎢ . ⎥ ⎢ ⎥=⎢ ⎥*K ⎢ . ⎥ ⎢ . ⎥ ⎢ . ⎥ ⎢ . ⎥ ⎢ ⎥ ⎢ ⎥ ⎢⎣ Asn ⎥⎦ ⎢⎣ Acn ⎥⎦ Classical Least Squares (CLS) In order to solve for K (Ac-1*As = K), Ac needs d tto be b an iinverse matrix ti – Therefore: AcT*As = (AcTAc)*K (1x1) = (1x1)*K Problems with Initial CLS Approach Baseline becomes unstable throughout the day day – It can shift, slope, or curve These changes can be compensated for in the calibrated absorption matrix Classical Least Squares (CLS) Accounting for these baselines changes the equation – The eqn. becomes: As = AcK1+ ⎡ As ⎢ As ⎢ ⎢ . ⎢ ⎢ . ⎢ . ⎢ ⎢⎣ As 1 2 n ⎤ ⎡ Ac ⎥ ⎢ Ac ⎥ ⎢ ⎥ ⎢ . = ⎥ ⎢ ⎥ ⎢ . ⎥ ⎢ . ⎥ ⎢ ⎥⎦ ⎣⎢ Ac 1 2 n 1 1 −1 . . . . 0 . . 1 1 1⎤ . ⎥⎥ .⎥ ⎥ * [K 0⎥ .⎥ ⎥ 1 ⎥⎦ K2+ 1 K 2 K K3+ 3 K 4 K4 ] The calibrated absorption matrix can be increased to accommodate the number of species p being g tested Weighted MultiMulti-band CLS A more complex version of the standard CLS The spectrum is separated into bands – Each band is then calculated After all the bands are calculated they are added in a weighted averaged fashion – The ones with the highest error and lowest signal are counted for less then the ones with the lowest error and highest signal Hardware Description Tab 2, 3, & 4 IRGAS Systems Thus far the oldest system in the field without ith t maintenance i t iis 4 yrs Out of 2020-30 systems, there has only be a need to perform maintenance on 3 of them The Bomem spectrometer p is high g in reliability and low in maintenance There has been 2 hardware failures – There was a burned out IR source IRGAS Systems There is one basic package that can be dressed up in several different ways One reason our throughput is higher than competitors is because of mirror quality and coating Our objective mirrors are adjustable – Sideways – Rotational Competitors have mirror that are locked into place ABB Bomem WorkIR Manual Manifold Purge Gas In Process Gas In Check Valve Maintenance Valve P Process Gas G Out O t Permeation Box Purifier Gas Cell Nitrogen Outflow Check Valve Pressure/Flow Transfer Optics Gas Flow Optical Path Pressure/Flow Spectrometer Nitrogen Outflow Manifold Parameters Flow Restrictor – A flow of 30 psi in will give a flow of 5 slpm to the instrument Purifier – Gives dry N2 to below 2 ppb – Has a lifetime of more than a year if it is used 24/7 Vibrations There are a number of designs of suspension i systems t to t counteract t t vibrations These designs help to keep the data from being affected by a simple bump of the instrument bench Typical Gas Cells Have a flow similar to turbulent flow and have a longer residence time Gas in Exhaust Laminar Flow Gas Cells The flow is like a waterfall – Therefore Th f there th will ill b be lless tturbulence b l Heated laminar flow gas cells – The gas is in contact with the walls letting it reach a temperature similar to the gas cell prior to entering the cell Gas in Gas Cell Flow Diagrams f/5 Beam Geometry IR B eam d Foc use d f.l. f/#= f f.l. l d f.l. = focal length g d = beam diameter The higher the f / #, the smaller the objective mirrors, the more light that is lost, the smaller the throughput SPGAS Software Tab 6, 7, 8, 9, & 10 Specialty Sp ecialty Gas Analysis Software (SPGAS SPGAS)) IRGAS 100 system – Collection & quantification Qmax – Quantification manager IRGAS Configuration Manager – Configures parameters Quantification Reprocessing Tool – Recalculating spectra IRGAS 100 System After opening the software the first window i th is the monitor it screen – On the right side there is the available species – On the bottom is the legend of the species that are being shown in the top window – The top shows the concentration of all the species over time IRGAS 100 Monitor Screen Concentration of species over time Available A il bl Species IRGAS 100 System Collecting a background – After opening the program, pressing the start button will automatically send the spectrometer to collect a background and then begin collecting a sample Seeing the sample – Clicking on the desired species tab at the top will show you that species in real time – That screen shows the fast concentration tracker (FCT) and the averaged sample Advantages to Spectra Stream Provides high sensitivity detection of