1 00:00:00,480 --> 00:00:04,060 All right. I guess we can we can get started now. Welcome back. 2 00:00:04,080 --> 00:00:07,650 It's the 13th lecture of the condensed matter course. 3 00:00:07,980 --> 00:00:12,120 When last we left off, we were talking about scattering the basic experiment. 4 00:00:12,630 --> 00:00:20,340 If you have some sample, you have a wave at some way vector K that you send into the sample and then it's scattered off to some wave vector. 5 00:00:20,970 --> 00:00:29,130 K prime. And by measuring how much and in what directions you have scattering, you're able to do something about what's actually in the sample. 6 00:00:29,160 --> 00:00:32,910 A couple of things that we know about these type of scattering experiments. 7 00:00:32,940 --> 00:00:40,080 First of all, in order to get scattering from chaotic prime, you must have K minus K prime equals reciprocal lattice vector g. 8 00:00:40,410 --> 00:00:49,340 And we derived in the last lecture that's equivalent to the Bragg condition two d sine theta equals and lambda. 9 00:00:49,350 --> 00:00:54,299 In other words, since a reciprocal lattice vector is orthogonal to a family of lattice planes, 10 00:00:54,300 --> 00:01:03,800 what you're actually getting is diffraction off a diffraction grating with lattice plane spacing D orthogonal to that vector g. 11 00:01:04,170 --> 00:01:12,989 The intensity of scattering at any reciprocal lattice vector is proportional to the structure factor of g squared, 12 00:01:12,990 --> 00:01:17,190 where the structure factors the 48 transform of the scattering potential in the unit cell. 13 00:01:17,340 --> 00:01:22,410 So this intensity gives you some amount of information about what's actually in the unit cell. 14 00:01:22,740 --> 00:01:26,220 Now, how you actually do this experiment is a little more complicated. 15 00:01:26,370 --> 00:01:28,200 There are several methods one can go about. 16 00:01:28,620 --> 00:01:38,250 There is the first method, which is the best method, but also the hardest method, best bit hardest, which I'll discuss only very briefly. 17 00:01:38,920 --> 00:01:43,230 The best method, but also the hardest method is to use a single crystal. 18 00:01:44,010 --> 00:01:48,750 Single crystal. So a single crystals look like this. 19 00:01:49,110 --> 00:01:55,980 This is a gorgeous single crystal of sodium chloride, a big single piece of the material without any defects. 20 00:01:56,400 --> 00:02:05,250 Now what you'll find so you take a single crystal, you put it in the path of your of your wave, and you look for four waves being scattered off of it. 21 00:02:05,340 --> 00:02:11,340 What you find is if you take your single crystal, you put it in some arbitrary orientation in front of your your beam. 22 00:02:11,340 --> 00:02:15,100 Here, for most orientations, you won't get any scattering at all. 23 00:02:15,120 --> 00:02:20,430 In other words, you will not manage to align the families of lattice planes just at the right angle, 24 00:02:20,580 --> 00:02:27,900 such that the Bragg condition is actually satisfied. So in order to actually get any scattering, what you need to do is to rotate the crystal. 25 00:02:29,130 --> 00:02:38,310 Rotate the crystal. Another way to get scattering is to vary the wavelength very lambda, do one or the other, 26 00:02:38,310 --> 00:02:43,620 and then at some angle of the crystal or at some value of the wavelength, you get scattering. 27 00:02:43,740 --> 00:02:47,400 You write down in which direction you get the scattering, you measure the intensity of the scattering, 28 00:02:47,520 --> 00:02:54,090 and you can deduce a lot of information about the structure factor and therefore about the structure of the crystal. 29 00:02:54,330 --> 00:03:00,569 Now, we're not actually going to go into how you analyse such data in any detail in this course. 30 00:03:00,570 --> 00:03:03,870 And the reason we're not going to do it is because this method is very rarely used, 31 00:03:04,140 --> 00:03:08,070 and the reason it's very rarely used is because it's actually the hardest thing to do. 32 00:03:08,460 --> 00:03:14,730 The reason it's hard is because, almost without exception, materials don't like to form nice big crystals. 33 00:03:14,730 --> 00:03:18,360 Sodium chloride is a suggestion. You have these beautiful big crystals of sodium chloride. 34 00:03:18,660 --> 00:03:23,280 Quartz makes nice big crystals. You can probably make a nice big crystal of sugar something. 35 00:03:23,280 --> 00:03:27,540 I mean, so there are a couple of materials that you can get to form nice big crystals, but most materials don't. 36 00:03:27,750 --> 00:03:34,020 If you cook up some new material in your laboratory or you find some new material in nature, usually it's not crystalline. 37 00:03:34,020 --> 00:03:40,200 It doesn't form big crystals. Frequently it's powder. Or even worse than that, you can have what's known as Polycrystalline. 38 00:03:40,560 --> 00:03:48,000 So this is a picture of a Polycrystalline material where you have tiny little crystal lights, which are about on the size of a micron. 39 00:03:48,000 --> 00:03:49,980 So there's a little crystal here, a little crystal here, 40 00:03:50,190 --> 00:03:54,900 and those crystals have their axes miss oriented with respect to each other, and they're also smushed together. 41 00:03:55,140 --> 00:03:59,400 You can think of it as like a powder of tiny little crystals all stuck together. 42 00:03:59,400 --> 00:04:03,719 And typically materials look like this when you make them. It's very, very difficult. 43 00:04:03,720 --> 00:04:09,750 It takes a very good chemist and very good material scientist to turn something that looks like this into something that looks like this. 44 00:04:10,080 --> 00:04:16,620 So most of the time, when one is doing experiment, one is working with something that looks like this, it's probably crystal. 45 00:04:17,190 --> 00:04:25,920 So to take data on a polycrystalline sample, you use what's known as the device Scherrer method to buy Scherrer. 46 00:04:28,800 --> 00:04:35,430 The buy is the same guy from the Buy Theory of Vibrations and Solids share someone else obviously. 47 00:04:36,810 --> 00:04:40,050 And the device share. This method is also known as powder diffraction. 48 00:04:43,690 --> 00:04:52,800 Diffraction. Because you can use a powder of the material, lots of tiny, tiny little crystal lights in a powder. 49 00:04:53,010 --> 00:04:57,210 And you can put that in your sample and get data out of it and actually make sense of it. 50 00:04:57,480 --> 00:05:01,770 Now, the general principle of the idea of powder diffraction or doing diffraction on 51 00:05:01,770 --> 00:05:08,130 polycrystalline samples is if you're sending a wave into your into your crystal here, 52 00:05:08,250 --> 00:05:11,550 if you imagine for a second you got a big a big single crystal, 53 00:05:11,700 --> 00:05:16,409 and you could rotate that single crystal around if there was any direction in which 54 00:05:16,410 --> 00:05:20,010 you rotated that single crystal and you could get diffraction out at this angle. 55 00:05:20,250 --> 00:05:26,280 Then somewhere in your powder, somewhere in your polycrystalline sample, the axes will be correctly oriented. 56 00:05:26,460 --> 00:05:32,790 In other words, the poly crystal material or the powder represents every possible orientation of the material. 57 00:05:32,970 --> 00:05:37,379 So somewhere in your material you'll have a situation where your family of lattice 58 00:05:37,380 --> 00:05:43,110 planes is aligned just in the right way in order to get diffraction from K2 K Prime. 59 00:05:43,110 --> 00:05:49,800 If there's any orientation that will do it, you'll find that crystal light with the right orientation somewhere in your sample. 