1 00:00:00,790 --> 00:00:07,320 [Music] 2 00:00:13,060 --> 00:00:09,900 [Applause] 3 00:00:15,220 --> 00:00:13,070 today I'm going to talk about the 4 00:00:16,269 --> 00:00:15,230 compact integrated Raman spectrometer 5 00:00:20,890 --> 00:00:16,279 thank you 6 00:00:22,720 --> 00:00:20,900 and basically this is a picture if we 7 00:00:26,439 --> 00:00:22,730 all know about the Euro Philander and 8 00:00:28,210 --> 00:00:26,449 the configuration that we were given so 9 00:00:31,210 --> 00:00:28,220 we're going to be taking a sample cup 10 00:00:34,600 --> 00:00:31,220 that we are going to be hand handed 11 00:00:37,479 --> 00:00:34,610 taking it into a sample chamber here 12 00:00:40,210 --> 00:00:37,489 where we will analyze this in its 13 00:00:42,970 --> 00:00:40,220 original state we may actually have this 14 00:00:44,229 --> 00:00:42,980 sitting outside in the cold so it had we 15 00:00:47,709 --> 00:00:44,239 get as low as temperature as possible 16 00:00:51,190 --> 00:00:47,719 but we like to look at the structure of 17 00:00:54,340 --> 00:00:51,200 the ice in its native form and we like 18 00:00:56,889 --> 00:00:54,350 to melt that sample and do chemometrics 19 00:00:59,560 --> 00:00:56,899 to look at quantitatively what the salts 20 00:01:01,560 --> 00:00:59,570 and things that are in the sample and 21 00:01:04,180 --> 00:01:01,570 finally we want to desiccate the sample 22 00:01:07,420 --> 00:01:04,190 so that we dry down all the solid 23 00:01:09,910 --> 00:01:07,430 material to the bottom of this clear 24 00:01:13,060 --> 00:01:09,920 bottom sample holder so that we can look 25 00:01:14,820 --> 00:01:13,070 at it with our raman spectrograph over 26 00:01:17,350 --> 00:01:14,830 here's a picture of our spectrograph and 27 00:01:20,560 --> 00:01:17,360 I'll talk a little bit more about this 28 00:01:23,770 --> 00:01:20,570 this is really based upon here a design 29 00:01:26,200 --> 00:01:23,780 we already have that I'll show you later 30 00:01:29,499 --> 00:01:26,210 and basically it's the same sized optics 31 00:01:32,230 --> 00:01:29,509 in this incarnation but this all fits in 32 00:01:34,270 --> 00:01:32,240 Box B but likely to make this a little 33 00:01:38,260 --> 00:01:34,280 smaller as we mature the architecture of 34 00:01:40,870 --> 00:01:38,270 the next two years so so any as I said 35 00:01:43,060 --> 00:01:40,880 the idea is to bring things in in its 36 00:01:45,010 --> 00:01:43,070 native form look things in a solid state 37 00:01:50,710 --> 00:01:45,020 this allows us to look at things like 38 00:01:53,020 --> 00:01:50,720 inclusions in the ice when when ice 39 00:01:56,080 --> 00:01:53,030 crystallizes oftentimes things that are 40 00:01:58,179 --> 00:01:56,090 not ice are excluded from and put in 41 00:02:00,609 --> 00:01:58,189 little grains that you can look at and 42 00:02:03,280 --> 00:02:00,619 identify so you get a benefit of some 43 00:02:05,800 --> 00:02:03,290 concentration by doing that we're 44 00:02:07,450 --> 00:02:05,810 interested in getting some quantitative 45 00:02:09,460 --> 00:02:07,460 idea of what's going on 46 00:02:12,100 --> 00:02:09,470 so by liquefying the sample we're able 47 00:02:14,830 --> 00:02:12,110 to do that and finally by desiccating 48 00:02:17,440 --> 00:02:14,840 the sample by book essentially letting 49 00:02:21,150 --> 00:02:17,450 thaw all the water boil off essentially 50 00:02:23,310 --> 00:02:21,160 at the bottom we'll collect all the same 51 00:02:26,580 --> 00:02:23,320 and hopefully get some concentration in 52 00:02:29,190 --> 00:02:26,590 that mechanism as well we have a 2d 53 00:02:32,090 --> 00:02:29,200 scanner in this