impurities (low ppb) Reduces the time response typically associated with FTIR (from minutes to seconds) Continuous collection of background Running average spectra R d ti iin spectrometer Reduction t t d drift ift Reduction of contribution of moisture System is very easy to use IRGAS Configuration Manager IRGAS Configuration Manager IRGAS Configuration Manager IRGAS Configuration Manager IRGAS Configuration Manager Data Retrieval Data storage – By default the data gets stored on the C drive C:\\Program Files C: Files\\CIC Photonics Photonics\\IRGAS – IRGAS data Quantification log Spectral records Quantification Log Folder Data stored as a text file Can be converted to an excel file – Copy file, paste in the same folder, rename with an .xls extension In the excel file Time BMI Species Concen. SE FCT SE-FCT 2nd Species Concen. SE FCT 6/14/2005 14 14:21 21 3 17E 02 3.17E-02 H2O 0 0 06 0.06 -0.16 0 16 0 06 0.06 CO2 0 011 0.011 0 013 0.013 0 011 0.011 Data storage names – Folder with YY YY--MM Folder with Quan YYYY-MM MM--DD.log Spectral Records Folder Stored with a .spc extension – All market k t software ft writes it and d reads d thi this fformatt This was created by Galatic, now ThermoGalactic Data storage names – Folder with YY YY--MM MM--DD Absorbance File – Abs YYYY-MM MM--DD HH:MM.zip Background File – Bck YYYY-MM MM--DD HH:MM.zip p Sample File – Smp YYYY-MM MM--DD HH:MM.zip Residual File – Res YYYY-MM MM--DD HH:MM.zip QMax Using existing calibration file: QMax Quantification Set Spectral Set Calibrated C lib t d S Spectral t lR Record d off specific molecule Non--linear Behavior Non As a rule of thumb a species behaves nonnonlinear when it is higher than 0.1 01a a.u. u The nonnon-linear correction graph’s curve is modeled by ax3+bx2+cx+d = 0 – In this equation the values that are necessary to find are a a, b b, and c – To do this nonnon-linear correction there needs to be at least 3 spectral records In general when the residual curve is flat line that indicates that there is nonnon-linear behavior QMax Starting a calibration from scratch: Synthetic Calibration Set Instrument Line Shape (ILS) – Each E h instrument i t t has h its it own HITRAN database – Contains C t i th the absorption b ti coefficients ffi i t off different components – Doesn Doesn’tt contain the ILS of specific instruments MALT software – Created by Dr Dr. David Griffith from the University of Wollongong in Australia – Models ILS parameters MALT Calculates spectra for single h homogeneous path th or ffor multiple lti l llayers Includes instrumental parameters into the calculations so the calculated spectra match the line shape, resolution and wavelength shift of the measured spectra Uses HITRAN molecular spectroscopy p py databases Gas Calibration When a gas is not in the HITRAN system, it is necessary to produce the calibration non--synthetically non Start collecting data Flush the gas cell several times with the gas – During this time find the equilibrium point of each flush – Take these points and average them to use for the calibration This will give a better signal to noise ratio HITRAN/MALT vs. Actual Calibration Advantages – Calibration data free of noise – Best match to the measured spectrum according to the least squares criteria – Operational costs reduction – Non Non--time consuming calibrations – Precision at least as good as that of traditional methods ( ≤ 3%) HITRAN/MALT vs. Actual Calibration Disadvantages – Provides analysis only over gases included in the HITRAN database* – System requires regeneration of calibration data if spectrometer or gas cell change *additional gases by standard calibration procedures IRGAS Spectra Reprocessing IRGAS Spectra Reprocessing Gas Analysis Modules HITRAN MALT SPGAS Gas Weighted Multi-Band CLS Analysis Spectra Stream TM Improved Gas Analysis Sensitivity Absorbance Data @ 1ppm/meter 0 0028 0.0028 0.0026 H2O NH3 0.0024 NO2 0 0022 0.0022 SO2 0.0020 CO NO Absorbance 0.0018 0.0016 H2CO CO2 0.0014 0.0012 0.0010 0.0008 0.0006 0.0004 0.0002 -0.0000 3000 2000 Wavenumbers (cm-1) 1000 Software Installation Software Installation The installation window should automatically t ti ll poppop-up After the installation has been