60 00:05:50,700 --> 00:05:53,010 That's the general principle we're going to live by. 61 00:05:53,220 --> 00:06:00,000 Now, if if you can get diffraction in this direction with some lattice planes that are sort of lined up parallel this way, 62 00:06:00,240 --> 00:06:06,420 you can also imagine that if you lined up your lattice planes this way, you could get diffraction out this way. 63 00:06:07,170 --> 00:06:07,770 And in fact, 64 00:06:08,010 --> 00:06:17,640 you can imagine rotating those crystal lights around the incoming axis and you realise that you can get a whole cone of diffraction outwards. 65 00:06:17,820 --> 00:06:25,860 If there's any direction that you can scatter, you can rotate that crystal light around the incoming access and get a get a cone of outgoing waves. 66 00:06:26,140 --> 00:06:30,360 So the way the experiment actually looks at in a setup is kind of like this. 67 00:06:30,660 --> 00:06:35,010 There's an incident x ray beam, there's a polycrystalline or powder powder specimen here. 68 00:06:35,340 --> 00:06:39,870 And then you get these cones of outgoing waves, which you then try to measure. 69 00:06:40,050 --> 00:06:46,110 Remember that the it's marked here, so you don't forget the total deflection angle is two theta very important. 70 00:06:46,770 --> 00:06:51,239 A common source of source of error and to theta can go anywhere from zero, 71 00:06:51,240 --> 00:06:56,040 meaning it's not scattered at all to 180 degrees, meaning it's directly back scattered. 72 00:06:56,230 --> 00:07:04,620 Now, the way one used to measure it is you would take this sort of round environment and you would line the inside with photographic paper, 73 00:07:04,770 --> 00:07:07,770 and you would just expose the photographic paper to the x rays, 74 00:07:07,770 --> 00:07:17,070 and you would see these nice conical signals coming out for these various different cones coming out like this from your polycrystalline sample. 75 00:07:17,400 --> 00:07:21,000 But in modern days, photographic paper is not used. 76 00:07:21,000 --> 00:07:27,059 It's much more it's much more convenient and actually much more accurate and much more sensitive to use semiconductor detectors. 77 00:07:27,060 --> 00:07:32,490 So it's usually what you actually get out of your sample, out of your experiment now is a plot that looks like this, 78 00:07:32,790 --> 00:07:37,859 where what's plotted across the bottom is the scattering angle and the intensity vertically. 79 00:07:37,860 --> 00:07:42,450 So you'll see there's a peak here at 20 something degrees, another peak at 30 something degrees, 80 00:07:42,450 --> 00:07:45,509 which might correspond to this ring and then that ring and so forth. 81 00:07:45,510 --> 00:07:49,410 And this is the kind of data that we're going to spend our time analysing. 82 00:07:49,620 --> 00:07:57,809 Okay. So this is sort of sort of a classic type of question for exams, analyse a powder diffraction pattern with the device sharing method. 83 00:07:57,810 --> 00:08:01,200 So there's a couple of rules for following this method, so I'll write them down. 84 00:08:01,920 --> 00:08:06,210 It's fairly difficult to find a book that explains this well, I think as explained well in my book, 85 00:08:06,420 --> 00:08:10,860 but if you don't like the explanation of my book, you're kind of out of luck because there aren't a lot of other books to explain it. 86 00:08:11,100 --> 00:08:20,129 So sorry about that, but that's just how it is. So rule number zero is no the wavelength, no your wavelength. 87 00:08:20,130 --> 00:08:23,850 Lambda Why do you know you're wavelength lambda? Well, you're the experimentalist. 88 00:08:24,090 --> 00:08:27,750 You put in the X-ray beam, you had the X-ray apparatus. 89 00:08:27,900 --> 00:08:31,620 So, you know, presumably what the wavelength of the X-ray is. So it's a good thing to start with. 90 00:08:31,860 --> 00:08:36,150 Know your wavelength, probably know it pretty accurately, actually, if you're a good experimentalist, 91 00:08:37,200 --> 00:08:47,160 step one measure the angles, measure angles, angle of scattering, which is two theta, not theta. 92 00:08:47,610 --> 00:08:52,110 Remember, that is going to be important. So here's some data we're actually going to analyse where they've done. 93 00:08:52,110 --> 00:08:54,540 The first two steps for this is aluminium. 94 00:08:54,540 --> 00:09:03,240 They're doing scattering off of aluminium, I guess, in this country and the wavelength is known extremely precisely in this setup. 95 00:09:03,390 --> 00:09:11,030 This is done with a typical X-ray tube and you only have six digits of precision as to how how precisely they know the wavelength and 96 00:09:11,040 --> 00:09:18,419 remember the reason they know their wavelength so precisely is because this is an electronic transition between two iron states in an atom. 97 00:09:18,420 --> 00:09:21,899 It's an electron falling down from one eigen state to another eigen state. 98 00:09:21,900 --> 00:09:25,230 So the the energies of the eigen states are very, very precisely defined. 99 00:09:26,370 --> 00:09:27,179 So so you know, 100 00:09:27,180 --> 00:09:34,740 the wavelength with very high precision then it you know you get this data all these peaks as a function of of scattering angle to theta. 101 00:09:35,040 --> 00:09:43,200 And fortunately in this particular picture they've actually measured the angles for us 38.43 degrees, 44.6, seven degrees and so forth. 102 00:09:43,410 --> 00:09:48,630 And I've also labelled the peaks with letters so we can keep track of them peak A, peak B peaks and so forth. 103 00:09:49,740 --> 00:09:55,800 Just one hint that if you're ever given a powder diffraction pattern and you have to measure the angles yourself, 104 00:09:55,980 --> 00:10:02,280 it will really help a lot if you get the angles very precise. If you get the angles off by a little bit, you can get very confused. 105 00:10:02,280 --> 00:10:07,230 It won't be obvious what the result is supposed to be, so try to measure it as precisely as you can. 106 00:10:08,070 --> 00:10:13,200 For each scattering angle you measure step two angle. 107 00:10:13,320 --> 00:10:20,520 Sorry. Angle. So step two is calculate the lattice plane spacing. 108 00:10:20,520 --> 00:10:34,800 So lattice plane spacing, plane spacing using Bragg's law and that is D equals lambda over two sine theta. 109 00:10:36,060 --> 00:10:43,050 So for each scattering angle, you see that's representing a family of lattice planes with the spacing d equals lambda over two sine theta. 110 00:10:43,320 --> 00:10:46,020 Now you might think it should be and lambda over to sine theta, 111 00:10:46,230 --> 00:10:52,350 but in fact you don't need the end up here because the higher values of end will correspond to different theta is that you will also measure, 112 00:10:52,350 --> 00:10:57,690 so you'll just be over counting if you put an end upstairs. So you just need to keep lambda over to sine theta. 113 00:10:57,690 --> 00:11:02,820 Each angle corresponds to one one lattice plane spacing. 114 00:11:03,090 --> 00:11:06,240 Okay. All right, so step three. 115 00:11:06,780 --> 00:11:13,350 So this is for us, this is sort of not in the real world. We can assume cubic of some sort assume cubic. 116 00:11:13,920 --> 00:11:22,560 It's actually not a bad assumption in the real world too. Meaning simple cubic, simple boxy or FCC. 117 00:11:23,040 --> 00:11:26,189 I have never seen in 25 years of exams. 118 00:11:26,190 --> 00:11:27,870 I have never seen a 30 year exam. 119 00:11:28,050 --> 00:11:34,470 There's asked you to figure out a powder diffraction pattern for anything more complicated than simple cubic beaker FCC. 120 00:11:34,770 --> 00:11:38,999 Those are the only lattices you'll run into on your 30 year exam. That's almost a promise. 121 00:11:39,000 --> 00:11:42,540 I mean, they could do something for the first time, but. But you're pretty. 122 00:11:42,540 --> 00:11:46,290 It's pretty good assumption that this is all you're ever going to run into in the real world. 