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  • MICHAEL SHORT: Anyway, today is going

  • to be a lot lighter than the past few days, which have been

  • heavy on theory and new stuff.

  • And I want to focus today on what can you

  • do with the photon and ion interactions with matter.

  • So we're going to go through a whole bunch

  • of different analytical and materials

  • characterization techniques that use the stuff that we've

  • been learning and see what you can actually do.

  • And I'll be drawing from examples

  • from the open literature, from textbooks,

  • and from my own work.

  • So stuff I was doing here on my PhD thesis

  • is actually a direct result of what do we do here in 22.01.

  • So a quick review just to get it all on the board of what

  • we've been looking at.

  • So I don't hit anyone on the way in.

  • We talked about different photon interactions, which include

  • the photoelectric effect.

  • Let's say this will be the energy

  • of the scattered whatever, and this will be its cross section.

  • We talked about Compton scattering.

  • We talked about pair production.

  • For the photoelectric effect, the energy of the photoelectron

  • comes off like the energy of the gamma

  • ray minus some very small difference, the binding

  • energy of the electron.

  • Let's just call it Eb.

  • And this effect starts when you hit what's

  • called the work function.

  • I'm just going to put this all up there,

  • so when we explain the analytical techniques,

  • we can point to different bits of this

  • and explain why we use these different things.

  • The cross-section, I made sure to keep this handy,

  • so I don't want to lose it.

  • Strongly proportional with z.

  • So the cross-section comes out of another line.

  • What was it proportional to?

  • Oh yeah, this is nuts.

  • It's like z to the fifth over energy to the 7/2,

  • which says that for higher z materials,

  • the photoelectron yield is much, much stronger,

  • and it's way more likely that way lower energy.

  • So you can imagine if you wanted to use

  • this in an analytical technique, and you

  • want to study which photoelectrons come from which

  • elements, you might think to use a low energy photon to excite

  • them, not a high energy photon, because like we had done

  • a couple of times before, if we draw

  • our energy versus major cross-section range,

  • we had a graph that looks something like this, where this

  • was the photoelectric effect.

  • This was Compton scattering.

  • This is pair production.

  • And so by knowing what energy--

  • oh, I'm sorry.

  • That's supposed to be z.

  • And this would give you the dominant process

  • that each the combination of energy and z.

  • So if you know what energy photons you've got

  • and what you're looking for, well, there you go.

  • Let's see.

  • What was the energy of the Compton electron?

  • Remember the wavelength formula.

  • It was like alpha 1 minus cosine theta over--

  • let's see.

  • Another 1 minus cosine theta.

  • In came the gamma ray energy.

  • What was the part that came beforehand?

  • That's why I have this here because I don't

  • want to write anything wrong.

  • It's good to have it all up there at once.

  • 1.

  • Yeah.

  • That's all I was missing.

  • Cool.

  • And the cross-section for Compton scattering

  • scaled something like z over energy, something pretty

  • simple, not nearly as strong as pair production

  • or photoelectric effect, so you can

  • think Compton scattering happens much more

  • dominantly at low z or the other two

  • don't really happen that much at low

  • z, whichever way you want to think of it.

  • And for pair production, you get a whole mess of stuff.

  • You get positrons coming out.

  • You get a bunch of 511 keV gamma rays

  • and all sorts of other things you can detect.

  • And the cross-section, this one's

  • got the funny scaling term.

  • This one, yeah.

  • It's like z squared log.

  • Energy over mec squared, so some z squared kind of dependence.

  • So let's keep those up for now.

  • Let's get the electron ones in.

  • AUDIENCE: [INAUDIBLE] mez squared?

  • MICHAEL SHORT: Was it z squared?

  • Let me check.

  • No, that's a c.

  • AUDIENCE: [INAUDIBLE]

  • MICHAEL SHORT: Yeah.

  • Yeah, just make sure that's clearly a c squared.

  • So now let's call it charged particle,

  • or just more generally ion electron interactions.

  • Since these are more fresh in our head,

  • what are the three ways in which charged

  • particles can interact with matter that we talked about?

  • Just rattle off any one of them.

  • AUDIENCE: Bremsstrahlung?

  • MICHAEL SHORT: Yeah, Bremsstrahlung or radiative.

  • What else?

  • AUDIENCE: [INAUDIBLE]

  • MICHAEL SHORT: Is what?

  • AUDIENCE: Ionization.

  • MICHAEL SHORT: Ionization.

  • Which we'll call inelastic collisions.

  • And?

  • AUDIENCE: Rutherford scattering.

  • MICHAEL SHORT: Yep, Rutherford scattering.