architecture which allow 54 00:02:36,150 --> 00:02:32,100 us to scan and target any of the points 55 00:02:39,480 --> 00:02:36,160 throughout that volume so this is the 56 00:02:41,550 --> 00:02:39,490 specs on the instrument it's a 532 green 57 00:02:43,820 --> 00:02:41,560 Rama an instrument that it's been under 58 00:02:46,080 --> 00:02:43,830 development for I think 25 years and 59 00:02:48,180 --> 00:02:46,090 it's we're using a single frequency 60 00:02:52,680 --> 00:02:48,190 laser that has a really good spatial 61 00:02:55,950 --> 00:02:52,690 mode focal spot is 20 microns or smaller 62 00:03:00,060 --> 00:02:55,960 actually and we can vary the power from 63 00:03:02,250 --> 00:03:00,070 3 to 50 millivolts to avoid burning the 64 00:03:05,190 --> 00:03:02,260 sample so we can start low and move high 65 00:03:08,250 --> 00:03:05,200 and do that adaptively with the laser 66 00:03:10,260 --> 00:03:08,260 that we have we use a high F number 67 00:03:12,330 --> 00:03:10,270 laser and I'll talk a little bit about 68 00:03:15,660 --> 00:03:12,340 the fact that this allows us to do a 69 00:03:17,880 --> 00:03:15,670 pencil beam and we use f/2 collection 70 00:03:20,370 --> 00:03:17,890 optics which is I think one of the 71 00:03:22,500 --> 00:03:20,380 lowest F numbers of any Raman instrument 72 00:03:26,040 --> 00:03:22,510 out there to give us the optimal 73 00:03:28,080 --> 00:03:26,050 sensitivity working distance currently 74 00:03:31,350 --> 00:03:28,090 is 25 millimeters we're going to try to 75 00:03:33,480 --> 00:03:31,360 scale that down as we since what the 76 00:03:34,830 --> 00:03:33,490 samples being handled handed to us as 77 00:03:36,990 --> 00:03:34,840 opposed to having the instrument on the 78 00:03:39,900 --> 00:03:37,000 end of a rover arm like it was 79 00:03:42,030 --> 00:03:39,910 originally designed since we have a cup 80 00:03:44,100 --> 00:03:42,040 we don't have to have an inch of working 81 00:03:48,090 --> 00:03:44,110 distance and this will allow us to scale 82 00:03:51,120 --> 00:03:48,100 the architecture proportionally we can 83 00:03:53,160 --> 00:03:51,130 cover from 150 to 4000 wave numbers so 84 00:03:56,190 --> 00:03:53,170 this allows us to cover really low 85 00:03:59,760 --> 00:03:56,200 vibrational modes cover the entire 86 00:04:02,130 --> 00:03:59,770 mineral fingerprint region as well as 87 00:04:05,160 --> 00:04:02,140 the O h and CH stretches that occur 88 00:04:07,800 --> 00:04:05,170 beyond 3000 wave numbers spectral 89 00:04:11,340 --> 00:04:07,810 resolution is just six wave numbers and 90 00:04:13,800 --> 00:04:11,350 we have a signal noise ratio of five or 91 00:04:15,630 --> 00:04:13,810 greater when we're one centimeter away 92 00:04:17,789 --> 00:04:15,640 from best focus so one of the other 93 00:04:20,880 --> 00:04:17,799 features of the architecture is that it 94 00:04:24,600 --> 00:04:20,890 doesn't require you to to autofocus in 95 00:04:26,580 --> 00:04:24,610 any way and we as I said we have we're 96 00:04:29,790 --> 00:04:26,590 looking in one centimeter we're going to 97 00:04:32,400 --> 00:04:29,800 have a spatial resolution with native 98 00:04:33,340 --> 00:04:32,410 spatial resolution with our context 99 00:04:38,770 --> 00:04:33,350 imager 100 00:04:40,360 --> 00:04:38,780 15:04 by 2 mm so one of the reasons to 101 00:04:42,550 --> 00:04:40,370 use green light is if you look at the 102 00:04:45,760 --> 00:04:42,560 absorption of ice and water 103 00:04:48,040 --> 00:04:45,770 5:32 is at the very minimum and other 104 00:04:51,520 --> 00:04:48,050 wavelengths you my choice choose or 105 00:04:56,230 --> 00:04:51,530 something