123 00:11:46,290 --> 00:11:49,859 It's you'll run into things that are more complicated, but it's not a bad thing to start with. 124 00:11:49,860 --> 00:11:54,450 This is an assumption. And if you can't get the data to fit these, then you go on to more complicated possibilities. 125 00:11:54,900 --> 00:12:00,900 All right. Assuming cubic we also have will remember that the lattice plane spacing this 126 00:12:00,900 --> 00:12:06,780 is something we derived corresponding to Miller indices h k l is the lattice 127 00:12:06,780 --> 00:12:11,790 constant a divided by the square root of h squared plus k squared plus l squared 128 00:12:13,140 --> 00:12:18,959 is something we derive I think in the last lecture or maybe the one before. So what does that give us. 129 00:12:18,960 --> 00:12:27,540 That gives us that a squared over D squared is h squared plus K squared plus L squared. 130 00:12:28,080 --> 00:12:33,690 Now we don't know what A is yet. We're going to try to figure it out, but we know a bunch of D's. 131 00:12:33,690 --> 00:12:34,860 So what is this going to tell us? 132 00:12:34,860 --> 00:12:45,149 The ratio of D's are going to be these k's and L's are integers, so the ratio of one over D squared are going to be an integer ratios. 133 00:12:45,150 --> 00:12:51,840 Okay. So we're going to declare this thing, this quantity h group plus case, but elsewhere we're going to call it N and step. 134 00:12:52,170 --> 00:12:56,730 Let's see what up we step up to step four. We're going to look for integer ratios. 135 00:12:58,210 --> 00:13:03,450 Four integer ratios. Ratios of N. 136 00:13:07,400 --> 00:13:15,470 And then once we have the integer ratios of and we will look for selection roles, look for selection roles. 137 00:13:20,880 --> 00:13:32,940 Rules. Rules. Okay, so let's, let's recall from the last lecture what the selection rules were given h can l if we had a simple cubic lattice. 138 00:13:33,660 --> 00:13:39,960 Simple cubic lattice. All h can l are allowed. 139 00:13:40,560 --> 00:13:47,250 All H can now correspond to reciprocal lattice vectors for the simple cubic layout lattice. 140 00:13:47,250 --> 00:13:51,870 So these are all allowed for a basic lattice. 141 00:13:52,230 --> 00:14:04,530 We derive the selection rule that h plus k plus l l must be even must be even for an FCC lattice. 142 00:14:04,950 --> 00:14:21,150 We derive the selection rule that hk l all even or all odd, so we can actually start making a table of the possibilities. 143 00:14:23,130 --> 00:14:33,150 Actually, maybe I'll put the table over here. So over first column we'll put h can l this is the family possible family's last place. 144 00:14:33,150 --> 00:14:39,060 We'll write the number n which is h squared plus k squared plus l squared. 145 00:14:39,450 --> 00:14:44,970 And then we'll write simple cubic boxy and FCC and ask whether they're allowed. 146 00:14:45,450 --> 00:14:49,499 So what's the simple as possible family of last place we can be talking about? 147 00:14:49,500 --> 00:14:59,390 We could be talking about 100. So n a square plus case proposal squared is one simple cubic yes that's allowed for simple cubic all a 148 00:14:59,400 --> 00:15:05,219 squared plus k all h can l are allowed for simple cubic bc it's not allowed because one +00 is odd. 149 00:15:05,220 --> 00:15:12,120 So this is no, the FCC is not allowed because they're not all odd or all even so it's not allowed for FCC. 150 00:15:12,600 --> 00:15:16,680 How about the next simplest 1110? 151 00:15:17,130 --> 00:15:20,610 A square plus l squared is two simple cubic well. 152 00:15:20,610 --> 00:15:27,749 Yes, that's also allowed bc well one plus one plus zero is even one plus one plus zero is two. 153 00:15:27,750 --> 00:15:38,970 So that's allowed. Yes, FCC is not allowed because they're not all odd or all even 111 what l squared is three. 154 00:15:39,270 --> 00:15:46,770 It's allowed for simple cubic for BC. It's not allowed because the sum is odd, but it is allowed for FCC because they're all odd. 155 00:15:47,310 --> 00:15:50,580 Then 200 keep going. 156 00:15:50,580 --> 00:15:54,780 So two squared +00 squared is four. It's allowed for simple cubic. 157 00:15:55,110 --> 00:15:59,820 The sum is even so it's allowed here and there all even so it's allowed here. 158 00:16:00,120 --> 00:16:10,140 And you can make up a big table of these things. It's worth doing to keep track of which indices you should observe for which possible lattice type. 159 00:16:10,410 --> 00:16:18,790 Now, from this type of table, you can make a list of the possible integers n that you would see for the different lattice types. 160 00:16:19,010 --> 00:16:30,750 So for simple cubic cubic you get and the possible ends you get are one, two, three, four, five, six, eight. 161 00:16:31,470 --> 00:16:41,290 So what happened to seven. So all the possible a's case ls are allowed, but you'll discover if you try there's no h can l that if you square them, 162 00:16:41,310 --> 00:16:45,950 take eight squared plus k squared plus l squared you'll get seven. Just can't find integers. 163 00:16:45,960 --> 00:16:51,870 It's sort of a number theory type of result that you just can't find three integers that when squared and added together give you seven. 164 00:16:52,020 --> 00:17:05,219 So seven is missing and so forth. And I think the next one that's missing is 15 for BC, for BC and is two, four, six, eight, so forth and so on. 165 00:17:05,220 --> 00:17:10,080 I think the first one that's missing is 28. Actually, FCC is the most interesting one. 166 00:17:10,500 --> 00:17:20,740 FCC, the series is an equals three, three, four, eight, 11, 12, 16, 16 and so forth. 167 00:17:20,810 --> 00:17:23,160 Actually, I think I wrote these all down already. Yeah. 168 00:17:23,160 --> 00:17:30,180 So on this on this slide, so here's exactly building that whole table again, we wrote down the first four elements of this table. 169 00:17:30,360 --> 00:17:34,530 Here's the ends. A square was case growth was L squared. One, two, three, four, five, six. 170 00:17:34,770 --> 00:17:38,820 When you get to seven, there's no set of Miller indices that when squared together gives you seven. 171 00:17:40,500 --> 00:17:46,200 And you look at FCC and the possible the possible indices that give you that are allowed for FCC. 172 00:17:46,200 --> 00:17:51,570 The first the first one is 111. Those are all odd that that gives you a total of three. 173 00:17:51,840 --> 00:17:57,840 The next one that's allowed is 200. Those are all even that gives you two squared +00 squared is four. 174 00:17:57,870 --> 00:18:04,260 That's allowed. The next one that's allowed is 220. All even two squared plus two squared plus zero squared is eight. 175 00:18:04,500 --> 00:18:09,690 The next one that's allowed is 311. All odd that gives you 11 and so forth. 176 00:18:09,690 --> 00:18:13,590 So these are the series that we want to want to look for. 177 00:18:14,550 --> 00:18:18,330 So actually let's do that for this aluminium data. Oh, and here's, here's. 178 00:18:18,420 --> 00:18:22,290 A series written out. One, two, three, four, five, six, eight, nine. 179 00:18:22,530 --> 00:18:29,520 Missing seven, 15 and 23. I I'll even integers excluding 28, 60 and so forth. 180 00:18:29,640 --> 00:18:34,620 Actually, it's not a coincidence. The 28 happens to be four times seven and 60 happens to be four times 15. 181 00:18:34,630 --> 00:18:42,960 You can convince yourself why that's true. And then FCC is three, four, eight, 11, 12 and and and so forth. 182 00:18:42,990 --> 00:18:48,930 Okay, so here's the data again. Let's go through this procedure, all the steps, one by one. 183 00:18:49,110 --> 00:18:53,250 So here we measured all of the the angles are someone measured it for us here. 184 00:18:53,300 --> 00:18:56,670 It's very nice of them. So we make a table of all these angles. 185 00:18:56,670 --> 00:19:00,060 We calculate D equals lambda over to sine theta. 