  • Which are kind of elastic or hard sphere collisions.

  • And if we had to make kind of a table of when

  • do we care about which effect, let's

  • say this was an ion or electron, scattering off

  • of either electrons or nuclei, in either elastic or inelastic

  • ways.

  • First of all, when do we actually

  • care about elastic scattering off

  • of electrons, which would be hard sphere collisions off

  • of electrons?

  • To help get you going, in an elastic collision,

  • the maximum energy transfer can be this formula gamma

  • times the incoming energy, where gamma

  • is 4 times the incoming mass times the mass of whatever

  • you're hitting over n plus big m squared.

  • Let's say if one of these masses was mass of an electron.

  • What is gamma approximately equal for most cases?

  • Well, let's say this was like electrons scattering off

  • of protons or vice versa.

  • How much energy could an electron

  • transfer to a proton in an elastic collision?

  • Basically zero.

  • The only time which this actually matters

  • is if it's an electron hitting another electron, in which case

  • you can have pretty significant energy transfer.

  • So I'd say for elastic collisions off of electrons,

  • you only care about those for other electrons.

  • And I'm going to put in low energy electrons.

  • Why do we only care about them for low energy electrons?

  • Or in other words, what are the other methods of stopping power

  • or interaction-- yeah, Chris.

  • AUDIENCE: [INAUDIBLE]

  • MICHAEL SHORT: Exactly.

  • Yep.

  • We already saw that Bremsstrahlung

  • the radiated power scales with something like z

  • squared over m squared.

  • So with a really small mass and a really high z

  • and also a higher energy, you end up

  • radiating most of that power away as Bremsstrahlung.

  • And there's not much of a chance of elastic collision.

  • So we only care about low energy electrons

  • when it comes to elastic collisions with electrons.

  • For inelastic collisions with electrons,

  • well, that's the hollow cylinder derivation

  • that we had done from before where

  • you have some particle with a mass m and a charge little ze,

  • getting slightly deflected by feeling the pull--

  • depending on what charge it is, it could be towards or away--

  • of that electron away from some impact parameter B.

  • So we care about this pretty much all the time.

  • Electrons and ions or stripped bare nuclei

  • actually matter in this case.

  • For elastic collisions off of nuclei,

  • this is what Rutherford scattering is.

  • It's a simple hard simple hard sphere collisions,

  • so this matters pretty much all the time.

  • What about inelastic collisions with nuclei?

  • What does an inelastic collision actually mean with a nucleus?

  • So fusion could be one of them, but let's go more generally.

  • We have some nuclear reaction, where it's the old thing

  • that I keep drawing all the time of some little nucleus striking

  • a large nucleus.

  • In an inelastic collision, this is

  • the case we haven't considered yet,

  • but I want to show you what actually happens.

  • In an inelastic collision, these two nuclei

  • join together to form what's called

  • a compound nucleus or CN, at which point

  • it breaks apart in some other way.

  • So there might be some different small particle

  • and some different large particle coming off.

  • But in an inelastic collision, it's

  • almost like the incoming particle is absorbed

  • and something else is readmitted.

  • It could be that same particle at a different energy,

  • and it could be a different energy altogether.

  • So yeah, I'd say fusion is an example.

  • It's kicked off by an inelastic collision,

  • because you've got to have some sort of absorption

  • event of the small nucleus by the big nucleus.

  • And then, maybe if it fuses and just stays that way,

  • it releases a ton of its binding energy,

  • well, that's pretty cool.

  • So these actually do matter, but not

  • for all energies in all cases.

  • So let's go back to the Janis database of cross-sections

  • to see when inelastic scattering actually matters.

  • Bring us back to normal size.

  • And we'll look at some of the cross-sections

  • to see when do we actually care about inelastic scattering?

  • So we haven't selected a database yet.

  • Let's say we're firing protons at things.

  • And pick a database that actually

  • has some elements listed.

  • Not a lot.

  • But iron, that works.

  • So we can look at the difference between the elastic scattering

  • cross-section and the anything cross-section.

  • So the red curve here--

  • can I make it thicker easily?

  • Probably.

  • Yeah, I can make it thicker pretty easily.

  • Easier to see.

  • Plots.

  • Wait.

  • That's not what I wanted.

  • I'm not going to mess around with this anymore.

  • Do you guys see the two lines?

  • OK, so this is the elastic scattering cross-section.

  • Kind of funny to see it negative.

  • But then there's the anything cross-section which

  • picks up at around 3 MeV or so.