like 7 to 10 times worse 106 00:04:59,430 --> 00:04:56,240 so actually more than that so so Green 107 00:05:03,490 --> 00:04:59,440 is an excellent wavelength to use it is 108 00:05:04,990 --> 00:05:03,500 giving you a lot of people use 785 if 109 00:05:07,630 --> 00:05:05,000 you looked at the number of Raman 110 00:05:09,550 --> 00:05:07,640 spectrometer sold 785 is the wavelength 111 00:05:13,060 --> 00:05:09,560 that people use but rocks don't have 112 00:05:14,680 --> 00:05:13,070 very good run on cross sections so sort 113 00:05:17,290 --> 00:05:14,690 of the runner-up in terms of the pie 114 00:05:19,120 --> 00:05:17,300 chart of Raman instruments sold is green 115 00:05:21,820 --> 00:05:19,130 and those allow you to interrogate 116 00:05:25,360 --> 00:05:21,830 things like minerals with good with good 117 00:05:30,490 --> 00:05:25,370 response so because silicon detectors 118 00:05:33,190 --> 00:05:30,500 cut off at 1100 nanometers by using 532 119 00:05:36,400 --> 00:05:33,200 are able to catch that higher beyond 120 00:05:40,180 --> 00:05:36,410 3000 wave numbers it's very important 121 00:05:42,640 --> 00:05:40,190 for astrobiology applications let's see 122 00:05:45,460 --> 00:05:42,650 we also avoid photo and thermal 123 00:05:48,310 --> 00:05:45,470 degradation by avoiding UV light by 124 00:05:52,810 --> 00:05:48,320 keeping the power low as low as possible 125 00:05:55,300 --> 00:05:52,820 to actually acquire signal and we do 126 00:05:58,300 --> 00:05:55,310 have this issue I'm sure everybody knows 127 00:06:00,160 --> 00:05:58,310 that there's concern over intrinsic 128 00:06:01,930 --> 00:06:00,170 fluorescence laser induced fluorescence 129 00:06:04,690 --> 00:06:01,940 with green light so we're going to talk 130 00:06:06,730 --> 00:06:04,700 about a new technique that we have Carl 131 00:06:12,130 --> 00:06:06,740 Terry shifted excitation to deal with 132 00:06:15,100 --> 00:06:12,140 that problem and so so anyhow this is a 133 00:06:17,920 --> 00:06:15,110 graph of the integration time as a 134 00:06:19,420 --> 00:06:17,930 function of focuses focal distance and 135 00:06:22,030 --> 00:06:19,430 you can imagine this going into your 136 00:06:25,090 --> 00:06:22,040 sample cup which is about a centimeter 137 00:06:27,610 --> 00:06:25,100 deep and what we know is that with dark 138 00:06:29,950 --> 00:06:27,620 pyroxene we're able to maintain a signal 139 00:06:31,600 --> 00:06:29,960 noise ratio of five and that's one of 140 00:06:34,530 --> 00:06:31,610 the weaker Raman scatterers that are 141 00:06:36,880 --> 00:06:34,540 around so we use that as a benchmark 142 00:06:39,220 --> 00:06:36,890 pencil beam we have going into the 143 00:06:41,650 --> 00:06:39,230 sample has f15 which allows us 144 00:06:44,920 --> 00:06:41,660 essentially to be out of focus yet still 145 00:06:46,959 --> 00:06:44,930 be on a small area relatively small spot 146 00:06:49,059 --> 00:06:46,969 somewhere between 15 and 147 00:06:52,359 --> 00:06:49,069 30 microns all the way through the 148 00:06:54,969 --> 00:06:52,369 sample but we use f2 to collect even 149 00:06:56,799 --> 00:06:54,979 though we're out of focus you know when 150 00:06:58,959 --> 00:06:56,809 we're not at best focus over a 151 00:07:04,059 --> 00:06:58,969 centimeter we're still able to see dark 152 00:07:06,069 --> 00:07:04,069 pyroxene so this is the this is an older 153 00:07:11,079 --> 00:07:06,079 incarnation of the instrument called mm 154 00:07:13,479 --> 00:07:11,089 RS mm RS uses this kind of spectrometer 155 00:07:15,789 --> 00:07:13,489 based upon a holographic rating and a 156 00:07:19,329 --> 00:07:15,799 fiber input