186 00:19:00,600 --> 00:19:04,770 So here is the lambda over to sine theta for all of these scattering peaks. 187 00:19:05,310 --> 00:19:12,210 Then we have this statement that one or a over eight squared over squared is squared, plus K squared plus L squared. 188 00:19:12,420 --> 00:19:16,460 And we want to find integer ratios of one over dx squared. 189 00:19:16,470 --> 00:19:17,310 So how do we do that? 190 00:19:17,580 --> 00:19:28,250 Well, let's declare this number here 2.3405 Angstroms we'll call it this of a and we'll make a table of this of a squared over dx squared where d is, 191 00:19:28,250 --> 00:19:37,050 is all of these possible values of D. So the first slot is by definition 12.3 squared over 2.3 squared is one. 192 00:19:37,380 --> 00:19:42,540 But the second 12.3 squared over 2.02 squared is 1.33 and so forth and so on. 193 00:19:42,540 --> 00:19:46,739 We get this in this table here. Those aren't integers, but they're pretty close to integers. 194 00:19:46,740 --> 00:19:51,060 If you multiply it by three, you get a set of things that are really, really close to integers, 195 00:19:51,360 --> 00:20:01,710 and you'll see that that pattern is really three, four, eight, 11, 12, 16, 1920, which is the FCC series three, four, eight, 11, 12, 16, 1920. 196 00:20:02,040 --> 00:20:12,870 So, so we've concluded from this that the the aluminium, the aluminium scattering pattern we found is corresponds to an FCC lattice. 197 00:20:13,110 --> 00:20:17,309 We can actually go on a little bit further to calculate lattice constants. 198 00:20:17,310 --> 00:20:29,760 This might be step five, calculate lattice constant the size of the units L constant a which would be d times the square root of k squared 199 00:20:30,150 --> 00:20:35,309 plus l squared plus h squared because I did that the wrong order e squared plus case proposal squared usually. 200 00:20:35,310 --> 00:20:39,629 All right, same thing. And if we do that there, 201 00:20:39,630 --> 00:20:43,590 the Miller indices have written down for their for the peaks and here's the 202 00:20:43,590 --> 00:20:47,669 A's and they're all pretty close to the same to about three or four digits. 203 00:20:47,670 --> 00:20:53,910 They're not exactly the same. So there's probably some error in the measurement of the angles or something like that has gone wrong. 204 00:20:54,150 --> 00:20:59,970 But within four digits of accuracy, we've measured the lattice constant, a four for aluminium. 205 00:21:00,240 --> 00:21:08,280 Okay, so that's generally how it works. Now when you get good at this, you don't even have to really do this whole calculation. 206 00:21:08,280 --> 00:21:12,120 You can sort of look at the pattern and have a pretty good idea what it is. 207 00:21:12,450 --> 00:21:15,599 So this oh, there's aluminium there. 208 00:21:15,600 --> 00:21:19,020 There's the Miller Indices labelled appropriately. 209 00:21:19,650 --> 00:21:28,290 So I'm going to show you a pattern. And without actually doing any calculation, we can tell what the lattice type is. 210 00:21:28,290 --> 00:21:32,220 Now, there's only three possibilities. If you give me a reason, just give me a reason. 211 00:21:32,460 --> 00:21:36,780 If it's simple cubic, what's the reason? Sound very good. 212 00:21:36,780 --> 00:21:40,830 All right, so that's a so No. Seven. That's a so that one's years. 213 00:21:41,550 --> 00:21:50,370 So you can see here that the first peak so that the spacing of the peaks is not completely uniform and that's because of the sine theta factor. 214 00:21:50,670 --> 00:21:56,460 That sine theta so expresses things out more when you're at low angles than it is that at at high angles. 215 00:21:56,790 --> 00:22:00,239 But, but you can kind of see that one. 216 00:22:00,240 --> 00:22:04,380 The spacing from 1 to 2 isn't so different from 2 to 3, 3 to 4, 4 to 5, 5 to 6. 217 00:22:04,500 --> 00:22:08,700 But then there's a hole where seven is supposed to be, and then 8 to 9, ten, 11, 12. 218 00:22:08,700 --> 00:22:10,829 And you see if they actually there's a hole where 15 is supposed to be. 219 00:22:10,830 --> 00:22:14,400 And if you go all the way up to 23, you'll notice there's a hole where 23 is supposed to be. 220 00:22:14,550 --> 00:22:17,310 And that's the series that you expect for a simple cubic. 221 00:22:17,310 --> 00:22:24,240 So you can just look at this at the scattering pattern for barium Titan eight and know that barium type Nate is a simple cubic lattice. 222 00:22:25,410 --> 00:22:32,549 That's how it works. Pretty cool. All right. It's only very tight. And it is a fairly important material for the Optoelectronics industry. 223 00:22:32,550 --> 00:22:37,230 It's used for various things. Now, there's more information in this. 224 00:22:38,040 --> 00:22:42,599 There is it. There's more information in this scattering pattern than we've used so far. 225 00:22:42,600 --> 00:22:47,880 All we've used is the angles of scattering. We haven't used anything about the intensity of scattering. 226 00:22:48,090 --> 00:22:51,990 And there's a lot of information in the intensity of scattering that we can make use of. 227 00:22:52,350 --> 00:23:00,500 So let's see if we can understand what how much scattering we should get for Miller Indices H Candle. 228 00:23:00,870 --> 00:23:08,130 Well, first of all, there's the structure factor, acid H candle, which gets squared now. 229 00:23:08,550 --> 00:23:14,700 All right, let's even write it out. So the structure factor, remember this s equals s lattice times s basis. 230 00:23:15,690 --> 00:23:24,030 Times s basis. And as Gladys does nothing more than enforce selection rules. 231 00:23:24,240 --> 00:23:32,229 Enforce selection rules. So we've done that. 232 00:23:32,230 --> 00:23:35,680 So that's not going to be interesting for us as a basis. 233 00:23:35,980 --> 00:23:39,879 Well, there's only one atom in this basis because it's just one type of atom. 234 00:23:39,880 --> 00:23:45,310 A single, single atom in the basis is just a pure FCC lattice with no, no interesting basis. 235 00:23:45,550 --> 00:23:50,890 So all you get is the the form factor for aluminium and this form factor for aluminium 236 00:23:51,070 --> 00:24:00,460 decays decays with increasing with increasing increasing g as we mentioned last time, 237 00:24:00,670 --> 00:24:06,190 or increasing angle or increased increase theta. 238 00:24:09,010 --> 00:24:14,700 So we expect that the total scattering is going to drop slowly as a function of increased scattering angle. 239 00:24:15,070 --> 00:24:18,970 But there's actually that's not all that contributes to the the intensity. 240 00:24:19,180 --> 00:24:27,100 There's two other factors which contribute to the intensity of first is the probability, probability of alignment. 241 00:24:30,480 --> 00:24:36,480 So this is the probability that a crystal light will align in just the right way in order to get scattering. 242 00:24:36,660 --> 00:24:42,030 It will come back to that in a moment. And the last factor is known as the Lorenz factor. 243 00:24:42,540 --> 00:24:45,690 LORENZ Or sometimes. LORENZ Polarisation factor. 244 00:24:46,260 --> 00:24:54,540 Polarisation factor, which is really a geometric factor. 245 00:24:54,540 --> 00:24:56,880 We're not going to say too much about it, but I'll show you what it looks like. 246 00:24:57,150 --> 00:25:05,219 So this function is a function which varies fairly rapidly as a function of angle, but then when you add in intermediate angles, 247 00:25:05,220 --> 00:25:11,880 it's fairly flat between around 60 and 140, and then it goes back up eventually at around 140, it starts going back up. 248 00:25:12,180 --> 00:25:17,490 It's the Lorenz polarisation factor. It's really a feature of how you set up your experiment. 249 00:25:17,700 --> 00:25:24,010 And so if you're an experimentalist, you will know what this factor is in advance before you do any sort of wave, 250 00:25:24,240 --> 00:25:25,440 before you do any sort of measurement. 