Solid State Physics Lab

PES 415 / PHYS 515

Spring 2005

AUGER ELECTRON SPECTROSCOPY Auger electron spectroscopy (AES) is a sensitive technique for investigating the chemical composition of the surface region of solids. All elements, except H and He can be uniquely identified in surface coverages down to about 0.01 monolayer. The theory and practice of AES are discussed in various sources [1-4]. The physical process involved in AES is demonstrated in Figure 1. A primary electron beam of 1 - 5 keV, incident on the sample, is used to ionize atoms in the solid (knocking out an L shell electron). An electron from a higher energy level (M) or the valence band drops down to fill the core hole and a third electron is emitted from the atom to conserve energy. This third electron is the Auger electron. The energy of the Auger electron depends on the difference in energy of the levels and is, therefore, characteristic of the element and independent of the incident beam which ionized the atom. Also shown in Figure 1 is the competing process of x-ray emission. Primary Electron Auger Fermi Energy Electron Level 0 3d M 4,5 3p M 2,3 3s M1 2p L 3 2p L 2 2p L1 1s AUGER PROCESS X-ray Process X-ray 3.7 eV 34.6 60.3

455.5 461.5 563.7 4966.4

Figure 1. Auger process. Figure adapted from http://dtwws1.vub.ac.be/meta/pages/AES.html and http://www.cea.com/cai/auginst/process.htm When an electron beam strikes a material surface, a variety of processes produce electrons which escape from the surface. The energy distribution of electrons from a surface with an incident primary electron beam of energy Ep is shown in Figure 2. At very low energies are the "true" secondary electrons resulting from a cascade of inelastic collisions between the primary beam electrons and electrons bound in the solid. At slightly higher kinetic energies, in the tail of the secondaries, are small peaks from the Auger electrons. Around the primary beam energy are those electrons which are scattered back from the surface in an approximately elastic manner. By examining the energies at which the Auger electrons come out, the elements present at the surface can be determined.

N(E)

elastic peak

Auger peaks

Ep E Figure 2. Energy distribution N(E) of backscattered electrons from a surface as a function of their energy. Ep is the energy of the primary electrons incident on the surface. AES is a very surface sensitive technique because the Auger electrons can only travel a very short distance through the solid before being stopped by collisions. Most Auger electrons will be detected only if they come from the top few atomic layers (about 30 ) of a solid. AES can detect very small amounts of elements because the probability of exciting an Auger electron out of an element is quite high. Other deexcitation processes, such as emission of x-rays, will occur, but for a typical AES system, the probability of an Auger electron emission is much higher. Simple AES systems, such as the one used in this lab, do not have particularly high lateral resolution of surface features. The beam diameter is typically on the order of 1 mm; the composition in this beam area is averaged. Newer, more sophisticated (and more expensive) scanning AES systems have beam diameters of less than 350 allowing good lateral resolution. The systems are widely used in the semiconductor industry to examine microelectronic chips. From Figure 2 it is obvious that the Auger peaks can be rather difficult to detect since they appear in the rather large tail of the secondary electrons. Experimentally we can improve our detection by differentiating the spectrum in Figure 2. A typical derivative spectrum is shown in Figure 3. The peaks are identified from known Auger transitions in the materials.

Figure 3. Auger electron spectrum of stainless steel. 2

(figure from http://www.mee-inc.com/sam.html) Qualitative identification of the elements present on the surface is a straight-forward procedure. Tables of Auger transitions are available [5]. By comparing your experimental spectrum with these tables, you can identify which elements are present. To determine how much of each element is present, however, is much more difficult. This requires detailed knowledge of how electrons react with each type of material present in the surface region. Equipment Our Auger system uses a single-pass cylindrical mirror analyzer with an electron gun in the center of it. Electrons from the sample enter the analyzer. Only those of the desired energy make it through to the detector. By varying the allowed energy, a spectrum can be taken. Figure 4 shows a typical analyzer set up.

Figure 4. Cylindrical Mirror Analyzer - (figure from Charles Evans and Associates http://www.cea.com/cai/auginst/eeanal.htm) Operation: Turn the power on to: Auger System Control Electron Gun Supply Electron Multiplier Supply Ion Gun Control Auger power supply (bottom of right rack): Main power, Auger power, stepper motor power Computer (lower right front) and monitor (lower right front) Beam Current Monitor X-Y stepper motor power supply - sitting on table between chamber and electronics rack To turn on the filament in the electron gun: On the Electron Gun Supply, turn on the red BEAM 3