and this is the probe head 157 00:07:21,459 --> 00:07:19,339 which uses a laser that is contact 158 00:07:23,529 --> 00:07:21,469 bonded and actually doesn't work real 159 00:07:25,959 --> 00:07:23,539 well it doesn't have any temperature 160 00:07:28,449 --> 00:07:25,969 control so as it got colder in the Attic 161 00:07:30,879 --> 00:07:28,459 hammer things things didn't work out so 162 00:07:33,039 --> 00:07:30,889 well as the temperature change turn a 163 00:07:35,769 --> 00:07:33,049 laser on it gets hot the response 164 00:07:38,109 --> 00:07:35,779 changes so we wanted to change the laser 165 00:07:42,489 --> 00:07:38,119 and work on this this was a category 1 166 00:07:45,579 --> 00:07:42,499 instrument for MSL but fibers caused a 167 00:07:47,769 --> 00:07:45,589 lot of concern so that is I think 168 00:07:52,089 --> 00:07:47,779 fundamentally why this instrument was 169 00:07:54,459 --> 00:07:52,099 not selected for MSL even though it was 170 00:07:56,949 --> 00:07:54,469 looked at in the early stages of the 171 00:07:58,779 --> 00:07:56,959 puzzle development so this is the 172 00:08:00,639 --> 00:07:58,789 current picture of the instrument so I 173 00:08:03,699 --> 00:08:00,649 got rid of two fibers and that about 174 00:08:05,589 --> 00:08:03,709 thousand wires know only about 100 so 175 00:08:07,269 --> 00:08:05,599 these are these are the wires between a 176 00:08:09,579 --> 00:08:07,279 controller which is a cots base 177 00:08:11,799 --> 00:08:09,589 instrument and this is the Rahman head 178 00:08:14,350 --> 00:08:11,809 here's the architecture we start with a 179 00:08:17,619 --> 00:08:14,360 laser going through like coming back 180 00:08:19,359 --> 00:08:17,629 that is longer than 532 is dispersed 181 00:08:22,239 --> 00:08:19,369 through the spectrometer and focuses on 182 00:08:27,569 --> 00:08:22,249 the back through CCD light is a shorter 183 00:08:30,879 --> 00:08:27,579 it's illuminated by 467 nanometer LEDs 184 00:08:32,679 --> 00:08:30,889 we also have UV LEDs but primarily these 185 00:08:35,259 --> 00:08:32,689 are the ones that are used this gives us 186 00:08:38,649 --> 00:08:35,269 a context imager we implement light 187 00:08:41,259 --> 00:08:38,659 field imaging like Chris does similar to 188 00:08:43,869 --> 00:08:41,269 what Chris does so that we don't need to 189 00:08:47,110 --> 00:08:43,879 implement an autofocus either for the 190 00:08:48,999 --> 00:08:47,120 context imager so here's a picture of 191 00:08:52,449 --> 00:08:49,009 some radiation testing we did with our 192 00:08:54,100 --> 00:08:52,459 JD su laser and so we ran it at two 193 00:08:56,049 --> 00:08:54,110 different currents that's kind of hard 194 00:08:57,850 --> 00:08:56,059 to see but the we're seeing hardly any 195 00:08:59,780 --> 00:08:57,860 change there's like a black shadow 196 00:09:03,770 --> 00:08:59,790 around this versus the blue 197 00:09:07,220 --> 00:09:03,780 for the 600 and the ends it's sorry for 198 00:09:09,230 --> 00:09:07,230 red and then for and and so essentially 199 00:09:11,360 --> 00:09:09,240 you can see very little change and you 200 00:09:14,360 --> 00:09:11,370 see the step like behavior that occurs 201 00:09:16,970 --> 00:09:14,370 as you switch across modes of this laser 202 00:09:20,360 --> 00:09:16,980 so it maintains single mode behavior 203 00:09:24,890 --> 00:09:20,370 over a wide distance and consists of a 204 00:09:26,540 --> 00:09:24,900 pump laser a KTP doubling crystal and a 205 00:09:29,930 --> 00:09:26,550 host crystal the vanadate laser that 206 00:09:33,170 --> 00:09:29,940 leaves us between these two places so 207 00:09:35,480 --> 00:09:33,180 