251 00:25:25,680 --> 00:25:33,600 Now, there's a there's sort of a glitch here, which is that sometimes when people present you with x ray patterns like this one, 252 00:25:33,840 --> 00:25:38,040 they'll have already divided by the Lorenz polarisation factor here. 253 00:25:38,040 --> 00:25:41,250 And other times they will not have divided by the range polarisation factor. 254 00:25:41,430 --> 00:25:45,120 So really, if someone shows you data like this, you should ask Is that raw data? 255 00:25:45,120 --> 00:25:48,480 Or have you divide it out by this Lorenz polarisation factor already? 256 00:25:48,690 --> 00:25:55,800 And embarrassingly enough, on many exams they'll ask you a question and they won't tell you whether they've divided by this or not. 257 00:25:55,830 --> 00:26:01,980 So if you want to be safe, you should say you should have told me whether you divide it by this factor or not, I'm assuming whatever. 258 00:26:02,310 --> 00:26:06,150 So anyway, so that's that's this factor. 259 00:26:06,360 --> 00:26:11,460 And it also for most angles. So here we're only scattering up to about 120 degrees here. 260 00:26:11,760 --> 00:26:18,150 So this so this factor here is decaying as a function of angle up to 120 degrees. 261 00:26:18,330 --> 00:26:24,750 This factor here is also decaying as a function of angle. So we'd sort of naively guess that we should always decay as a function of angle. 262 00:26:24,750 --> 00:26:29,790 As you increase the angle and and more or less the scattering amplitude is decaying is a function of angle. 263 00:26:30,030 --> 00:26:33,600 But we haven't looked at this piece here. Probability of alignment. 264 00:26:33,930 --> 00:26:40,229 Well, you might think to yourself, you know, all the crystal lights are aligned completely randomly, so that that factor should be trivial. 265 00:26:40,230 --> 00:26:43,260 It should be just one. But think about this for a second. 266 00:26:44,220 --> 00:26:47,400 You remember when we talked about families of lattice planes. 267 00:26:47,640 --> 00:26:53,100 If we're thinking about a lattice plane spacing, which is associated with the one one, one family of lattice planes, 268 00:26:53,310 --> 00:26:59,430 it could have been the 111 bit family of large planes or the one one bar one or the one bar one one or the one by one bar one. 269 00:27:00,030 --> 00:27:07,470 I mean, there's eight possibilities, which would all give you exactly the same lattice plane spacing that you can scatter off of. 270 00:27:07,830 --> 00:27:17,520 So in fact, this probability of alignment is actually the multiplicity of a scale. 271 00:27:19,350 --> 00:27:24,179 So if we go back to this table here to see where yeah. 272 00:27:24,180 --> 00:27:26,010 Add the multiplicity on to this table. 273 00:27:26,310 --> 00:27:33,480 If we're thinking about the 100 and the Miller indices, there's six possible directions which would present the same lattice. 274 00:27:33,480 --> 00:27:37,290 Plane spacing is 100, the six possible axes of the cube. 275 00:27:37,620 --> 00:27:45,689 But if we're looking at the 110, there would be 12 different phases for 12 different faith ways you could face the cube, 276 00:27:45,690 --> 00:27:54,570 that you would present the same lattice plane spacing. And someone wanted a chocolate bar for realising that 3 to 1 has a multiplicity of 48. 277 00:27:54,960 --> 00:28:01,320 So these are the factors that we want to keep track of if we want to understand the intensity of the scattering. 278 00:28:01,320 --> 00:28:04,560 Now let's look at this. 279 00:28:05,490 --> 00:28:08,370 Let's look at two peaks that are actually fairly close to each other, an angle. 280 00:28:08,370 --> 00:28:11,580 Why do I want to look at two things that are fairly close to each other an angle? 281 00:28:11,850 --> 00:28:19,200 Well, if you both F and L are decaying kind of slowly as a function of angle. 282 00:28:19,410 --> 00:28:28,230 So here, if we're take if we take angles somewhere in the middle, you know, around 100, 120, then then this thing is pretty flat. 283 00:28:28,380 --> 00:28:32,130 This thing is decaying only slowly, and we can only worry about the multiplicity. 284 00:28:32,400 --> 00:28:37,110 So let's take these two peaks here. Three, one, one and two, two, two, three, one, one and two, two, two. 285 00:28:37,500 --> 00:28:40,530 They're they they have these F's and L's in them. 286 00:28:40,530 --> 00:28:45,870 But an L are pretty much the same because we're scattering at about the same angle for three, one, one and two, two, two. 287 00:28:45,870 --> 00:28:51,900 Just a slight difference in the angle. But the multiplicity is let's back up to the multiplicity here. 288 00:28:52,860 --> 00:28:59,700 311 has a where is it. 311 has a multiplicity of 24 where a two, two, two has a multiplicity of eight. 289 00:29:00,060 --> 00:29:06,930 So we would guess at the peak, four, three, one, one should be three times higher than the peak for eight and indeed the peak four, 290 00:29:06,930 --> 00:29:11,610 three, one one is pretty close to three times higher than the peak for 2 to 2. 291 00:29:12,090 --> 00:29:15,750 Okay. So that's how the multiplicity is get in the game as well. 292 00:29:16,320 --> 00:29:23,520 Okay. So these intensities of scattering can actually be very useful for analysing data as well. 293 00:29:23,520 --> 00:29:28,470 I'm going to show you a sort of artificial example of where this might be useful. 294 00:29:28,790 --> 00:29:34,339 So here is some fairly bad data for a taken on iron. 295 00:29:34,340 --> 00:29:38,960 That was bad for a couple of reasons. The first reason is because the peaks are pretty broad. 296 00:29:39,200 --> 00:29:42,319 The second reason is because you only see three peaks with three peaks. 297 00:29:42,320 --> 00:29:45,170 It's pretty hard to tell which series you're talking about here. 298 00:29:45,170 --> 00:29:49,370 You can't count out to the seventh and see if the seventh is missing because you only have three peaks. 299 00:29:49,760 --> 00:29:56,239 So this is going to be a little bit difficult, but we have the amplitudes of the scattering and that actually might be might be helpful. 300 00:29:56,240 --> 00:30:05,690 So we'll see if we can we can make use of that. So we go through the same exercise of measuring the the angles, calculate the latest plane spacing, 301 00:30:05,990 --> 00:30:11,870 take the ratio of the first lattice plane spacing to the various last plane spacing da2 302 00:30:11,870 --> 00:30:18,770 .03 squared over 1.4 squared is two is 22.13 squared over 1.17 squared is about three. 303 00:30:19,100 --> 00:30:25,819 We realise those are in the integer ratios of one, two and three. So those could be two possibilities. 304 00:30:25,820 --> 00:30:32,540 Either it's simple cubic and then these scattering peaks correspond to 100110 and 111, 305 00:30:32,750 --> 00:30:41,120 meaning this integer and a squared plus k squared plus l squared is one, two or three or it could be and is two, four and six. 306 00:30:41,120 --> 00:30:48,050 Those would still be in the ratio of one, two and three, but they would correspond to Miller Indices of 110200 and 211, 307 00:30:48,410 --> 00:30:51,770 which when added squared and added up, give you two, four and six. 308 00:30:51,980 --> 00:30:55,160 So we don't know which one it is just by looking at this data. 309 00:30:56,450 --> 00:31:06,469 So what do we do? Well, there's a couple of approaches we could take. One approach is that we could try calculating the the lattice constant. 310 00:31:06,470 --> 00:31:13,400 A So if we calculated that we could assume simple cubic calculate the lattice constant and we 311 00:31:13,400 --> 00:31:18,260 would get d times square root of a square plus k squared plus l squared gives us 2.03 angstroms. 