  • And it usually takes somewhere between 1 and 10 MeV

  • for inelastic scattering to quote unquote turn on,

  • and that's because you have to be

  • able to excite the nucleus to some next energy level.

  • So sending in a proton at like 0.01 MeV

  • is not going to excite any of the internal particles

  • to a higher energy level.

  • So if you want to see some pretty interesting cases,

  • let's go to incident neutron data

  • where we have a ton of this data.

  • And I'll show you some examples.

  • We've got lots more data for neutrons.

  • So now we can look at some of these cross-sections.

  • Like this z n prime.

  • Let's take a look at what that looks like.

  • That means a neutron comes in.

  • Different neutron comes out.

  • Notice that the scale only starts at 862 keV.

  • So let's make it something else.

  • Oh my.

  • Look at that.

  • Nothing going on until you reach almost 1 MeV, which means,

  • hey, inelastic scattering doesn't really

  • turn on until that.

  • So I would say that this can matter,

  • but for higher energy collisions.

  • So yeah, it matters pretty much all the time.

  • But higher energy collisions.

  • And there's actually-- yeah.

  • AUDIENCE: What does it say in the top left box?

  • MICHAEL SHORT: Only for low energy electrons.

  • That's the sort of compound reason that I and Chris said,

  • one, is that you can't transfer much mass

  • in an elastic collision, or I'm sorry,

  • much energy in an elastic collision

  • unless the masses are close enough to each other.

  • And two, at higher energies, the electron

  • radiates Bremsstrahlung much, much, much faster.

  • As we saw at around 10 MeV, Bremsstrahlung

  • and inelastic scattering give about equal contributions

  • to the stopping power for high z materials like lead.

  • So once you're down and let's say like the keV range,

  • yeah, electron elastic collisions might matter.

  • So we talked about those three.

  • Now I think we can launch into the analytical technique.

  • So for the rest of the lecture today, it's all going to be

  • what can you do with the stuff that we've been

  • learning since the first exam.

  • I know it hasn't been long since,

  • but we've actually learned a ton.

  • And I want to show you what's actually possible.

  • And this is not going to be with slides.

  • It's all live from websites that I'd

  • love for you guys to be able to follow along with or check out

  • at home.

  • So I'm going to show you an awesome resource

  • through the MIT libraries and how to get there.

  • If you go to vera.mit.edu, there's

  • a great tool called the ASM Handbook.

  • You can see I've been there before.

  • There's the ASM handbooks online,

  • and this is kind of that's everything

  • to know about material science, metallurgy,

  • and analytical techniques, absolutely everything

  • from corrosion to fractography, to characterization,

  • to structure of materials to where you can find

  • every single alloy, to binary phase diagrams of how

  • things mix, and we're going to head to one of these handbooks.

  • Number nine or 10, materials characterization,

  • because with the stuff that's on this board,

  • you can understand how most materials characterization

  • techniques work.

  • And I want to show you a few of them.

  • One of which-- no, two of which, we're going to demo

  • out next Friday's recitation.

  • So I think I told you guys in the syllabus

  • and probably in person that we're

  • going to try out some scanning electron

  • microscopy and some energy dispersive X-ray or EDC

  • analysis.

  • So with the X-ray transition stuff you've learned,

  • you actually know how to elementally analyze

  • different materials.

  • And with scanning electron microscope,

  • you can get some idea about how electrons can make images much

  • better than optical images.

  • So let's head to electron optical methods, scanning

  • electron microscopy, and show you what one of these things

  • actually looks like.

  • Let's take a look at an SEM, or scanning electron microscope.

  • So up at the top, there is a device called the electron gun.

  • For now, just imagine it's a source of electrons,

  • but in a few minutes, we'll actually

  • explain how it works using the principle

  • of thermionic emission, which we talked about last Friday.

  • You've got some electronic lenses,

  • some focusing coils, that caused this beam to get

  • focused further and further.

  • So let's say you had this electron filament giving off

  • electrons in all directions.

  • When you see boxes with x's like this on an electron optics

  • diagram, it usually means this is like a focusing coil

  • of some sort.

  • So that will cause the electrons to get bent and focused.

  • There'll be another set of coils that focuses them further

  • and some scanning coils that actually raster or xy

  • scan this beam across the surface of a material.

  • And so in this way, what you're actually

  • doing is putting the electron beam at one

  • part of your material and then with another detector,

  • let's call it a secondary electron detector.

  • Looking at the electrons produced from collisions

  • with those other electrons that then get detected here,

  • and the number of electrons produced at a point

  • gives you the brightness of the image.

  • That's kind of as simple as it is despite how

  • complicated this diagram looks.

  • There's an electron source.