anyhow this is the art this is the 208 00:09:37,730 --> 00:09:35,490 architecture of that laser we because we 209 00:09:41,680 --> 00:09:37,740 have a birefringence crystal did student 210 00:09:43,730 --> 00:09:41,690 and doubling it also causes 211 00:09:47,720 --> 00:09:43,740 implementation of something called Ali 212 00:09:49,970 --> 00:09:47,730 Leo filter which basically will vary its 213 00:09:52,160 --> 00:09:49,980 face as you teint change the temperature 214 00:09:54,140 --> 00:09:52,170 as you change the temperature the laser 215 00:09:57,050 --> 00:09:54,150 slightly what'll happen is this will 216 00:09:59,570 --> 00:09:57,060 start allowing this this mode or this 217 00:10:01,370 --> 00:09:59,580 mode of this motor this mode to lase and 218 00:10:03,800 --> 00:10:01,380 that's what's giving you the behavior 219 00:10:05,720 --> 00:10:03,810 here that we're seeing so what we do is 220 00:10:08,300 --> 00:10:05,730 we use this because we know that the 221 00:10:10,790 --> 00:10:08,310 Raman spectrum will shift with weight 222 00:10:13,820 --> 00:10:10,800 rady with wavelength shifts but the 223 00:10:16,370 --> 00:10:13,830 fluorescence things for s the lowest 224 00:10:18,350 --> 00:10:16,380 excited state and this will so this 225 00:10:21,080 --> 00:10:18,360 allows to separate these two things so 226 00:10:24,170 --> 00:10:21,090 we observe the raw spectra set for let's 227 00:10:27,410 --> 00:10:24,180 say 10 different samples we look at that 228 00:10:30,320 --> 00:10:27,420 and we mathematically solve for the 229 00:10:32,030 --> 00:10:30,330 fluorescence component separately from 230 00:10:34,640 --> 00:10:32,040 the Raman component and we can show 231 00:10:37,100 --> 00:10:34,650 here's some examples here of enstatite 232 00:10:39,610 --> 00:10:37,110 and here we have Dena caucus radiate 233 00:10:43,010 --> 00:10:39,620 Duran's which happens to have a 234 00:10:45,440 --> 00:10:43,020 carotenoid in it that is made without 235 00:10:47,300 --> 00:10:45,450 the use of light by the way and so this 236 00:10:51,080 --> 00:10:47,310 is a reasonable biomarker and we can do 237 00:10:53,570 --> 00:10:51,090 because green is a longer wavelength 238 00:10:55,040 --> 00:10:53,580 than UV you see longer molecules like 239 00:10:59,180 --> 00:10:55,050 carotenoids and you can get resin 240 00:11:02,990 --> 00:10:59,190 enhancement down to symptom - well or 241 00:11:04,760 --> 00:11:03,000 low picomolar type concentrations so 242 00:11:07,400 --> 00:11:04,770 we're also using light field imaging and 243 00:11:09,140 --> 00:11:07,410 I'll try to skim past this but since 244 00:11:11,490 --> 00:11:09,150 Chris talked about this but we're able 245 00:11:13,470 --> 00:11:11,500 to essentially do it 246 00:11:16,650 --> 00:11:13,480 we can look at various planes all in one 247 00:11:19,850 --> 00:11:16,660 shot and do this without any moving 248 00:11:22,650 --> 00:11:19,860 parts just wanted to show an example of 249 00:11:24,600 --> 00:11:22,660 sort of what happens in the in terms of 250 00:11:27,270 --> 00:11:24,610 RAW images as you put the images 251 00:11:29,610 --> 00:11:27,280 together you essentially can tell by 252 00:11:31,320 --> 00:11:29,620 looking at you cross-correlate these 253 00:11:34,170 --> 00:11:31,330 little sub regions and this allows you 254 00:11:35,970 --> 00:11:34,180 to get range information and allow you 255 00:11:39,270 --> 00:11:35,980 to all of them lace stitch the image 256 00:11:41,910 --> 00:11:39,280 back together and finally this is our 257 00:11:43,530 --> 00:11:41,920 cameras so so we have two different 258 00:11:46,410 --> 00:11:43,540 cameras now