312 00:31:18,480 --> 00:31:24,260 We did the same thing for BC. We'd get something that square root of two bigger because we're multiplying all the ends by two. 313 00:31:24,290 --> 00:31:28,459 So this thing inside the square root is multiplied by two overall. 314 00:31:28,460 --> 00:31:31,510 So instead of getting 2.3, we get 2.86 OC. 315 00:31:31,670 --> 00:31:36,950 So we have a different lattice plane, a different size of the, of the unit. 316 00:31:36,960 --> 00:31:40,010 So conventional units l for a BC case. 317 00:31:40,370 --> 00:31:42,409 Now why does that help us? 318 00:31:42,410 --> 00:31:48,590 Because we don't know what the lattice constant is for iron, but it does help us because we could try calculating the atomic density. 319 00:31:49,660 --> 00:31:58,059 For the simple Cuba case, we would have one atom per 2.03 angstroms cubed, whereas for a BBC it's two atoms. 320 00:31:58,060 --> 00:32:03,010 Two atoms in the conventional unit cell per 2.86 angstroms cubed. 321 00:32:03,010 --> 00:32:06,160 And those densities differ from each other by a factor of square root of two. 322 00:32:06,460 --> 00:32:10,930 So if we knew the atomic density of ion, we could tell which one it is, so we'd be done. 323 00:32:11,650 --> 00:32:15,160 But suppose we don't happen to know the atomic density of ion. So what do we do then? 324 00:32:15,250 --> 00:32:23,610 Okay. There are other. Other things we could invoke. We can look at the scattering amplitudes, which was what I was leading up to now, remember. 325 00:32:23,670 --> 00:32:28,410 So at this at this scattering angle, the Lorentz factor is decreasing. 326 00:32:28,770 --> 00:32:32,310 The form factor is always decreasing as a function of increased angle. 327 00:32:32,520 --> 00:32:38,400 So you would sort of naively expect that A should be bigger than B should be bigger than C, but it's not C is bigger. 328 00:32:38,640 --> 00:32:45,660 The only thing that could possibly explain that is if the multiplicity of the peak C is bigger than the multiplicity of B. 329 00:32:46,260 --> 00:32:50,740 So if you look at the simple cubic, the simple cubic, we identify the first peak is 100. 330 00:32:50,760 --> 00:32:54,020 The second peak is 110 and the third peak as 111. 331 00:32:54,030 --> 00:33:00,660 The multiplicity of B is bigger than multiplicity of C. So there's no reason you would ever get the C peak to be bigger than B peak. 332 00:33:01,020 --> 00:33:05,579 However, for BC, the multiplicity of the C peak to one one is 24 ways. 333 00:33:05,580 --> 00:33:10,620 The multiplicity of peak is 200, so c should actually be bigger than B. 334 00:33:11,040 --> 00:33:14,820 Now if you just look at the multiplicity as you would expect a factor of four, 335 00:33:14,940 --> 00:33:22,470 that C should be four times bigger than B and it's not four times bigger than B, it's only about two, maybe two and a bit bigger times bigger than B. 336 00:33:22,740 --> 00:33:26,969 But the reason it's not a four, four times bigger is because F is dropping, 337 00:33:26,970 --> 00:33:30,360 the form factor is dropping and Lawrence Factor is dropping also at the same time. 338 00:33:30,570 --> 00:33:34,710 So it's competing with this decreasing effect from these other two terms. 339 00:33:34,980 --> 00:33:41,040 But at any rate, just by looking at this data, we can we can tell just from the amplitudes that this must be BC. 340 00:33:41,880 --> 00:33:48,360 Of course, we also know that iron is not simple cubic because there's only one element that takes a simple cubic lattice, 341 00:33:48,360 --> 00:33:53,880 and that's polonium and iron isn't polonium. And so that does it also in sort of a cheating way to go about it. 342 00:33:54,990 --> 00:33:58,830 All right. So let's do one more example. 343 00:33:59,970 --> 00:34:05,940 This is an example of neutron scattering. Neutron scattering, very similar to X-ray scattering. 344 00:34:06,120 --> 00:34:09,540 But it's a little simpler because the form factor is just a constant. 345 00:34:09,630 --> 00:34:16,440 It's just a nuclear scattering length. It's not a function of g. So what's the latest type? 346 00:34:18,190 --> 00:34:22,350 Oh, my gosh. Oh, yes, yes. 347 00:34:22,780 --> 00:34:25,620 Not so good at this. So. Yes. 348 00:34:25,630 --> 00:34:35,260 So it's so you can tell it's it's this is FCC without doing any calculation because of the pattern that you can sort of imagine if this is three, 349 00:34:35,260 --> 00:34:41,650 this is four, then there's a big spacing to eight, then a little spacing to 11, 12, close together. 350 00:34:41,830 --> 00:34:45,970 So you can kind of see that the spacing is the right spacing for an FCC lattice. 351 00:34:47,170 --> 00:34:54,700 Okay. So but if you want to go through the whole the whole the whole story, we can go through the whole story carefully, measure the angles, 352 00:34:55,180 --> 00:35:05,260 calculate the lattice plane spacings, take the ratios of the one over the one over the square of the last plane spacings you get one, 1.3, 2.6. 353 00:35:05,410 --> 00:35:12,790 We really multiply these by three. We realise these are integer ratios, three, four, pretty close to eight, pretty close to 11 actually. 354 00:35:12,790 --> 00:35:17,740 The data isn't so great and if you back up well you'll realise that these peaks are pretty broad. 355 00:35:17,980 --> 00:35:21,130 They're not really that accurately resolved. 356 00:35:21,340 --> 00:35:24,610 It's not the greatest data. This was data taken in 1959. 357 00:35:24,610 --> 00:35:28,950 I mean, modern, modern data is much better. But but okay, 358 00:35:28,980 --> 00:35:40,270 it's you can definitely see that it's going to be FCC and you can also label the the Miller Indices and get an estimate of the lattice constant. 359 00:35:40,270 --> 00:35:45,910 Okay. So the lattice constant, maybe you don't know it within a few percent, but you have a pretty good estimate of what it is. 360 00:35:46,330 --> 00:35:51,940 But in fact, what we have here and we can write out the multiplicity is we can label the peaks as well. 361 00:35:52,030 --> 00:35:57,879 Actually, I noticed that by doing this you'll notice that there's you would have predicted a slight peak here, 362 00:35:57,880 --> 00:36:00,910 a peak of 40 zero peak here where the shoulder is. 363 00:36:00,910 --> 00:36:06,640 It's not there you. But if you kind of look at it carefully, you see that there's kind of a weak shoulder. 364 00:36:06,940 --> 00:36:11,380 You can imagine that it's just a very small peak that's sitting there now. 365 00:36:12,480 --> 00:36:17,100 So this tells us where where the peaks are. But we there's more information that we would like to get. 366 00:36:17,310 --> 00:36:24,780 We would like to know what the basis is. So we know that titanium carbide titanium carbide is F.C.C. 367 00:36:25,020 --> 00:36:32,130 And it has to have a basis with the basis that it has two elements in it, with the basis of two atoms. 368 00:36:32,640 --> 00:36:38,000 Of two atoms. And we'd like to know what is the form of the basis. 369 00:36:38,010 --> 00:36:42,040 In other words, where do you put the titanium? Where do you put the carbon in the unit cell? 370 00:36:42,510 --> 00:36:51,299 So can we figure that out? Well, okay, so arbitrarily we can we can always assign titanium to the position at position 000. 371 00:36:51,300 --> 00:36:55,230 And the unit cell will just define the titanium position to be 000. 372 00:36:55,530 --> 00:37:01,080 But then carbon we'll put at position u, v w which we don't know. 373 00:37:01,440 --> 00:37:05,580 Incidentally, I should have mentioned Titanium Carbide is actually a a really important material. 374 00:37:05,590 --> 00:37:09,420 Does anyone know? Here's another one. Anyone know why? Titanium Carbide is really important? 375 00:37:12,070 --> 00:37:16,480 Use it for what? Yeah, yeah. Anything that needs to be really hard then. 376 00:37:16,630 --> 00:37:21,670 Yeah. Okay. So. So Titanium Carbide is one of the hardest materials out there. 