  • There's coils that scan it back and forth.

  • Like has anyone ever seen the old cathode ray tube,

  • CRT televisions?

  • There's going to come a day when that answer is no.

  • And I'm kind of worried for that,

  • because that's the day I'll officially become old.

  • But for now, everyone's seen a CRT,

  • and the way that actually works is

  • there's an electron gun that fires and scans left to right

  • and up to down our rasters and produces that electron image.

  • In an SEM, you use an electron gun, kind of similar, and then

  • collect the electrons generated in the specimen, what's

  • called secondary electrons.

  • And the number that you see gives you

  • the brightness of the image.

  • The cool thing is this actually allows

  • you to look at both secondary electron contrast

  • and topology of a sample.

  • So let's say this was your secondary electron detector.

  • And you had an electron beam scanning across your sample

  • to some of those peaks and valleys.

  • And I'll probably draw one right here for a good reason.

  • Let's say the electrons hit right here,

  • and you send out a wave of secondary electrons.

  • The material partly determines how many electrons come off,

  • but also, so does the geometry.

  • There will usually be a little cage

  • with some sort of a positive voltage on it

  • to attract those secondary electrons.

  • And some of them will curve into the detector and become part

  • of your signal, but some of them won't.

  • Meanwhile, if you have this beam right here producing

  • secondary electrons, pretty much all of them

  • go slamming into your detector.

  • And that's what actually allows the electron

  • microscope to get topology.

  • That's why images in the SEM look fairly 3D.

  • So I want to show you a few examples from my own boredom

  • when I was doing a lot of science.

  • There we go.

  • I have a whole gallery of SEM images

  • when I was supposed to be doing something better.

  • Oh no.

  • 404.

  • My website's broken.

  • Oh yeah.

  • This is also what you do when you're bored, right?

  • Make your own 404 page.

  • My SEM galleries are dead.

  • Well, that's OK.

  • I have other images ready to show you guys.

  • So this is a neat-- this is a paper that I published out

  • of my PhD work that shows the real difference

  • between optical and electron microscopy.

  • Part of it is the limit of your resolution

  • depends on the wavelength or de Broglie wavelength of the thing

  • you're using to make the image.

  • So an optical microscope, in this case,

  • you can't get better resolution than about half a micron,

  • because even the blue wavelengths of light

  • are getting down into about the 450 nanometer regime.

  • And it's very difficult without interference techniques

  • or other fancy things to beat that diffraction limit,

  • to beat the sort of wavelength limit of optical microscopy.

  • So this is a 500x optical microscope image,

  • and you can see these little fingers--

  • in this case, it's liquid lead bismuth

  • penetrating into a stainless steel

  • that we were doing corrosion experiments on.

  • And that's as good as the image can

  • get in an optical microscope.

  • Switch down to an SEM, and then all of a sudden

  • the picture becomes much, much, much more clear.

  • You can start to see things-- the best SEM we have in our lab

  • has an ultimate resolution of about 1 nanometer.

  • Now, resolution is kind of a funny thing.

  • It's neat to tell you what that means.

  • It doesn't mean that if you have a pattern of lines

  • that are exactly one nanometer thick, that you will see them

  • as lines 1 nanometer thick.

  • It means that if you then plot, let's

  • say, your signal or your brightness versus x,

  • you'll have some barely distinguishable and fuzzy

  • lines, just enough for you to say those are two optically

  • distinct features.

  • So what you'll actually see in a 1 nanometer microscope

  • is maybe something like this.

  • That's technically resolved at the level of 1 nanometer.

  • So the best you can do for crisp objects in this thing

  • is about 20 nanometers.

  • Not bad.

  • It's like something that's a few thousand atoms on a side.

  • Pretty cool.

  • And so what you can see in here is liquid lead bismuth

  • penetrating into this stainless steel,

  • and you notice a few different things.

  • This image was taken in backscatter electron mode.

  • Back scattering is-- we've talked about this before.

  • When you have a scattering event where theta equals pi,

  • we call that backscatter.

  • Let's kind of split this into regular and backscatter.

  • For a backscattering, the cross-section for this

  • is proportional to z squared, another one

  • of those extremely z dependent cross-sections, which

  • means that the larger the z, the higher the atomic number

  • the more backscatter contrast you get,

  • so if you want to figure out where the little lead whiskers

  • are penetrating into the stainless steel,

  • since lead has a z of like 82, and iron has a z of like 26,

  • it shows up like night and day.

  • Do you have a question, Julia?

  • OK.

  • Yeah, so this is something we'll actually be able to do.