we have to mitigate issues 259 00:11:49,260 --> 00:11:46,420 of radiation so replacing what we're 260 00:11:53,460 --> 00:11:49,270 currently using the 47 - 20 tip with a 261 00:11:56,190 --> 00:11:53,470 much rad heart hard 347 - 20 chip same 262 00:11:59,400 --> 00:11:56,200 amount same electronics lower voltages 263 00:12:02,670 --> 00:11:59,410 bias voltages to make it operate and and 264 00:12:04,830 --> 00:12:02,680 so this has been developed by E - V and 265 00:12:06,480 --> 00:12:04,840 so our currently just essentially taking 266 00:12:07,980 --> 00:12:06,490 that chip in implementing electronics 267 00:12:10,350 --> 00:12:07,990 for it it's very similar to what we 268 00:12:12,720 --> 00:12:10,360 already have and we can't use the ki 269 00:12:14,220 --> 00:12:12,730 2020 which is what we which is in Mali 270 00:12:16,560 --> 00:12:14,230 but it's just not going to work with 271 00:12:19,950 --> 00:12:16,570 radiation we're replacing that with a 272 00:12:22,110 --> 00:12:19,960 CMOS CIS 115 which is used in Juneau and 273 00:12:23,730 --> 00:12:22,120 as they said where we love this 274 00:12:27,210 --> 00:12:23,740 architecture but we're gonna have to 275 00:12:28,860 --> 00:12:27,220 shift to special optics to make sure 276 00:12:32,130 --> 00:12:28,870 that they don't turn dark with radiation 277 00:12:34,320 --> 00:12:32,140 either here's two examples of the lasers 278 00:12:36,030 --> 00:12:34,330 I talked about this one this little tiny 279 00:12:38,130 --> 00:12:36,040 one we're also looking at that we just 280 00:12:41,970 --> 00:12:38,140 exposed to 10 times the radiation dose 281 00:12:44,250 --> 00:12:41,980 it's on Europa and it's working great so 282 00:12:46,110 --> 00:12:44,260 I think that's it this is a summary that 283 00:12:47,640 --> 00:12:46,120 I'll let you guys read but if I can 284 00:12:48,630 --> 00:12:47,650 answer any questions that would be great 285 00:12:53,120 --> 00:12:48,640 thanks 286 00:13:01,050 --> 00:12:58,170 any questions good I particularly like 287 00:13:03,000 --> 00:13:01,060 the use of the shifted laser wavelength 288 00:13:07,140 --> 00:13:03,010 to address the fluorescence background 289 00:13:08,880 --> 00:13:07,150 and amusingly in another life I spent 290 00:13:12,030 --> 00:13:08,890 about 30 or 40 years doing Raman 291 00:13:15,060 --> 00:13:12,040 spectroscopy and way back about 1992 and 292 00:13:16,980 --> 00:13:15,070 II Shrieve was working on looking at 293 00:13:18,570 --> 00:13:16,990 photosynthetic reaction Center residents 294 00:13:21,150 --> 00:13:18,580 Raman where the fluorescence is a real 295 00:13:22,800 --> 00:13:21,160 killer and we invented a technique which 296 00:13:24,090 --> 00:13:22,810 we called shifted excitation ROM on 297 00:13:26,610 --> 00:13:24,100 different spectroscopy 298 00:13:28,620 --> 00:13:26,620 so the acronym serdes never really 299 00:13:29,880 --> 00:13:28,630 caught on because it's kind of ugly but 300 00:13:31,290 --> 00:13:29,890 if you don't know about the reference 301 00:13:34,500 --> 00:13:31,300 I'll give it to you oh I certainly know 302 00:13:36,060 --> 00:13:34,510 about sir thank you very much so that's 303 00:13:38,880 --> 00:13:36,070 sort of what started the whole thing 304 00:13:43,140 --> 00:13:38,890 going this is search you bet 305 00:13:45,450 --> 00:13:43,150 well by the way I want to also just just 306 00:13:47,370 --> 00:13:45,460 offer up that we are looking for MPP 307 00:13:50,160 --> 00:13:47,380 postdoc applications which are coming 308 00:13:51,300 --> 00:13:50,170 due so if any of your students or any 309 00:13:53,640 --> 00:13:51,310 students in this room won't be