completed, check that the computer and spectrometer are communicating with each other Establishing Communication Network: Instrument Network Computer – Instrument address: 192.168.0.127 – Computer address: 192.168.0.YYY Where YYY is any number between 0 and 225 that is not 127 Establishing Communication Two Ethernet configurations: – Straight through Instrument Ethernet Hub Switch Computer – Crossover Instrument Computer Ethernet Connection Straight through configuration 1 2 3 4 5 6 7 8 1 2 3 4 5 6 7 8 Ethernet Connection Crossover configuration 1 2 3 4 5 6 7 8 1 2 3 4 5 6 7 8 Verifying Communication Changing network address – Control panel Network connection – Local L l network t k Properties Last check for communication – Control panel ABB Bomem M k ti and Marketing d Selling S lli Strategies and Techniques Tab 13 Worldwide Customers Semiconductor Applications Wafer yield enhancement – By reducing O O--atom defects Process reaction monitoring – By confirming reactants/products Supply gas quality monitoring Abatement tool efficiency Semiconductor Dry Process http://www.jp.horiba.com/semicon_e/measurement/gas.htm Semiconductor Industry SemiConductor Fab a) Thin films b) Etching c) Implant Raw Material a) Silicon Wafer (EPI) b) Hi Purity Gases c) Photomasks 1.Thin Film 2. Etching Equipment a)) Thin films 1. HDP-CVD 2. In-situ EPI b) Etching c) Implant Semiconductor Applications A large amount is spent on equipment in the fab area In--situ monitoring is being looked at to prevent In the damage of large quantities of goods The equipment section is also supplying the raw materials section section, not just the Semi fab Getting the companies to upgrade current equipment is difficult but results is a large sale Chemical Applications Specialty gas purification Combustion thermodynamics Aero--engine optimization Aero Destructive testing: release of hazardous gases Gas blending Environmental Applications Plant air monitoring Stack gas emissions PFC emissions Homeland Security – Chemical Weapon Agents – Toxic Industrial Chemicals – Illicit Drugs Our Product Line FTIR gas analyzer systems Long and short path gas cells Custom g gas cells Fiber optic probes (UV/VIS/NIR) Resell UV/VIS FO spectrometers FTIR sampling accessories – ATR, transmission, reflectance, MM-Press Competitor Analysis Ideal Characteristics Customer Needs Detection of impurities C C Low ppb & high S/N IR Reflectivity & throughput g p C C Process control C IR C IR Fast & correctable C C FTIR response time Baseline drift High IR None C CIR C C No false positives Customizable Total cost of C C C None IR C C Competitor Research conducted by Los Alamos National Laboratories marketing interns Fast (min --> sec) IR IR Highly Low IR IRGAS Total Solution C Competitors tit and dC Competing ti Products Tab 5,12,14 Competitors FTIR gas analyzers – MKS Instrument – MIDAC – Thermo Nicolet Other technologies g – Tiger Optics – Delta e ta F Other Technology Competitors Tiger Optics – Cavity Ring Down Spectroscopy (CRDS) – Single gas at a time Delta F – Tunable laser – Single gas at a time Differentiators Gas Cells Laminar flow – Faster g gas exchange g – Eliminates dead space 316L Stainless steel / Nickel plated body – More chemically resistant to acid gases and retain less moisture 304 Stainless steel mirror Proprietary fabrication and coating process – Radius of curvature – Surface finish smoothness – 98.5% reflectivity High pressure tolerance – 20 atm, 300 psi Hand aligned by expert personal to maximize throughput IRGAS System Spectrometer – ABB Bomem WorkIR Industrial ruggedness Compactness Very low failure rate Cost competitive Software – Unique q because it offers the weighted g multi-band,, multimultimulti-variant classical least squares method – Patented on Spectra Stream w/ the fast tracker for early warning – User friendly Configurations – One package that can be dressed different ways Pre and post technical support Scientific Package 4Runner gas cell ABB Bomem WorkIR spectrometer Coupling optics Suspension system The 4Runner 0.6 liter volume 125 mm base path 304 stainless i l steell body Metal and Kalrez® seals Welded VCR fittings for gas porting Heatable to 260° 260°C I t Integrated t