377 00:37:21,670 --> 00:37:25,360 Short of diamond, I think there's only one or two others that are as hard as titanium carbide. 378 00:37:25,360 --> 00:37:29,319 It's easy to, um. And it's easier to make titanium carbide. 379 00:37:29,320 --> 00:37:36,940 It's not as expensive a diamond. It's so whenever you need anything that needs to be very tough, it's very frequently used for things like tools. 380 00:37:36,940 --> 00:37:40,300 If you need a saw or a drill bit, that's going to cut through something very hard. 381 00:37:40,510 --> 00:37:46,239 It's very frequently titanium carbide. So that's why they did this experiment way back in in 1959, 382 00:37:46,240 --> 00:37:50,770 because it was an interesting material even back in 1959, and they didn't even know its structure. 383 00:37:51,220 --> 00:37:57,790 So. Okay, so I think they did maybe they did know this structure from something else. 384 00:37:57,790 --> 00:38:04,779 I don't I'm not sure, but I don't I don't think they knew it. So anyway, we don't know where the carbon is in the, in itself. 385 00:38:04,780 --> 00:38:10,750 So we're going to see if we can use this intensity data from these peaks to figure out where in the units all it is. 386 00:38:11,590 --> 00:38:20,050 So generally the piece we're going to be interested in is the basis structure factor, which is which ends up getting squared. 387 00:38:20,800 --> 00:38:28,630 And that is, well, maybe I'll write this out here first as basis equals sum over alpha in the units l 388 00:38:28,750 --> 00:38:38,980 and units l e to the i g dot are alpha times b alpha for the two atoms in the cell. 389 00:38:39,310 --> 00:38:50,500 So space is squared here will be v titanium plus b carbon e to that will write it as either the two pi i h k l 390 00:38:51,010 --> 00:38:59,590 dotted into u v w and then you take that thing and you square it and that will give you the basis structure factor. 391 00:38:59,860 --> 00:39:08,470 Now if you knew what these nuclear scattering lengths were, b titanium in b b carbon, you might have a fighting chance of figuring out what you were. 392 00:39:09,610 --> 00:39:14,620 But suppose we didn't know that. Can we still make any progress? Well, we can make a little bit of progress. 393 00:39:14,620 --> 00:39:24,130 If I give you a hint. This is a kind of hint. You get an exam. The kind of hit you get on an exam is that F.C.C. with two atom basis. 394 00:39:25,210 --> 00:39:28,960 Atom basis. There's only two common ones. 395 00:39:28,960 --> 00:39:33,130 Only two common ones. Common possibilities. 396 00:39:38,400 --> 00:39:42,450 In fact, I don't even know of any cases that are not one of these two. 397 00:39:42,480 --> 00:39:45,480 There may be even a theorem that you can't have anything else. I'm not sure about that. 398 00:39:45,480 --> 00:39:49,590 So don't quote me. But anyway, the two possibilities we've both we've seen them both before. 399 00:39:49,890 --> 00:39:54,719 There's a so-called zinc blend structure, which is the same as the gallium arsenide structure, 400 00:39:54,720 --> 00:40:02,220 which we talked about in class, which puts you BW at the position of one quarter, one quarter, one quarter. 401 00:40:04,500 --> 00:40:14,850 And the other possibility we also discussed is the sodium chloride structure which has you've w at one half, one half, one half. 402 00:40:17,520 --> 00:40:21,630 So can we figure out which one of these two possibilities it is. 403 00:40:23,160 --> 00:40:31,260 Okay. Well, let's see if we can do it. So let's try first try one, try zinc blend structure. 404 00:40:32,130 --> 00:40:35,400 Okay. So in this case s basis. 405 00:40:37,480 --> 00:40:48,730 Squared equals well, we have b titanium plus B carbon either the two pi i h k l and then one quarter of one quarter, 406 00:40:48,730 --> 00:40:55,209 one quarter, which we can also write this factor here. 407 00:40:55,210 --> 00:41:01,600 This exponential factor here is also equivalent to E2 the pi over two times I 408 00:41:01,900 --> 00:41:08,920 times h plus k plus l or equivalently this would be I to the h plus k puzzle. 409 00:41:10,720 --> 00:41:31,450 So I'm out of room here. We're here so we have s basis squared equals b titanium plus v carbon times I to the h plus k plus l squared. 410 00:41:32,020 --> 00:41:36,520 Okay. And what is that as a function of H canal? Well, there's three possibilities. 411 00:41:37,180 --> 00:41:45,970 Case one, I mean, in case A is that H plus k plus l is a multiple of four equals four times an integer n. 412 00:41:47,140 --> 00:41:57,130 So in that case we get SBC squared equals v titanium plus v carbon absolute value squared. 413 00:41:57,940 --> 00:42:08,290 The second possibility case b e is h plus plus l is still even, but it's not a multiple of four. 414 00:42:08,290 --> 00:42:20,170 So we'll call for n plus two, in which case we get spaces squared equals B titanium minus B carbon squared. 415 00:42:21,430 --> 00:42:27,720 And the third case, Casey. Is H plus k plus l is odd. 416 00:42:29,070 --> 00:42:45,450 Odd in which case s basis squared is B titanium plus or minus i times b carbon squared which is b titanium squared plus b carbon squared. 417 00:42:48,140 --> 00:42:53,510 Good. All right. So with the stare at that for a second. 418 00:42:53,690 --> 00:42:59,149 And what can you conclude from this? Well, no matter what B, titanium and B carbon are, as long as they're real, 419 00:42:59,150 --> 00:43:04,580 which they are the largest of the three possibilities is always either case or case. 420 00:43:04,580 --> 00:43:10,550 B, if they be titanium, be carbon to have the same sine in case A is the largest of the three possibilities 421 00:43:10,730 --> 00:43:14,300 if they have opposite sign in case B is the largest of three possibilities. 422 00:43:14,570 --> 00:43:19,070 So the largest peaks should definitely have even H plus K plus l. 423 00:43:19,370 --> 00:43:26,990 Now let's look at this data and you'll see H plus K, plus L and you'll notice that. 424 00:43:28,280 --> 00:43:35,740 The highest peaks always have od plus k plus l systematically always there. 425 00:43:35,750 --> 00:43:40,220 So if 111 is high, 311 is high 331 is high, 333 is high. 426 00:43:40,400 --> 00:43:47,900 All the other ones are small are even so this does not agree with the data does not agree but agree. 427 00:43:51,470 --> 00:44:02,000 Well, we can try something else. We can try the sodium chloride structure, so try sodium chloride, in which case we have. 428 00:44:02,840 --> 00:44:07,160 Well, I wrote it over here. Somewhere over there is one half, one half, one half. 429 00:44:07,460 --> 00:44:15,860 So s basis squared is then b titanium plus. 430 00:44:16,400 --> 00:44:27,350 B carbon times e to the to pi i h k now dotted into one half, one half, one half, and then all squared. 431 00:44:28,620 --> 00:44:40,920 And that we can be right as v titanium plus v carbon times minus one to the H plus k plus l all squared. 432 00:44:41,490 --> 00:44:50,430 So there's two cases we can have. Case one case or case a is h plus k plus l is odd. 433 00:44:51,030 --> 00:44:56,220 In which case we have B titanium minus v carbon squared is the answer. 434 00:44:57,300 --> 00:45:12,150 Whereas case B case v is h plus k plus l equals, even in which case we have b titanium plus b carbon squared. 435 00:45:14,660 --> 00:45:18,140 Okay. So now what's which one is largest here? 436 00:45:18,470 --> 00:45:25,440 Well, you can see that if vitamin B carbon have the same sign, then the even will always be larger. 437 00:45:25,460 --> 00:45:29,550 Whereas if they have the opposite sign, then the odd will have larger. 438 00:45:29,570 --> 00:45:33,770 Well, if you look at the data, the H plus Capossela Ott is clearly much larger. 439 00:45:33,950 --> 00:45:46,790 And so that tells us it's it's consistent with this case that if B titanium be titanium has opposite sine it sine of be carbon. 