  • So for the two folks I asked to bring in samples,

  • if you want to bring in something with very

  • different elements in it, we should

  • be able to see it in backscatter contrast very, very clearly.

  • And in the image of the SEM, I'll go back to that--

  • which one of these pages is it?

  • Notice here that there is a backscatter detector.

  • So it will detect which of those electrons

  • scatter back at almost 180 degrees.

  • And that's at about z squared proportionality, super useful

  • tool, because if you want to see, for example, where

  • the circuit board traces are, and you want

  • to look at aluminum versus oxygen contrast,

  • that'll help you really well.

  • If you want to see where is lead penetrating

  • into stainless steel, it shines up clear as day,

  • which is pretty fun.

  • The other thing the electrons will

  • do when they enter into a material

  • is excite lots of things.

  • So anything from X-rays to Auger electrons.

  • So now I'd like to bring up Auger electron spectroscopy.

  • Electron or X-ray spectroscopic methods.

  • Auger electron spectroscopy, it's

  • not just a thing to trip you up on the exam

  • or a little minutia from radioactive decay.

  • It's actually incredibly useful, because

  • of where the Auger electrons are generated

  • and what they tell you about the material.

  • So as a quick refresher, normally you could have,

  • let's say, if a photon comes in and injects a photo electron

  • as another electron comes to fill that hole,

  • either an X-ray will be emitted or an Auger electron

  • will be emitted.

  • And it's those Auger electrons, they're

  • outer binding energy electrons.

  • They have very low binding energy, which means--

  • let's see.

  • I keep running out of room.

  • You know, I'm not going to draw it.

  • I'm going to show you, because I know there is a diagram of what

  • I want to show you here.

  • If you want to see where the Auger electrons are actually

  • produced in the material--

  • here we go.

  • Since they're such low energy, the only Auger electrons

  • that actually get out would be in this outer few mono layers.

  • In fact, there's some Auger electron energies

  • that can only get out one or two atomic mono

  • layers from a material.

  • So it's one of the best surface analysis

  • techniques that we have.

  • You can both use Auger electrons to make an electron image,

  • like any other SEM.

  • And you can collect them and measure their energy

  • to figure out which elements they came from.

  • And this kind of teardrop shape is a--

  • one, it's a great synthesis of all the information

  • you need to know in the SEM that we'll see on Friday.

  • And two, its why people screw up SEM analysis a lot.

  • A lot of the X-ray excitation happens down here.

  • Why do you think that the X-ray exaltation would happen

  • near the end of the path of the electron beam

  • from what you know about stopping power?

  • Or, if I asked you to draw a graph of let's say

  • energy versus stopping power for ionization, what would

  • it look like?

  • Yeah.

  • AUDIENCE: It comes up like a peak at low energy.

  • MICHAEL SHORT: Yeah.

  • AUDIENCE: And then drops back down.

  • MICHAEL SHORT: Yeah.

  • AUDIENCE: And as the energy goes out, it sort of flattens out.

  • MICHAEL SHORT: Yep, sort of flattens out,

  • and then eventually starts picking up again but not very

  • much.

  • So as the energy of whatever you're going into--

  • I'm sorry, whatever particle you're

  • sending in it gets lower, it's stopping power increases,

  • and you have a much higher chance of this ionization

  • happening, especially in the case of electrons.

  • They usually come in at between 10 and 40 kV.

  • And so near the end of their range

  • is where they produce a lot of the X-rays.

  • Now there's a lot of other nuances

  • to say, well, which X-rays were produced here

  • and what elements are they from.

  • Let's say you had the same material here or here.

  • Fewer X-rays will get out of the bottom region

  • than they will from the top region.

  • So if you happen to be analyzing something

  • that has a gradient in composition

  • or a change in composition from the top to the bottom,

  • you might be like, oh, well, I have a few nanometers

  • of oxygen on silicon.

  • Why aren't I seeing any oxygen X-rays?

  • Because you're probably generating them down here.

  • That's one of those things to note.

  • So sometimes you'll see and elect

  • an elemental map of things that shows X-rays

  • of certain element coming from somewhere,

  • and you can't see it at all in the image.

  • That's because they might be underneath what

  • you can see in the image.

  • It's kind of tricky like that.

  • I'll show you some examples of what those maps look

  • like also from this paper.

  • So from the electron image, we sort of

  • concluded, all right, lead is probably penetrating

  • into the stainless steel.

  • How do we know for sure?

  • You can make EDX or elemental dispersive--

  • I'm sorry, energy dispersive X-ray maps

  • by focusing the electron beam at one point,

  • collecting all the different X-rays

  • and then moving from one point to another

  • to see when do you get characteristic X-rays from each

  • of those elements.