VOLTAGE button. The voltage should be set at 3kV. The EMISSION knob should be fully clockwise. Turn the FILAMENT knob slowly clockwise 5 full revolutions. After 5 revolutions you will start to see the meter register a current. Continue to turn the FILAMENT knob up until the arrow points at the "M" in FILAMENT. The current will slowly drift up to 2 ma over about a 10 minute period. If the meter reads over 2 ma, turn the filament knob down slightly. While observing the beam current on the Beam Current Monitor, turn the EMISSION knob on the Electron Gun Supply counter clockwise to maximize the beam current. To access the Auger data acquisition program: from the AUGER directory, type AUGER followed by a return. You can clear the opening screen with a return. sample alignment: The sample must be correctly positioned in the chamber at the focus of the analyzer. We can check this by examining the energy of the elastically scattered electrons. They should have the same energy as the incident beam. Set the BEAM VOLTAGE on the Electron Gun Control to 2 kV. Turn on the red HIGH VOLTAGE button on the Electron Multiplier Supply. Type <Alt-A> to enter the Alignment menu. Select the Automatic alignment option using the up and down arrow keys. The computer will automatically adjust the stepper motor position of the sample so that the peak on the screen occurs at 2 kV. Press any key when done. data acquisition: Turn on the red HIGH VOLTAGE button on the Electron Multiplier Supply. Type <Alt-D> to access the Data menu and select Acquire Data. The software will often provide you with information during procedures which you can read and then clear by hitting <ENTER>. The system will now acquire data and display it as N(E) vs. E. To differentiate the data, hit the spacebar to clear the screen. Type <Alt-D> to get back into the Data menu and use the arrow keys to select Data Analysis. The data returns to the screen with a menu at the bottom. Type <D> to differentiate the data. You now have a traditional Auger spectrum. To save or print the data, type <E> to exit the analysis screen. Type <Alt-F> to access the File menu. Use the arrow keys to select Save, or Save as or Print graph. To change the data acquisition parameter, type <Alt-S> from the main screen to open the Settings menu. Select Change Sweep Parameters. You can change the number of sweeps to average over and the range of the sweeps. For noisy data, we find the most effective parameter is to increase the Time/step to around 100 ms. To analyze the data using the computers internal library, type <Alt-D> to access the data menu and select Set Composition File Name. Select the ELEFILES directory by using the Tab and down arrow keys. Select the file DEFAULT.ELE and hit <ENTER>. The preceding step only needs to be done once each time the program is run. Return to the data analysis window and type <A>. The data will display circles at the top and bottom of each derivative peak which the software recognizes. The energy, peak-to-peak height and POSSIBLE composition will also be displayed. Use the left and right arrow keys to move between peaks. Type <D> when done. You can print a copy of all the energies and heights by choosing Print Report in the File Menu. The Change (C) feature in the Data Analysis window allows you to change the minimum peak-to-peak height which the software will search for. When done with the Auger software, type <Alt-X> to exit from the program. Turn equipment off as follows: 4

Turn off the HIGH VOLTAGE button on Electron Multiplier Supply. Turn the EMISSION on the Electron Gun Control fully clockwise. Turn the FILAMENT on the Electron Gun Control fully (5+ turns) counter clockwise. Turn off the red BEAM VOLTAGE button on the Electron Gun Control. Turn off the Power on everything (except the pump and ion gauge). Ion gun If you need to clean off the sample or depth profile, you need to use the ion gun. Turn on the power to the Ion Gun Control. Allow it to warm up for about 5 minutes. Turn the EMISSION knob clockwise slowly until the meter reads 25 mA. Close the gate valve to the ion pumps (large handle on left side under table). Open the leak valve (slanted knurled knob - back left on chamber) slowly. The valve sometimes sticks a little. You may need to apply downward pressure in the vicinity of the knob as you turn it. After about 3 revolutions of the knob you will see the pressure start to rise. Bring the pressure up to about 1 x 10-5 torr. (You are letting Argon gas into the chamber). Then close the leak valve. On the Ion Gun Control, turn on the RASTER and BEAM VOLTAGE switches. Leave the system on for about 5 minutes to clean the sample surface. When done, turn the BEAM VOLTAGE and RASTER off. Turn the EMISSION down and off. Open the gate valve to the ion pumps to pumps out the chamber. Turn the power off. Analysis of Auger Electron spectra Qualitative: It is relatively easy for simple surfaces to get an idea from the spectrum of what elements are present. Figure 5 shows an Auger spectrum for a piece of stainless steel fractured inside the vacuum system. We can see peaks which correspond to Cr, Fe, and Ni. This is not surprising, since that what stainless steel is made from. Quantitative: To get more specific information, we need to do some type of more quantitative analysis of the data. One relatively simple method is to use the major peak of each element which we identified. These are the peaks marked with a star in Figure 5. I can measure the peak to peak heights off of the figure using a ruler. I will also need to know the relative sensitivities of Auger to each element. I can obtain these from Figure 6. element Fe Cr Ni height 65 mm 30 10 sensitivity 0.32 0.27 0.21

I need to correct all of the heights for the instrument sensitivity factors. The concentrations of each element present in the sample can be found from: Cx = heightx / sensitivityx -----------------------------! (heighti / sensitivityi)
all elements

The denominator is simply (65/0.21) + (30/0.32) + (10)/0.27) = 440. We now find the corrected concentrations for each element: Fe: Cr : Ni: (65/0.21) / 440 = 0.70 (30/0.32) / 440 = 0.21 (10/0.27) / 440 = 0.08

We can compare these to the actual bulk concentrations which were: 0.702, 0.205, and 0.093. We see that we did very well. References 1. G. Ertl and J. Kuppers, "Low Energy Electrons and Surface Chemistry", (Verlag Chemie, Weinheim, 1974). 2. C. C. Chang, Surface Science 25, 53 (1971). 3. A. Joshi, L. E. Davis, and P. W. Palmberg, in "Methods of Surface Analysis" , A. W. Czanderna, ed. (Elsevier Scientific Publishing Co., Amsterdam, 1975) Ch. 5. 4. R. Weissmann and K. Muller, Surface Science Reports 1, 251 (1981). 5. L. Davis et al. , "Handbook of Auger Electron Spectroscopy" (Physical Electronics, Eden Prairie, MN, 1976). AES Web pages: Charles Evans and Associates: excellent tutorial: http://www.cea.com/cai/auginst/caiainst.htm brief summary: http://www.mee-inc.com/sam.html