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Analytical figures of merit, noise, and S/N ratio Chemistry 243 Noise A signal is only of analytical value if it can be definitively attributed to the species/system of interest in the presence of noise. Probably noise, or not very useful; a hint of a signal 2.5 2.5 2 2 signal signal Looks like a real signal 1.5 1 1.5 1 0.5 0.5 0 20 40 60 data point 80 100 0 20 40 60 data point 80 100 What is signal and noise? Signal-to-Noise Ratio (S/N) Signal-to-noise ratio (S/N) is a measure of the quality of an instrumental measurement Ratio of the mean of the analyte signal to the standard deviation of the noise signal High value of S/N : easier to distinguish analyte signal from the noise signal Mostly Signal signal S x N s S 1 N RSD Std. Dev. Mostly Noise Rev. Sci. Inst., 1966, 37, 93-102. Where does noise come from? Chemical noise Temperature, pressure, humidity, fumes, etc. Instrumental noise Detector and post-detector noise Thermal (Johnson) noise Shot noise Flicker (1/f) noise Environmental noise Popcorn (burst) noise Microphonic noise Thermal (Johnson) noise Random motions of charge carriers (electrons or holes) that accompany thermal motions of solid lattice of atoms. Lead to thermal current fluctuations that create voltage fluctuations in the presence of a resistive element Resistor, capacitor, etc. rms 4kTRf rms = root-mean-square noise voltage k = Boltzman’s constant T = temperature R = resistance of element (W) f = bandwith (Hz) = 1/(3tr) tr = rise time Thermal (Johnson) noise continued Dependent upon bandwidth (f) but not f itself Can be reduced by narrowing bandwidth white noise Slows instrument response time More time required for measurement Reduced by lowering T Common to cool detectors 298K77K lowers thermal noise by factor of ~2 rms 4kTRf rms = root-mean-square noise voltage k = Boltzman’s constant T = temperature R = resistance of element (W) f = bandwith (Hz) = 1/(3tr) tr = rise time N2(l): bp=77K Shot noise Arises from statistical fluctuations in quantized behaviors Electrons crossing junctions or surfaces Independent of frequency Example: current 11 e-/s 10.5 e-/s 10 e-/s irms 2Ief irms = root-mean-square noise current I = average direct current e = electron charge f = bandwidth (Hz) Flicker (1/f) noise Magnitude is inversely proportional to the frequency of the signal Significant at frequencies lower than 100 Hz Long-term drift Origin is not well understood Dependent upon materials and device shape Metallic resistors have 10-fold less flicker noise than carbon-based resistors. Referred to as “pink” noise—more red (low frequency) components Environmental noise Comes from the surroundings Biggest source is “antenna” effect of instrument cabling J. Chem. Educ., 1968, 45, A533-542. Noise contributions in different frequency regimes Frequency independent Supposedly 1/f— mostly at low frequencies Occurs at discrete frequencies Enhancing signal-to-noise Hardware methods Grounding and shielding Difference and Instrumentation Amplifiers Analog Filtering Lock-In Amplifiers Modulation and Synchronous Demodulation Software methods Ensemble averaging Boxcar averaging Digital filtering Correlation methods Grounding and shielding Surround circuits (most critical conductors) with conducting material that is connected to ground Noise will be picked up by shield and not by circuit Faraday cage http://www.autom8.com/images_product/table_farady_benchtop.jpg http://farm2.static.flickr.com/1227/578199978_17e8133c7c_o.jpg Analog filtering Low pass filter removes high frequency noise High pass filter removes low frequency noise Thermal and shot noise High freq removed. Low freq preserved (passed). Drift and flicker noise Narrow-band electronic filters Example of low-pass filter Lock-in amplifiers Modulation Translate low frequency signal (prone to 1/f noise) to a high frequency signal which can amplified and then filtered to remove 1/f noise Mechanical chopper Lock-in amplifiers continued Synchronous demodulation Converts AC signal to DC signal synchronous with chopper—follows reference Low-pass filtering Back converts high frequency DC signal to return filtered, low frequency output. Ensemble averaging to increase S/N Averaging multiple data sets taken in succession Divide sum of data sets by number of data sets n S i Sx i 1 n J. Chem. Educ., 1979, 56, 148-153. Ensemble averaging continued Signal-to-noise improves with increasing number of data sets S N N n S n i N = rms noise n = number of replicate scans i = number of replicate scans in other data set # Scans, n 1 4 16 64 Relative S/N 1 2 4 8 Boxcar averaging Smoothing irregularities and increasing S/N Assumes signal varies slowly in time Multiple points are averaged to give a single value Often performed in real time Detail is lost and utility limited for rapidly changing samples Boxcar integrators commonly used in fast (pico- to microsecond) measurements using pulsed lasers. Moving average smooth Similar to a boxcar average, but changes in time signal (arb units) 0 200 400 600 data point 800 1000 Average Standard Deviation S/N Relative S/N Original 100.2 6.0 16.6 1 4 point 100.2 3.0 33.4 2.0 16 point 100.2 1.5 67.1 4.0 100 point 100.2 0.6 160 9.7 Downside of moving average smoothing 140 130 signal (arb units) 120 110 100 90 80 70 60 50 0 200 600 400 data point 800 1000 Digital filtering Fourier transform Convert data from time- to frequency-domain, manipulate to remove higher frequency noise components, regenerate time-domain signal Polynomial data smoothing Moving average smooth Least-squares polynomial smoothing