  • So you can actually prove to say,

  • yes, those little fingers are indeed bismuth and lead,

  • and you can see that, in this case, where the lead in bismuth

  • is, the iron is not.

  • But the curious thing we found is

  • that in this whole band right here, most of the chromium

  • disappeared.

  • So it turns out that the corrosion mechanism

  • was chromium dissolution.

  • And we would not have been able to know that without this EDX

  • mapping, and without understanding how the EDX

  • maps are made from the electrons interacting with matter

  • and producing characteristic X-rays,

  • wouldn't have been able to prove this.

  • Yet another example where the basic stuff

  • you're learning in 22.01 is the theoretical underpinning

  • of the techniques that we use all the time

  • in material science, which I thought was pretty cool.

  • I've got more examples of that that

  • are even more striking, because I let

  • it collect for a little longer.

  • You can actually see right here that where the bismuth is,

  • the iron isn't, but the iron's not dissolving.

  • The chromium is.

  • It's just the lead and bismuth are

  • kind of sucking the chromium out of the metal right there,

  • and that's what making the stainless steel less stainless.

  • It's pretty neat.

  • Then on to EDX analysis, what sort of information

  • are we looking at every one of these pixels?

  • I have a couple of other example X-ray spectra.

  • So now we're in a position to understand

  • why one of these X-ray spectra looks the way it does.

  • In this case, we're firing electrons at a material.

  • Let's see.

  • Where is our material we're firing at?

  • Right here.

  • So we're firing in electrons.

  • And in some cases, let's say we had an iron atom.

  • That electron can eject another electron.

  • And then one of those other electrons

  • will fall down in that shell, giving off

  • a characteristic X-ray.

  • In this case, since it's from the third to the second shell,

  • that would be what we call an L X-ray or a something

  • to level two transition.

  • And every element has got its characteristic X-ray

  • transitions, like we saw on the NIST X-ray transition database.

  • And since we know what all of those are,

  • we know where to expect them.

  • So we know where we expect to see chromium's X-rays

  • and iron's X-rays.

  • Gold's kind of an interesting one.

  • There's two things about doing analysis with gold.

  • A lot of times you have to coat your materials in gold

  • to boost their secondary electron contrast.

  • But also gold, I think it's its L line or M line,

  • I forget which one, is the same as argon's K line.

  • And we have an expression in the electron microscopy

  • world, the probability of finding argon in your sample

  • decreases with experience.

  • Takes a second to parse that.

  • Chances are, if you're looking at a solid material.

  • You don't have argon in it.

  • But there are extra lines that overlap with each other,

  • like the L line for gold and the K line for argon

  • are at pretty much the same energy, certainly

  • similar enough that it's within the resolution

  • or like full width of half maximum of these two peaks.

  • So remember how we were analyzing the uncertainty

  • of our banana spectra with the FWHM or full width

  • at half maximum?

  • Same thing here, and you can really

  • see that the energy resolution of this detector

  • is not the best.

  • So if you see a peak, it might be

  • due to two or more peaks crowding in that right there.

  • And with a lot of correction factors that I won't get into,

  • you can then use this information

  • to integrate the area under these peaks

  • and get elemental analysis.

  • You can say how much chromium or how much iron and silicon is

  • in one of these samples.

  • What's this stuff here on the bottom?

  • Anyone tell me?

  • That continuum of observed X-ray energies?

  • AUDIENCE: Compton.

  • MICHAEL SHORT: Compton scattering is a photon effect,

  • so that would be--

  • if this were a photon analysis spectrum, then

  • you would see something like this but of a different shape.

  • You'd have that Compton bowl with an edge.

  • But this is, in this case, electrons

  • interacting with material.

  • What do you think is causing that broad background?

  • Well, what are the different ways in which electrons

  • can interact with matter?

  • You're seeing the ionizations here.

  • We're not really seeing Rutherford scattering.

  • What's left?

  • AUDIENCE: Bremsstrahlung?

  • MICHAEL SHORT: Bremsstrahlung.

  • Yep, that's exactly it.

  • So the observed Bremsstrahlung spectrum

  • follows this sort of characteristic peak

  • early and then tail off curve.

  • What's the actual Bremsstrahlung spectrum

  • that we're not sensing?

  • What would it look like?

  • Always running out of room.

  • If this is what we're actually observing,

  • let's say we have a few peeks, that would be intensity,

  • and that would be energy, what's really going on physically

  • that we're not seeing?

  • Yeah.

  • AUDIENCE: Isn't it sort of like almost like exponential decay.