440 00:45:49,510 --> 00:45:54,219 So the large peaks are be titanium minus be carbon squared with be titanium and be carbon having 441 00:45:54,220 --> 00:46:00,550 opposite side and the small peaks are the sum of the two with them having opposite sine as well. 442 00:46:01,070 --> 00:46:04,600 Okay. Everyone happy with that? More or less. 443 00:46:04,850 --> 00:46:07,960 Little bit. Yes, please. Yes. All right. Thank you. 444 00:46:08,350 --> 00:46:11,950 All right. Good. So let's see. 445 00:46:11,950 --> 00:46:16,690 So here's the summary. Summary slide. So we conclude it has to be sodium chloride structure. 446 00:46:18,010 --> 00:46:21,639 Let's see. So we can actually go on and discuss. 447 00:46:21,640 --> 00:46:25,150 Oh, here. Let's discuss how you make neutrons for a second. So. 448 00:46:26,420 --> 00:46:32,780 We discussed how you make how you make ashtrays in the last in the last last lecture, I think. 449 00:46:33,080 --> 00:46:38,180 But we haven't discussed how you make neutrons. This is a neutron facility escalation. 450 00:46:38,180 --> 00:46:44,000 Neutron source, also right down the road next to the synchrotron source, rather large and expensive apparatus. 451 00:46:44,690 --> 00:46:48,140 What we need is we need neutrons with a wavelength on the order of one angstrom. 452 00:46:49,310 --> 00:46:56,540 How do we get that? Well, if the wavelength is one angstrom, the momentum is two pi h bar over lambda. 453 00:46:56,900 --> 00:47:09,050 And from that we can calculate that the energy we need is p squared over two m equals approximately 80 million electron volts or about 800 kelvin. 454 00:47:09,150 --> 00:47:12,770 You put in the appropriate factor Botswana's constant to make energy a temperature. 455 00:47:13,100 --> 00:47:18,530 And this might sound to you like it's hot, but in fact, 800 Kelvin is really, really cold for neutrons. 456 00:47:18,740 --> 00:47:21,980 Why is that? Well, how do you get the neutrons in the first place? 457 00:47:23,720 --> 00:47:27,710 Making neutrons make neutrons. 458 00:47:28,250 --> 00:47:31,790 Well, back in the old days, they didn't have neutrons. 459 00:47:32,060 --> 00:47:36,260 And then along came the the Second World War and the Atomic Bomb Project. 460 00:47:36,410 --> 00:47:42,830 And after the atomic bomb project, they had nuclear reactors. And nuclear reactors have neutrons as a by-product. 461 00:47:42,890 --> 00:47:48,170 So possibly one is a by-product of vision. 462 00:47:51,470 --> 00:47:56,120 And you can imagine that when a neutron comes off of a of a nucleus and some fission process, 463 00:47:56,300 --> 00:48:01,040 it's coming out with millions of electron volts rather than miller electron volts. 464 00:48:01,040 --> 00:48:07,910 So it's extremely, extremely energetic. So this 800 Kelvin is extremely low energy. 465 00:48:08,150 --> 00:48:14,090 There's a more favoured method for making because people don't like to have atomic reactors in their backyard these days. 466 00:48:14,840 --> 00:48:21,020 There's a more favourite method for making neutrons and in fact it's more efficient method as well, which is known as spoliation. 467 00:48:22,640 --> 00:48:26,480 And that's what this source is. This neutron source is a separation source. 468 00:48:26,780 --> 00:48:33,409 The idea of a separation source is not unlike the idea of an X-ray tube, where you take usually a proton, 469 00:48:33,410 --> 00:48:41,690 a proton, and you accelerate it to about a giga electron volt and you hit it onto a target target. 470 00:48:42,950 --> 00:48:47,600 And the idea is to smash some nucleus, some nuclei, and kick off some neutrons. 471 00:48:48,170 --> 00:48:57,110 Now, again, since you're hitting it with such a high a high energy, you're going to kick off neutrons with some very, very high energy as well. 472 00:48:57,410 --> 00:49:04,160 So whichever method you use to create neutrons, they're coming off with an incredibly high energy and you have to make them cold. 473 00:49:04,430 --> 00:49:13,220 So to make them cold, what you use is you use a moderator and a moderator is basically just a big tank of some substance 474 00:49:13,490 --> 00:49:18,770 where the neutrons can go in the substance and bounce around giving off their energy to the substance. 475 00:49:18,770 --> 00:49:21,920 So frequently people use carbon graphite. 476 00:49:22,250 --> 00:49:27,200 Graphite is carbon graphite, carbon water, heavy water, lots of materials, 477 00:49:27,200 --> 00:49:32,870 anything that the neutrons can bump into and give off their energy to and eventually out. 478 00:49:32,870 --> 00:49:40,430 The other end of this thing you get you get neutrons and you want to kill them down until they have about 800 kelvin worth of energy. 479 00:49:40,700 --> 00:49:43,280 Now, once you have the the neutrons coming out, 480 00:49:43,490 --> 00:49:53,330 you need to somehow figure out how to make them a monochromatic monochrome, meaning you just want to get one wavelength. 481 00:49:53,330 --> 00:49:59,190 Remember, that was the first rule. Know your wavelength. So you have to monochrome eight. 482 00:49:59,210 --> 00:50:02,980 So how do you monochrome one way method one is to distract. 483 00:50:04,040 --> 00:50:08,240 So you can use a crystal. It's known we mentioned this in the case of X-rays as well. 484 00:50:08,450 --> 00:50:11,600 Different from a known crystal. From known crystal. 485 00:50:15,380 --> 00:50:21,140 And that sometimes works. But there's another method which is also used, which is very nice for neutrons, 486 00:50:21,380 --> 00:50:29,390 which is a time of flight method, time of flight, which works in the following way. 487 00:50:29,930 --> 00:50:35,240 So you have a beam of neutrons coming in over here, and then you have sort of a window which you can open and close, 488 00:50:35,660 --> 00:50:39,200 open and close whenever you want, and then you have a long spacing. 489 00:50:39,610 --> 00:50:43,730 L From here to here and another window which you can open and close. 490 00:50:44,210 --> 00:50:47,960 So you open up and close the window very quickly to let in a little pulse of neutrons. 491 00:50:48,260 --> 00:50:52,220 And then at some time Delta T later you open up the other window. 492 00:50:52,700 --> 00:51:00,230 So then you know l you know T So if it made it from the first window to the second window in Delta T You know, it's velocity. 493 00:51:00,590 --> 00:51:03,740 So L divided by delta t is its velocity. 494 00:51:03,830 --> 00:51:07,250 If it's no, it's velocity, you know, it's momentum. If you know it's momentum, you know it's wavelength. 495 00:51:07,610 --> 00:51:12,110 So you can select by knowing how by giving it a certain amount of time to get from 496 00:51:12,110 --> 00:51:15,530 the first window to the second window you can select for a particular velocity, 497 00:51:15,530 --> 00:51:19,700 therefore predict particular momentum, therefore a particular wavelength. 498 00:51:20,720 --> 00:51:25,670 One more thing that I do want to mention about neutrons will say maybe just one or two more things about them in the. 499 00:51:25,750 --> 00:51:29,560 Next lecture. But I do want to mention now is one of the reasons people like neutrons. 500 00:51:30,400 --> 00:51:38,460 Is the neutrons actually have a spin. And that enables you to see things that have important where the spin is important. 501 00:51:38,470 --> 00:51:42,730 If you have more spins in one region than another region that neutrons are sensitive to, 502 00:51:42,730 --> 00:51:48,500 that they feel to the local magnetic environment as a potential, whereas photons do not. 503 00:51:48,520 --> 00:51:52,840 They don't care about the local magnetic environment. Neutrons do because the neutrons have some spin. 504 00:51:53,140 --> 00:51:57,250 Okay, we'll stop there and we'll pick up. Finish this off next next lecture.