d purge box b with movable reference optics MgF g 2p protected,, g goldgoldcoated stainless steel mirrors Evacuable & pressurizable: 1010-4 Torr to 300 psig Ranger--EN Ranger 9.6 meter fixed pathlength 1.7 liter cell volume 0.05 sq. m/L surface/volume Gold--coated SS Gold mirrors All--metal, All electropolished SS body External transfer optics p Heatable to 200° 200°C Optional aluminum body & glass mirror Pathfinder--EN Pathfinder 0.4-10 meter variable 0.4pathlength Pressurizable to 50 psig Heatable to 200° 200°C Gold--coated SS mirrors Gold All--metal, electropolished All SS body Very high energy throughput Extremely chemicallychemicallyinert Scout--EN Scout Nickel plated stainless steel 10cm gas cell for toxic and corrosive gas analyses; heated and unheated versions. 28--cm3 volume 28 Teflon--encapsulated Viton®, Teflon Viton®, or Kalrez® O O--rings for chemical resistance and temperature considerations KBr, CaF2, ZnSe, quartz, or sapphire window materials for UV--VIS and FTIR applications UV Evacuable and pressurizable: 10 100-4 Torr o to 150 50 ps psig g Heatable to 200° 200°C with heating mantle, tape, or dual bands 5 cm & 15 cm pathlength versions also available O i Optional l temperature controller ll Easy adaptation to all spectrometers Montero 1.0 meter fixed pathlength 82 6 mm basepath 82.6 Anodized aluminum cell body Gold--coated Pyrex Gold mirrors Internal transfer optics Low 600 ml volume Purgeable beam conduits Swagelok (tm) gas ports Viton® OO-rings Choice of windows High energy throughput Unheated and heated versions Fits totally inside FTIR compartments CR--V CR Extremely short path length – 0.5mm to 1cm High Pressure – Up to 100 atm Heated Option IRGAS Options Tab 11 O-Ring Material Working Temperature Ranges Modulus of p (p (psi)) Rupture m Window Thickness Unsupported Diameter ((mm)) d Window Thickness Analysis AgCl 19 400.0 Pressure (psi) p Unclamped p Clamped 0.866 1.05 14.0 9.5 56.1 38.2 126.3 85.9 224.6 152.8 350.9 238.7 350.0 Thickness (mm) 1 2 3 4 5 300.0 250.0 PSI 3,800 200.0 150.0 1 Material AgCl BaF2 C B CsBr CaF2 CsI Diamond KBr Sapphire ZnSe Custom Modulus of Rupture (psi) 3,800 3,900 1 220 1,220 5,300 800 54,400 160 65,000 8 000 8,000 900 100.0 50 0 50.0 0.0 1 2 3 4 5 Thickness (mm) Clamped Window Unclamped Window The modulus of rupture, m , determines the size of the window needed to withstand a pressure, p . For a four times safety factor, the thickness of a mounted window, t , with an unsupported diameter, d , is: ⎛ t Clamped p = m ⎜⎜ ⎝ 0 . 866 d ⎞ ⎟⎟ ⎠ 2 ⎛ t Unclam ped p = m ⎜⎜ ⎝ 1 . 05 d ⎞ ⎟⎟ ⎠ 2 Options Pressure and temperature based on ideal gas parameters t Automated manifold systems System outputs – Text based – Analog and digital outputs IRGAS Moisture+ Plus IRGAS--SP IRGAS IRGAS EPI IRGAS 100T IRGAS 100MT IRGAS 200RM IRGAS 400 IRGAS XFlo IRGAS Worksheet Tab 13 IRGAS Worksheet Important because it guides us in system parameters,, options, p p , and price p q quoting g Important parameters – Gases present in the mixture Estimated concentrations – Temperature and pressure range – Sampling time The parameters help to determine: – O-Ring material – Window material – Gas cell All of these can really vary the price of the product d t IRGAS Worksheet Part A of the worksheet is for customers that th t only l wantt a gas cellll The entire worksheet is necessary for customers that want the whole IRGAS system Customers should fill out as much of the worksheet as possible p W Warranties ti and d Technical T h i l Support Tab 16 Warranty 1 yr parts and labor for gas cell and software ft 30 day on critical optical elements, ex. mirrors – This is because we have no control over how the system is treated by the user 1 yyr telephone p and ee-mail technical supprt pp Technical Support 24/7 technical support is provided to the b t off our abilities best biliti System Maintenance Tab 15 Service and Maintenance Handled on a case to case basis Repair, test, ship – System repaired – Quality tested – Shipped pp back to customer CIC Photonics pays the shipment back to customer if still under warranty, if not it is paid both ways by the user C Contact Information f (505) 343343-1489 (505) 343343-9520 [email protected]