  • So it starts out with very high intensity and goes down.

  • MICHAEL SHORT: That's right.

  • You actually should get more low energy Bremsstrahlung.

  • One of some of the reasons you don't is

  • that the lower energy, those X-rays come out,

  • the more they get self-absorbed in the material in the few gas

  • molecules in the SEM and in the window of the detector.

  • So just because this is what you see

  • doesn't mean this is what's actually

  • going on in your material.

  • If we think back then to where the electrons and X-rays are

  • generated, the X-rays that are generated down here,

  • the lower energy ones are going to be shielded more.

  • And this kind of messes up your elemental analysis,

  • because if the X-rays produced here,

  • proportionally more of the low energy

  • ones will get out than the ones produced here.

  • So as you change your--

  • as you change your electron beam energy,

  • you might see your elemental composition appear to change

  • when you know it's really not.

  • And that's because where the X-rays are being generated

  • change, and proportionately, more of the low energy

  • ones get self shielded by your material.

  • So you actually have to correct for that

  • and input your beam energy into the EDX analyzer

  • so it knows how to correct for this.

  • But with the understanding I've been giving you

  • guys in this class you can understand like well,

  • why can you get screwed up?

  • Why do we have to have all these correction factors?

  • I think it's pretty neat.

  • Then let's get on to some of the other methods, like X-ray photo

  • electron spectroscopy or XPS.

  • This is something I hinted to a little bit

  • earlier that actually uses the photoelectric effect,

  • because it's a photo electron spectroscopy method.

  • This one's incredibly useful because not only does it

  • tell you what elements are there,

  • but in what binding state they are,

  • because photo electron spectrometers

  • can be incredibly precise.

  • The energy equation should look pretty familiar to you

  • it's whatever photo electron you get

  • is the gamma ray energy that comes

  • in minus the binding energy of that electron

  • and the work function.

  • And so you can very, very simply figure out

  • for a given element and a given electron

  • shell what photo electron energy's do you expect.

  • So you can collect them.

  • So I'll show you another example from this paper, where

  • we started to do that.

  • We wanted to answer the question, what

  • are the oxides forming on the stainless steel

  • when lead corrodes it?

  • And just telling you which elements

  • are there and in what proportion doesn't give

  • the answer, because what if there's

  • multiple phases of each oxide?

  • Like, for example, iron can take forms like FeO, Fe2O3, Fe3O4,

  • and this FeO can actually have a range of stoichiometries.

  • So how do you know?

  • You don't know.

  • There could be like scores of phases of this iron oxide.

  • The question is how you know which ones are there.

  • The photo electrons will tell you.

  • So what you can do first is fire monochromatic X-rays, so single

  • energy X-rays, in this case from aluminum at your material

  • and see which photo electrons of which energy come off.

  • And you can tell which atomic shell

  • they're from and which elements they should

  • be to a very high precision.

  • In this case, this is done to 100 milli MeV or 0.1 MeV

  • precision, 0.1 eV precision.

  • So we can tell not only what elements are there,

  • but what shells they came from.

  • Then you can get even crazier.

  • You can scan very slowly over one

  • of these peaks with 0.001 eV precision

  • and start to see something pretty cool.

  • If you look at the carbon 1s electrons,

  • you can see that there are actually three of them

  • only a couple eV apart, and this corresponds

  • to different binding states of molecules with that carbon.

  • For an even more subtle example, but ended up

  • being incredibly important for us,

  • here's one of the chromium 2p shell peaks.

  • You can actually see there's three

  • of them superimposed give that funny

  • looking peak shape right there.

  • What that actually tells us is that there's

  • chromium in three different binding states in that oxide.

  • And the ones we figured out must be there,

  • we saw the ones corresponding to Cr2O3, FeCr2O4,

  • and I forget which other one, but we have them tabulated.

  • There we go.

  • Oh wow.

  • Fe 2.4 Cr 0.64, known crystallographic phases

  • of these oxides.

  • So you can look at the peaks found

  • to have resolution of like 100th of an electron volt,

  • compared to reference values taken on pure compounds

  • and materials to figure out what actual oxides do you have.

  • That can help tell you things like how protective are they,

  • how fast are they going to grow, and are they

  • going to be a problem if you want

  • to use this new stainless steel that we developed

  • in a lead bismuth reactor.

  • The biggest problem with lead bismuth reactors

  • is lead corrodes like everything.

  • And so the whole point of my graduate studies

  • was design an alloy that doesn't corrode and lead

  • and make ab alloy composite out of it.

  • But you can't prove that it works unless you not only know

  • how fast it corrodes, but how it corrodes, which oxides form,

  • and in what order.

  • That's the last part I haven't told

  • you about yet is what order.

  • So I want to switch to another technique called secondary ion

  • mass spectroscopy or SIMS.

  • In this case, you start off with firing ions

  • at a material, which will then eject or sputter away

  • secondary ions.

  • In this case, this process of sputtering--

  • let's say this is your material here.

  • You send in something like oxygen ions, which

  • might be like O2 minus with a mass of 32,

  • and then you blast off or sputter away.

  • A few atoms at a time from that surface,

  • and they'll come off the various masses and charges,

  • and in this case, the sputtering could

  • be due to Rutherford scattering, because you might directly

  • ballistically slam and ion out of the surface.

  • Then every one of these ions has a different mass

  • and a different charge.

  • And by sending it through a mass spectrometer,

  • something that separates these materials by their mass

  • to charge ratio, because the higher the charge,

  • the more deflected an ion will be.

  • But the higher the mass, the less deflected it will be.

  • That should sound really familiar.

  • In our idea here where how these ionization collisions happen,

  • if you remember the higher the charge,

  • the stronger the Coulomb force--

  • that q1, q2 over r squared.

  • I think there was a constant in there.

  • So the higher the charge, the higher those q's,

  • and the stronger the Coulomb forces.

  • But the larger the masses, the less momentum it can impart.

  • And so the deflection will be weaker.

  • Exact same thing's happening here.

  • And you can separate out atoms not only

  • by their charge and their mass, but specifically

  • by their isotope.

  • So this is one of those ways that you

  • can figure out and make an isotopic map of a material

  • in three dimensions.

  • You can scan your ion beam across the material

  • and collect the ions at every point.

  • And as you sputter, you slowly wear away

  • layers of this material.

  • And so you can actually reconstruct a 3D map

  • with almost nanometer precision of every single isotope that

  • was at every location, which is quite cool.

  • As you can see, these master charge ratios

  • can depend on which isotope of silicon you have,

  • what sort of cluster, what molecule, what charge you have.

  • And you can do some pretty crazy analysis of things

  • to even figure out what sort of compounds

  • exist on surfaces, because sometimes you sputter off

  • whole molecules.

  • They're going to have their own mass to charge ratio.

  • And that's what we did for this lead bismuth work.

  • Lots of XPS spectra to jump through.

  • We wanted to find out which oxides were forming

  • and in what order.

  • Which one's the best one I want to show?

  • Think it's this one.

  • So in this case, we used ion sputtering

  • to sputter away surface layers to a depth of a few hundred

  • nanometers, and we're actually able to show that the chromium

  • oxide, right here, was on the outside of the sample,

  • followed by silicon oxide, followed by iron metal.

  • So in this way, we were able to figure out

  • using XPS, the nature of the oxides

  • and using SIMS, the order of the oxides,

  • so not only how fast were they growing to nanometer precision,

  • but in what order did they form.

  • And that helped us figure out this sort

  • of synergistic chromium and silicon oxidation mechanism

  • that helps really protect the layers of the stainless steel

  • and explain why it's corrosion resistant lead bismuth,

  • all using principles from 22.01.

  • So it's about two of five of.

  • So I wanted to stop and see if you guys have

  • any questions on these analytical techniques,

  • knowing that we're actually going to go do

  • a couple of these next Friday.

  • Has anyone used any of these before?

  • Yeah, which ones have you used?

  • AUDIENCE: SEM and XPS, XPS [INAUDIBLE]

  • MICHAEL SHORT: SEM and XPS?

  • OK, cool.

  • Yeah, we've got all these instruments

  • I think except for SIMS here at MIT.

  • Yeah.

  • Yeah.

  • AUDIENCE: Sorry, what is that second equation

  • on the energy for Compton scattering?

  • MICHAEL SHORT: This would be the energy of the Compton electron

  • that comes out when a photon scatters off of it.

  • So the photon will end up losing some energy,

  • and the Compton electron will pick up that energy.

  • AUDIENCE: [INAUDIBLE]

  • MICHAEL SHORT: Sorry?

  • AUDIENCE: What's the denominator of that?

  • MICHAEL SHORT: It's a 1 plus alpha times 1

  • minus cosine theta, where alpha--

  • I'll mention what alpha is.

  • It's a ratio of the photon energy to the electron rest

  • mass energy.

  • This is kind of a nice-- on these two boards right here,

  • it's kind of a nice summary of the stuff we've

  • been doing over the last three weeks or so,

  • and then all the stuff I showed you today

  • is what you can do with it.

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